Title:
NON-CROSSLINKED POLYETHENE
Document Type and Number:
WIPO Patent Application WO/2000/064952
Kind Code:
A2
Abstract:
The invention relates to non-crosslinked polyethene which value of the normalised difference between its storage modulus G' and its loss modulus G'', determined by dynamic rheological measurement, is continuously below 0,5 under frequencies from 0,01 to 100 rad/s and at the temperature 190 °C. Preferably, said difference is essentially constant under said frequencies. Such polyethenes are preferably prepared by using metallocene catalysts, most preferably based on rac-ethylene bis(3-tri-isopropylsiloxy)indenyl zirconium dichloride or rac-ethylene bis(3-tert-butyldimethylsiloxy)indenyl zirconium dichloride.
Inventors:
MALMBERG ANNELI (FI)
LOEFGREN BARBRO (FI)
Application Number:
PCT/FI2000/000366
Publication Date:
November 02, 2000
Filing Date:
April 27, 2000
Assignee:
BOREALIS TECH OY (FI)
MALMBERG ANNELI (FI)
LOEFGREN BARBRO (FI)
International Classes:
C08F10/00; C08F10/02; C08F4/659; C08F110/02; C08F210/16; (IPC1-7): C08F10/00
Domestic Patent References:
| WO1997044371A1 | 1997-11-27 | | | |
| WO1996007680A1 | 1996-03-14 | | | |
| WO1997029138A1 | 1997-08-14 | | | |
Foreign References:
| EP0729978A1 | 1996-09-04 | | | |
| EP0743324A2 | 1996-11-20 | | | |
| EP0676421A1 | 1995-10-11 | | | |
Attorney, Agent or Firm:
BERGGREN OY AB (P.O. Box 16 Helsinki, FI)
Claims:
Claims
| 1. |
Non crosslinked polyethene, characterised in that the value of the normalise difference between its storage modulus G'and its loss modulus G", determined by dynamic rheological measurement, is continuously below 0,5 under frequencies from 0,01 to 100 rad/s and at the temperature 190°C. |
| 2. |
Non crosslinked polyethene according to claim 1, characterised in that the absolute value of the difference between its storage modulus G'and its loss modu lus G", determined by dynamic rheological measurement, is continuously higher than 0 under frequencies from 0,1 to 100 rad/s and at the temperature 190°C. |
| 3. |
Non crosslinked polyethene according to claim 2, characterised in that said absolute value of the difference between its storage modulus G'and its loss modu lus G"is essentially constant. |
| 4. |
Non crosslinked polyethene according to any preceding claim, characterised in that it has been prepared by selecting for the polymerisation a catalyst system comprising a metallocene complex. |
| 5. |
Non crosslinked polyethene according claim 4, characterised in that said metallocene complex is a metallocene having a sandwich bonding ligand comprising a sandwich bonding moiety having an unsaturated 5membered ring or having a 6 membered ring fused to an unsaturated 5membered ring which moiety is covalently substituted by an organic group via a heteroatom. |
| 6. |
Non crosslinked polyethene according to claim 5, characterised in that said moiety comprises an indenyl, dihydroindenyl or tetrahydroindenyl ring system. |
| 7. |
Non crosslinked polyethene according to claim 5 or 6, characterised in that said moiety is substituted by a silyloxy or germyloxy group. |
| 8. |
Non crosslinked polyethene according to claim 7, characterised in that said metallocene complex is racethylene bis (3triisopropylsiloxy) indenyl zirconium di chloride. |
| 9. |
Non crosslinked polyethene according to claim 7, characterised in that said metallocene complex is racethylene bis (3tertbutyldimethylsiloxy) indenyl zirco nium dichloride. |
| 10. |
Non crosslinked polyethene according to any of claims 49, characterised in that said metallocene complex is supported. |
| 11. |
Non crosslinked polyethene according to claim 10, characterised in that said metallocene complex is supported on silica, alumina and/or magnesium dichloride. |
| 12. |
Non crosslinked polyethene according to any of claims 411, characterised in that said polymerisation is carried out in a slurry process. |
| 13. |
Non crosslinked polyethene according to claim 12, characterised in that a C3 C8 inert hydrocarbon e. g. propane, isobutane, pentane, heptane, hexane, toluene or any other aliphatic or aromatic solvent is used as medium in said slurry polymerisa tion. |
| 14. |
Non crosslinked polyethene according to claim 12 or 13, characterised in that said slurry polymerisation is carried out at a temperature from 60 to 110°C, pref erably at a temperature from 75 to 100°C. |
| 15. |
Non crosslinked polyethene according to any of claims 1214, characterised in that the ethene partial pressure in the polymerisation is from 0,25 to 40,0 bar, preferably from 2,0 to 15,0 bar, most preferably from 5,0 to 7,0 bar. |
| 16. |
Non crosslinked polyethene according to any of claims 1215, characterised in that hydrogen is optionally used in said slurry polymerisation. |
| 17. |
Non crosslinked polyethene according to any of claims 1216, characterised in that comonomer is used in said slurry polymerisation. |
| 18. |
Non crosslinked polyethene according to claim 17, characterised in that said comonomer is an aolefin, preferably a C4Cg aolefin. |
| 19. |
Non crosslinked polyethene according to claim 17 or 18 characterised in that the amount of comonomer is such that the comonomer content of the final product is from 1,0 to 10,0 wt%, preferably from 3,0 to 10,0 wt%, most preferably from 5,0 to 8,0 wt%. |
| 20. |
Non crosslinked polyethene according to any of claims 1219, characterised in that an alkyl aluminoxane is used as cocatalyst in said slurry polymerisation. |
| 21. |
Non crosslinked polyethene according to claim 20, characterised in that said alkyl aluminoxane is methyl aluminoxane, hexaisobutyl aluminoxane and/or tetrai sobutyl aluminoxane. |
| 22. |
Non crosslinked polyethene according to claim 20 or 21, characterised in that the amount of alkyl aluminoxane used is such that Al/Metalratio is from 50 to 2500, preferably from 100 to 1500. |
| 23. |
Slurry polymerisation process for the preparation of non crosslinked polyeth ene, which value of the normalise difference between its storage modulus G'and its loss modulus G", determined by dynamic rheological measurement, is continu ously below 0,5 under frequencies from 0,01 to 100 rad/s and at temperature 190 °C, wherein the process parameters are chosen from the following: (i) reaction medium is an inert C3C8 hydrocarbon or toluene, (ii) catalyst is based on a metallocene complex, and is optionally supported, (iii) reaction temperature is 60110 °C, (iv) ethene partial pressure is 0,2540,0 bar, (v) hydrogen is optionally used, (vi) comonomer is optionally used, (vii) cocatalyst is an alkyl aluminoxane, and Al/Metalratio is 502500. |
Description:
INTERNA17ONALSEARCHREPORTInternationalapplicationNo. PCT/FI00/00366 C(Continuation).DOCUMENTSCONSIDEREDTOBERELEVANT Category*Citationofdocument,withindication,whereappropriate,
oftherelevantpassagesRelevanttoclaimNo. AWO9729138A1(EXXONCHEMICALPATENTSINC.),1-23 14August1997(14.08.97),page1, line4-line35;page5,line13-line30; page13,line25-line29,claims AEP0743324A2(UNIONCARBIDECHEMICALS&PLASTICS1-23 TECHNOLOGYCORPORATION),20November1996 (20.11.96) AEP0676421A1(BPCHEMICALSLIMITED),1-23 11October1995(11.10.95) INTERNATIONALSEARCHREPORTInternationalapplicationNo. PCT/FI00/00366 BoxIObservationswherecertainclaimswerefoundunsearchable(Cont
inuationofitem1of firstsheet) Thisinternationalsearchreporthasnotbeenestablishedinrespecto
fcertainclaimsunderArticle17(2) (a)forthefollowingreasons: 1.nClaimsNos.: becausetheyrelatetosubjectmatternotrequiredtobesearchedbythi
sAuthority,namely: claimsNos.:1-23(allinpart) becausetheyrelatetopartsoftheinternationalapplicationthatdon
otcomplywiththeprescribedrequirementstosuch anextentthatnomeaningfulinternationalsearchcanbecarriedout,s
pecifically: seenextpage 3.ClaimsNos.: becausetheyaredependentclaimsandarenotdraftedinaccordancewit
hthesecondandthirdsentencesofRule6.4(a).: BoxnObservationswhereunityofinventionislacking(Continuationo
f item2offirstsheet) ThisInternationalSearchingAuthorityfoundmultipleinventionsin
thisinternationalapplication,asfollows: 1.Asallrequiredadditionalsearchfeesweretimelypaidbytheapplic
ant,thisinternationalsearchreportcoversall searchableclaims. 2.As allsearchableclaimscouldbesearchedwithouteffortjustifyingana
dditionalfee,thisAuthoritydidnotinvitepayment ofanyadditionalfee. 3.Asonlysomeoftherequiredadditionalsearchfeesweretimelypaidb
ytheapplicant,thisinternationalsearchreport coversonlythoseclaimsforwhichfeeswerepaid,specificallyclaims
Nos.: 4.gNorequiredadditionalsearchfeesweretimelypaidbytheapplican
t.Consequently,thisinternationalsearchreportis restrictedtotheinventionfirstmentionedintheclaims;itiscovere
dbyclaimsNos.: RemarkonProtestThe additionalsearchfeeswereaccompaniedbytheapplicant'sprotest. NoNo protestaccompaniedthepaymentofadditionalsearchfees. FormPCT7tSA/2) 0 (continuationoffirstsheet(1))(Julyl992) INTERNATIONALSEARCHREPORTInternationalapplicationNo. PCT/FI00/00366 Present claims 1-23 relate to a polymer defined by reference to the following parameters: P1: Storage modulus, G' P2: Loss modulus, G" The use of these parameters in the present context is considered to lead to lack of clarity within the meaning of Article 6 PCT. It is impossible to compare the parameters the applicant has chosen to use with what is set out in prior art. The lack of clarity is such as to render a meaningful complete search impossible. Consequently, the search has been restricted to: Homo-and copolymers of polyethylene with good processability, increased shear thinning and long chain branching. INTERNATIONAL SEARCH REPORT International application No. Informationonpatentfamilymembers 08/05/00 PCT/FI 00/00366 08/05/00PCT/FI00/00366 PatentdocumentPublication Patent citedinsearchreportdate member(s)date WO9744371A127/11/97AU 3067297 A 09/12/97 BR 9709008 A 28/09/99 CA 2255756 A 27/11/97 CZ 9803662 A 14/04/99 EP 0898585 A 03/03/99 NO 985328 A 15/01/99 PL 329952 A 26/04/99 SK 157598 A 11/06/99 ZA 9704267 A 16/11/98 EP0729978A104/09/96US 5710224 A 20/01/98 WO9607680A114/03/96AU 3541795 A 27/03/96 BR 9509196 A 21/10/97 CA 2199411 A 14/03/96 CH 688092 A 15/05/97 EP 0782589 A 09/07/97 IL 115104 D 00/00/00 US 5783638 A 21/07/98 US 5986028 A 16/11/99 WO9729138A114/08/97CA 2244815 A 14/08/97 EP0743324A220/11/96AU 706842 B 24/06/99 AU 5228496 A 28/11/96 BR 9602268 A 07/04/98 CA 2176623 A 17/11/96 JP 8311121 A 26/11/96 US 5852143 A 22/12/98 EP0676421A111/10/95CA 2146205 A 08/10/95 GB 9406895 D 00/00/00 JP 8048711 A 20/02/96 GB 9417365 D 00/00/00
