CN106589239A - Butadiene/isoprene copolymer preparation method - Google Patents
Butadiene/isoprene copolymer preparation method Download PDFInfo
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- CN106589239A CN106589239A CN201510679313.9A CN201510679313A CN106589239A CN 106589239 A CN106589239 A CN 106589239A CN 201510679313 A CN201510679313 A CN 201510679313A CN 106589239 A CN106589239 A CN 106589239A
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- aluminum
- alkyl
- butadiene
- rare
- phenyl
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229920001577 copolymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 46
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 75
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 71
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- -1 normal-butyl Chemical group 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052779 Neodymium Inorganic materials 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 13
- 150000001721 carbon Chemical group 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 229910052684 Cerium Chemical group 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000091 aluminium hydride Inorganic materials 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- VTZJFPSWNQFPCQ-UHFFFAOYSA-N dibutylaluminum Chemical compound CCCC[Al]CCCC VTZJFPSWNQFPCQ-UHFFFAOYSA-N 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 235000010210 aluminium Nutrition 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 235000010290 biphenyl Nutrition 0.000 description 10
- 239000004305 biphenyl Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000005292 vacuum distillation Methods 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 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 2
- 239000007789 gas Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- MBULCFMSBDQQQT-UHFFFAOYSA-N (3-carboxy-2-hydroxypropyl)-trimethylazanium;2,4-dioxo-1h-pyrimidine-6-carboxylate Chemical compound C[N+](C)(C)CC(O)CC(O)=O.[O-]C(=O)C1=CC(=O)NC(=O)N1 MBULCFMSBDQQQT-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- QIICJUWNVJOFPS-UHFFFAOYSA-N 4,4,5,5,6,6-hexaethyl-3H-azadisiline Chemical compound C(C)C1(C(C(N=[SiH][SiH2]1)(CC)CC)(CC)CC)CC QIICJUWNVJOFPS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 101800000021 N-terminal protease Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 150000001206 Neodymium Chemical class 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical class CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- ACOLQZDYRBEHEV-UHFFFAOYSA-K decanoate;neodymium(3+) Chemical compound [Nd+3].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O ACOLQZDYRBEHEV-UHFFFAOYSA-K 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000006437 ethyl cyclopropyl group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to the field of catalytic polymerization, and discloses a butadiene/isoprene copolymer preparation method, wherein the copolymer contains a butadiene chain segment unit and an isoprene chain segment unit, the cis-1,4 bond content in the butadiene chain segment unit is more than or equal to 98.0%, the cis-1,4 bond content in the isoprene chain segment unit is more than or equal to 98.0%, and the molecular weight distribution of the copolymer is 1.2-2.1. The preparation method comprises that under a polymerization reaction condition, a butadiene monomer, an isoprene monomer and a rare earth catalyst composition are subjected to a contact reaction, wherein the rare earth catalyst composition contains a rare earth metal organic compound, an aluminum-containing compound and a halogen source, and the rare earth metal organic compound has a structure represented by a formula (I). According to the present invention, the cis-1,4 bond contents in the butadiene chain segment unit and the isoprene chain segment unit of the butadiene/isoprene copolymer are high, and the molecular weight distribution is narrow. The formula (I) is defined in the specification.
Description
Technical field
The present invention relates to catalytic polymerization field, in particular it relates to one kind to prepare butadiene/isoprene common
The method of polymers.
Background technology
For catalytic polymerization conjugated diene rare earth catalyst composition it is general all by rare earth catalyst, help
Catalyst and halogen source are constituted.Conjugated diene can be catalyzed becomes the polymer with high-cis structure.It is special
Not, these polymer can be widely used on manufacture automobile tire.In rare earth catalyst, neodymium series
The low price of catalyst, expression activitiy is high.
CN102464745A describes a kind of rare earth catalyst composition for conjugate diene polymerization,
Said composition includes：
- as the neodymium caprate or neodymium naphthenate of rare earth catalyst,
- diethyl aluminium hydride, the triethyl aluminum mixture of one or two or more kinds therein,
- one chloro-di-isobutyl aluminum or aluminium diethyl monochloride.
In this carbon monoxide-olefin polymeric, the cis-Isosorbide-5-Nitrae linkage content of resulting polyisoprene is 96.6 weights
Amount weight % of % to 97.2.
CN1484657A describes a kind of rare earth catalyst composition for conjugate diene polymerization, should
Compositionss include：
A kind of-conjugated diene monomer,
The rare earth metal salt of-organic phosphoric acid,
- formula is AlR3Or HAlR2Alkyl aluminum,
- the halogen donor being made up of alkyl aluminium halide.
In this carbon monoxide-olefin polymeric, the cis-Isosorbide-5-Nitrae linkage content of resulting polyisoprene is 95.7 weights
Amount weight % of % to 98.7.
Conventional Nd-based catalyst includes alkyl carboxylic acid neodymium, alkoxyl neodymium and phosphate ester neodymium, and these parts are all
It is that coordinate bond is formed with oxygen and neodymium.Up to now, polyreaction is carried out with what nitrogen and neodymium formed coordinate bond
It is Catalyzed by Organometallic Compounds agent research and few.
Boisson has used Nd (N (SiMe on Macro.Chem.Phys. (200,1163)3)2)3As urging
Agent is polymerized to butadiene, and in addition to neodymium catalyst, the carbon monoxide-olefin polymeric also includes：
- as the butadiene of conjugated diene monomer,
- as the triisobutyl aluminium of alkylating reagent,
- as the diethylaluminum chloride of aikyl aluminum halide.
In this carbon monoxide-olefin polymeric, nitrogen and neodymium define coordinate bond in rare earth catalyst, and resulting is poly-
The cis-1,4 chaining of butadiene is 93.1 weight % to 99.0 weight %.But the carbon monoxide-olefin polymeric
Preparation method it is excessively simple, be simply simply mixed.This carbon monoxide-olefin polymeric is only used for the poly- of butadiene
Close, when the copolymerization for butadiene and isoprene, harshness is required to reaction condition, and by condition shadow
Sound is larger, and the cis-content of the product of acquisition is not high and molecular weight distribution is wider, and this is unfavorable for industrial metaplasia
Optimum catalyst compositing formula carries out the preparation of polymer used in product.
The content of the invention
The purpose of the present invention is the defect for overcoming prior art, there is provided a kind of cis- Isosorbide-5-Nitrae linkage content is in butadiene
Higher and narrow molecular weight distribution butadiene/isoprene in chain segment unit and isoprene segment unit
Copolymer and preparation method thereof.
To achieve these goals, the present invention provides a kind of side for preparing butadiene/isoprene copolymer
Method, the method includes：Under the polymerization conditions, by divinylic monomer and isoprene monomer and rare earth
Carbon monoxide-olefin polymeric carries out haptoreaction, organises containing rare earth metal in the rare earth catalyst composition
Compound, the compound containing aluminium element and halogen source, the compound containing aluminium element is alkyl aluminum and/or hydrogen
Change alkyl aluminum, the Rare-earth chemicals have the structure shown in formula (I)：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl,
C6-12Aryl, and the R1、R2、R3、R4、R5And R6It is asynchronously in hydrogen and methyl
It is at least one；
L is-OR7Or-NR8, wherein, the R7Formed together with oxygen atom containing 2-10 carbon atom
Heterocycle, the R8The heterocycle containing 2-10 carbon atom or the R are formed together with nitrogen-atoms8
For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
The butadiene segment unit and isoprene chain of butadiene/isoprene copolymer that the present invention is provided
Cis- 1,4 linkage content is higher in segment unit and narrow molecular weight distribution.
In addition, the present inventor is found that under study for action the novel rare-earth based on rare earth metal salt is catalyzed
Agent compositionss, the novel rare-earth carbon monoxide-olefin polymeric includes the rare earth metal organic compound as catalyst
Thing, the Rare-earth chemicals are based on No. 57 elements in the periodic table of elements between No. 71 elements
Element, the novel rare-earth carbon monoxide-olefin polymeric forms coordinate bond by nitrogen and rare earth element, carry out butadiene/
The polymerization of isoprene copolymer, realizes butadiene segment unit and isoprene chain in copolymer
Cis-content in segment unit is all higher than or equal to 98 weight %, preferably greater than or equal to 99 weight %,
Molecular weight distribution is less than or equal to 2.1.
Butadiene/isoprene copolymer that the present invention is provided also has good resistance to low temperature, wear-resisting
The performance such as property and low temperature rolling resistance.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method for preparing butadiene/isoprene copolymer, the method includes：
Under the polymerization conditions, divinylic monomer and isoprene monomer are carried out with rare earth catalyst composition
Haptoreaction, in the rare earth catalyst composition containing Rare-earth chemicals, containing aluminium element
Compound and halogen source, the compound containing aluminium element is alkyl aluminum and/or alkyl aluminium hydride, described dilute
Earth metal organic compound has the structure shown in formula (I)：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl,
C6-12Aryl, and the R1、R2、R3、R4、R5And R6It is asynchronously in hydrogen and methyl
It is at least one；
L is-OR7Or-NR8, wherein, the R7Formed together with oxygen atom containing 2-10 carbon atom
Heterocycle, the R8The heterocycle containing 2-10 carbon atom or the R are formed together with nitrogen-atoms8
For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
Under preferable case, in the structure shown in formula (I), M is neodymium or cerium；R1、R2、R3、R4、
R5And R6It is identical or different, it is each independently selected from hydrogen, C1-6Alkyl, C6-10Aryl, it is and described
R1、R2、R3、R4、R5And R6It is asynchronously at least one in hydrogen and methyl；L is-OR7
Or-NR8, wherein, the R7The heterocycle containing 2-7 carbon atom is formed together with oxygen atom, it is described
R8The heterocycle containing 2-7 carbon atom or the R are formed together with nitrogen-atoms8For C1-4Alkyl；x
For 1,2 or 3, and y=3-x.
In the case of more preferably, in the structure shown in formula (I), M is neodymium or cerium；R1、R2、R3、
R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, ethyl, n-pro-pyl, isopropyl
Base, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methyl ring
Propyl group, ethyl cyclopropyl, cyclopenta, methylcyclopentyl, cyclohexyl, phenyl, aminomethyl phenyl, ethyl
Phenyl, 3,5-dimethylphenyl, trimethylphenyl, Methylethyl phenyl, diethyl phenyl and triethyl group phenyl,
And the R1、R2、R3、R4、R5And R6It is asynchronously at least one in hydrogen and methyl；L
For-OR7Or-NR8, wherein, the R7The heterocycle containing 2-4 carbon atom is formed together with oxygen atom,
The R8The heterocycle containing 2-5 carbon atom or the R are formed together with nitrogen-atoms8For C1-4Hydrocarbon
Base；X is 1,2 or 3, and y=3-x.
Under preferable case, in the structure shown in formula (I), the L is bonded with the M by coordination
Connect.
According to a kind of preferred embodiment, in the structure shown in formula (I) in the present invention, M
For neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, first
Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, front three
Base phenyl, Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl, and the R1、
R2、R3、R4、R5And R6It is asynchronously at least one in hydrogen and methyl；L is selected from tetrahydrochysene furan
Mutter, pyridine and acetonitrile；X is 1,2 or 3, and y=3-x.
According to another kind of preferred embodiment, in the structure shown in formula (I) in the present invention, M
For neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, first
Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, front three
Base phenyl, Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl, and the R1、
R2、R3、R4、R5And R6It is asynchronously at least one in hydrogen and methyl；X is 3, and y is
0。
According to the third preferred embodiment, in the structure shown in formula (I) in the present invention, M
For neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different, be each independently selected from methyl,
N-pro-pyl, normal-butyl, phenyl and cyclohexyl, and the R1、R2、R3、R4、R5And R6When different
For methyl；L is selected from tetrahydrofuran, pyridine and acetonitrile；X is 1 or 2, and y=3-x.
According to the 4th kind of preferred embodiment, in the structure shown in formula (I) in the present invention, M
For neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different, be each independently selected from methyl,
Normal-butyl and phenyl, and the R1、R2、R3、R4、R5And R6It is asynchronously methyl；X is 3, and
Y is 0.
The present invention is no special to the method for preparing the Rare-earth chemicals of the structure shown in formula (I)
Other restriction.Those skilled in the art can take the synthesis coordinationization of routine in the art according to structural formula
The method of compound is prepared.
Under preferable case, the invention provides a kind of method for preparing Rare-earth chemicals, this is dilute
Earth metal organic compound has the structure shown in formula (I), and the method includes：In protective gas and
In the presence of organic solvent, rare earth metal source is contacted with the compound of structure shown in formula (II), institute
It is the compound containing the element shown in M to state rare earth metal source, the organic solvent selected from halogenated hydrocarbons,
Alcohols, aromatic hydrocarbons, halogenated aryl hydrocarbon, formula OR7Shown Oxygenic heterocyclic compounds and formula NR8Shown chemical combination
At least one in thing,
Wherein, M, R1、R2、R3、R4、R5、R6、L、R7、R8, x and y definition as this
It is bright aforementioned to be defined.
Each in structure and the compound of structure shown in formula (II) shown in wherein involved formula (I)
The definition of group is identical with the foregoing teachings of the present invention, and the present invention will not be described here, art technology
Personnel should not be construed as limiting the invention.
Preferably, the rare earth metal source can be the salt containing the element shown in M, for example, can be
Any one in chloride containing the element shown in M, nitrate, sulfate.
Preferably, the consumption mole in the compound of structure shown in the formula (II) and the rare earth metal source
Than for 0.5-10：1；Preferably 1-4：1.
The species of the organic solvent is not particularly limited, as long as enabling to the rare earth metal
Wherein just, preferably the organic solvent is polarity to the compound dissolution of source and structure shown in formula (II)
Organic solvent, the more preferably organic solvent are the chemical combination that coordinate bond can be formed with the M element
Thing.
The consumption of the organic solvent is had no particular limits, those skilled in the art can be according to ability
The conventional amount used in domain is selected.Preferably, those skilled in the art can also prepare as needed
Target compound in x and y ratio determining the consumption of organic solvent.
The protective gas can be the noble gases for being not involved in reacting, for example, can be nitrogen, argon
Deng.
Preferably, the condition for being contacted includes：Temperature is 0-80 DEG C, and the time is 5-500 minutes.
The present invention can also be concentrated the product that above-mentioned contact is obtained, and preferably, by dense
The crystal for adding appropriate non-polar solven such as ether higher to obtain purity in the product of contracting.
The halogen source be refer to provide halogen element compound, the halogen element include fluorine, chlorine, bromine,
Iodine.
In the rare earth catalyst composition, the Rare-earth chemicals, the change containing aluminium element
The content mol ratio of compound and halogen source is 1：2-10：1-30；More preferably 1：4-8：1-15.
It should be strongly noted that can also contain aluminium element in the halogen source, the present invention is especially defined
Compound containing halogen element and aluminium element falls within halogen source of the present invention；And contain aluminium element and not
Compound containing halogen element belongs to the compound containing aluminium element of the present invention.
Alkyl in the alkyl aluminum can be C2-C8Alkyl, specifically, the alkyl aluminum can be
In trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium and three amyl group aluminum one
Plant or various；At least one preferably in triethyl aluminum, triisobutyl aluminium and triethyl aluminum；More preferably
For triisobutyl aluminium or triethyl aluminum.
Alkyl in the alkyl aluminium hydride can be C2-C4Alkyl, specifically, the alkyl hydrides
Aluminum can be diethyl aluminium hydride and/or hydrogenation dibutyl aluminum；Preferably hydrogenate dibutyl aluminum.
Preferably, when the M in Rare-earth chemicals is neodymium, the alkyl aluminum is preferably hydrogen
Change diisobutyl aluminum or triisobutyl aluminium.
The halogen source can be aikyl aluminum halide；It is preferred that the aikyl aluminum halide be diethyl aluminum chloride and/
Or diisobutyl aluminum chloride.
The haptoreaction can be carried out in the presence of an organic；It is preferred that the organic solvent selected from just oneself
At least one in alkane, pentane, hexane, heptane, hexamethylene, toluene, dimethylbenzene and chlorobenzene；More
Preferably normal hexane.
The catalytic condition can include：Temperature is 0-100 DEG C, and the time is 0.1-24h；It is preferred that
Ground, the catalytic condition includes：Temperature is 5-80 DEG C, and the time is 0.2-12h.Especially,
The catalytic time zero exists in same system to participate in catalytic whole key elements
When middle.
Preferably, the total amount of the divinylic monomer and the isoprene monomer with terms of rare earth metal
The mol ratio of the consumption of the rare earth catalyst composition is 1000-10000：1；More preferably
2000-9000：1；Particularly preferably 3500-9000：1.
Preferably, the consumption mol ratio of the divinylic monomer and the isoprene monomer is 1-10：1；
More preferably 1-5：1.
Can also contain in the rare earth catalyst composition and be ready to use in the monomer for carrying out polyreaction.Institute
In stating rare earth catalyst composition, the monomer that carries out polyreaction and the rare earth metal of being ready to use in has
The mol ratio of machine compound is 1-120：1；Preferably 10-80：1.Under this condition, can obtain more
Good catalysis activity.
It is divinylic monomer and/or the isoprene list to be ready to use in and carry out the monomer of polyreaction
Body.
The rare earth catalyst composition can be generated in the course of reaction situ of polyreaction, it is also possible to
Using the method production for preparing in advance.Specifically, the preparation method of the carbon monoxide-olefin polymeric can include：
By Rare-earth chemicals, the compound containing aluminium element and halogen source and it is optional be ready to use in into
The monomer of row polyreaction is mixed in inert hydrocarbon solvent.
In the present invention, it is described " by Rare-earth chemicals, the compound containing aluminium element and halogen source
And optional being ready to use in carries out the monomer of polyreaction and is mixed in inert hydrocarbon solvent " refer to,
The mixing can presence or absence of it is described be ready to use in the monomer for carrying out polyreaction in the case of enter
OK, that is to say, that carry out mixing needs or described need not being ready to use in described in aforesaid carrying out being polymerized instead
The monomer answered.
According to a kind of preferred embodiment, by Rare-earth chemicals, the change containing aluminium element
Compound and halogen source and the optional monomer for carrying out polyreaction that is ready to use in are carried out in inert hydrocarbon solvent
The step of mixing, includes：
(1) by the Rare-earth chemicals and compound containing aluminium element and it is optional described in
Be ready to use in the conjugated diene for carrying out polyreaction carries out hybrid reaction in inert hydrocarbon solvent；
(2) halogen source is introduced in mixture system to be aged.
Under preferable case, in the present invention, in step (1), the condition of the hybrid reaction includes：
Temperature is 5-40 DEG C；Time is 0.01-2h.
Under preferable case, in the present invention, in step (2), the condition of the ageing includes：Temperature
Spend for 45-85 DEG C；Time is 0.02-5h.
The inert hydrocarbon solvent includes but is not limited to arsol (such as toluene) or aliphatic or alicyclic
Solvent is (such as pentane, pentane, isopentane, hexanes mixtures, normal hexane, hexamethylene, methyl cyclohexane
Alkane, heptane mixture or normal heptane).
The consumption of the inert hydrocarbon solvent is caused in the rare earth catalyst composition, preferably described dilute
Concentration >=the 0.0002mol/L of earth metal organic compound.
The whole polymerization process of the present invention is steadily easily controllable, is very suitable for serialization commercial production, institute
Containing butadiene segment unit and isoprene segment unit, the butadiene in the copolymer product for obtaining
Cis- Isosorbide-5-Nitrae linkage content >=98.0% in chain segment unit, the cis- Isosorbide-5-Nitrae key in the isoprene segment unit contains
Amount >=98.0%, the molecular weight distribution of the copolymer is 1.2-2.1.Under preferable case, the butadiene
Cis- Isosorbide-5-Nitrae linkage content >=98.5% in chain segment unit, the cis- Isosorbide-5-Nitrae key in the isoprene segment unit contains
Amount >=98.5%, the molecular weight distribution of the copolymer is 1.4-1.9.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Hereinafter will be described the present invention by embodiment.
In following examples, butadiene segment unit and isoprene segment unit in the copolymer product
In cis- 1,4 linkage content measured using C13 nuclear magnetic resonance methods or near-infrared analysis method；The butadiene/
The molecular weight distribution of isoprene copolymer is by gpc measurement；Prepare metal-organic raw material by
Commercial sources are obtained, especially, in the purchase of Sigma-Aldrich medicaments company.
Preparation example 1-9 is used to prepare Rare-earth chemicals.
Embodiment 1-9 is used to illustrate the method for preparing butadiene/isoprene copolymer of the present invention.
Preparation example 1
The preparation of three (1,3- diphenyl -1, the silicon substrate amine of 1,3,3- tetramethyl two) neodymiums, structural formula is as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (6.5 mMs), and 25 milliliters of THF is added thereto, at 25 DEG C
Stirring 30 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 2
The preparation of three (1,3- dibutyl -1, the silicon substrate amine of 1,3,3- tetramethyl two) neodymiums, structural formula is as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.0 mMs) and 1,3- dibutyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (7.5 mMs)；And be added thereto 25 milliliters of pyridine, stir at 20 DEG C
Mix 60 minutes, subsequently vacuum distillation to solution is carried out at 50 DEG C and be condensed into 1-2 milliliters, be subsequently added
0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 3
The preparation of three (1,3- diphenyl -1, the silicon substrate amine of 1,3,3- tetramethyl two) ceriums, structural formula is as follows：
In the presence of nitrogen, CeCl is introduced in flask3(2.0 mMs) and 1,3- diphenyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (7.0 mMs)；And be added thereto 25 milliliters of acetonitrile, at 40 DEG C
Stirring 20 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 4
The preparation of two (1,3- diphenyl -1, the silicon substrate amine of 1,3,3- tetramethyl two) tetrahydrofuran neodymiums, structural formula is as follows
It is shown：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (4.0 mMs)；And be added thereto 25 milliliters of THF, at 30 DEG C
Stirring 30 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 5
The preparation of two (1,3- diphenyl -1, the silicon substrate amine of 1,3,3- tetramethyl two) pyridine neodymiums, structural formula is as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (4.0 mMs)；And be added thereto 25 milliliters of pyridine, at 40 DEG C
Stirring 20 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 6
The preparation of two (1,3- diphenyl -1, the silicon substrate amine of 1,3,3- tetrapropyl two) tetrahydrofuran ceriums, structural formula is as follows
It is shown：
In the presence of nitrogen, CeCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
The silicon substrate amine of tetrapropyl two (4.0 mMs)；And be added thereto 25 milliliters of THF, at 45 DEG C
Stirring 20 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 7
The preparation of (1,3- dipropyl -1, the silicon substrate amine of 1,3, the 3- tetrabutyl two)-two tetrahydrofuran ceriums, structural formula is such as
Shown in lower：
In the presence of nitrogen, CeCl is introduced in flask3(2.1 mMs) and 1,3- dipropyl -1,1,3,3-
The silicon substrate amine of the tetrabutyl two (2.0 mMs)；And be added thereto 25 milliliters of THF, at 30 DEG C
Stirring 25 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 8
The preparation of (1,3- dicyclohexyl -1, the silicon substrate amine of 1,3,3- tetramethyl two)-two pyridine neodymiums, structural formula is as follows
It is shown：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- dicyclohexyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (2.0 mMs)；And be added thereto 25 milliliters of pyridine, at 50 DEG C
Stirring 20 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 9
The preparation of two (the silicon nitrogen amine of 1,3- Hexaethyl two) acetonitrile neodymiums, structural formula is as follows：
Under a nitrogen, NdCl is introduced in flask3(1.1 mMs) and hexaethyl disilazine (2.1
MM)；And be added thereto 25 milliliters of acetonitrile, stir 30 minutes at 35 DEG C, subsequently exist
Vacuum distillation to solution is carried out at 50 DEG C and is condensed into 1-2 milliliters, be subsequently added 0.5 milliliter of ether.
Clear crystal is obtained in solution.
Embodiment 1
In the presence of nitrogen, the normal hexane of 50mL is introduced in flask, 0.24mmol preparation examples 1 are obtained
Rare-earth chemicals and 4.1mmol butadiene, temperature be 30 DEG C at contact 5 minutes；
1.0mmol triisobutyl aluminiums are subsequently introduced, are contacted 30 minutes in the case where temperature is for 30 DEG C；It is subsequently introduced
0.72mmol diethyl aluminum chlorides, in the case where temperature is for 60 DEG C 2h is aged；It is subsequently introduced 0.48mol fourths two
Alkene and 0.48mol isoprene are polymerized, and 3h are reacted in the case where temperature is for 30 DEG C, subsequently by adding
Methanol makes reaction terminating, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 99.2 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 99.0 weight %, and molecular weight distribution is 1.8.
Embodiment 2
In the presence of nitrogen, the normal hexane of 50mL is introduced in flask, 0.24mmol preparation examples 2 are obtained
Rare-earth chemicals and 7.2mmol isoprene, temperature be 35 DEG C at contact 7 minutes；
1.44mmol diisobutylaluminium hydrides are subsequently introduced, are contacted 20 minutes in the case where temperature is for 35 DEG C；Subsequently
0.72mmol diisobutyl aluminum chlorides are introduced, in the case where temperature is for 60 DEG C 2.5h is aged；It is subsequently introduced 0.4mol
Butadiene and 0.6mol isoprene are polymerized, and 4h are reacted in the case where temperature is for 35 DEG C, subsequently by adding
Entering methanol makes reaction terminating, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 99.5 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 98.9 weight %, and molecular weight distribution is 1.5.
Embodiment 3
In the presence of nitrogen, the normal hexane of 50mL is introduced in flask, 0.24mmol preparation examples 3 are obtained
Rare-earth chemicals and 7.2mmol butadiene, temperature be 20 DEG C at contact 15 minutes；
1.44mmol triethyl aluminums are subsequently introduced, are contacted 30 minutes in the case where temperature is for 20 DEG C；It is subsequently introduced
0.72mmol diisobutyl aluminum chlorides, in the case where temperature is for 50 DEG C 3h is aged；It is subsequently introduced 0.8mol fourths two
Alkene and 0.2mol isoprene are polymerized, and 3h are reacted in the case where temperature is for 60 DEG C, subsequently by adding first
Alcohol makes reaction terminating, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 99.2 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 99.0 weight %, and molecular weight distribution is 1.7.
Embodiment 4-5
Embodiment 4-5 is carried out using method similar to Example 1, except that, in embodiment 4
Made using the preparation example 1 in the Rare-earth chemicals alternative embodiment 1 that preparation example 4 is prepared
The standby Rare-earth chemicals for obtaining；The rare earth gold prepared using preparation example 5 in embodiment 5
The Rare-earth chemicals that preparation example 1 in category organic compound alternative embodiment 1 is prepared.
Remaining is in the same manner as in Example 1.
As a result：Cis- 1,4 linkage content of butadiene segment unit is 99.0 in the polymer that embodiment 4 is obtained
Weight %, the cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.0 weight %, and molecular weight distribution is 1.7；
The cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit is 99.1 weight % in the polymer that embodiment 5 is obtained,
The cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.0 weight %, and molecular weight distribution is 1.7.
Embodiment 6-7
Embodiment 6-7 is carried out using method similar to Example 3, except that, in embodiment 6
Made using the preparation example 3 in the Rare-earth chemicals alternative embodiment 3 that preparation example 6 is prepared
The standby Rare-earth chemicals for obtaining；The rare earth gold prepared using preparation example 7 in embodiment 7
The Rare-earth chemicals that preparation example 3 in category organic compound alternative embodiment 3 is prepared.
Remaining is in the same manner as in Example 3.
As a result：Cis- 1,4 linkage content of butadiene segment unit is 99.3 in the polymer that embodiment 6 is obtained
Weight %, the cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.0 weight %, and molecular weight distribution is 1.6；
The cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit is 99.2 weight % in the polymer that embodiment 7 is obtained,
The cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.1 weight %, and molecular weight distribution is 1.7.
Embodiment 8-9
Embodiment 8-9 is carried out using method similar to Example 2, except that, in embodiment 8
Made using the preparation example 2 in the Rare-earth chemicals alternative embodiment 2 that preparation example 8 is prepared
The standby Rare-earth chemicals for obtaining；The rare earth gold prepared using preparation example 9 in embodiment 9
The Rare-earth chemicals that preparation example 2 in category organic compound alternative embodiment 2 is prepared.
Remaining is in the same manner as in Example 2.
As a result：Cis- 1,4 linkage content of butadiene segment unit is 99.5 in the polymer that embodiment 8 is obtained
Weight %, the cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.1 weight %, and molecular weight distribution is 1.6；
The cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit is 99.4 weight % in the polymer that embodiment 9 is obtained,
The cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 98.9 weight %, and molecular weight distribution is 1.5.
Comparative example 1
Polymeric articles are prepared according to the method described in embodiment 1, except that, adopt in this comparative example
The Rare-earth chemicals prepared with the preparation example 1 in Neodymium chloride alternative embodiment 1.
Remaining is in the same manner as in Example 1, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 68.2 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 64.0 weight %, and molecular weight distribution is 3.7.
Comparative example 2
Polymeric articles are prepared according to the method described in embodiment 2, except that, adopt in this comparative example
The Rare-earth chemicals prepared with the preparation example 2 in neodymium oxalate alternative embodiment 2.
Remaining is in the same manner as in Example 2, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 74.5 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 85.7 weight %, and molecular weight distribution is 2.4.
Comparative example 3
Polymeric articles are prepared according to the method described in embodiment 3, except that, adopt in this comparative example
With the Nd (N (SiMe in Macro.Chem.Phys. (200,1163)3)2)3Preparation example in alternative embodiment 3
3 Rare-earth chemicals for preparing.
Remaining is in the same manner as in Example 3, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 86.3 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 94.2 weight %, and molecular weight distribution is 2.6.
Comparative example 4
Polymeric articles are prepared according to the method described in embodiment 2, except that, adopt in this comparative example
With the Nd (N (SiMe in Macro.Chem.Phys. (200,1163)3)2)3Preparation example in alternative embodiment 2
2 Rare-earth chemicals for preparing.
Remaining is in the same manner as in Example 2, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 79.8 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 89.3 weight %, and molecular weight distribution is 3.5.
Comparative example 5
Polymeric articles are prepared according to the method described in embodiment 1, except that, adopt in this comparative example
With the Nd (N (SiMe in Macro.Chem.Phys. (200,1163)3)2)3Preparation example in alternative embodiment 1
1 Rare-earth chemicals for preparing.
Remaining is in the same manner as in Example 1, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 8.3 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 89.2 weight %, and molecular weight distribution is 3.7.
By the result of embodiment 1-9 and comparative example 1-5 it is recognised that being prepared into using the method for the present invention
To butadiene/isoprene copolymer butadiene segment unit and isoprene segment unit in it is suitable
- Isosorbide-5-Nitrae linkage content is higher, and the product molecular weight distribution for obtaining is narrower, is adapted to industrialized production.
And, can also be seen that from the result of embodiment 1-9：The copolymerization produce that the method for the present invention is obtained
The cis-content of product is little with the change fluctuation of reaction condition, and molecular weight distribution is also narrower.However, comparative example
The result of 3-5 shows, using containing Nd (N (SiMe3)2)3Catalyst polyreaction when, obtain
Copolymer product in cis-content it is big with the change fluctuation of reaction condition, and the molecular weight of the product for obtaining
Distribution is also wider.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible compound modes.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method for preparing butadiene/isoprene copolymer, the method includes：In polyreaction
Under the conditions of, divinylic monomer and isoprene monomer are carried out into haptoreaction with rare earth catalyst composition,
In the rare earth catalyst composition containing Rare-earth chemicals, the compound containing aluminium element and
Halogen source, the compound containing aluminium element is alkyl aluminum and/or alkyl aluminium hydride, it is characterised in that described
Rare-earth chemicals have the structure shown in formula (I)：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl,
C6-12Aryl, and the R1、R2、R3、R4、R5And R6It is asynchronously in hydrogen and methyl
It is at least one；
L is-OR7Or-NR8, wherein, the R7Formed together with oxygen atom containing 2-10 carbon atom
Heterocycle, the R8The heterocycle containing 2-10 carbon atom or the R are formed together with nitrogen-atoms8
For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
2. method according to claim 1, wherein, in the structure shown in formula (I), M is
Neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-6Alkyl,
C6-10Aryl, and the R1、R2、R3、R4、R5And R6It is asynchronously in hydrogen and methyl
It is at least one；
L is-OR7Or-NR8, wherein, the R7Formed together with oxygen atom containing 2-7 carbon atom
Heterocycle, the R8The heterocycle containing 2-7 carbon atom or the R are formed together with nitrogen-atoms8For
C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
3. method according to claim 2, wherein, in the structure shown in formula (I), M is
Neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, second
Base, n-pro-pyl, isopropyl, normal-butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl,
Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl, and the R1、R2、R3、
R4、R5And R6It is asynchronously at least one in hydrogen and methyl；
L is selected from tetrahydrofuran, pyridine and acetonitrile；
X is 1 or 2, and y=3-x.
4. method according to claim 2, wherein, in the structure shown in formula (I), M is
Neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, second
Base, n-pro-pyl, isopropyl, normal-butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl,
Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl, and the R1、R2、R3、
R4、R5And R6It is asynchronously at least one in hydrogen and methyl；
X is 3, and y is 0.
5. the method according to any one in claim 1-4, wherein, in the rare earth catalyst
In agent compositionss, the content of the Rare-earth chemicals, the compound containing aluminium element and halogen source
Mol ratio is 1：2-10：1-30；Preferably 1：4-8：1-15.
6. the method according to any one in claim 1-4, wherein, the alkyl aluminum is three
One kind in aluminium methyl, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium and three amyl group aluminum
Or it is various；It is preferred that the alkyl aluminum is triisobutyl aluminium and/or triethyl aluminum；
The alkyl aluminium hydride is diethyl aluminium hydride and/or hydrogenation dibutyl aluminum；It is preferred that the hydrogenation alkane
Base aluminum is hydrogenation dibutyl aluminum.
7. the method according to any one in claim 1-4, wherein, the halogen source is alkyl
Aluminum halide；It is preferred that
The aikyl aluminum halide is diethyl aluminum chloride and/or diisobutyl aluminum chloride.
8. method according to claim 1, wherein, the haptoreaction exists in organic solvent
Under carry out, the organic solvent selected from normal hexane, pentane, hexane, heptane, hexamethylene, toluene, two
At least one in toluene and chlorobenzene；It is preferred that
The organic solvent is normal hexane.
9. method according to claim 1, wherein, the catalytic condition includes：Temperature
Spend for 0-100 DEG C, the time is 0.1-24h；It is preferred that
The total amount of the divinylic monomer and the isoprene monomer with it is described dilute in terms of rare earth metal
The mol ratio of the consumption of native carbon monoxide-olefin polymeric is 1000-10000：1.
10. method according to claim 1, wherein, the divinylic monomer and the isoamyl two
The consumption mol ratio of alkene monomer is 1-10：1；Preferably 1-5：1.
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| CN1568332A (en) * | 2001-10-12 | 2005-01-19 | 陶氏环球技术公司 | Metal complex compositions and their use as catalysts to produce polydienes |
| CN101260164A (en) * | 2008-04-29 | 2008-09-10 | 中国科学院长春应用化学研究所 | Catalyst system for cis-1,4-selective polymerization of isoprene or butadiene, its preparation method and usage |
| CN102532368A (en) * | 2010-12-10 | 2012-07-04 | 北京化工大学 | Rare earth catalyst and method for polymerizing conjugated diene by using same |
| CN103980425A (en) * | 2014-06-09 | 2014-08-13 | 山东玉皇化工有限公司 | Preparation method of high-cis-content butadiene-isoprene copolymer |
| CN104130350A (en) * | 2013-05-02 | 2014-11-05 | 中国石油化工股份有限公司 | Butadiene-isoprene co-polymer rubber and preparation method thereof |
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| CN1568332A (en) * | 2001-10-12 | 2005-01-19 | 陶氏环球技术公司 | Metal complex compositions and their use as catalysts to produce polydienes |
| CN101260164A (en) * | 2008-04-29 | 2008-09-10 | 中国科学院长春应用化学研究所 | Catalyst system for cis-1,4-selective polymerization of isoprene or butadiene, its preparation method and usage |
| CN102532368A (en) * | 2010-12-10 | 2012-07-04 | 北京化工大学 | Rare earth catalyst and method for polymerizing conjugated diene by using same |
| CN104130350A (en) * | 2013-05-02 | 2014-11-05 | 中国石油化工股份有限公司 | Butadiene-isoprene co-polymer rubber and preparation method thereof |
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