CN101157737B - Nitrocyclic Carbene Rare Earth Catalysts for Crystalline 3,4-Polyisoprene - Google Patents
Nitrocyclic Carbene Rare Earth Catalysts for Crystalline 3,4-Polyisoprene Download PDFInfo
- Publication number
- CN101157737B CN101157737B CN200710056254A CN200710056254A CN101157737B CN 101157737 B CN101157737 B CN 101157737B CN 200710056254 A CN200710056254 A CN 200710056254A CN 200710056254 A CN200710056254 A CN 200710056254A CN 101157737 B CN101157737 B CN 101157737B
- Authority
- CN
- China
- Prior art keywords
- polyisoprene
- rare earth
- title complex
- sime
- carbine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 89
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- -1 Carbene Rare Earth Chemical class 0.000 title claims description 13
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 25
- 150000001638 boron Chemical class 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 4
- 125000006606 n-butoxy group Chemical group 0.000 claims description 4
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 193
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 60
- 238000006243 chemical reaction Methods 0.000 abstract description 53
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 35
- 239000000178 monomer Substances 0.000 abstract description 25
- 238000006116 polymerization reaction Methods 0.000 abstract description 24
- 230000009477 glass transition Effects 0.000 abstract description 23
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 238000010550 living polymerization reaction Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 3
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 42
- 238000005303 weighing Methods 0.000 description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 40
- 238000004458 analytical method Methods 0.000 description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 30
- 239000001257 hydrogen Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 24
- 238000001291 vacuum drying Methods 0.000 description 24
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 20
- 238000004062 sedimentation Methods 0.000 description 20
- 239000012265 solid product Substances 0.000 description 20
- 230000009466 transformation Effects 0.000 description 20
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 18
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000002902 bimodal effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910052805 deuterium Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- HEGSVUSPVZIRFI-UHFFFAOYSA-N CC.C[P]C Chemical compound CC.C[P]C HEGSVUSPVZIRFI-UHFFFAOYSA-N 0.000 description 1
- TWDJIKFUVRYBJF-UHFFFAOYSA-N Cyanthoate Chemical compound CCOP(=O)(OCC)SCC(=O)NC(C)(C)C#N TWDJIKFUVRYBJF-UHFFFAOYSA-N 0.000 description 1
- 239000000899 Gutta-Percha Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000000342 Palaquium gutta Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005138 cryopreservation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920000588 gutta-percha Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000012781 shape memory material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
用本发明的氮杂环卡宾稀土配合物与烷基铝和有机硼盐组成的催化体系，可以催化异戊二烯进行溶液聚合，制备结晶性、高3，4-结构、高玻璃化转变温度(Tg)的聚异戊二烯。烷基铝与稀土配合物的摩尔比例在1～100范围内，有机硼盐与稀土配合物的摩尔比例在0.5～2.0范围内；聚合所用的溶剂可以是甲苯、溴苯、正己烷、二氯甲烷或氯苯；聚合温度范围是-20℃～80℃，在-20℃聚合时反应时间为36小时，在80℃聚合时反应时间为1小时，单体转化率均可达100％。反应具有活性聚合的特点，产物的分子量可由单体与催化剂的摩尔比控制，所得聚异戊二烯的分子量最高可达36万，玻璃化转变温度Tg＝5℃～50℃。聚异戊二烯3，4结构的含量受稀土配合物的空间效应和电子效应、聚合反应溶剂类型和聚合反应温度等影响，在76％～99％之间变化。The catalytic system composed of the nitrogen-heterocyclic carbene rare earth complex, alkylaluminum and organic boron salt can catalyze the solution polymerization of isoprene to prepare crystallinity, high 3,4-structure, high glass transition temperature (T g ) of polyisoprene. The molar ratio of alkylaluminum to rare earth complexes is in the range of 1 to 100, and the molar ratio of organic boron salts to rare earth complexes is in the range of 0.5 to 2.0; the solvent used for polymerization can be toluene, bromobenzene, n-hexane, dichloro Methane or chlorobenzene; the polymerization temperature ranges from -20°C to 80°C, the reaction time is 36 hours at -20°C, and 1 hour at 80°C, and the monomer conversion rate can reach 100%. The reaction has the characteristics of living polymerization, and the molecular weight of the product can be controlled by the molar ratio of the monomer and the catalyst. The molecular weight of the obtained polyisoprene can reach up to 360,000, and the glass transition temperature T g =5°C-50°C. The content of the polyisoprene 3,4 structure is affected by the steric and electronic effects of the rare earth complex, the type of polymerization solvent and the polymerization temperature, etc., and varies between 76% and 99%.
Description
Technical field
The present invention relates to crystallinity 3, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used.
Background technology
Conjugated diolefin obtains the polymkeric substance of various stereoregular structures by polyreaction, wherein many is synthetic rubber of excellent property, thus the rubber synthetic technology is advanced to the brand-new stage, makes the quality of elastomeric structure, product and quantity that great reform and growth all arranged.Synthetic polyisoprene is called for short polyisoprene rubber (IR), mainly is divided into along 1, and 4-IR, anti-1,4-IR and 3 ', 4-IR three major types.Along 1,4-IR is a kind of universal synthetic rubber, because its molecular structure and performance and natural rubber are very similar, therefore can replace natural rubber.Anti-1,4-IR is called synthetic Chinese gutta percha or Ba Lata glue again, exists with the crystalline polymer form under the normal temperature, has developed to be used for medical material, shape-memory material etc.Along 1,4 structure and anti-1,4 structure is naturally occurring structure, yet 3,4-IR also has important effect, thereby people synthesize it at finding method always.
Along with the construction of rapid development of automobile industry, high-grade highway and improving constantly of automobile speed per hour, people have proposed more and more higher requirement to the safety performance of automobile, and hauling ability and wet-sliding resistant performance become the important indicator of weighing the doughnut performance.But the dynamic viscous-elastic behaviour of rubber intrinsic makes when improving the tire hauling ability, often can't avoid the increase of its rolling resistance and Sheng Re and the decline of abrasion resistance.For this reason, with the synthetic rubber of different glass transition temperature (Tg) and natural rubber blend or adopt integrated rubber to prepare tire tread glue.Because 3, the molecular structure characteristics of 4-polyisoprene rubber are that double bond content is low in the main chain, and containing a large amount of bigger side chains on the building block, good wet performance and the low hysteresis loss of high temperature of grabbing is arranged, is the tartan of a kind of low-heat-generation, high wet-sliding resistant.Make the tread rubber with its preparation both have excellent wet-sliding resistant performance, do not have again styrene-butadiene rubber(SBR) (SRR) serious give birth to heat, can improve the safety performance of tire running, also can be used as sealing material, anti-seismic material and polypropylene toughness-increasing modified dose thereby receive much attention.
But in the catalysis isoprene polymerization research of existing numerous reports, most catalyzed polymerization products are 1,4-cis and 1, the polyisoprene of 4-transconfiguration.Up to now, had only the minority bibliographical information 3, the polyisoprene catalyzer of 4-structure.As AlEt
3-Ti (OR)
4(R is an alkyl), (dmpe)
2CrCl
2-MAO (dmpe 1,2-two (dimethyl-phosphorus) ethane), and some contain nitrogen-atoms coordinate Fe-series catalyst etc.In these catalyst polymerization gained polyisoprene 3, the content of 4-structure is lower than 80%.Hou Zhaomin etc. have reported a kind of double-core yttrium alkyl complexes that contains cyclopentadienyl, can the catalysis isoprene polymerization obtain complete with 3,4-polyisoprene (reference: L.Zhang, Y.Luo, Z.Hou, J.Am.Chem.Soc.2005,127,14562), this is that present rare earth metal complex causes isoprene 3, the unique one piece of report of 4-polymeric.Between Lido Porri etc. has reported with 3,4-polyisoprene (reference: C.Bazzini, L.Porri, Polymer.2004,45,2871), but 3,4 content are 80%.Therefore, the polyisoprene of high 3,4 content of acquisition isostructure seems more and more important.
Summary of the invention
The purpose of this invention is to provide crystallinity 3, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used, form by rare earth compounding, aluminum alkyls and organic boron salt, it is characterized in that, the rare earth metal of rare earth compounding is with the part chelating that contains N-heterocyclic carbine (NHC) group and be connected initiating group, and its structural formula is as follows:
Formula 1
Wherein, R
1Be the modification group of N-heterocyclic carbine, this group and rare earth ion chelating, normally fluorenyl, indenyl, cyclopentadienyl, amino (=NCH (CH
3)
2Or=NC (CH
3)
3), alkoxyl group (OCH
2-,-OCH (
nBu)-,-OCH (CH
2CH
3)-or-OC (CH
3)
2-);
R
2Being the substituting group on the N-heterocyclic carbine, is methyl, ethyl, n-propyl, sec.-propyl, butyl, the tertiary butyl, (2,4,6) trimethylphenyl, (2,6) diisopropyl phenyl, phenyl, pyridyl, cyclohexyl or adamantyl;
Rare earth metal (Ln) is scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu);
R
3Being the initiating group that links to each other with rare earth metal, is alkyl (CH
2SiMe
3, CH (SiMe
3)
2), benzyl, amino (N (SiMe
3)
2), methoxyl group (OCH
3), oxyethyl group (OC
2H
5), isopropoxy (O
iPr), positive propoxy (OPr), n-butoxy (OBu), tert.-butoxy (O
tBu) or halogen atom (F, Cl, Br or I);
R
4Also being the initiating group that links to each other with rare earth metal, is alkyl (CH
2SiMe
3, CH (SiMe
3)
2), benzyl, amino (N (SiMe
3)
2), methoxyl group (OCH
3), oxyethyl group (OC
2H
5), isopropoxy (O
iPr), positive propoxy (OPr), n-butoxy (OBu), tert.-butoxy (O
tBu) or halogen atom (F, Cl, Br or I); R
3And R
4Can be identical, also can be inequality; N=1,2,3 or 4.
Preferred catalysis isoprene 3,4-polymeric aza cyclic carbine rear earth title complex has suc as formula the molecular structural formula of the title complex 1-5 shown in 2 or the molecular structural formula of the title complex 6-10 shown in the formula 3:
Ln=Y, title complex 1
Ln=Ho, title complex 2
Ln=Lu, title complex 3
Ln=Sc, title complex 4
Ln=Gd, title complex 5
Formula 2
Ln=Y, title complex 6
Ln=Ho, title complex 7
Ln=Lu, title complex 8
Ln=Sc, title complex 9
Ln=Gd, title complex 10
Formula 3
Described aluminum alkyls is (CH
3)
3Al, (CH
3)
2AlCl, (CH
3) AlCl
2, (CH
3)
3Al
2Cl
3, (C
2H
5)
3Al, (C
2H
5)
2AlCl, (C
2H
5) AlCl
2, (C
2H
5)
3Al
2Cl
3, (C
2H
5)
2AlOC
2H
5, (
iPr)
3Al, (Pr)
3Al, (
iPr)
2AlH, (
iBu)
3Al, (
iBu)
2AlCl, (
iBu) AlCl
2, (
iBu)
2AlH, (Bu)
3Al or MAO, wherein preferred (
iBu)
3Al and (C
2H
5)
3Al.The molar ratio of aluminum alkyls and rare earth compounding is in 1～100 scope, and preferred molar ratio is 10.
Described organic boron salt is [Ph
3C] [B (C
6F
5)
4], [PhMe
2NH] [B (C
6F
5)
4] or B (C
6F
5)
3, preferred [Ph
3C] [B (CF
5)
4]; The molar ratio of organic boron salt and rare earth compounding is in 0.5～2.0 scope, and preferred molar ratio is 1.0.
The preparation method of catalysis isoprene 3, the 4 selective polymerisation aza cyclic carbine rear earth title complexs among the present invention is described below, and process is as follows:
Under the anhydrous and oxygen-free condition, part that the following formula of equimolar amount is given (Ligand) and lithium alkylide (LiCH
2SiMe
3) be mixed in 20ml～60ml toluene, react after 1～6 hour, their toluene solution is joined trivalent rare earth compound L nR
3R
4(CH
2SiMe
3)
3(THF)
nToluene solution in, reacted 1～24 hour, be concentrated into 2ml～6ml, add the normal hexane of 1ml～10ml, be put in recrystallization in-30 ℃ of refrigerators, spend the night, solid that obtains or crystal are exactly the synthetic title complex of wanting (Complex), wash with normal hexane, vacuum-drying 2 hours, getting its productive rate is 50-60%.
The aza cyclic carbine rear earth catalyst system that crystallinity 3 of the present invention, 4-polyisoprene are used, its step and condition that is used for catalytic method is as follows:
(1), earlier isoprene with dry 2 days of hydrolith, the pure system of underpressure distillation is frozen with liquid nitrogen then, takes out repeatedly with pump, to remove oxygen, cryopreservation is standby under the anhydrous and oxygen-free condition afterwards.
(2), the solution polymerization process of isoprene:
Polymer solvent is selected toluene, normal hexane and chlorobenzene for use, and polymeric reaction temperature is-20 ℃～80 ℃.When polymerization temperature is 25 ℃, carry out polyreaction in glove box, the polyreaction under other temperature shifts out glove box and carries out outward.The mol ratio of monomer and catalyzer is 500～5000, and the reaction times is 1～72 hour, after reaction finishes, is the ethanolic soln termination reaction of 10% hydrochloric acid with volume ratio, solution is put in a large amount of ethanolic solns precipitated again, obtains polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h claims its quality, calculates monomer conversion.
3 of gained polyisoprene, 4-structural content are 76%～99%.The molecular weight of polyisoprene is measured with gel permeation chromatograph (Waters 410), 3 of polyisoprene, and the 4-structural content is calculated by proton nmr spectra.
Beneficial effect: aza cyclic carbine rear earth alkyl complexes of the present invention and Al (
iBu)
3[Ph
3C] [B (C
5F
5)
4] catalyst system catalysis isoprene 3, the 4 selective polymerisations reaction formed has the feature of living polymerization.At normal temperatures, in the hexane solvent, polymerization rate is very fast, and the reaction times is 12 hours, and monomer can reach 100% and transform.Gained polyisoprene molecular weight is higher, and molecular weight distribution is narrower.And, utilization contains the side group (as fluorenyl or indenyl) of different spaces obstacle, regulate the steric effect and the electronic effect of catalyst active center, change the spatial obstacle and the temperature of reaction of promotor simultaneously, the final realization optionally controlled polymer areas, obtains 3, and the 4-structural content is up to 99%, it wherein, is 60% crystallinity polyisoprene product with content.
Embodiment
Preparation embodiment 1 title complex 1 ((Flu-NHC) Y (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.168g part (Flu-H-NHC-H) Br is joined wherein, behind the room temperature reaction 3h, reaction soln is joined 20ml, 0.1.81g Y (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 5h, concentrate toluene solution to 2ml, add the 2ml normal hexane, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 1.With the normal hexane washing, vacuum-drying 2 hours gets 0.145g.Productive rate is 61.7%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum and elemental analysis the structure of title complex 1.
1H?NMR(400MHz，C
6D
6，25℃)：
1.90，-1.59(AB，
2J
H-H＝10.8Hz，4H，Y-CH
2SiMe
3)，0.22(s，18H，Y-CH
2SiMe
3)，1.85(s，6H，C
6H
2Me
3)，2.17(s，3H，C
6H
2Me
3)，3.05(t，
3J
H-H＝4.8Hz，2H，CH
2CH
2)，3.90(t，
3J
H-H＝4.8Hz，2H，CH
2CH
2)，5.89(s，1H，NCH)，6.12(s，1H，NCH)，6.70(s，2H，C
6H
2Me
3)，7.26(t，
3J＝7.4Hz，2H，fluorene)，7.30(d，
3J＝8.4Hz，2H，fluorene)，7.40(d，
3J＝7.4Hz，2H，fluorene)，8.39(d，
3J
H-H＝8.4Hz，1H，fluorene)。With elemental analysis the structure of title complex 1, its molecular formula is C
35H
47YN
2Si
2Wherein carbon content is 64.33; Hydrogen richness is 7.13; Nitrogen content is 4.19.
Preparation embodiment 2 title complexs 2 ((Flu-NHC) Ho (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.168g part (Flu-H-NHC-H) Br is joined wherein, behind the room temperature reaction 3h, reaction soln is joined 30ml, 0.209g Ho (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 6h, concentrate toluene solution to 2ml, add the 2ml normal hexane,, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 2.With the normal hexane washing, vacuum-drying 2 hours gets 0.164g.Productive rate is 62.4%.With elemental analysis the structure of title complex 2, its molecular formula is C
35H
47HoN
2Si
2Wherein carbon content is 57.53; Hydrogen richness is 6.81; Nitrogen content is 3.16.
Preparation embodiment 3 title complexs 3 ((Flu-NHC) Lu (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.168g part (Flu-H-NHC-H) Br is joined wherein, behind the room temperature reaction 6h, reaction soln is joined 30ml, 0.213g Lu (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 6h, concentrate toluene solution to 2ml, add the 2ml normal hexane, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 3.With the normal hexane washing, drying gets 0.180g.Productive rate is 67.7%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum and elemental analysis the structure of title complex 3.
1H NMR (400MHz, C
6D
6, 25 ℃): δ-2.18 ,-1.90 (AB,
2J
H-H=10.8Hz, 4H, Lu-CH
2SiMe
3), 0.22 (s, 18H, Lu-CH
2SiMe
3), 1.85 (s, 6H, C
6H
2Me
3), 2.18 (s, 3H, C
6H
2Me
3), 3.05 (t,
3J
H-H=4.8Hz, 2H, CH
2CH
2), 3.91 (t,
3J
H-H=4.8Hz, 2H, CH
2CH
2), 5.90 (d,
3J
H-H=1.2Hz, 1H, NCH), 6.12 (d,
3J
H-H=1.2Hz, 1H, NCH), 6.70 (s, 2H, C
6H
2Me
3), 7.27 (t,
3J=6.8Hz, 2H, fluorene), 7.32 (d,
3J=8.4Hz, 2H, fluorene), 7.40 (d,
3J=6.8Hz, 2H, fluorene), 8.39 (d,
3J
H-H=8.4Hz, 1H, fluorene); With elemental analysis the structure of title complex 3, its molecular formula is C
35H
47LuN
2Si
2Wherein carbon content is 57.03; Hydrogen richness is 6.67; Nitrogen content is 3.73.
Preparation embodiment 4 title complexs 6 ((Ind-NHC) Y (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.150g part (Ind-H-NHC-H) Br is joined wherein, behind the room temperature reaction 5h, reaction soln is joined 10ml, 0.181g Y (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 6h, concentrate toluene solution to 2ml, add the 3ml normal hexane, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 6.With the normal hexane washing, drying gets 0.135g, and productive rate is 62.5%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum and elemental analysis the structure of title complex 6.
1H NMR (400MHz, C
6D
6, 25 ℃): δ-2.09 ,-1.81 (ABX, dd,
2J
H-H=12.0Hz,
2J
Y-H=4.0Hz, 2H, Y-CH
2SiMe
3) ,-0.86 ,-0.57 (ABX, dd,
2J
H-H=12.0Hz,
2J
Y-H=4.0Hz, 2H, Y-CH
2SiMe
3), 0.28 (s, 9H, Y-CH
2SiMe
3), 0.44 (s, 9H, Y-CH
2SiMe
3), 1.79 (s, 3H, C
6H
2Me
3), 1.92 (s, 3H, C
6H
2Me
3), 2.21 (s, 3H, C
6H
2Me
3), 2.72-2.77 (multi, 1H, CH
2CH
2), 2.81-2.87 (multi, 1H, CH
2CH
2), 3.57-3.62 (multi, 1H, CH
2CH
2), 3.81-3.87 (multi, 1H, CH
2CH
2), 5.88 (d,
3J
H-H=1.2Hz, 1H, NCH), 6.07 (d,
3J
H-H=1.2Hz, 1H, NCH), 6.70 (s, 1H, C
6H
2Me
3), 6.80 (s, 1H, C
6H
2Me
3), 6.77,6.81 (AB,
3J
HH=3.2Hz, 2H, indene), 7.08-7.19 (multi, 3H, indene), 7.93-7.95 (d,
3J
H-H=8.4Hz, 1H, indene); With elemental analysis the structure of title complex 6, its molecular formula is C
31H
45YN
2Si
2Wherein carbon content is 62.91; Hydrogen richness is 7.56; Nitrogen content is 4.69.
Preparation embodiment 5 title complexs 7 ((Ind-NHC) Ho (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.150g part (Ind-H-NHC-H) Br is joined wherein, behind the room temperature reaction 4h, reaction soln is joined 30ml, 0.209gHo (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 1h, concentrate toluene solution to 3ml, add the 4ml normal hexane,, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 7.With the normal hexane washing, drying gets 0.154g, and productive rate is 63.1%.With elemental analysis the structure of title complex 7, its molecular formula is C
31H
45HoN
2Si
2, wherein carbon content is 64.92; Hydrogen richness is 6.87; Nitrogen content is 4.08.Preparation embodiment 6 title complexs 8 ((Ind-NHC) Lu (CH
2SiMe
3)
2) preparation, its process is as follows:
In glove box, with the LiCH of 0.035g
2SiMe
3Be dissolved in the toluene of 30mL, and 0.150g part (Ind-H-NHC-H) Br is joined wherein, behind the room temperature reaction 1h, reaction soln is joined 30ml, 0.213g Lu (CH
2SiMe
3)
3(THF)
2Toluene solution in, continue reaction 6h, concentrate toluene solution to 2ml, add the 3ml normal hexane, be put in recrystallization in-30 ℃ of refrigerators, spend the night, obtain yellow crystals title complex 8.With the normal hexane washing, drying gets 0.171g, and productive rate is 68.9%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum and elemental analysis the structure of title complex 8.
1H NMR (400MHz, C
6D
6, 25 ℃): δ-2.44 ,-2.09 (AB,
2J
H-H=2.0Hz, 2H, Lu-CH
2SiMe
3) ,-1.08 ,-0.78 (AB,
2J
H-H=12.0Hz, 2H, Lu-CH
2SiMe
3), 0.30 (s, 9H, Lu-CH
2SiMe
3), 0.45 (s, 9H, Lu-CH
2SiMe
3), 1.77 (s, 3H, C
6H
2Me
3), 1.92 (s, 3H, C
6H
2Me
3), 2.21 (s, 3H, C
6H
2Me
3), 2.70-2.76 (multi, 1H, CH
2CH
2), 2.79-2.86 (multi, 1H, CH
2CH
2), 3.54-3.59 (multi, 1H, CH
2CH
2), 3.83-3.90 (multi, 1H, CH
2CH
2), 5.87 (d,
3J
H-H=1.6Hz, 1H, NCH), 6.06 (d,
3J
H-H=1.6Hz, 1H, NCH), 6.69 (s, 1H, C
6H
2Me
3), 6.75,6.76 (AB,
3J=2.4Hz, 2H, indene), 6.79 (s, 1H, C
6H
2Me
3), 7.10 (s, 1H, Indene), 7.11 (s, 1H, indene), 7.16-7.21 (multi, 1H, indene), 7.93-7.95 (d,
3J
H-H=8.0Hz, 1H, indene); With elemental analysis the structure of title complex 8, its molecular formula is C
31H
45LuN
2Si
2Wherein carbon content is 54.49; Hydrogen richness is 6.11; Nitrogen content is 3.97.
Application Example 1
In glove box, take by weighing 0.0064g (10 μ mol) title complex 1, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and title complex 1 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.7 ten thousand, M
w/ M
n=1.09.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 98% in the chain microstructure.Glass transition temperature Tg=42 ℃.
Application Example 2
In glove box, take by weighing 0.0072g (10 μ mol) title complex 2, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 2 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=3.9 ten thousand, M
w/ M
n=1.08.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 98% in the chain microstructure.Glass transition temperature Tg=43 ℃.
Application Example 3
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.0 ten thousand, M
w/ M
n=1.12.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 99% in the chain microstructure.Glass transition temperature Tg=45 ℃.
Application Example 4
In glove box, take by weighing 0.0059g (10 μ mol) title complex 6, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 6 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.17g, transformation efficiency 50%.Use gpc analysis, the molecular weight M of polyisoprene
n=2.1 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 89% in the chain microstructure.Glass transition temperature Tg=23 ℃.
Application Example 5
In glove box, take by weighing 0.0067g (10 μ mol) title complex 7, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 7 is 500.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.1 ten thousand, M
w/ M
n=1.4.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 76% in the chain microstructure.Glass transition temperature Tg=5 ℃.
Application Example 6
In glove box, take by weighing 0.0068g (10 μ mol) title complex 8, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 8 is 500.React on 25 ℃ and carry out 36h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=3.7 ten thousand, M
w/ M
n=1.16.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 91% in the chain microstructure.Glass transition temperature Tg=20 ℃.
Application Example 7
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 40 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 40 ℃ carry out 3h after, after the ethanolic soln that adds 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=3.3 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 97% in the chain microstructure.Glass transition temperature Tg=49 ℃.
Application Example 8
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 50 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 50 ℃ and carry out 3h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.0 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 97% in the chain microstructure.Glass transition temperature Tg=47 ℃.
Application Example 9
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 60 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 60 ℃ and carry out 2h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=3.5 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 95% in the chain microstructure.Glass transition temperature Tg=47 ℃.
Application Example 10
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mo1) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 70 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 70 ℃ and carry out 2h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight of polyisoprene is bimodal distribution, M
n=4.6 ten thousand, 1.2 ten thousand, M
w/ M
n=1.2,1.1.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 95% in the chain microstructure.Glass transition temperature Tg=45 ℃.
Application Example 11
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 80 ℃ of oil baths, after 5 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 80 ℃ and carry out 2h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight of polyisoprene is bimodal distribution, M
n=4.6 ten thousand, 1.2 ten thousand, M
w/ M
n=1.2,1.1.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 94% in the chain microstructure.Glass transition temperature Tg=46 ℃.
Application Example 12
In glove box, take by weighing 0.0068g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Hexane solution, again to the hexane that wherein adds 2.6ml; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4, and with [Ph
3C] [B (C
6F
5)
4] powder is in the round-bottomed flask of containing catalyzer.After 30 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 25 ℃ and carry out 12h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.05g, transformation efficiency 15%.Use gpc analysis, the molecular weight of the molecular weight isoprene of polyisoprene is bimodal distribution, M
n=5.1 ten thousand, 3.3 ten thousand, M
w/ M
n=1.2,1.6.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 98% in the chain microstructure.Glass transition temperature Tg=42 ℃.
Application Example 13
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Hexane solution, add the hexane of 2.6ml again; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], and with [Ph
3C] [B (C
6F
5)
4] powder is added in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 40 ℃ of oil baths, after 10 minutes, in reaction vessel, add 0.5ml (5mmol) isoprene, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 40 ℃ and carry out 12h, after the ethanolic soln of adding 1ml10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight of polyisoprene is bimodal distribution, M
n=3.5 ten thousand, 2.2 ten thousand, M
w/ M
n=1.2,1.7.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 97% in the chain microstructure.Glass transition temperature Tg=41 ℃.
Application Example 14
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 100ml polymerization bottle, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Hexane solution, add the hexane of 2.6ml again; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], and with [Ph
3C] [B (C
6F
5)
4] powder is added in the polymerization bottle of containing catalyzer, with the stopper plug good after, reaction vessel is taken out glove box, place 50 ℃ of oil baths, after 10 minutes, in reaction vessel, add 0.5ml (5mmol) isoprene, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 50 ℃ and carry out 12h, after the ethanolic soln of adding 1ml10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight of polyisoprene is bimodal distribution, M
n=2.8 ten thousand, 1.6 ten thousand, M
w/ M
n=1.2,1.8.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 97% in the chain microstructure.Glass transition temperature Tg=40 ℃.
Application Example 15
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Chlorobenzene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 2.6ml chlorobenzene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 0.5ml (5mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 500.React on 25 ℃ and carry out 3h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.34g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=4.2 ten thousand, M
w/ M
n=1.07.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 98% in the chain microstructure.Glass transition temperature Tg=45 ℃.
Application Example 16
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 5.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 1.0ml (10mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 1000.React on 25 ℃ and carry out 24h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 0.68g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=8.6 ten thousand, M
w/ M
n=1.2.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 96% in the chain microstructure.Glass transition temperature Tg=49 ℃.
Application Example 17
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 8.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 2.0ml (10mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 2000.React on 25 ℃ and carry out 36h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 1.36g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=23.8 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 96% in the chain microstructure.Glass transition temperature Tg=48 ℃.
Application Example 18
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 10.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 3.0ml (30mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 3000.React on 25 ℃ and carry out 48h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 2.04g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=30.9 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 96% in the chain microstructure.Glass transition temperature Tg=49 ℃.
Application Example 19
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 10.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add 4.0ml (40mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 4000.React on 25 ℃ and carry out 56h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 2.64g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=32.5 ten thousand, M
w/ M
n=1.4.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 94% in the chain microstructure.Glass transition temperature Tg=46 ℃.
Application Example 20
In glove box, take by weighing 0.0073g (10 μ mol) title complex 3, be put in the 25ml round-bottomed flask, then to wherein add 0.4ml (0.25M) Al (
iBu)
3Toluene solution; Take by weighing 0.0088g (10 μ mol) [Ph
3C] [B (C
6F
5)
4], with the dissolving of 12.6ml toluene, and with [Ph
3C] [B (C
6F
5)
4] toluene solution be added drop-wise in the round-bottomed flask of containing catalyzer.After 30 minutes, add emerging 5.0ml (50mmol) isoprene in reaction vessel, wherein the mol ratio of monomer and catalyzer 3 is 5000.React on 25 ℃ and carry out 6h, after the ethanolic soln of adding 1ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the 100ml ethanol into, get the white solid product polyisoprene.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets polyisoprene net weight 3.40g, transformation efficiency 100%.Use gpc analysis, the molecular weight M of polyisoprene
n=35.9 ten thousand, M
w/ M
n=1.3.Use the hydrogen nuclear magnetic resonance spectrum analysis, 3,4 content 93% in the chain microstructure.Glass transition temperature Tg=47 ℃.
Claims (7)
1. crystallinity 3, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used, form by rare earth compounding, aluminum alkyls and organic boron salt, it is characterized in that, the rare earth metal of described rare earth compounding is with the part chelating that contains N-heterocyclic carbine (NHC) group and be connected initiating group, its structural formula as shown in Equation 1:
Formula 1
Wherein, R
1Be fluorenyl, be the modification group of N-heterocyclic carbine, this group and rare earth ion chelating;
R
2Being the substituting group on the N-heterocyclic carbine, is the tertiary butyl, (2,4,6) trimethylphenyl, (2,6) diisopropyl phenyl, phenyl, cyclohexyl or adamantyl;
Rare earth metal (Ln) is scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu);
R
3Being the initiating group that links to each other with rare earth metal, is CH
2SiMe
3, CH (SiMe
3)
2, benzyl, N (SiMe
3)
2, methoxyl group (OCH
3), oxyethyl group (OC
2H
5), isopropoxy (O
iPr), positive propoxy (OPr), n-butoxy (OBu), tert.-butoxy (O
tBu) or the F of halogen atom, Cl, Br or I;
R
4Also being the initiating group that links to each other with rare earth metal, is CH
2SiMe
3, CH (SiMe
3)
2, benzyl, N (SiMe
3)
2, methoxyl group (OCH
3), oxyethyl group (OC
2H
5), isopropoxy (O
iPr), positive propoxy (OPr), n-butoxy (OBu), tert.-butoxy (O
tBu) or the F of halogen atom, Cl, Br or I; R
3And R
4Identical or inequality; N=1,2,3 or 4;
Wherein said aluminum alkyls is (CH
3)
3Al, (CH
3)
2AlCl, (CH
3) AlCl
2, (CH
3)
3Al
2Cl
3, (C
2H
5)
3Al, (C
2H
5)
2AlCl, (C
2H
5) AlCl
2, (C
2H
5)
3Al
2Cl
3, (C
2H
5)
2AlOC
2H
5, (
iPr)
3Al, (
iPr)
2AlH, (
iBu)
3Al, (
iBu)
2AlCl, (
iBu) AlCl
2, (
iBu)
2AlH or MAO; The molar ratio of aluminum alkyls and rare earth compounding is 10～100.
2. crystallinity 3 as claimed in claim 1, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, the R of described rare earth compounding
1Be fluorenyl, the molecular structural formula of title complex 1-5 is as follows:
Ln=Y, title complex 1
Ln=Ho, title complex 2
Ln=Lu, title complex 3
Ln=Sc, title complex 4
Ln=Gd, title complex 5.
3. crystallinity 3 as claimed in claim 1, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, described aluminum alkyls be (
iBu)
3Al or (C
2H
5)
3Al.
4. crystallinity 3 as claimed in claim 1 or 2, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, the mol ratio of described aluminum alkyls and rare earth compounding is 10.
5. crystallinity 3 as claimed in claim 1, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, described organic boron salt is [Ph
3C] [B (C
6F
5)
4], [PhMe
2NH] [B (C
6F
5)
4] or B (C
6F
5)
3The mol ratio of organic boron salt and rare earth compounding is 0.5～2.0.
6. crystallinity 3 as claimed in claim 5, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, described organic boron salt is [Ph
3C] [B (C
6F
5)
4].
7. as claim 5 or 6 described crystallinity 3, the aza cyclic carbine rear earth catalyst that the 4-polyisoprene is used is characterized in that, the mol ratio of described organic boron salt and rare earth compounding is 1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710056254A CN101157737B (en) | 2007-10-30 | 2007-10-30 | Nitrocyclic Carbene Rare Earth Catalysts for Crystalline 3,4-Polyisoprene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710056254A CN101157737B (en) | 2007-10-30 | 2007-10-30 | Nitrocyclic Carbene Rare Earth Catalysts for Crystalline 3,4-Polyisoprene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101157737A CN101157737A (en) | 2008-04-09 |
| CN101157737B true CN101157737B (en) | 2010-05-26 |
Family
ID=39305984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710056254A Active CN101157737B (en) | 2007-10-30 | 2007-10-30 | Nitrocyclic Carbene Rare Earth Catalysts for Crystalline 3,4-Polyisoprene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101157737B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8664343B2 (en) * | 2008-06-20 | 2014-03-04 | Bridgestone Corporation | Catalysts for preparing cis 1,4-polydienes |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675614A (en) * | 2012-05-08 | 2012-09-19 | 南京工业大学 | Method for preparing polyamino acid block polyhydroxy acid copolymer |
| CN103739747B (en) * | 2013-12-16 | 2016-06-01 | 中国科学院长春应用化学研究所 | Rare earth catalyst combination and the 3,4-for isoprene compounds thereof are polymerized |
| CN104311585A (en) * | 2014-09-10 | 2015-01-28 | 安徽师范大学 | Rare earth complex, catalyst composition for preparation of isoprene rubber and preparation method thereof, and preparation method of isoprene rubber |
| CN104650270B (en) * | 2014-11-10 | 2018-04-27 | 中国科学院长春应用化学研究所 | A kind of preparation method of the poly- beta-myrcenes of 3,4- |
| CN106397648B (en) * | 2016-08-30 | 2019-03-05 | 中国科学院长春应用化学研究所 | The poly- conjugated diolefin of high 3,4- of the side arm with unsaturated group or functional group and its their preparation method |
| CN106632767B (en) * | 2016-12-23 | 2019-08-20 | 大连理工大学 | A class of rare earth catalysts containing nitrogen-containing heterocyclic carbene ligands and a method for catalyzing olefin polymerization |
| CN110218274B (en) * | 2019-06-20 | 2020-07-31 | 中国科学院长春应用化学研究所 | Preparation method of ethylene-conjugated diene random copolymer |
| CN114437273B (en) * | 2020-10-30 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of butyl rubber |
| CN113307901B (en) * | 2021-06-09 | 2022-07-15 | 中国科学院长春应用化学研究所 | A kind of preparation method of ethylene-isoprene random copolymer, rubber composition and rubber product |
-
2007
- 2007-10-30 CN CN200710056254A patent/CN101157737B/en active Active
Non-Patent Citations (6)
| Title |
|---|
| Baoli Wang et al..Synthesis of the first rare earth metal bis(alkyl)s bearing anindenyl functionalized N-heterocyclic carbene.Organometallics26 13.2007,26(13),3167-3172. |
| Baoli Wang et al..Synthesis of the first rare earth metal bis(alkyl)s bearing anindenyl functionalized N-heterocyclic carbene.Organometallics26 13.2007,26(13),3167-3172. * |
| Baoli Wang et al..Synthesis of the first rare earth metal bis(alkyl)s bearinganindenyl functionalized N-heterocyclic carbene.Organometallics26 13.2007,26(13),3167-3172. |
| Baoli Wang et al..Synthesis of the first rare earth metal bis(alkyl)s bearinganindenyl functionalized N-heterocyclic carbene.Organometallics26 13.2007,26(13),3167-3172. * |
| Stephen P. Downing et al..Indenyl- and fluorenyl-functionalized N-heterocyclic carbenecomplexes of Titanium, Zirconium, Vanadium, Chromium, andYttrium.Organometallics26 15.2007,26(15),3762-3770. |
| Stephen P. Downing et al..Indenyl- and fluorenyl-functionalized N-heterocyclic carbenecomplexes of Titanium, Zirconium, Vanadium, Chromium, andYttrium.Organometallics26 15.2007,26(15),3762-3770. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8664343B2 (en) * | 2008-06-20 | 2014-03-04 | Bridgestone Corporation | Catalysts for preparing cis 1,4-polydienes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101157737A (en) | 2008-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101157737B (en) | Nitrocyclic Carbene Rare Earth Catalysts for Crystalline 3,4-Polyisoprene | |
| JP6302565B2 (en) | Metallocene complex, method for producing the same, and catalyst composition | |
| CN103030724B (en) | Copolymerization method of alpha-olefin and polar group-containing olefin | |
| CN110272515A (en) | The preparation method of ethylene copolymer | |
| CN103739747B (en) | Rare earth catalyst combination and the 3,4-for isoprene compounds thereof are polymerized | |
| CN102336846A (en) | Loaded alpha-palladium diimine and method for preparing hyperbranched polyethylene by catalyzing with same | |
| CN110272513A (en) | The method of post-metallocene catalyst precursor and preparation method thereof and catalyst and its application and ethylene homo | |
| CN101792498B (en) | Alpha-diimine rare-earth metal catalyst and preparation method and application thereof | |
| CN101397348B (en) | Catalytic system for isoprene or butadiene high cis-1,4- selective polymerization, preparation method and use thereof | |
| CN104177529B (en) | Ternary rare earth ethylene propylene rubber and preparation method thereof | |
| CN101704848B (en) | Rare earth allyl complex with constrained geometry configuration, preparation method thereof and applications thereof in conjugated diene high-cis-1, 4-selective polymerization | |
| CN105037588B (en) | A kind of iso-indoles rare-earth metal catalyst, preparation method and application | |
| CN101100490B (en) | Catalytic 3,4 Selective Polymerization of Non-Rare Earth Alkyl Complexes of Isoprene | |
| CN101519469A (en) | Diene polymer and production process thereof | |
| CN107312115B (en) | A kind of bisindole rare earth metal catalyst, preparation method and application | |
| CN102633840A (en) | Clamp-type iron complex and preparation method and application thereof | |
| CN102432758B (en) | Method for preparing styrene-isoprene-butadiene terpolymer | |
| CN107286280B (en) | Preparation method of coordination polymerization of 1,4-poly-3-methylenecyclopentene | |
| CN108822237A (en) | A kind of pyridine imine palladium（Ⅱ）The method that catalyst preparation and catalysis ethylene prepare oily phase oligomer | |
| CN103724378B (en) | Isoprene-butadiene bipolymer and preparation method thereof | |
| CN104017121B (en) | The method being prepared the region block copolymer of isoprene, myrcene by chain transfer reaction | |
| CN112194748A (en) | Polyisoprene and preparation method thereof | |
| CN103936974B (en) | A kind of rare earth metal complex catalyst and its preparation method and application | |
| CN106916240B (en) | Method for preparing rare earth isoprene rubber catalyst | |
| CN104710444B (en) | Rare earth catalyst is combined and its for preparing the isoprenoid polymer of crystallinity 3,4 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20130926 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 130022 CHANGCHUN, JILIN PROVINCE TO: 213000 CHANGZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130926 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190116 Address after: 130022 No. 5625 Renmin Street, Jilin, Changchun Patentee after: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences Address before: No. 9, river Hai Dong Road, Changzhou, Jiangsu Province Patentee before: Changzhou Institute of Energy Storage Materials & Devices |