This invention relates to a process for treating rubber utilising certain classes of cationic surfactants in the form of surface active plasticiser accelerators (hereinafter referred to as SAPA).

To enable rubbers to be processed it is customary to intimately

5 mix into than liquids and lew melting solids which function as internal lubricants or plasticisers during processing causing a reduction in viscosity, easing filler incorporation and reducing the frictional heat generated during the high shear rate processing operations of internal mixing, extruding etc. These plasicisers are considered to function in a

10 physical rather than chemical manner and their function is not usually dependent on the temperature of mixing or curing. Usually their relative coπpatibility with a particular rubber is considered iπportant -and the solubility parameter concept is frequently used to predict ccrnpatibility, on the basis of a rubber and plasticiser possessing approximately similar

15 solubility parameters being more likely to be compatible than the reverse situation. Corrpatibility of a plasticiser with rubber must be considered a concept or cαribination of properties, rather than a specific individual property and is assessed as follows. Processing of Unvulcanised Rubber

201. The plasticiser's effect is measured by the rate at which it can be assimilated into the rubber during mixing ^* and by the subsequent temperature generated and heat history of the mix.

2. The quantity of plasticiser able to be assimilated by the rubber without subsequent blooming and exudation of surface liquid is important together with the effect of plasticiser proportions on viscosity of the rubber mix.

3. Influence of a plasticiser on cure rate and state is also iπportant and, as a generalisation, cure retardation is regarded as undesirable leading to loss of properties and greater costs.

304. The effect on dielectric properties of a rubber by a plasticiser can also be inport-ant.

OMPI

Properties of Vulcanised Rubber

As a generalisation, at present, with the exception of polymerisable and crosslinkable plasticisers, such as acrylics and phenolics, the presence of a plasticiser in a rubber reduces the strength of its vulcanisate to a greater or lesser degree. Hence the relative effect of different plasticisers on strength reduction in a rubber mix is corπmonly used to assess its compatibility or efficiency. Sometimes, due to the lack of sensitivity of the rubber test techniques, changes in strength properties due to the presence of a plasticiser cannot be measured. Other properties often used to assess plasticiser compatibility and effectiveness are:- staining, colour stability, ageing resistance, volatility from the rubber during processing, curing and service; fluid extractability and retention of flexibility at low tenperatures. This investigation concerns the effect of a cationic surfactant as a rubber compounding ingredient.

Cationic surfactants comprising the fatty acid salts of primary amines have been mixed with rubber in an attempt to improve flow characteristics, and the release and strength properties of rubber. However, the use of these primary amines has proved unsatisfactory for a number of reasons including scorching where the scorch properties of the rubber are very poor.

According to one aspect of the present invention there is provided a process of treating a rubber to produce a rubber compound having irrproved flew characteristics and release properties, comprising taking a rubber and mixing the rubber with a cationic surfactant comprising a fatty acid salt of an alkyl alkylene diamine.

According to another aspect of the present invention there is provided a process of treating a rubber to produce a rubber oon ^* pound having irrproved flow charateristics and release properties, coπprising taking a rubber and mixing the rubber with a cationic surfactant comprising a fatty acid salt of an alkyl alkane diamine.

According to yet -another aspect of the present invention there is provided a process of treating a rubber to produce a rubber compound having irrproved flow characteristics and release properties, cαiprising taking a rubber and mixing the rubber with a cationic surfacant comprising a fatty acid salt of an alkyl imidazoline. Preferably, the fatty acid salt of an alkyl imidazoline is selected from one of l(2-hydroxyet_hyl)-2-heptadecenyl _L 2] irnidazoline and 1 hydroxyethyl 2 oleyl imidazoline.

According to a further aspect of the present invention the use of a cationic surfactant comprising a fatty acid salt of an alkyl alkylene diamine in the treatment of rubber wherein the cationic surfactant is mixed with the rubber to provide a rubber compound with irrproved flew characteristics and release properties. According to yet a further aspect of the present invention there is provided the use of cationic surfactant corrprising a fatty acid salt of an alkyl alkane diamine in the treatment of rubber wherein the cationic surfactant is mixed with the rubber to provide a rubber compound with irrproved flow characteristics and release properties. According to an additional aspect of the present invention there is provided a process of treating a rubber to produce a rubber compound having improved flow characteristics and release properties, coπprising taking a rubber and mixing the rubber with a cationic surfactant, coπprising an alkyl bis alkylamide. According to yet another aspect of the present invention there is provided the use of a cationic surfacant ooπprising an alkyl bis alkylamide in the treatment of irubber wherein the cationic surfactant is mixed with the rubber to provide a rubber compound with iπproved flow characteristics and release properties. Conveniently, the cationic surfactant is used as a dispersing and wetting agent for filler in rubber.

Preferably, in one process of treating rubber the fatty acid salt is used in the presence of a metal oxide retardant. Alternatively, the fatty acid salt of an alkyl imidazoline is used in the presence of a metal oxide retardant. Conveniently, the metal oxide retardant is selected from the group coπprising zinc oxide and lead oxide.

The fatty acid salt is preferably selected from the group coπprising lauric acid; palmitic acid; soya acid; hydrogenated tallow acid; N-coco-1, 3- diamino-propane; N-tallow-1, 3-3iamino-propane; N- leyl-1, 3-diamino-propane; N-tallcw-1, 3-diamino-propane di-oleate; N,stearic-1, 3-diamino-propane distearate; N-oleyl-1, 3-diaπ_Lno-propane dioleate, and alkyl propylene diamine.

Preferably, the alkyl bis alkylamide is selected from the group coπprising N,N'-ethylene bis lauramide; N,N'-ethylene bis stearamide; N,N'- ethylene bis myristamide; N,N'-ethylene bis oleamide; N,N*-ethylene bis eruca ide; -and N,_J--ethylene bis behenamide.

O P

In the process of treating rubber the mixture of rubber and cationic surfactant is vulcanised by heating in the presence of sulphur or a sulphur donating compound.

Embodixtients of the present invention will now be described by way of exaπple with reference to the accoπpanying drawings, in which:- Figure 1 is a graph illustrating the curding properties achieved ty the use of SAPA in natural rubber (NR).

Figure 2 is a graph illustrating the curing properties achieved by the use of SAPA in styrene butadiene rubber (SBR),

Figure 3 is a graph illustrating the curing properties of polychloroprene rubber (CR) with SAPA,

Figure 4 is a graph illustrating the curing properties of Nitrile rubber with SAPA,

Figure 5 is a graph illustrating the ccttparative cure properties of SAPA with various rubber processing oils and processing additives, Figure 6 is a graph, illustrating the shear stress/shear rate properties of tread rubber with processing oils and SAPA,

Figure 7 (a) and 7 (b) illustrate the use of SAPA as a processing aid in both black and silica filled mixes,

Figure 8 (a) and 8 (b) illustrate SEM micrographs which demonstrate the ability of the SAPA surfactant as a filler dispersion and wetting agent in natural rubber, and

Figure 9 (a) and 9 (b) illustrate SEM micrographs which demonstrate the ability of the SAPA surfactant as a wetting agent in SBR.

A number of experiments illustrating the irrproved properties of a rubber achieved using SAPA are described belcw. The rubber prepared in each case is generally banded on a rubber mixing two roll mill in the conventional tenperature range 30° to lOO^, but more usually at approximately 50 ^** ^. The SAPA and other small chemical coπpounds together with 1/3 of the filler content are then added to the irubber and dispersed. The remaining filler and any other processing oil, if any, are then added and also dispersed. The step is followed by the addition and dispersion of sulphur.

Finally the mix is refined at least six times. During the treatment of the rubber SAPA dissociates at higher temperatures used for vulcanisation, that is greater than 140°C, to form, for exaπple, a secondary amine, which functions as an organic accelerator of cure.

OMP

Test methods are conventional, as far as possible, and based on BS, ASTM or ISO rubber test method procedures. The mixing procedure used cure as follows:-

1. Mill rolls set to approximately 50+5°C and friction ration of 1.1:1. 10 2. NR banded around rolls and masticated to form a smooth coherent band.

3. Zinc oxide, stearic acid, CBS, Permanax BL were added with half the carbon black and incorporated into the rubber.

4. Remainder of carbon black was added together with the high strength plasticiser and dispersed.

155. Sulphur was added.

6. Mix was refined six times through a tight nip and sheeted off at 3 ιtτn thickness for preparation of test specimens. Series 1 Experiments

During an investigation of the prcperties of various processing aids 0 and plasticisers in particulate filler and fibre reinforced rubbers, it was observed that one class of liquids behaved unconventionally ty, in certain instances, increasing both the Mooney viscosity and strength prcperties of unfilled (gum) and filled natural rubber. The particular experiment and series of compounds which this observation was made is detailed in Table 1 5 below, see Formulation 9.

-6-

TabLe 1 (a) Eto ^* alat__a ⁱ u_*e ani proparties of Gun (Urifilled) \Λ_lcar_Lsates Orrtairαng L Efererrt Types of B nding Agarits

pphr 1 2 3 4 5 6 7 8 9

NR (a R 5) 103 100 100 100 103 100 100 100 100

__Lnc CKifJe 5 5 5 5 5 5 5 5 5 St ric acάd 2 2 2 2 2 2 2 2 2 aojiu 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 CBS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Perrrarax B 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Q hei∑r R3 3.5 3.5 3.5 BIT 1.8 1.8

^• Λύkasi S 15 GdrjaitrA 2.5 α_hed ^* r RL 5.5 Itesiπene 3520 Si69

*s?

Prqperties 5 6 8 9

Suc∑ch tine ts 7.0 3 ^{^} 12T ^0 ^" 83 TTLT ΥΛ 13 ^" 33 ^" at _3C ;(m_ns) ²

O re -ϋπe (Tgς) 15.0 17.0 21.0 26.5 28.0 20.0 19.0 21.0 12.5 tθ3 ^** ue 22.5 26.5 33.5 23.0 23.5 26.0 24.0 13.0 14.5 (cN-m)

Cure rate (<_N.ιr 4.5 4.25 4.0 1.7 3.0 3.0 3.5 1.0 4.25 in)

(slcpe of steep rεgicn)

*SP£A is the surface actixe pi Table 1 (a) ccπtiπjed oerLeaf

-7-

Table 1 (a) Q_πti jθd.

ED-perties ααrrt.. 8

lersile strtargth 19.6 16.0 20.8 17.3 19.3 24.2 22.9 13.8 28.4

M&)

Elα-gatLcn at 775 575 625 725 725 675 725 675 690 hareak (%)

Tensile pxdxt 152 92 130 125 140 163 166 93 196 (Ma x %) x 10~ ²

M3i__us at 100% 0.82 1.02 1.38 0.82 0.86 1.08 0.81 0.83 1.1

(MRa)

Tear straxfti 49.8 37.5 41.0 56.3 42.2 54.9 45.7 47.3 54.6

( Nn ^"1 )

Iferdress (USD) 35 40 46 36 36 40 36 36 41 α_npre3sicn set 45.2 39.1 36.4 36.4 42.0 52.2 38.9 34.7 41.6

<a lOCft; for 24 hrs (%)

0.7354 0.7122 0.7018 0.7523 0.7462 0.7277 0.7310 0.7395 0.7115

^V l Aged pp ^** p ^* _rties (7CfC for 1 \_-έk)

Itensile strorgth 12.6 13.8 13.6 13.4 15.2 15.8 1.9 2.2 16.0

(Mra)

∑teta±i n. % 64.3 86.3 65.4 77.5 78.8 65.3 8.3 15.9 66.1

El_π--_±im at 650 450 475 550 635 635 220 315 536 breek (%)

Ifetenticn. % 83.8 72.2 76 75. 87.6 79.3 30 47 77.5

] __π__ ^* ess (IfflD) 43 44 50 39 38 44 41 40 46 hcrareiTt 3 4 4 3 2 4 5 4 5 ^" *SS_sA in the surface a ^* ±ive p___sticiser

Table 1 (b) RxiiTJlaticn Used art! Σ-rq ^* erties of Black ^" Λ__x___-__sates α__±aining I^iffsareπt t ^* ypes of Brrr f.r!g Agar±s

Fcπiulatiαi Mix No. pp r 1 2 3 4 5 6 7 8 9

N OΦ. 5) 100 ICO 100 100 100 100 100 100 100

Zinc αxide 5 5 5 5 5 5 5 5 5

Stearic acid 2 2 2 2 2 2 2 2 2

Suljϊxπr 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5

CES 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Permarax EL 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5

Ca ^* ±cn Black 30 30 30 30 30 30 30 30 30 (EE N330) α_hsd_r RS - 3.5 3.5 3.5 - - - - -

IMP - 1.8 1.8 - - - - - -

TODcasil S - — 15 - - - - - -

Gt_h=d_rA - - - 2.5 - - - - - α±e±πr RL - - - - 5.5 - - - -

Fesdmεre 3520 - - - - - 2.0 - - -

Si69 - - - - - - 2.0 - -

Si ^" J re 26062 — - - - - - - 2.0 - sm_* - - - - - - - - 2.0

Prqperties 1 2 3 4 5 6 7 8 9

S αrd ^* . tine ts at 15Cfc(rπins) ² 4.8 2.5 3.5 4.0 6.0 4.8 5.8 2.0 3.0

Cure tine (Tgg) 14 15 22 28 28 21 19 13 13 at 15CRz(ιrr_ns)

M_x_ιruτ. tαrjje (c ^* N-m) 31 43 49 39 37 37 33 34 37

Table 1 (b)

-9-

Prqpetrties c nt.. 1 8

Cure rate (c π ^* / 5.5 8.5 5.5 2.5 3.5 4.8 4.0 5.5 6.0 rrin)

(slqpe αf steep r ^y gicn)

Tensile starength 26.1 21.4 19.8 17.3 15.8 26.8 28.8 25.6 30.4 MEa)

Elα pticn at 600 425 425 460 525 590 620 575 600 break (%)

Tensile pexze et (Ma x %) x 10~ ² 157 91 84 80 83 158 179 147 182

M_d_0us at 100%

(M3ι) 2.0 4.0 3.9 3.0 2.6 2.5 2.3 2.2 2.4

Tear strength 54.3 130.8 U7.3 27.3 29.5 138 126.2 115 122 (FNtT ¹ ) ϊ___3_r__ss (IEHD) 54 72 77 72 72 64 60 55 62

G rpressicn set 50 39.1 47.0 50.3 55.4 51.9 49.4 64.3 45.7 @ 1GG--C for 24 hrs (%)

V - V

0.6661 0.6191 0.6327 0.6795 0.6794 0.6640 0.6696 0.6705 0.6391

A^ j

(at 7CR for 1 vαaek)

Tensile strength 25.9 19.1 12.9 13.5 14.3 21.7 16.9 18.9 22.0 (MEa)

R≡teπt n % 99 79.9 65.2 77.9 90.4 80.9 58.7 64.5 72.5

E]__tr-_tιαι at 550 320 275 325 350 445 425 400 475 breεk (%)

Retaiticn % 91.7 75.3 64.9 70.7 66.7 75.4 68.5 69.6 79.2

Iferdness (IfflD) 58 77 83 79 77 70 66 60 67

Ihciyitart 4 5 5 7 5 6 6 5 5

- ^* __ ^" ø_ is the surface active plasticiser

-£ πτ__

Series 2 Experiments

Surface Active Plasticiser Accelerator in Natural Rubber

Following this observation another experiment was carried out in our laboratory to ascertain whether this apparent reinforcing effect would also apply to both unfilled NR (gum) and carbon black reinforced NR. The formulations used and results obtained are given in Table 2 below and Figure 1; the physical properties at two cure states were measured, namely tgg and gc-| cure.

SUEGTsiU ; ;- cjh_ ^; i-i

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Table 2- Reinforcing Effect of Surface Active Plasticiser Accelerator (SAPA no. 1) on Unfilled and Filled NR

(i) BS903. (ii) An occasional very high value was observed.

C_) %•■,*<" ^■ r » ^{• ■} .' ^• .',t_V_'

^' _.-. _.\ ⁴ ET OVIP

Examination of these results show the following features: the addition of SAPA: i) Increases the cure state of both unfilled (47%) and filled (61%) NR and reduces the induction time (processing safety) before cure ccrr-rences (see figure 1). ii) Increases the strength properties significantly, i.e. UTS increases by 45% and 16% in unfilled and filled vulcanisates respectively and the comparative tear strength increases are 10% and 33%. iii) Hardness increases significantly ty 17% in unfilled and 15% in filled vulcanisates. iv) Ccirpression set reduces by 12% in unfilled and 8.5% in filled vulcanisates. v) tfost unexpectedly and inexplicably the addition of the liquid SAPA increases Mooney Viscosity by small but significant amounts with the increase being 12.5% in unfilled and 4% in filled mixes.

During the Series 1 and Series 2 e-φeriirents the unvulcanised rubbers were observed to possess outstandingly good flew and processing properties and these characteristics were now observed in more detail.

Series 3 Experiments

Exaιrd_nation of SAPA in some Synthetic Rubbers

SAPA was examined in some coπrπon synthetic nαbbers for its effect on processing and properties and the results are now systematically given and cαiroented upon.

SBR Rubber This rubber was examined in the filler reinforced condition, as in the unfilled condition it has only very poor strength; both carbon black and precipitated silica reinforced rubbers were investigated. Results are given in Table 3 below and Figure 2.

Continued

-14-

Tahle 3 - Gtaritinjed

The b-h_Rά.cur of SAB. in -SER is di Ffera±. fcσπ its respe-. ^* se in ER as can be seen ty the ir-Jlαdng ir ^* fasιpretcrl-_--n of the <5__ta in Table 3 and Figure 2. In SB -the plastiriser Si*__ _ t_eba ^* =s cg-Mail iα ^** *1 ly as its irrtTusicn lowers the

Mooney viscosity, whereas in NR the Mooney viscosity was increased indicating some chemical response was occurring; in carbon black rubbers the reduction in Mooney viscosity, for the addition of only a small amount (2phr) was 12% for SAPA compared with 6% with aromatic oil and in a silica filled rubber the viscosity reduction compared with triethanolamine was also considerable.

Moulding

The SBR mixes containing SAPA possessed markedly superior flow and processing properties to their controls by producing undistorted stress free test specimen sheets when compression moulded from a cold thick round blank (of 10mm thickness) by the simple application of pressure. The equivalent control rubber all gave moulded sheets possessing defects due to flow proble s.

Physical properties of particular note, however, are the cure activation effect of SAPA in an all-silica filled rubber where it out-performs the standard activator, triethanolamine; it should be noted that both SAPA and triethanolamine (TEA) in a silica filled SBR give the same state of cure, as determined by an oscillating disc rheometer (ODR). The inclusion of SAPA increases the tensile strength (50%), elongation at break (39%) and the tear strength (17%) over the conventional TEA containing silica SBR; compression set is inferior. SAPA gives about the same physical properties in a carbon black filled SBR as does a standard aromatic oil (see Table 3 and Figure 2) but gives substantially better release for metal surfaces.

Series 4 Experiments

Examination of SAPA in some Synthetic Rubbers For this purpose rubbers were divided into two classes; strain crystallisable (CR) and non-strain crystallisable (NBR). The results are shown in Tables 4 and 5 and Figures 3 and 4 shewing a coπparison of SAPA effects versus conventional plasticisers as controls.

-16-

Table 4 - Polychloroprene. SAPA compared with Dioctylphthalate

Unfilled (gum stock) Carbon Black filled

Control SAPA present Control SAPA present

Neoprene GRT 100 100 100 100

ZnO 5 5 5 5

Magnesia (MgO) 4 4 4 4

Robac 22 0.5 0.5 0.5 0.5

HAF Black - - 50 50

Per anax B 1 1 1 1

SAPA - 2 - 2

DOP - - 2 -

Mooney Viscosity 30 29 15 16

ML 1+4 at 100 C

Cure conditions ^" --95% -^ ^0DR ~ Figure 3

Tensile Strength MPa 6.4 9.9 19.7 19.8

Tensile Strength MPa 5.9 4.8 18.4 18.3

After 7 days at 70°C

Elongation at break % 580 840 350 330

Elongation at break %

After 7 days at 70°C 480 500 345 335

Hardness IRHD 42 45 80 81

Hardness IRHD 43 47 81 82

After 7 days at 70°C

Tear Strength N 87 37.5 115 112

Corrpression set 20 22 9 12

48 hr at 70 C

Processing Properties Poor flow Mill flow and Mill flow Easy and mill roll release difficult processing roll excellent. due to high rubber; low release. No stress black heat

Difficult lines or content. generation to mill distortion High shear during mixing and mould. of cured heat gener¬ Moulds readil

Stress mouldings. ation with no flow lines on during or stress cured mixing. problems in mouldings. Distorted final mouldings moulding. if blank preparation not

Table 5 - Nitrile Rubber. SAPAcoπpared with Dioctylphthalate in a Carbon Blac Reinforced Mix

Cure Conditions 15"/150°C

Polychloroprene and SAPA

The effect of SAPA on the Mooney viscosity of CR is similar to a conventional plasticiser in both unfilled and filled rubbers. Cure rate is not significantly affected by SAPA but the cure state (tg5 Modulus) of the unfilled CR is considerably erihanced; the cure state of the filled CR is only maginally erihanced, possibly because insufficient SAPA has been added to the CR mix which contains 50 phr of HAF black for maxi_πum tensile strength (the NR and SBR mixes only contained 30 phr of black). Processing of the SAPA containing rubbers is markedly irrproved by the presence of SAPA both during milling and moulding with mouldings possessing flaw free surfaces and being free of stress and distortion problems. Physical properties are not improved by the presence of SAPA in CR where its effect seems similar to that of a conventional plasticiser.

Nitrile Rubber and SAPA (Table 5 and Figure 4)

The effect of SAPA on the viscosity and cure properties of NBR is similar to that of a conventional ester pl-asticiser such as di-octyl phthalate (DOP). With the proportion of SAPA used in this corrparison the effect on physical properties is increased as SAPA contradictorily given NBR a higher tensile strength but lower tear strength; an explanation of this may be seen by observing that the compression set of the SAPA/NBR is exceptionally low (6.5%) hence the SAPA/NBR may have a greater degree of cure and hence crossliriking than its DOP/NBR counterpart though this is not indicated by the ODR results of Figure 4 which shew DOP -and SAPA to give the NBR similar rates and states of cure. Processability of SAPA cont_aining nitrile rubber was markedly superior to the DOP control.

Series 5 Experiments. SAPA as an accelerator of rubber vulcanisation

In all these investigations a ccrπmon feature is the ability of the SAPA to act as a cure rate and cure state promoter and it was decided to examine its potential as a rubber accelerator. As a base compound for this investigation a typical NR/SBR truck tyre sidewall con-pound (see Table 6) was chosen in which to vary SAPA and the other ingredients of a conventional curing system.

-19-

Table 6 - Truck Tyre Compound used to examine the potential of SAPA as an accelerator.

NR (SMR20) 30 pbw

SBR 1500 70

FEF Carbon Black 51

IPPD 2

Microcrystalline WAX 3

Zinc oxide 4

Stearic acid 2

Santocure MOR 0.25

CBS 0.25

Sulphur 2

Processing oil/additive Variable

- » I D T! j - ' Ε 8HEE ^"

Ccπ-parison of SAPA with C_oιτ-rι-on Rubber Processing Oils (Table 7)

It is noteworthy, from the data in Table 7, that the SAPA contai ing rubber (10 phr SAPA) has a higher strength than its hydrocarbon oil analogues; its strength is about the same as that of a non-oil containing mix, but, the SAPA mixes process and flows exceptionally easily.

Also, it is observed that the mix containing only SAPA has a very short scorch time, 3 ^* , at the relatively high level of 10 phr SAPA used and hence is acting as a cure rate accelerator to the extent of perhaps being able to induce scorch problems. This aspect of scorch control is now examined in detail as mixes with scorch times of 3' are not usually considered as practical for processing by the rubber industry's tyre manufacturers.

It was thought possible that SAPA was performing similarly to stearic acid but the data in Table 7 demonstrates that the modes of action of SAPA and stearic acid must be different.

SUBST.TUTfΞ SHEET

-21- Table 7 - Camparison of SAPA with Rubber Processing Oils/Additives

No oil Aroπatic Naphthenic Stearic Strucktol SAPA oil oil acid SWB 212

Tensile strength 19.3 17.9 16.4 19.5 19.5 19.5 MPa

% E.B. 580 660 660 580 570 595

300% modulus, MPa 8.4 6.5 5.7 8.6 8.7 8

Hardness IRHD 61 53 51 65 62 57

% Resilience 47 44 46 44 44 50

Tear strength 91 85 115 114 94 129 N/2 mm sample

Cure Properties t ₉₀ at 160°C 16 2C 22 21fc 20

Mooney viscosity 47 43 42 40 42 50 100^

Mooney scorch 20 mins 24 19*2 22^ 24±_. 3 ML 125°C

Banbury mixing 13 mins 10 10 10 10 10 time

Duπp terrperature 135 115 115 124 126 120 °C

Proportions of Processing aid in phr 0 10 10 10 10 10

O PI

i*

Elimination of the Cure Activation and Acceleration Systems

It was observed from the results of Table 7 that whilst the physical properties of SAPA containing irubber vulcanisates were better than its processing oil analogues by between 5-15% though similar to the flew additives Struktol SWB 212 and Stearic Acid, the scorch time of the SAPA mixes was short at the relatively high proportions (1 to 10) used, preferably 7.5p. Hence an investigation using the base corrpound of Table 6, was conducted to try and resolve this scorch problem; the method was to omit the zinc oxide/stearic acid activator and accelerator system from the rubber formulation; initially seme PVI (") was retained to try and retard cure but this was found to be ineffective (see Table 8) and not required.

Table 8 - Elixiination of the cure activator and accelerator systems from SAPA containing irubber formulations

Base mix, as shewn in Table 6.

All mixes contained 2phr of sulphur (Baribury mixed)

The results of Table 8 show that relatively high SAPA proportions (e.g. 7.5p) give short scorch times (6-7 minutes) but by reducing the SAPA to 1-3 phr level increases the scorch time to 17-13 minutes, usually considered industrially acceptable. Also, using SAPA, it is possible to eliminate the conventional cure activation system (ZnO and Stearic Acid) and the delayed action accelerators (CBS and Santocure MOR) and, the prevulcanisation inhibitor PVI, whilst retaining the principal cross-linking agent, sulphur, at the modest proportion of 2 phr. Physical properties remain consistently good over the range of SAPA proportions used, 1-7 phr, with only a reduction in hardness becoming apparent at the higher (7.5 p) SAPA levels.

The processing and flow properties of all SAPA containing systems were found to be outstandingly good (see later).

This combination of cure activation and acceleration plus processability properties in a rubber mix is considered to be unique.

Series 6 Experiments. Zinc Oxide as a Scorch Control Additive in NR/SBR Rubber Mixes Accelerated with SAPA (Table 9).

Table 9 demonstrates the effect of first introducing ZnO and then later stearic acid into a irubber mix containing only sulphur as a curative and from which the conventional accelerators have been omitted. It can be seen that when no ZnO and stearic acid is present a mix with 1.5 phr of SAPA has a scorch time of 15' and an optimum (tg ₀ ) cure time of 22'. Introducing 1 phr of ZnO increases the scorch time from 15' to 100' and the _ _Q cure time from 22' to 42'; further additions of ZnO (mixes A and B) and later stearic acid (mix B) have little to no effect on further extensions of scorch time or t_ _Q curing time. The inclusion of the ZnO results in some reduction of tensile strength.

The use of stearic acid as part of the acitvator system does not seem to be necessary in the formulation.

-2&-

Ta Qe 9 - Zinc oxide as a search crnb-ol additive in NR/SER -gEA rιϋ ^* er irrbes

SUBSTITUTE SHEET

OMPI

Zinc Oxide as Scorch Control Additive in NR mixes containing SAPA. (Table

10)

An investigation was conducted to ascertain whether the scorch retardation effect of ZnO, apparent in the NR/SBR blend, also applied to a single polymer system, n-amely NR. The results are given in Table 10 for a carbon black reinforce formulation similar to that of Table 6 but based on only NR the accelerators CBS and Santocure MOR were also present at 0.25/0.25 parts respectively (as in Table 6). It is seen that decreasing the ZnO content progressively from 4 part to 1 parts increases the scorch time in a regular and uniform manner from 14' to 24' in mixes containing 0.5 p SAPA at higher SAPA levels, i.e. 1.5 parts the effect of the ZnO on reducing scorch, whils apparent, is not so pronounced. This observation ∞nfiirms, in principle, the ability of ZnO to control scorch in SAPA containing rubber formulations It is considered that stearic acid plays no role in scorch control in this instance.

!I

A Siirple Mechanism Proposed to Account for the Multiplicity of Functions of SAPA in Rubber Ctaπpounding - Ambient Teirperature State

The surfactant can take the form of a fatty acid salt of N-akyl propylene diamine (R(NH ₂ ) (CH ₂ ) ₃ NH ₃ ) ²⁺ 2(R ₁ C00~) vΛere R and R _χ are long chain alkyl groups and R_ is stearic acid or it can be in the form of an aliphatic diamine as represented by N-tallow-1,3-diamincr-propane di- oleate.

In this form the salt of the diamine functions as an internal processing aid and a filler-rubber surfactant enabling wetting to take place between the rubber (hydrcphobic)/filler (hydrophilic) interfaces. On heating to vulcanisation teirperature, dissociation takes place forming a secondary amine vulcanisation accelerator R H2(CH2)3NH2 and a fatty acid 2 R _j _ C00H as an internal mould release agent and cure rate contoller.

Proposed Mechanism to Account for Increase Scorch Time (Cure Retardation) Vfaen Zinc Oxide is used in a SAPA accelerated Rubber Formulation

The surfactant may take the form of the salt of an alkyl propylene diamine, shewn as (R NH (CH2)3NH3) ²⁺ 2(RC00)~ which on heating in the presence of the zinc oxide (or lead oxide) is represented by (RCOO^Zn + H ₂ 0 + R lsH(CH2) _n r-2 where the zinc salt of the fatty acid which acts as a retarder (being acidic) to the diamine accelerator produced, and the diamine acts as an accelerator of cure.

Also ZnO is thought to react with ^S, considered to be produced during all sulphur type cures, hence causing a decrease in the quantity of the hydrogen sulphide normally available and required to produce the nucleophilic hydrosulphide, sulphide, or sulphite ions? these ions axe considered essential to effect the hydrolysis of the cyclic S - S chain of

sulphur, enabling it to function as a crosslinking agent in rubber. Hence a reduction in their availability due to H ₂ S reacting with ZnO would account for cure retardation.

Series 7 Experiments. Effect of SAPA on Coπpression'Set (and Cure State) (Table 11)

Table 11 and Figure 5 illustrate the effect on compression set of SAPA (3 phr) coirpcured with zero oil and other ccraτon rubber mineral based processing

5 oils (7.5p) and mineral oil/processing aid combinations (5p + 5p). It is obvious from these results that the SAPA containing conpound reaches a higher state of cure than the non-oil and oil and oil/processing aid formulations as shown by the ODR of Figure 5, and that this observation is confirmed by the lower coπpression set data for SAPA mixes of Table 11. 0 SAPA containing mixes have a compression set value about 12% better (i.e. 25.5%) than the non-oil containing control which has the next best value of 30% coirpression set. Both SAPA and non-oil formulations are superior to all oil containing formulations.

15 A further point of interest is that the density (S.G. ) of SAPA mixes was less than that of all other indicating relatively lew volume cost potential.

Table 11 - Effect of SAPA on Compression Set (and cure state) 20

Formulation *Corηpression Set Specific Gravity

25 Zero oil i.e. no plasticiser 30 1.1385

7.5 phr Iraqi oil (aromatic oil) 31 1.1328

7.5 phr naphthenic oil. Cirosol 4240 (1) 31 1.1293

7.5 phr Sun oil. Sundex 790 (1) 32 1.1343

(Aromatic oil)

307.5 phr Dutrex 729 (aromatic oil) (2) 31.5 1.1328

5 phr Iraqui oil + 5 phr Strucktol Sb 212 (3) 32 1.1356

Surface active plasticiser 3phr (+0.5 p ZnO) 25.5 1.1166

Accelerator

*Cα-pression set was performed at 25% strain and 7θSθ for 48 hours.

35 (1) Trade name of sun Oil Coπpany

(2) Trade name of Shell

(3) Trade name of Schill and Seilacker

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Series 8 Experiments. Processing Studies using SAPA (Tables 12-14) (Figure m

The processing properties of rubber (NR/SBR of table 6) containing SAPA was coπpared with various aromatic and naphthenic mineral oils, and also with those mixes which contained mineral oils plus the processing aids, stearic acid and Struktol SWb 212. Details of the experimental procedures used and results obtained are given in Tables 12-14 with the exception of the extrusion conditions which are given belcw.

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1(A) Zero Oil 20 135 47 0.535 1533 13 4.5 i.e. No (Plasticiser) First Stage Only

2(A) 7.5 phr Iraqi Oil 18 119 41 0.38 1089.2 10 4.5 (Aromatic Oil) 3(A) 7.5 phr Naphthenic Oil 21 117 42 0.3625 1039 10 4.5 Circosol 4240 (1)

■M

CO 4(A) 7.5 phr Dutrex 729 19 115 45 0.3875 1110 10 4.5 (Aromatic Oil) (2) 5(A) 7.5 phr Sun Oil 20 119 45 0.39 1117 10 4.5 Sundex 790 (1) (Aromatic Oil)

6(A) 5 phr Iraqi Oil + 5 phr 18 112 44 0.3575 1024 10 4.5 Stearic Acid

Table 12 (continued)

Formulation A Phr

SMR 20 30

SBR 1500 70

ZnO 4

S 2

CBS 0.25

Santocure MOR 0.25

Flectol-H 0.75

IPPD 2

Stearic Acid 2

Wax 3

Plasticiser as mentioned in the table

FEF 51

** Die Swell : it is calculated ty dividing the die swell index by the Specific Gravity of each compound and then dividing the products ty 0.5cm ² which is the cross sectional area of Garvey Die.

Formulation B Plasticiser containing fo

Phr

SMR 20 30

SBR 1500 70

ZnO ^' 0.5 ) used to extend scorch time from 13 mins

S 2 ) to 27 minutes.

Flectol-H 0.75

IPPD 2

Wax 3 anti-ozonant type

Plasticiser As mentioned in the table

FEF Black 51

1. Each compound was passed once through an open mill having a 9 inch di-ameter and 18 inches length and the nip was kept constant (3mm opening) throughout the passing of each ccrrpound.

2. Total Work is calculated as follows:

Total Work is mJ/rrr = Total energy

Fill Factor x Banbury chamber volume

= mJ

0.8 x 1570 cc

= ml

1256 cc

= mJ x 10 ^c

1256 m ^"

Total energy was calculated using a counter which is directly connected to the main power meter of the Banbury, and it was found that each unit is equal to 18 kJ. So for each mix the number of units was counted and accordingly the power was calculated.

SUBSTITUTE SHEET

(ie. No Plasticiser)

* The barrel temperature was between 97 - 10

7.5 phr Iraqi Oil 3.99 1.20 243 (Aromatic Oil) * The die used has the following dimensions:

7.5 phr Naphthentic 3.99 1.20 253 1. length = 15mm Oil Circosol 4240 (1) 2. diameter = 2 mm

7.5 phr Dutrex 72g (2) 3.99 1.17 260 Note m

I

7.5 phr Sun Oil 3.99 1.17 260 The following equations were the basis for t Sundex 790 (1) calculation of the shear rate and the shear (Aromatic Oil)

Shear rate Y (sec ^"1 ) = 4Q

5 phr Iraqi Oil + 5 phr 4 1.20 243 17r3 Stearic Acid where Q = volumetric flow rate - output rat

5 phr Iraqi Oil + 5 phr 4.06 1.15 278 r = radius of die Strucktol SWB 212 (3)

Shear Stress (TW) =Δ Pr kN/m ²

Surface Active 4.11 1.25 351 2 Plasticiser Accelerator o CO 3phr (+0.5 p ZnO) P •= pressure in barrel ιo r = radius of die

ID Sun Oil Company L - length of die

CO (2) Shell o (3) Schill and Seilacker

Zero Oil (ie 4.22 0.833 1.463 4343 98 No plasticiser)

7.5 phr Iraqi Oil 4.24 0.842 1.486 3723 95 (Aromatic Oil)

7.5 phr Naphthenic 4.25 0.838 1.484 4033 95 Oil Circosol 4240 (1)

I in 7.5 phr Dutrex 729 4.30 0.842 L.486 4095 95 i (Aromatic Oil) (2)

7.5 phr Sun Oil ^" T 0.842 1.484 3909 ^" 95 ^" Sundex 790 (Arατatic Oil) (1)

5 phr Iraqi Oil + 4.24 0.84 1.489 3971 ^" 9 5phr Stearic Acid

5 phr Iraqi Oil + 4.26 0.84 1.479 4288 94 5 phr Strucktol Slffi 212 (3)

© eo ιo ^"■" Surface Active 473Ϊ 0.835 1.496 4964 94 4 4 4 4

_° Plasticiser *- ^* .<

CO Accelerator

O 3 phr (+0.5 ZnO)

(l) Sun Oil Company; [2 Shell; (T) Schill and Seilacker Extruder used was a cold feed type of L/D ratio

Extrusion Conditions for SAPA Evaluation The conditions for extrusion were kept constant throughout the extrusion of the eight coπpot-nds and these conditions were as follows:- 1.. Temperature of the mill was kept constant at 20 ^C> C and the mixing

(war-niing) of the cxsrpounds also kept constant, for a period of 4 minutes cutting of the corrpound was carried out through an interval of 30 seconds.

2. Extruder

A. - Temperature of the barrel = 7Pc

B. - Teπperature of thehead = llO'-'C

C. - Terrperature of the die = llO ⁰ ^

D. - Screw Speed = 45 rpm

3. A take off conveyor was kept constant as a speed of 4ft/min to prevent any stretching.

The type of extruder used is 1_" extruder of Farrel-Bridge Ltd which has a length to diameter ratio of 20:1. Formulations used were the same as those given in Table 12 for the mixing study.

Die swell was calculated ty dividing the die swell index by the specific gravity of each cccrpound and the results were divided by the cross-

_ sectional area of that of Garvey die which is 0.5 cm .

Extrusion Figure 7 also demonstrates use of SAPA as a processing aid in both black and silica filled mixes. It is self-evident that the inclusion of SAPA in the formulation has resulted in a considerable reduction in the otherwise rough surfaces of both of the extrudates. However, SAPA is found particularly effective as a flow additive in the silica filled mix turning on otherwise unprocessable rubber with a compound possessing satisfactory flew. This observation has been found to be generally applicable and SAPA is a particularly effective flow additive for turning "difficult to flow" silica filled rubber mixes into readily processed materials; an additional advantage is that as SAPA, when heated, decomposes and produces in situ a secondary amine then high silica containing formulations can use rruch lower quantities of accelerators whilst still attaining the same cure state.

Internal Fixing Properties (Table 12)

The mixing parameters of the oil, oil + processing aid, and SAPA rubber mixes were all found to be similar in nature with respect to mixing time, electrical power consuπption, and total work input as a result of the mixing operation. However, a special feature observed is that the Mooney viscosity of the SAPA mixes is 8 points greater than the zero oil mixes and 8-14 points greater than the oil and oil/processing aid mixes. This is considered to indicate that as a result of the heat generated in the rubber by mixing, the SAPA is undergoing or promoting a chemical reaction between itself and the irubber mix which results in an increase in Mooney viscosity. It is postulated that the SAPA is, to some extent, functioning as a coupling agent between the filler and the irubber and, or, perhaps as a surfactant between the filler and the rubber. The proposal that SAPA acts as a coupling agent is also based on the observation that all SAPA mixes possess higher modulus values than their oil containing controls (e.g. see Table 7).

As this increase in Mooney viscosity is also observed to occur in unfilled (gum) rubber mixes (see Tables 1(a) & 2) an alternative possibility that must be considered is the reaction of the SAPA directly with the rubber molecule itself to produce in situ a few chemical crosslinks; should such a process occur it would be analogous to the formation of a lightly gelled rubber similar to the SP natural rubber or di inyl benzene SBR series.

Extrusion Process-ability (Tables 13 and 14 and Figure 6) (graphs A to H) Table 13 gives the extrusion processability measured by capillary rheometer; the results apparently show that the use of SAPA as an alternative to mineral oils for processing purposes give unvulcanised irubber with higher green strength as indicated by an extrusion shear stress of 351 kfc&n ^-2 for SAPA mixes coπpared with a range of 243-278 for the more conventional rubber mixes: this cranfirms the earlier observation of SAPA mixes possessing higher Mooney viscosity vfaich is new reflected in the higher shear stress needed for extrudates. Table 14 gives Garvey Die data for all SAPA mineral oil, and mineral oil plus processing oil mixes.

All this data confirms the excellent processability of SAPA mixes compared with the conventional rubber formulations demonstrating that no abnormal or adverse processing phenomenon result from the use of SAPA as a rubber compounding ingredient. _ _^ ^* _R fjRE-A

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Chemical Ccπposition of the Surface Active Plasticiser Accelerator (SAPA)

Series

The cαrposition of the SAPA used in this investigation is:-

(R ( H ₂ )(CH2) H ₃ 2+ ^" - ^" 2(R ^* .C00~)

where R= tallow and R'= oleate.

This ccπpound has the ability to partially dissociate on heating into some of its primary components and it is this property viiich is considered to account for its simultaneous multiplicity of uses as a rubber processing aid, cure rate activator and accelerator, and as a surface active plasticiser that enhances filler re__n-5Drcerrent of rubber by means of the irechanism disclosed above.

The fatty acid salt of an alkyl alkylene diamine is selected from the group comprising lauric acid; palmitic acid; soya acid; hydrogenated tallow acid; N-coco-1, N-tallσw-1, 3-diamino-propane N-oleyl-1, 3-diamino-propane; N-tallσw-1, 3-diamino-propane di-oleate; N,stearic-1, 3- dia ino-prcpane distearate; N-oleyl-1, 3-diamino-propane dioleate, and alkyl propylene diamine.

Alternatively, the following cαπpositions may be utilised:-

that is:- l(2-hydro^thyl)-2-heptadecerιy[2] imidazoline or 1 hydroxyethyl 2 oleyl imidazoline.

In yet a further alternative class of cationic surfactants alkyl bis alkylamide may be selected from the group comprising N,N'-ethylene bis lauramide; N,N'-ethylene bis stearamide; N,N'-ethylene bis ityristamide; N,N'- ethylene bis oleamide; N^'-ethylene bis eiruc-ut de; and N,N'-ethylene bis behenamide.

SAPA as a dispersant in Natural Rubber (an example of a strain crystallisable rubber)

SEM micrograph (x 7,000 magnification) of a torn vulcanisate surface to illustate the ability of the SAPA surfacant as a filler dispersion and wetting agent in Natural Rubber.

(a) contains no SAPA. Figure 8(a)

(b) contains 2 phr of SAPA. Figure 8(b)

The micrograph (a) clearly shews lumps of undispersed filler aggregates vΛilst in (b) the number of undispersed aggregates is considerably reduced. The tensile strength of the SAPA containing mix is ca. 20% greater than its non-SAPA containing coπparison.

(Forπulation: NrlOO, FEF Blade 50, Aromatic Oil 5, Flectol H 2, CBS 0.5, Suphur 2)

SAPA as a filler wetting agent in SBR (an example of a non-strain crystallisable rubber)

SEM micrograpih (x7,000 magnification) of a torn SBR vulcanisate surface.

(c) contains no SAPA and the relatively poor dispersion of filler aggregates can be seen as represented by large lurrps. Figure 9(a) Tensile strength = 18 MPa, 300% modulus 8 MPa

(d) contains SAPA (2 phr) and this has the result of reducing the number of filler aggregates (fewer lumps and voids are visible) and also reducing the relative size of residual aggregates. Tensile strength = 22 MPa. 300% modulus 11 MPa. Figure 9(b) The better dispersion of the filler through the use of SAPA has increased the tensile strength by 22% and the 300% modulus by 37%.

ώi-ϊ. i i i '_> - >_ .»H__1__T

Filler dispersing properties of SAPA

The use of a cationic surfactant as a dispersing and wetting agent for filler in irubber can be seen by inspecting the scanning electron microscopy (SEM) micrographs in Figures 8 and 9. The torn surface of irubber vulcanisates cxsntaining no SAPA shew relatively large rugosities and voids on their torn surfaces, whilst SAPA containing formulations have almost smooth protrusion and void free surfaces. This is taken to indicate superior aggregate breakdown, filler dispersion and also surface wetting of SAPA containing foirmulations. Results are shown in Figures 8 and 9. The better filler dispersion has also resulted in higher tensile strength in these particular rubber mixes filler dispersion was only of average quality. It is speculated that the use of SAPA and similar cationic surfactants in irubber coiipounding would result in more reproducible irubber mixing operations.

Discussion

It is considered that SAPA has demonstrated multiple functions when used as a -rubber compounding additive in various rubbers. In all the classes of rubber examined it functioned as an excellent processing aid or flow additive at low proportions (ca. 0.5 - 2.0 phr). With certain rubbers such as NR, and N/SBR blends in both unfilled and filler reinforced compounds it increases Mooney viscosity and hence green strength; in other rubbers such as SBR, CR and NBR it functions as a flew additive only and does not increase the green strength. SAPA is universal in its effect as a processing flow additive with all cctrmon rubbers; it also provides excellent roll release and mould release properties.

Physical properties of vulcanisates of non-polar rubbers such as NR, NR/SBR blends are all increased ty the inclusion of SAPA with increases typically between 15-30% of the control mixes based on conventional oils or other flow additives. SAPA is observed to be particulary effective when used in precipitated silica reinforced SBR rubber (see Table 3) where it outperforms TEA.

SAPA also can function as a cure rate promoter; rubber mixes based on the conventional organic accelerator/zinc oxide/stearic and acceleration system can be further accelerated ty the inclusion of 0.5 - 2.0 phr of SAPA in the formulation enabling if desired, the proportion of organic accelerator to be reduced. However, it is also observed that for NR, SBR and NR/SBR blends the SAPA will function as an accelerator system in its own right enabling fast curing formulations to be obtained without the presence of any organic acclerator (e.g. CBS/zinc oxide/stearic acid combination (Table 8). Delayed action curing of SAPA mixes (i.e. longer scorch times) can be obtained by using combinations of SAPA with zinc oxide e.g. 2p of SAPA + 0.5 p ZnO (Table 9) .

It is observed that several types of cationic chemical coπpounds demonstrate, in principle, iriltipurpose roles similar to SAPA but with interesting variants. For example, degrees of delayed action cure effects are shown dependent on the particular chemical structure of the 5 surfactant.

It is considered that a new class of irubber compounding ingredient has been identified possessing a multipurpose role by cc_rfo__ning into a single c-hemical structure the functions of intern ^** ! processing aid and rrr ^* uld 0 release agent, accelerator, and, filler-rubber ccupling/wetting agent properties which enhance the strength of irubber vulcanisates.

In addition to enhancing processability of rubber by increasing flow and simultaneoulsy providing mould release and enhancing the properties of the 5 final vulcanisate the cost of a typical SAPA containing rubber foππulation is expected to be less than its conventionally accelerated counterpart.

Other properties are also considered to be capable of being irrproved in 0 irubber formulations by the inclusion of SAPA in the recipe and are identified as follows:

1. Electrical conductivity is increased giving rise to possible advantages in ccrripounds that need to be micro-wave heated more quickly, also by acting as a non-black anti-static agent in -rubber

25 compounds.

2. An anti-static agent for non-black (coloured) rubber vulcanisates. 3.- Rubber vulcanisates incorporating SAPA have significantly lower coefficient of friction surfaces and may be useful in applications where lew surface drag is iπportant. 304. Reduction in irculd fouling - has also been observed, especially with fluoroelastomer rubbers, and also with other elastomers.

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