TITfrE STABILIZED POLYACETAL COMPOSITIONS BACKGROUND Technical Field Recently, new types of stabilizers have been developed for polyacetal compositions, also commonly referred to as polyoxymethylene compositions. These new stabilizers are microcrystalline cellulose, fibrous cellulose, and non-meltable polymers containing formaldehyde reactive hydroxy groups or formaldehyde reactive nitrogen groups or both. These new stabilizers impart better melt processing stability to polyacetal compositions than do conventional nylon stabilizers. It has now been found that the stability of the polyacetal compositions containing such new types of stabilizers can be improved even further. Specifically, for polyacetal compositions stabilized with microcrystalline or fibrous cellulose, even further improvements in the melt processing stability, as measured by thermally evolved formaldehyde tests, of the compositions can be achieved by the inclusion therein of certain polyamide based stabilizers and certain meltable hydroxy containing stabilizers. For polyacetal compositions stabilized with a non-meltable polymer stabilizer that contains formaldehyde reactive nitrogen groups or formaldehyde reactive hydroxy groups or both, the long term stability, as measured by air oven aging tests, of said compositions can be improved by either incorporating therein at least one amide-containing phenolic antioxidant or alternatively, incorporating therein at least one primary antioxidant along with at least one of certain conventional polyacetal thermal stabilizers, which are described in further detail below.

The compositions of the present invention are useful wherever enhanced melt processing stability and enhanced long term stability are desired. βac σround Art The following references are cited as background art for the improved cellulose-stabilized polyacetal compositions of the present invention:

U.S. patent 4,766,168 discloses hydroxy- containing polymers or oligomers as stabilizers for polyacetal. Microcrystalline and fibrous cellulose, both of which are non-melting at the melt processing temperature of polyacetal, are not specifically disclosed within this reference. Further, there is no recognition in this reference of the advantages that are obtained with the specific stabilizer combination used in the present invention.

U.S. patent 4,722,662 discloses a process for manufacturing oxymethylene copolymers stabilized against thermal degradation, said process comprising the heating of the copolymer in a medium containing water and a disubstituted cellulose ether to hydrolyze unstable oxymethylene ends and then separating said oxymethylene copolymer from said aqueous medium containing a disubstituted cellulose ether. Disubstituted cellulose ethers are known thermoplastics.

U.S. patent 4,111,887 discloses polyoxymethylene molding compositions exhibiting improved physical properties comprising an admixture of a polyoxymethylene polymer, a fibrous reinforcement which can include cellulosic fiber, and a polycarbodiimide.

U.S. patent 3,406,129 discloses melt blends of moldable cellulose polymer having free hydroxyl groups with up to 50% of acetal polymer and U.S.

patent 3,406,130 discloses colloidal dispersions of such blends with certain solvents for the cellulose polymer, which compositions are alleged to have improved melt strength and elongation. U.S. 3,406,129 specifically teaches that the use of greater than 50 weight percent polyacetal is detrimental to the melt blend. The cellulose disclosed in these references is not microcrystalline cellulose as it is moldable, and therefore, meltable at the melt processing temperature of polyacetal.

While some of the references discussed above disclose incorporating certain particular cellulosics into polyacetal compositions, none disclose the specific cellulosics used in the compositions of the present invention, nor do any disclose that microcrystalline or fibrous cellulose, in combination with at least one of certain co-stabilizer compounds, improves the thermal stability of polyacetal compositions. The following references are cited as background for the improved non-meltable polymer stabilized polyacetal compositions of the present invention:

U.S. patent 4,098,843 discloses polyoxymethylene compositions containing a dispersion of (1) a semicrystalline polyamide having a melting temperature about 25*C higher than the melting temperature of the polyoxymethylene or (2) an amorphous polyamide having a glass transition temperature at least about 5 ^# C higher than the melting temperature ^" of the polyoxymethylene, either of which must be dispersed in a polymeric carrier resin that melts at or below the melt processing temperature of the polyoxymethylene.

U.S. patent 4,640,949 discloses polyoxymethylene compositions stabilized with a stabilizer blend of 50-97 percent thermoplastic polyurethane and 3-50 percent polyamide wherein the polyamide is dispersed within the polyurethane and the melting temperature of the polyamide is above the melting temperature of the polyoxymethylene.

Japanese patent application publication 42-7107 discloses a polyoxymethylene or copolymer composition comprising polyoxymethylene polymer or its copolymer and a copolymer of acrylamide and styrene or vinyl napthalene. It is required that the copolymer of acrylamide and styrene or vinyl napthalene have a melting point equal to or below the melting point of the polyoxymethylene polymer or copolymer.

Japanese patent publication koho 43-14329 discloses a method of stabilizing formaldehyde polymers consisting of an addition of a copolymer of acrylamide or an acrylamide derivative. Japanese patent application publication

Kohai 59-213752 discloses a polyacetal composition containing a fine poly-beta-alanine powder as a heat stabilizer, wherein the poly-beta-alanine is obtained by hydrogen transfer polymerization of acrylamide. Hydrogen transfer polymerization yields nylon-3, wherein the majority of formaldehyde reactive nitrogen groups are in the backbone of the polymer.

West German published application no. P3715117 discloses a thermal stabilizer for polyacetal purported to be improved over that of the Japanese 59-21375 reference. In this particular reference, there is disclosed as a thermal stabilizer for polyacetal a poly-beta-alanine compound containing: (X) monomer units having the formula -(CH2CH2CONH)- and

(Y) monomer units having the formula -(CH ₂ CH)-

I

CONH2 characterized in that the content of monomer units (Y) lies in the range from 1.4 to 10 mM per gram of the compound, preferably from 5 to 9 mM per gram of the compound.

U.S. patent 4,814,397 discloses a thermal stabilizer for polyacetal consisting of polymers and oligomers containing both hydroxyl groups and at least one other functional group that is a stronger Lewis base than the hydroxyl groups. Excessively high stabilizer viscosity (from molecular weight or chemical composition) is undesirable because it can make it difficult to disperse the stabilizer in the polyacetal.

U.S. patent 4,766,168, also cited above for cellulose-stabilized polyacetal compositions, discloses a thermal stabilizer for polyacetal consisting of hydroxyl containing polymers and hydroxyl containing oligomers. The importance of stabilizer particle size is not recognized in this reference. U.S. patent 3,204,014 discloses a thermally stable polyacetal composition comprising a polyacetal and a ternary stabilizer system comprised of (a) a copolymer of N-vinylpyrrolidone and a monoolefinic monomer copolymerizable therewith, (b) a phenolic antioxidant, and (c) a diester of 3,3 ^, -thiodipropionic acid. TherQ is no recognition of the importance of the average particle size of the stabilizer or the non-meltable nature of the stabilizer.

U.S. patent 3,219,727 discloses polyoxymethylene compositions having enhanced heat

stability due to the incorporation therein of a vinyl polymer having side chains containing the structure

O

II -C-N- and particularly containing groups of the class consisting of amide groups and lactam groups. There is no recognition of the importance of small number average particle size in this reference, nor is there recognition that the stabilizer should be non-meltable.

U.S. patent 3,235,531 discloses a method for stabilizing oxymethylene copolymer. U.S. patent 3,210,322 discloses a method of treating a trioxane polymerization product comprised of an oxymethylene polymer, a trioxane polymerization catalyst, and unreacted trioxane. U.S. patent 3,236,929 discloses a method of injection molding oxymethylene copolymers. U.S. patent 3,418,280 discloses a method of stabilizing a polymer which is susceptible to thermal degradation because it contains monomeric units susceptible to degradation. In the immediately preceding four references, the oxymethylene polymer or copolymer may contain thermal stabilizers such as substituted polyacrylamides or compounds having 1-6 amide groups.

U.S. patent 4,230,606 discloses a melamine-formaldehyde polycondensate as a thermal stabilizer for polyoxymethylene. It is advantageous to form the melamine-formaldehyde precondensate in the presence of one or more protective colloids, which may include copolymers of acrylamide. There is no suggestion that copolymers of acrylamides are stabilizers for polyacetal.

U.S. patent 4,522,735 discloses polyphosphoramidite oligomers as effective stabilizers to protect polymers from degradation due to heat. Polymeric stabilizers are not disclosed. U.S. patent 4,555,357 discloses a polyacetal composition comprising polyacetal, carbon black, and an amide compound having a maximum of 6 repeat units.

U.S. patent 4,596,847 discloses a polyacetal composition comprising polyacetal, carbon black, and a nonionic surfactant.

U.S. patent 4,657,970 and U.S. patent 4,657,971 disclose compositions comprised of at least one thermoplastic polymer, such as polyoxymethylene, and at least one modified block copolymer comprised of t least one monovinyl substituted aromatic hydrocarbon polymer block A and at least one olefin compound polymer block B. The composition has improved impact resistance.

U.S. patent 3,215,671 discloses a process for crosslinking with ultraviolet light a mixture of polyoxymethylene and a functional derivative of a carboxylic acid selected from the group consisting of amides, esters, and imides.

U.S. patent 3,281,499 discloses a process for preparing polyoxymethylene copolymers from ethylenically unsaturated comonomers, including acrylamide. This is related to the preparation of a polyoxymethylene copolymer, not to stabilizing polyoxymethylene. U.S. patent 3,338,872 discloses a polyoxymethylene copolymer prepared from formaldehyde and an acrylic monomer such as acrylamide and methacrylamide. This is related to the preparation of a polyoxymethylene copolymer, as opposed to a means to stabilize polyoxymethylene.

U.S. patent 3,366,561 discloses a method for producing polyoxymethylene copolymers by polymerizing trioxane with a copolymerizable monomer, which can be acrylamide. There is no recognition or teaching of the particular parameters of the present invention in this reference.

U.S. patent 3,470,135 discloses a process for preparing a stabilized polyoxymethylene comprised of polymerizing formaldehyde in the presence of a catalyst which is an organic compound of tetravalent tin.

U.S. patent 3,518,326 discloses thermosetting resins derived from acrylamide and formaldehyde. It does not disclose means by which to impart thermal stability to polyacetal.

U.S. patent 4,464,435 discloses a polyacetal composition comprised of (a) a polyacetal, (b) a carbonate, phosphate, acetate, or their mixture of a metal belonging to Group II of the Periodic Table, and (c) a polymer or copolymer selected from the group consisting of, amongst others, amides of acrylic acid or methacrylic acid. Component (c) is added for the purpose of preventing a molded product from encountering crack formation. There is no mention of improving thermal stability during melt processing.

None of the references discussed above disclose the particular embodiments of the present invention and specifically, none disclose the advantages that can be obtained when the mixed stabilizer systems or particular antioxidants of the present invention are incorporated into a polyacetal composition.

SUMMARY OF THE INVENTION The present invention relates to cellulose-stabilized polyacetal compositions having

improved thermal stability. More specifically, it relates to polyacetal compositions stabilized with 0.05 to 5 weight percent of microcrystalline or fibrous cellulose and 0.05 to 4 weight percent of at least one co-stabilizer compound selected from the group consisting of polyamide-based co-stabilizers and co-stabilizers that are meltable polymers or meltable oligomers containing hydroxy groups, wherein the microcrystalline cellulose has an average particle size of 100 microns or less and the co-stabilizer meltable polymer or meltable oligomer containing hydroxy groups is substantially free of acidic materials, with the above weight percents being based upon the weight of the cellulose, the co-stabilizer compounds, and the polyacetal. The resultant polyacetal compositions are characterized as having improved thermal stability, on average, over that of polyacetal alone, polyacetal stabilized with polyamide-based stabilizers alone, and polyacetal stabilized only with stabilizers that are meltable polymers or meltable oligomers containing hydroxy groups.

The present invention further relates to non-meltable polymer stabilized polyacetal compositions having improved thermal stability. More specifically, it relates to polyacetal compositions stabilized with 0.05-3.0 weight percent of a non-meltable polymer stabilizer, described below, and 0.02-1.0 weight percent of at least one amide-containing phenolic antioxidant, with the above weight percents being based upon the weight of the polyacetal, the non-meltable polymer stabilizer, and the amide-containing phenolic antioxidant. Alternatively, the thermal stability of such non-meltable polymer stabilized polyacetal

compositions can be improved by the inclusion therein of 0.05-3.0 weight percent of a non-meltable polymer stabilizer, 0.02-1.0 weight percent of at least one primary antioxidant, and 0.01-1.00 weight percent of at least one meltable co-stabilizer compound, with the above weight percents being based upon the weight of the polyacetal, the non-meltable polymer stabilizer, the anti-oxidant, and the meltable co-stabilizer compound. The non-meltable polymer stabilizer contains formaldehyde reactive hydroxyl groups and/or formaldehyde reactive nitrogen groups, has a number average particle size, in the polyacetal, of less than ten microns, is non-meltable, and is used to increase the melt processing stability of polyacetal. The meltable co-stabilizer compound used in such non-meltable polymer stabilized polyacetal compositions is selected from known meltable thermal stabilizers for polyacetal. The antioxidants, both primary and amide-containing phenolic, are known in the art. The meltable co-stabilizer and the antioxidants are used not to provide increased stability during processing but rather, to provide increased stability over time upon exposure to air. The presence of an amide-containing phenolic antioxidant or alternatively, a meltable co-stabilizer compound and a primary antioxidant, in the polyacetal composition results in a significant improvement in the long term, aerobic stability of the polyacetal composition.

DETAILED DESCRIPTION OF THE INVENTION This invention relates to improving the stability of cellulose-stabilized polyacetal

compositions and to improving the stability of non-meltable polymer stabilized polyacetal compositions.

I. CELLULOSE STABILIZED POLYACETAL COMPOSITIONS It has been found that polyacetal compositions stabilized with a mixed stabilizer system of microcrystalline or fibrous cellulose and at least one co-stabilizer compound have improved thermal stability, as measured by lower evolution of formaldehyde. The mixed stabilizer system, which consists of microcrystalline or fibrous cellulose, said microcrystalline and fibrous cellulose being non-melting at the temperature at which polyacetal is melt processed, and at least one co-stabilizer compound has been found to not degrade as readily as the conventional nylon stabilizers. Further, the thermal stability of polyacetal compositions stabilized with the mixed cellulose-based stabilizer system of the present invention is, on average, better than the thermal stability, as measured by a thermally evolved formaldehyde test, of polyacetal compositions stabilized with only an individual component of the present stabilizer system.

To achieve the improvements mentioned above, i.e., lower evolution of formaldehyde, the cellulose-stabilized compositions of the present invention will consist essentially of (a) 0.05 to 5 weight percent microcrystalline or fibrous cellulose stabilizer, (b) 0.05 to 4 weight percent of at least one co-stabilizer compound selected from the group consisting of polyamides-based co-stabilizers and meltable hydroxy containing polymer or oligomer co-stabilizers, and (c) 91.0 to 99.9 weight percent of a polyacetal. Preferably, the cellulose-stabilized compositions of the present invention consist

essentially of 0.05 to 2 weight percent of component (a) cellulose stabilizer, 0.05 to 2 weight percent of component (b) co-stabilizer compound, and 96.0 to 99.9 weight percent of component (c) polyacetal. Most preferably, the cellulose-stabilized compositions of the present invention consist essentially of 0.05 to 1 weight percent of component (a) cellulose stabilizer, 0.05 to 1 weight percent of component (b) co-stabilizer compound, and 98.0 to 99.9 weight percent of component (c) polyacetal. All the above weight percents are based upon the total weight of components (a) , (b) , and (c) only. If more than one co-stabilizer compound is used in the cellulose-stabilized compositions of the present invention, the total weight percent of such co-stabilizer compounds in the cellulose-stabilized compositions should be within the range disclosed above for component (b) .

1(a). Component (c) : Polyacetal The term "polyacetal* as used herein includes homopolymers of formaldehyde or of cyclic oligomers of formaldehyde, the terminal groups of which are end-capped by esterification or etherification, and copolymers of formaldehyde or of cyclic oligomers of formaldehyde and other monomers that yield oxyalkylene groups with at least two adjacent carbon atoms in the main chain, the terminal groups of which copolymers can be hydroxyl terminated or can be end-capped by esterification or etherification.

The polyacetals used in the compositions of the present invention can be branched or linear and will generally have a number average molecular weight in the range of 10,000 to 100,000, preferably 20,000 to 70,000. The molecular weight can conveniently be

measured by gel permeation chromatography in m-cresol at 160"C using a Du Pont PSM bimodal column kit with nominal pore, size of 60 and 1000 A. Although polyacetals having higher or lower molecular weight averages can be used, depending on the physical and processing properties desired, the polyacetal molecular weight averages mentioned above are preferred to provide optimum balance of good mixing of the various ingredients to be melt blended into the composition with the most desired combination of physical properties in the molded articles made from such compositions.

As indicated above, the polyacetal can be either a homopolymer, a copolymer or a mixture thereof. Copolymers can contain one or more comonomers, such as those generally used in preparing polyacetal compositions. Comonomers more commonly used include alkylene oxides of 2-12 carbon atoms and their cyclic addition products with formaldehyde. The quantity of comonomer will not be more than 20 weight percent, preferably not more than 15 weight percent, and most preferably about 2 weight percent. The most preferred comonomer is ethylene oxide. Generally polyacetal homopolymer is preferred over copolymer because of its greater stiffness. Preferred polyacetal homopolymers include those whose terminal hydroxyl groups have been end-capped by a chemical reaction to form ester or ether groups, preferably acetate or methoxy groups, respectively. 1(b). Components (a) and (b) : The Cellulose- based Stabilizer System

The stabilizer system used in the cellulose-stabilized compositions of the present invention is comprised of component (a) microcrystalline or fibrous cellulose and component

(b) at least one co-stabilizer compound selected from polyamide-based co-stabilizers and certain meltable hydroxy containing polymer and oligomer co-stabilizers.

1(b) (i). Component (a): Microcrystalline and Fibrous Cellulose

The component (a) cellulose stabilizer is specifically either microcrystalline or fibrous cellulose. Microcrystalline cellulose is preferred.

Both microcrystalline and fibrous cellulose are derived from naturally occurring cellulose and are non-melting at the melt processing temperature of polyacetal.

Microcrystalline cellulose is known in the art and is commercially available. It is described in detail in U.S. patent 3,023,104, incorporated herein by reference, and it is referred to therein as

"cellulose crystallite aggregates". Microcrystalline cellulose is also described in "Hydrolysis and Crystallization of Cellulose", Industrial and

Engineering Chemistry, vol. 42, 502-507 (1950).

Consistent with that which is taught in U.S. patent 3,023,104, the microcrystalline cellulose useful in the cellulose-stabilized compositions of the present invention can be obtained from a commercial source or can be prepared by acid hydrolysis of cellulose. In either case, the microcrystalline cellulose should meet the purity requirements set forth below. In the acid hydrolysis of cellulose, the acid dissolves any amorphous portion of the original cellulose chains. The undissolved portion remaining from such hydrolysis is in a particulate, non-fibrous or crystalline form, said form being the result of the disruption of the continuity of the fine structures between the crystalline and amorphous regions of the

original cellulose. The undissolved portion, which is in crystalline form, is known to be non-melting at the melt processing temperature of polyacetal. The melt processing temperature of polyacetal generally does not exceed 280*C. The methods of preparing microcrystalline cellulose by the acid hydrolysis of cellulose are known to those in the art and are, for example, described in U.S. patent 3,023,104, column 2 and the examples. The microcrystalline cellulose used in the cellulose-stabilized compositions of the present invention has a certain level-off degree of polymerization. Level-off degree of polymerization is described in U.S. patent 3,023,104. More specifically, it is described therein as being the point at which the cellulose that is subjected to acid hydrolysis reaches, after a certain period of time, a substantially constant molecular weight. In other words, it is the point at which the number of repeating units or monomers, sometimes designated anhydroglucose units, which make up the cellulosic material, becomes relatively constant. It is at this point that it is apparent that the degree of polymerization of the material has leveled off, hence the name level-off degree of polymerization.

Consistent with what is disclosed in U.S. patent 3,023,104, the microcrystalline cellulose useful in the cellulose-stabilized compositions has a preferred average level-off degree of polymerization of 125 to 375 anhydroglucose units. Ideally, within this range all of the material should have the same degree of polymerization but as this is difficult, if not impossible, to achieve, it is preferred that at least 85% of the material have an actual degree of polymerization not less than 50 and not more than 550.

More preferably, within the average level-off degree of polymerization of 125 to 375, at least 90% of the material should have an actual degree of polymerization within the range of 75 to 500, and it is still more preferred that at least 95% of the material has an actual degree of polymerization in the range of 75 to 450. The more preferred average level-off degree of polymerization for the microcrystalline cellulose useful herein is in the range of 200 to 300, of which material at least 90% has an actual degree of polymerization in the range of 75 to 550. The most preferred average level-off degree of polymerization for the microcrystalline cellulose useful herein ranges from 175 to 225. As taught in U.S. patent 3,023,104, microcrystalline cellulose will usually have an average particle size of 300 microns. For purposes of this invention, the average particle size is the point at which 50% of the particles are greater than average and 50% of the particles are less than average.

Average particle size can be determined by standard techniques, such as microscopic inspection, gravitational sedimentation, sieve analysis, and electron microscopy. The preferred method of determining particle size is gravitational sedimentation.

It has been found that, for cellulose-stabilized compositions, stability increases as the average particle size of the microcrystalline cellulose decreases. As such, although microcrystalline can have an average particle size of about 300 microns, it is preferred that the average particle size of the microcrystalline cellulose used herein be 100 microns or less, more preferably 50

microns or less, even more preferably 25 microns or less, and most preferably 10 microns or less.

Fibrous cellulose is known in the art and is commercially available. It can be prepared from naturally occurring cellulose by techniques readily available to those skilled in the art. For example, a fibrous cellulose can be made by pulverizing wood pulp and then subsequently purifying it to meet the purity requirements described below. It is also a naturally occurring substance, an example of which is cotton linter. Fibrous cellulose generally exists in the form of flat ribbons. The width and thickness of these flat ribbons of fibrous cellulose is not considered critical in achieving the results exemplified herein. In general, however, the width of these flat ribbons will be, on average, approximately 25 microns and the thickness of these flat ribbons will be, on average, 6 microns. The length of the flat ribbons of the fibrous cellulose is also not considered critical in achieving the results exemplified herein. Fibrous cellulose is commercially available over a range of average fiber lengths, including from 300 microns down through less than 22 microns. Although average fiber length is not considered critical, it is expected that stability results will improve as average fiber length decreases due to the increase that such a decrease in average fiber length causes in the surface area of the fibrous cellulose stabilizer.

Another type of naturally occurring fibrous cellulose can be obtained from cellulose-producing bacteria, such as acetobacter and gluconobacter, via standard fermentation processes. After the fermentation process, the bacterial cells are destroyed via a hot caustic treatment and bacterial cellulose fibers are isolated by a series of washing

and de-watering steps. The bacterial cellulose fibers that result can occur as intricately cross-linked networks or as distinct fibers. The thickness of these bacterial cellulose fibers is typically about 0.1 microns.

It is important that both the microcrystalline cellulose and the fibrous cellulose used in the cellulose-stabilized compositions herein be substantially free of compounds which destabilize acetal resins. Destabilizing impurities that are likely to occur in commercially available microcrystalline and fibrous cellulosics that are useful in the compositions of the present invention can be assayed via (1) the pH of an aqueous suspension of 1-10 weight percent microcrystalline or fibrous cellulose, (2) the non-volatile ash content of the microcrystalline or fibrous cellulose, and/or (3) the heavy metal content of the microcrystalline or fibrous cellulose. More specifically, it is recommended that, for optimum results, the pH of an aqueous suspension of 1-10 weight percent of the microcrystalline or fibrous cellulose useful in the compositions of the present invention be in the range of 5.5-7 for homopolymer polyacetal and in the range of 5.5-8 for copolymer polyacetal. It is more preferred that the pH of the suspension be in the range of 5.5-7 for both homopolymer and copolymer polyacetal. It is recommended that the non-volatile ash content (ashing conducted at greater than or equal to 800*C) of the microcrystalline cellulose or fibrous cellulose be less than 0.25%, more preferably less than 0.10%, and most preferably less than 0.02%. It is also recommended that the heavy metal content of the microcrystalline cellulose and the fibrous cellulose

be less than 10 ppm. For maximum thermal stability results, it is generally recommended that the non-volatile _. ash content and the heavy metal content of the microcrystalline cellulose and the fibrous cellulose be minimized.

1(b) (ii). Component (b) : Co-stabilizer Compound

The term "co-stabilizer compound" as used in the cellulose-stabilized compositions herein means those compounds selected from the group consisting of polyamide-based co-stabilizers and certain co-stabilizers that are meltable polymers or meltable oligomers containing hydroxy groups. By "meltable" it is meant that the polymer or oligomer containing hydroxy groups has a melting point or glass transition temperature less than the temperature at which the polyacetal is melt processed or alternatively, it is meant that said co-stabilizer has a melt flow rate greater than the one-tenth that of the polyacetal at the temperature at which the polyacetal is melt-processed. The melting point and glass transition temperature can be determined by standard DSC analysis techniques and the melt flow rate can be determined by techniques known to those in the art, such as ASTM-D 1238. Acceptable techniques are described below in the section on non-meltable polymer stabilizers. The component (b) co-stabilizer compound may be one co-stabilizer compound or it may be more than one co-stabilizer compound.

The polyamide-based co-stabilizers useful in the cellulose-stabilized compositions herein are known in the art and are further known to be a thermal stabilizers for polyacetal. The polyamide-based stabilizers may be meltable or non-meltable at the temperature at which the polyacetal is melt processed.

Such polyamide co-stabilizer compounds are commercially available and can be prepared by techniques readily available to those skilled in the art. Specific polyamide-based co-stabilizers useful in the compositions of the present invention are described in several U.S. patents, including Alsup et al, U.S.P. 2,993,025 and Johnson, U.S.P. 4,098,843, each of which is incorporated herein by reference. A preferred polyamide-based co-stabilizer is nylon 66 predispersed in a carrier resin (as described in Johnson, U.S.P. 4,098,843). Another preferred polyamide-based co-εtabilizer is a 33/23/43 terpolymer of nylon 66, nylon 6/10, and nylon 6, respectively. Yet another preferred polyamide-based co-stabilizer is an 85/15 copolymer of nylon 66 and nylon 6, respectively, predispersed in a carrier resin, such as, for example, a thermoplastic polyurethane carrier resin. Polyamide copolymers of the immediately preceding type are described in detail in Wagman,

U.S.P. 4,640,949, incorporated herein by reference. The certain meltable polymers or meltable oligomers containing hydroxy groups co-stabilizers useful in the cellulose-stabilized compositions herein are known in the art and are described in U.S. patent 4,766,168 and U.S. patent 4,814,397, each of which is incorporated herein by reference.

Specifically, the meltable polymer or meltable oligomer containing hydroxy groups co-stabilizer described in U.S. patent 4,766,168 is a polymer, orOligomer containing hydroxy groups wherein the atoms in the backbone to which the hydroxy groups are attached, either directly or indirectly, are separated from each other by not more than twenty chain atoms. Preferably, the meltable polymer or

meltable oligomer containing hydroxy groups co-stabilizer compound is an hydroxy containing polymer or oligomer containing on average at least one hydroxy group per each twenty carbon atoms in the backbone of the polymer or oligomer and not more than one hydroxy group per carbon atom in the backbone. More preferably, the ratio of carbon atoms in the backbone will be 1:2-1:10, and most preferably 1:2-1:5. Specific preferred meltable polymers containing hydroxyl groups co-stabilizers include poly(vinyl alcohol), poly(ethylene vinyl alcohol), hydroxyesters of poly( eth)aerylates, such as poly(hydroxypropyl methacrylate) or poly(hydroxyethyl methacrylate) , and vinyl alcohol/methylmethacrylate copolymers. The preferred meltable polymer containing hydroxyl groups co-εtabilizer is poly(ethylene vinyl alcohol) .

Specifically, the meltable polymer or meltable oligomer containing hydroxy groups co-stabilizer described in U.S. 4,814,397 is a polymer or oligomer containing both hydroxy groups and at least one other functional group that is a stronger Lewis base than the hydroxy groups wherein the atoms in the backbone of the polymer or oligomer to which the hydroxy groups are attached, indirectly or directly, are separated, on average, by not more than twenty chain atoms. Examples of the other functional groups include amides, amines, ureas, and urethanes. Amides and amines are preferred; amides are most preferred. Specific preferred examples of this particular meltable hydroxy containing co-stabilizer include copolymers of hydroxypropyl methacrylate with acrylamide, methacrylamide, dimethyl minoethyl methacrylate, or vinyl 2-pyrrolidone.

Ifc). Purity Recommendations for the Components It is important that both the microcrystalline or fibrous cellulose and the co-stabilizer compounds used in the cellulose-stabilized compositions herein be substantially free of compounds which destabilize acetal resins. Heavy metal content, ash content, and pH range for microcrystalline and fibrous cellulose has been detailed above. Other purity recommendations are detailed below.

In stabilizing ester-capped or partially ester-capped polyacetal homopolymer, it is recommended that the microcrystalline and fibrous cellulose and the co-stabilizers be substantially free of basic materials, such as metals, ammonium hydroxide, sodium acetate, and other alkali and alkali earth acetates which can destabilize the polyacetal. Basic impurities in microcrystalline and fibrous cellulose should preferably be removed to levels of not more than 200 ppm and most preferably to not more than 10 ppm while basic impurities in the co-stabilizers should preferably be removed to levels of not more than 50 ppm and most preferably to not more than 10 ppm. In stabilizing polyacetal copolymer or homopolymer that is substantially all ether-capped, higher concentrations of basic materials in the microcrystalline and fibrous cellulose and the co-stabilizers can be tolerated. In addition, it should be understood that if the impurity in the microcrystalline and/or fibrous cellulose or the co-stabilizer is only weakly basic, relatively higher amounts ^" can be tolerated.

In using the microcrystalline and fibrous cellulose and the co-stabilizers in stabilizing both homopolymer and copolymer polyacetal, it is also

recommended that acidic impurities in the microcrystalline and fibrous cellulose and the co-stabilizer compound should be minimized. For microcrystalline and fibrous cellulose, acidic impurities should preferably be removed to levels of not more than 250 ppm and most preferably to not more than 10 ppm while for the co-stabilizer, such impurities should preferably be removed to not more than 50 ppm and most preferably to not more than 10 ppm. As with the basic impurities, it should be understood that if the impurity in the microcrystalline and/or fibrous cellulose or the co-stabilizer is only weakly acidic, relatively higher amounts can be tolerated. Accordingly, when such acidic and/or basic impurities are present in the microcrystalline and/or fibrous cellulose and/or the co-stabilizers in amounts large enough to cause destabilization of the cellulose-stabilized polyacetal compositions, then the microcrystalline and/or fibrous cellulose and/or the co-stabilizer should be purified before it is introduced into the cellulose-stabilized compositions herein. Volatile impurities in the microcrystalline and/or fibrous cellulose and/or the co-stabilizer can be removed by use of a vacuum oven. Non-volatile impurities in the microcrystalline and/or fibrous cellulose and/or the co-stabilizer can be purified by washing the microcrystalline and/or fibrous cellulose or the co-stabilizer with an appropriate liquid, such as, for example, water.

1(d)..Other Components

It should be understood that the cellulose-stabilized polyacetal compositions of the present invention can include, in addition to the

polyacetal, the microcrystalline or fibrous cellulose, and the at least one co-stabilizer compound, other ingredients, modifiers and additives as are generally used in polyacetal molding resins, including co-stabilizers other than those described herein, anti-oxidants, pigments, colorants, toughening agents, reinforcing agents, uv εtabilizerε, hindered amine εtabilizers, nucleating agents, lubricants, glass fibers, silicone oil, polytetrafluoroethylene powder or fiber, and fillers. It should also be understood that some pigments and colorants can, themselves, adversely affect the stability of polyacetal compositions.

II. NON-MELTABLE POLYMER STABILIZED POLYACETAL COMPOSITIONS

This invention further relates to improving the long term stability of polyacetal compositions stabilized for melt processing purposes with a non-meltable polymer stabilizer by the inclusion therein of an amide-containing phenolic antioxidant or alternatively, by the inclusion therein of a primary antioxidant and a meltable co-stabilizer compound.

II(a) . Non-Meltable Polymer Stabilized Compositions Improved With An Amide-Containing Phenolic Antioxidant

Polyacetal compositions containing non-meltable polymer stabilizers have been found to possess excellent processing stability. However, said compositions may undergo loss of physical properties over time upon exposure to air. Due to the excellent processing stability that these compositions possess, it is highly desirous to use these compositions in commercial applications. As such, it is also desirous to improve upon the long term stability, or the retention of properties over time, for these

non-meltable polymer stabilized polyacetal compositions.

It has been found that a particular antioxidant will significantly improve upon the long term stability, as evidenced by the long term retention of properties, of polyacetal compositions containing a non-meltable polymer stabilizer. It is important to note that while antioxidants are known to provide enhanced stability to many compositions, they are not always readily transferable from one polyacetal composition to another. The effectiveness of an antioxidant can be dependent upon several variables, such as, for example, the particular base polymer in the composition and the particular stabilizer in the composition. Further, interactions can occur between the antioxidant and the stabilizer, or any other component in the composition, that can limit the effectiveness of the antioxidant or that will result in a composition with unacceptable properties.

Specifically, it has been found that the antioxidant that is most effective in improving the long term stability of polyacetal compositions containing at least one non-meltable polymer stabilizer is an amide-containing phenolic antioxidant. When the non-meltable polymer stabilized polyacetal composition contains at least one amide-containing phenolic antioxidant, the composition retains its overall physical properties to a much greater and more significant extent than it does when there is no antioxidant present or when the antioxidant added is a non-amide-containing phenolic antioxidant.

The non-meltable polymer stabilized compositions that are improved with an amide-

containing phenolic antioxidant consist essentially of (a) 0.05-3.0 weight percent of at least one non-meltable polymer stabilizer, (b) 0.02-1.0 weight percent of at least one amide-containing phenolic antioxidant, and (c) 96.0-99.93 weight percent of the polyacetal. Unless otherwise specified, all weight percentages discloεed in this paragraph are based upon the weight of the polyacetal, the non-meltable polymer stabilizer, and the amide-containing phenolic antioxidant. Preferably, the composition contains 0.15-1.5 weight percent, most preferably 0.2-1.0 weight percent, of the component (a) non-meltable polymer stabilizer. The amide-containing phenolic antioxidant iε preferably present at 0.02-0.5 weight percent, most preferably 0.05-0.25 weight percent.

Optionally, non-amide-containing phenolic antioxidant may be incorporated into the composition at 0.05-0.50 weight percent, preferably 0.05-0.25, and most preferably, 0.10-0.20 weight percent of the composition, said weight percent being based upon the weight of the polyacetal, the non-meltable polymer stabilizer, and all antioxidant types.

It haε been further found that the long term εtability of polyacetal compositions containing a non-meltable polymer stabilizer can be improved with the addition to the composition of at least one primary antioxidant and a minor amount of at least one meltable co-stabilizer for polyacetal.

IIfa)(i). Component (c) : Polyacetal The component (c) polyacetal polymer useful in these non-meltable polymer stabilized compositions is identical to the component (c) polyacetal polymer described above for cellulose-stabilized polyacetal compositions.

11(a) (ii). Component (a): Non-meltable Polymer Stabilizer

The non-meltable polymer stabilizer used herein is a homopolymer or copolymer containing formaldehyde reactive nitrogen groups, formaldehyde reactive hydroxyl groups, or both formaldehyde reactive nitrogen and formaldehyde reactive hydroxyl groups. By "formaldehyde reactive" it is meant that the hydroxyl group contains an oxygen with a hydrogen atom bonded to it and the nitrogen group contains a nitrogen with one or two hydrogen atoms bonded to it. Formaldehyde will react with the -OH or the -NH bonds of the non-meltable polymer stabilizer. These reactive sites are referred to herein as formaldehyde reactive sites. It is preferred that the non-meltable polymer stabilizer contain formaldehyde reactive nitrogen or hydroxyl groups having the maximum number of formaldehyde reactive siteε. For example, a non-meltable polymer stabilizer containing formaldehyde reactive nitrogen groups wherein there are two hydrogen atoms attached directly to the nitrogen atom (i.e., two formaldehyde reactive sites in the group) is preferred over one containing formaldehyde reactive nitrogen groups wherein there is only one hydrogen atom attached directly to the nitrogen atom (i.e., one formaldehyde reactive site in the group) .

The non-meltable polymer stabilizer has at least ten repeat units. It preferably has a weight average molecular weight of greater than 5,000, most preferably,greater than 10,000. Higher weight average molecular weights are most preferred and further, such higher weight average molecular weights may be advantageous for reducing mold deposit formation.

The non-meltable polymer stabilizer is further non-meltable at the temperature at which the polyacetal is melt processed. By the term "non-meltable", it is meant that the non-meltable polymer stabilizer has its "major melting point" above the temperature at which the polyacetal is melt processed and thus remains essentially a solid during melt processing of the polyacetal. Alternatively, a non-meltable polymer stabilizer iε "non-meltable" if the non-meltable polymer stabilizer has its "major melting point" below the temperature at which the polyacetal is melt procesεed but, it does not undergo significant melt flow at that temperature. The melt flow rate of the non-meltable polymer stabilizer may not be significant because the non-meltable polymer εtabilizer haε a high viεcoεity, attributed to, for example, high molecular weight or crosslinking.

In the case where the non-meltable polymer stabilizer has its "major melting point" below the temperature at which the polyacetal is melt processed, the melt flow rate of the non-meltable polymer stabilizer, as measured in accordance with ASTM-D 1238, is preferably less than one-tenth that of the polyacetal. The "major melting point" of the non-meltable polymer εtabilizer can be determined on a differential scanning calorimeter. "Major melting point" is the temperature at which the amount of heat absorbed, by the non-meltable polymer stabilizer, is greatest; i.e., it is the temperature at which the polymer εtabilizer shows the greatest endotherm. As an example of how to measure melt flow rate, and in accordance.with ASTM-D 1238, the melt flow rate should be measured at 200*C under a load of 2.16 kilograms. The non-meltable polymer stabilizer should be dried at about 90'C for about 12 hours prior to measuring the

melt flow rate. The non-meltable polymer stabilizer εhould then be loaded into the plugged melt indexer and heated to teεt temperature over a εix minute time period, after which time the plug iε releaεed. The melt flow rate is determined over three minute intervals. The technique for measuring melt flow rate is further discussed below, after the disclosure relating to the preparation of the non-meltable polymer stabilizer. The major melting point of the non-meltable polymer stabilizer can, for example, be determined on a DUPONT Model 9900 DIFFERENTIAL SCANNING CALORIMETER (DSC) in a nitrogen atmosphere. To eliminate the possible effect of small amounts of moisture or solventε, each non-meltable polymer stabilizer should be first heated to about 140'C and held there for about 10 minuteε. The samples should then be cooled to about 25 'C and then heated at a rate of about 20'C/minute up to about 350*C. On the particular DSC above, the temperature at which endotherms occur will be given. Also, the amount of heat absorbed, in Joules/gram, at each respective endotherm will be given. The major melting point iε the temperature at which the greateεt amount of heat, in Joules/gram, is absorbed.

Polyacetals are usually melt processed at melt temperatures of about 170-260*C, preferably 185-240'C, most preferably 200-230 ^# C. The non-meltable polymer εtabilizer should be non-meltable at the particular temperature at which the polyacetal is melt processed.

The non-meltable polymer stabilizer must further have a number average particle size of less than 10 microns after melt processing with the polyacetal. It εhould also have a number average

particle size of less than 10 microns before melt proceεsing with the polyacetal. It εhould be underεtood that a high degree of looεe agglomeration of particleε in the non-meltable polymer εtabilizer may occur during the preparation and iεolation of the non-meltable polymer εtabilizer, such as, for example, during the drying of the non-meltable polymer stabilizer. In order for one to obtain a true and accurate measurement of the number average particle size, prior to melt processing, for a non-meltable polymer εtabilizer containing a high degree of looεe agglomerateε, the loose agglomerates should be broken up prior to measuring or, alternatively, they should be discounted in making εaid measurement. Whether or not a non-meltable polymer εtabilizer contains a high degree of loose agglomerates can be determined by standard techniques of transmiεsion electron microscopy. The details of determining the number average particle size, both before and after melt processing, are disclosed below.

The formaldehyde reactive hydroxyl groups can be incorporated into the non-meltable polymer εtabilizer by using an appropriate hydroxyl containing, monomer, such as, for example, hydroxyl alkyl acrylates or methacrylates. Alternatively, the formaldehyde reactive hydroxyl groups can be generated on the non-meltable polymer stabilizer by transforming another group into a hydroxyl group, such as, for example, by hydrolysis of esterε or epoxideε, or by reduction of carbonyl groups. Regardlesε of the methodε by- hich the formaldehyde reactive hydroxyl groups are incorporated, the non-meltable polymer stabilizer prepared therefrom must be non-meltable, or capable of being made non-meltable, at the temperature at which the polyacetal is melt processed.

Similarly, the formaldehyde reactive nitrogen groups can be incorporated into the non-meltable polymer stabilizer by using an appropriate nitrogen containing monomer, such as, for example, acrylamide and methacrylamide. Preferred nitrogen containing monomers are those that result in the polymer stabilizer containing formaldehyde reactive nitrogen groups wherein there are two hydrogen atoms attached to the nitrogen. The particularly preferred monomer is acrylamide which, when polymerized, results in a polymer stabilizer having substantially all of the formaldehyde reactive nitrogen groups attached directly aε a side chain of the polymer backbone or indirectly as a side chain of the polymer backbone. Alternatively, the formaldehyde reactive nitrogen groups can be generated on the non-meltable polymer stabilizer by modification of the polymer or copolymer. The formaldehyde reactive nitrogen groups may be incorporated by either method as long as the resultant polymer is non-meltable, or is capable of being made non-meltable, at the temperature at which the polyacetal is melt processed.

The quantity of the formaldehyde reactive hydroxyl or nitrogen groups in the non-meltable polymer stabilizer must be such that the atoms in the backbone to which the formaldehyde reactive groups are attached, either directly or indirectly, are separated from each other (i.e., connected to each other) by not more than twenty chain atoms. Preferably, the non-meltable polymer εtabilizer will contain at least one formaldehyde reactive hydroxyl or nitrogen group per each twenty carbon atoms in the backbone of the polymer. More preferably, the ratio of formaldehyde reactive hydroxyl or nitrogen groups to carbon atoms

in the backbone will be 1:2-1:10, most preferably 1:2-1:5.

The formaldehyde reactive nitrogen groups should further be present in the non-meltable polymer stabilizer εuch that the amount of the formaldehyde reactive nitrogen groups as, or part of, the side chains of the non-meltable polymer stabilizer backbone is at least 3 times, preferably at least ten times, the amount of the formaldehyde reactive nitrogen groups, if any, present in the backbone of the non-meltable polymer εtabilizer. In other words, the formaldehyde reactive nitrogen groups, attached directly or indirectly to the atoms in the backbone of the non-meltable stabilizer, εhould be at least three times as great, preferably at least ten times as great, as those in the backbone of the non-meltable polymer stabilizer, if such are present. The formaldehyde reactive nitrogen groups attached directly or indirectly to the side of the polymer backbone are preferably present in a εubstantially greater quantity than the formaldehyde reactive nitrogen groups, if any, present in the the polymer backbone. Most preferably, nearly one hundred percent of the formaldehyde reactive nitrogen groups are attached to the sides of the polymer backbone.

The non-meltable polymer εtabilizer can be a homopolymer or a copolymer, provided it iε non-meltable. It is preferred that the non-meltable polymer stabilizer be polymerized from acrylamide or methacrylamide monomer by free radical polymerization and that the polymer stabilizer prepared therefrom consist of at least 75 mole percent of a unit of the form

R

-(CH ₂ -C)-

I CNH ₂

II O where R=hydrogen or methyl. More preferably, it consiεtε of at least 90 mole percent of the above units, even more preferably, it consists of at least 95 mole percent of the above units, and most preferably, it conεists of at least 99 mole percent of the above unit.

The non-meltable polymer εtabilizer may be a copolymer in that it is polymerized from more than one monomer. The comonomer may or may not contain formaldehyde reactive nitrogen and/or formaldehyde reactive hydroxyl groups. Examples of other monomers that may be thus incorporated include styrene, ethylene, alkyl acrylates, alkyl methacrylates, N-vinylpyrrolidone, and acrylonitrile. The non-meltable polymer stabilizer that is a copolymer must still be non-meltable. It further must possess the required quantity of formaldehyde reactive hydroxyl and/or nitrogen groups, in the required ratio, and it must have the required number average particle size. The comonomer preferably should be added such that it does not unduly minimize the number of moles of formaldehyde reactive groups per gram of polymer stabilizer. Further, it should not unduly minimize the number of formaldehyde reactive siteε per gram of polymer stabilizer.

Specific preferred non-meltable polymer stabilizers that are copolymeric include copolymers of

hydroxypropyl methacrylate with acrylamide, methacrylamide, or dimethylaminoethyl methacrylate.

When the non-meltable polymer stabilizer has a high number of formaldehyde reactive hydroxyl groups in comparison to the number of formaldehyde reactive nitrogen groups or, alternatively, when it has only formaldehyde reactive hydroxyl groups, it may be advantageous to include other groups in the stabilizer that are basic. This is because for optimum performance as a εtabilizer for polyacetal, the stabilizer εhould be reactive with both formaldehyde and acid. Preferably, these other groups are nitrogen containing groups, such as amines, amides, ureaε, and urethanes. The non-meltable polymer εtabilizer must have a number average particle size of leεs than 10 microns, preferably leεε than 5 microns, and most preferably leεs than 2 microns, as measured before processing in polyacetal. Along with the polymer stabilizer being non-meltable, the number average particle size of the non-meltable polymer εtabilizer is important in achieving the improved procesεing εtability for polyacetal demonεtrated herein. If the polymer εtabilizer particle size is, on average, too large, then the interaction between the polyacetal and the polymer stabilizer can be negligible and the polymer stabilizer may have greatly reduced effectivenesε. Stability iε related to the interaction that occurε between the polyacetal and the polymer εtabilizer and as such, it is desirable to have good interaction between the polyacetal and the non-meitable polymer stabilizer. Maximizing the surface area/gram of the non-meltable polymer stabilizer increaεeε interaction between the polymer stabilizer and the polyacetal. The surface area/gram

of polymer stabilizer increaseε aε the particle εize of the polymer εtabilizer decreaεes. Thus, a non-meltable polymer εtabilizer with small particle εize iε highly desired. if the non-meltable polymer stabilizer particle size iε, on average, on the order of 10-100 icronε, then the εtabilizer may impart stability to the polyacetal but the physical properties of the articles manufactured from the polyacetal may be reduced. Relatively large particles may alεo cause uneven surface in the articles manufactured from polyacetal containing εtabilizer with large particles. In some caεeε, it may however be desirable to produce articles with surfaces having reduced surface gloss. in that case, a stabilizer of large particle size, more near the upper limit of the number average particle size, may actually be preferred.

The small number average particle εize of the non-meltable polymer εtabilizer may be obtained directly during the polymerization of the monomer or comonomerε. To obtain the small average particle size, the stabilizer polymerization is carried out by conventional disperεion polymerization methods in an organic media or by conventional emulsion polymerization methods in water, the techniques of each of which are well known in the art. Whether the polymerization technique iε diεperεion polymerization or emulsion polymerization, the non-meltable polymer stabilizer prepared therefrom should be insoluble in the polymerization media. Thus, the particular media selected for polymerization is dependent upon the particular monomer or comonomers chosen and the polymer that will result therefrom. For example, where acrylamide or methacrylamide is a monomer for polymerization, the preferred media iε a lower alkyl

alcohol. The polymerization may be by addition or condenεation polymerization or free radical polymerization. The moεt preferred method is one that will result in the number of formaldehyde reactive sites in the formaldehyde reactive group being maximized. Generally, free radical polymerization is the preferred method of polymerization. Non-meltable polymer εtabilizer prepared from acrylamide iε most preferably prepared by free radical polymerization. In any event, the polymerization method must be such that it results in a non-meltable polymer εtabilizer having formaldehyde reactive nitrogen groups or formaldehyde reactive hydroxyl groups in the quantities and amounts previously defined. in εome caεeε, the non-meltable polymer εtabilizer produced by the polymerization to small particle εize will have a sufficient major melting point or have a sufficiently low melt flow rate such that it is non-meltable as polymerized. In other cases, the polymer εtabilizer may not be non-meltable as polymerized but, prior to or during the melt processing in polyacetal, it will crosslink, due to, for example, application of heat, to a sufficiently high molecular weight such that it has a low melt flow rate and is thus considered non-meltable at the temperature at which the polyacetal is melt processed. Whether the polymer stabilizer will be non-meltable as polymerized or will become non-meltable after polymerization depends upon the nature of the particular monomer or comonomerε being polymerized.

In some cases, the polymer εtabilizer produced by the polymerization of the monomer or comonomers will not be non-meltable as polymerized and it will not become non-meltable subsequent to polymerization. This can be easily determined by

measuring the melting point or melt flow rate of the stabilizer after it has been compounded with polyacetal. In such cases, it is desirable to include at least one monomer that crosslinks the polymer stabilizer either during polymerization or at a later time. Monomers that will cause croεεlinking during polymerization include polyfunctional, unεaturated monomers, εuch aε, for example, acrylates, methacrylates, aσrylamideε, and methacrylamides, and derivatives thereof. Specifically preferred monomers are ethylene glycol dimethacrylate, N,N'-methylenebis- acrylamide, and 1,4-butanediol diacrylate. Monomers that may cause crosslinking after polymerization of the εtabilizer polymer is complete include, for example, glycidyl methacrylate, acrylic acid, methacrylic acid, and derivatives thereof. The crosslinking monomer should be added in an amount that is sufficient to yield a polymer stabilizer that is non-meltable at the temperature at which the polyacetal is melt processed.

During the polymerization to small particle εize in an organic media, with or without a crosslinking monomer, it can be advantageous to have a disperεing aid preεent. During the polymerization to εmall particle εize in an emulsion, it can be advantageous to have an emulsifier present. Dispersing aids and the methods of preparing them are well known in the art. A description of the methods of making and choosing disperεing aidε iε included in Diεpersion Polymerization in Organic Media (by K. E. J. Barrett, New York: John Wiley & Sons, 1975) . Particularly preferred disperεing aidε include polyethylene glycol and itε derivativeε, methyl methacrylate copolymerε, and poly(oxypropylene)-poly(oxyethylene) glycol block copolymers. Emulsifierε and the method of preparing

them are well known in the art. Emulsion polymerizations are discuεεed in Emulsion Polymerization Theory and Practice (by D. C. Blackley, New York: John Wiley & Sons, 1975). The dispersant or dispersant solution or the emulsifier is added to the polymerization reaction vessel si ultaneouεly with the monomer and polymerization medium, and, where applicable, comonomer and croεεlinking monomer. When a dispersant or dispersant solution or emulsifier is added to the εtabilizer, it is advantageous remove the disperεant or dispersant solution or emulsifier from the stabilizer polymer by washing the εtabilizer polymer, after it iε prepared, with a εolvent in which the diεperεant εolution or diεperεant or emulεifier is soluble but in which the polymer stabilizer iε insoluble. This is particularly true if the dispersant or dispersant εolution or emulεifier is known to destabilize polyacetal. If the disperεant or dispersant solution or emulsifier iε not known to destabilize polyacetal, it may be advantageous to leave it in the εtabilizer polymer aε it can act to reduce any agglomeration of particleε that may occur during the drying of the polymer εtabilizer. Further, regarding the measurement of the melt flow rate, it is known that water and other liquids or low molecular weight solids have substantial effectε on melt flow. Depending upon the technique uεed to isolate the non-meltable polymer εtabilizer, diεperεant, when uεed, may be retained with the εtabilizer polymer. To obtain an accurate melt fiow rate, the diεperεant εhould be removed by washing the εtabilizer with a liquid that iε a εolvent for the dispersant and is a non-solvent for the stabilizer prior to measuring the melt flow rate.

After washing, the stabilizer εhould be redried prior to testing for melt flow rate.

The small number average particle size of the non-meltable polymer stabilizer may alternatively be obtained subsequent to the polymerization of the monomer or comonomers, while the polymer stabilizer is still in the polymerization medium or is in solution. In such cases, the small number average particle size of the stabilizer may be obtained by adding a crosslinking monomer to the polymer stabilizer in the polymerization medium, after which the stabilizer polymer becomes insoluble in the medium. Alternatively, the small number average particle size of the stabilizer may be obtained by adding a εolvent in which the εtabilizer polymer is insoluble to the polymer stabilizer in the polymerization medium. Similarly, the polymer εtabilizer in the polymerization medium may be added to a solvent in which the polymer εtabilizer is insoluble. Small number average particle size can be obtained by other known means of separating the polymer from the polymerization medium. It can be advantageous to use dispersing aids or emulsifiers such as those previously described to separate the stabilizer polymer from the polymerization medium.

Any method may be used to prepare the polymer stabilizer provided that such method will yield a polymer stabilizer having small particles, with a number average size leεε than 10 microns, prior to melt processing with polyacetal. Further, the small particles εhould be non-meltable at the temperature at which the polyacetal is melt processed and εhould not coalesce or agglomerate to such an extent that they are not readily disperεible in the polyacetal melt.

The number average particle size of the non-meltable polymer stabilizer before it is melt processed with polyacetal can be meaεured by any means capable of determining number average particle size. The preferred meanε is the MICROTRAC II SMALL PARTICLE ANALYZER (ANALYZER) , manufactured by Leeds & Northrup. By this method, the polymer εtabilizer is added to a liquid, such as, for example, 2-propanol, and shaken by hand to diεperse the polymer εtabilizer in the liquid. In εome cases, a high concentration of loose agglomerates may have occurred during the preparation of the polymer εtabilizer. In such cases, more intensive mixing may be desired in order to break up the loose agglomerates. An example of a device capable of providing such intensive mixing iε a "POLYTRON" (Brinckman Inεtruments) . From this diεperεion of non-meltable polymer εtabilizer in liquid, the number average particle εize for the polymer εtabilizer iε determined by the ANALYZER. An example of a εpecific ANALYZER is the

Model 158705/158708, which is equipped with a 17 channel detector syεtem that coverε a particle εize range of 0.17 to 60 micronε. The ANALYZER prints the percent of particle volume that has a diameter of leεs than the given detector channel. From the diameter and particle volume, the number average particle size is calculated. In this calculation, the particle diameter for a given detector channel iε approximated by the channel diameter. The number of particleε in each channel iε calculated by the following formula:

N - (10000V%)/(0.5236d ³ /6) where N = number of particles in a given channel V% = volume of particles in that channel d - channel diameter By summing the number of particles in all 17 channels,

the total number of particles is calculated. By multiplying the number of particles in a channel by 100, and dividing the reεult by the total number of particles, the percent of particles in each channel is calculated. To calculate the total number percent having a diameter of less than that channel, starting with the smallest diameter channel, a cumulative number percent iε calculated by adding the number percent in all channels that have a diameter less than or equal to that particular channel. From this cumulative sum of number percents, the median number average particle size is calculated.

The number average particle size of the stabilizer after it has been melt processed with polyacetal should be less than 10 microns, preferably leεs than 5 microns, and moεt preferably leεε than 2 micronε. It can be meaεured by any technique capable of measuring number average particle size for particles in a polymer. The preferred method of measuring the number average particle size of the εtabilizer in the polyacetal iε by transmission electron microscopy.

The following illustrateε how the number average particle size of the non-meltable polymer stabilizer can be determined after it has been melt-processed and formed into pellets with polyacetal. A pellet is sectioned using a Reichert-Jung Ultracut E model FC4E diamond knife microtome. Using standard -90*C cryo-ultramicrotomy techniques, 90-120 nanometer sections of the pellet are microtomed. The microtomed eectionε, εtill on the diamond blade, are picked off the diamond blade and mounted directly onto a copper transmission electron microscopy (TEM) grid. The sections, as mounted, are placed in a Denton vacuum evaporator model D V-502

and, under high vacuum, coated with a thin layer of spectroscopically pure carbon less than 20 nanometers thick. The carbon coating gives acetal sections more stability when exposed to the electron beam inside the transmiεsion electron microscope. The carbon coated sections on the TEM grids are then examined using a Zeiss EM10CR transmiεsion electron microscope. Images are recorded at nominal magnifications of lOOOx, 2520x, and 5000x on 70 mm (Kodak 5302) film, and printed. Magnification calibrations performed on an annual basiε uεing a commercially available grating replica are combined with the photographic enlargement factor to give the final image magnification, which includes 464Ox, 1180Ox, and 23000X. The number average particle εize iε determined from the recorded images by measuring, with a ruler, the diameter of at least 50 particles, including large particles and any particles that may have agglomerated. Agglomerated particles are treated as one particle. The number average particle εize is calculated-by averaging the valueε obtained from the at least 50 particles.

11(a) (iii). Component (b) : Amide-containing Phenolic Antioxidant

The component (b) antioxidant useful herein is amide-containing and is also phenolic. The amide may be primary, εecondary, or tertiary. The phenol εhould be εterically hindered. As the examples below will show, an antioxidant that contains both amide and phenol functionalities imparts significantly better long term stability to polyacetal compositionε containing a non-meltable polymer εtabilizer than does a non-amide-containing phenolic antioxidant alone.

Amide-containing phenolic antioxidants are known in the art. Exampleε of amide-containing phenolic antioxidantε include, but are not limited to.

amides of beta-(3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid, εuch aε, for example, 1,3,5- tris-3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)- hexahydro-8-triazine and N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) .

Amide-containing phenolic antioxidants also include 2,2'-oxalyldia idobisethyl-

3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate. The preferred amide-containing antioxidant is N,N'-hexamethylene bis(3,5-di-tert- butyl-4-hydroxyhydrocinnamide) .

The improvement in the long term εtability of the non-meltable polymer stabilized polyacetal composition occurs when the amide-containing phenolic antioxidant is present alone or as part of a mixture of antioxidants. The mixture can consist of more than one amide-containing phenolic antioxidant or optionally it can consist of a combination of an amide-containing phenolic antioxidant and a non-amide-containing antioxidant. In any event, there must be present in the polyacetal composition 0.02-1.0 weight percent of the amide-containing phenolic antioxidant, said weight percent being based upon the weight of the polyacetal, the non-meltable polymer stabilizer, and the amide-containing phenolic antioxidant.

The non-amide-containing antioxidantε are primary, or chain terminating, antioxidantε that do not contain amide functionality. These antioxidants are also frequently referred to as radical scavengerε. The majority of primary antioxidantε are sterically hindered phenolε or secondary aromatic amines. Preferably, the non-amide-containing antioxidant is of the sterically hindered phenol type.

Exampleε of non-amide-containing εterically hindered phenolic antioxidantε that may be added along with the amide-containing phenolic antioxidant to the compoεition include, but are not limited to, the following:

Simple antioxidantε, such as 2,6-dialkylphenols, including, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert- butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol and 2,6-di-octadecyl-4-methyl phenol.

Derivatives of alkylated hydroquinones, such as for example, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di-tert-butyl- hydroquinone, 2,6-di-tert-butyl-4-hydroxy-anisole, 3,5-di-tert-butyl-4-hydroxy-anisole, 3,5-di-tert-butyl-4-hydroxyphenyl εtearate, and bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

Alkylidene-bisphenolε, εuch aε, for example, 2,2'-methylene-biε-(6 tert-butyl-4-methylphenol) , 2,2'-methylene-bis-(6 tert-butyl-4-ethylphenol) , 4,4'-methylene-bis-(6 tert-butyl-2-methylphenol) , 4,4'-methylene-biε-(2,6-tert-butyl-phenol) , 2,6-di-tert-butyl-5-methyl-2-hydroxybenzyl)- 4-methylphenol, 2,2 ^/ -methylene-biε-[4-methyl-6-(4- methylcyclohexyl)-phenol], 1,1-biε-(3,5-dimethyl-2- hydroxyphenyl)-butene, 1,1-biε-(5-tert-butyl-4- hydroxy-2-methylphenyl)-butane, 2,2-biε-(3,5-di-tert- butyl-4-hydroxyphenyl)-propane, 1,1,3-triε-(5-tert- butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5- tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmer- captobύtaήe, 1,1,5,5-tert-butyl-4-hydroxy-2- methylphenyl)-pentane and ethylene glycol bis [3,3- biε-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate] .

o- and N-benzyl compounds, such as, for example, 3,3 ',5,5'-tetra-tert-butyl-4,4'-dihydroxy- dibenzyl ether and tris-(3,5-di-tert-butyl-4- hydroxybenzyl)-amine. Hydroxybenzylated malonateε, εuch aε, for example, dioctadecyl 2,2-biε-(3,5-di-tert-butyl- 2-hydroxybenzyl)-malonate, dioctadecyl 2-(3-tert- butyl-4-hydroxy-5-methylbenzyl)-malonate, di- dodecylmercapto-ethyl, 2,2-biε-(3,5-di-tert-butyl-4- hydroxybenzyl)-malonate and di-[4-(l,l,3,3-tetra- methylbutyl)-phenyl] 2,2-biε-(3,5-di-tert-butyl-4- hydroxybenzyl)-malonate.

Hydroxybenzyl-aromatic compoundε, εuch as, for example, l,3,5-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethylbenzene, l,4-bis-(3,5- di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl- benzene and 2,4,6-tri-(3,5-di-tert-butyl-4- hydroxybenzyl)-phenol. s-Triazine compoundε, εuch as, for example, 2,4,6-tris-(3,5-di-tert-butyl-4- hydroxyphenoxy)-s-triazine, 2,4,6-triε-(3,5-di-tert- butyl-4-hydroxyphenylethyl)-s-triazine and 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl)iεocyanurate. Eεterε of beta-(3,5-di-tert-butyl-4- hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol diethylene glycol, triethylene glycol, neopentylglycol, pentaerythritol, trimethylhexanediol, trimethylolethane, triethylolpropane, and tris- hydroxyethyl isocyanurate.

Esters of beta(5-tert-butyl-4-hydroxy- 3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, εuch aε for example, with

methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, triethylene glycol, neopentylglycol, pentaerythritol, trimethylhexane-diol, trimethyolethane, trimethylolpropane, and tris-hydroxyethyl isocyanurate.

Eεterε of 3,5-di-tert-butyl-4- hydroxyphenylacetic acid with monohydric or polyhydric alcohols, εuch aε, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, neopentylglycol, pentaerythritol, trimethylhexanediol, trimethylolethane, trimethylol- propane, and tris-hydroxyethyl isocyanurate.

Examples of secondary aromatic amine antioxidants that may be added along with the amide-containing phenolic antioxidant to the composition include, but are not limited to, the following:

Diarylamineε, εuch aε N-phenyl-alpha-naphthylamine, p-oriented εtyrenated diphenylamine, and octylated diphenylamines. p-Phenylenediamines, εuch as N,N'-diphenyl-p-phenylenediamine and

N,N'-di-beta-naphthyl-p-phenylenediamine.

It is preferred that the non-amide-containing antioxidant be selected from triethylene glycol bis(3-(3'-tert-butyl- '-hydroxy-5'-methylphenyl)propionate) ; tetrakis(methylene(3,5-di-tert-butyl- 4-hydroxyhydrocinnamate))methane; tris(methylene(3,5-di-tert-butyl-4- hydroxyphenyl)-l,3,5-cyanuric acid; and 1-octadecanol(3,5-di-tert-butyl-4-

hydroxyhydrocinnamate) .

II(b) . Non-Meltable Polymer Stabilized

Compoεitionε Improved with a Meltable Co-stabilizer Compound and a Primary Antioxidant The non-meltable polymer stabilized compositions that are improved with a meltable co-stabilizer compound and a primary antioxidant consist essentially of (a) 0.05-3.0 weight percent of at least one non-meltable polymer stabilizer, (b) 0.01-1.0 weight percent of at least one meltable co-stabilizer compound, (c) 0.02-1.0 weight percent of at least one primary antioxidant, and (d) 95-99.92 weight percent of a polyacetal. The preferred compositionε consist essentially of 0.15-1.5 weight percent of the at leaεt one non-meltable polymer εtabilizer, 0.01-0.50 weight percent of the at leaεt one meltable co-εtabilizer compound, 0.02-0.50 weight percent of the at leaεt one primary antioxidant, and 97.5-99.8 weight percent of polyacetal. The moεt preferred compoεition conεists essentially of 0.2-1.0 weight percent of the at least one non-meltable polymer εtabilizer, 0.05-0.30 weight percent of the at least one meltable co-stabilizer compound, 0.05-0.25 weight percent of the at least one primary antioxidant, and 98.4-99.7 weight percent of the polyacetal. All the above weight percents are based upon the weight of the non-meltable polymer stabilizer, the meltable co-stabilizer compound, the primary antioxidant, and the polyacetal. IΙ(b)fi). Component fd) : Polyacetal

The component (d) polyacetal uεeful herein is identical to the component (c) polyacetal described above for cellulose-stabilized polyacetal compositionε.

11(b) (ii). Component (a): Non-meltable Polymer Stabilizer

The component (a) non-meltable polymer stabilizer is identical to the component (a) non-meltable polymer εtabilizer described above for the non-meltable polymer stabilized compositions improved with an amide-containing phenolic antioxidant.

III(b)(iii). Component (b) : Meltable Co-stabilizer Compound

The component (b) "co-stabilizer" compound useful in the non-meltable polymer εtabilized compoεitions herein is any compound that iε a meltable thermal εtabilizer for polyacetal. By the term "meltable", it iε meant that the co-εtabilizer has a melting point or glasε tranεition temperature less than the temperature at which the polyacetal iε melt processed or alternatively, it is meant that the co-stabilizer has a melt flow rate greater than one-tenth that of the polyacetal at the temperature at which the polyacetal is melt processed. The melting point and glasε tranεition temperature can be determined by DSC analysis, as described previously. The melt flow rate can also be determined as previously described.

Meltable thermal stabilizers for polyacetal are well known in the art. Examples of such meltable thermal stabilizerε for polyacetal include, but are not limited to, polyamideε, amide-containing compounds, urethanes, ureaε, amine-containing compounds, and hydroxy-containing compounds. It iε important ;to note that highly baεic compounds may have a de-stabilizing effect on polyacetal homopolymer and therefore, any such compound εhould be purified or

reduced in basicity to the appropriate levels prior to incorporating it into the polyacetal homopolymer composition. This is disσusεed in further detail below. Polyamide εtabilizerε are well known in the art. The uεe of a polyamide aε a thermal εtabilizer for polyacetal, along with the method for preparing such polyamides, is disclosed in the following patents: U.S.P. 2,993,025; U.S.P. 2,966,467; U.S.P. 3,001,966; U.S.P. 3,235,624; U.S.P. 3,288,885; U.S.P. 3,103,499; U.S.P. 4,744,934; U.S.P. 3,960,984; U.S.P. 4,098,843; and U.S.P. 3,116,267. The preferred polyamide is a 33/23/43 weight percent terpolymer of nylon 66, nylon 6/10, and nylon 6, respectively. Amide-containing compounds are well known in the art. The use of an amide-containing compound as a thermal stabilizer for polyacetal, along with the method for preparing εuch a compound, iε diεcloεed in the following patentε: U.S.P. 3,574,786; U.S.P. 3,592,873; U.S.P. 3,355,514; U.S.P. 3,787,353; and U.S.P. 3,156,669.

Urethanes and ureas are well known in the art. Their use aε a polyacetal thermal εtabilizer, along with the method of making the urethane or urea, is disclosed in the following patents: U.S.P.

4,780,498; U.S.P. 2,893,972; and U.S.P. 3,144,431.

Amine-containing compounds are well known in the art. The use of amine-containing compounds as polyacetal thermal stabilizers, along with the method for preparing said compound, is diεcloεed in the following patentε: U.S.P. 3,133,896; U.S. . 2,920,059; U.S.P. 2,376,354; U.S.P. 2,810,708; U.S.P. 4,751,272; U.S.P. 3,406,222; U.S.P. 3,249,582; U.S.P. 3,448,169; and U.S.P. 3,442,850.

Hydroxy-containing materialε are well known in the art. The uεe of εuch materialε, along with the method for preparing such materials, is diεcloεed in the following patentε, each of which iε incorporated herein by reference: U.S.P. 4,766,168; U.S.P.

2,936,298; U.S.P. 2,966,476; U.S.P. 2,376,354; U.S.P. 3,219,621; U.S.P. 4,555,357; U.S.P. 3,240,753; and U.S.P. 3,459,789. The preferred hydroxy-containing compound iε that which iε diεcloεed in U.S. . 4,766,168. Specifically, the hydroxy containing compound diεcloεed in U.S. 4,766,168 iε a hydroxy containing polymer or oligomer wherein the atomε in the backbone of the polymer or oligomer to which the hydroxy groups are attached, directly or indirectly, are separated from each other, on average, by not more than twenty chain atoms and wherein the hydroxy containing polymer or oligomer is subεtantially free of acidic materialε. Specific hydroxy-containing compounds disclosed in U.S.P. 4,766,168 include poly(vinyl alcohol), poly(ethylene vinyl alcohol), hydroxyeεterε of poly(meth)acrylates, such as poly(hydroxypropyl methacrylate), and vinyl alcohol/methylmethacrylate copolymers. The preferred hydroxy-containing compound for the compositions of the present invention is poly(ethylene vinyl alcohol) .

The meltable co-stabilizer may be a single compound or it may be a mixture of more than one meltable co-εtabilizer. The preferred co-εtabilizer for the non-meltable polymer stabilized polyacetal compositions of the present invention is either a

33/23/43 weight percent terpolymer of nylon 66, nylon 6/10, and nylon 6, respectively or the hydroxy-containing polymer deεcribed in U.S.P. 4,766,168. If the co-εtabilizer is added aε a mixture, it iε .preferred that it be a 1:1-1:5 mixture of the

33/23/43 weight percent terpolymer of nylon 66, nylon

6/10, and nylon 6, respectively with the hydroxy-containing polymer described in

U.S.P. 4,766,168. 11(b) (iv). Component (c) : Primary Antioxidant

The component (c) primary antioxidant used in the non-meltable polymer stabilized compositions along with a meltable co-stabilizer compound herein is known in the art. Primary antioxidants are also referred to in the art as chain terminating antioxidants or radical scavengers. The majority of primary antioxidants are sterically hindered phenols or secondary aromatic amines. It is preferred that the primary antioxidant used in the compositions of the present invention be of the sterically hindered phenol type.

Examples of primary antioxidants that are sterically hindered phenolic antioxidants include, but are not limited to simple antioxidants, derivatives of alkylated hydroquinones, alkylidene-biεphenolε, O- and

N-benzyl compoundε, hydroxybenzyl ted malonateε, hydroxybenzyl-aromatic compoundε, ε-triazine compounds, amides of beta-(3,5-di-tert-butyl-4- hydroxyphenyl) propionic acid, esterε of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esterε of beta(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, and esterε of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols. Specific examples of each type of sterically hindered phenolic antioxidants useful herein include those provided above in section 11(a) (iii) for non-amide-containing primary antioxidants.

The preferred primary antioxidants that are sterically hindered phenolic antioxidantε are amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, εuch as, for example, 1,3,5-tris-3,5-di-tert-butyl-4-hydroxyphenyl- propionyl)-hexahydro-ε-triazine and N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) ; 2,2'-oxalyldiamidobisethyl-3-(3,5-di-tert-butyl-4-hyd¬ roxyphenyl) propionate; triethylene glycol biε(3-3'-tert-butyl-4'-hydroxy-5'-methyl(phenyl) proprionate) ; and tetrakiε(methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ) methane. The moεt preferred antioxidant iε N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) . Examples of primary antioxidants that are εecondary aromatic amine antioxidantε include, but are not limited to, diarylamineε and p-phenylenediamines. The primary antioxidant may be added as one single primary antioxidant or it may be added as a mixture of more than one primary antioxidant. Preferably, the mixture iε compriεed only of εterically hindered phenolic type primary antioxidantε. Regardleεε of whether the primary antioxidant iε added alone or aε a mixture, the total weight percent of primary antioxidant in the polyacetal composition must range from 0.02-1.0 weight percent, εaid weight percent being baεed upon the weight of the non-meltable polymer stabilizer, the primary antioxidant(s) , the co-εtabilizer, and the polyacetal.

II(c>.- Non-meltable Polymer Stabilized

Compositions: Other Componentε and Purity Recommendations

It εhould be understood that the non-meltable polymer stabilized compositionε described

herein can additionally contain other ingredientε, modifiers, and additives as are generally used in polyacetal molding resins, including pigments, colorants, UV stabilizerε, light εtabilizerε, toughening agents, polytetrafluoroethylene fibers or powder, nucleating agentε such aε boron nitride and talc, lubricating agentε εuch aε silicone oil, and ethylene bis-εtearamide, and fillers, such as glass, carbon black, and talc. It should also be understood that some pigments, colorants, and other additives can, themselves, adverεely affect the εtability of polyacetal compositions.

It is important that the non-meltable polymer εtabilizer, the meltable co-εtabilizer compound, the antioxidant, and any other ingredient, modifier, or additive used in the non-meltable polymer stabilized polyacetal compositions of the present invention be εubεtantially free of compoundε or impuritieε which destabilize acetal resins.

In stabilizing eεter-capped or partially eεter-capped polyacetal homopolymer, the components to be added to the polyacetal should be εubεtantially free of basic materials which can destabilize the polyacetal. Basic impurities should preferably be removed to levels of not more than 50 ppm and most preferably to not more than 10 ppm. In εtabilizing polyacetal copolymer or homopolymer that is subεtantially all ether-capped, higher concentrationε of baεic materialε can be tolerated. In addition, it εhould be underεtood that if the impurity is only weakly basic relatively higher amountε can be tolerated.

In stabilizing both homopolymer and copolymer polyacetal, acidic impurities in the components of the polyacetal composition should be

minimized. Acidic impurities εhould preferably be removed to levelε of not more than 50 ppm and moεt preferably to not more than 10 ppm. Aε with baεic impuritieε, it should be understood that if the impurity is only weakly acidic, relatively higher amounts can be tolerated.

If acidic and/or basic impurities are present in any of the components to be added to the polyacetal in amounts large enough to cauεe deεtabilization of the polyacetal compoεition, then the component εhould be purified before it iε introduced into the compositions of the present invention. For example, the non-meltable polymer stabilizers used in the compositions of the present invention can be purified by washing with an III. METHOD OF PREPARATION

The compositionε of the present invention can be prepared by mixing the components with the polyacetal polymer at a temperature above the melting point of the polyacetal component of the compositions using any intensive mixing device conventionally uεed in preparing thermoplaεtic polyacetal compositions, such as rubber mills, internal mixerε εuch as "Banbury" and "Brabender" mixers, single or multiblade internal mixers with a cavity heated externally or by friction, "Ko-kneaders", multibarrel mixerε εuch aε "Farrel Continuouε Mixerε", injection molding machineε, and extruders, both single screw and twin screw, both co-rotating and counter rotating. These devices can be uεed alone or in combination with εtatic mixerε, mixing torpedoeε and/or variouε devices to increase internal presεure and/or the intenεity of mixing, εuch aε valveε, gates or screwε designed for the purpose. Extruderε are preferred. Of course, such mixing should be conducted at a temperature below

which significant degradation of the polyacetal component of the composition will occur. Generally, polyacetal compositionε are melt processed between 170*C to 280 ^β C, preferably between 185*C to 240*C, and most preferably 195'C to 225*C.

Shaped articles can be made from the compositions of the present invention using any of several common methods, including compression molding, injection molding, extruεion, blow molding, rotational molding, melt εpinning and thermoforming. Injection molding iε preferred. Examples of shaped articles include sheet, profiles, rod stock, film, filamentε, fiberε, εtrapping, tape tubing and pipe. Such εhaped articles can be poεt treated by orientation, εtretching, coating, annealing, painting, laminating and plating. Such εhaped articleε and εcrap therefrom can be ground and remolded.

Processing conditions used in the preparation of the compositionε of the preεent invention and εhaped articles made therefrom include melt temperatures of about 170-280*C, preferably 185-240'C, most preferably 200-230*C. When injection molding the compositions of the present invention, it is preferred that the mold be aε cold aε posεible consistent with the intricacy of the εhape being produced. Generally, the mold temperature will be 10-120'C, preferably 10-100*C, and most preferably about 50-90*C.

EXAMPLES In the following examples, there are shown specific embodimentε of the preεent invention and certain comparisons with embodiments of control experiments outside the limits of the present invention. It will be seen that the compositions of the present invention are characterized by improved thermal εtability. All parts and percentages are by weight, and all temperatures are in degrees Celsius unless otherwise εpecified. Meaεurementε not originally in SI unitε have been so converted and rounded where appropriate.

I. COMPONENTS OF THE EXAMPLES a. Polyacetal Polymer Component The polyacetal polymers used in the examples below were as followε:

(a) Polyacetal A - an acetate end-capped homopolymer having a number average molecular weight of about 40,000 and

(b) Polyacetal B - an acetate end-capped homopolymer having a number average molecular weight of about 33,000. b. Microcryεtalline Celluloεe Stabilizer Component

The microcrystalline cellulose stabilizers used in the examples below were as follows:

(a) "MC3" was a commercially available microcrystalline cellulose which was ground via standard techniques of air jet milling to an average particle εize of about 3 micronε, (b) "MC6" was a commercially available microcrystalline cellulose having an average particle size of about 6 microns,

(c) "MC11" was a commercially available microcryεtailine celluloεe which waε air jet milled by

standard techniques to an average particle εize of about 11 micronε,

(d) "MC20" was a commercially available microcrystalline celluloεe having an average particle εize of about 20 microns,

(e) "MC50" waε a commercially available microcryεtalline celluloεe having an average particle εize of about 50 micronε, and

(f) "MC100" waε a commercially available

₁₀ microcrystalline cellulose having an average particle size of about 100 microns.

The average level-off degree of polymerization for each microcrystalline cellulose used in the examples ranged from 190 to 200. Each - ₅ microcryεtalline celluloεe uεed in the examples had less than 10 ppm heavy metalε and leεε than 0.05% ash. The pH of a 10% aqueous suspension of each microcrystalline celluloεe used in the examples ranged from about 5.5-7.

20 c. Fibrous Cellulose Stabilizer Component

The fibrous cellulose εtabilizerε used in the examples below were as follows:

"FC1" waε a commercially available fibrous cellulose having an average fiber length of about 300

25 microns, an ash content of about 0.16%, and a pH, measured on a 5% aqueous suspension of the fibrous cellulose, of 5.95.

"FC2" was a commercially available fibrous cellulose having an average fiber length of less than 90 microns, an ash content of 0.15%, and a pH,

30 meaεured on both 5% and 10% aqueouε εuspensionε of the fibrous cellulose, of 5.2 d. Non-meltable Polymer Stabilizer Component

The non-meltable polymer stabilizers used in the examples were prepared as detailed below.

•53

Total polymerization time was measured from the time at which the initiator was initially charged into the reaction vesεel to the time when the polymerization was completed and heat was withdrawn from the vessel. DSC measurements were made using the DU PONT Model 9900 as previously deεcribed. The particle εize of the non-meltable polymer εtabilizer prior to melt compounding waε meaεured on the ANALYZER as described previouεly. "PEG", where εo uεed, is polyethylene glycol, a disperεant, having a molecular weight of about 8000.

Non-meltable polvmer εtabilizer A waε prepared by polymerizing 298.5 grams of acrylamide, 1.5 grams of N,N'-methylenebiεacrylamide, and 36 grams of PEG in 3000 ml. of 2-propanol. The polymerization reaction was εtarted at about 72.5*C using an initial charge of 0.15 grams of 2,2'-azobiε-

(isobutyronitrile) initiator. Additional initiator was added, in increments of 0.03 grams, over the next approximately 200 minutes until the total amount of initiator added waε 0.45 grams. Approximately 20 minutes after the initial charge of initiator was added, 91 ml. of a εolution of 20 grams of PEG in 100 ml. of methanol solution were fed into the reaction vessel over a period of about 180 minutes. The polymerization temperature was maintained between about 72*C and 76 ^* C. The total polymerization time was 240 minutes. The reaction mixture waε cooled to 25 ^β C, at which point 250 ml. of 2-propanol were added. The resulting polyacrylamide εtabilizer diεperεion waε filtered in order to iεolate the polymer εtabilizer. The polymer εtabilizer waε rinεed with 1000 ml. of 2-propanol and dried in a 60*C vacuum oven.

DSC analyεiε εhowed that the polymer stabilizer had a small endotherm of 4.98 Jouleε/gram

at 57.4 ^β C, attributed to a polyethylene glycol. DSC analyεis further showed a second endotherm of 2.6 Joules/gram at 189.6*C. The major melting point was 291.3"C, with an endotherm of 114.5 Joules/gram. The melt flow rate, in gramε/10 min., waε as follows: 5.16 at 6-7 minutes, 4.12 at 7-8 minuteε, and 4.03 at 8-9 minutes. The stabilizer had a number average particle size of 1.4 microns.

The polymer εtabilizer was washed with hot methanol to remove the polyethylene glycol dispersant and it was then redried. DSC analysis on the washed polymer stabilizer εhowed a εmall endotherm of 2.6 Joules/gram at 187.0*C. The major melting point was 295.0*C, with an endotherm of 209.5 Joules/gram. The washed polymer εtabilizer showed no flow at 6-9 minutes. This illustrates that the presence of dispersant may adverεely affect melt flow rate measurements. The number average particle size was 1.4 microns.

Non-meltable polymer εtabilizer B was prepared by adding a solution of 52.50 grams of acrylamide and 0.53 grams 1,4-butanediol diacrylate in methanol (78.75 gramε) to a εolution of 7.00 grams tert-butylperoxypivylate and 26.25 grams PEG in methanol (802.00 grams). The resulting solution was heated to reflux (approximately 74*C). When the reaction began turning milky-white, two εolutionε, one consisting of 472.50 grams acrylamide and 4.72 grams 1,4-butanediol diacrylate in methanol (708.75 grams) and the other consiεting of 26.25 grams PEG in methanol (172.50 grams), were simultaneouεly added to the refluxing reaction εuεpenεion over 2 hourε. The resulting reaction suεpenεion waε allowed to reflux an additional 2.5 hourε. The reaction suspension was

filtered and the resulting white solid was washed with methanol (400 ml.) and dried at 55 ^β C-60 ^β C for 6 hours.

Non-meltable polymer stabilizer C was prepared by adding a solution of 14.3 kg acrylamide and 145.15 gramε of 1,4-butanediol diacrylate to a refluxing εolution of 1.44 kg PEG in 48.06 kg methanol (approximately 64*C) over about 2 hourε. Throughout thiε addition, a total of 195.04 grams tert-butylperoxypivylate polymerization initiator was portionwiεe added. The resulting white solid was washed with methanol and dried in a vacuum oven (6.75X10 ⁴ Pa) at 70'C for 1 day and at 100'C for 1 day.

Non-meltable polymer stabilizer D waε prepared by gradually by adding a εolution of 201.8 grams of acrylamide, 2.04 grams of N,N'-methylenebis- acrylamide, and 20.4 grams of PEG in about 3800 ml. of methanol to a refluxing solution of 8.2 grams of tert- butyl peroxypivylate polymerization initiator and 10.2 grams of PEG in about 5000 ml. of methanol. The resultant reaction mixture was allowed to stir at reflux until the reaction waε complete. The resulting reaction suεpension was cooled to room temperature and filtered. The resulting white εolid was washed in additional methanol and dried. e. Co-stabilizer Compound Component

The co-stabilizer compounds, each of which were meltable, used in the examples were as follows: "Nylon" was a 33/23/43 terpolymer of nylon 66, nylon 6/10 and nylon 6, respectively. It had a melting point, as determined by DSC analysiε, of about 140'C. The nylon terpolymer was ground and pasεed through a 20 MESH screen prior to compounding. A 20 MESH εcreen has openingε of 1.44 mm.

"EVOH-1" waε an ethylene/vinyl alcohol copolymer containing 29 weight percent ethylene and 71 weight percent vinyl alcohol, and having an apparent melt viεcosity at 210*C of 9500 P, which was purified by washing at 75"C for 16 hours uεing water (pH adjuεted to 3 with H3PO4) . The acidic water wash was drained from the washing veεεel and the ethylene/vinyl alcohol copolymer was washed at 75*C for 4 hours with demineralized water and then dried. This co-stabilizer was prepared in accordance with the teachings of U.S.P. 4,766,168. It was ground and treated in the same manner as the Nylon co-stabilizer, above. It had a melting point, as determined by DSC analysiε, of about 187"C. "EVOH-2" waε ethylene/vinyl alcohol copolymer containing 29 weight percent ethylene and 71 weight percent vinyl alcohol, and having an apparent melt viεcosity at 210*C of 9500 P, which had been purified εuch that it contained leεε than 10 ppm ash.

"TPU" was a polyurethane elastomer comprised of 37 wt% adipic acid, 39 wt% 1,4-butanediol, and 24 wt% methylene bis(4-phenyl iεocyanate) having an inherent viscosity of 1.33, as measured in accordance ^• with ASTM D-2857 (solvent; dimethylformamide (DMF) ; temperature: 30*C; concentration: 0.01% co-stabilizer C in DMF) . It had a melting point, as determined by DSC analyεis, of about 150'C. e. Other Additive Components

"PEG" was a polyethylene glycol having a molecular weight between about 7,000-9,000 and sold commercially under the trade name of Carbowax* 8000 (Union Carbide) .

"PPPE" waε a polyoxypropylene- polyoxyethylene block copolymer having an approximate

molecular weight of 13000 (sold commercially as

Pluronic ^® F98 by BASF Wyandotte Company) .

"PTFE" was a polytetrafluoroethylene powder irradiated at the level of 7.5 mrad. "Si oil" waε a polydimethyl εiloxane, trimethylεiloxy terminated εilicone oil having a viscosity of 500 centistokes and a nominal molecular weight of 17,250.

II. EXAMPLES: CELLULOSE-STABILIZED POLYACETAL COMPOSITIONS IMPROVED WITH A CO-STABILIZER COMPOUND

Exampleε 1-17 below relate to cellulose-stabilized polyacetal compositionε.

In Exampleε 1-17, along with Examples C1-C18, the thermal stability of the compoεitions was determined using a thermally evolved formaldehyde (TEF) test procedure. A weighed sample of the polyacetal composition was placed in a tube and the tube was fitted with a cap for introduction of nitrogen to the test sample for removal of any evolved gases from the apparatus while maintaining the sample in an oxygen-free environment. The sample was heated at either 250*C or 259*C in a εilicone oil bath. The nitrogen and any evolved gaεeε transported thereby were bubbled through 75 ml of a 40 g/1 sodium εulfite in water εolution. Any evolved formaldehyde reactε with the εodium εulfite to liberate εodium hydroxide. The εodium hydroxide was continuously neutralized with standard 0.1 N HC1. The resultε were obtained aε a chart of ml of titer versus test time. The percent evolved formaldehyde was calculated by the formula

0.03 x 100 (V) (N) _sw where V is the volume of titer in milliliters N is the normality of the titer, and SW is the sample weight in grams.

The factor "0.03" iε the milliequivalent weight of formaldehyde in g/milliequivalent.

Thermally evolved formaldehyde results are reported in the data tables below under columns headed "Wt % CH ₂ 0 at x ^# C". The time period for which the sample was heated is also indicated in said data tables.

The antioxidants uεed in Examples 1-17 and C1-C18 were as follows: ( ^a ) "antioxidant A" was triethyleneglycol bis(3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)pro- prionate) ;

(b) "antioxidant B* waε N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) ; and

(c) "antioxidant C" was tetrakis(methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) )methane.

Examples 1-6 and C1-C8

The components of Examples 1-6 and C1-C8 are listed in Tables IA-IC. below. For each example, the components were mixed together and melt compounded on a 28 mm Werner and Pfleiderer twin screw extruder with barrel temperature settingε of 150*C to 180*C, die temperature settings of 200*C, and a εcrew speed of 150 rpm. The temperature of the melt aε it exited the die for the exampleε ranged from 221*C to 224'C. The melt compounded εample waε teεted by the TEF test, described above. The resultε are reported below in Tables IA-IC.

The resultε in Table IA. below, εhowed that when microcryεtalline celluloεe and at leaεt one co-εtabilizer compound were together incorporated into polyacetal, the thermal εtability obtained on the resultant polyacetal composition (Example 1) was better than the thermal εtability obtained for the εame polyacetal composition with the co-stabilizer

compound but without the microcrystalline cellulose (Example Cl) and it was also better than the thermal stability obtained for the same polyacetal composition with microcrystalline cellulose but without the co-stabilizer compound (Example C2) . Example 2 showed that improved stability is imparted to the polyacetal when there is incorporated therein microcrystalline cellulose and more than one co-stabilizer compound. The reεultε below in Table IB and Table IC again εhowed that beεt thermal εtability results for polyacetal were obtained when the stabilizer incorporated into the polyacetal was a combination of microcrystalline cellulose and at leaεt one co-stabilizer compound.

TABLE IA. EFFECT OF MICROCRYSTALLINE CELLULOSE

t % Wt % Wt % CH _? 0 @ 259

Eg. t % Microcrystalline Costabilizer Wt % 15 30 No. PAc Cellulose Compound AO min mi

Cl 99.7A - 0.2 EVOH-2 0.1B 0.18 0.9

C2 99.4A 0.5 MC11 - 0.1B 0.27 0.

1 99.2A 0.5 MC11 0.2 EVOH-2 0.1B 0.09 0.

C3 99.6A - 0.2 EVOH-2 0.1B 0.14 0. 0.1 Nylon

2 99.IA 0.5 MC11 0.2 EVOH-2 0.1B 0.07 0. 0.1 Nylon

PAc = polyacetal AO = - antioxidant

TABLE IB. EFFECT OF MICROCRYSTALLINE CELLULOSE AND A "NYLON" CO-STABILIZER COMPOUND

Wt % Wt % % Cfl ₂ 0 @ 259

Eg. t % Microcrystalline Costabilizer t % 15 30 No. PAC CeiJuJpse Compound O pin win

C4 99.4A 0.5 MC20 - 0.1A 0.13 0.5

C5 98.9A - 1.0 Nylon 0.1A 0.05 0.4

3 99.4A 0.25 MC20 0.25 Nylon 0.1A 0.04 0.2

4 99.4A 0.4 MC20 0.1 Nylon 0.1B 0.04 0.2

PAc = polyacetal AO = antioxidant

TABLE IC. EFFECT OF MICROCRYSTALLINE CELLULOSE AND AN "EVOH" CO-STABILIZER COMPOUND ON POLYACETAL STABILITY t % Wt % Wt % CH O § 259S

Eg. t % Microcrystalline Costabilizer t % 15 30 o¬ PAc Cellulose Compound AP pin min ci 99.4A 0.5 MC20 - 0.1B 0.20 0.66

C8 98.9A - 1.0 EVOH-2 0.1B 0.09 0.69

5 99.4A 0.25 MC20 0.25 EVOH-2 0.1B 0.05 0.33

C4 99.4A 0.5 MC20 - 0.1A 0.13 0.53

6 99.4A 0.25 MC20 0.25 EVOH-2 0.1A 0.04 0.26

PAc = polyacetal

C4 is the same composition as reported in TABLE IB

AO = antioxidant

Examples 7-11 and C9-C11

The components of Examples 7-11 and C9-C11 are listed in Table II. below. The compositions of the examples further each contained 0.1 weight percent antioxidant B. The components were mixed together, melt compounded, and extruded on a 2.5 inch Sterling single εcrew extruder with barrel temperature εettings ranging from 150*C-200'C and with a εcrew εpeed of 50 rpm. The temperature of the melt aε it exited the die ranged from 202*C to 207'C. Each εample was subjected to the TEF test, described above.

The results for Examples 7-11 and C9-C11 are reported in Table II. below. The resultε εhowed that microcrystalline cellulose in combination with two co-stabilizer compounds improved the thermal stability of polyacetal, at short test times, to a greater extent than did a conventional polyamide stabilizer alone (Example C9) . The results further showed that as the average particle size of the microcrystalline cellulose decreased, the εtability imparted to the polyacetal increaεed.

TABLE II. POLYACETAL WITH MICROCRYSTALLINE CELLULOSE OF VARYING PARTICLE SIZE

Wt% CH?Q g 259°C Eg. Wt % Wt% Microcrystalline Wt% 15 30 No. PAc Cellulose CoStab min min

C9 98.9B 1.00B 0.13 0.59

CIO 98.9B 0.75B 0.05 0.34

0.25A

Cll 99.4B 0.35B 0.07 0.35 0.15A

7 98.9B 0.5 MC3 0.35B 0.03 0.26 0.15A

8 98.9B 0.5 MC6 0.35B 0.02 0.21 0.15A

9 98.9B 0.5 MC20 0.35B 0.03 0.24 0.15A

10 98.9B 0.5 MC50 0.35B 0.06 0.52 0.15A

11 98.9B 0.5 MC100 0.35B 0.08 0.78 0.15A

PAc = polyacetal CoStab = co-stabilizer compound Costabilizer B - EVOH-2 Costabilizer A = nylon

Examples 12-13 and C12-C15

The components of Exampleε 12-13 and C12-C15 are listed in Table III, below. For each example, the components were mixed together, melt compounded, and extruded under the same conditionε aε were Examples 1-6 above. The melt compounded sample was tested by the TEF test, described above. The resultε are reported in Table III, below. Exampleε C14 and C15 illustrate the type of results that may be obtained when the fibrous cellulose used has a pH of less than 5.5

TABLE III. EFFECT OF FIBROUS CELLULOSE

AND A CO-STABILIZER COMPOUND ON POLYACETAL STABILITY

Eg. Wt % No. PAc

C12 99.IB - 0.8 EVOH-2 0.1B 0.06 0.

C13 99.IB - 0.5 EVOH-2 0.1B 0.08 0.

0.3 Nylon

12 94.IB 5.0 FC1 0.8 EVOH-2 0.1B 0.28 0.

13 94.IB 5.0 FC1 0.3 Nylon 0.1B 0.13 0.

C14 99.2B 5.0 FC2 0.5 EVOH-2 0.1B 0.60 3.

0.3 Nylon

C15 79.3B 20.2 FC2 0.4 EVOH-2 0.08B 1.31 5.

0.2 Nylon

PAC = polyacetal AO = antioxidant

Examples 14-17 and C16-C18

The components of Exampleε 14-17 and C16-C18 are liεted in Table IV. below. Each composition contains an additive in addition to the stabilizers and the antioxidantε. For each example, the components were melt compounded on a 53 mm twin screw extruder with a barrel temperature setting of about 210 ^β C. The temperature of the melt as it exited the die ranged from about 210"C to 235*C. Each sample was subjected to the TEF teεt, deεcribed above.

Thermal εtability reεultε εhowed the best stability at longer test time was achieved when the composition tested contained microcrystalline cellulose and a co-stabilizer compound.

TABLE IV. POLYACETAL COMPOSITIONS CONTAINING MICROCRYSTALLINE CELLULOSE, CO-STABILIZERS AND OTHER ADDITIVES t. % t. % wt _t * CH?0 6 2S0θ

Eg. t. % Mic]rocrystalline Costabilizer t. % Wt. % 15 30 60

No. PAC ςei:Lulose Compound AO Additive min min rain

C16 99.35A - 0.25 nylon 0.075B 1.50 PTFE 0.24 0.93 2.13 0.75 EVOH-2 0.075A powder

14 97.35A 0.50 MC6 0.15 nylon 0.075B 1.50 PTFE 0.18 0.52 1.14 0.35 EVOH-2 0.075A powder

C17 97.35A - 0.25 nylon 0.075B 1.50 PTFE 0.21 0.78 1.84 0.75 EVOH-2 0.075C powder

15 97.35A 0.50 MC6 0.15 nylon 0.075B 1.50 PTFE 0.20 0.60 1.22 0.35 EVOH-2 0.075C powder

C18 78.85A - 0.25 nylon 0.075B 20.0 PTFE 0.23 0.96 2.28 0.75 EVOH-2 0.075A fiber

16 78.85A 0.50 MC6 0.15 nylon 0.075B 20.0 PTFE 0.29 0.85 2.16 0.35 EVOH-2 0.075A fiber

17 77.85A 0.50 MC6 0.15 nylon 0.075B 20.0 PTFE 0.14 0.50 1.32 0.35 EVOH-2 0.075A fiber 1.0 Si oil

AO = antioxidiant

III. EXAMPLES: NON-MELTABLE POLYMER STABILIZED

POLYACETAL COMPOSITIONS IMPROVED WITH AN AMIDE- CONTAINING PHENOLIC ANTIOXIDANT EXAMPLES

Examples 18-28 and C19-C27 relate to non- meltable polymer stabilized polyacetal compositions improved with at least one amide-containing phenolic antioxidant.

The amide-containing phenolic antioxidant used in Examples 18-28 and C19-C27 was aε followε:

"AmConl" waε N,N'-hexamethylene bis(3,5- di-tert-butyl-4-hydroxyhydrocinnamide) ; this was the same as antioxidant B, above.

The non-amide-containing antioxidants used in Examples 18-28 and C19-C27 were as follows:

(a) "antioxidant A" was triethylene glycol bis(3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl) propionate) ;

(b) "antioxidant E" was 1,6-hexanediol bis(3,5- di-tert-butyl-4-hydroxyhydrocinnamate) ;

(c) "antioxidant C" was tetrakis(methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) )methane;

(d) "antioxidant G" was 2,2'-methylene-bis- (4-methyl-6-tert-butyl phenol) ;

(e) "antioxidant H" was 4,4'-butylidene- bis-(6-tert-butyl-3-methyl phenol) ; (f) "antioxidant I" was bis(3,5-di-tert- butyl-4-hydroxyhydrocinnamyl)-1,2-hydrazide;

(g) "antioxidant J" waε triε(methylene(3,5- di-tert-butyl-4-hydroxyphenyl)-1,3,5-cyanuric acid; and (h) "antioxidant K" waε l-octadecanol(3,5- di-tert-butyl-4-hydroxyhydrocinnamate) .

In Examples 18-28 and C19-C27, data were obtained on polyacetal compositions that had been compounded on an extruder and then molded into 1/8-inch thick tensile bars. Exact extrusion

conditions are detailed below for each set of examples. The tensile bars of each composition were preweighed and were placed in a circulating air oven at 150'C for the times noted in each Table below. Oven location effects were averaged by distributing bars of a sample throughout the oven or by continuously rotating the bars on a carousel. At the end of the specified time period, the sampleε were removed from the oven, weighed, and teεted for tensile strength and elongation according to ASTM Method D-638 (0.2 in/min. crosεhead εpeed) . The percent weight loss waε calculated from the following formula: [1-(weight after aging)/weight before aging)] x 100 Examples 18 and C19-C24

The compositionε liεted in Table VA. below, were compounded on a 2-inch εingle εcrew extruder equipped with a barrier εcrew and a valve die (190*C barrel εettings, 50-80 rpm screw speed, 50 pεi preεεure) . The compounded reεinε were injection molded into 1/8-inch thick tensile bars on a Van Dorn Model 150 RS3 6 oz. reciprocating εcrew injection molding machine equipped with a two-cavity mold (45/20 injection/hold cycle, 1000 pεig preεεure, 200 ^β C barrel temperature εettings, 90*C mold temperature setting) . The tensile bars of each composition were placed in a circulating air oven at 150*C for the times notes in Table VB. below. The data reported in Table VB. below, were averages of measurements performed on three tensile bars.

TABLE VA. POLYACETAL COMPOSITIONS CONTAINING A NON-MELTABLE

POLYMER STABILIZER AND AN AMIDE-CONTAINING PHENOLIC

ANTIOXIDANT

Example Wt.% Wt. % Non-Meltable t. % No. Polyacetal A Polymer Stabilizer B Antioxidant Antioxidan

18 99.40 0.50 AmConl 0.10

C19 99. .40 0.50 A 0. ,10

C20 99. .10 0.50 A 0. ,40

C21 99. .40 0.50 E 0. .10

C22 99. .40 0.50 C 0. ,10

C23 99. .40 0.50 G 0. .10

C24 99. .40 0.50 H 0. .10

TABLE VB. EVALUATION OF POLYACETAL COMPOSITIONS IN TABLE VA

Initial Testing at 150 Degrees C 0 days 2 days 5 days 9 days 16 days

Example TS/E TS/E/WL TS/E/WL TS/E/WL TS/E/WL No. ( * A) ( * A) ( * Λ/%) ( * ( * AA)

18 694/27 619/9/0.51 519/9/0.62 591/9/1.27 520/6/4.16

C19 686/14 632/11/0/48 551/6/1.03 518/5/5.79 406/4/15.63

C20 680/20 601/8/0. 52 545/6/1.53 481/4/7.16 316/2/22.72

C21 690/23 638/11/0.41 597/9/0.85 562/8/4.68 472/5/12.32

C22 690/27 612/8/0.51 569/7/1.37 535/6/5.29 371/3/13.83

C23 693/34 603/8/0.57 507/4/1.00 479/4/4.01 Disintegrated

C24 691/23 581/7/0.71 517/5/2.26 372/2/9.13 Disintegrated

TS tensile strength E elongation

WL weight loss * unit for tensile strength is kg/cm ²

Comparison of Example 18 with C19-C24 demonstrates the present invention. The polyacetal stabilized with a non-meltable polymer stabilizer had significantly improved long term εtability when an amide-containing phenolic antioxidant, aε opposed to a non-amide-containing phenolic antioxidant, was added to the polyacetal composition containing a non-meltable polymer stabilizer.

Compariεon of Example C21 with Example 18 highlights the significance of the amide functionality in achieving significantly improved long term stability. The only difference between the two compositions was that the composition of Example 18 had an amide-containing antioxidant and the composition of C21 had a non-amide-containing antioxidant. More εpecifically, antioxidant E of C21 was exactly the same aε the amide-containing antioxidant (A Conl) of Example 18 except that it contained ester functionaltiy in place of amide functionality. The structure of antioxidant E was as follows:

The structure of the amide-containing phenolic antioxidant AmConl waε as follows:

The weight loss, after 16 days, for the composition of Example C21, which contained the non-amide-containing phenolic antioxidant E, was about three times greater than the weight losε experienced by the compoεition of Example 18, which contained the amide-containing compound.

Examples 19-20 and C25

The compositions listed in Table VIA, below, were melt compounded, extruded, and molded into tensile bars as described for Examples 18 and C19-C24. The tensile bars were treated the same as in Example 18 and Examples C1-C6. Results reported in Table VIB. below, are based on an average of the values obtained from three tensile bars.

TABLE VIA. POLYACETAL COMPOSITIONS CONTAINING A

NON-MELTABLE POLYMER STABILIZER AND AN AMIDE-CONTAINING PHENOLIC ANTIOXIDANT

Wt.% Non-Meltable

Polymer

Stabilizer

Example t. % B:A Anti- Wt. % No. PQlyagetal ft (30:70) Qxiflgnt AntJQxictønt

19 99.40 0.50 AmConl o. io

20 99.10 0.50 AmConl 0.40

C25 99.40 0.50 A 0. 10

TABLE VIB. EVALUATION OF POLYACETAL COMPOSITIONS IN TABLE VIA

Initial Testing at 150 Degrees C 0 Days 2 Days 5 Days 9 Days 16 Days

Example TS/E TS/E/WL TS/E/WL TS/E/WL TS/E/WL No. ( * A) ( * rtrt) ( * /%/ ) f * ( * AAi

19 679/26 657/15/0.26 555/9/0.63 576/10/0.79 522/3/3.64

20 677/25 597/8/0.49 568/8/0.45 552/9/1.21 517/5/3.31

C25 680/25 619/12/0.35 595/11/1.05 542/9/4. 30 420/2/12.3

TS tensile strength

E elongation

WL weight loss

* unit for tensile strength is kg/cm ²

The results again showed that εignificantly better long term stability was achieved when an amide-containing phenolic antioxidant was present in the polyacetal composition containing at least one non-meltable polymer stabilizer than when a non-amide-containing phenolic antioxidant was present. The weight loss after 16 days for a composition containing the amide-containing phenolic antioxidant was approximately four times less than that of the same composition containing a non-amide-containing phenolic antioxidant.

Examples 21-28 and C26-C27

The compositions listed in Table VIIA. below, were compounded on a 2-inch εingle εcrew extruder. The nominal extruder barrel temperature was approximately 210*C. The extruded resins were injection molded into 1/8-inch thick tensile bars with an extruder temperature of approximately 207*C and a mold temperature of approximately 88*C. The tensile bars of each composition were placed in a circulating air oven at 150*C for the times noted in Table VIIB. below. The data, reported in Table VIIB. below, were the average of meaεurementε performed on five tensile bars.

TABLE VIIA. POLYACETAL COMPOSITIONS CONTAINING A

NON-MELTABLE POLYMER STABILIZER AND AN AMIDE-CONTAINING PHENOLIC ANTIOXIDANT

Wt. % Wt. %

Example Wt. % Non-meltable Polymer Anti¬ wt. % No. Polyacetal Stabilizer C Antioxidant oxidant Additive

21 99.35 0. ,50 AmConl:A 0.05:0.10 -

22 99.25 0. ,50 AmConl:A:J 0.05:0.10:0 .10 -

23 99.20 0. ,50 AmConl:A 0.10:0.20 -

24 98.85 0. .50 AmConl:A 0.05:0.10 0.50 PEG

25 98.85 0. .50 AmConl:A 0.05:0.10 0.50 PPP

26 99.35 0. .50 AmConl:K 0.05:0.10

27 99.35 0. .50 AmConl:A 0.10:0.05 -

28 99.35 0. .50 AmConl:C 0.05:0.10 - C26 99.30 0, .50 A 0:20 - C27 99.35 0, .50 I:A 0.05:0.10 _

TABLE VIIB. EVALUATION OF POT.YAHETAT. COMPOSITIONS IN TABLE VIIA

In t al Testing at 150 Degrees C 0 Days 10 Days 15 Days 16 Days

Example TS/E TS/E/WL TS/E/WL TS/E/WL No. ( * /%) ( * /%/%) ( * /%/%) ( * /%/%)

21 671/40 495/4/1.77 501/5/4.62

22 683/21 668/9/0.27 - 582/4/0.83

23 678/23 668/10/0.33 - 578/5/0.67

24 672/27 638/8/0.31 - 566/5/0.9

25 670/23 599/6/0.32 - 564/6/1.07

26 681/17 544/5/0.56 - 554/6/3.1

27 685/21 625/8/0.68 - 554/5/1.3

28 673/36 644/8/0.32 - 602/5/0.58

C26 671/37 488/4/5.27 382/3/14.21 -

C27 680/21 403/4/11.26 305/3/20.08

TS = tensile strength E = elongation

WL = weight loss * - kg/cm ²

Compariεon of Exampleε 21-28 with Exampleε C26-C27 further demonstrates the present invention. A comparison of Example C26 with Example 21 shows that when an amide-containing phenolic antioxidant was added along with a non-amide-containing phenolic antioxidant to a polyacetal composition containing a non-meltable polymer stabilizer, the retention of physical properties over time was εignificantly better than that of the εame polyacetal composition with a non-amide- containing phenolic antioxidant alone.

Example C27 shows the results that were achieved when the antioxidant had a nitrogen-containing group but where the nitrogen-containing group was of a hydrazide functionality and not of an amide functionality. These results illustrate the importance of having amide functionality in the antioxidant. Examples

24-25 demonstrate an additional feature of the present invention; namely, that procesεing aidε may be incorporated into the εtabilized polyacetal composition without loss of properties. Finally,

Examples 21-28 show that an antioxidant mixture, which contained at least one amide-containing phenolic antioxidant, imparted better retention of properties to the non-meltable polymer εtabilized polyacetal composition than did either a non-amide-containing phenolic antioxidant alone or a mixture of more than one non-amide-containing phenolic antioxidant.

IV. EXAMPLES: NON-MELTABLE POLYMER STABILIZED

POLYACETAL COMPOSITIONS IMPROVED WITH A CO- STABILIZER COMPOUND AND A PRIMARY ANTIOXIDANT Examples 29-38 and C28-C34 relate to non-meltable polymer stabilized polyacetal compositions improved with a meltable co-εtabilizer compound and at leaεt one primary antioxidant. The primary antioxidantε uεed in the examples below were as follows:

(a) "antioxidant A" was triethylene glycol bis(3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl) proprionate) ;

(b) "antioxidant B" waε N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide) ; this is the same as AmConl, above; and

(c) "antioxidant C" was tetrakis(methylene

(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ) methane. In Examples 29-38 and C28-C34, data were obtained on polyacetal compositions that had been compounded on an extruder and then molded into 1/8-inch thick tensile bars. Exact extrusion conditions are detailed below for each εet of exampleε. The tensile barε of each composition were preweighed and were placed in a circulating air oven at 150 ^* C for the times notes in each Table below. Oven location effects were averaged by distributing bars of a sample throughout the oven or by continuouεly rotating the barε on a carouεel. At the end of the specified time period, the samples were removed from the oven, weighed, and tested for tensile strength and elongation according to ASTM Method D-638 (0.2 in/min. crosshead speed). The percent weight loss was calculated from the following formula: [1-(weight after aging)/weight before aging)] x 100. Examples 29-32 and C28-C31

The compositionε liεted in Table VTIIA. below, were compounded on a 2-inch εingle εcrew extruder equipped with a barrier εcrew and a valve die (190'C barrel temperature εettingε, 50-80 rpm screw speed, 500 psi pressure) . The compounded resins were injection molded into 1/8-inch tensile bars on a Van Dorn Model 150 RS3 6 oz. reciprocating εcrew injection molding machine equipped with a two-cavity mold (45/20

injection/hold cycle, 1000 psig presεure, 200'C barrel temperature εettings, 90'C mold temperature setting).

The tensile bars of each compoεition were placed in a circulating air oven at 150'C for the timeε noted in Table VIIIB. below. The reported data were averageε of meaεurementε performed on three tenεile bars.

TABLE VIIIA. POLYACETAL COMPOSITIONS CONTAINING

A NON-MELTABLE POLYMER STABILIZER WITH A MELTABLE CO-STABILIZER COMPOUND AND A PRIMARY ANTIOXIDANT

Wt. % t. % t. %

Eg. Wt. % Non-Meltable Non-Meltable Co- Anti-

HQ PolvacetalA Polymer Stabilizer Polvmer Stabilizer Stabiliser oyj φ

C28 9 999..4400 7 700AA::3300BB 0.50 - 0.10A

29 9 999..2200 7 700AA::3300BB 0.50 0.20 Nylon 0.10A

30 9 988..4400 7 700AA::3300BB 0.50 1.00 TPU 0.10A C29 9 999..4400 7 700AA::3300BB 0.50 - 0.10B

C30 9999..1100 7700AA::3300BB 0.50 - 0.40B

31 9999..2200 7700AA::3300BB 0.50 0.20 Nylon 0.10B

32 9988..9900 7700AA::3300BB 0.50 0.50EVOH-1 0.10B C31 9999..1133 _- - 0.80EVOH-1 0.07B

TABLE VIIIB. EVALUATION OF POLYACETAL COMPOSITIONS IN TABLE VIIIB

Initial Testing at 150 Degrees C 0 days 2 days 5 days 9 days 16 days

Eg. TS/E TS/E/WL TS/E/WL TS/E/WL TS/E/WL No. ( * A) ( * / /\) ( * nm ( * nm ( * nm

C28 680/25 624/12/0.35 595/11/1.05 542/9/4.70 420/2/12.38

29 680/22 697/16/0.26 648/15/0.48 620/13/1.57 594/8/4.72

30 669/26 665/17/0.22 641/15/0.41 575/12/1.30 521/5/4.52

C29 679/26 657/15/0.26 555/9/0.63 575/10/0.79 522/3/3.64

C30 677/25 597/8/0.49 568/8/0.45 552/9/1.21 517/5/3.31

31 680/27 687/20/0.33 652/14/0.47 607/12/1.01 572/7/3.72

32 689/23 692/17/0.33 670/14/0.51 636/12/0.97 604/7/3.20

C31 699/32 686/15/0.40 624/8/0.74 613/9/1.52 491/4/4.44

TS = tensile strengl-h E = elongation

WL = weight loss * = unit for tensiiLe strength is ]kg/cm ²

The examples show that the overall retention of properties, and thereby the long term stability, of the polyacetal compositions containing a minor amount of a meltable co-stabilizer compound and a primary antioxidant waε improved over the εame compositions lacking the meltable co-stabilizer compound. Examples 33-35 and C32-C34

The compositions listed in Table IXA. below, were compounded on a 2-inch single screw extruder. The barrel temperature was approximately 210 ^* C. The compounded resins were injection molded into 1/8-inch thick tensile bars with a barrel temperature of approximately 207*C and a mold temperature of approximately 88*C. The tensile barε of each compoεition were placed in a circulating air oven at 150*C for the times noted in Table IXB. below. The reported data were the averages of measurements performed on five tensile barε.

TABLE IXA. POLYACETAL COMPOSITIONS CONTAINING

A NON-MELTABLE POLYMER STABILIZER WITH A MELTABLE CO-STABILIZER COMPOUND AND A PRIMARY ANTIOXIDANT

Wt. % Wt. % Wt. % Eg. Wt. % Non-Meltable Non-Meltable Co- Anti- Mo. Polyacetal Polvmer Stabilizer Polvmer Stabilizer Stabilizer oxida

C32 99.30 C 0.50 - 0.20

33 98.95 C 0.50 0.10 Nylon 0.10

0.15EVOH-1 0.20

C33 99.35 C 0.50 - 0.05

0.10

34 99.10 C 0.50 O.lONylon 0.05

0.15EVOH-1 0.10

C34* 98.85 C 0.50 - 0.05

0.10

35* 98.60 C 0.50 O.lONylon 0.05

O.lOEVOH-l 0.10

♦composition also contained 0.50 weight percent PEG

TABLE IXB. EVALUATION OF POLYACETAL COMPOSITIONS IN TABLE IXA

initial Testing at 150 Degrees C

0 days 10 days 14 days 16 days TS/E TS/E/WL TS/E/WL TS/E/WL

( * m ( * ,ΛA) ( * nm f * nm

C32 671/37 488/4/5.27 382/3/14.21

33 683/32 728/20/0.26 737/16/0.24

C33 671/40 495/4/1.77 501/5/4.62

34 688/30 739/20/0.30 729/17/0.29

C34 673/27 638/8/0.31 566/5/0.91

35 673/37 744/24/0.27 716/14/0.40

TS = tensile \ strength E = elongat ^■ -ion

WL = weight loss * = unit of : tensile istrength is kg/cm ²

The examples show that the overall long term retention of properties was greater for polyacetal compositions containing a mixed meltable co-stabilizer system and a mixed primary antioxidant syεtem than for thoεe correεponding polyacetal compoεitions lacking the meltable co-stabilizer component. Examples 36-38

The compoεitionε of Exampleε 36-38 contain additives such as PTFE and Si oil. The compositions listed in Table XA, below, were compounded on a 53 mm twin screw extruder. The barrel temperature was approximately 210*C. The temperature of the melt as it exited the extruder ranged from about 210*C to 235*C. The compounded resins were injection molded into 1/8 inch thick tensile bars on a molding machine (barrel temperature setting 207*C, mold temperature setting 88*C) .

The tensile bars of each composition were placed in a circulating air oven at 130*C for the times noted in Table XB. below. The reported data were the average of measurements performed on five tensile bars.

TABLE XA. POLYACETAL COMPOSITIONS CONTAINING

A NON-MELTABLE POLYMER STABILIZER WITH A MELTABLE CO-STABILIZER COMPOUND AND A PRIMARY ANTIOXIDANT

Non-Meltable

Eg. t . % Polymer Meltable Wt. % Additive No. ppiyacetai Stabilizer Co-stabilizer Antiwidant

36 96.35 0.50 D 0. 15 Nylon 0.075 B 1.50 PTF 0. 35 EVOH-1 0.075 A 1.0 Si o

37 97.35 0.50 D 0. 15 Nylon 0.075 B 1.50 PTF 0. 35 EVOH-1 0.075 A

38 97.35 0.50 D 0. 15 Nylon 0.075 B 1.50 PTF 0. 35 EVOH-1 0.075 C

TABLE XB. EVALUATION OF POLYACETAL COMPOSITIONS IN TABLE XB

Initial Testing at 130 Degrees C 0 days 10 Days 40 Days

Eg. TS/E TS/E/WL TS/E/WL No. (psiA) (psi/%/%) (psiAA)

36 9180/27 9660/14/0.28 8510/5.1/0.51

37 9690/20 10290/15/0.32 10260/12/0.74

38 9620/23 10210/16/0.40 9730/10/0.88

TS = tensile strength E = elongation WL = weight loss