CN101492514B - High cis-, low-molecular weight narrow-molecular weight distribution polyisoprene and method for preparing the same - Google Patents
High cis-, low-molecular weight narrow-molecular weight distribution polyisoprene and method for preparing the same Download PDFInfo
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Abstract
The present invention provides a high cis polyisoprene with low molecular weight and narrow molecular weight distribution, as well as a preparation method thereof. The high cis-1, 4 structure content of the polyisoprene is of greater than 95 percent, the low molecular weight of the polyisoprene is weight average molecular weight (Mw) which is 5,600-120,000, and the narrow molecular weight distribution of the polyisoprene is as follows: Mw/Mn is greater than or equal to 1.1-2.0. Polymerization is carried out in a solvent or a body condition without a solvent, and the mixture ratio in a catalyst system is as follows: the mol ratio of dialkylaluminum hydride, chloride, conjugated dialkene and rare-earth carboxylate is 5 to 20: 1.0 to 3.0: 5 to 20: 1; and the catalysts can polymerize isoprene at higher polymerization temperature, and a polymer with the above structural characteristics can be obtained with high yield coefficient.
Description
Technical field
The invention belongs to high-cis, lower molecular weight, narrow molecular weight distributions polyisoprene and preparation method thereof.
Background technology
Low-molecular-weight polyisoprene at room temperature is in a liquid state, and is called the liquid polyisoprene rubber again.The bonding equalization performance excellence of low molecular weight polycaprolactone isoprene and modified product thereof can be used as reactive plasticizer and tenderizer, improves the process operation of rubber, improves low-hardness rubber physical properties of articles and processing characteristics; When using, can improve mechanical property with white carbon black or clay; Can improvement and metallic substance, glass material between clinging power.Itself and conventional rubber consistencies such as natural rubber, polyisoprene rubber, isoprene-isobutylene rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, chloroprene rubber and ethylene-propylene rubber(EPR) are good and can carry out covulcanization, in goods, there is not migration, solvent-free extraction has improved the ageing-resistant and chemical resistance of goods.The lower molecular weight polyisoprene can be applicable in the rubber items such as tyre industry, electric wire, sealed strip, sebific duct, sealing member, printing and textile rubber roll, footwear industry; Also can be applicable to industries such as tackiness agent, seal gum, self-vulcanizing goods, polyamine fat material modification, gluing goods, asphalt modification and lubricating oil additive.
The ideal liquid polyisoprene should have suitable molecular weight ranges, high-cis content and narrow molecular weight distributions.As tenderizer, molecular weight is low excessively with liquid polyisoprene, and the thermotolerance of goods is relatively poor, and molecular weight is too high, the snappiness deficiency of goods; High-cis content is better with mechanical properties such as the tensile strength that guarantees goods, elongation at breaks; Narrow molecular weight distributions is to guarantee the controllability of product properties.
The method for preparing the lower molecular weight polyisoprene has multiple, but the preparation method who satisfies the lower molecular weight polyisoprene of high-cis content and narrow molecular weight distributions simultaneously still is not reported.Radical polymerization technique can obtain low-molecular-weight polyisoprene, but along 1, the 4-structural content is very low.The lithium series anionic living polymerization can prepare the narrow molecular weight distributions polyisoprene of various molecular weight, but prepared polyisoprene suitable-1,4 structural content is on the low side.Prepare the method for lower molecular weight polyisoprene as a kind of lithium-based catalyst of being reported among the patent US4181635, molecular weight of product is 8,000～77, and between 000, molecular weight distributing index is 1.0～2.7, and suitable-1,4 structural content is 75%～87%.Traditional Ziegler-Natta type catalyzer also can prepare low-molecular-weight polyisoprene, but the distribution of the molecular weight of product of gained is very wide, and very easily produces gel [JP 3831/1977] in the polymerization process.
(" rare earth catalyst synthetic rubber collected works " Science Press, 1980) have only summed up the method that rare earth catalyst prepares the polyisoprene of high molecular Gao Shun-1,4 structural content.Mention among the patent CN200710055516 and adopt the homogeneous phase rare earth catalyst, can obtain the polyisoprene of high-cis content (＞96%), narrow molecular weight distributions (＜2.0), but gained is the high molecular polyisoprene rubber.
Summary of the invention
The purpose of this invention is to provide polyisoprene of a kind of high-cis, lower molecular weight, narrow molecular weight distributions and preparation method thereof.
The Gao Shun of this polyisoprene-1,4 structural content＞95%, lower molecular weight are weight-average molecular weight: M
w=5,600～120,000 and narrow molecular weight distributions: M
w/ M
n=1.1～2.0.
A kind of high-cis provided by the invention, lower molecular weight, narrow molecular weight distributions polyisoprene preparation method's step and condition are as follows:
1) catalyst body of Cai Yonging is three component homogeneous catalysts of rare earth carboxylate, and its composition and proportioning are as follows:
A. rare earth carboxylate, preferred neodecanoic acid neodymium, neodymium naphthenate or isocaprylic acid neodymium;
B. hydrogenation aluminum dialkyl, preferred diisobutylaluminium hydride or diethyl aluminium hydride;
C. muriate, preferred dichlorodimethylsilane, trimethylchlorosilane, trichloromethyl silane, silicon tetrachloride, dichloro diphenyl silane or trichlorosilane;
D. conjugated diolefin, preferred isoprene;
The mol ratio of each component is: hydrogenation aluminum dialkyl: muriate: conjugated diolefin: rare earth carboxylate 5～20: 1.0～3.0: 5～20: 1;
2) preparation of three component homogeneous catalysts
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add rare earth carboxylate, conjugated diolefin, the hydrogenation aluminum dialkyl of step 1) successively, reacted 5～10 minutes down in 30～60 ℃; Add muriate then, reacted 5～60 minutes down, obtain three component homogeneous catalysts in 0～60 ℃;
3) preparation of the polyisoprene of high-cis, lower molecular weight, narrow molecular weight distributions
Polyreaction is carried out in solvent or is carried out under solvent-free bulk conditions, and monomeric mass concentration is 15-100%; The polyreaction kick off temperature is 0～50 degree; Catalyst consumption is Nd/Ip=9.8 * 10
-6Mol/g～6.0 * 10
-5Mol/g; Solvent is hexane, hexanaphthene or heptane; The anticaustic concentration g/ml of polymerization be 1% 2, the ethanolic soln of 6-di-tert-butyl methyl phenol stops; Condense polymkeric substance with ethanol, after washing with alcohol, vacuum-drying obtains a kind of high-cis, lower molecular weight, narrow molecular weight distributions polyisoprene again.
Resulting polymers be colourless, do not have smell, the liquid of transparent and gel-free.
The microtexture of polymkeric substance is measured (comprising embodiment) and is adopted the dithiocarbonic anhydride coating method, records on the Vertex-70FTIR of Bruker company type infrared spectrometer.Press document (an aromatic plant metioned in ancient books in Shen etc., Chinese science, 1981, (11): 1340-1349) method, by 836,890cm
-1The absorption band intensity A at place
836, A
890Calculate the suitable-1 of polyisoprene, 4-and 3,4-structural unit molar fraction:
Suitable-1,4 structural unit content (%)=100 * (145 * A
836-1.95 * A
890)/B
3,4-structural unit content (%)=100 * (19.9 * A
890-1.79 * A
836)/B
B＝(145×A
836-1.95×A
890)+(19.9×A
890-1.79×A
836)
The molecular weight distribution of polymkeric substance (comprising embodiment) adopts gel permeation chromatograph (515 type HPLC pumps and 2414 type RI-detector) to measure, four root chromatogram column (HMW7, HMW6E * 2, HMW2), moving phase is tetrahydrofuran (THF), and probe temperature is 30 ℃, and flow velocity is 1.0mL/min, the concentration of solution is 0.2～0.3mg/10mL, utilizes the strainer of 0.45 μ m to filter the back sample introduction.With vinylbenzene is the number-average molecular weight (M that interior mark calculates polymkeric substance
n) and weight-average molecular weight (M
w), and by the ratio (M of weight-average molecular weight and number-average molecular weight
w/ M
n) molecular weight distributing index of characterize polymers.
Description of drawings
Fig. 1 be embodiment 10 high-cis (cis-1,4=96.2%), lower molecular weight (Mn=4700, Mw=5600), the infrared spectrum of the polyisoprene of narrow molecular weight distributions (Mw/Mn=1.17).
Fig. 2 be embodiment 10 high-cis (cis-1,4=96.2%), lower molecular weight (Mn=4700, Mw=5600), the GPC spectrogram of narrow molecular weight distributions (Mw/Mn=1.17).
Embodiment
Embodiment 1
Under nitrogen protection; in exsiccant catalyst reaction bottle; add neodecanoic acid neodymium (Nd), isoprene (IP) and diisobutylaluminium hydride (Al) successively; after reacting 5 minutes under 50 ℃; add dimethyldichlorosilane(DMCS) (Cl) again; reacted 30 minutes down in 25 ℃, obtain being used for the rare earth catalyst of isoprene polymerization.In this catalyzer, the molar ratio of [Nd]/[IP]/[Al]/[Cl] is 1/10/10/3.0.
Under nitrogen protection, in exsiccant 50mL reaction flask, add isoprene monomer 20mL.Add the aforementioned rare earth catalyst for preparing then.Catalyst levels is (Nd/Ip=1.5 * 10
-5Mol/g).Be aggregated under 25 ℃ and carry out.Polyreaction uses the ethanolic soln of the antioxidant 264 that contains 1% (g/ml) to stop after 4 hours.Obtain low-molecular-weight isoprene with the ethanol cohesion.The yield of polymkeric substance is 91%, and suitable-1,4 structural content is that 97.1%, 3,4 structural contents are 2.9%, weight-average molecular weight (M
w) be 25,000, molecular weight distributing index is 1.32.
Embodiment 2
As described in embodiment 1, identical at other conditionally completes, the molar ratio of [Nd]/[IP]/[Al]/[Cl] is under 1/10/10/6.0 the situation when only preparing catalyzer, the yield that obtains polymkeric substance is 93%, and suitable-1,4 structural content is 97.5%, 3,4 structural contents are 2.5%, weight-average molecular weight (M
w) be 86,000, molecular weight distributing index is 1.54.
Embodiment 3
Under nitrogen protection; in exsiccant catalyst reaction bottle; add neodecanoic acid neodymium (Nd), isoprene (IP) and diisobutylaluminium hydride (Al) successively; after reacting 10 minutes under 30 ℃; add dimethyldichlorosilane(DMCS) (Cl) again; reacted 60 minutes down in 0 ℃, obtain being used for the rare earth catalyst of isoprene polymerization.In this catalyzer, the molar ratio of [Nd]/[IP]/[Al]/[Cl] is 1/10/10/3.0.
Under nitrogen protection, in exsiccant 50mL reaction flask, add isoprene monomer 20mL.Add the aforementioned rare earth catalyst for preparing then.Catalyst levels is (Nd/Ip=1.5 * 10
-5Mol/g).Be aggregated under 25 ℃ and carry out.Polyreaction uses the ethanolic soln of the antioxidant 264 that contains 1% (g/ml) to stop after 4 hours.Obtain low-molecular-weight isoprene with the ethanol cohesion.The yield of polymkeric substance is 82%, and suitable-1,4 structural content is that 96.3%, 3,4 structural contents are 3.7%, weight-average molecular weight (M
w) be 30,000, molecular weight distributing index is 1.64.
Embodiment 4
Under nitrogen protection; in exsiccant catalyst reaction bottle; add neodecanoic acid neodymium (Nd), isoprene (IP) and diisobutylaluminium hydride (Al) successively; after reacting 8 minutes under 60 ℃; add dimethyldichlorosilane(DMCS) (Cl) again, react the rare earth catalyst that obtained being used for isoprene polymerization in 5 minutes down at 60 ℃.In this catalyzer, the molar ratio of [Nd]/[IP]/[Al]/[Cl] is 1/10/10/3.0.
Under nitrogen protection, in exsiccant 50mL reaction flask, add isoprene monomer 20mL.Add the aforementioned rare earth catalyst for preparing then.Catalyst levels is (Nd/Ip=1.5 * 10
-5Mol/g).Be aggregated under 25 ℃ and carry out.Polyreaction uses the ethanolic soln of the antioxidant 264 that contains 1% (g/ml) to stop after 4 hours.Obtain low-molecular-weight isoprene with the ethanol cohesion.The yield of polymkeric substance is 94%, and suitable-1,4 structural content is that 96.5%, 3,4 structural contents are 3.5%, weight-average molecular weight (M
w) be 22,000, molecular weight distributing index is 1.22.
Embodiment 5
As described in embodiment 1, identical at other conditionally completes, only replace diisobutylaluminium hydride with diethyl aluminium hydride, preparation during catalyzer the molar ratio of [Nd]/[IP]/[Al]/[Cl] be that the yield of resulting polymers is 91% under 1/10/10/9.0 the situation, suitable-1,4 structural contents are 97.2%, 3,4 structural contents are 2.8%, weight-average molecular weight (M
w) be 25,000, molecular weight distributing index is 1.39.
Embodiment 6
As described in embodiment 1, identical at other conditionally completes, only replace under the situation of neodecanoic acid neodymium with the isocaprylic acid neodymium, the yield of resulting polymers is 92%, suitable-1,4 structural content is that 97.3%, 3,4 structural contents are 2.7, weight-average molecular weight is 36,000, and molecular weight distributing index is 1.44.
Embodiment 7
As described in embodiment 1, identical at other conditionally completes, only replace the neodecanoic acid neodymium with the isocaprylic acid neodymium, silicon tetrachloride replaces dimethyldichlorosilane(DMCS), [Nd] in the catalyzer/[IP]/[Al]/[Cl] molar ratio is that the yield of resulting polymers is 85% under 1/10/10/4 the situation, suitable-1,4 structural contents are 96.8%, 3,4 structural contents are 3.2%, and weight-average molecular weight is 38,000, molecular weight distributing index is 1.67.
Embodiment 8
As described in embodiment 1, identical at other conditionally completes, only replace under the situation of dimethyldichlorosilane(DMCS) with trichloromethyl silane, the yield of resulting polymers is 89%, suitable-1,4 structural contents are 97.0%, 3,4 structural contents are 3.0%, and weight-average molecular weight is 39,000, molecular weight distributing index is 1.62.
Embodiment 9
As described in embodiment 1, identical at other conditionally completes, only [Nd]/[IP]/[Al] in the catalyzer/[Cl] molar ratio is 1/10/20/4, and catalyst levels is Nd/Ip=2.0 * 10
-5Under the situation of mol/g, the yield of resulting polymers is 96%, and suitable-1,4 structural content is that 97.2%, 3,4 structural unit content are 2.8%, and weight-average molecular weight is 34,000, and molecular weight distributing index is 1.89.
Under nitrogen protection; in exsiccant catalyst reaction bottle; add neodecanoic acid neodymium (Nd) successively; isoprene (IP); diisobutylaluminium hydride (Al); add dimethyldichlorosilane(DMCS) (Cl) in reaction under 50 ℃ after 5 minutes, reacted 30 minutes down, obtain being used for the homogeneous phase rare earth catalyst of isoprene polymerization in 25 ℃.[Nd]/[IP]/[Al] in this catalyzer/[Cl] mol ratio is 1/10/20/4.
Under nitrogen protection, in the 50mL of dry deacration reaction flask, add 17mL heptane and 3mL isoprene monomer.Add aforementioned rare earth catalyst then.Catalyst levels is Nd/Ip=6.0 * 10
-5Mol/g.Be aggregated under 50 ℃ and carry out reacting balance.Reacting the ethanolic soln of using the antioxidant 264 that contains 1% (g/ml) after 4 hours stops.With the ethanol cohesion, obtain the lower molecular weight polyisoprene.The yield of polymkeric substance is 91%, and suitable-1,4 structural content is that 96.2%, 3,4 structural contents are 3.8%, and weight-average molecular weight is 5,600, and molecular weight distributing index is 1.17.
Embodiment 11
Under nitrogen protection; in exsiccant catalyst reaction bottle; add neodecanoic acid neodymium (Nd) successively; isoprene (IP); diisobutylaluminium hydride (Al); add dimethyldichlorosilane(DMCS) (Cl) in reaction under 50 ℃ after 5 minutes, reacted 30 minutes down, obtain being used for the homogeneous phase rare earth catalyst of isoprene polymerization in 25 ℃.[Nd]/[IP]/[Al] in this catalyzer/[Cl] mol ratio is 1/10/20/4.
Under nitrogen protection, in the 50mL of dry deacration reaction flask, add 17mL heptane and 3mL isoprene monomer.Add aforementioned rare earth catalyst then.Catalyst levels is Nd/Ip=3.0 * 10
-5Mol/g.Be aggregated under 50 ℃ and carry out reacting balance.Reacting the ethanolic soln of using the antioxidant 264 that contains 1% (g/ml) after 4 hours stops.With the ethanol cohesion, obtain the lower molecular weight polyisoprene.The yield of polymkeric substance is 100%, and suitable-1,4 structural content is that 96.4%, 3,4 structural contents are 3.8%, and weight-average molecular weight is 11,000, and molecular weight distributing index is 1.10.
Embodiment 12
Under nitrogen protection; in exsiccant catalyst reaction bottle; add neodecanoic acid neodymium (Nd) successively; isoprene (IP); diisobutylaluminium hydride (Al); add dimethyldichlorosilane(DMCS) (Cl) in reaction under 50 ℃ after 5 minutes, reacted 30 minutes down, obtain being used for the rare earth catalyst of isoprene polymerization in 25 ℃.The molar ratio of [Nd]/[IP]/[Al]/[Cl] is 1/10/10/4.0 in this catalyzer.
Under nitrogen protection, in the 50mL reaction flask, add 17mL hexanaphthene and 3mL isoprene.Add aforementioned rare earth catalyst then.Catalyst levels is Nd/Ip=6.0 * 10
-5Mol/g.Be aggregated under 20 ℃ and carry out reacting balance.Reacting the ethanolic soln of using the antioxidant 264 that contains 1% (g/ml) after 4 hours stops.With the ethanol cohesion, obtain the lower molecular weight polyisoprene.The yield of polymkeric substance is 98%, and suitable-1,4 structural content is that 96.6%, 3,4 structural contents are 3.4%, and weight-average molecular weight is 19,000, and molecular weight distributing index is 1.27.
Embodiment 13
Under nitrogen protection; in the catalyst reaction bottle; add neodecanoic acid neodymium (Nd) successively; isoprene (IP); diisobutylaluminium hydride (Al); add dimethyldichlorosilane(DMCS) (Cl) in reaction under 50 ℃ after 5 minutes, reacted 30 minutes down, obtain being used for the rare earth catalyst of isoprene polymerization in 25 ℃.The molar ratio of [Nd]/[Ip]/[Al]/[Cl] is 1/10/10/4.0 in this catalyzer.
Under nitrogen protection, in the 50mL of dry deacration reaction flask, add 14mL hexane and 6mL isoprene.Add aforementioned rare earth catalyst then.Catalyst levels is Nd/Ip=6.0 * 10
-5Mol/g.Be aggregated under 0 ℃ and carry out reacting balance.Reacting the ethanolic soln of using the antioxidant 264 that contains 1% (g/ml) after 4 hours stops.With the ethanol cohesion, obtain the lower molecular weight polyisoprene.The yield of polymkeric substance is 60%, and suitable-1,4 structural content is that 97.6%, 3,4 structural contents are 2.4%, and weight-average molecular weight is 13,000, and molecular weight distributing index is 1.21.
Embodiment 14
Under nitrogen protection; in the catalyst reaction bottle; add neodecanoic acid neodymium (Nd) successively; isoprene (IP); diisobutylaluminium hydride (Al); add dimethyldichlorosilane(DMCS) (Cl) in reaction under 50 ℃ after 5 minutes, reacted 30 minutes down, obtain being used for the rare earth catalyst of isoprene polymerization in 25 ℃.The molar ratio of [Nd]/[Ip]/[Al]/[Cl] is 1/10/10/4.0 in this catalyzer.
Under nitrogen protection, in the 50mL reaction flask, add 10mL hexane and 10mL isoprene monomer.Add aforementioned rare earth catalyst then.Catalyst levels is Nd/Ip=6.0 * 10
-5Mol/g.Be aggregated under 30 ℃ and carry out reacting balance.React after 4 hours and stop with ethanolic soln with the antioxidant 264 that contains 1% (g/ml).With the ethanol cohesion, obtain the lower molecular weight polyisoprene.The yield of polymkeric substance is 100%, and suitable-1,4 structural content is that 96.6%, 3,4 structural contents are 3.4%, and weight-average molecular weight is 19,000, and molecular weight distributing index is 1.29.
Embodiment 15
Under nitrogen protection, in the catalyst reaction bottle, add neodecanoic acid neodymium (Nd) successively, isoprene (IP), diisobutylaluminium hydride (Al) adds dimethyldichlorosilane(DMCS) (Cl) in reaction under 50 ℃ after 5 minutes.After 25 ℃ of room temperatures are reacted 30 minutes down, obtain being used for the rare earth catalyst of isoprene polymerization.The molar ratio of [Nd]/[Ip]/[Al]/[Cl] is 1/10/20/4.0 in this catalyzer.
Under nitrogen protection, in the 5L still, add 1500mL (1008g) hexane and 450mL (306g) isoprene.10 ℃ and stir under, add aforementioned rare earth catalyst, initiated polymerization.After 1 hour, add 450mL (306g) isoprene; After 2 hours, add 600mL (409g) isoprene again.Total catalyst levels is [Nd]/IP=9.8 * 10
-6Mol/g.Stable polymerization reaction is carried out.After 3 hours, stop polymerization with the ethanolic soln that contains 1% (g/ml) anti-aging agent-264, the polymkeric substance that in ethanol, settles out again, after washing with alcohol, the polyisoprene of the son amount that makes low score.The yield of polymkeric substance is 100%, and suitable-1,4 structural content is that 96.7%, 3,4 structural contents are 3.3%, and number-average molecular weight is 116,000, and molecular weight distributing index is 2.16.
Claims (4)
1. the preparation method of a high-cis, lower molecular weight, narrow molecular weight distributions polyisoprene is characterized in that, the height of described polyisoprene is along 1,4 structural content＞95%, and lower molecular weight is weight-average molecular weight: M
w=5,600～120,000, narrow molecular weight distributions: M
w/ M
n=1.1～2.0;
1) catalyst body of Cai Yonging is three component homogeneous catalysts of rare earth carboxylate, and its composition and proportioning are as follows:
A. rare earth carboxylate;
B. hydrogenation aluminum dialkyl;
C. muriate;
D. conjugated diolefin;
The mol ratio of each component is: hydrogenation aluminum dialkyl: muriate: conjugated diolefin: rare earth carboxylate 5～20: 1.0～3.0: 5～20: 1;
2) preparation of three component homogeneous catalysts
Under nitrogen protection, in the exsiccant hydrogen-catalyst reactor, add rare earth carboxylate, conjugated diolefin, the hydrogenation aluminum dialkyl of step 1) successively, reacted 5～10 minutes down in 30～60 ℃; Add muriate then, reacted 5～60 minutes down, obtain three component homogeneous catalysts in 0～60 ℃;
3) preparation of the polyisoprene of high-cis, lower molecular weight, narrow molecular weight distributions
Polyreaction is carried out in solvent or is carried out under solvent-free bulk conditions, and monomeric mass concentration is 15-100%; The polyreaction kick off temperature is 0～50 degree; Catalyst consumption is Nd/Ip=9.8 * 10
-6Mol/g～6.0 * 10
-5Mol/g; Solvent is hexane, hexanaphthene or heptane; Polymerization finish with g/ml concentration be 1% 2, the ethanolic soln termination of 6-di-tert-butyl methyl phenol; Condense polymkeric substance with ethanol, after washing with alcohol, vacuum-drying obtains a kind of high-cis, lower molecular weight, narrow molecular weight distributions polyisoprene again; The muriate of described step 1) is dichlorodimethylsilane, trimethylchlorosilane, trichloromethyl silane, silicon tetrachloride, dichloro diphenyl silane or trichlorosilane.
2. the preparation method of a kind of high-cis as claimed in claim 1, lower molecular weight, narrow molecular weight distributions polyisoprene is characterized in that, the rare earth carboxylate of described step 1) is the neodecanoic acid neodymium, neodymium naphthenate or isocaprylic acid neodymium.
3. the preparation method of a kind of high-cis as claimed in claim 1, lower molecular weight, narrow molecular weight distributions polyisoprene is characterized in that, the hydrogenation aluminum dialkyl of described step 1) is diisobutylaluminium hydride or diethyl aluminium hydride.
4. the preparation method of a kind of high-cis as claimed in claim 1, lower molecular weight, narrow molecular weight distributions polyisoprene is characterized in that, the conjugated diolefin of described step 1) is an isoprene.
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| CN101838350B (en) * | 2010-06-09 | 2011-11-02 | 中国科学院长春应用化学研究所 | Rare earth catalyst composition and preparation method of rare earth catalyst |
| CN102464745A (en) * | 2010-11-18 | 2012-05-23 | 中国石油天然气股份有限公司 | Adjustment method for molecular weight distribution of rare-earth isoprene rubber |
| CN102181002B (en) * | 2011-03-04 | 2012-11-14 | 中国石油天然气股份有限公司吉林石化分公司 | Wet coagulation method for rare-earth isoprene rubber |
| CN102898565A (en) * | 2011-07-29 | 2013-01-30 | 中国石油天然气股份有限公司 | Cooling method for isoprene rubber polymerization reaction |
| CN102911327B (en) * | 2012-10-30 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method of conjugated diene and polar monomer segmented copolymer with low molecular weight |
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| CN114230696B (en) * | 2021-12-14 | 2023-04-04 | 青岛科技大学 | Homogeneous rare earth catalyst and preparation method and application thereof |
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