CN101260164B - Syn form 1,4-selectivity polymerization catalysis system for Isoprene or butadiene and preparation method and using method - Google Patents
Syn form 1,4-selectivity polymerization catalysis system for Isoprene or butadiene and preparation method and using method Download PDFInfo
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Abstract
The invention relates to an isoprene or butadiene cis 1, 4-selective polymerization catalyst system and a preparation method and a use method. The catalyst system consists of NCN-imine forcipate rare earth complex and alkylating reagent, wherein the molecular formula of the rare earth complex is [2, 6-(2, 6-R<3>2-4-R<4>-C6H2N=CR<2>)2-4-R<1>-C6H2] LnX2 (THF)2; during the catalytic polymerization of diolefin, hexane, benzene, toluene, xylene or chlorobenzene is used as the solvent; alkylating reaction between the alkylating reagent and the NCN-imine forcipate rare earth complex is carried out at 20 to 80 DEG C for 0.5 to 5 hours according to proportioning; moreover, polymerization temperature ranges between minus 20 and plus 120 DEG C, and polymerization time is 1 hour to 30 hours; monomer conversion rate is 100 percent; the content of cis 1, 4 in the synthesized polyisoprene and polybutadiene reaches 98 to 99.9 percent; number-average molecular weight ranges between 50,000 and 3,000,000 and molecular weight distribution is less than 3.0; moreover, the catalyst system has tension crystallinity and transparency.
Description
Technical field
The present invention relates to isoprene or divinyl along 1, the catalyst system of 4-selective polymerisation and method for making and usage.
Background technology
High is one of synthetic rubber kind of high comprehensive performance along 1 and polyisoprene, has a wide range of applications at aspects such as civilian, automobile, aircraft manufacturing, aerospace.Particularly since in the polyisoprene structure along 1,4-content reaches 99% o'clock its performance and can compare favourably with natural rubber.Since first invention rare earth compound of the sixties in last century China can catalysis diolefin polymerization, each big rubber company develops a series of catalyst system on this basis, and applied for series of patents, major cause is to compare with other metals such as catalyst system such as titanium, nickel, rare-earth catalysis system is in the catalytic activity and suitable 1 to isoprene and polymerizing butadiene, 4-selectivity aspect all is better than other system, and the polyisoprene of gained and polybutadiene rubber to have over-all properties superior to characteristics such as few, the easy processing of gel, wear-resisting, anti tear and green strength height.Yet the catalyst system prescription that these patents are related is the improvement on the bases such as rare earth carboxylate of China scientific worker invention basically, and primary catalyst component changes very little.Roughly be divided into soluble three component neodymium series: soluble carboxylic acid neodymium/alkylating reagent (as aluminum alkyls)/halogenide; Bicomponent system: insoluble Neodymium trichloride/Lewis yogurt alcohol, amine, phosphoric acid etc.; In recent years four catalytic systems have been developed again: soluble carboxylic acid neodymium/alkylating reagent (as aluminum alkyls)/alkyl halide/conjugative monomer.The catalyst system that adopts such as the anti-slippery and low-rolling-resistance rubber of Japanese JSR company exploitation is made up of the product that reacts with rare earth compound, aikyiaiurnirsoxan beta, aluminum alkyls and the metal chloride of Lewis alkali reaction and Lewis base that (US 4,468,496 (1985)); Adopt rare earth carboxylate/aikyiaiurnirsoxan beta/metal chloride catalysis divinyl along 1,4-polymerization selectivity is no more than 90%, molecular weight distribution broad (＜4.0) (US6,391,990 B1 (2002), US 6,838,526 B1 (2005), US 2003/0065083A1, US2005/0009979 A1).RE phosphate/alkylating reagent/the halogen donator of France Mechelin company application or RE phosphate/alkylating reagent/halogen donator/conjugative monomer catalyst system energy catalysis diolefin polymerization, along 1, the 4-selectivity is brought up to more than 98%, but if realize greater than 99% along 1, the 4-selectivity select to need reduces polymerization temperature to-55 ℃, and rubber is no more than 80 (US6,838 at 100 ℃ Mooney point, 534 B2 (2005), US 6,858,686 B2 (2005), US 6,949,489 B1 (2005), US 6,992,157 B2 (2006)).U.S. Goodyear Tire ﹠amp; The patent US6 of Rubber company application, 713,565 B2, S7,022,783B2 (2006); US H2036H (2002); US2005/0137338A1 (2005) relates to carboxylic acid neodymium/aluminum alkyls/halogen contained compound/conjugative monomer catalyst system, catalysis isoprene high cis 1, the 4-polymerization or with the divinyl random copolymerization, along 1, the 4-selectivity can reach more than 98%.The equal polymerization of conjugated alkene is reached rare earth metallocene/aluminum alkyls/organic boron salt cation catalyst system of Riken researchist's application and the copolymerization of halogen-containing alkene has very high catalytic activity, and polyreaction has characteristics (US2002/0119889, the US6 of living polymerization, 596,828 (2003), US6,960,631B2, US6,683,140B2), but obtain to be higher than suitable 1,4 selectivity 95% or more, must be lower than under-20 ℃ the polymerization temperature and carrying out.
The contriver has invented the cationic catalyst system of three components that NCN-imines clamp type rareearth halogenide and aluminum alkyls, organic boron salt are formed, to divinyl or isoprene polymerization have greater than 98% suitable-1,4 selectivity, catalytic efficiency is about 20%, monomer and catalyst molar ratio can reach 2000: 1, described catalyst system is different fully with any catalyst system of reporting in the past, it is along 1, the 4-selectivity can keep (reference: Wei Gao in 20～80 ℃ of scopes, Dongmei Cui, J.Am.Chem.Soc.2008,130,4984-4991; Chinese patent 200710056309.2.)
Summary of the invention
The purpose of this invention is to provide isoprene or divinyl along 1, the catalyst system of 4-selective polymerisation and method for making and usage.
The contriver further expands NCN-imines clamp type rareearth halogenide, has invented to contain substituent NCN-imines clamp type rareearth halogenide, NCN-imines clamp type rareearth alkylide, the carboxylated thing of NCN-imines clamp type rareearth, NCN-imines clamp type rareearth alcoxylates and NCN-imines clamp type rareearth phenolic group thing; And by with above-mentioned NCN-imines clamp type rareearth complexes and alkylating reagent at 20～80 ℃, carry out alkylated reaction under 5～0.5 hours conditions, prepare at C
5～C
20Aliphatic solvents in soluble two-pack catalyst system; Adopt that described catalyst system can prepare that number-average molecular weight is adjustable in 5～3,000,000 scopes, molecular weight distribution less than 3.0, stretch crystallization, transparent polyisoprene or polyhutadiene.Monomer and catalyst molar ratio are (500: 1)～(40000: 1).
Isoprene provided by the invention or divinyl be along 1, the catalyst system of 4-selective polymerisation, be by molecular formula for [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2The NCN-imines clamp type rareearth complexes and the two-pack of alkylating reagent form;
Described alkylating reagent is that molecular formula is AlR
3Aluminum alkyls or molecular formula be HAlR
2Alkyl-al hydride, the molar ratio of itself and described NCN-imines clamp type rareearth complexes is (2: 1)～(100: 1);
Described alkylating reagent is that molecular formula is AlR
2The alkyl aluminum chloride of Cl, the molar ratio of itself and described NCN-imines clamp type rareearth complexes is (2: 1)～(50: 1);
Described alkylating reagent is an aikyiaiurnirsoxan beta, and the molar ratio of itself and described NCN-imines clamp type rareearth complexes is (2: 1)～(1000: 1).
R in the molecular formula of described NCN-imines clamp type rareearth complexes
1Be the substituting group on the skeleton phenyl ring, be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, methoxyl group, phenyl, benzyl, chlorine, bromine, iodine or trimethyl silicon based; R
2Be the substituting group on the imines carbon atom, be methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl or hydrogen; R
3Be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, methoxyl group, nitro, phenyl, benzyl, chlorine, bromine, iodine or trimethyl silicon based; R
4Be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, methoxyl group, nitro, phenyl, benzyl, chlorine, bromine, iodine or trimethyl silicon based; Rare earth metal (Ln) is scandium (Sc), yttrium (Y), lanthanum (La), Cerium (Ce), Praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu); Wherein, preferred yttrium (Y), lanthanum (La), neodymium (Nd), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) or lutetium (Lu); X is F
-, Cl
-, Br
-Or I
-, preferred Cl
-Or Br
-Perhaps, X is CH
2SiMe
3, CH
2C
6H
4-6-N (CH
3)
2, CH (SiMe
3)
2, preferred CH
2SiMe
3Perhaps, X is OCH
3, OCH
2CH
3, OCH (CH
3)
2, OCH (CH
3)
2, preferred OCH (CH
3)
2Perhaps, X is OCO (CH
2)
6CH
3, OCOCH (C
2H
5) (CH
2)
3CH
3, OC
6H
5, OC
6H
3-2,6-(CH
3)
2, OC
6H
3-2,6-(CH
2CH
3)
2, OC
6H
3-2,6-
iPr
2, preferred OC
6H
3-2,6-(CH
3)
2
Described molecular formula is AlR
3Aluminum alkyls be preferably trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium, diethyl benzyl aluminium, preferred triisobutyl aluminium, three amyl group aluminium or three hexyl aluminium; The mol ratio of its consumption and NCN-imines clamp type rareearth complexes is (2: 1)～(100: 1), preferred (10: 1)～(50: 1);
Described molecular formula is HAlR
2Alkyl-al hydride be preferably dimethyl hydrogenation aluminium, ADEH, di aluminum hydride, di-n-butyl aluminum hydride, di-isopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, phenylbenzene aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride, ethyl p-methylphenyl aluminum hydride, preferred di-isopropyl aluminum hydride or diisobutyl aluminium hydride; The mol ratio of its consumption and NCN-imines clamp type rareearth complexes is (2: 1)～(100: 1), preferred (10: 1)～(50: 1);
Described molecular formula is AlR
2The alkyl aluminum chloride of Cl is preferably dimethylaluminum chloride, ADEH, di aluminum hydride, di-n-butyl aluminum hydride, di-isopropyl aluminum hydride, diisobutyl aluminum chloride, diamyl aluminum chloride, dihexylaluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, phenylbenzene aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, Ethylbenzyl chlorination aluminium, ethyl p-methylphenyl aluminum chloride, preferred di-isopropyl aluminum hydride, diisobutyl aluminum chloride, diamyl aluminum chloride; The mol ratio of its consumption and NCN-imines clamp type rareearth complexes is (2: 1)～(100: 1), preferred (5: 1)～(15: 1);
Described aikyiaiurnirsoxan beta is preferably methylaluminoxane, ethyl aikyiaiurnirsoxan beta, n-propyl aikyiaiurnirsoxan beta, normal-butyl alumina alkane.The mol ratio of its consumption and NCN-imines clamp type rareearth complexes is (2: 1)～(1000: 1), preferred (10: 1)～(500: 1).
Preferred molecular formula be [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2NCN-imines clamp type rareearth complexes be in the following 1-9 chemical formula any one:
Title complex 1:Ln is Y, R
1, R
2, R
4Be H, R
3Be CH
3Title complex 2:Ln is Y, R
1Be CH
3, R
2, R
4Be H, R
3Be CH
2CH
3, X is Cl; Title complex 3:Ln is Y, R
1Be CH
2CH
3, R
2, R
4Be H, R
3For
iPr, X are Cl; Title complex 4:Ln is Nd, R
1, R
2, R is H, R
3Be CH
2CH
3, X is Cl; Title complex 5:Ln is Gd, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is Br; Title complex 6:Ln is La, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is Br; Title complex 7:Ln is Ho, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is CH
2SiMe
3Title complex 8:Ln is Lu, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is OCO (CH
2)
6CH
3Title complex 9:Ln is Sc, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is OC
6H
3-2,6-(CH
3)
2
Molecular formula of the present invention be [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2The reactional equation of NCN-imines clamp type rareearth complexes suc as formula shown in the 1-1:
Formula 1-1
Among the formula 1-1, Ln represents rare earth element; X represents haloid element, alkyl, alkoxyl group, carboxyl and phenol oxygen base; THF is a coordinate tetrahydrofuran solvent molecule; M is the ligancy of tetrahydrofuran (THF), and the span of m is 0～2.
Isoprene of the present invention or divinyl are along 1, and the preparation method's of the catalyst system of 4-selective polymerisation step and condition are as follows:
Molecular formula be [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2The preparation of NCN-imines clamp type rareearth complexes:
Under-80～10 ℃ of conditions, with concentration is that the hexane solution of the butyllithium of 1.0～3.0mol/L is added drop-wise to part 2,6-(2, the two alkyl phenyl imines of 6-) between in the hexane suspension liquid of phenyl aldehyde imido grpup-1-bromine, the molar ratio of butyllithium and part is (0.9: 1)～(1.5: 1), reacted 3～10 hours, rare earth chloride is added in this reaction solution, the mol ratio of rare earth chloride and part is 1: 1, question response liquid continues reaction 8～10 hours after being raised to room temperature naturally, and vacuum is taken out and desolvated, and resistates extracts with toluene, concentrate toluene solution, obtain NCN-imines clamp type rareearth muriate;
NCN-imines clamp type rareearth muriate is dissolved in the toluene, adds the tetrahydrofuran solution that waits the mole lithium alkylide, react to remove after 1 hour and desolvate, obtain NCN-imines clamp type rareearth alkylate;
NCN-imines clamp type rareearth alkylide is dissolved in the toluene, the tetrahydrofuran solution of mol of alcohol, carboxylic acid or phenol such as slowly splashes into respectively, react to remove after 10 minutes and desolvate, obtain NCN-imines clamp type rareearth alkoxyl group, phenol oxygen base or carboxylic acid group's title complex respectively;
Isoprene or divinyl is along 1, the preparation of the catalyst system of 4-selective polymerisation:
By proportioning be molecular formula [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2NCN-imines clamp type rareearth complexes and aluminum alkyls, alkyl-al hydride, alkyl aluminum chloride or the aikyiaiurnirsoxan beta of alkylating reagent, at C
5～C
20Aliphatic solvents in mix, at 20～80 ℃, carried out alkylated reaction 0.5～3 hour, obtain two-pack solubility homogeneous catalysis system.
Isoprene or divinyl are along 1, the usage of the catalyst system of 4-selective polymerisation: get isoprene or divinyl along 1, the hexane of the catalyst system of 4-selective polymerisation or toluene solvant place through anhydrous, in the reactor that anaerobic is handled, the ratio of clamp type rareearth complexes is 100～1000 liters/mole in described solvent and the described catalyst system, gained solution adds isoprene or divinylic monomer at 20～80 ℃ of stirring reactions after 0.5～3 hour, the mol ratio of clamp type rareearth complexes is 500: 1～40000: 1 in isoprene or divinylic monomer and the described catalyst system, polyreaction was carried out under-20～80 ℃ 15 minutes～24 hours, the ethanol solution hydrochloride of adding 10% stops polyreaction, pour reaction soln in ethanol sedimentation, get polyisoprene or polyhutadiene white solid product, this isoprene or polyhutadiene white solid product are placed vacuum drying oven, under 40 ℃, dry 48 hours, obtain the isoprene or the polyhutadiene polymerisate of drying.
The molecular weight of polyisoprene or polyhutadiene is measured with gel permeation chromatograph, along 1,4 content nucleus magnetic resonance
13The C wave spectrum calculates.
Embodiment
The preparation of preparation embodiment 1 title complex 1
Under 0 ℃ of condition, be that (0.8mL 1.2mmol) is added drop-wise to 2 for the hexane solution of the butyllithium of 1.5mol/L with concentration, 6-(N-2, the 6-3,5-dimethylphenyl) (0.5g in the suspension liquid of hexane 1.2mmol) (20mL), reacts after 4 hours YCl phenyl aldehyde imido grpup-1-bromine between
3(THF)
3.5(0.64g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 10 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains the crystalline title complex 1 of glassy yellow 0.57g altogether, productive rate 74%.Its molecular formula of ultimate analysis is C
32H
39Cl
2N
2O
2Y (%): C, 59.65; H, 5.89; N, 4.25; Y, 18.32.
The preparation of preparation embodiment 2 title complexs 2
Under 0 ℃ of condition, be that (0.8mL 1.2mmol) is added drop-wise to 2, and (0.59g is in hexane 1.2mmol) (20mL) suspension liquid for phenyl aldehyde imido grpup 4-methyl isophthalic acid-bromine between 6-(N-2,6-diethyl phenyl) for the hexane solution of the butyllithium of 1.5mol/L with concentration.Reaction solution under this temperature the reaction 6 hours after with YCl
3(THF)
3.5(0.64g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 8 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains the crystalline title complex 2 of glassy yellow 0.58g altogether, productive rate 68%.Its molecular formula of ultimate analysis is C
37H
49Cl
2N
2O
2Y:C, 61.79; H, 6.47; N, 3.99; Y, 12.46.
The preparation of preparation embodiment 3 title complexs 3
Under 0 ℃ of condition, be that (0.8mL 1.2mmol) is added drop-wise to 2, and (0.67g is in hexane 1.2mmol) (20mL) suspension liquid for phenyl aldehyde imido grpup 4-ethyl-1-bromine between 6-(N-2,6-diisopropyl phenyl) for the hexane solution of the butyllithium of 1.5mol/L with concentration.Reaction solution under this temperature the reaction 3 hours after with YCl
3(THF)
3.5(0.62g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains glassy yellow crystal title complex 3 0.57g altogether, productive rate 86%.Its molecular formula of ultimate analysis is C
42H
59Cl
2N
2O
2Y:C, 64.01; H, 7.39; N, 3.37; Y, 11.34.
The preparation of preparation embodiment 4 title complexs 4
Under-10 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 2, and (0.57g is in hexane 1.2mmol) (20mL) suspension liquid for phenyl aldehyde imido grpup-1-bromine between 6-(N-2,6-diethyl phenyl) for the hexane solution of the butyllithium of 1.5mol/L with concentration.Reaction solution under this temperature the reaction 3 hours after with NdCl
3(THF)
2(0.57g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 8 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains glassy yellow crystal title complex 4 0.64g altogether, productive rate 71%.Its molecular formula of ultimate analysis is C
36H
47Cl
2N
2NdO
2: C, 57.01; H, 6.18; N, 3.64; Nd, 19.11.
The preparation of preparation embodiment 5 title complexs 5
Under-80 ℃ of conditions, be that (0.4mL 1.2mmol) is added drop-wise to 2, and (0.57g is in hexane 1.2mmol) (20mL) suspension liquid for phenyl aldehyde imido grpup-1-bromine between 6-(N-2,6-diethyl phenyl) for the hexane solution of the butyllithium of 3.0mol/L with concentration.Reaction solution under this temperature the reaction 3 hours after with GdBr
3(THF)
3(0.87g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 8 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains glassy yellow crystal title complex 5 0.67g altogether, productive rate 65%.Its molecular formula of ultimate analysis is C
36H
47Br
2GdN
2O
2: C, 50.21; H, 5.33; N, 3.07; Gd, 18.35.
The preparation of preparation embodiment 6 title complexs 6
Under 10 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 2, and (0.57g is in hexane 1.2mmol) (20mL) suspension liquid for phenyl aldehyde imido grpup-1-bromine between 6-(N-2,6-diethyl phenyl) for the hexane solution of the butyllithium of 1.5mol/L with concentration.Reaction solution under this temperature the reaction 3 hours after with LaBr
2(THF)
2(0.84g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 15 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains glassy yellow crystal title complex 6 0.69g altogether, productive rate 69%.Its molecular formula of ultimate analysis is C
36H
47Br
2LaN
2O
2: C, 51.47; H, 5.55; N, 3.14; La, 16.57.
The preparation of preparation embodiment 7 title complexs 7
Under-20 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 2, and (0.57g is in hexane 1.2mmol) (20mL) suspension liquid for phenyl aldehyde imido grpup-1-bromine between 6-(N-2,6-diethyl phenyl) for the hexane solution of the butyllithium of 1.8mol/L with concentration.Reaction solution under this temperature the reaction 3 hours after with HoCl
3(THF)
3(0.68g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 8 hours, adds lithium alkylide LiCH
2SiMe
3(0.14g 1.44mmol) reacts 4 hours again, and vacuum is taken out and desolvated, and resistates extracts with toluene, and vacuum is removed toluene solvant and obtained solid complexes 7 0.70g altogether, productive rate 72%.Its molecular formula of ultimate analysis is C
44H
69HoN
2O
2Si
2: C, 60.00; H, 7.81; N, 3.11; Ho, 18.76.
The preparation of preparation embodiment 8 title complexs 8
Under 0 ℃ of condition, be that (0.5mL 1.2mmol) is added drop-wise to 2, and (0.57g is in hexane 1.2mmol) (20mL) suspension liquid for phenyl aldehyde imido grpup-1-bromine between 6-(N-2,6-diethyl phenyl) for the hexane solution of the butyllithium of 2.5mol/L with concentration.Reaction solution under this temperature the reaction 3 hours after with LuCl
3(THF)
3(0.71g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 8 hours, adds HOOC (CH
2)
6CH
3(0.15g 1.0mmol), 12 hours vacuum of 40 ℃ of reactions are taken out and are desolvated, and resistates extracts with toluene, and vacuum is removed toluene solvant and is obtained solid complexes 8 0.81g altogether, productive rate 67%.Its molecular formula of ultimate analysis is C
52H
77LuN
2O
6: C, 62.18; H, 7.55; N, 2.17; Lu, 17.45.
The preparation of preparation embodiment 9 title complexs 9
Under 0 ℃ of condition, be that (0.8mL 1.2mmol) is added drop-wise to 2, and (0.57g is in hexane 1.2mmol) (20mL) suspension liquid for phenyl aldehyde imido grpup-1-bromine between 6-(N-2,6-diethyl phenyl) for the hexane solution of the butyllithium of 1.5mol/L with concentration.Reaction solution under this temperature the reaction 3 hours after with ScCl
3(THF)
3(0.51g 1.44mmol) is added in the above-mentioned reaction solution, and reaction solution is raised to room temperature naturally and continues reaction 8 hours, adds HOC
6H
3-2,6-(CH
3)
2(0.12g, 1.0mmol), vacuum is taken out and is desolvated, and resistates extracts with toluene, and vacuum is removed toluene solvant and is obtained solid complexes 9 0.82g altogether, productive rate 83%.Its molecular formula of ultimate analysis is C
52H
65N
2O
4Sc:C, 75.42; H, 7.82; N, 3.29; Sc, 5.44.
The polymeric Application Example:
Application Example 1
Under the room temperature, to 25ml in the polymerization bottle that anhydrous, anaerobic is handled, add 10 μ mol clamp type rareearth complexes, 1,100 μ mol Al (
iBu)
3With the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol isoprene monomer (monomer and catalyst molar ratio are 500: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.17g, transformation efficiency 50%.Molecular weight M with the gpc analysis polyisoprene
n=13.5 ten thousand, M
w/ M
n=1.77.Along 1,4 content 97.7%.
Application Example 2
Under the room temperature, to 25ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 200 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 40 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 2 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.36g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=45.3 ten thousand, M
w/ M
n=1.72, along 1,4 content 98.5%.
Application Example 3
Under the room temperature, to 25ml in the polymerization bottle that anhydrous, anaerobic is handled, add rare earth compounding 2, the 200 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 20ml, 60 ℃ of reactions add 40mmol isoprene monomer (monomer and catalyst molar ratio are 2000: 1) after 1 hour.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 5 hours.After adding the ethanolic soln termination reaction of 2ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 2.72g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=79.3 ten thousand, M
w/ M
n=1.81, along 1,4 content 98.8%.
Application Example 4
Under the room temperature, to 100ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 4, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 25ml, 80 ℃ of reactions add 30mmol isoprene monomer (monomer and catalyst molar ratio are 3000: 1) after 0.5 hour.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 6 hours.After adding the ethanolic soln termination reaction of 2ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 2.04g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=95.3 ten thousand, M
w/ M
n=1.79, along 1,4 content 98.7%.
Application Example 5
Under the room temperature, to 150ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 5, the 200 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 30ml, 20 ℃ of reactions add 50mmol isoprene monomer (monomer and catalyst molar ratio are 5000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 10 hours.After adding the ethanolic soln termination reaction of 5ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 3.40g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=134.4 ten thousand, M
w/ M
n=1.87, along 1,4 content 98.6%.
Application Example 6
Under the room temperature, to 200ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 6, the 400 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 50ml, 20 ℃ of reactions add 200mmol isoprene monomer (monomer and catalyst molar ratio are 10000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 20 hours.After adding the ethanolic soln termination reaction of 10ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 13.6g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=159.5 ten thousand, M
w/ M
n=1.65, along 1,4 content 98.7%.
Application Example 7
Under the room temperature, to 500ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 7, the 400 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 100ml, 20 ℃ of reactions add 400mmol isoprene monomer (monomer and catalyst molar ratio are 40000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 30 hours.After adding the ethanolic soln termination reaction of 10ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 27.2g, transformation efficiency 98.2%.Molecular weight M with the gpc analysis polyisoprene
n=300.6 ten thousand, M
w/ M
n=1.53, along 1,4 content 98.8%.
Application Example 8
Under the room temperature, in the polymerization bottle anhydrous, that anaerobic is handled, add the HAl of clamp type rareearth complexes 8, the 100 μ mol of 10 μ mol to 25ml
iPr
2With the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol isoprene monomer (monomer and catalyst molar ratio are 500: 1) after 5 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.34g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=13.7 ten thousand, M
w/ M
n=1.64, along 1,4 content 98.5%.
Application Example 9
Under the room temperature, to the methylaluminoxane of 25ml clamp type rareearth complexes 9,1000 μ mol of adding 10 μ mol in the polymerization bottle anhydrous, that anaerobic is handled and the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol isoprene monomer (monomer and catalyst molar ratio are 500: 1) after 5 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.34g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=12.7 ten thousand, M
w/ M
n=1.69, along 1,4 content 98.5%.
Application Example 10
Under the room temperature, to the methylaluminoxane of 25ml clamp type rareearth complexes 9,20 μ mol of adding 10 μ mol in the polymerization bottle anhydrous, that anaerobic is handled and the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol isoprene monomer (monomer and catalyst molar ratio are 500: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.03g, transformation efficiency 10%.Molecular weight M with the gpc analysis polyisoprene
n=1.30 ten thousand, M
w/ M
n=1.29, along 1,4 content 97.5%.
Application Example 11
Under the room temperature, to the methylaluminoxane of 25ml clamp type rareearth complexes 9,10000 μ mol of adding 10 μ mol in the polymerization bottle anhydrous, that anaerobic is handled and the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol isoprene monomer (monomer and catalyst molar ratio are 500: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.34g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=6.3 ten thousand, M
w/ M
n=2.19, along 1,4 content 91.5%.
Application Example 12
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 200 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 40 ℃ of thermostatic baths, stirs reaction down 3 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.36g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=40.7 ten thousand, M
w/ M
n=1.79, along 1,4 content 98.4%.
Application Example 13
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 200 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 60 ℃ of thermostatic baths, stirs reaction down 3 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.35g, transformation efficiency 98%.Molecular weight M with the gpc analysis polyisoprene
n=43.8 ten thousand, M
w/ M
n=1.88, along 1,4 content 98.1%.
Application Example 14
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 200 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 80 ℃ of thermostatic baths, stirs reaction down 1 hour.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.28g, transformation efficiency 94%.Molecular weight M with the gpc analysis polyisoprene
n=45.3 ten thousand, M
w/ M
n=1.86, along 1,4 content 97.7%.
Application Example 15
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 200 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 120 ℃ of thermostatic baths, stirs reaction down 1 hour.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.17g, transformation efficiency 86%.Molecular weight M with the gpc analysis polyisoprene
n=28.3 ten thousand, M
w/ M
n=12.33, along 1,4 content 95.7%.
Application Example 16
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 400 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places-20 ℃ of thermostatic baths, stirs reaction down 20 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.19g, transformation efficiency 87.5%.Molecular weight M with the gpc analysis polyisoprene
n=48.99 ten thousand, M
w/ M
n=1.81, along 1,4 content 98.7%.
Application Example 17
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 400 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places under 25 ℃ of thermostatic baths stirrings and carried out 1 hour.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.36g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=28.99 ten thousand, M
w/ M
n=1.81, along 1,4 content 98.7%.
Application Example 18
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 800 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 0.5 hour.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.36g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=14.85 ten thousand, M
w/ M
n=2.09, along 1,4 content 98.6%.
Application Example 19
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 2000 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths to stir down, and reaction was carried out 0.5 hour.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.36g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=5.01 ten thousand, M
w/ M
n=2.81, along 1,4 content 98.1%.
Application Example 20
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 40 μ mol of 20 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 20mmol isoprene monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 10 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.43g, transformation efficiency 63%.Molecular weight M with the gpc analysis polyisoprene
n=7.01 ten thousand, M
w/ M
n=1.81, along 1,4 content 98.1%.
Application Example 21
Under the room temperature, in the polymerization bottle anhydrous, that anaerobic is handled, add the AlMe of 10 μ mol clamp type rareearth complexes, 2,100 μ mol to 25ml
3With the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol isoprene monomer (monomer and catalyst molar ratio are 500: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.17g, transformation efficiency 50%.Molecular weight M with the gpc analysis polyisoprene
n=10.5 ten thousand, M
w/ M
n=1.79.Along 1,4 content 97.7%.
Application Example 22
Under the room temperature, in the polymerization bottle anhydrous, that anaerobic is handled, add the AlEt of 10 μ mol clamp type rareearth complexes, 2,100 μ mol to 25ml
3With the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol isoprene monomer (monomer and catalyst molar ratio are 500: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyisoprene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.24g, transformation efficiency 70%.Molecular weight M with the gpc analysis polyisoprene
n=11.7 ten thousand, M
w/ M
n=1.63.Along 1,4 content 97.8%.
Application Example 23
Under the room temperature, to 25ml in the polymerization bottle that anhydrous, anaerobic is handled, add 10 μ mol clamp type rareearth complexes, 7,100 μ mol Al (
iBu)
3With the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol divinylic monomer (monomer and catalyst molar ratio are 500: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.27g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=10.5 ten thousand, M
w/ M
n=1.79.Along 1,4 content 99.7%.
Application Example 24
Under the room temperature, in the polymerization bottle anhydrous, that anaerobic is handled, add clamp type rareearth complexes 8, the 500 μ mol's of 10 μ mol to 25ml
iBu
2The normal hexane solvent of AlCl and 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.34g, transformation efficiency 50%.Molecular weight M with the gpc analysis polyhutadiene
n=17.3 ten thousand, M
w/ M
n=1.64, along 1,4 content 99.5%.
Application Example 25
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 9, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 20ml, 20 ℃ of reactions add 20mmol divinylic monomer (monomer and catalyst molar ratio are 2000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 5 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.08g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyhutadiene
n=64.3 ten thousand, M
w/ M
n=1.57, along 1,4 content 99.8%.
Application Example 26
Under the room temperature, to 100ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 4, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 25ml, 20 ℃ of reactions add 30mmol divinylic monomer (monomer and catalyst molar ratio are 3000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 6 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 1.62g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyhutadiene
n=85.7 ten thousand, M
w/ M
n=1.57, along 1,4 content 99.7%.
Example 27 is executed in application
Under the room temperature, to 150ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 5, the 200 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 30ml, 20 ℃ of reactions add 50mmol divinylic monomer (monomer and catalyst molar ratio are 5000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 10 hours.After adding the ethanolic soln termination reaction of 5ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 2.7g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyhutadiene
n=127.7 ten thousand, M
w/ M
n=1.56, along 1,4 content 99.9%.
Application Example 28
Under the room temperature, to 200ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 6, the 200 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 50ml, 20 ℃ of reactions add 100mmol divinylic monomer (monomer and catalyst molar ratio are 10000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 20 hours.After adding the ethanolic soln termination reaction of 10ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 5.4g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyhutadiene
n=149.4 ten thousand, M
w/ M
n=1.63, along 1,4 content 99.8%.
Application Example 29
Under the room temperature, to 500ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 7, the 400 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 100ml, 20 ℃ of reactions add 400mmol divinylic monomer (monomer and catalyst molar ratio are 40000: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 30 hours.After adding the ethanolic soln termination reaction of 15ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 21.6g, transformation efficiency 98.2%.Molecular weight M with the gpc analysis polyhutadiene
n=179.7 ten thousand, M
w/ M
n=1.61, along 1,4 content 99.6%.
Application Example 30
Under the room temperature, to 25ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 8, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol divinylic monomer (monomer and catalyst molar ratio are 500: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.34g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyhutadiene
n=9.7 ten thousand, M
w/ M
n=1.64, along 1,4 content 99.5%.
Application Example 31
Under the room temperature, to 25ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 9, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 6ml, 20 ℃ of reactions add 5mmol divinylic monomer (monomer and catalyst molar ratio are 500: 1) after 3 hours.Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 4 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.27g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyhutadiene
n=8.1 ten thousand, M
w/ M
n=1.59, along 1,4 content 99.5%.
Application Example 32
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 40 ℃ of thermostatic baths, stirs reaction down 2 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.54g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyhutadiene
n=34.3 ten thousand, M
w/ M
n=1.68, along 1,4 content 99.4%.
Application Example 33
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 7, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 60 ℃ of thermostatic baths, stirs reaction down 1 hour.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.50g, transformation efficiency 93%.Molecular weight M with the gpc analysis polyhutadiene
n=31.7 ten thousand, M
w/ M
n=1.68, along 1,4 content 98.7%.
Application Example 34
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places 80 ℃ of thermostatic baths, stirs reaction down 1 hour.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.52g, transformation efficiency 96%.Molecular weight M with the gpc analysis polyhutadiene
n=29.7 ten thousand, M
w/ M
n=1.79, along 1,4 content 97.9%.
Application Example 35
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 7, the 100 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places-20 ℃ of thermostatic baths, stirs reaction down 20 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.38g, transformation efficiency 70%.Molecular weight M with the gpc analysis polyhutadiene
n=23.3 ten thousand, M
w/ M
n=1.68, along 1,4 content 100%.
Application Example 36
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 7, the 200 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places under 25 ℃ of thermostatic baths stirrings and carried out 3 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.54g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=23.8 ten thousand, M
w/ M
n=1.79, along 1,4 content 99.7%.
Application Example 37
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 400 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places under 25 ℃ of thermostatic baths stirrings and carried out 2 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.54g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=17.3 ten thousand, M
w/ M
n=1.82, along 1,4 content 99.6%.
Application Example 38
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 2, the 1000 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places under 25 ℃ of thermostatic baths stirrings and carried out 1 hour.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.54g, transformation efficiency 100%.Molecular weight M with the gpc analysis polyisoprene
n=14.2 ten thousand, M
w/ M
n=1.84, along 1,4 content 99.4%.
Application Example 39
Under the room temperature, to 50ml in the polymerization bottle that anhydrous, anaerobic is handled, add clamp type rareearth complexes 7, the 20 μ mol of 10 μ mol Al (
iBu)
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places under 25 ℃ of thermostatic baths stirrings and carried out 20 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.24g, transformation efficiency 44%.Molecular weight M with the gpc analysis polyisoprene
n=10.4 ten thousand, M
w/ M
n1.74, along 1,4 content 99.7%.
Application Example 40
Under the room temperature, in the polymerization bottle anhydrous, that anaerobic is handled, add the AlMe of clamp type rareearth complexes 2, the 100 μ mol of 10 μ mol to 50ml
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places under 25 ℃ of thermostatic baths stirrings and carried out 20 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.28g, transformation efficiency 52%.Molecular weight M with the gpc analysis polyisoprene
n=8.83 ten thousand, M
w/ M
n=1.69, along 1,4 content 89.2%.
Application Example 41
Under the room temperature, in the polymerization bottle anhydrous, that anaerobic is handled, add the AlEt of clamp type rareearth complexes 2, the 100 μ mol of 10 μ mol to 50ml
3With the normal hexane solvent of 15ml, 20 ℃ of reactions add 10mmol divinylic monomer (monomer and catalyst molar ratio are 1000: 1) after 3 hours.Polymerization bottle places under 25 ℃ of thermostatic baths stirrings and carried out 20 hours.After adding the ethanolic soln termination reaction of 1ml 10% hydrochloric acid (volume ratio), pour reaction solution in ethanol sedimentation, get white polyhutadiene solid, place vacuum drying oven, drying is 48 hours under 40 ℃, net weight 0.33g, transformation efficiency 61%.Molecular weight M with the gpc analysis polyisoprene
n=8.99 ten thousand, M
w/ M
n=1.72, along 1,4 content 88.6%.
Claims (11)
1. isoprene or divinyl are along 1, and the catalyst system of 4-selective polymerisation is characterized in that, its be by molecular formula for [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2The NCN-imines clamp type rareearth complexes and the two-pack of alkylating reagent form;
Described alkylating reagent is that molecular formula is AlR
3Aluminum alkyls, perhaps, also have triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium or diethyl benzyl aluminium; Or molecular formula is HAlR
2Alkyl-al hydride, perhaps, also have phenylbenzene aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride or ethyl p-methylphenyl aluminum hydride; With the molar ratio of described NCN-imines clamp type rareearth complexes be (2: 1)～(100: 1); Or
Described alkylating reagent is that molecular formula is AlR
2The alkyl aluminum chloride of Cl perhaps, also has phenylbenzene aluminum chloride; Di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, Ethylbenzyl chlorination aluminium or ethyl p-methylphenyl aluminum chloride; With the molar ratio of described NCN-imines clamp type rareearth complexes be (2: 1)～(50: 1); Or
Described alkylating reagent is that the molar ratio of aikyiaiurnirsoxan beta and described NCN-imines clamp type rareearth complexes is (2: 1)～(1000: 1);
R in the molecular formula of described NCN-imines clamp type rareearth complexes
1Be the substituting group on the skeleton phenyl ring, be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, methoxyl group, phenyl, benzyl, chlorine, bromine, iodine or trimethyl silicon based; R
2Be the substituting group on the imines carbon atom, be methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl or hydrogen; R
3Be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, methoxyl group, nitro, phenyl, benzyl, chlorine, bromine, iodine or trimethyl silicon based; R
4Be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, methoxyl group, nitro, phenyl, benzyl, chlorine, bromine, iodine or trimethyl silicon based; Rare earth metal Ln is scandium, yttrium, lanthanum, Cerium, Praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium; Wherein, X is F
-, Cl
-, Br
-Or I
-Perhaps, X is CH
2SiMe
3, CH
2C
6H
4-6-N (CH
3)
2Or CH (SiMe
3)
2Perhaps, X is OCH
3, OCH
2CH
3,-OCH (CH
3)
2Perhaps, X is OC
6H
3-2,6-(CH
3)
2
2. isoprene as claimed in claim 1 or divinyl are along 1, and the catalyst system of 4-selective polymerisation is characterized in that, described molecular formula is AlR
3Aluminum alkyls be trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium or trioctylaluminum.
3. isoprene as claimed in claim 1 or divinyl are along 1, and the catalyst system of 4-selective polymerisation is characterized in that, described molecular formula is HAlR
2Alkyl-al hydride be dimethyl hydrogenation aluminium, ADEH, di aluminum hydride, di-n-butyl aluminum hydride, di-isopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride or dioctyl aluminum hydride.
4. isoprene as claimed in claim 1 or divinyl are along 1, and the catalyst system of 4-selective polymerisation is characterized in that, described molecular formula is AlR
2The alkyl aluminum chloride of Cl is dimethylaluminum chloride, diisobutyl aluminum chloride, diamyl aluminum chloride, dihexylaluminum chloride, dicyclohexyl aluminum chloride or dioctyl aluminum chloride.
5. isoprene as claimed in claim 1 or divinyl are along 1, and the catalyst system of 4-selective polymerisation is characterized in that, described aikyiaiurnirsoxan beta is methylaluminoxane, ethyl aikyiaiurnirsoxan beta, n-propyl aikyiaiurnirsoxan beta, normal-butyl alumina alkane.
6. isoprene as claimed in claim 1 or divinyl are along 1, the catalyst system of 4-selective polymerisation, it is characterized in that, described aluminum alkyls or alkyl-al hydride, with the molar ratio of described NCN-imines clamp type rareearth complexes be (10: 1)～(50: 1).
7. isoprene as claimed in claim 1 or divinyl are along 1, and the catalyst system of 4-selective polymerisation is characterized in that the molar ratio of described alkyl aluminum chloride and described NCN-imines clamp type rareearth complexes is (5: 1)～(15: 1).
8. isoprene as claimed in claim 1 or divinyl are along 1, and the catalyst system of 4-selective polymerisation is characterized in that, the molar ratio of described aikyiaiurnirsoxan beta and described NCN-imines clamp type rareearth complexes is (10: 1)～(500: 1).
9. isoprene as claimed in claim 1 or divinyl are along 1, and the catalyst system of 4-selective polymerisation is characterized in that, described molecular formula be [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2NCN-imines clamp type rareearth complexes be any one of following 1-9: title complex 1:Ln is Y, R
1, R
2, R
4Be H, R
3Be CH
3Title complex 2:Ln is Y, R
1Be CH
3, R
2, R
4Be H, R
3Be CH
2CH
3, X is Cl; Title complex 3:Ln is Y, R
1Be CH
2CH
3, R
2, R
4Be H, R
3For
iPr, X are Cl; Title complex 4:Ln is Nd, R
1, R
2, R is H, R
3Be CH
2CH
3, X is Cl; Title complex 5:Ln is Gd, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is Br; Title complex 6:Ln is La, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is Br; Title complex 7:Ln is Ho, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is CH
2SiMe
3Title complex 8:Ln is Lu, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is OCO (CH
2)
6CH
3With title complex 9:Ln be Sc, R
1, R
2, R
4Be H, R
3Be CH
2CH
3, X is OC
6H
3-2,6-(CH
3)
2
10. isoprene as claimed in claim 1 or divinyl are along 1, and the method for making of the catalyst system of 4-selective polymerisation is characterized in that step and condition are as follows:
Molecular formula be [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2The preparation of NCN-imines clamp type rareearth complexes:
Under-80～10 ℃ of conditions, with concentration is that the hexane solution of the butyllithium of 1.0～3.0mol/L is added drop-wise to part 2,6-(2, the two alkyl phenyl imines of 6-) between in the hexane suspension liquid of phenyl aldehyde imido grpup-1-bromine, the molar ratio of butyllithium and part is (0.9: 1)～(1.5: 1), reacted 3～10 hours, rare earth chloride is added in this reaction solution, the mol ratio of rare earth chloride and part is 1: 1, question response liquid continues reaction 8～10 hours after being raised to room temperature naturally, and vacuum is taken out and desolvated, and resistates extracts with toluene, concentrate toluene solution, obtain NCN-imines clamp type rareearth muriate;
NCN-imines clamp type rareearth muriate is dissolved in the toluene, adds the tetrahydrofuran solution that waits the mole lithium alkylide, react to remove after 1 hour and desolvate, obtain NCN-imines clamp type rareearth alkylate;
NCN-imines clamp type rareearth alkylide is dissolved in the toluene, the tetrahydrofuran solution of mol of alcohol, carboxylic acid or phenol such as slowly splashes into respectively, react to remove after 10 minutes and desolvate, obtain NCN-imines clamp type rareearth alkoxyl group, phenol oxygen base or carboxylic acid group's title complex respectively;
Isoprene or divinyl is along 1, the preparation of the catalyst system of 4-selective polymerisation:
By proportioning be molecular formula [2,6-(2,6-R
3 2-4-R
4-C
6H
2N=CR
2)
2-4-R
1-C
6H
2] LnX
2(THF)
2NCN-imines clamp type rareearth complexes and aluminum alkyls, alkyl-al hydride, alkyl aluminum chloride or the aikyiaiurnirsoxan beta of alkylating reagent, at C
5～C
20Aliphatic solvents in mix, at 20～80 ℃, carried out alkylated reaction 0.5～3 hour, obtain two-pack solubility homogeneous catalysis system.
11. isoprene as claimed in claim 1 or divinyl are along 1, the usage of the catalyst system of 4-selective polymerisation is characterized in that step and condition are as follows:
Get isoprene or divinyl along 1, the hexane of the catalyst system of 4-selective polymerisation or toluene solvant place through anhydrous, in the reactor that anaerobic is handled, the ratio of clamp type rareearth complexes is 100～1000 liters/mole in described solvent and the described catalyst system, gained solution adds isoprene or divinylic monomer at 20～80 ℃ of stirring reactions after 0.5～3 hour, the mol ratio of clamp type rareearth complexes is 500: 1～40000: 1 in isoprene or divinylic monomer and the described catalyst system, polyreaction was carried out under-20～80 ℃ 15 minutes～24 hours, the ethanol solution hydrochloride of adding 10% stops polyreaction, pour reaction soln in ethanol sedimentation, get polyisoprene or polyhutadiene white solid product, this polyisoprene or polyhutadiene white solid product are placed vacuum drying oven, under 40 ℃, dry 48 hours, done-dry polyisoprene or polyhutadiene polymerisate.
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|---|---|---|---|
| CN2008100506662A CN101260164B (en) | 2008-04-29 | 2008-04-29 | Syn form 1,4-selectivity polymerization catalysis system for Isoprene or butadiene and preparation method and using method |
| EP09737625.5A EP2289949B1 (en) | 2008-04-29 | 2009-04-28 | Isoprene or butadiene cis 1,4-polymeric bi-component catalyst system and polymerization process |
| US12/747,490 US8394901B2 (en) | 2008-04-29 | 2009-04-28 | Bi-component catalyst system for isoprene or butadiene cis 1, 4-polymerization and polymerization process |
| PCT/CN2009/000449 WO2009132514A1 (en) | 2008-04-29 | 2009-04-28 | Isoprene or butadiene cis 1,4-polymeric bi-component catalyst system and polymerization process |
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|---|---|---|---|
| CN2008100506662A CN101260164B (en) | 2008-04-29 | 2008-04-29 | Syn form 1,4-selectivity polymerization catalysis system for Isoprene or butadiene and preparation method and using method |
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| ITMI20111652A1 (en) * | 2011-09-14 | 2013-03-15 | Polimeri Europa Spa | OSS-AZOTATO COMPLEX OF LANTANIDES, CATALYTIC SYSTEM INCLUDING THE BONE-AZOTHATE COMPLEX AND PROCEDURE FOR THE (CO) POLYMERIZATION OF CONJUGATED DIENES |
| ITMI20111650A1 (en) * | 2011-09-14 | 2013-03-15 | Polimeri Europa Spa | BIS-IMMINICO COMPLEX OF LANTHANIDES, CATALYTIC SYSTEM INCLUDING THE BIS-IMMINICO COMPLEX AND PROCEDURE FOR (CO) POLYMERIZATION OF CONJUGATED DIENES |
| FR2990946B1 (en) | 2012-05-28 | 2017-03-03 | China Petroleum & Chem Corp | POLYISOPRENE, PROCESS FOR THE PREPARATION, RUBBER OF POLYISOPRENE AND PRODUCT THEREFROM VULCANIZATION OF THE SAME |
| ITMI20122201A1 (en) * | 2012-12-20 | 2014-06-21 | Versalis Spa | BONE-AZOTHATE COMPLEX OF COBALT, CATALYTIC SYSTEM INCLUDING THE BONE-AZOTHATE COMPLEX AND PROCEDURE FOR THE (CO) POLYMERISATION OF CONJUGATED DIENES |
| CN103980425B (en) * | 2014-06-09 | 2019-03-12 | 华宇橡胶有限责任公司 | The preparation method of high cis-contents butadiene isoprene copolymer |
| CN106589239B (en) * | 2015-10-19 | 2019-04-19 | 中国石油化工股份有限公司 | A method of preparing butadiene/isoprene copolymer |
| CN106632432A (en) * | 2015-10-30 | 2017-05-10 | 中国石油化工股份有限公司 | Rare earth metal complex as well as preparation method and application thereof |
| JP7191017B2 (en) * | 2017-06-14 | 2022-12-16 | 株式会社ブリヂストン | Catalyst composition, method for producing modified conjugated diene polymer, modified conjugated diene polymer, rubber composition and tire |
| CN117264103B (en) * | 2023-11-21 | 2024-02-20 | 传化智联股份有限公司 | Rare earth catalyst containing neodecanoic acid neodymium and preparation method of polybutadiene based on catalyst |
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