CN1031406C - High cis-1,4-polybutadiene suitable for prepn. of high anti-impact polystyrene - Google Patents

High cis-1,4-polybutadiene suitable for prepn. of high anti-impact polystyrene Download PDF

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CN1031406C
CN1031406C CN 94102595 CN94102595A CN1031406C CN 1031406 C CN1031406 C CN 1031406C CN 94102595 CN94102595 CN 94102595 CN 94102595 A CN94102595 A CN 94102595A CN 1031406 C CN1031406 C CN 1031406C
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divinyl
viscosity
nickel
aluminium
cis
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CN1093375A (en
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姜连升
黄健
冯志豪
余赋生
王佛松
阎铁良
张守信
吕作君
毛正陶
柳希春
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SYNTHETIC RUBBER PLANT BEIJING
Changchun Institute of Applied Chemistry of CAS
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SYNTHETIC RUBBER PLANT BEIJING
Changchun Institute of Applied Chemistry of CAS
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Abstract

The present invention relates to high cis-1, 4-polybutadiene suitable for preparing polystyrene of high impact resistance and a preparing method. A nickel-aluminium-boron catalyst system is adopted. The molar ratios of nickel and aluminium to butadiene are respectively (1.0 to 6.0) X0.00001 and (3.0 to 10.0) X0.00001. The molar ratio of aluminium to boron is 0.075 to 0.70. The molar ratio of water in a mixed solution of solvents and butadiene to butadiene is (0 to 13.0) *0.00001. The polyreaction temperature is 60 to 120 DEG C. The structure content of the product of cis-1, 4-polybutadiene prepared by the method of the present invention is not smaller than 93%, the mooney viscosity is 30 to 55, and Nz/ml is not larger than 2*100000; the specific viscosity namber n] in toluene at 30 is 1.5 to 2: the viscosity of 5% of styrene solution is 50 to 139 centipoises, and the insoluble matter content of styrene is smaller than 0.03%.

Description

Be applicable to high-cis 1,4-polyhutadiene of preparation high impact resistance polystyrene and preparation method thereof
The present invention relates to 1,3-butadiene solution polymerization process, be particularly related to a kind of have certain mooney viscosity, suitably low intrinsic viscosity and soltion viscosity, the unusual high-cis 1 of low-styrene insolubles content, the preparation method of 4-polyhutadiene, and relate to by prepared product of the inventive method and uses thereof.
According to different service requirementss, high-cis 1,4-polyhutadiene can be made into the material based on good mechanical property, be used to make tire, also can be made into material, be used for plastics, resin modified, particularly prepare high impact resistance polystyrene (being called for short HIPS) based on solution properties.
Household electrical appliance such as televisor, video recorder and office automation device housings, the past mainly is with ABS (acrylonitrile-butadiene-styrene) resin manufacture, and shock resistance and glossiness are all had very high requirement.But ABS resin than resins for universal use costlinesses such as polyethylene, polypropylene many.In order to reduce the goods cost, replace ABS resin with cheap resin, each big manufacturer is studied always.Utilize the polystyrene resin of modified rubber to have advantages such as shock resistance is higher, surface gloss good, easy injection moulding, and price is more cheap than ABS resin.Therefore, obtain promoting in replacement ABS application facet.
When adopting body or suspension polymerization to produce HIPS, the 5% styrene solution viscosity and the vinylbenzene insolubles content of polyhutadiene directly influence the HIPS quality.Desire preparation quality HIPS preferably, used rubber must have suitably low soltion viscosity and low-down vinylbenzene insolubles content under certain mooney viscosity.
Up to the present, be used to produce the rubber of HIPS, low cis 1, the 4-polybutadiene rubber of lithium-based catalyst production and high-cis 1,4-polybutadiene rubber that cobalt series catalyst is produced are arranged.Be used for result and the performance of HIPS as for polybutadiene rubber, do not see open report so far with nickel-aluminium-boron series catalysts preparation.Do not see the open method that is applicable to the polybutadiene rubber of producing HIPS in the document with nickel-aluminium-B catalyst preparation yet.
Though disclosed day of on March 9th, 1981, the disclosure was speciallyyed permit clear 56-24412 employing nickel catalysts, but its objective is the low-molecular-weight polyhutadiene of preparation, in 30 ℃ of toluene, its limiting viscosity is 0.3-1.2, and polymkeric substance is liquid, heavy-gravity maltosemalt sugar shape thing extremely; Disclosure special permission on disclosed day of March 30 nineteen ninety flat 2-91105 also belongs to nickel-aluminium-B catalyst system, but its objective is that improving polyhutadiene extrudes processing and rolling processing characteristics, requires the Z-average molecular weight and the mooney viscosity ratio (M of polyhutadiene Z/ ML) 3 * 10 4More than.And the objective of the invention is to prepare the needed polybutadiene rubber of a kind of production HIPS, and its Z-average molecular weight is 40-60 ten thousand, and limiting viscosity is 1.5-2.2, and mooney viscosity is 30-55, M Z/ ML≤2 * 10 -4
Industrial, as to adopt nickel catalyst to produce universal high-cis 1,4-polybutadiene rubber, intrinsic viscosity generally is higher than 2.2,5% styrene solution viscosity is more than 140mPa.s, and the vinylbenzene insolubles content far can not satisfy the requirement of preparation high-quality HIPS greater than 0.07%.
The objective of the invention is to avoid the weak point in the above-mentioned background technology, provide a kind of improved be that catalyzer, stable hydrocarbon are that solvent prepares high-cis 1 with nickel-aluminium-boron, the method of 4-polyhutadiene, make the polyhutadiene product of preparation under certain mooney viscosity, have suitably low soltion viscosity and low-down vinylbenzene insolubles content, be applicable to preparation high-quality HIPS.
Purpose of the present invention can reach by following measure:
Make catalyzer with carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound, make 1,3-divinyl carry out solution polymerization.Water-content is respectively in each amounts of components of catalyzer and solvent and the divinyl mixed solution:
Nickel is (1.0-6.0) * 10 to the mol ratio of divinyl -5
Aluminium is (3.0-10.0) * 10 to the mol ratio of divinyl -5
Aluminium is 0.075-0.70 to the mol ratio of boron;
Water is (0-13.0) * 10 to the mol ratio of divinyl -5
The butadiene polymerization temperature is 60-120 ℃.
By control, adjusting, make the polybutadiene rubber that obtains satisfy the requirement of preparation high impact resistance polystyrene to water-content in catalyst formulation, polymerization process condition and solvent and the divinyl.
Polybutadiene rubber cis 1,4 structural content 〉=93% that makes under above cooperation condition, mooney viscosity is 30-55, M Z/ ML≤2 * 10 4, intrinsic viscosity [η] is that 1.5-2.2,25 ℃, 5% styrene solution viscosity are 50-139mPa.s in 30 ℃ of toluene, vinylbenzene insolubles content＜0.03%.
The carboxylic acid nickel salt is soluble nickel compounds such as nickel naphthenate, nickel acetate, nickel octoate.
Aluminum alkyls is organo-aluminium compounds such as triisobutyl aluminium or triethyl aluminum.
Boron trifluoride or its complex compound are boron trifluoride ethyl ether complex or boron trifluoride ether complex.
The aliphatic saturated hydrocarbon that is in a liquid state when polymer solvent is polymerization, aromatic hydrocarbons, alkane aromatic hydrocarbons or its mixture are raffinated oil such as refinery, hexane, heptane, benzene, toluene or its mixture etc.
Catalyzer give processing mode, feed way, identical with the universal nickel polymerized BR of preparation.
Polymerizing butadiene can intermittently or carry out continuously.
Butadiene conversion＞85%.
Catalyst component nickel is (1.0-6.0) * 10 to the mol ratio of divinyl -5, preferred value is (2.5-6.0) * 10 -5Nickel is lower than 1.0 * 10 to the mol ratio of divinyl -5, molecular weight distribution is widened, and under certain mooney viscosity, soltion viscosity increases.
Catalyst component aluminium is (3.0-10.0) * 10 to the mol ratio of divinyl -5, preferred value is (4.4-8.5) * 10 -5Aluminium is lower than 3.0 * 10 to the mol ratio of divinyl -5, be not enough to a nickel Restore All and become nickel at a low price; Be higher than 10.0 * 10 -5, then easily generating high polymer, mooney viscosity increases, and the gel growing amount increases.
Aluminium is 0.075-0.70 to the mol ratio of boron, and preferred value is 0.075-0.3.
Water is (0-13.0) * 10 to the mol ratio of divinyl in solvent and the divinyl mixed solution -5, preferred value is (0-10.0) * 10 -5Water is higher than 13.0 * 10 to the mol ratio of divinyl -5, the molecular weight distribution of polyhutadiene broadens, and soltion viscosity increases.
The butadiene polymerization temperature is 60-120 ℃, and preferred value is 80-120 ℃.Polymeric reaction temperature is lower than 60 ℃, and the degree of branching of polyhutadiene reduces, and soltion viscosity increases.
The present invention regulates structure, molecular weight and molecular weight distribution that polymerization formula and processing condition are come telomerized polymer by the water number in the controlled polymerization system.
Water number in solvent and the divinyl mixed solution can be controlled, regulate by dehydration or the method that adds water, and polymer solvent and divinyl can be through solvent and butadiene recovery unit processed.
According to the inventive method, adopt technique scheme, regulate each amounts of components of catalyzer, micro-water content and polymeric reaction temperature can stably be controlled Z-average molecular weight, mooney viscosity, intrinsic viscosity, 5% styrene solution viscosity and the vinylbenzene insolubles content of polyhutadiene in control solvent and the divinyl in above-mentioned scope.Otherwise, then be difficult to reach purpose of the present invention.
According to the polyhutadiene of the cooperation condition of the inventive method preparation, cis 1,4 structural content 〉=93%, Z-average molecular weight are 40-60 ten thousand, and mooney viscosity is 30-55, z/ML≤2.0 * 10 4, intrinsic viscosity [η] is that 1.5-2.2,25 ℃, 5% styrene solution viscosity are 50-139mPa.s in 30 ℃, toluene, vinylbenzene insolubles content≤0.03%.
Polybutadiene rubber intrinsic viscosity [η] is controlled in 1.5-2.2 scopes, and preferred value is 1.5-2.0.The intrinsic viscosity of polyhutadiene [η] is higher than 2.2, and 5% styrene solution viscosity height then is bad with the HIPS glossiness of the glue preparation of high soltion viscosity.
Polyhutadiene 5% styrene solution viscosity in the time of 25 ℃ is 50-139mPa.s, and preferred value is 50-80mPa.s.Be lower than 50mPa.s, prepared HIPS resistance to impact shock descends; Be higher than 139mPa.s, prepared HIPS surface gloss descends.
The vinylbenzene insolubles content is less than 0.03%, and preferred value is less than 0.010%.Be higher than 0.03%, surface gloss and the resistance to impact shock of the HIPS of preparation all descend.
According to high-cis 1, the 4-polybutadiene rubber of the inventive method preparation, Z-average molecular weight and mooney viscosity are moderate, and intrinsic viscosity, 5% styrene solution viscosity are low, and the vinylbenzene insolubles content is very low.Test result sees Table 1.
The salient features of table 1 polyhutadiene of the present invention
Index name The scope of application Analytical procedure
Generally Preferably
Cis 1,4 structural content (%) ＞85 ≥94 Infrared analysis
Z-average molecular weight (ten thousand) 40—60 40-50 Gpc analysis
[η](dl/g) 1.5-2.2 1.5-2.0 Gpc analysis
M Z/ML(×10 4) 2 0.8-1.5
Viscosity-average molecular weight (ten thousand) 16—23 16-19 Gpc analysis
Mooney viscosity 30—55 35-45 ASTMD1416-63AT (USS)
25 ℃ of 5% styrene solution viscosity (mPa.s) 50-139 50-80 RMS—R 2B (Dow company)
Vinylbenzene insolubles (%) ＜0.03 ＜0.010 RMS—R 2B (Dow company)
Colourity (APHA) ＜10 RMS—R 2B (Dow company)
Dissolution time (hour) ＜2 RMS—R 2B (Dow company)
Polybutadiene rubber according to the inventive method preparation can be used for preparing the high-quality high impact resistance polystyrene.With the HIPS of this glue preparation, test physical and mechanical properties by analysis and reach following level: shock strength is that 106.4J/M, flexural strength are that 44.9MPa, modulus in flexure are that 37.0MPa, breaking tenacity are that 34.9MPa, elongation are 51.6%.
Major advantage of the present invention is: according to method of the present invention, can utilize device, the equipment of producing common nickel polymerized BR, prepare the polybutadiene rubber of various soltion viscosities.According to the low solution viscosity polybutadiene rubber of the inventive method preparation, the vinylbenzene insolubles content is very low, and Heat stability is good can be in order to preparation high-quality HIPS.Polymerization process of the present invention, energy consumption is low, polymeric kettle and pipeline kiss-coating are light, easy to operate, stable production process, running period is long.
In the text, except that elongation, umber and hundred umbers are all by weight.
The mooney viscosity day automatic Mooney viscometer determining of island proper Tianjin company production (value was rotated 4 minutes in preheating 1 minute down at 100 ℃); Soltion viscosity is to be made into 5% styrene solution, at 25 ℃, usefulness card farming-Fen Sike viscometer determining; Micmstructure of polymer is measured with Hitachi's 260-50 type infrared spectrophotometers; Polymkeric substance viscosity-average molecular weight, Z. average molecular weight are measured with the GPC instrument that Wa-ters company produces; The vinylbenzene insolubles uses the aperture to measure as the stainless (steel) wire filtration of 40u; Minor amount of water is pressed the karl Fischer method and is measured; Intrinsic viscosity [η] is measured in 30 ℃ of toluene.The unit of [η] is dl/g in the literary composition.
The shock strength of HIPS, flexural strength and modulus in flexure, breaking tenacity and elongation adopt ASTM-D256, ASTM-D747 and ASTM-D638 method to carry out analytical test respectively.
Further specify the present invention below in conjunction with embodiment, but do not limit the scope of the invention.
Embodiment 1
5 liters of polymeric kettles with having ribbon stirring, chuck, temperature, pressure indication make 1,3-divinyl carry out batchwise polymerization.
At first, strict raffinate oil to heat up with clean refinery wash still, with high-purity nitrogen extrude wash still and raffinate oil after, under nitrogen protection, adding is raffinated oil and 54 parts of divinyl for 201.4 parts in the polymeric kettle, stirs.Raffinate oil and all process retrieving arrangement dehydrations in advance of divinyl.Get 3.34 * 10 -2Part nickel naphthenate, 1.17 * 10 -2Part triisobutyl aluminium, 6.39 * 10 -2Part boron fluoride etherate respectively with 1 part of dilution of raffinating oil, mixes aluminium, nickel component then, adds in the polymeric kettle with the boron component again.Raffinate oil with the divinyl mixed solution in moisture 1.29 * 10 -3Part.Under 100 ℃ of temperature, make 1,3-divinyl reaction 2 hours, in polymeric kettle, add ethanol 1.62 * 10 -2Part, 0.162 part in anti-aging agent " 1076 " (3,5 di-t-butyls-4-hydroxy phenyl propionic acid stearyl alcohol ester) takes out glue then, the water steam boiling, and hot roller drying obtains product of the present invention.Butadiene conversion is 89.2%.
Reaction conditions and product test the results are shown in Table 2.
Comparative Examples 1
Add nickel naphthenate 0.42 * 10 -2Part.Butadiene conversion is 82%.
All the other are with embodiment 1.
Embodiment 2
Nickel octoate 1.99 * 10 -2Part, triisobutyl aluminium 1.39 * 10 -2Part, boron trifluoride ethyl ether complex is 6.82 * 10 -2Part.The butadiene polymerization temperature is 95 ℃, raffinate oil and the divinyl mixed solution in moisture 2.07 * 10 -3Part.
All the other are with embodiment 1.
Comparative Examples 2
Raffinate oil with the divinyl mixed solution in moisture 5.41 * 10 -3Part.
Butadiene conversion is 85.3%.
All the other are with embodiment 2.
Embodiment 3
Replace raffinating oil with benzene.Nickel naphthenate 2.64 * 10 -2Part, boron trifluoride ether complex is 11.50 * 10 -2Part, triisobutyl aluminium 0.89 * 10 -2Part, in benzene and the divinyl mixed solution moisture 1.93 * 10 -3Part, the butadiene polymerization temperature is 110 ℃.Butadiene conversion is 87.2%.
All the other are with embodiment 1.
Comparative Examples 3
The butadiene polymerization temperature is 40 ℃.Butadiene conversion is 80.6%.
All the other are with embodiment 3.
Embodiment 4
Replace raffinating oil nickel naphthenate 1.74 * 10 with hexane -2Part, triethyl aluminum 0.93 * 10 -2Part, boron trifluoride ethyl ether complex 4.40 * 10 -2Part, in hexane and the butylene mixed solution moisture 1.81 * 10 -3, polymerizing butadiene system response temperature is 78 ℃.
All the other are with embodiment 1.
Comparative Examples 4
Triethyl aluminum 1.42 * 10 -3Part, in hexane and the divinyl mixed solution moisture 3.75 * 10 -3Part.
All the other are with embodiment 4.
Embodiment 5
Nickel naphthenate 1.03 * 10 -2Part, triisobutyl aluminium 1.68 * 10 -2Part, boron trifluoride ethyl ether complex 6.39 * 10 -2Part.
Divinyl is twice immersion of KOH dehydration of drying in advance, the reflux dewatering in the presence of LiAlH4 in advance of raffinating oil.85 ℃ of paradigmatic system temperature of reaction.Butadiene conversion is 90.3%.
All the other are with embodiment 1.
Embodiment 6
Replace raffinating oil with toluene.Nickel naphthenate 1.39 * 10 -2Part, triisobutyl aluminium 1.84 * 10 -2Part, boron trifluoride ethyl ether complex 3.27 * 10 -2Part, use 1 part of dilution with toluene respectively after, add in the polymeric kettle separately.In toluene and the divinyl mixed solution moisture 3.05 * 10 -3Part, 115 ℃ of polymeric reaction temperatures.Butadiene conversion is 85.0%.
All the other are with embodiment 1.
Embodiment 7
Replace raffinating oil with heptane.Nickel naphthenate 0.70 * 10 -2Part, triisobutyl aluminium 0.59 * 10 -2Part, boron trifluoride ethyl ether complex 1.45 * 10 -2Part, after diluting with 1 part of heptane respectively, ageing together adds in the polymeric kettle again, in heptane and the divinyl mixed solution moisture 0.94 * 10 -3Part, 120 ℃ of polymeric reaction temperatures.
All the other are with embodiment 1.
Embodiment 8
Mixed solution (hexane accounts for 70%, and benzene accounts for 30%) with hexane and benzene replaces raffinating oil.
Nickel naphthenate 1.39 * 10 -2Part, triisobutyl aluminium 1.98 * 10 -2Part, boron trifluoride ethyl ether complex 2.13 * 10 -2Part, in hexane, benzene mixed solution and the divinyl moisture 2.58 * 10 -3Part, 63 ℃ of polymeric reaction temperatures.Butadiene conversion is 86.2%.
All the other are with embodiment 1.
Table 2 butadiene polymerization condition and product test result
Sequence number Nickel component (part) (* 10 -2) Aluminium component (part) (* 10 -2) Boron component (part) (* 10 -2) Minor amount of water (part) (* 10 -3) Polymerization temperature (℃) [η] (dl/g) Mooney viscosity 5% vinyl solution viscosity (mPa.s) Vinylbenzene insolubles content (%) Cis 1,4 structure (%) Z-average molecular weight (ten thousand)
Embodiment 1 3.34 1.17 6.39 1.29 100 1.5 37.7 51.0 0.007 95.3 40.1
Comparative Examples 1 0.42 1.17 6.39 1.29 100 2.5 70.0 242.6 0.42 94.5
Embodiment 2 1.99 1.39 6.82 2.07 95 1.5 41.0 50.0 0.006 94.4 40.0
Comparative Examples 2 1.99 1.39 6.82 5.41 95 2.4 35.0 210.5 0.50 95.5
Embodiment 3 2.64 0.89 11.50 1.93 110 1.6 40.0 55.0 0.008 94.6 42.4
Comparative Examples 3 2.64 0.89 11.50 1.93 40 2.6 60.0 378.6 0.70 95.9
Embodiment 4 1.74 0.93 6.39 1.93 78 1.8 43.4 77.0 0.009 96.3 43.8
Comparative Examples 4 1.74 1.42 4.40 3.75 78 2.3 44.0 188 0.35 95.4
Embodiment 5 1.03 1.68 6.39 0 85 1.6 42.0 62.3 0.008 95.7 42.5
Embodiment 6 1.39 1.84 3.27 3.05 115 1.9 47.6 98.6 0.012 94.7 48.4
Embodiment 7 0.70 0.59 1.45 0.94 120 2.1 54.0 138.6 0.015 94.6 55.0
Embodiment 8 1.39 1.98 2.13 2.58 63 2.0 51.0 123.0 0.014 95.0 50.5
Embodiment 9
The polymeric kettle that adopts 3 40 liters bands to stir carries out successive polymerization.
With nitrogen replacement, wash still after, raffinate oil, divinyl adds first polymeric kettle with the inlet amount of 10.37kg/hr and 2.8kg/hr respectively, water-content is 5.5PPm in control divinyl and the solvent.The add-on of nickel naphthenate, triisobutyl aluminium and boron trifluoride ethyl ether complex is respectively 1.44 * 10 -3Kg/hr, 7.19 * 10 -4Kg/hr and 2.50 * 10 -3Kg/hr.Enter second still after first still is full of, enter the 3rd still after second still is full of.The temperature of reaction of three polymeric kettles is respectively 88 ℃, 95 ℃ and 104 ℃.
Add ethanol 7.49*10 respectively at the 3rd still outlet line -4Kg/hr, anti-aging agent " 1076 " 8.4 * 10 -3Kg/hr, glue enters basin.Glue through hot cooking, drying, obtain polybutadiene rubber of the present invention and test by analysis, butadiene conversion is 89.8%, Mooney point is 38.0, limiting viscosity in 30 ℃ of toluene is 1.6,5% styrene solution viscosity (25 ℃) is 55.0mPa.s, and the vinylbenzene insolubles content is 0.008%, cis 1,4 structural contents are 95.8%, and Z-average molecular weight is 41.2 ten thousand.
By table 2 and embodiment 9 as seen, according to method of the present invention, can prepare have certain mooney viscosity, the suitably low solution viscosity and unusual high-cis 1, the 4-polybutadiene rubber of low-styrene insolubles content.Otherwise, the polyhutadiene product of preparation, limiting viscosity, soltion viscosity and vinylbenzene insolubles content are all than higher.
Embodiment 10
With 1.68 kilograms of products of the present invention, after 24 kilograms of vinylbenzene dissolvings, add in 40 liters of polymeric kettles, add 3.85 kilograms of ethylbenzene and 0.012 kilogram of 1,1-cyclohexane di-tert-butyl peroxide again, under agitation reacted 4 hours, polymerization temperature is 160 ℃.
High-viscosity polymer is heated to 245 ℃, removes fugitive constituent, cooling obtains the HIPS product.
Test by analysis, shock strength is 106.4J/M, and flexural strength is 44.9MPa, and modulus in flexure is 37.0MPa, and breaking tenacity is 34.9MPa, degree of stretching rate is 51.6%.
From embodiment 10 as can be seen, polybutadiene rubber of the present invention can be prepared the high-quality high impact resistance polystyrene.

Claims (13)

1, a kind of high-cis 1 that is applicable to the preparation high impact resistance polystyrene, the preparation method of 4-polyhutadiene, comprise with carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound and make catalyzer, make divinyl carry out solution polymerization, it is characterized in that:
(1) water-content is respectively in catalyst formulation and solvent and the divinyl mixed solution:
A. nickel is (1.0-6.0) * 10 to the mol ratio of divinyl -5
B. aluminium is (3.0-10.0) * 10 to the mol ratio of divinyl -5
C. aluminium is 0.075-0.70 to the mol ratio of boron;
D. water is (0-13.0) * 10 to the mol ratio of divinyl -5
(2) polymeric reaction temperature is 60-120 ℃;
(3) polybutadiene rubber cis 1,4 structural content 〉=93% that under above cooperation condition, makes, mooney viscosity is 30-55, Z-average molecular weight and mooney viscosity ratio are (M Z/ ML)≤2 * 10 4, the intrinsic viscosity in 30 ℃, toluene is that 1.5-2.2,25 ℃, 5% styrene solution viscosity are 50-139mPa.s, vinylbenzene insolubles content＜0.03%.
2,, it is characterized in that described carboxylic acid nickel salt is nickel naphthenate, nickel acetate, nickel octoate according to the method for claim 1.
3,, it is characterized in that alkylaluminium cpd is triisobutyl aluminium or triethyl aluminum according to the method for claim 1.
4,, it is characterized in that described boron trifluoride complex is boron trifluoride ethyl ether complex or boron trifluoride ether complex according to the method for claim 1.
5,, it is characterized in that aliphatic saturated hydrocarbon, aromatic hydrocarbons, alkane aromatic hydrocarbons or its mixture that described polymer solvent is in a liquid state when being polymerization according to the method for claim 1.
6, according to the method for claim 5, it is characterized in that this polymer solvent is that refinery is raffinated oil, hexane, heptane, benzene or toluene, or its mixture.
7,, it is characterized in that nickel is (2.5-6.0) * 10 to the mol ratio of divinyl according to the method for claim 1 -5
8,, it is characterized in that aluminium is (4.4-8.5) * 10 to the mol ratio of divinyl according to the method for claim 1 -5
9,, it is characterized in that aluminium is 0.075-0.3 to the mol ratio of boron according to the method for claim 1.
10,, it is characterized in that water is (0-10.0) * 10 to the mol ratio of divinyl according to the method for claim 1 -5
11,, it is characterized in that polymeric reaction temperature is 80-120 ℃ according to the method for claim 1.
12, according to the high-cis 1 that is applicable to the preparation high impact resistance polystyrene of the method for claim 1-11 preparation, 4-polyhutadiene is characterized in that cis 1,4 structural content 〉=93%, mooney viscosity is 30-55, and Z-average molecular weight and mooney viscosity ratio are (M Z/ ML)≤2 * 10 4, the intrinsic viscosity in 30 ℃, toluene is that 1.5-2.2,25 ℃, 5% styrene solution viscosity are 50-139mPa.s, vinylbenzene insolubles content＜0.03%.
13, according to high-cis 1, the 4-polyhutadiene that is applicable to the preparation high impact resistance polystyrene of claim 12, it is characterized in that mooney viscosity is 35-43, Z-average molecular weight and mooney viscosity ratio (0.8-1.5) * 10 4, intrinsic viscosity [η] is 1.5-2.0, and at 25 ℃, 5% styrene solution viscosity is 50-80mPa.s, and the vinylbenzene insolubles is less than 0.010%.
CN 94102595 1994-03-16 1994-03-16 High cis-1,4-polybutadiene suitable for prepn. of high anti-impact polystyrene Expired - Lifetime CN1031406C (en)

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