CN113493540A - 环状二烯基共聚物 - Google Patents
环状二烯基共聚物 Download PDFInfo
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- CN113493540A CN113493540A CN202110368315.1A CN202110368315A CN113493540A CN 113493540 A CN113493540 A CN 113493540A CN 202110368315 A CN202110368315 A CN 202110368315A CN 113493540 A CN113493540 A CN 113493540A
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- Prior art keywords
- copolymer
- group
- combinations
- cyclic
- cyclohexadiene
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 101
- -1 Cyclic diene Chemical class 0.000 title claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 39
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001993 dienes Chemical class 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 19
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 229930003658 monoterpene Natural products 0.000 claims abstract description 12
- 150000002773 monoterpene derivatives Chemical class 0.000 claims abstract description 12
- 235000002577 monoterpenes Nutrition 0.000 claims abstract description 12
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 11
- 150000003440 styrenes Chemical class 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims description 24
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 21
- 239000005060 rubber Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007848 Bronsted acid Substances 0.000 claims description 11
- 239000002841 Lewis acid Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000007517 lewis acids Chemical class 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000011925 1,2-addition Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229920006037 cross link polymer Polymers 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 claims description 6
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical compound C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 claims description 6
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 6
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 6
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims description 6
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 claims description 6
- NDVASEGYNIMXJL-UHFFFAOYSA-N sabinene Chemical compound C=C1CCC2(C(C)C)C1C2 NDVASEGYNIMXJL-UHFFFAOYSA-N 0.000 claims description 6
- OGLDWXZKYODSOB-UHFFFAOYSA-N α-phellandrene Chemical compound CC(C)C1CC=C(C)C=C1 OGLDWXZKYODSOB-UHFFFAOYSA-N 0.000 claims description 6
- QSVDFJNXDKTKTJ-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1h-indene Chemical compound C1CCCC2=C1CC=C2 QSVDFJNXDKTKTJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 claims description 4
- 235000001510 limonene Nutrition 0.000 claims description 4
- 229940087305 limonene Drugs 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920001021 polysulfide Polymers 0.000 claims description 4
- NDVASEGYNIMXJL-NXEZZACHSA-N (+)-sabinene Natural products C=C1CC[C@@]2(C(C)C)[C@@H]1C2 NDVASEGYNIMXJL-NXEZZACHSA-N 0.000 claims description 3
- LFJQCDVYDGGFCH-JTQLQIEISA-N (+)-β-phellandrene Chemical compound CC(C)[C@@H]1CCC(=C)C=C1 LFJQCDVYDGGFCH-JTQLQIEISA-N 0.000 claims description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 3
- LFJQCDVYDGGFCH-SNVBAGLBSA-N (+/-)-beta-Phellandrene Natural products CC(C)[C@H]1CCC(=C)C=C1 LFJQCDVYDGGFCH-SNVBAGLBSA-N 0.000 claims description 3
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 3
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 claims description 3
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims description 3
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 3
- OGLDWXZKYODSOB-SNVBAGLBSA-N alpha-phellandrene Natural products CC(C)[C@H]1CC=C(C)C=C1 OGLDWXZKYODSOB-SNVBAGLBSA-N 0.000 claims description 3
- KQAZVFVOEIRWHN-UHFFFAOYSA-N alpha-thujene Natural products CC1=CCC2(C(C)C)C1C2 KQAZVFVOEIRWHN-UHFFFAOYSA-N 0.000 claims description 3
- LFJQCDVYDGGFCH-UHFFFAOYSA-N beta-phellandrene Natural products CC(C)C1CCC(=C)C=C1 LFJQCDVYDGGFCH-UHFFFAOYSA-N 0.000 claims description 3
- 229930006722 beta-pinene Natural products 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229930006739 camphene Natural products 0.000 claims description 3
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims description 3
- 229930006737 car-3-ene Natural products 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 229930009668 farnesene Natural products 0.000 claims description 3
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000007823 ocimene derivatives Chemical class 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229930006696 sabinene Natural products 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- XJPBRODHZKDRCB-UHFFFAOYSA-N trans-alpha-ocimene Natural products CC(=C)CCC=C(C)C=C XJPBRODHZKDRCB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 claims description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 claims 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims 2
- 239000011968 lewis acid catalyst Substances 0.000 claims 2
- 125000003447 alpha-pinene group Chemical group 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 125000006575 electron-withdrawing group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 229920005604 random copolymer Polymers 0.000 abstract description 2
- 230000000930 thermomechanical effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- 229920006026 co-polymeric resin Polymers 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 244000043261 Hevea brasiliensis Species 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229920003052 natural elastomer Polymers 0.000 description 9
- 229920001194 natural rubber Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002174 Styrene-butadiene Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229920005549 butyl rubber Polymers 0.000 description 5
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 4
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- FAXJFVQAGPWKHQ-UHFFFAOYSA-N 2,2,3-trichlorobutanoic acid Chemical compound CC(Cl)C(Cl)(Cl)C(O)=O FAXJFVQAGPWKHQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LFXZSGVZSSMCMB-UHFFFAOYSA-N 2,5-dichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=CC=C1Cl LFXZSGVZSSMCMB-UHFFFAOYSA-N 0.000 description 1
- OIXNFJTTYAIBNF-UHFFFAOYSA-N 2-(chloromethyl)oxirane;oxirane Chemical compound C1CO1.ClCC1CO1 OIXNFJTTYAIBNF-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/045—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated conjugated hydrocarbons other than butadiene or isoprene
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- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/02—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F132/06—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
公开了一种共聚物,其通过在催化剂存在下阳离子聚合一种或多种环状二烯和选自单萜烯、支化苯乙烯、及其组合中的共聚单体形成。可以制备具有得自环状共轭二烯例如1,3‑环己二烯和共聚单体例如单萜烯的的重复单元的无规共聚物作为在烃溶剂中可溶的产物。可以用各种交联剂交联所述共聚物,以形成具有良好氧化稳定性和阻燃性的材料。未交联和交联的共聚物具有有用的性能,例如低耗散因子、低介电常数、以及使它们在电子应用中具有价值的热机械和电性能的良好平衡。
Description
技术领域
本公开涉及基于环状二烯的聚合物,制备聚合物的方法及其应用。
背景技术
在过去的半个世纪中,陶瓷和聚合物科学家已经密集地研究了具有多种电气、热、化学和机械性能的低介电材料。在许多情况下,低介电常数材料的应用由这些性能决定,并且低介电材料的选择可能对设备的性能和寿命产生巨大影响。微电子行业的快速发展也为这些应用的更先进的工艺和材料产生了越来越多的需求。电子元件的小型化的趋势也加强了对具有最佳电气和功能性能特征(例如所需的电气、热、化学、粘合和机械性能的结合)的介电材料的搜索。
因此,持续需要用于电子应用的具有所需性能的聚合物材料,所需性能例如为高水解稳定性、非常低的吸湿性、良好的加工性、高玻璃化转变温度(Tg)、低密度和优异的介电性能。
发明概述
一方面,公开了一种共聚物。所述共聚物通过在催化剂存在下阳离子聚合一种或多种环状二烯和选自单萜烯、支化苯乙烯、及其组合的共聚单体而形成。所述共聚单体选自单萜烯、支化苯乙烯、及其组合。所述环状二烯选自1,3-环己二烯(CHD)、环戊二烯(CPD)、1,3-环庚二烯、4,5,6,7-四氢茚、降冰片二烯(NBD)、及其组合。所述催化剂选自布朗斯台德酸、路易斯酸、及其组合。所述共聚物具有300-5,000道尔顿的Mn和2000-25,000道尔顿的Mz。所述共聚物在烃溶剂中的溶解度为0.1-2g共聚物/g烃溶剂,和Tg为80-180℃。
另一方面,公开了一种形成共聚物的方法。所述方法包括在催化剂存在下和在烃溶剂中阳离子聚合包括一种或多种环状二烯的单体和共聚单体,以形成共聚物;和分离所述共聚物。所述共聚单体选自单萜烯、支化苯乙烯、及其组合;所述催化剂选自布朗斯台德酸、路易斯酸、及其组合。
本公开的其他方面包括通过上述共聚物与交联剂反应形成的交联聚合物,以及未交联的共聚物用于形成用于电子应用的预浸料的用途。
附图简述
图1是显示交联共聚物树脂的Tg的变化与交联前的共聚物树脂(B)中存在的C=C的摩尔%的函数关系图,其采用50:50的重量比的CHD和α-蒎烯制备共聚物树脂。
发明内容
在整个说明书中使用下述术语。
MW重均分子量描述根据下式计算的分子量平均分布:
其中Ni是分子量Mi的分子的数目。
Mn是根据下式计算的分子量的数均值:
其中Ni是分子量Mi的分子的数目。
Mz是更高阶分子量均值或三次方分子量,其根据下式计算:
其中Ni是物种i的物质的量,Mi是物种i的分子量。可以使用ASTM D5296(2005)中的GPC-SEC方法来确定Mz、Mw和Mn。
根据PDI=Mw/Mn来计算多分散指数(PDI)
杯和球(C&B)SP(软化点)可以通过ASTM E28,或杯和球(C&B)软化点测试,或ASTMD 6090杯和球测量。
根据ASTM D 6604,在0-200℃之间,采用10℃/min的加热速率,测量树脂的玻璃化转变温度(Tg)。
“环状二烯”是指具有2个双键的环状化合物。当两个双键形成共轭体系时,环状二烯被称为“环状共轭二烯”。“环状二烯”包括环状非共轭二烯和环状共轭二烯。
耗散因子(Df)定义为耗散系统中电能的损耗率。
介电常数(Dk)定义为物质在电场中存储电能的能力。
共聚物、用于形成它们的方法以及共聚物的用途如下进一步详细描述。
共聚物:通过在催化剂存在下阳离子聚合一种或多种环状二烯和共聚单体而形成的共聚物具有得自环状二烯和共聚单体的重复单元。
在某些实施方案中,环状二烯包括一种或多种环状共轭二烯、一种或多种环状非共轭二烯、或其组合。环状共轭二烯的非限制性实例包括1,3-环己二烯(CHD)、环戊二烯(CPD)、1,3-环庚二烯、4,5,6,7-四氢茚(THI)、及其组合。环状非共轭二烯的非限制性实例包括降冰片二烯(NBD)、1,5-环辛二烯、二环戊二烯、及其组合。在某些实施方案中,环状二烯选自CHD、CPD、1,3-环庚二烯、THI、NBD、及其组合。
在某些实施方案中,环状二烯是包含最多10重量%的1,4-环己二烯的1,3-环己二烯,相对于环状二烯的总重量。使用含有少量1,4-环己二烯的1,3-环己二烯可能是有利的,因为无需对1,3-和1,4-异构体进行繁琐的分离。
所述共聚单体可以是选自单萜烯、支化苯乙烯、及其组合中的一种或多种。单萜烯可以是具有C10H16的一般分子式的一种或多种化合物。在某些实施方案中,单萜烯选自α-蒎烯、β-蒎烯、柠檬烯、月桂烯、罗勒烯、α-水芹烯、β-水芹烯、法呢烯、莰烯、α-萜烯、桧烯、γ-萜烯、3-蒈烯、及其组合。
所述共聚单体还可以是在烯烃基团的C-2碳处具有取代基R(例如烷基)的式(III)的支化苯乙烯化合物,所述取代基R对阳离子聚合条件是惰性的:
在某些实施方案中,当环状共轭二烯经历阳离子聚合时,产物可同时含有得自二烯的1,2-加成单元和1,4-加成单元。1,4-加成通常比1,2-加成有利。例如,1,3-环己二烯经历阳离子聚合,得到主要的1,4-加成单元(式I)和少量的1,2-加成单元(式II),其中Pol代表聚合物链:
通过改变催化剂和反应条件,可以改变1,4-加成与1,2-加成的相对比例。在某些实施方案中,所述共聚物包含的环状共轭二烯中1,4-加成单元和共轭二烯的1,2-加成单元的相对摩尔比为90:10-10:90,或50:50,或30:70-70:30,或40:60-60:40,或20:80-80:20。
可以获得具有宽范围的相对摩尔比(例如5:95至95:5)的环状二烯和共聚单体的共聚物。在某些实施方案中,通过聚合1,3-环己二烯和共聚单体形成的共聚物具有的环状二烯和共聚单体的相对摩尔比为5:95-95:5,或50:50,或30:70-70:30,或40:60-60:40,或20:80-80:20。
共聚物的制备:所述共聚物可以通过在合适的溶剂中在催化剂存在下通过阳离子聚合一种或多种环状二烯和共聚单体来制备。
烃溶剂是优选的,因为它们通常对催化剂和聚合期间产生的阳离子中间体惰性。合适的烃溶剂包括芳烃、脂环族烃或脂族烃、或其组合。非限制性实例包括己烷、庚烷、烷基苯、柠檬烯、松节油、辛烷、异辛烷、环己烷、漆用石脑油(VM&P石脑油)、石油醚、甲苯、二甲苯及其混合物。
所述催化剂可以广泛地是布朗斯台德酸、路易斯酸、或其组合。催化剂可以是布朗斯台德酸类型、路易斯酸类型、或同时具有布朗斯台德酸和路易斯酸类型催化活性。在某些实施方案中,催化剂包括负载的布朗斯台德酸、未负载的布朗斯台德酸、路易斯酸、其前体、或其组合。可以使用各种非限制性催化剂,例如有机酸、有机磺酸、无机酸、酸性沸石、基于来自元素周期表3-11和12-15族金属的任何路易斯酸、及其混合物。
非限制性实例包括硫酸,磷酸,连二磷酸,多磷酸,杂多酸,例如磷钨酸和硅钨酸,2,2,3-三氯丁酸,2,5-二氯苯磺酸,氯磺酸,甲磺酸,对甲苯磺酸,三氟甲磺酸,苯磺酸,2,5-二氯苯磺酸,β-萘酚-3,6,8-三磺酸,磺基水杨酸,对甲苯胺-间-磺酸,磺化固体酸衍生物,例如磺化苯乙烯-二乙烯基苯,磺化二氧化硅,磺化含氟聚合物和聚苯乙烯负载的磺酸;其他类型的固体无机酸催化剂,例如但不限于基于硅、二氧化硅、铝和/或氧化铝的那些,例如无定形二氧化硅-氧化铝(二氧化硅含量为0.1-99.9%和/或孔径为0.1-5ml/g和/或表面积BET为100-1000m2/g,在200-1000℃的温度下煅烧);层状硅酸盐,例如来自下述各组的天然或合成粘土:高岭土组(例如高岭石、埃洛石、地开石),蒙脱土组(例如蒙脱石、绿脱石,锂蒙脱石、皂石),伊利石/云母组(例如海绿石、白云母、钠云母),绿泥石组(例如鲕绿泥石、锂绿泥石、镍绿泥石,在200-1000℃的温度下煅烧、处理、洗涤、活化、或与诸如硫酸或盐酸的无机酸结合使用,使用盐诸如锂、钠、镁、铁的盐改变,和/或在诸如水的介质中交换,使用质子或阳离子形式的铝、天然或合成微孔铝硅酸盐改性或柱撑),沸石组(例如USY,丝光沸石,镁碱沸石,ZSM-5,β,二氧化硅含量为0.1-99.9%和/或孔径为0.1-5ml/g和/或表面积BET为100-1000m2/g,在200-1000℃下煅烧),质子化或阳离子形式的中孔材料,例如硅铝磷酸盐,如SAPO-11、SAPO-34,或例如铝硅酸盐如MCM-41、MCM-48,或例如硅酸盐如SBA-15、SBA-16(二氧化硅含量为0.1-99.9%和/或孔径为0.1-5ml/g的和/或表面积BET为100-1000m2/g,在200-1000℃的温度下煅烧负载的金属例如Ni、Pt、Au、Fe或Co,处理,洗涤,活化或与诸如硫酸或盐酸的无机酸结合使用,使用铝、氢碘酸改性或柱撑)。
在某些实施方案中,所述催化剂是基于选自锌、硼、铝、镓、铟、钛、锆、锡、钒、砷、锑和铋的金属的路易斯酸,示例性实例包括AlCl3、(烷基)AlCl2、(C2H5)2AlCl和(C2H5)3Al2Cl3、BF3、B(C6F5)3、SnCl4、TiCl4、ZnCl2、SnCl2、CuCl2及其组合或其与路易斯碱的络合物。茂金属卤化物,例如二氯二茂锆,二氯二茂钛和二氯二茂铪;也可以使用与甲基铝氧烷组合的茂金属卤化物以及甲基铝氧烷。
非氧化性布朗斯台德酸是优选的,以预防或最小化环状二烯和/或所述共聚单体的氧化或氧化降解。非限制性实例包括全氟烷磺酸,例如三氟甲磺酸;全氟烷酸,如三氟乙酸;和烷磺酸,例如甲磺酸,乙磺酸,苯磺酸等。
聚合反应通常形成包含得自环状二烯和共聚单体的聚合单元的无规共聚物。在一些情况下,所述共聚单体可以用作链转移剂,其可限制所述共聚物的分子量。
通过在-100℃至+120℃,或-50℃至80℃,或环境温度至120℃,或50-80℃的温度下,将单体的混合物加入到催化剂和溶剂的混合物中,来进行反应5分钟到几小时的时间。反应时间可根据单体的反应性变化。在较低的反应温度下可能需要更长的反应时间。在加入所有单体之后,如果需要,可以搅拌所得反应混合物额外的5分钟至几小时的时间,直至所有单体基本上消失,或者直到反应混合物的分析表明已经形成了足够的分子量的共聚物产物。
取决于各种因素,例如单体的结构和反应性、反应溶剂的性质和温度,所产生的共聚物可以保持完全可溶于所述溶剂、部分可溶于所述溶剂或者大部分不溶于所述溶剂。通常,优选共聚物保持可溶于所述溶剂。在某些实施方案中,共聚物在烃溶剂中的溶解度为10-80重量%或25-75重量%或35-65重量%或20-60重量%或30-50重量%,相对于溶剂的重量。
在反应结束时,如果需要,可以通过用水将反应混合物淬灭、然后分离有机溶剂层并汽提所述溶剂来分离共聚物。可以在高真空下从产品中去除痕量有机物。
交联共聚物:如上所述获得的共聚物具有得自环状二烯单元的聚合的双键。这些双键对交联剂(例如作为固化剂或固化引发剂的自由基生成化合物)是反应性的,其允许制备交联的共聚物。自由基引发剂是特别理想的。它们在高温下或在UV或其他能量添加的触发效果下产生自由基。实例包括硫基试剂、过氧化物基试剂、碲、硒、多硫化物聚合物、金属氧化物和二异氰酸酯。硫基交联剂的非限制性实例包括S2Cl2、元素硫和在交联条件下释放硫的硫供体化合物。硫供体化合物的一些实例包括四甲基秋兰姆二硫化物,4,4'-二硫基二吗啉,双亚戊基秋兰姆四硫化物,硫代氨基甲酰基次磺酰胺,二苯并噻唑,N-环己基-2-苯并噻唑,二甲基二硫代氨基甲酸锌,硫脲,黄原酸盐和硫代磷酸盐。
当使用时,固化引发剂或交联剂的含量为0.1-10重量%,或0.3-7重量%,或1-5重量%,基于共聚物的总重量。
可以通过在从环境温度至90℃,或者最高300℃,或≤280℃的温度下与交联剂反应最多1小时或最多30分钟或至少5分钟,来实现共聚物链的交联,从而提供交联的共聚物。交联密度取决于许多因素,例如交联剂的量、温度和采用的其他物理条件。使用S2Cl2交联剂,交联密度可以在例如1-10的范围内变化,对应于每100个聚合的环状二烯单元1-10分子的S2Cl2的反应。
在某些实施方案中,在交联(固化)后和当溶解在烃溶剂中形成基本上无凝胶的溶液时,交联的组合物的特征在于具有50重量%以上或>70重量%或>90重量%或>85重量%的凝胶含量,相对于共聚物的总重量。
交联聚合物可具有良好的化学和氧化稳定性。交联还导致所得交联共聚物的Tg升高,如图1所示,其中使用85:15的重量比的CHD和α-蒎烯制备的共聚物。在交联密度最高10的某些实施方案中,Tg以大致线性的方式增加;在交联密度大于10,例如最达20,Tg不会显著增加。
交联共聚物也具有增强的阻燃性,这是使它们可用作电子材料的应用的性能之一。可以通过测量从样品点火开始的时间到完全形成焦炭的时间,来测量阻燃性。
共聚物的性能:所述共聚物通常是树脂材料。通过借由阳离子溶液聚合的阳离子聚合一种或多种环状二烯形成共聚物,其中(i)单体通过1,2-和1,4插入模式成链(enchain);和(ii)同时成链的单元经过歧化反应,将部分紧密结合的环己烯基转化为苯基和环己烷单元。苯基和环己烷基团的化学变化与环己烯基不同。通过阳离子聚合的转化可以通过质子和/或碳13NMR示出,例如,>0.1%或>0.2%或>0.5%的大于NMR敏感水平的苯基存在,基于共聚物组合物的总重量。
随着将成链的环己烯基转化为苯基和环己烷单元,最终的聚合物Tg基本上随转化率的增加而增加。在某些实施方案中,在10%环己烯基的转化率下,聚合物Tg从100-120℃增加到高达150-160℃。另外,共聚物在烃溶剂(例如甲苯,环己烷等)中的溶解度显著增加。
在某些实施方案中,使用上述方法制备的共聚物的Mn通常为300-5,000道尔顿,或500-3,000道尔顿,或<2000道尔顿,或<1500道尔顿,或>500道尔顿。在某些实施方案中,制备的共聚物的Mz为2000-30,000道尔顿,或3,000-25,000道尔顿,或<20,000道尔顿,或<18,000道尔顿,或>2,500道尔顿,或>3,000道尔顿z。
所述共聚物的特征在于可溶于烃溶剂,其溶解度为0.1-2g共聚物/g溶剂,或>0.2g共聚物/g溶剂,或>1.0g共聚物/g溶剂,或<1.5g共聚物/g溶剂,或>0.5g共聚物/g溶剂,或1g共聚物/g溶剂。希望具有可溶性共聚物,因为它们方便进一步的下游加工和应用。在某些实施方案中,共聚物固体溶解在烃溶剂中形成基本上无凝胶的溶液,其中<15重量%或<10重量%或<5重量%的固体保持不溶于溶剂,例如甲苯或环己烷。
所述共聚物的玻璃化转变温度(Tg)为80-180℃,或85-170℃,或90-150℃,或>95℃,或>100℃,或90-160℃,使用DSC(差示扫描量热法)或DMA(动态机械分析仪)测量。
交联后,共聚物对诸如铝、铜等的金属表现出粘附性。在某些实施方案中,交联的共聚物的由180°剥离强度给出的对金属的粘附性为0.2-1.5N/m2,或0.5-1.25N/m2,或>0.50N/m2,或>0.8N/m2,或<1.8N/m2。对铜的良好粘附性使得所述共聚物在电子应用中具有价值。在某些实施方案中的交联聚合物的Tg为120-250℃,或130-240℃,或>180℃,或>160℃,或>200℃。
在某些实施方案中的交联共聚物具有的用于PCB应用良好的电性能,包括<0.01、<0.006、或<0.0055、或0.0025-0.0045、或0.0035-0.0055的低耗散因子(Df),和<4.5、或<4.0、或<3.5或2-4.0的低介电常数(Dk),其中Df和Dk根据IPC TM-650 2.5.5.13测量。
交联的共聚物表现出良好的阻燃性。可以通过测量试样从点火到完全形成焦炭的时间来评估样品的阻燃性,例如,从点火时间开始小于或等于60秒,或<50秒,或<40秒。在某些实施方案中,树脂具有UL 94等级的V-0等级,或至少V-1或至少V-2等级。
交联的共聚物进一步具有低吸湿性,导致基底对在使用期间和储存期间的环境条件不那么敏感。在某些实施方案中,在23℃在水中浸泡24小时后,湿吸度是0.05-0.5%,或<0.3%,或<0.2%。
交联的共聚物进一步表现出0.2-0.7W/mK或0.3-0.5W/mK或>0.1W/mK(瓦特/米-开尔文)的优异导热率。
交联的共聚物特别适用于电子应用,例如,140-240℃的高Tg,由>0.35-0.5N/m2的180°剥离强度给出的对金属的粘附性,0.0025-0.0055%的低耗散因子(Df),从点火时间开始小于或等于20秒的阻燃性,和2.0-3.0的低介电常数(Dk)。使用硫基交联剂制备的交联共聚物表现出比交联前的共聚物更好的阻燃性。
共聚物在电子应用中的用途:所述共聚物是用于形成电子元件的有价值的材料,所述电子元件例如印刷电路板(PCB)和柔性打印机电路(FPC)。可以使用所述共聚物制备用于制备PCB的预浸料。对于预浸料,交联共聚物与橡胶组分组合使用。
所述橡胶成分包括天然橡胶及其各种原料和回收形式,以及各种合成橡胶。在某些实施方案中,橡胶组分包括任何弹性体嵌段共聚物,选自聚丁二烯、天然橡胶、合成聚异戊二烯、丁二烯共聚物、异戊二烯共聚物及其混合物的不饱和二烯弹性体。
在某些实施方案中,橡胶选自丁基橡胶,卤代丁基橡胶和EPDM(乙烯丙烯二烯单体橡胶),以及它们的混合物。在某些实施方案中,橡胶组分选自天然橡胶(NR),苯乙烯-丁二烯橡胶(SBR),丁二烯橡胶,合成聚异戊二烯橡胶,环氧基化天然橡胶,聚丁二烯橡胶,例如高-顺聚丁二烯橡胶,腈-氢化丁二烯橡胶HNBR,氢化SBR,乙烯丙烯二烯单体橡胶,乙烯丙烯橡胶,马来酸改性乙烯丙烯橡胶,丁基橡胶,异丁烯-芳族乙烯基或二烯单体共聚物,溴化NR,氯化-NR,溴化异丁烯对甲基苯乙烯共聚物,氯丁橡胶,表氯醇均聚物橡胶,表氯醇-环氧乙烷或烯丙基缩水甘油醚共聚物橡胶,表氯醇-环氧乙烷-烯丙基缩水甘油醚三聚物橡胶,氯磺化聚乙烯,氯化聚乙烯,马来酸改性的氯化聚乙烯,甲基乙烯基硅橡胶,二甲基硅橡胶,甲基苯基乙烯基硅橡胶,多硫化物橡胶,偏二氟乙烯橡胶,四氟乙烯-丙烯橡胶,氟化硅橡胶,氟化磷橡胶,苯乙烯弹性体,热塑性烯烃弹性体,聚酯弹性体,氨基甲酸酯弹性体和聚酰胺弹性体。
SBR橡胶的实例包括乳液聚合的苯乙烯-丁二烯橡胶(未改性的E-SBR),溶液聚合的苯乙烯-丁二烯橡胶(未改性的S-SBR)和通过改性末端获得的改性的SBR(改性E-SBR和S-SBR)。橡胶组分包括除SBR和BR之外的组分,如天然橡胶(NR),异戊二烯橡胶(IR),环氧化天然橡胶(ENR),丁基橡胶,丙烯腈丁二烯橡胶(NBR),乙烯丙烯二烯橡胶(EPDM),氯丁二烯橡胶(CR)苯乙烯-异戊二烯-丁二烯橡胶(SIBR),其可单独使用或组合使用。
橡胶组分可以用偶联和/或星形支化或官能化试剂偶联、星形支化、支化和/或官能化。支化橡胶可以是支化(星形支化)的丁基橡胶、卤代星形支化的丁基橡胶、聚(异丁烯-共-对甲基苯乙烯)、溴化丁基橡胶、氯化丁基橡胶、星形支化的聚异丁烯橡胶及其混合物中的任何一种。
当制成预浸料组合物时,所述组合物可进一步包含一种或多种添加剂,其包括但不限于多官能的可共-固化的添加剂,二烯基橡胶,卤化或非卤化阻燃剂,无机或有机填料或纤维,单乙烯基化合物,或本领域已知的其他添加剂,例如抗氧化剂,着色剂或稳定剂,粘合促进剂,增韧剂,膜形成添加剂,其量为0.1-50重量%,相对树脂组合物的重量。
包含所述共聚物的组合物可以层压到金属基底例如铜上。层压体表现出几种有用的性能,使它们对电子应用具有价值,例如,在使层压体进行高压锅测试后低水平或没有起泡或分层,在无铅焊接期间低水平或没有分解,对抗酸、碱和氧化物质的耐化学性,没有或低吸水性,对内部层压体电迁移的良好抗性(即对导电阳极长丝CAF失效的抗性),低热膨胀系数(CTE),高玻璃化转变温度,以用于在使用条件下具有稳定的性能。
所述共聚物作为介电材料是具有价值的,因为它们具有下述性能的良好平衡:电性能、热稳定性、用于良好尺寸稳定性的良好热机械和热性能,和化学稳定性。电性能包括低介电常数、低介电损耗和漏电流,Df和Dk,高击穿电压,对使用条件下的金属例如铜的稳定和高粘附性,对用于压制工艺的预浸料的共聚物树脂流动的影响低或没有影响,和令人满意的光学品质,例如,没有层压材料的附聚物。
当使用预浸料时,所述组合物还包含增强材料。预浸料用于制备金属箔包覆的层压体,其具有预浸料的片材和在所述预浸料的一侧或两侧上的金属箔覆层。
实施例
提供以下实施例以说明本发明的公开内容。
实施例1:制备1,3-环己二烯-共-α-蒎烯共聚物树脂(A)
将挡板1L圆底反应器烧瓶配有搅拌器叶片、氮气入口、压力出口和温度探针。向该反应器中加入300克甲苯溶剂(含有230ppm水)。将10.0克AlCl3加入该反应器中,并将反应器内容物加热至45℃。在40分钟内通过膜泵将由150克1,3-环己二烯和150克α-蒎烯组成的单体混合物缓慢加入该反应器中。通过用水/冰浴冷却,在单体添加期间将反应器温度保持在45℃。在完成单体添加后,将反应器保持在45℃下另外15分钟。通过将4.3克浓硫酸加至150ml水来制备稀硫酸溶液。将稀硫酸溶液加入反应器中,继续搅拌,将温度升至80℃。20分钟后,停止搅拌,使水层和有机层分离,并除去水层。进行额外的水洗,之后将1.1克溶解在150ml水中的碳酸钠加入反应器中。20分钟后,使水层和有机层分离并除去水层,然后进行另外的水洗涤并除去水层。通过蒸馏从有机级分中除去溶剂,逐步将熔融树脂加热至240℃。通过氮汽提15分钟除去残留的溶剂、单体和轻质油。将熔融树脂从反应器中排出。获得1,3-环己二烯-共-α-蒎烯共聚物树脂A,Mettler杯和球软化点(TSP)为148℃和产率为79%。
实施例2:制备1,3-环己二烯-共-α-蒎烯共聚物树脂(B)
将挡板1L圆底反应器烧瓶配有搅拌器叶片、氮气入口、压力出口和温度探针。将374克甲苯溶剂(含有230ppm水)加入该反应器中。将9.1克三氯化铝加入反应器中,并将反应器内容物加热至45℃。在40分钟内通过膜泵将由238克1,3-环己二烯和42克α-蒎烯组成的单体混合物缓慢加入反应器中。通过用水/冰浴冷却,在单体添加期间将反应器温度保持在45℃。在完成单体添加后,将反应器保持在45℃下另外15分钟。通过将3.7克浓硫酸加至150ml水来制备稀硫酸溶液。将稀硫酸溶液加入反应器中,继续搅拌,将温度升至80℃。20分钟后,停止搅拌,使水层和有机层分离,并除去水层。进行额外的水洗,之后将1.1克溶解在150ml水中的碳酸钠加入反应器中。20分钟后,使水层和有机层分离并除去水层,然后进行另外的水洗涤并除去水层。通过蒸馏从有机级分中除去溶剂,将熔融树脂逐步加热至280℃。通过氮汽提1分钟除去残留溶剂、单体和轻质油。将熔融树脂从反应器中排出。获得1,3-环己二烯-共-α-蒎烯共聚物B,Mettler杯和球软化点(C&B SP)为172℃和产率为92%。表1示出了1,3-环己二烯基共聚物树脂A和B的Tsp、Tg、产率、Mn、MW和MZ。分子量是道尔顿(Da)。
表1
产物 | T<sub>sp</sub>(℃) | Tg | Mn(Da) | Mw(Da) | Mz(Da) | PDI | 产率(%) |
树脂A | 148 | 85 | 638 | 1319 | 2736 | 2.1 | 79 |
树脂B | 172 | 100 | 790 | 3193 | 24972 | 4.9 | 92 |
实施例3:制备1,3-环己二烯-共-α-蒎烯共聚物树脂(C)
将100ml圆底反应器烧瓶配备有磁力搅拌棒、氮气入口、压力出口和温度探针。向反应器中加入40克甲苯溶剂(含有230ppm水),然后加入1.5克AlCl3。通过滴液漏斗在10分钟内将1,3-环己二烯(25.5g)和α-蒎烯(4.5g)的单体混合物缓慢加入反应器中。通过用水/冰浴冷却,在单体添加期间将反应器温度保持在45℃。在完成单体添加后,将反应器在45℃下再保持10分钟。通过将1.0克浓硫酸加至50ml水来制备稀硫酸溶液。将稀硫酸溶液加入反应器中,继续搅拌。20分钟后,停止搅拌,使水层和有机层分离,并除去水层。进行另外的水洗,并从反应器中排出的有机层。通过尺寸排阻色谱法在树脂溶液上测定Mn、Mw和Mz。在通过将3克树脂溶液在Mettler HG53卤素水分分析仪中放置在150℃下150分钟去除溶剂而获得的材料上测定Tg。获得树脂C,Tg为107℃。以类似的方式获得树脂D-H,表2中列出了条件。
实施例4:制备1,3-环己二烯-共-α-蒎烯和1,3-环己二烯-共-α-甲基苯乙烯共聚物树脂(D-H)
使用如制备树脂C的工序,除了1,3-CHD和共聚单体的量改变。表2概述了用于制备1,3-环己二烯-共-α-蒎烯共聚物树脂D-H的单体组成、反应物和反应条件。表3概述了共聚物树脂C-H的TSP、Tg、Mn、Mw和Mz。
表2
表3
产物 | T<sub>sp</sub>(℃) | Tg(℃) | Mn(Da) | Mw(Da) | Mz(Da) | PDI |
树脂C | N/A | 107 | 1098 | 4913 | 16509 | 4.5 |
树脂D | N/A | 107 | 1211 | 4774 | 15669 | 3.9 |
树脂E | 154 | 58 | 564 | 1475 | 3373 | 2.6 |
树脂F | 110 | 43 | 578 | 1361 | 3253 | 2.4 |
树脂G | N/A | 96 | 802 | 2570 | 6469 | 3.2 |
树脂H | N/A | 65 | 670 | 1922 | 4767 | 2.9 |
实施例4
通过在用S2Cl2将共聚物交联获得的共聚物树脂上测试共聚物树脂的阻燃性。参数“T”表示点火开始时间和熄火时间之间的时间,对应于完整的焦炭形成。“RU”表示共聚物树脂中的残留不饱和水平,由C=C基团的摩尔%给出。“RU”和重量%的氯化物基于100%消耗的硫化物单氯化物估计。结果如表4所示。
表4
实施例5
测量实施例4中的交联树脂的剥离强度、Tg、Dk和Df。根据IPC TM-650 2.5.5.13测量耗散因子(Df)和Dk。样品的Dk(10GHz)在3.3-3.7,Df(10GHz)在0.0035-0.0045,Tg为160-180℃,剥离强度为0.5-1.5N/m2。
实施例6-9
在这些实施例中,将80重量份的树脂(分别是A,B,C和D)与50重量份的作为溶剂的甲基苯混合,从而完全溶解到树脂溶液中,然后加入20重量份作为交联剂的三烯丙基异氰脲酸酯(TAIC)、3重量份作为引发剂的过氧化二异丙苯DCP、15重量份作为含溴的阻燃剂的乙烯双(四溴邻苯二甲酰亚胺)和45重量份作为填料的二氧化硅SO-C2到溶液中。将混合物搅拌以溶于均匀的树脂组合物,即胶溶液。
接下来用制备的均匀的胶溶液饱和E-玻璃纤维布并在155℃下加热并干燥E-玻璃纤维布3-10分钟以完全使溶剂挥发,从而获得预浸料。重叠制备的预浸料片,然后将两片35-m-厚的铜箔包覆到重叠的预浸料的两个表面上。通过在200℃的温度和3.0MPa的压力下热压所述两片铜箔和八片预浸料的组件90分钟进行加工,从而获得双面铜包覆的层压体。测量样品的剥离强度、Tg、Dk和Df。根据IPC TM-650 2.5.5.13测量耗散因子(Df)和Dk。样品的Dk(10GHz)为3.3-3.7,Df(10GHz)为0.0035-0.0045,Tg为180-200℃,剥离强度为0.5-1.5N/m2。
尽管本文已经使用了术语“包含”和“包括”来描述各种方面,但术语“基本上由…组成”和“由..组成”可以用于代替“包含”和“包括”以提供更具体的方面的本发明公开的内容。
Claims (15)
1.一种共聚物,其通过在催化剂存在下阳离子聚合一种或多种环状二烯和共聚单体而形成,其中:
所述共聚单体选自单萜烯、支化苯乙烯、及其组合;
所述一种或多种环状二烯选自1,3-环己二烯(CHD)、环戊二烯(CPD)、1,3-环庚二烯、4,5,6,7-四氢茚、降冰片二烯(NBD)、及其组合;
所述催化剂选自布朗斯台德酸、路易斯酸、及其组合;
所述共聚物的Mn为300-5,000道尔顿和Mz为2,000-30,000道尔顿,且具有下述特征:
(i)在烃溶剂中的溶解度为0.1-2g共聚物/克烃溶剂,和
(ii)80-180℃的Tg。
2.根据权利要求1所述的共聚物,其中所述共聚物含有至少0.1重量%的苯基,通过质子NMR测量。
3.根据权利要求1所述的共聚物,其中所述支化苯乙烯包括α-甲基苯乙烯、1,1-二苯基乙烯或其组合中的任何一种,其中所述单萜烯选自α-蒎烯、β-蒎烯、柠檬烯、月桂烯、罗勒烯、α-水芹烯、β-水芹烯、法呢烯、莰烯、α-萜烯、桧烯、γ-萜烯、3-蒈烯、及其组合。
4.根据权利要求1所述的共聚物,其中所述一种或多种环状二烯与所述共聚单体的摩尔比为5:95至95:5。
5.根据权利要求1-4中任一项所述的共聚物,其中所述一种或多种环状二烯包括环状共轭二烯,和其中所述环状共轭二烯是含有最多10重量%的1,4-环己二烯的1,3-环己二烯,相对于所述环状共轭二烯的总重量。
6.根据权利要求1-4中任一项所述的共聚物,其中所述一种或多种环状二烯包括环状共轭二烯,和其中所述环状共轭二烯包括摩尔比为90:10-10:80的聚合的1,4-加成单元和聚合的1,2-加成单元。
7.根据权利要求1-4中任一项所述的共聚物,其中所述催化剂是路易斯酸催化剂,和所述路易斯酸催化剂包含3-8族或12-15族金属和一种或多种吸电子基团。
8.根据权利要求1-4中任一项所述的共聚物,其中所述共聚物在烃溶剂中的溶解度为10-80重量%,相对于所述烃溶剂的重量,和其中所述烃溶剂选自芳烃、脂环烃、脂族烃、及其组合。
9.根据权利要求1-4中任一项所述的共聚物,其中:
所述共聚单体选自α-甲基苯乙烯、1,1-二苯基乙烯、α-蒎烯、β-蒎烯、柠檬烯、月桂烯、罗勒烯、α-水芹烯、β-水芹烯、法呢烯、莰烯、α-萜烯、桧烯、γ-萜烯、3-蒈烯、及其组合;
所述一种或多种环状二烯包括环状共轭二烯,和其中所述环状共轭二烯是含有最多10重量%的1,4-环己二烯的1,3-环己二烯,相对于环状共轭二烯的总重量;
所述共聚物具有5-95摩尔%的得自1,3-环己二烯的聚合单元和95-5摩尔%的得自所述共聚单体的聚合单元;
所述共聚物含有至少0.1重量%的苯基,通过质子NMR测量。
10.一种交联的聚合物,其通过使共聚物与选自硫基试剂、过氧化物基试剂、碲、硒、多硫化物聚合物、金属氧化物、二异氰酸酯及其组合的交联剂反应而形成,
其中所述共聚物通过在催化剂存在下阳离子聚合一种或多种环状二烯和共聚单体而形成,其中所述共聚单体选自单萜烯、支化苯乙烯、及其组合,所述一种或多种环状二烯选自1,3-环己二烯(CHD)、环戊二烯(CPD)、1,3-环庚二烯、4,5,6,7-四氢茚、降冰片二烯(NBD)、及其组合,所述催化剂选自布朗斯台德酸、路易斯酸、及其组合,
所述共聚物的Mn为300-5,000道尔顿和Mz为2000-30,000道尔顿,
所述交联聚合物具有下述一种或多种特征:
(i)140-250℃的Tg,
(ii)0.2-1.5N/m2的对铜的180°剥离强度,
(iii)0.0025-0.0045的耗散因子,根据IPC TM-650 2.5.5.13测量,
(iv)<4.5的介电常数Dk,根据IPC TM-650 2.5.5.13测量,和
(v)<40秒的阻燃性,对应于从样品点火时间至完整焦炭形成所花费的时间。
11.一种预浸料组合物,其包含权利要求10的交联聚合物、增强材料和橡胶组分。
12.一种形成共聚物的方法,其包括:
在催化剂的存在性下和在烃溶剂中阳离子聚合包括一种或多种环状二烯的单体和共聚单体,以形成共聚物;和
回收所述共聚物;
其中所述催化剂选自布朗斯台德酸、路易斯酸、及其组合,
所述共聚单体选自单萜烯、支化苯乙烯、及其组合,
所述一种或多种环状二烯选自1,3-环己二烯(CHD)、环戊二烯(CPD)、1,3-环庚二烯、4,5,6,7-四氢茚、降冰片二烯(NBD)、及其组合,和
其中所述共聚物的Mn为300-5,000道尔顿和MZ为2000-30,000道尔顿,且具有下述特征:
(i)在烃溶剂中的溶解度为0.1-2g共聚物/克烃溶剂,和
(ii)80-180℃的Tg。
其中所述共聚物含有至少0.1重量%的苯基,通过质子NMR测量。
13.根据权利要求12所述的方法,其中所述一种或多种环状二烯包括环状共轭二烯,和其中所述环状共轭二烯包括摩尔比为90:10至10:80的聚合的1,4-加成单元和聚合的1,2-加成单元。
14.根据权利要求12-13中任一项所述的方法,其中所述阳离子聚合在-100℃至120℃的反应温度下进行。
15.根据权利要求12-13中任一项所述的方法,其还包括用交联剂将回收的聚合物交联,以提供交联聚合物,其中所述交联剂选自硫基试剂、过氧化物基试剂、碲、硒、多硫化物聚合物、金属氧化物、二异氰酸酯、及其组合。
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