CN1479754A - 合成聚异戊二烯及其制备方法 - Google Patents
合成聚异戊二烯及其制备方法 Download PDFInfo
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- CN1479754A CN1479754A CNA018203507A CN01820350A CN1479754A CN 1479754 A CN1479754 A CN 1479754A CN A018203507 A CNA018203507 A CN A018203507A CN 01820350 A CN01820350 A CN 01820350A CN 1479754 A CN1479754 A CN 1479754A
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- polyisodiene
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- 238000000034 method Methods 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 37
- -1 alkylaluminium halide Chemical class 0.000 claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 27
- 238000004458 analytical method Methods 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000002168 alkylating agent Substances 0.000 claims abstract description 14
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 14
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
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- 239000000725 suspension Substances 0.000 claims description 9
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 8
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 8
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
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- 229910019142 PO4 Inorganic materials 0.000 claims description 3
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- 235000021317 phosphate Nutrition 0.000 claims description 3
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical group CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract description 2
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 abstract 1
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 21
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
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- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910017544 NdCl3 Inorganic materials 0.000 description 2
- 238000011000 absolute method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- 230000010354 integration Effects 0.000 description 2
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- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000010690 paraffinic oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- HMWCQCYUKQZPRA-UHFFFAOYSA-N 2,4-dimethyl-3-methylidenepent-1-ene Chemical compound CC(C)C(=C)C(C)=C HMWCQCYUKQZPRA-UHFFFAOYSA-N 0.000 description 1
- PJXJBPMWCKMWLS-UHFFFAOYSA-N 2-methyl-3-methylidenepent-1-ene Chemical compound CCC(=C)C(C)=C PJXJBPMWCKMWLS-UHFFFAOYSA-N 0.000 description 1
- OAOZZYBUAWEDRA-UHFFFAOYSA-N 3,4-dimethylidenehexane Chemical compound CCC(=C)C(=C)CC OAOZZYBUAWEDRA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229920004941 NATSYN® 2200 Polymers 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
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- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010966 qNMR Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and 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
- C08F36/04—Homopolymers and 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
- C08F36/08—Isoprene
-
- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/08—Isoprene
-
- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
催化体系 | 溶剂化(溶剂/持续时间/T) | Bd/Nd(mol) | Al/Nd(mol) | 烷基化持续时间/T | Cl/Nd(mol) | 采用DEAC预先形成持续时间/T |
体系1 | CH2小时,30℃ | 50 | 4 | 15分钟/30℃ | 3 | 4小时,60℃ |
体系2 | CH4小时,60℃ | 50 | 3 | 15分钟/30℃ | 3 | 2小时,60℃ |
体系3 | MCH30分钟,30℃ | 50 | 3 | 15分钟/30℃ | 3 | 4小时,60℃ |
体系4 | MCH30分钟,30℃ | 50 | 1.8 | 15分钟/30℃ | 3 | 2小时,60℃ |
体系5 | MCH | 50 | 1.8 | 15分钟/30℃ | 2.6 | 2小时,60℃ |
体系6 | CH2小时,60℃ | 50 | 4 | 15分钟/30℃ | 3 | 2小时,60℃ |
聚合条件 | 聚异戊二烯的特性 | |||||||
试验 | 反应器类型 | Nd数量(μMcm) | 反应时间(小时) | 转化率(%) | 比浓对数粘度(dl/g) | ML(1+4) | 由13C-NMR测量的顺式-1,4含量 | 由MIR测量的顺式-1,4含量 |
A | 静态 | 500 | 64 | 100 | 4.9 | 79 | 99.2 | 99.1 |
400 | 64 | 100 | 5.3 | 87 | - | - | ||
B | 静态 | 400 | 64 | 100 | 5.2 | 82 | - | - |
搅拌的 | 400 | 64 | 100 | - | 83 | - | - | |
C | 静态 | 300 | 64 | 100 | 6.0 | 93 | 99.1 | 99.0 |
D | 静态 | 200 | 64 | 100 | 7.2 | - | 99.2 | - |
150 | 64 | 100 | 8.5 | - | 99.3 | - | ||
E | 静态 | 150 | 64 | 100 | 8.6 | - | - | - |
搅拌的 | 150 | 64 | 100 | 8.9 | - | - | - | |
F | 静态 | 150 | 64 | 100 | - | - | - | 99.1 |
47 | 98 | 8.0 | - | - | 99.2 | |||
38 | 94 | - | - | - | 99.1 | |||
22 | 60 | 7.4 | - | - | 99.2 | |||
14 | 42 | 6.8 | - | - | 99.2 |
试验 | 催化体系 | 聚合条件 | 获得的聚戊二烯 | |||||
聚合溶剂 | Nd数量(μMcm) | 异戊二烯数量(g) | 比例S/M | ML(1+4) | 由13C-NMR的顺式-1,4含量 | 由MIR的顺式-1,4含量 | ||
G | 2 | 无 | 500 | 50 | 0 | 52 | - | 99.3 |
1000 | 50 | 0 | 35 | - | 99.3 | |||
正庚烷 | 1000 | 50 | 1 | 30 | 99.4 | 99.4 | ||
甲基环戊烷 | 1000 | 50 | 1 | 40 | - | 99.4 | ||
CH | 1000 | 50 | 1 | 34 | - | 99.3 | ||
MCH | 1000 | 50 | 1 | 39 | - | 99.3 | ||
H | 3 | MCH | 1000 | 36 | 9 | 69 | - | 99.4 |
700 | 36 | 9 | 79 | - | 99.4 | |||
I | 3 | MCH | 700 | 72 | 5 | 80 | - | 99.5 |
J | 3 | MCH | 700 | 72 | 5 | 79 | - | 99.5 |
K | 3 | MCH | 700 | 72 | 5 | 81 | - | 99.4 |
L | 3 | MCH | 700 | 72 | 5 | 84 | - | 99.4 |
4 | MCH | 700 | 72 | 5 | 89 | - | 99.4 | |
5 | MCH | 700 | 72 | 5 | 97 | - | 99.3 |
试验 | 催化体第 | 聚合条件 | 聚异戊二烯 | ||||||
Nd数量(μMcm) | 异戊二烯数量(g) | 溶剂 | 比例S/M | 反应时间(h) | 转化率(%) | 比浓对数粘度(dl/g) | 由MIR的顺式-1,4含量(%) | ||
M | 3 | 700 | 72 | MCH | 5 | 144 | 14 | 6.3 | 99.6 |
1500 | 72 | MVH | 5 | 144 | 22 | 5.4 | 99.6 |
试验 | 催化体系 | 聚合条件 | 聚异戊二烯 | |||||||
比例S/M | Nd数量(μMcm) | 反应时间(h) | 转化率(%) | 比浓对数粘度(dl/g) | ML(1+4) | 由13C-NMR测量的顺式-1,4含量(%) | 由MIR测量的顺式-1,4含量(%) | |||
N | 6 | 9 | 130 | 48 | 100 | - | 97 | 99.1 | - | |
O | 5 | 9 | 300 | 18 | 100 | 7.6 | 97 | - | 99.0 | |
700 | 18 | 100 | 5.8 | 84 | - | 99.1 | ||||
P | 5 | 9 | 700 | .025 | 15 | - | - | - | - | |
1.5 | 50 | - | - | - | - | |||||
2 | 60 | 4.9 | - | - | 99.1 | |||||
18 | 100 | 6.0 | 86 | - | 99.0 | |||||
Q | 9 | 9 | 700 | 18 | 100 | - | 85 | - | 99.0 | |
7 | 700 | 18 | 100 | - | 86 | - | 99.0 |
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EP (1) | EP1358229B1 (zh) |
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JP3813926B2 (ja) | 2006-08-23 |
EP1358229A1 (fr) | 2003-11-05 |
MXPA03004138A (es) | 2004-02-12 |
ZA200303544B (en) | 2003-11-13 |
DE60133671T2 (de) | 2009-06-10 |
JP2004513998A (ja) | 2004-05-13 |
DE60133671D1 (de) | 2008-05-29 |
BR0115305B1 (pt) | 2011-06-14 |
US20040019171A1 (en) | 2004-01-29 |
BR0115305A (pt) | 2004-02-03 |
AU2177702A (en) | 2002-05-21 |
RU2003117447A (ru) | 2004-11-20 |
EP1358229B1 (fr) | 2008-04-16 |
TW574228B (en) | 2004-02-01 |
ATE392441T1 (de) | 2008-05-15 |
CA2428463A1 (fr) | 2002-05-16 |
US6992157B2 (en) | 2006-01-31 |
ES2305127T3 (es) | 2008-11-01 |
CN100523021C (zh) | 2009-08-05 |
RU2304151C2 (ru) | 2007-08-10 |
KR100827941B1 (ko) | 2008-05-13 |
WO2002038635A1 (fr) | 2002-05-16 |
KR20030097791A (ko) | 2003-12-31 |
CA2428463C (fr) | 2011-10-11 |
AU2002221777B2 (en) | 2006-04-27 |
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