CN1649919A - 制造聚丁二烯的催化体系及其制备方法 - Google Patents
制造聚丁二烯的催化体系及其制备方法 Download PDFInfo
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- CN1649919A CN1649919A CNA038095475A CN03809547A CN1649919A CN 1649919 A CN1649919 A CN 1649919A CN A038095475 A CNA038095475 A CN A038095475A CN 03809547 A CN03809547 A CN 03809547A CN 1649919 A CN1649919 A CN 1649919A
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- Prior art keywords
- catalytic system
- salt
- rare earth
- alkylating agent
- polybutadiene
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 80
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 16
- -1 rare earth salt Chemical class 0.000 claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 239000002168 alkylating agent Substances 0.000 claims abstract description 26
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 23
- 150000002367 halogens Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 150000001993 dienes Chemical class 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 15
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 46
- 229910052779 Neodymium Inorganic materials 0.000 claims description 29
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 26
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical group CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 22
- 239000005062 Polybutadiene Substances 0.000 claims description 21
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001542 size-exclusion chromatography Methods 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 235000021317 phosphate Nutrition 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 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 7
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 6
- 125000002723 alicyclic group Chemical group 0.000 abstract description 2
- 101100378709 Arabidopsis thaliana AIR3 gene Proteins 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 47
- 239000000243 solution Substances 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 23
- 150000001206 Neodymium Chemical class 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000007614 solvation Methods 0.000 description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 229910017544 NdCl3 Inorganic materials 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 239000002841 Lewis acid Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011208 chromatographic data Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012156 elution solvent Substances 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000010690 paraffinic oil Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical group N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000011000 absolute method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- JFICPAADTOQAMU-UHFFFAOYSA-L ethylaluminum(2+);dibromide Chemical compound CC[Al](Br)Br JFICPAADTOQAMU-UHFFFAOYSA-L 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000000691 measurement method Methods 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
- DZNFWGVDYGAMJB-UHFFFAOYSA-K neodymium(3+);phosphate Chemical class [Nd+3].[O-]P([O-])([O-])=O DZNFWGVDYGAMJB-UHFFFAOYSA-K 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010238 partial least squares regression Methods 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
-
- 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
-
- 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
- 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
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)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
分析的盐样品 | 络合滴定的百分比Nd含量 | 由ICP/AES的百分比Nd含量 | 在2种方法之间的相对偏差 |
磷酸盐化的Nd盐[[RO]2P(O)O]3Nd | 12.8(9) | 12.8(3) | 0% |
磷酸盐化的Nd盐[[RO]2P(O)O]3Nd | 12.8(4) | 12.6(3) | 1.6% |
磷酸盐化的Nd盐[[RO]2P(O)O]3Nd | 12.7(6) | 12.2(4) | 4% |
磷酸盐化的Nd盐[[RO]2P(O)O]3Nd | 12.6(6) | 12.5(4) | 0.8% |
乙酰丙酮Nd“对照物” | 31.7(6) | 32.4(4) | 2.2% |
草酸Nd“对照物” | 37.7(3) | 38.0(3) | 0.8% |
催化体系 | 最终Ndconc.(mol/l) | 溶剂化-时间-温度-溶剂 | 预形成丁二烯:Nd | 烷基化-试剂-试剂浓度(mol/l)-Al∶Nd | 烷基化-时间-温度 | 卤化-使用的HD-HD浓度(mol/l)-DH∶Nd | 老化-时间-温度 |
“对照物”1 | 0.0002 | 30min.30℃MCH | 50 | DiBAH0.87510 | 15min.30℃ | DEAC1.0183 | 120min.60℃ |
“对照物”2 | 0.0201 | 30min.30℃MCH | 50 | DiBAH0.88510 | 15min.30℃ | SESQUICHL0.9681.85 | 120min.60℃ |
本发明1 | 0.0201 | 180min.20-25℃CH | 47 | DiBAH1.1710 | 15min.20-25℃ | DEAC2.452.2 | 120min.60℃ |
本发明2 | 0.0201 | 180min.20-25℃CH | 47 | DiBAH1.1715 | 15min.20-25℃ | DEAC2.452.2 | 120min.60℃ |
本发明3 | 0.0201 | 180min.20-25℃CH | 47 | DiBAH1.1720 | 15min.20-25℃ | DEAC2.452.2 | 120min.60℃ |
本发明4 | 0.0201 | 30min.30℃MCH | 50 | DiBAH0.88510 | 15min.30℃ | DEAC0.9683 | 120min.60℃ |
本发明5 | 0.0201 | 无溶液 | 50 | DiBAH0.88510 | 15min.30℃ | DEAC0.9683 | 120min.60℃ |
本发明6 | 0.0201 | 30min.30℃MCH | 50 | TiBA0.77810 | 15min.30℃ | DEAC0.9683 | 120min.60℃ |
本发明7 | 0.0200 | 30min.30℃MCH | 50 | DiBAH0.9476 | 15min.30℃ | DEAC3 | 120min.60℃ |
测试 | 催化体系 | Nd数量(μmol) | 比例S∶M和T(℃) | 反应时间(min) | 转化率(%) | ηinh(dl/g) | 门尼ML(1+4)100℃ | Ip | 顺式-1,4单元(%) | 反式单元(%) | 1,2单元(%) |
T1 | “对照物”1 | 2453 | 9450℃ | 70 | 99 | 2.27 | 未测量 | 27.44 | 94.5 | 4.2 | 1.3 |
T1’ | “对照物”1 | 2044 | 7950℃ | 120 | 100 | 2.64 | 未测量 | 21.70 | 95.3 | 3.7 | 1.0 |
T1″ | “对照物”1 | 1531 | 5950℃ | 180 | 100 | 3.41 | 21 | >25 | 96.0 | 2.9 | 1.1 |
T2 | “对照物”2 | 247 | 9.850℃ | 390 | 86 | 2.15 | 未测量 | 2.72 | 99.1 | 0.8 | 0.1 |
T2′ | “对照物”2 | 309 | 9.850℃ | 390 | 97 | 1.96 | 未测量 | 2.76 | |||
T2″ | “对照物”2 | 618 | 9.850℃ | 170 | 100 | 1.22 | 未测量 | 2.71 | |||
I1 | 本发明1 | 130 | 760℃ | 20 | 80 | 2.37 | 1.77 | 98 | 1 | 1 | |
I2 | 本发明2 | 80 | 760℃ | 35 | 83 | 2.53 | 1.56 | 98 | 1 | 1 | |
I3 | 本发明3 | 60 | 760℃ | 40 | 81 | 2.62 | 1.75 | 98 | 1 | 1 | |
I4 | 本发明4 | 155 | 9.850℃ | 120 | 100 | 2.67 | 未测量 | 1.95 | |||
I4′ | 本发明4 | 155 | 10.450℃ | 150 | 100 | 2.53 | 47 | 1.88 | 97.6 | 2.4 | 0 |
I4″ | 本发明4 | 184 | 10.450℃ | 150 | 100 | 2.37 | 41 | 1.91 | 97.1 | 2.9 | 0 |
I5 | 本发明5 | 155 | 9.350℃ | 90 | 100 | 2.43 | 未测量 | 1.84 | 96.8 | 3.2 | 0 |
I6 | 本发明6 | 618 | 9.350℃ | 5 | 100 | 2.85 | 未测量 | 2.05 | 96.9 | 3.1 | 0 |
I7 | 本发明7 | 280 | 7.250℃ | 16 | 97 | 2.50 | 未测量 | 1.56 | 97.3 | 2.4 | 0.3 |
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AU (1) | AU2003233065A1 (zh) |
BR (1) | BR0309644B8 (zh) |
DE (1) | DE60302891T2 (zh) |
ES (1) | ES2254934T3 (zh) |
MX (1) | MXPA04011261A (zh) |
RU (1) | RU2301811C2 (zh) |
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Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6023406A (ja) * | 1983-07-18 | 1985-02-06 | Asahi Chem Ind Co Ltd | ポリブタジエンの製造方法 |
JP2595539B2 (ja) * | 1987-05-29 | 1997-04-02 | 日本合成ゴム株式会社 | 新規な共役ジエン系重合体の製造方法 |
JPH0822881B2 (ja) * | 1987-08-19 | 1996-03-06 | 旭化成工業株式会社 | 共役ジエン系重合体類の製造方法 |
KR910008275B1 (ko) * | 1987-08-19 | 1991-10-12 | 아사히가세이고오교 가부시끼가이샤 | 공역 디엔 화화물 예비중합체 용액 제조를 위한 예비중합방법 |
JP4067592B2 (ja) * | 1996-12-04 | 2008-03-26 | Jsr株式会社 | 共役ジエン系重合体の製造方法 |
CA2695838C (en) * | 1999-05-19 | 2011-11-01 | Bridgestone Corporation | Low molecular weight high-cis polybutadienes and their use in high molecular weight/low molecular weight high-cis polybutadiene blends |
ATE416203T1 (de) * | 2000-11-09 | 2008-12-15 | Michelin Soc Tech | Katalytisches system und verfahren zur herstellung von elastomeren unter verwendung dieses systems |
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2003
- 2003-04-25 ES ES03727363T patent/ES2254934T3/es not_active Expired - Lifetime
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- 2003-04-25 EP EP03727363A patent/EP1509557B1/fr not_active Expired - Lifetime
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CN103694378A (zh) * | 2013-12-19 | 2014-04-02 | 山东玉皇化工有限公司 | 一种合成溶液型稀土橡胶催化剂的方法 |
CN103694386B (zh) * | 2013-12-19 | 2017-03-08 | 华宇橡胶有限责任公司 | 一种有机磷酸钕催化剂体系的制备方法 |
CN108219046A (zh) * | 2016-12-15 | 2018-06-29 | 中国石油天然气股份有限公司 | 一种稀土催化剂及其制备方法和应用 |
CN112204058A (zh) * | 2018-05-25 | 2021-01-08 | 米其林集团总公司 | 官能化聚丁二烯合成方法 |
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CN117209638A (zh) * | 2023-11-08 | 2023-12-12 | 传化智联股份有限公司 | 一种两性离子稀土元素烷基催化剂及其制备方法和应用 |
CN117209638B (zh) * | 2023-11-08 | 2024-02-13 | 传化智联股份有限公司 | 一种两性离子稀土元素烷基催化剂及其制备方法和应用 |
Also Published As
Publication number | Publication date |
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EP1509557A1 (fr) | 2005-03-02 |
RU2004136857A (ru) | 2005-05-27 |
US7056998B2 (en) | 2006-06-06 |
ES2254934T3 (es) | 2006-06-16 |
WO2003097708A1 (fr) | 2003-11-27 |
JP4685442B2 (ja) | 2011-05-18 |
ZA200407894B (en) | 2009-07-29 |
EP1509557B1 (fr) | 2005-12-21 |
DE60302891T2 (de) | 2006-08-03 |
KR101010865B1 (ko) | 2011-01-26 |
BR0309644B8 (pt) | 2013-02-19 |
ATE313573T1 (de) | 2006-01-15 |
JP2005530872A (ja) | 2005-10-13 |
AU2003233065A1 (en) | 2003-12-02 |
MXPA04011261A (es) | 2005-02-17 |
CN100386352C (zh) | 2008-05-07 |
BR0309644A (pt) | 2005-03-01 |
RU2301811C2 (ru) | 2007-06-27 |
TW200406431A (en) | 2004-05-01 |
KR20050000550A (ko) | 2005-01-05 |
BR0309644B1 (pt) | 2013-01-08 |
DE60302891D1 (de) | 2006-01-26 |
TWI273107B (en) | 2007-02-11 |
US20050130835A1 (en) | 2005-06-16 |
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