CN101927186B - Rare earth catalyst system and method for preparing high cis-1,4-polyisoprene - Google Patents
Rare earth catalyst system and method for preparing high cis-1,4-polyisoprene Download PDFInfo
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Abstract
The invention relates to a rare earth catalyst system, in particular to a rare earth catalyst system used for polymerizing isoprene and a method for preparing high cis-1,4-polyisoprene. A compound rare earth carboxylate catalyst system with homogeneous phase can prepare polyisoprene rubber at polymerization temperature of -80-50 DEG C or under the condition of heat insulation polymerization while keeping high catalytic activity and stable catalytic performance, wherein the cis-1,4 structure content of the polyisoprene is more than 96%, namely above 98%, weight-average molecular weight (Mw) is1.1*105-1.1*106, and the narrow molecular weight distribution (Mw/Wn) is 1.6-2.7.
Description
Technical field:
The present invention relates to a kind of rare-earth catalysis system especially for the rare-earth catalysis system of isoprene polymerization and prepare the method for high cis-1,4-polyisoprene.
Background technology:
The structure of high cis-1,4-polyisoprene rubber (abbreviation isoprene rubber) and performance and natural rubber are approximate, are a kind of general purpose synthetic rubbers with excellent combination property, are mainly used in the production tire.Initiation/the catalyst system and catalyzing that is generally used for synthetic isoprene rubber comprises lithium series initiators, Titanium series catalyst and rare earth catalyst.
Suitable-1,4 structural content of isoprene rubber has bigger influence to its rubber performance and cured properties, especially when suitable-1; 4 structural contents further improved suitable-1,4 structural content greater than 96% o'clock; Can make the performance of rubber be able to significantly improve; Suitable-1,4 structural content improves 1%, and hot strength can improve 6kg/cm
2(referring to rare earth catalyst synthetic rubber collected works, Changchun applied chemistry institute of the Chinese Academy of Sciences the 4th research department work, Science Press,, 255-265 page or leaf in 1980; Performance evaluation of high cis1,4-polybutadiene, J Appl Polym Sci, 2006,99:88-99).And, for tyres for passenger cars, improve polymer molecular weight, reduction molecular weight distribution and minimizing chain end concentration and all help reducing resistance to rolling, wherein reducing molecular weight distribution is one of most important factor.In recent years, the synthetic high polymer amount is devoted in research, Gao Shun-1,4 microstructure (＞96%) reaches than Narrow Molecular Weight Distribution (M
w/ M
n＜3.0) isoprene rubber.
CN101045768 discloses a kind of employing rare earth carboxylate, alkyl aluminum, chloride (chloro-di-isobutyl aluminum, aluminium diethyl monochloride, tertiary butyl chloride, benzyl chloride, allyl chloride or silicon tetrachloride) and conjugated diolefin and has formed rare earth catalyst system; Its mole proportioning is a rare earth carboxylate: alkyl aluminum: chloride: conjugated diolefin is 1: 5～30: 1～4: 5～20; At 40 ℃ of following catalysis isoprene polymerizations; Can obtain suitable-1,4 structural content and be 96.0%～97.2%, weight average molecular weight (M
w) be 1.1 * 10
6～2.2 * 10
6And molecular weight distributing index (M
w/ M
n) be 2.1～2.9 high-cis isoprene rubber.
Under 30 ℃～60 ℃ conditions, adopt the MMAO activation by Nd (O
i-C
3H
7)/AlEt
2Cl, t-BuCl or Me
3When the catalyst that SiCl ([Al]/[Nd]=100 (mol ratio)) forms is used for isoprene polymerization, can prepare Narrow Molecular Weight Distribution (M
w/ M
n≤1.3) isoprene rubber, but its suitable-1,4 structural content is merely about 94%, and in the catalyst MMAO consumption too high (Dong W M, Masuda T.Polymer, 2003,44,1561-1567).
US2005/0137338 discloses a kind of prepared catalyst system of carboxylic acid neodymium, alkyl aluminum and tert-amyl chloride that adopts and is used for the method for isoprene 60 ℃～90 ℃ of following polymerizations; Its mole proportioning is the carboxylic acid neodymium: alkyl aluminum: tert-amyl chloride is 1: 10～30: 2; Condition can obtain M
wBe 1.0 * 10
6～2.4 * 10
6, M
w/ M
nBe 1.7～2.5 isoprene rubber, but suitable-1,4 structural content is less than 96%.
Disclose a kind of preparation among CN1479754 and the US6992157 and had Gao Shun-1; The method of the isoprene rubber of 4 structures and Narrow Molecular Weight Distribution; The catalyst isoprene that phosphonate, alkyl aluminum, alkyl aluminium halide and the conjugated diene of employing rare earth metal formed is-45 ℃～0 ℃ following polymerization; Its mole proportioning is the rare earth metal phosphonate: alkyl aluminum: alkyl aluminium halide: conjugated diolefin is 1: 1～4: 2～3: 50, can obtain suitable-1,4 structural content more than 99%, M
wBe 8.1 * 10
5～2.3 * 10
6And Narrow Molecular Weight Distribution (M
w/ M
n～2.4) high-cis isoprene rubber, however this rare earth phosphonate is insoluble to alkane solvent, and prepared catalyst is thickness and unsettled suspension (heterogeneous system).
Disclose a kind of catalyst system of preparation Gao Shun-1,4 structural content isoprene rubber among the CN101186663, this catalyst is by based on [NCN]
-The clamp type rareearth complexes of coordination, alkyl aluminum and organic boron salt ([Ph
3C] [B (C
6F
5)
4]) form, when clamp type rareearth complexes: alkyl aluminum: when organic boron salt was 1: 20～40: 1～3, catalysis isoprene polymerization under-20 ℃～80 ℃ condition can obtain suitable-1,4 structural content and be 96.5%～98.8%, M
w/ M
nBe 1.7～3.0 isoprene rubber, but molecular weight is lower, M
wBe 7.3 * 10
4～3.3 * 10
5, and organic boron salt costs an arm and a leg the clamp type rareearth complexes complicated process of preparation.
Adopt cyclopentadienyl rare-earth metal catalyst system (C
5Me
5)
2The Gd [(AlMe of μ-Me)
2(μ-Me)] Gd (C
5Me
5)
2/ [Ph
3C] [B (C
6F
5)
4]/Al
iBu
3And (C
5Me
4 iPr)
2The Gd [(AlMe of μ-Me)
2(μ-Me)] Gd (C
5Me
4 iPr)
2/ [Ph
3C] [B (C
6F
5)
4]/Al
iBu
3, work as Al
iBu
3: the Gd molar ratio is respectively 50 and at 20 o'clock, and catalysis isoprene polymerization under-20 ℃ and 0 ℃ of condition can obtain having high suitable-1,4 structural content (＞99%) and Narrow Molecular Weight Distribution (M respectively
w/ M
nIsoprene rubber～2.1) (Kaita S, DoiY, Kaneko K, Horiuchi A C, Wakatsuki Y.Macromolecules 2004,37,5860-5862), but this cyclopentadienyl rare-earth metal catalyst structure is complicated, costs an arm and a leg.
Summary of the invention:
The purpose of this invention is to provide a kind of method that can be used for the homogeneous phase rare-earth catalysis system of isoprene polymerization and prepare high cis-1,4-polyisoprene.Adopt the catalyst system and catalyzing based on rare earth carboxylate of homogeneous phase; When guaranteeing that high catalytic activity and catalytic performance are stable; Through changing catalytic component proportioning and polymerization process condition, can prepare suitable-1,4 structural content＞96% (can reach more than 98%), weight average molecular weight (M
w) be 1.1 * 10
5～1.1 * 10
6, Narrow Molecular Weight Distribution (M
w/ M
n=1.6～2.7) polyisoprene rubber.
A kind of rare-earth catalysis system provided by the present invention, it basic composition is:
A. the rare earth carboxylate compound is C
6-C
10Neodymium naphthenate or branched alkyl carboxylic acid's neodymium.
B. organo-aluminum compound is AlR
3Or AlHR
2Or both mixtures, wherein R is C
1-C
6Alkyl; Can be the mixture of any in the following material group or several kinds: triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride, hydrogenation dipropyl aluminium, hydrogenation dibutyl aluminium.Preferred triethyl aluminum, tri-butyl aluminum, diethyl aluminium hydride, hydrogenation dibutyl aluminium.
C. molecular formula is R
1Cl
mChlorohydrocarbon or molecular formula be R
2Cl
nCOOR
3Chlorinated carboxylic acid ester or both mixtures, wherein R
1～R
3Expression contains alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1～12 carbon atom, can be the same or different; M=1-3, n=1-3, Cl can link to each other with same carbon atom and also can link to each other with different carbon atoms; Can be the mixture of any in the following material or several kinds: chlorohexane, chloroheptane, 2-phenyl-2 cbloropropane isopropyl chloride, 1,4-two (2-chloro-propyl group) benzene, carrene, dichloroethanes, dichloropropane, dichloroetane, chloroform, trichloroethanes, three chlorobutanes, three chloropentanes, methyl chloroacetate, ethyl chloroacetate, monoxone propyl ester, butyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, dichloroacetic acid propyl ester, dichloroacetic acid butyl ester, dichloro methyl propionate, dichloropropionic acid ethyl ester, dichloro-butyric acid ethyl ester, methyl trichloroacetate, ethyl trichloroacetate, trichloroacetic acid propyl ester, butyl trichloroacetate, chloropon ethyl ester, trichlorobutyric acid ethyl ester.Be preferably: 2-phenyl-2 cbloropropane isopropyl chloride, 1,4-two (2-chloro-propyl group) benzene, dichloroethanes, dichloropropane, dichloroetane, chloroform, trichloroethanes, three chlorobutanes, three chloropentanes, ethyl chloride, ethyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, trichloroacetic acid propyl ester, butyl trichloroacetate, chloropon ethyl ester, trichlorobutyric acid ethyl ester.
D.C
1-C
10Straight chain alcohol, branched-chain alcoho or aromatic alcohol: can be any in the following material or their mixture: methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, cyclohexanol, phenmethylol.Preferred alcohol, propyl alcohol, butanols, amylalcohol or hexanol.
The mol ratio of each component is A: B: C: D=1: 7～40: 5～85: 0.1～2.5
Catalyst system and catalyzing preparation method of the present invention is fairly simple, under the inert gas shielding, under-30～60 ℃, each component of ABCD is fully mixed after ageing, can make the high-activity catalyst systems of homogeneous stability.Can also in catalyst, add few butadiene and/or isoprene, addition and catalytic component A mol ratio are 0.1-4.5, to improve catalytic activity and catalytic stability.
The present invention also provides a kind of method for preparing high cis-1,4-polyisoprene; Under the inert gas shielding; In isoprene monomer, add above-mentioned catalyst system and catalyzing in-80 ℃～50 ℃ down or under " thermal insulation " (being meant the situation that does not have external heat source among the present invention) condition, carry out the isoprene polymerization reaction, it is 1.0 * 10 that the addition of catalyst system and catalyzing makes component A and monomer mole ratio
-4～1.0 * 10
-3, polymerization can not have to carry out polymerisation in bulk under the solvent, can adopt C yet
6～C
8Saturated alkane, cycloalkane a kind of or their mixture be to carry out polymerisation in solution in the solvent.
Catalyst system and catalyzing provided by the invention has high catalytic activity and high directionality, even under-80 ℃, also can start polymerisation, suitable-1,4 structural content of prepared polyisoprene can reach 98.4% greater than 96%.The good stability of catalyst system and catalyzing still keeps equal phase, high catalytic activity and high directionality at long digestion time (like 480h).
Isoprene polymerization method provided by the invention, suitable-1, the 4 microstructure content of prepared polyisoprene particularly can be greater than 98.0% greater than 96.0%, and its weight average molecular weight is 1.08 * 10
5～1.14 * 10
6Between, and gained HMW high cis-1,4-polyisoprene product also has the narrower characteristics of molecular weight distribution, and Narrow Molecular Weight Distribution index can reach 1.6.
Description of drawings:
Gel permeation chromatography (GPC) spectrogram of Fig. 1: embodiment 2 gained high cis-1,4-polyisoprene products, visible resulting polymers GPC spectrogram presents monomodal molecular weight distribution from figure, the peak shape symmetry, molecular weight distribution is narrower.
The specific embodiment:
The present invention further specifies with following embodiment, does not constitute the restriction to the scope of the invention and implementation method.
The inherent viscosity of polymer [η] utilizes Ubbelohde viscometer 30 ℃ of tests down in the following example, and as solvent, computing formula is [η]=[2 (η with toluene
Sp-1n η
r)]
1/2/ c, wherein η
r=t/t
0, η
Sp=η
r-1, t is that concentration is the flowing time of the polymer toluene solution of c, t
0Flowing time for toluene; Utilize gel permeation chromatography (GPC) to characterize the weight average molecular weight (M of polyisoprene
w) and molecular weight distribution (M
w/ M
n), with the polystyrene standards curve of formulating standard, calculate (K=1.09 * 10 with K, the α value of natural rubber in 25 ℃ of following tetrahydrofuran solvents
-4, α=0.79); The cis-content of polymer and composition utilize fourier infrared (FTIR) characterize (with reference to Shen Zhiquan, Song Xiangyu, Xiao Shuxiu, etal, JAppl Polym Sci, 1983,28:1585-1597; The shed people, literary composition is prolonged in filial piety, China Synthetic Rubber Industry, 1982,5 (4): 299-301).
Embodiment 1
Under nitrogen protection, in the catalyst preparation device, add 0.25mmol neodymium octoate, 8.7mmol triisobutyl aluminium, 0.27mmol diisobutyl aluminium hydride, 3.8mmol chloroform, 0.1mmol ethyl trichloroacetate and 0.11mmol ethanol; 30 ℃ of ageings 1 hour, form light blue homogeneous catalyst system.
Under nitrogen protection, in polymer reactor, add 35mL hexane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-4Start polymerization at 11 ℃, reaction is 22 hours under " thermal insulation " condition, adds and contains 2 of 1% quality; The ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol; Be placed in 45 ℃ of vacuum drying ovens with clear water washing and be dried to constant weight, the polyisoprene yield is 87.1%, weight average molecular weight (M
w) be 7.9 * 10
5, molecular weight distributing index (M
w/ M
n) be 2.1, cis-1,4 content is 96.9%.
Embodiment 2
Under nitrogen protection, in the catalyst preparation device, add 0.25mmol isooctyl acid neodymium, 2mmol triisobutyl aluminium, 3.75mmol chloroform and 0.11mmol ethanol,, form light blue homogeneous catalyst system 50 ℃ of ageings 1 hour.
Under nitrogen protection, in polymer reactor, add 20mL hexane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-4Behind-24 ℃ of following catalysis isoprene polymerizations, add and contain 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The polyisoprene yield is 55.0%, M
wBe 6.93 * 10
5, M
w/ M
nBe 1.6, cis-1,4 content is 98.2%.
Embodiment 3
Under nitrogen protection, in the catalyst preparation device, add 3.5mmol triisobutyl aluminium, 1.6mmol chloroform, 0.15mmol trichloroethanes and 0.05mmol ethanol; Be added to after mixing in the 0.25mmol isooctyl acid neodymium; Further, form light blue homogeneous catalyst system 40 ℃ of ageings 3 hours.
Under nitrogen protection, in polymer reactor, add 35mL hexane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-4Start polymerization at 20 ℃, reaction is 5 hours under " thermal insulation " condition, adds and contains 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The polyisoprene weight average molecular weight is 2.0 * 10
5, M
w/ M
nBe 1.9, inherent viscosity ([η]) is 1.85dL/g, and cis-1,4 content is 96.4%.
Embodiment 4
Under nitrogen protection, in the catalyst preparation device, add 0.25mmol neodecanoic acid neodymium, 4.4mmol triisobutyl aluminium, 0.13mmol diisobutyl aluminium hydride, 3.75mmol chloroform, 0.08mmol hexanol and 0.63mmol butadiene; 50 ℃ of ageings 1 hour, form the pale bluish green homogeneous catalyst system.
Under nitrogen protection, in polymerization bottle, add 35mL hexane, 5mL isoprene monomer and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-425 ℃ of following polymerizations 6 hours, add and contain 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The polyisoprene yield is 41.5%, M
wBe 3.34 * 10
5, M
w/ M
nBe 2.1, [η] is 3.89dL/g, and cis-1,4 content is 96.2%.
Embodiment 5
Under nitrogen protection, in the catalyst preparation device, add 0.25mmol isooctyl acid neodymium, 6.25mmol triisobutyl aluminium, 2.2mmol chloroform, the 0.05mmol chloroacetic acid tert-butyl ester and 0.07mmol propyl alcohol;-24 ℃ of following ageings 480 hours form light blue homogeneous catalyst system.
Under nitrogen protection, in polymer reactor, add 35mL hexane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-40 ℃ of following polymerisation 14 hours, add and contain 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The M of polyisoprene
wBe 8.6 * 10
5, M
w/ M
nBe 2.4, cis-1,4 content is 97.5%.
Embodiment 6
Under nitrogen protection, in the catalyst preparation device, add 0.25mmol neodecanoic acid neodymium, 3.75mmol triisobutyl aluminium, 2.5mmol chloroform and 0.07mmol ethanol,, form light blue homogeneous catalyst system 50 ℃ of ageings 1 hour.
Under nitrogen protection, in polymerization bottle, add 20mL hexane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-4Mix the back and reacted 2.5 hours down, add and contain 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol at 20 ℃.The polyisoprene yield is 38.4%, M
wBe 1.14 * 10
6, M
w/ M
nBe 2.4, [η] is 6.2dL/g, and cis-1,4 content is 97.0%.
Embodiment 7
Under nitrogen protection, in the catalyst preparation device, add 0.2mmol isooctyl acid neodymium, 2.8mmol triisobutyl aluminium, 1.8mmol chloroform and 0.05mmol ethanol,, form light blue homogeneous catalyst system 40 ℃ of ageings 1 hour.
Under nitrogen protection, in polymer reactor, add 35mL hexane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-4Mix the back 50 ℃ of reactions 5 hours, add and contain 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The M of polyisoprene
wBe 4.23 * 10
5, M
w/ M
nBe 2.3, cis-1,4 content is 96.0%.
Embodiment 8
Under nitrogen protection, in the catalyst preparation device, add 0.25mmol isooctyl acid neodymium, the triisobutyl aluminium of 4.5mmol, 3.6mmol chloroform, 0.15mmol1; 4-two (2-chloro-propyl group) benzene and 0.15mmol ethanol; 50 ℃ of ageings 1 hour, form light blue homogeneous catalyst system.
Under nitrogen protection, in polymer reactor, add 35mL hexane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-4After carrying out the polymerisation reaction under-14 ℃, add and contain 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The polyisoprene yield is 67.4%, M
wBe 5.38 * 10
5, M
w/ M
nBe 2.1, [η] is 5.55dL/g, and cis-1,4 content is 98.4%.
Embodiment 9
Under nitrogen protection, in the catalyst preparation device, add 0.02mmol neodecanoic acid neodymium, 0.2mmol triisobutyl aluminium, 0.2mmol chloroform and 0.006mmol ethanol, mix the back, form light blue homogeneous catalyst system 50 ℃ of ageings 1 hour.
Under nitrogen protection, in polymerization bottle, add 20mL hexane, 5mL isoprene monomer and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 4.0 * 10
-4Start polymerization at-80 ℃, reaction is 4 hours under " thermal insulation " condition, adds and contains 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The polyisoprene yield is 31.8%, M
wBe 7.3 * 10
5, M
w/ M
nBe 2.1, [η] is 6.8dL/g, and cis-1,4 content is 97.4%.
Embodiment 10
Under nitrogen protection, in the catalyst preparation device, add 0.2mmol isooctyl acid neodymium, 4.8mmol triisobutyl aluminium, 16mmol chloroform and 0.48mmol ethanol,, form light blue homogeneous catalyst system 40 ℃ of ageings 1 hour.
Under nitrogen protection, in polymerization bottle, add 20mL hexane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 4.0 * 10
-4Mix the back and reacted 4 hours down, add and contain 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol at 30 ℃.The polyisoprene yield is 93.2%, M
wBe 8.78 * 10
5, cis-1,4 content is 96.8%.
Embodiment 11
Under nitrogen protection, in the catalyst preparation device of 50mL, add 0.2mmol isooctyl acid neodymium, 2.8mmol triisobutyl aluminium, 2.6mmol chloroform, 0.1mmol ethyl trichloroacetate and 0.78mmol ethanol; 40 ℃ of ageings 1 hour, form light blue homogeneous catalyst system.
Under nitrogen protection, in polymerization bottle, add 35mL isopentane, 5mL isoprene and above-mentioned catalyst, the mol ratio of catalytic component A and monomer is 5.0 * 10
-4Start polymerization down at 10 ℃, reaction is 5 hours under " thermal insulation " condition, adds and contains 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The polyisoprene yield is 92.9%, M
wBe 1.25 * 10
5, M
w/ M
nBe 1.7, cis-1,4 content is 96.4%.
Embodiment 12
Under nitrogen protection, in the catalyst preparation device, add 0.2mmol isooctyl acid neodymium, 2.0mmol triisobutyl aluminium, 0.08mmol diisobutyl aluminium hydride, 2.0mmol chloroform and 0.06mmol isopropyl alcohol; 30 ℃ of ageings 4 hours, form light blue homogeneous catalyst system.
Under nitrogen protection, in polymerization bottle, add the 4mL isoprene, add above-mentioned catalyst then, the mol ratio of catalytic component A and monomer is 4.0 * 10
-4Reacted 4 hours down at 35 ℃, add and contain 2 of 1% quality, the ethanolic solution cessation reaction of 6-di-tert-butyl methyl phenol.The polyisoprene yield is 95.6%, M
wBe 3.70 * 10
5, M
w/ M
nBe 2.0, [η] is 3.71dL/g, and cis-1,4 content is 96.4%.
Claims (10)
1. rare-earth catalysis system, it basic composition is:
A: the rare earth carboxylate compound is C
6-C
10Neodymium naphthenate or branched alkyl carboxylic acid's neodymium,
B: organo-aluminum compound is AlR
3Or AlHR
2Or both mixtures, wherein R is C
1-C
6Alkyl,
C: molecular formula is R
1Cl
mChlorohydrocarbon or molecular formula be R
2Cl
nCOOR
3Chlorinated carboxylic acid ester or both mixtures, wherein R
1～R
3Represent the identical or different alkyl that contains 1～12 carbon atom, cycloalkyl, aryl, alkaryl or aralkyl, m=1-3, n=1-3, Cl links to each other with same carbon atom or links to each other with different carbon atoms,
D:C
1-C
10Straight chain alcohol, branched-chain alcoho or aromatic alcohol,
The mol ratio of each component is A: B: C: D=1: 7～40: 5～85: 0.1～0.6.
2. according to the catalyst system and catalyzing of claim 1, it is characterized in that: the B component is any in the following material or their mixture: triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride, hydrogenation dipropyl aluminium, hydrogenation dibutyl aluminium.
3. according to the catalyst system and catalyzing of claim 1; It is characterized in that: the C component is the mixture of any in the following material or several kinds: chlorohexane, chloroheptane, 2-phenyl-2 cbloropropane isopropyl chloride, 1,4-two (2-chloro-propyl group) benzene, carrene, dichloroethanes, dichloropropane, dichloroetane, chloroform, trichloroethanes, three chlorobutanes, three chloropentanes, methyl chloroacetate, ethyl chloroacetate, monoxone propyl ester, butyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, dichloroacetic acid propyl ester, dichloroacetic acid butyl ester, dichloro methyl propionate, dichloropropionic acid ethyl ester, dichloro-butyric acid ethyl ester, methyl trichloroacetate, ethyl trichloroacetate, trichloroacetic acid propyl ester, butyl trichloroacetate, chloropon ethyl ester, trichlorobutyric acid ethyl ester.
4. according to the catalyst system and catalyzing of claim 1, it is characterized in that: the D component is the mixture of any in the following material or several kinds: methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, cyclohexanol, phenmethylol.
5. according to any catalyst system and catalyzing of claim 1 to 4, it is characterized in that: add few butadiene and/or isoprene in the catalyst system and catalyzing, the mol ratio of addition and catalytic component A is 0.1-4.5.
6. according to the catalyst system and catalyzing of claim 1 or 2, it is characterized in that: the B component is the mixture of any in the following material or several kinds: triethyl aluminum, tri-butyl aluminum, diethyl aluminium hydride, hydrogenation dibutyl aluminium.
7. according to the catalyst system and catalyzing of claim 1 or 3; It is characterized in that: the C component is the mixture of any in the following material or several kinds: 2-phenyl-2 cbloropropane isopropyl chloride, 1,4-two (2-chloro-propyl group) benzene, dichloroethanes, dichloropropane, dichloroetane, chloroform, trichloroethanes, three chlorobutanes, three chloropentanes, ethyl chloride, ethyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, trichloroacetic acid propyl ester, butyl trichloroacetate, chloropon ethyl ester, trichlorobutyric acid ethyl ester.
8. according to the catalyst system and catalyzing of claim 1 or 4, it is characterized in that: the D component is the mixture of any in the following material or several kinds: ethanol, propyl alcohol, butanols, amylalcohol, hexanol.
9. method for preparing high cis-1,4-polyisoprene; Under the inert gas shielding; In isoprene monomer, add any catalyst system and catalyzing in the claim 1 to 8; Descend or do not having to carry out under the external heat source condition isoprene polymerization to react in-80 ℃～50 ℃, it is 1.0 * 10 that the addition of catalyst system and catalyzing makes component A and monomer mole ratio
-4～1.0 * 10
-3
10. according to the method for claim 9, it is characterized in that: polymerisation is with C
6～C
8Saturated alkane or cycloalkane a kind of or their mixture be solvent condition under carry out.
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| CN104130350B (en) * | 2013-05-02 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of butadiene-isoprene copolymer rubber and preparation method thereof |
| CN104231120B (en) * | 2013-06-24 | 2016-03-30 | 北京化工大学 | A kind of long chain branching high cis-1,4-polyisoprene and preparation method thereof |
| CN104725564A (en) * | 2013-12-24 | 2015-06-24 | 青岛伊科思新材料股份有限公司 | Polymerization method of isoprene and butadiene |
| CN105859932B (en) * | 2015-01-23 | 2018-07-13 | 中国石油天然气股份有限公司 | A kind of rare-earth isoprene rubber catalyst process method |
| CN105037588B (en) * | 2015-07-23 | 2017-12-05 | 北京理工大学 | A kind of iso-indoles rare-earth metal catalyst, preparation method and application |
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