CN102020757A - Linear high-impact butadiene/isoprene/styrene terpolymer resin and preparation method thereof - Google Patents
Linear high-impact butadiene/isoprene/styrene terpolymer resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to linear high-impact butadiene/isoprene/styrene terpolymer resin. The terpolymer resin is characterized in that: the polymer is linear butadiene/isoprene/styrene segmented copolymer with a structure shown by surface impedance boundary condition-polystyrene (SIBC-PS) and an in-situ complex of linear styrene homopolymer with a structure shown by the PS, wherein the SIBC is a butadiene/isoprene/styrene terpolymer segment; the PS is a styrene homopolymer segment; the styrene content in the linear high-impact butadiene/isoprene/styrene terpolymer resin is 70 to 95 mass percent; the sum of conjugated alkadiene butadiene content and isoprene content is 5 to 30 mass percent; and the matching mass ratio Bd/Ip of butadiene monomer to isoprene monomer is 95/5 to 5/95. The linear high-impact butadiene/isoprene/styrene terpolymer resin has higher physical and mechanical properties.
Description
Technical field
The invention belongs to the synthetic and preparing technical field of macromolecular material, relate to the linear high-impact divinyl/isoprene of a class/styrene copolymer resin and preparation method thereof.More particularly, the present invention relates to linear high-impact divinyl/isoprene/styrene copolymer resin that has following structure composition and preparation method thereof, linear high-impact divinyl/isoprene/styrene copolymer resin is the original position mixture that has the linear divinyl/isoprene/styrene block copolymer of structure shown in the SIBC-PS and have the linear styrene homopolymers of structure shown in the PS, wherein: SIBC is divinyl/isoprene/styrene copolymer block, and PS is the styrene homopolymers block.
Background technology
High-impact polystyrene (HIPS) normally adopts (R-HIPS) of radical polymerization mechanism preparation, adopt mostly at present with DOW and BASF AG is the body continuous process preparation of representative, at first toughness reinforcing rubber (polybutadiene rubber or butylbenzene copolymer rubber) is dissolved in the vinylbenzene, again by heat or initiator initiated polymerization, monomer is difficult to realize whole conversions, and transformation efficiency is generally about 80%.Weak point: must carry out MONOMER RECOVERY, polymerization process is easy to generate the vinylbenzene oligopolymer, the polystyrene that the head links to each other is easy to chain rupture in the course of processing, the molecular weight distribution broad, more to prepare difficulty bigger for high molecular weight polystyrene, and level of residual monomers is big (being controlled at about 150ppm) usually.
Anionoid polymerization is to realize the most accurate, the effective means of polymer molecular structure design, and monomer can be realized whole conversions, and product is pure, and level of residual monomers can reach below the 10ppm.Compare with the successive polymerization of above-mentioned vinylbenzene free radical body, the mass polymerization of vinylbenzene negatively charged ion exists following shortcoming: under the high monomer concentration, polymerization rate is very fast, and heat of polymerization is difficult in time remove, the polymerization system difficult control of temperature; Under the hot conditions, side reaction takes place in anionoid polymerization easily, increases the active centre and is easy to decompose isomerization.Therefore, anionoid polymerization normally with the solution polymerization mode (mass percent is less than 20% generally speaking) of low concentration, under lower temperature (less than 60 ℃) implement.
BASF AG's employing retardance anionic polymerization (Retarded Anionic Polymerization) has successfully prepared high-impact polystyrene (being called for short A-HIPS:Anionic High Impact Polystyrene) [the Philippe Desbois based on anionic polymerisation process, Volker Warzelhan, et al, Anionic High Impact Polystyrene:A New Process for Low Residual and Low Cost HIPS, Macromolecular Symposia, 2006,240:194-205].Realize vinylbenzene negatively charged ion bulk polymerization speed is controlled, (Retarder) is most important for retarding agent.BASF AG is an initiator with the lithium alkylide, has developed a series of supporting with it retarding agents, starts with from first-generation alkyl magnesium system, develops into present sophisticated s-generation alkyl aluminum system.Discover: aluminum alkyls is neither initiator, neither chain-transfer agent, only play the effect that suppresses polymerization rate, and polymerization process has kept the characteristics of anionoid polymerization.When Al/Li 〉=1, polymerization system is in dormant state; When Al/Li＜1, can regulate and control polymerization rate according to the Al/Li size.
Because the toughner that BASF AG adopts is the Butadiene copolymer, the structure of toughner and performance all have certain limitation, and the integrated rubber with outstanding overall characteristic is divinyl/isoprene/styrene copolymer, and it has abundant structures and more effectively toughening effect more.The present invention adopts divinyl/isoprene/styrene copolymer toughner, adopts the prepared linear high-impact divinyl/isoprene/styrene copolymer resin of retardance anionic polymerisation process to have very excellent shock resistance.Linear high-impact divinyl/isoprene of the present invention/styrene copolymer resin can also be by further functionalized, and for example hydrogenation, epoxidation, hydroxylation, carboxylated etc. also can be used for the rubber plastic blend modification.
Summary of the invention
The objective of the invention is to prepare the linear high-impact divinyl/isoprene of a class/styrene copolymer resin.With traditional processing technology adopt the prepared high-impact polystyrene (HIPS) of free radical polymerisation process and BASF AG adopt prepared high-impact polystyrene (A-HIPS) difference of anionic polymerisation process just be the present invention prepared be high-impact divinyl/isoprene/styrene copolymer resin that a class has linear structure, be toughner, adopt the retardance anionic polymerisation process to realize with divinyl/isoprene/styrene copolymer.Divinyl/isoprene/styrene copolymer toughner has been given linear high-impact divinyl/isoprene/styrene copolymer resin excellent physical and mechanical performance more.
A kind of linear high-impact divinyl/isoprene/styrene copolymer resin that the present invention is prepared with following structure, it is characterized in that having the linear divinyl/isoprene/styrene block copolymer and original position mixture of structure shown in the SIBC-PS with linear styrene homopolymers of structure shown in the PS, wherein: SIBC is divinyl/isoprene/styrene copolymer block, SIBC can be divinyl/isoprene/polystyrene ternary random copolymers, also can be to contain divinyl, isoprene, the ternary block polymer of styrene homopolymers or copolymer block; PS is the styrene homopolymers block.Above-mentioned linear high-impact divinyl/isoprene/styrene copolymer resin, wherein styrene content general range mass percent is 70%-95%, the optimum range mass percent is 80%-90%; Conjugated diene divinyl and isoprene content sum general range mass percent are 5%-30%, and the optimum range mass percent is 10%-20%; Wherein: divinyl and isoprene monomer proportioning Bd/Ip general range mass ratio are 95/5-5/95, and the optimum range mass ratio is 85/15-15/85.SIBC-PS content general range mass percent is 10%-60% in above-mentioned linear high-impact divinyl/isoprene/styrene copolymer resin, and the optimum range mass percent is 20%-40%; The content general range mass percent of PS is 90%-40%, and the optimum range mass percent is 80%-60%.The number-average molecular weight scope general range of above-mentioned linear polystyrene PS is 10 * 10
4-100 * 10
4, optimum range is 20 * 10
4-80 * 10
4SIBC is 1/5-5/1 with the block of PS than SIBC/PS general range mass ratio among the above-mentioned SIBC-PS, and the optimum range mass ratio is 1/2-2/1.Above-mentioned linear divinyl/isoprene/styrol copolymer block SIBC number-average molecular weight general range is 10 * 10
4-30 * 10
4, optimum range is 15 * 10
4-25 * 10
4Styrene content general range mass percent is 5%-55% among above-mentioned divinyl/isoprene/styrene copolymer block SIBC, and the optimum range mass percent is 15%-35%; Conjugated diene divinyl and isoprene content sum general range mass percent are 45%-95%, and the optimum range mass percent is 65%-85%; Wherein: divinyl and isoprene monomer proportioning Bd/Ip general range mass ratio are 95/5-5/95, and the optimum range mass ratio is 85/15-15/85.
Another object of the present invention is to provide the preparation method of the linear high-impact divinyl/isoprene of a class/styrene copolymer resin.The preparation method of linear high-impact divinyl/isoprene/styrene copolymer resin involved in the present invention is as follows: press monomer ratio with divinylic monomer (Bd), isoprene monomer (Ip), first styrene monomer (St in the non-polar hydrocarbon kind solvent
1), optional polar additive joins in the reactor, adds alkyl lithium initiator RLi for the first time
1Prepare linear divinyl/isoprene/styrol copolymer SIBC, the consumption that adds for the first time alkyl lithium initiator is decided according to the size of linear divinyl/isoprene/styrol copolymer block SIBC number-average molecular weight, after divinyl, isoprene and first vinylbenzene total overall reaction finish, add optional anionoid polymerization retarding agent, the consumption of anionoid polymerization retarding agent is (with anionoid polymerization retarding agent consumption and alkyl lithium initiator total amount (RLi
1+ RLi
2) mol ratio metering) general range is 0.50-1.0, optimum range is 0.70-0.90.Press monomer ratio again with second crowd of styrene monomer (St
2) join in the reactor, add alkyl lithium initiator (RLi for the second time
2), begin to prepare linear polystyrene PS, linear divinyl/isoprene/styrol copolymer SIBC continues to increase generation styrene homopolymers block simultaneously, finally obtain shape block copolymer SIBC-PS, the consumption that adds for the second time alkyl lithium initiator is decided according to the number-average molecular weight size of linear polystyrene PS, after the vinylbenzene total overall reaction finishes, stop polyreaction in a conventional manner, reclaim and obtain linear high-impact divinyl/isoprene/styrene copolymer resin (the original position mixture of SIBC-PS and PS).
The preferred version of linear high-impact divinyl/isoprene/styrene copolymer process for preparing resins involved in the present invention is as follows: press monomer ratio with divinyl in the non-polar hydrocarbon kind solvent, isoprene, first vinylbenzene, optional polar additive joins in the reactor, the purpose that adds polar additive is to change divinyl, isoprene and cinnamic reactivity ratio, the regulation and control that realization distributes and forms divinyl/isoprene/styrol copolymer sequence, look the microtexture of polyhutadiene, how many polar additives the requirement that the microtexture of polyisoprene and divinyl/isoprene/distribution of styrol copolymer sequence is formed determines whether to use and use, the polar additive consumption is decided on the kind of polar compound, open stirring, after reaching kick off temperature, add alkyl lithium initiator, the initiation reaction temperature is 30 ℃-80 ℃, begin to prepare linear divinyl/isoprene/styrol copolymer SIBC, the consumption that adds for the first time alkyl lithium initiator is decided according to the size of linear divinyl/isoprene/styrol copolymer block SIBC number-average molecular weight, and linear divinyl/isoprene of the present invention/styrol copolymer block SIBC number-average molecular weight general range is 10 * 10
4-30 * 10
4The various monomeric total concn mass percent that each step of control is added is 10%-30%, after divinyl, isoprene and first styrene monomer total overall reaction finish, add a certain proportion of anionoid polymerization retarding agent, by monomer ratio second batch of styrene monomer joined in the reactor again, add alkyl lithium initiator, begin to prepare polystyrene, the consumption that adds for the second time alkyl lithium initiator is decided according to the size of linear polystyrene PS number-average molecular weight, and linear polystyrene PS number-average molecular weight general range of the present invention is 10 * 10
4-100 * 10
4After the vinylbenzene total overall reaction is finished, add terminator, stop polyreaction, also can randomly add conventional additives, as anti-aging agent, anti-aging agent can be selected from Irganox1010 (trade(brand)name, Ciba-Geigy company is on sale), Antigene BHT or 2.4.6 (trade(brand)name, SUMITOMO CHEMICAL KCC is on sale) etc. one or more the mixture in the general anti-aging agent of macromolecular material, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain linear high-impact divinyl/isoprene/styrene copolymer resin.
The used alkyl lithium initiator of the present invention is the simple function group alkyl lithium initiator, the simple function group alkyl lithium initiator is for being the disclosed any divinyl that can be used for of prior art, a kind of initiator of anionic polymerization of styrene reaction or the mixture of several initiators, generally be selected from: RLi, the mixture of one or more simple function group alkyl lithium initiators among the MRLi, R is that carbonatoms is the alkyl of 2-20, R can be alkyl or aryl, M is atoms metal or nitrogen-atoms, be generally tin Sn, silicon Si, plumbous Pb, titanium Ti, metallic elements such as germanium Ge, preferably certainly: lithium ethide, the sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, the tertiary butyl lithium, the simple function group alkyl lithium initiator of stanniferous or nitrogen atom etc.
The anionoid polymerization retarding agent used in the present invention disclosed any anionoid polymerization retarding agent that can be used for the lithium alkylide initiator system of technology of selecting oneself, and can be the mixture of a kind of anionoid polymerization retarding agent or several anionoid polymerization retarding agents, generally be selected from alkyl metal cpds such as alkyl magnesium, alkyl barium, aluminum alkyls, preferably from aluminum alkyls.Aluminum alkyls used in the present invention is selected from the disclosed any aluminum alkyls that can be used for the anionoid polymerization retarding agent of prior art, and can be the mixture of a kind of aluminum alkyls or several aluminum alkylss, generally be selected from: the mixture of one or more aluminum alkylss in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three tertiary butyl aluminium and the tri-butyl aluminum, preferably certainly: triethyl aluminum, triisobutyl aluminium.
Polar additive used in the present invention is selected from the disclosed any polar additive that can be used for the anionoid polymerization system of prior art, and can be the mixture of a kind of polar additive or several polar additives, generally be selected from and contain oxygen, nitrogenous, sulfur-bearing, contain Phosphorus polar compound.For example: (1) oxygenatedchemicals generally is selected from ether, tetrahydrofuran (THF), R
1OCH
2CH
2OR
2(R wherein
1And R
2Be that carbonatoms is the alkyl of 1-6, R
1And R
2Can be the same or different preferred R
1And R
2Difference is as glycol dimethyl ether, ethylene glycol diethyl ether), R
1OCH
2CH
2OCH
2CH
2OR
2(R wherein
1And R
2Be that carbonatoms is the alkyl of 1-6, R
1And R
2Can be the same or different preferred R
1And R
2Difference is as diethylene glycol dimethyl ether, dibutyl ethylene glycol ether), crown ether; (2) nitrogenous compound generally is selected from triethylamine, Tetramethyl Ethylene Diamine (TMEDA), two piperidines ethane (DPE), preferred TMEDA; (3) P contained compound is generally selected HMPA (HMPA) for use; (4) alkoxide compound generally is selected from the compound shown in the formula ROM, and wherein R is that carbonatoms is the alkyl of 1-6, and O is a Sauerstoffatom, and M is metal ion sodium Na or potassium K, preferred tertiary butoxy potassium or uncle's pentyloxy potassium.
Non-polar hydrocarbon kind solvent used in the present invention is to be selected from a kind of varsol in nonpolar aromatic hydrocarbons and the nonpolar aliphatic hydrocarbon or the mixture of several varsols, generally be selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, BTX aromatics (as xylol), mixed aliphatic series hydrocarbon (as raffinating oil) etc., preferably from: hexane, hexanaphthene, raffinate oil.
The termination of polyreaction uses terminator to carry out usually.The used terminator of the present invention is the disclosed any terminator that can be used for anionic polymerisation of prior art, as water, methyl alcohol, ethanol or Virahol etc.
Can randomly add conventional additives and filler in Starlike high impact divinyl/isoprene of the present invention/styrene copolymer resin, as oxidation inhibitor etc., specific examples has Irganox 1010 (trade(brand)names, available from Switzerland Ciba-Geigy company) and Antigene BHT or 2.6.4 (trade(brand)name, be 2, the 6-di-tert-butyl-4-methy phenol is available from SUMITOMO CHEMICAL chemistry Zhu Shi commercial firm).
Embodiment
Further specify the present invention below in conjunction with embodiment, Comparative Examples, but and the scope of unrestricted claim protection of the present invention.
Embodiment 1
In 0.5 liter of stainless steel cauldron that has a stirring, add 100g hexanaphthene, 3.8 gram divinyl (Bd), 3.8 gram isoprene (Ip), 3.8 gram vinylbenzene (St
1), be warming up to 60 ℃, add n-Butyl Lithium RLi
1Initiator 0.076mmol, the number-average molecular weight that makes divinyl/isoprene/styrene copolymer block is 10 * 10
4, divinyl, isoprene and styrene polymerization reaction are all finished after polyreaction proceeds to 3 hours, add a certain amount of anionoid polymerization retarding agent triisobutyl aluminium i-Bu
3Al (TIBA) 0.126mmol adds 150 gram hexanaphthenes and 36.4 gram vinylbenzene (St again
2), mix the back and add n-Butyl Lithium RLi
2Initiator 0.085mmol, continue reaction 4 hours, after the styrene polymerization reaction is all finished, add terminator and finish reaction, add anti-aging agent (Irganox 1010 mixes with mass ratio with 2.6.4 at 1: 1) 1 gram, adopt traditional method to carry out the glue aftertreatment, classical way specimen structure and performance are adopted in dry back, and the result is shown in No.1 in the table 1.
Embodiment 2-7
Polymerization process and processing condition are with embodiment 1, the consumption difference of different, the retarding agent triisobutyl aluminium of consumption of divinyl, isoprene, styrene monomer proportioning difference, first time and the alkyl lithium initiator second time just, prepared linear high-impact divinyl/isoprene/styrene copolymer resin, polymerization process condition, product structure transitivity test result are respectively shown in No.2-7 in the table 1.
The structure and the performance of the linear high-impact divinyl/isoprene of table 1/styrene copolymer resin
Annotate: Mn-ps and HIps are respectively linear polystyrene molecular weight and the molecular weight distributing index thereof that adopts gel permeation chromatography (GPC) to record.
Claims (14)
1. the linear high-impact divinyl/isoprene of a class/styrene copolymer resin, it is characterized in that: this polymkeric substance is the original position mixture that has the linear divinyl/isoprene/styrene block copolymer of structure shown in the SIBC-PS and have the linear styrene homopolymers of structure shown in the PS, wherein: SIBC is divinyl/isoprene/styrene copolymer block, and PS is the styrene homopolymers block; The styrene content mass percent is 70%-95% in above-mentioned linear high-impact divinyl/isoprene/styrene copolymer resin, conjugated diene divinyl and isoprene content sum mass percent are 5%-30%, and divinyl and isoprene monomer proportioning Bd/Ip mass ratio are 95/5-5/95; SIBC-PS content mass percent is 10%-60% in above-mentioned Starlike high impact divinyl/isoprene/styrene copolymer resin, and PS content mass percent is 90%-40%; The number-average molecular weight scope of above-mentioned linear polystyrene PS is 10 * 10
4-100 * 10
4SIBC is 1/5-5/1 with the block of PS than SIBC/PS mass ratio among the above-mentioned SIBC-PS; Above-mentioned linear divinyl/isoprene/styrol copolymer block SIBC number-average molecular weight is 10 * 10
4-30 * 10
4The styrene content mass percent is 5%-55% among above-mentioned divinyl/isoprene/styrene copolymer block SIBC, conjugated diene divinyl and isoprene content sum mass percent are 45%-95%, and divinyl and isoprene monomer proportioning Bd/Ip mass ratio are 95/5-5/95.
2. linear high-impact divinyl/isoprene according to claim 1/styrene copolymer resin, it is characterized in that: wherein the styrene content mass percent is 80%-90%, conjugated diene divinyl and isoprene content sum mass percent are 10%-20%, and divinyl and isoprene monomer proportioning Bd/Ip mass ratio are 85/15-15/85.
3. linear high-impact divinyl/isoprene according to claim 1/styrene copolymer resin is characterized in that: wherein SIBC-PS content mass percent is 20%-40%, and the content mass percent of PS is 80%-60%.
4. linear high-impact divinyl/isoprene according to claim 1/styrene copolymer resin is characterized in that: the number-average molecular weight of wherein linear polystyrene PS is 20 * 10
4-80 * 10
4
5. linear high-impact divinyl/isoprene according to claim 1/styrene copolymer resin is characterized in that: wherein the block of SIBC and PS is 1/2-2/1 than SIBC/PS mass ratio among the SIBC-PS.
6. linear high-impact divinyl/isoprene according to claim 1/styrene copolymer resin is characterized in that: wherein linear divinyl/isoprene/styrol copolymer block SIBC number-average molecular weight is 15 * 10
4-25 * 10
4
7. linear high-impact divinyl/isoprene according to claim 1/styrene copolymer resin, it is characterized in that: wherein the styrene content mass percent is 15%-35% among divinyl/isoprene/styrene copolymer block SIBC, conjugated diene divinyl and isoprene content sum mass percent are 65%-85%, and divinyl and isoprene monomer proportioning Bd/Ip mass ratio are 85/15-15/85.
8. the preparation method of each described linear high-impact divinyl/isoprene/styrene copolymer resin of claim 1-7 is characterized in that: press monomer ratio with divinylic monomer (Bd), isoprene monomer (Ip), first styrene monomer (St in the non-polar hydrocarbon kind solvent
1), optional polar additive joins in the reactor, adds simple function group alkyl lithium initiator RLi for the first time
1Prepare linear divinyl/isoprene/styrol copolymer SIBC, the consumption that adds for the first time the simple function group alkyl lithium initiator is decided according to the size of linear divinyl/isoprene/styrene copolymer block SIBC number-average molecular weight, and linear divinyl/isoprene of the present invention/styrol copolymer block SIBC number-average molecular weight is 10 * 10
4-30 * 10
4After divinyl, isoprene and first vinylbenzene total overall reaction finish, add optional anionoid polymerization retarding agent, the anionoid polymerization retarding agent is selected from the mixture of one or more aluminum alkylss in the alkyl metal cpd aluminum alkyls, presses monomer ratio again with second crowd of styrene monomer (St
2) join in the reactor, add simple function group alkyl lithium initiator RLi for the second time
2Begin to prepare linear polystyrene PS, linear divinyl/isoprene/styrene copolymer SIBC continues to increase generation styrene homopolymers block simultaneously, finally obtain shape block copolymer SIBC-PS, the consumption that adds for the second time the simple function group alkyl lithium initiator is decided according to the number-average molecular weight size of linear polystyrene PS, and linear polystyrene PS number-average molecular weight of the present invention is 10 * 10
4-100 * 10
4After the vinylbenzene total overall reaction finishes, stop polyreaction in a conventional manner, recovery obtains linear high-impact divinyl/isoprene/styrene copolymer resin (the original position mixture of SIBC-PS and PS), the styrene content mass percent is 70%-95% in wherein said linear high-impact divinyl/isoprene/styrene copolymer resin, conjugated diene divinyl and isoprene content sum mass percent are 5%-30%, and divinyl and isoprene monomer proportioning Bd/Ip mass ratio are 95/5-5/95; SIBC-PS content mass percent is 10%-60% in described linear high-impact divinyl/isoprene/styrene copolymer resin, and PS content mass percent is 40%-90%.
9. the preparation method of linear high-impact divinyl/isoprene according to claim 8/styrene copolymer resin, it is characterized in that: wherein the simple function group alkyl lithium initiator is selected from the mixture of one or more simple function group alkyl lithium initiators among RLi, the TRLi, R is that carbonatoms is the alkyl of 2-20, R can be alkyl or aryl, T is atoms metal or nitrogen-atoms, is generally metallic elements such as tin Sn, silicon Si, plumbous Pb, titanium Ti, germanium Ge.
10. the preparation method of linear high-impact divinyl/isoprene according to claim 9/styrene copolymer resin, it is characterized in that: wherein the simple function group alkyl lithium initiator is selected from n-Butyl Lithium, s-butyl lithium.
11. the preparation method of linear high-impact divinyl/isoprene according to claim 8/styrene copolymer resin is characterized in that: wherein anionoid polymerization retarding agent alkyl metal cpd aluminum alkyls is selected from the mixture of one or more aluminum alkylss in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three tertiary butyl aluminium and the tri-butyl aluminum.
12. the preparation method of linear high-impact divinyl/isoprene according to claim 11/styrene copolymer resin is characterized in that: wherein the anionoid polymerization retarding agent is selected from the alkyl metal cpd aluminum alkyls and is selected from triethyl aluminum, triisobutyl aluminium.
13. the preparation method of linear high-impact divinyl/isoprene according to claim 8/styrene copolymer resin is characterized in that: wherein the mol ratio of anionoid polymerization retarding agent consumption and alkyl lithium initiator total amount is 0.50-1.0.
14. the preparation method of linear high-impact divinyl/isoprene according to claim 13/styrene copolymer resin is characterized in that: wherein the mol ratio of anionoid polymerization retarding agent consumption and alkyl lithium initiator total amount is 0.70-0.90.
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| CN103204973A (en) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | Trans-1,4-polydiene copolymer having low molecular weight, and preparation method and use thereof |
| CN103204973B (en) * | 2012-01-12 | 2017-07-25 | 青岛科技大学 | A kind of trans 1,4 polydiene copolymer thing of low molecule amount and its production and use |
| CN103772879A (en) * | 2014-01-02 | 2014-05-07 | 大连理工大学 | Low temperature fusion linetype styrene thermoplastic elastomer and preparation method thereof |
| CN105331035A (en) * | 2014-06-25 | 2016-02-17 | 中国石油化工股份有限公司 | Butylbenzene resin composition and preparation method thereof |
| CN105331035B (en) * | 2014-06-25 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of butadiene styrene resin composition and preparation method thereof |
| CN104072744B (en) * | 2014-07-10 | 2016-08-24 | 大连理工大学 | A kind of polar butadiene/isoprene/styrol copolymer containing poly-ethylene oxide block and preparation method |
| CN104072744A (en) * | 2014-07-10 | 2014-10-01 | 大连理工大学 | Polyethylene oxide block containing polarized butadiene/isoprene/styrol copolymer and preparation method thereof |
| CN106632927A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Linear styrene-butadiene block copolymer and preparation method and application thereof |
| CN106632927B (en) * | 2015-10-28 | 2019-04-19 | 中国石油化工股份有限公司 | Line style butadiene-styrene block copolymer and its preparation method and application |
| CN110128607A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene block copolymer and block copolymer composition and vulcanized rubber and its application |
| CN110128606A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | Block copolymer and block copolymer composition and vulcanized rubber and its preparation method of application and block copolymer |
| CN110128606B (en) * | 2018-02-09 | 2021-07-02 | 中国石油化工股份有限公司 | Block copolymer, block copolymer composition, vulcanized rubber, application of vulcanized rubber, and preparation method of block copolymer |
| CN111217969A (en) * | 2018-11-26 | 2020-06-02 | 中国石油化工股份有限公司 | Block copolymer, block copolymer composition, preparation method of block copolymer, vulcanized rubber, application of vulcanized rubber, tire tread and tire |
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