JPS6223777B2 - - Google Patents
Info
- Publication number
- JPS6223777B2 JPS6223777B2 JP53080952A JP8095278A JPS6223777B2 JP S6223777 B2 JPS6223777 B2 JP S6223777B2 JP 53080952 A JP53080952 A JP 53080952A JP 8095278 A JP8095278 A JP 8095278A JP S6223777 B2 JPS6223777 B2 JP S6223777B2
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- crosslinking
- copolymer
- ethylene
- silane compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 unsaturated silane compound Chemical class 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- 229920013716 polyethylene resin Polymers 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000465 moulding Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920003020 cross-linked polyethylene Polymers 0.000 description 3
- 239000004703 cross-linked polyethylene Substances 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
〔〕 発明の背景
技術分野
本発明は、架橋性すなわち架橋可能なポリエチ
レン樹脂組成物に関する。さらに具体的には、本
発明は、架橋性基として加水分解可能シラン基を
有するエチレン−エチレン性不飽和シラン化合物
ランダム共重合体と架橋反応触媒とを含む水架橋
可能ポリエチレン樹脂組成物に関する。
低密度ポリエチレンその他のポリエチレン樹脂
を架橋してその機械的強度および耐熱性等を改良
することは周知であり、各種の架橋手段が知られ
ている。
先行技術
そのような架橋手段の一つは、ポリエチレンに
架橋剤としての有機過酸化物を添加し、高温に加
熱して過酸化物を分解させて架橋反応を生起させ
ることからなるものである。しかし、この場合に
は、過酸化物の分解に基く架橋がポリエチレン成
形工程以前に行なわれるので、しばしば成形品の
品質が不良となり、甚だしい場合には成形の進行
が不可能となるという難点がある。架橋を成形工
程より後で行なおうとすれば、成形温度に耐える
高温分解過酸化物を使用しなければならないとこ
ろ、そのような過酸化物を分解させるためには成
形温度より高い温度に成形品を加熱しなければな
らないので、その結果、架橋工程で成形品の軟化
による変化が生じて、やはり成形品の品質が不良
となるのである。
化学架橋にみられるこのような問題点を伴なわ
ないものとして、シリコーングラフトポリエチレ
ンがある（特公昭48−1711号公報、特開昭47−
8389号、同50−138042号および同52−9073号公報
参照）。シリコーングラフトポリエチレンは、水
に暴露することによつてシリコーン部分が加水分
解されて架橋反応が進行するのであり、この加水
分解は比較的低温で生じるので、化学架橋の際に
必要となる膨大な架橋設備が不要となるところか
ら、架橋成形品への適用が検討されている。しか
し、この場合には、基材ポリエチレンの製造およ
びシリコーングラフト化の複数工程が必要であ
り、しかもこのようにして製造され、架橋された
ポリエチレン成形品たとえばシートは、臭気、機
械的強度、耐熱性および熱融着性に関して満足で
きるものではない。
一方、エチレンとビニルアルコキシランとの共
重合体を加熱または機械的加工で架橋させる方法
が知られている（米国特許第3225018号および同
3392156号明細書参照）。この方法によれば、架橋
性ポリエチレンはエチレン重合工程だけの単一工
程で得られる点で上記グラフト化法より有利であ
るが、この場合は架橋は成形加工以前に行なわざ
るを得ないので、前記化学架橋の場合と同じ問題
点があり、架橋反応後に成形して得た成形品の機
械的強度も満足できるものではない。
〔〕 発明の概要
要 旨
本発明は上記の点に解決を与えることを目的と
し、水架橋可能なエチレン−エチレン性不飽和シ
ラン化合物ランダム共重合体と水架橋用触媒とを
組合せることによつてこの目的を達成しようとす
るものである。
従つて、本発明によるポリエチレン樹脂組成物
は、下記の成分(A)および(B)を含むこと、を特徴と
するものである。
(A) エチレンとエチレン性不飽和シラン化合物と
の高圧ラジカル重合による共重合体（ただし、
このエチレン性不飽和シラン化合物単位の含有
率は、0.001〜15重量％である）、
(B) シラノール縮合触媒
効 果
本発明は、グラフト化でなくランダム共重合体
化（本発明で共重合体というときは、グラフト共
重合体を含まないものとする。ただし、不可避的
に併起するかも知れないグラフト共重合を排除す
るものではない。）によつて、ポリエチレン分子
中に導入したシラン基を有するポリエチレン樹脂
に水架橋可能性を与えたものである。
本発明組成物を成形し、水に暴露して架橋させ
て得た架橋成形品はすぐれた機械的強度および耐
熱性を有するのみならず、架橋シート成形品（シ
ート成形品は、本発明組成物の成形品の一つであ
る）は従来の架橋ポリエチレンシートの最大の欠
点とされていた熱融着性に関しても通常の低密度
ポリエチレンシートと実用上同等の性能を、また
耐熱性に関してはより優れた性能を有する。
なお、本発明ではグラフト化工程が無い代りに
不飽和シラン化合物を共重合させたポリエチレン
を別途つくらなければならないが、不飽和シラン
化合物使用量が少ないこともあつてこの共重合は
エチレンのホモ重合と操作上実質的に同一の方法
で製造可能であり、ポリエチレンの多種類化の一
環としてとらえられるものである。
〔〕 発明の具体的説明
１ エチレンと不飽和シラン化合物との共重合体
不飽和シラン化合物としては、エチレンと共
重合可能なエチレン性不飽和結合と加水分解可
能なシラン基を有する各種の化合物が使用可能
である。
このような化合物を一般式で示せば、たとえ
ば下式で表わされるものがある。
RSiR′oY3-o
（ここで、Ｒはエチレン性不飽和ヒドロカル
ビルまたはヒドロカルビルエーテル基を表わ
し、R′は脂肪族飽和ヒドロカルビル基を表わ
し、Ｙは加水分解可能な有機基を表わし、ｎは
０または１または２を表わす。Ｙが複数個ある
ときは、それぞれ同一でなくてもよい。）
この不飽和シラン化合物の具体例は、Ｒがた
とえばビニル、アリル、イソプロペニル、ブテ
ニル、シクロヘキセニル、γ−（メタ）アクリ
ロイルオキシプロピル、Ｙがメトキシ、エトキ
シ、ホルミルオキシ、アセトキシ、プロピオノ
キシ、アルキルないしアリールアミノ、R′が
メチル、エチル、プロピル、デシル、フエニ
ル、であるものである。
特に好ましい不飽和シラン化合物は、下式で
表わされるものである。
CH2＝CHSi（OA）3
（ここで、Ａは炭素数１〜８、好ましくは１
〜４、のヒドロカルビル基である）
最も好ましい化合物は、ビニルトリメトキシ
シラン、ビニルトリエトキシシラン、およびビ
ニルトリアセトキシシランである。
エチレンと不飽和シラン化合物との共重合
は、たとえば圧力500〜4000Kg／cm2、好ましく
は1000〜4000Kg／cm2、温度100〜400℃、好まし
くは150〜350℃、の条件下、ラジカル重合開始
剤および必要ならば連鎖移動剤の存在下に、槽
型または管型反応器、好ましくは、槽型反応器
内で両単量体を同時にあるいは、段階的に接触
させる。
本発明においては、エチレンの重合または、
共重合に用いることの知られているいずれのラ
ジカル重合開始剤および連鎖移動剤も使用する
ことができる。重合開始剤としては、ラウロイ
ルパーオキシド、ジプロピオニルパーオキシ
ド、ベンゾイルパーオキシド、ジ−ｔ−ブチル
パーオキシド、ｔ−ブチルヒドロパーオキシ
ド、ｔ−ブチルパーオキシイソブチレートのよ
うな有機過酸化物、分子状酸素、アゾビスイソ
ブチロニトリル、アゾイソブチルバレロニトリ
ルのようなアゾ化合物があり、連鎖移動剤とし
ては、メタン、エタン、プロパン、ブタン、ペ
ンタンのようなパラフイン系の炭化水素、プロ
ピレン、ブテン−１、ヘキセン−１のようなα
−オレフイン、ホルムアルデヒド、アセトアル
デヒド、ｎ−ブチルアルデヒドのようなアルデ
ヒド、アセトン、メチルエチルケトン、シクロ
ヘキサノンのようなケトン、芳香族炭化水素、
塩素化炭化水素等をあげることができる。
本発明組成物で使用する共重合体は、不飽和
シラン化合物単位の含量が0.001〜15重量％、
好ましくは0.01〜５重量％、特に好ましくは
0.05〜２重量％、のものである。一般に、不飽
和シラン化合物含量の多い共重合体の水架橋物
ほど機械的強度および耐熱性がすぐれている
が、含量が過度に多いと引張り伸びおよび熱融
着性が低下する。0.001〜15重量％という含量
範囲は、この点から決定されたものである。
２ シラノール縮合触媒
シリコーンのシラノール間の脱水縮合を促進
する触媒として使用しうるものが一般に本発明
で対象となる。このようなシラノール縮合触媒
は、一般に、錫、亜鉛、鉄、鉛、コバルト等の
金属のカルボン酸塩、チタン酸エステルおよび
キレート化物等の有機金属化合物、有機塩基、
無機酸、および有機酸である。
シラノール縮合触媒の具体例を挙げれば、下
記の通りである。ジブチル錫ジラウレート、ジ
ブチル錫ジアセテート、ジブチル錫ジオクトエ
ート、酢酸第一錫、カプリル酸第一錫、ナフテ
ン酸鉛、カプリル酸亜鉛、ナフテン酸コバル
ト、チタン酸テトラブチルエステル、チタン酸
テトラノニルエステル、エチルアミン、ジブチ
ルアミン、ヘキシルアミン、ピリジン、硫酸、
塩酸などの無機酸、トルエンスルホン酸、酢
酸、ステアリン酸、マレイン酸などの有機酸が
ある。
シラノール縮合触媒の使用量は、所与の共重
合体に対して所与の触媒について後記実施例を
参考にして実施者が適当に決定すればよい。一
般的にいえば、組成物中に配合する量は、混合
組成物中の共重合体量に対して0.001〜10重量
％程度、好ましくは0.01〜５重量％、特に好ま
しくは0.03〜３重量％である。
３ 組成物調製
熱可塑性樹脂に各種添加物を配合するのに使
用しうる任意の手段によつて本発明組成物をつ
くることができる。
本発明組成物を調製する方法としては、種々
のものが適用可能である。組成物調整法は一般
にエチレン−不飽和シラン化合物共重合体また
はシラノール触媒の熔融ないし溶解（特に前
者）を併なうものであることがふつうであつ
て、たとえば押出機中で共重合体とシラノール
縮合触媒（そのまままたは溶液ないし分散液と
して）と必要に応じて配合する補助資材とを混
練して、所望成形品（たとえば、型物、棒状
材、パイプ、シート、その他）またはペレツト
等に押出せばよい。
また、前記のようにシラノール縮合触媒は共
重合体に比べれば少量である。従つて、少量成
分の配合にしばしば行なわれるように、シラノ
ール縮合触媒をポリエチレンなどの分散媒に高
濃度に配合したマスターバツチをつくり、これ
を所定触媒濃度になるように共重合体に配合す
ることが便利である。
また他の方法としては、共重合体を所望成形
品に成形加工後、シラノール触媒を含む溶液ま
たは分散液に該成形品を浸漬して含浸させる方
法がある。この方法によれば成形された状態で
の本発明組成物が得られる訳である。
本発明組成物は、樹脂組成物にしばしばみら
れるように、各種の補助資材を含むことができ
る。このような補助資材には、混和可能熱可塑
性樹脂、安定剤、滑剤、充填剤、着色剤、発泡
剤、その他がある。
４ 架橋
本発明組成物の成形物を水に暴露させれば、
架橋反応が生起する（なお、本発明は、架橋を
要件とするものではない）。
水に対する暴露は、成形物を常温〜200℃程
度、通常は常温〜100℃程度、の水（液状また
は蒸気状）と10秒〜１週間程度、通常は１分〜
１日程度、にわたつて接触させればよい。加圧
下に水と接触させることもできる。成形物の濡
れをよくするため、水は湿潤剤ないし界面活性
剤、水溶性有機溶媒その他を含んでいてもよ
い。水は通常の水の他に、加熱された水蒸気ま
たは空気中の水分などの形態であることもでき
る。また、本発明組成物の調製および成形の際
に水を暴露させることによつて組成物の調製お
よび成形と架橋反応とを同時に行なうこともで
きる。
５ 実験例
実施例 １〜３
内容積1.5の撹拌式オートクレーブに、エ
チレン、ビニルトリメトキシシラン及び連鎖移
動剤としてのプロピレンの混合物を送入し、重
合開始剤としてｔ−ブチルパーオキシイソブチ
レートを添加して、圧力2400Kg／cm2、温度220
℃の条件下にて、エチレン−ビニルトリメトキ
シシラン共重合体を連続的に合成した。得られ
た生成物はほとんど無臭である。重合条件と生
成共重合体の物性を表−１に示す。
この共重合体に、ジブチル錫ジラウレート１
重量％を含有するマスターバツチを５重量％を
加え、ロールミルで温度120〜125℃にて、７分
間混合した後、プレスシートに成形し、100℃
の温水に１日間、浸漬して架橋させ、引張強伸
度および熱融着性を測定した。結果を表２〜３
に示す。
比較例 １
メルトインデツクス２ｇ／10分、及び密度
0.919ｇ／c.c.を有する低密度ポリエチレン（三
菱油化社製「ユカロンEH−30」）に、ビニルト
リメトキシシラン２重量％とジクミルパーオキ
シド0.1重量％とを分散させ、これをＬ／Ｄ＝
24の50mmφダルメージスクリユー押出機を用い
て、押出温度200℃で、グラフト重合を行なわ
せた。得られたシリコーングラフト化ポリエチ
レンは極めて臭気が強いが、さらにこれを用い
て実施例１〜３に示す方法によつて、プレスシ
ートに成形、架橋させた。
比較例 ２
米国特許3392156号明細書実施例３に示した
エチレン−ビニルトリメトキシシラン共重合体
を、ロールミルで温度145乃至150℃にて３時間
熱及び機械的処理を行なつて架橋させた。得ら
れた架橋体をプレス・シートに成形した。
比較例 ３
メルトインデツクス１ｇ／10分及び密度
0.920ｇ／c.c.を有する低密度ポリエチレン（三
菱油化社製「ユカロンZF−30」）をプレス・シ
ートに成形した。
比較例１〜３で得られた架橋シートの物性を表
２〜３に示す。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to crosslinkable or crosslinkable polyethylene resin compositions. More specifically, the present invention relates to a water-crosslinkable polyethylene resin composition comprising an ethylene-ethylenically unsaturated silane compound random copolymer having a hydrolyzable silane group as a crosslinkable group and a crosslinking reaction catalyst. It is well known that low density polyethylene and other polyethylene resins can be crosslinked to improve their mechanical strength, heat resistance, etc., and various crosslinking methods are known. PRIOR ART One such crosslinking means consists of adding an organic peroxide as a crosslinking agent to polyethylene and heating it to a high temperature to decompose the peroxide and cause a crosslinking reaction. However, in this case, crosslinking based on the decomposition of peroxide occurs before the polyethylene molding process, which often results in poor quality of the molded product, and in extreme cases, the problem is that molding cannot proceed. . If crosslinking is to be carried out after the molding process, it is necessary to use a high temperature decomposing peroxide that can withstand the molding temperature. As a result, the molded product undergoes softening changes during the crosslinking process, resulting in poor quality of the molded product. Silicone-grafted polyethylene is a product that does not have these problems that occur with chemical crosslinking (Japanese Patent Publication No. 1711-1982, Japanese Patent Application Laid-Open No. 1983-1989).
8389, 50-138042 and 52-9073). When silicone-grafted polyethylene is exposed to water, the silicone portion is hydrolyzed and a crosslinking reaction proceeds, and this hydrolysis occurs at relatively low temperatures, resulting in a large amount of crosslinking that is required during chemical crosslinking. Application to cross-linked molded products is being considered since no equipment is required. However, in this case, multiple steps of manufacturing the base polyethylene and silicone grafting are required, and the crosslinked polyethylene moldings produced in this way, such as sheets, have odor, mechanical strength, and heat resistance. And the heat fusion properties are not satisfactory. On the other hand, a method is known in which a copolymer of ethylene and vinyl alkoxylan is crosslinked by heating or mechanical processing (U.S. Pat. No. 3,225,018 and
3392156). This method has an advantage over the above-mentioned grafting method in that crosslinkable polyethylene can be obtained in a single step of ethylene polymerization, but in this case, crosslinking must be performed before the molding process. There are the same problems as in the case of chemical crosslinking, and the mechanical strength of the molded product obtained by molding after the crosslinking reaction is also not satisfactory. [] Summary of the Invention The present invention aims to solve the above-mentioned problems by combining a water-crosslinkable ethylene-ethylenic unsaturated silane compound random copolymer with a water-crosslinking catalyst. The goal is to achieve this goal. Therefore, the polyethylene resin composition according to the present invention is characterized by containing the following components (A) and (B). (A) A copolymer produced by high-pressure radical polymerization of ethylene and an ethylenically unsaturated silane compound (however,
The content of this ethylenically unsaturated silane compound unit is 0.001 to 15% by weight), (B) silanol condensation catalyst effect. In this case, the silane group introduced into the polyethylene molecule shall not be included. However, this does not exclude graft copolymerization that may unavoidably occur. This gives the polyethylene resin water-crosslinking ability. The crosslinked molded product obtained by molding the composition of the present invention and crosslinking it by exposing it to water not only has excellent mechanical strength and heat resistance, but also has excellent mechanical strength and heat resistance. ) is one of the molded products of conventional cross-linked polyethylene sheets, which has practically the same performance as ordinary low-density polyethylene sheets in terms of heat fusion properties, which were considered to be the biggest drawback of cross-linked polyethylene sheets, and has superior heat resistance. It has excellent performance. In addition, in the present invention, there is no grafting step, but instead, polyethylene copolymerized with an unsaturated silane compound must be separately produced, but since the amount of unsaturated silane compound used is small, this copolymerization is a homopolymerization of ethylene. It can be manufactured using substantially the same method as that of polyethylene, and can be seen as part of the diversification of polyethylene. [] Detailed description of the invention 1 Copolymer of ethylene and unsaturated silane compound As the unsaturated silane compound, there are various compounds having an ethylenically unsaturated bond copolymerizable with ethylene and a hydrolyzable silane group. Available for use. If such a compound is represented by a general formula, for example, there is one represented by the following formula. RSiR′ o Y 3-o (where R represents an ethylenically unsaturated hydrocarbyl or hydrocarbyl ether group, R′ represents an aliphatic saturated hydrocarbyl group, Y represents a hydrolyzable organic group, and n is 0 or 1 or 2. When there are two or more Y's, they do not have to be the same.) Specific examples of this unsaturated silane compound include R's such as vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, γ -(meth)acryloyloxypropyl, Y is methoxy, ethoxy, formyloxy, acetoxy, propionoxy, alkyl or arylamino, and R' is methyl, ethyl, propyl, decyl, phenyl. Particularly preferred unsaturated silane compounds are those represented by the following formula. CH 2 =CHSi(OA) 3 (where A has 1 to 8 carbon atoms, preferably 1
The most preferred compounds are vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane. Copolymerization of ethylene and an unsaturated silane compound is carried out by initiating radical polymerization under the conditions of, for example, a pressure of 500 to 4000 Kg/cm 2 , preferably 1000 to 4000 Kg/cm 2 , and a temperature of 100 to 400°C, preferably 150 to 350°C. Both monomers are brought into contact simultaneously or stepwise in a tank or tube reactor, preferably a tank reactor, in the presence of an agent and, if necessary, a chain transfer agent. In the present invention, polymerization of ethylene or
Any radical polymerization initiator and chain transfer agent known for use in copolymerization can be used. As a polymerization initiator, organic peroxides such as lauroyl peroxide, dipropionyl peroxide, benzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxyisobutyrate; Molecular oxygen, azo compounds such as azobisisobutyronitrile, azoisobutylvaleronitrile, and chain transfer agents include paraffinic hydrocarbons such as methane, ethane, propane, butane, and pentane, propylene, and butene. -1, α like hexene-1
- olefins, aldehydes such as formaldehyde, acetaldehyde, n-butyraldehyde, ketones such as acetone, methyl ethyl ketone, cyclohexanone, aromatic hydrocarbons,
Examples include chlorinated hydrocarbons. The copolymer used in the composition of the present invention has an unsaturated silane compound unit content of 0.001 to 15% by weight,
Preferably 0.01 to 5% by weight, particularly preferably
0.05 to 2% by weight. In general, water-crosslinked copolymers with a higher content of unsaturated silane compounds have better mechanical strength and heat resistance, but if the content is too high, tensile elongation and heat fusion properties decrease. The content range of 0.001 to 15% by weight was determined from this point of view. 2 Silanol Condensation Catalyst The present invention generally targets catalysts that can be used as catalysts that promote dehydration condensation between silanol in silicone. Such silanol condensation catalysts generally include organometallic compounds such as carboxylates, titanate esters, and chelates of metals such as tin, zinc, iron, lead, and cobalt, organic bases,
Inorganic acids and organic acids. Specific examples of silanol condensation catalysts are as follows. Dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous caprylate, lead naphthenate, zinc caprylate, cobalt naphthenate, tetrabutyl titanate, tetranonyl titanate, ethylamine, dibutylamine, hexylamine, pyridine, sulfuric acid,
These include inorganic acids such as hydrochloric acid, and organic acids such as toluenesulfonic acid, acetic acid, stearic acid, and maleic acid. The amount of the silanol condensation catalyst to be used may be appropriately determined by a practitioner with reference to the Examples described below for a given copolymer and a given catalyst. Generally speaking, the amount added to the composition is about 0.001 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.03 to 3% by weight, based on the amount of copolymer in the mixed composition. It is. 3 Composition Preparation The composition of the present invention can be prepared by any means that can be used to incorporate various additives into a thermoplastic resin. Various methods can be used to prepare the composition of the present invention. The composition preparation method generally involves melting or dissolving an ethylene-unsaturated silane compound copolymer or a silanol catalyst (particularly the former); for example, the copolymer and silanol are combined in an extruder. The condensation catalyst (as it is or as a solution or dispersion) and auxiliary materials added as necessary are kneaded and extruded into desired molded products (for example, molds, rods, pipes, sheets, etc.) or pellets, etc. Bye. Further, as mentioned above, the amount of the silanol condensation catalyst is small compared to that of the copolymer. Therefore, as is often done when blending small amounts of components, it is possible to create a masterbatch in which a silanol condensation catalyst is blended in a dispersion medium such as polyethylene at a high concentration, and then blend this into a copolymer at a predetermined catalyst concentration. It's convenient. Another method is to mold the copolymer into a desired molded article and then immerse the molded article in a solution or dispersion containing a silanol catalyst to impregnate it. According to this method, the composition of the present invention can be obtained in a molded state. The compositions of the present invention can contain various auxiliary materials, as are often found in resin compositions. Such auxiliary materials include miscible thermoplastics, stabilizers, lubricants, fillers, colorants, blowing agents, and the like. 4 Crosslinking When a molded product of the composition of the present invention is exposed to water,
A crosslinking reaction occurs (note that the present invention does not require crosslinking). Exposure to water involves exposing the molded product to water (liquid or steam) at room temperature to 200°C, usually room temperature to 100°C, for 10 seconds to 1 week, usually for 1 minute to 100°C.
It is sufficient to allow contact for about one day. It is also possible to contact water under pressure. In order to improve wetting of the molded article, the water may contain a wetting agent or surfactant, a water-soluble organic solvent, and the like. In addition to regular water, the water can also be in the form of heated steam or moisture in the air. Further, by exposing the composition to water during the preparation and molding of the composition of the present invention, the preparation and molding of the composition and the crosslinking reaction can be carried out simultaneously. 5 Experimental Examples Examples 1 to 3 A mixture of ethylene, vinyltrimethoxysilane, and propylene as a chain transfer agent was introduced into a stirred autoclave with an internal volume of 1.5, and t-butylperoxyisobutyrate was added as a polymerization initiator. Addition, pressure 2400Kg/cm 2 , temperature 220
An ethylene-vinyltrimethoxysilane copolymer was continuously synthesized under conditions of .degree. The product obtained is almost odorless. Table 1 shows the polymerization conditions and physical properties of the resulting copolymer. In this copolymer, dibutyltin dilaurate 1
Add 5% by weight of the masterbatch containing 5% by weight and mix for 7 minutes at a temperature of 120 to 125°C with a roll mill, then form into a press sheet and mix at 100°C.
It was immersed in hot water for one day to cause crosslinking, and its tensile strength and elongation and thermal fusion properties were measured. Tables 2-3 show the results.
Shown below. Comparative example 1 Melt index 2g/10min and density
2% by weight of vinyltrimethoxysilane and 0.1% by weight of dicumyl peroxide are dispersed in low density polyethylene (Yukalon EH-30 manufactured by Mitsubishi Yuka Co., Ltd.) having a density of 0.919 g/cc, and L/D=
Graft polymerization was carried out at an extrusion temperature of 200° C. using a 50 mmφ Dalmage screw extruder. Although the obtained silicone-grafted polyethylene had a very strong odor, it was further used to form and crosslink a press sheet by the method shown in Examples 1 to 3. Comparative Example 2 The ethylene-vinyltrimethoxysilane copolymer shown in Example 3 of US Pat. No. 3,392,156 was crosslinked by heat and mechanical treatment in a roll mill at a temperature of 145 to 150° C. for 3 hours. The obtained crosslinked body was molded into a press sheet. Comparative example 3 Melt index 1g/10min and density
Low density polyethylene ("Yukalon ZF-30" manufactured by Mitsubishi Yuka Co., Ltd.) having a density of 0.920 g/cc was molded into a press sheet. The physical properties of the crosslinked sheets obtained in Comparative Examples 1 to 3 are shown in Tables 2 and 3.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
る、架橋性ポリエチレン樹脂組成物。 (A) エチレンとエチレン性不飽和シラン化合物と
の高圧ラジカル重合による共重合体（ただし、
このエチレン性不飽和シラン化合物単位の含有
率は、0.001〜15重量％である） (B) シラノール縮合触媒。[Scope of Claims] 1. A crosslinkable polyethylene resin composition characterized by containing the following components (A) and (B). (A) A copolymer produced by high-pressure radical polymerization of ethylene and an ethylenically unsaturated silane compound (however,
The content of this ethylenically unsaturated silane compound unit is 0.001 to 15% by weight) (B) Silanol condensation catalyst.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8095278A JPS559611A (en) | 1978-07-05 | 1978-07-05 | Cross-linkable polyethylene resin composition |
| DE2926830A DE2926830C3 (en) | 1978-07-05 | 1979-07-03 | Crosslinkable polyethylene plastic masses |
| FR7917460A FR2430432B1 (en) | 1978-07-05 | 1979-07-05 | CROSSLINKABLE POLYETHYLENE RESIN COMPOSITIONS |
| GB7923560A GB2028831B (en) | 1978-07-05 | 1979-07-05 | Moisture-curable polymer composition |
| US06/235,749 US4413066A (en) | 1978-07-05 | 1981-02-18 | Crosslinkable polyethylene resin compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8095278A JPS559611A (en) | 1978-07-05 | 1978-07-05 | Cross-linkable polyethylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS559611A JPS559611A (en) | 1980-01-23 |
| JPS6223777B2 true JPS6223777B2 (en) | 1987-05-25 |
Family
ID=13732830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8095278A Granted JPS559611A (en) | 1978-07-05 | 1978-07-05 | Cross-linkable polyethylene resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS559611A (en) |
| DE (1) | DE2926830C3 (en) |
| FR (1) | FR2430432B1 (en) |
| GB (1) | GB2028831B (en) |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5695940A (en) * | 1979-12-28 | 1981-08-03 | Mitsubishi Petrochem Co Ltd | Ethylene polymer composition |
| JPS6055929B2 (en) * | 1980-04-02 | 1985-12-07 | 日立電線株式会社 | Insulated wire for underwater motor |
| JPS57207632A (en) * | 1981-06-16 | 1982-12-20 | Mitsubishi Petrochem Co Ltd | Crosslinkable polyethylene resin composition |
| JPS5861129A (en) * | 1981-10-08 | 1983-04-12 | Sekisui Plastics Co Ltd | Preparation of foam |
| NO824291L (en) * | 1981-12-29 | 1983-06-30 | Dainichi Nippon Cables Ltd | ADHESIVE AND PROCEDURE FOR COMPOUNDING POLYOLEFINE OBJECTS BY USING THEREOF |
| JPS58141213A (en) * | 1982-02-18 | 1983-08-22 | Nippon Soda Co Ltd | Curing of thermosetting resin |
| FR2546172B1 (en) * | 1983-05-17 | 1987-03-20 | Sogecan | THERMOPLASTIC COMPOSITIONS CONTAINING A SILAN-GRAFT POLYMER |
| GB8400150D0 (en) * | 1984-01-05 | 1984-02-08 | Bp Chem Int Ltd | Polymer composition |
| GB8418592D0 (en) * | 1984-07-20 | 1984-08-22 | Bp Chem Int Ltd | Polymer composition |
| GB8427615D0 (en) * | 1984-11-01 | 1985-01-03 | Bp Chem Int Ltd | Cross-linkable elastomeric materials |
| JPH0615644B2 (en) * | 1985-02-25 | 1994-03-02 | 三菱油化株式会社 | Silane crosslinkable copolymer composition |
| GB2201677A (en) * | 1987-02-14 | 1988-09-07 | Bp Chem Int Ltd | Process for producing a shaped, extruded product from a crosslinkable polymeric composition |
| GB8713868D0 (en) * | 1987-06-13 | 1987-07-15 | Bp Chem Int Ltd | Crosslinkable polymer |
| US5288771A (en) * | 1988-06-15 | 1994-02-22 | Kansai Paint Company, Limited | Water-dispersible core-shell resin which exhibits excellent sagging resistance in coatings |
| DE3930141A1 (en) * | 1989-09-09 | 1991-03-21 | Bayer Ag | NETWORKED PEARL POLYMERISATES AND THEIR PRODUCTION |
| SE465165B (en) * | 1989-12-13 | 1991-08-05 | Neste Oy | COMPOSITIONABLE POLYMER COMPOSITION CONTAINING HYDROLYZERABLE SILANE GROUPS AND AN ACID ANHYDRIDE AS A CATALYST |
| JPH05261789A (en) * | 1992-03-23 | 1993-10-12 | Sumitomo Bakelite Co Ltd | Production of extrusion molded piece of polyolefin resin |
| JPH05262934A (en) * | 1992-03-23 | 1993-10-12 | Sumitomo Bakelite Co Ltd | Polyolefin resin composition |
| JPH05261786A (en) * | 1992-03-23 | 1993-10-12 | Sumitomo Bakelite Co Ltd | Production of extrusion molded piece of polyolefin resin |
| SE502171C2 (en) * | 1993-12-20 | 1995-09-04 | Borealis Holding As | Polyethylene compatible sulfonic acids as silane crosslinking catalysts |
| US5578690A (en) * | 1995-04-28 | 1996-11-26 | Northwestern University | Silyl-terminated interpolymer of ethylene and method for preparing silyl-terminated polyolefins |
| SE504455C2 (en) | 1995-07-10 | 1997-02-17 | Borealis Polymers Oy | Cable sheath composition, its use and methods for its manufacture |
| US6165387A (en) * | 1997-02-04 | 2000-12-26 | Borealis A/S | Composition for electric cables |
| SE9703798D0 (en) | 1997-10-20 | 1997-10-20 | Borealis As | Electric cable and a method of composition for the production thereof |
| SE513362C2 (en) | 1997-11-18 | 2000-09-04 | Borealis As | Procedure for reducing reactor fouling |
| SE9802087D0 (en) | 1998-06-12 | 1998-06-12 | Borealis Polymers Oy | An insulating composition for communication cables |
| SE9802386D0 (en) | 1998-07-03 | 1998-07-03 | Borealis As | Composition for electric cables |
| SE9804407D0 (en) | 1998-12-18 | 1998-12-18 | Borealis Polymers Oy | A multimodal polymer composition |
| DE10016518B4 (en) * | 2000-04-03 | 2009-07-02 | Maschinenfabrik Niehoff Gmbh & Co Kg | Method and device for producing an insulated cable |
| JP4763878B2 (en) * | 2000-06-06 | 2011-08-31 | 日東電工株式会社 | Adhesive sheet for semiconductor wafer dicing |
| CN1520431A (en) * | 2001-11-16 | 2004-08-11 | ��Ļ���Ű˾ | Copolymers of olefins and vinyl-and allysilanes |
| JP2006342284A (en) * | 2005-06-10 | 2006-12-21 | Nippon Polyethylene Kk | Crosslinkable resin for fuel tank and molded article |
| WO2007071274A1 (en) * | 2005-12-22 | 2007-06-28 | Prysmian Cavi E Sistemi Energia S.R.L. | Electric cable comprising a foamed polyolefine insulation and manufacturing process thereof |
| EP1834987B1 (en) * | 2006-03-15 | 2015-08-12 | Borealis Technology Oy | Method for the production of a polypropylene composition with selective cross-linkable dispersed phase |
| EP2138538A1 (en) * | 2008-06-27 | 2009-12-30 | Borealis AG | Polyolefin composition reinforced with a filler and pipe comprising the polyolefin composition |
| KR101329678B1 (en) | 2009-06-22 | 2013-11-14 | 보레알리스 아게 | Chlorine dioxide resistant polyethylene pipes, their preparation and use |
| EP3139417A1 (en) * | 2015-09-03 | 2017-03-08 | Borealis AG | Polyethylene composition for a layer element of a photovoltaic module |
| KR20210049146A (en) * | 2018-11-06 | 2021-05-04 | 보레알리스 아게 | Silane crosslinkable foamable polyolefin composition and foam |
| US11840587B2 (en) | 2019-02-13 | 2023-12-12 | Dow Global Technologies Llc | Moisture-curable polyolefin formulation |
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|---|---|---|---|---|
| US3225018A (en) * | 1961-12-15 | 1965-12-21 | Union Carbide Corp | Heat curing of ethylene/vinylsilane copolymers |
| US3392156A (en) * | 1964-07-10 | 1968-07-09 | Nat Distillers Chem Corp | Copolymers of ethylene and vinyl triethoxysilanes and mechanically worked products thereof |
| GB1372453A (en) * | 1971-01-15 | 1974-10-30 | Hoechst Ag | Process for making fibrous material water-repellent |
| GB1415194A (en) * | 1972-03-23 | 1975-11-26 | Dow Corning Ltd | Preparation of copolymers containing silicon |
| JPS51134884A (en) * | 1975-05-19 | 1976-11-22 | Furukawa Electric Co Ltd:The | Manufacturing method of electric cable |
| JPS5380953A (en) * | 1976-12-27 | 1978-07-17 | Toshiba Corp | A-d converter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL256104A (en) * | 1959-09-22 | |||
| US3577399A (en) * | 1968-09-23 | 1971-05-04 | Monsanto Co | Ethylene interpolymers |
| BE794718Q (en) * | 1968-12-20 | 1973-05-16 | Dow Corning Ltd | OLEFINS CROSS-LINKING PROCESS |
| BE759417A (en) * | 1969-11-26 | 1971-05-25 | Union Carbide Corp | ETHYLENE INTERPOLYMERS SHOWING IMPROVED SLIP AND ANTI-BLOCKING PROPERTIES. |
| GB1346588A (en) * | 1970-10-14 | 1974-02-13 | Dow Corning Ltd | Cross linked polyolefin sheets and films and the preparation thereof |
| GB1408154A (en) * | 1972-02-29 | 1975-10-01 | Dow Corning Ltd | Foamable ethylene polymer compositions |
| GB1406680A (en) * | 1972-10-10 | 1975-09-17 | Dow Corning Ltd | Crosslinking process |
| JPS51109069A (en) * | 1975-03-20 | 1976-09-27 | Sekisui Chemical Co Ltd |
-
1978
- 1978-07-05 JP JP8095278A patent/JPS559611A/en active Granted
-
1979
- 1979-07-03 DE DE2926830A patent/DE2926830C3/en not_active Expired - Lifetime
- 1979-07-05 FR FR7917460A patent/FR2430432B1/en not_active Expired
- 1979-07-05 GB GB7923560A patent/GB2028831B/en not_active Expired
Patent Citations (6)
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|---|---|---|---|---|
| US3225018A (en) * | 1961-12-15 | 1965-12-21 | Union Carbide Corp | Heat curing of ethylene/vinylsilane copolymers |
| US3392156A (en) * | 1964-07-10 | 1968-07-09 | Nat Distillers Chem Corp | Copolymers of ethylene and vinyl triethoxysilanes and mechanically worked products thereof |
| GB1372453A (en) * | 1971-01-15 | 1974-10-30 | Hoechst Ag | Process for making fibrous material water-repellent |
| GB1415194A (en) * | 1972-03-23 | 1975-11-26 | Dow Corning Ltd | Preparation of copolymers containing silicon |
| JPS51134884A (en) * | 1975-05-19 | 1976-11-22 | Furukawa Electric Co Ltd:The | Manufacturing method of electric cable |
| JPS5380953A (en) * | 1976-12-27 | 1978-07-17 | Toshiba Corp | A-d converter |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2926830C2 (en) | 1990-08-23 |
| FR2430432A1 (en) | 1980-02-01 |
| JPS559611A (en) | 1980-01-23 |
| DE2926830A1 (en) | 1980-01-17 |
| DE2926830C3 (en) | 1995-09-07 |
| GB2028831B (en) | 1982-12-01 |
| FR2430432B1 (en) | 1985-10-11 |
| GB2028831A (en) | 1980-03-12 |
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