CN113999355A - HIPS resin containing DPE derivative, butadiene and styrene star copolymer block and preparation method thereof - Google Patents

HIPS resin containing DPE derivative, butadiene and styrene star copolymer block and preparation method thereof Download PDF

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CN113999355A
CN113999355A CN202111349585.4A CN202111349585A CN113999355A CN 113999355 A CN113999355 A CN 113999355A CN 202111349585 A CN202111349585 A CN 202111349585A CN 113999355 A CN113999355 A CN 113999355A
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sbr
butadiene
phenyl
styrene
block
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CN113999355B (en
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李杨
冷雪菲
王艳色
韩丽
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/048—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers, conjugated dienes and polar monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/042—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a polyfunctional initiator
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • C08F4/48—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium
    • C08F4/486—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium at least two metal atoms in the same molecule
    • C08F4/488—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium at least two metal atoms in the same molecule at least two lithium atoms in the same molecule
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

In order to solve the problems of poor impact resistance and the like of the resin in the prior art, a HIPS resin with ultrahigh impact strength containing a DPE derivative, butadiene and a styrene star copolymer block is provided, and the HIPS resin is styrene/[ (SN-SBR) -BR ] n-C copolymer resin; SN-SBR is a DPE derivative, a butadiene and styrene copolymer block, BR is a butadiene homopolymer block, and C is a polyfunctional alkyl lithium initiator residue; the (SN-SBR) block contains 5-80% of butadiene, 5-80% of isoprene, 5-50% of styrene and 0.5-20% of DPE derivative; (SN-SBR) with a BR block ratio of 10/90-90/10; the content of [ (SN-SBR) -BR ] n-C is 3-35 percent based on the HIPS resin mass as 100 percent.

Description

HIPS resin containing DPE derivative, butadiene and styrene star copolymer block and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis and preparation of high polymer materials, and particularly relates to HIPS (high impact polystyrene) resin containing a DPE (high performance polyethylene) derivative, butadiene and styrene star copolymer block and a preparation method thereof.
Background
Because of the problems of synthesis and purification of lithium, no industrialization has been achieved so far. The multi-lithium initiation method adopts organic lithium containing multiple functional groups as an initiator, directly initiates polymerization by an anion polymerization method, and forms a star-shaped block polymer by a one-step method. A plurality of patents are applied in research of multi-lithium system star block copolymers by Beijing Yanshan petrochemical company research institute, a polyfunctional group organic lithium initiator is adopted to initiate the copolymerization of conjugated dienes such as styrene, isoprene, butadiene and the like to obtain a series of star block copolymers, and the star block copolymers have the following structures: (SBR-BR) n-C, (SBR-IR) n-C, (SBR-IBR) n-C, and the like.
The functionalized solution polymerized styrene-butadiene rubber is highly valued in the rubber industry in China, the university of the major graduates starts to research the chain-end functionalized solution polymerized styrene-butadiene rubber as early as the middle and later 90 s, and the research and development of the prior chain-end functionalized solution polymerized styrene-butadiene rubber have achieved certain achievements but are difficult to form a competitive core technology. The single-end and double-end functionalized solution polymerized styrene-butadiene rubber is synthesized by adopting a functionalized alkyl lithium initiation system (nitrogen lithium, tin lithium and the like) and a functionalized end-capping reagent (silicon reagent, nitrogen reagent and the like). However, the functionalized initiator and the functionalized end-capping agent are difficult to realize the precise regulation and control of the microstructure and the sequence structure of the functionalized solution-polymerized styrene-butadiene rubber. Because the DPE derivative can only be copolymerized but not homopolymerized in the process of active anion polymerization reaction by using alkyl lithium as an initiator, and the microstructure and the sequence structure of a functionalized polymer can be accurately regulated and controlled, the DPE derivative becomes the best choice for designing and synthesizing the functionalized solution-polymerized styrene-butadiene rubber.
Functionalization is the most effective method for realizing high performance of the solution polymerized styrene-butadiene rubber, in-chain functionalization becomes the inevitable trend of development of chain-end functionalized solution polymerized styrene-butadiene rubber, and the multi-functionalized solution polymerized styrene-butadiene rubber in a chain-end chain inevitably becomes green tire rubber with more excellent comprehensive performance. Based on a living anionic polymerization method, the multifunctional solution polymerized styrene-butadiene rubber in a synthetic chain end chain is designed most scientifically and reasonably by adopting the copolymerization reaction of a functionalized DPE derivative and butadiene and styrene. However, the synthesis and purification of multifunctional DPE derivative monomers with complex structures, especially DPE derivative monomers containing silicon-oxygen groups, amine groups and silicon-oxygen groups, are difficult, and no literature report is available. The polymerization mechanism of the multi-functional DPE derivative monomer with various complex structures and the copolymerization of butadiene and styrene, and the precise regulation and control method of microstructure and sequence structure are all studied in depth and systematically, and these problems become the bottleneck of the multi-functional solution polymerized styrene-butadiene rubber in the chain end of the synthetic chain which needs to be solved urgently.
The impact-resistant polystyrene resin is prepared by dissolving a toughening agent in styrene according to a certain proportion by using classical polybutadiene rubber or butadiene-styrene copolymer rubber as the toughening agent and adopting an initiator initiation method. After the rubber toughening agent is added, the impact resistance of the polystyrene resin is greatly improved, but the polystyrene resin with ultrahigh impact strength is difficult to obtain by adopting the general rubber as the toughening agent, and the impact strength of the polystyrene resin prepared by adopting the classical polybutadiene rubber or butadiene-styrene copolymer rubber as the toughening agent is difficult to be more than 200J/m, so that the use of the impact-resistant polystyrene resin is limited to a certain extent. There is no report on how to effectively further improve the impact resistance of polystyrene resin.
In order to further promote the development of the field of resin toughening, a functionalized polymer with good biocompatibility and excellent mechanical properties is provided to improve the problems of poor impact resistance and the like of polystyrene resin in the prior art, which is a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems of poor impact resistance and the like of polystyrene resin in the prior art, the invention provides HIPS resin containing a DPE derivative, butadiene and styrene star copolymer block and a preparation method thereof.
In a first aspect, the present invention provides a HIPS resin containing a DPE derivative, butadiene and a star copolymer block of styrene monomers, wherein the HIPS resin is styrene/[ (SN-SBR) -BR]The n-C copolymer resin is [ (SN-SBR) -BR]Graft copolymers of n-C with monomeric styrene; the [ (SN-SBR) -BR ] is calculated by taking the mass of the HIPS resin as 100 percent]The content of n-C is 3-35%; the HIPS resin has a number average molecular weight in the range of 5 x 104-80×104g/mol；
Wherein the [ (SN-SBR) -BR]n-C is a DPE derivative, a butadiene, styrene star copolymer blockSection, (SN-SBR) is DPE derivative, butadiene, styrene copolymer block, BR is butadiene homopolymer block; c is a polyfunctional alkyl lithium initiator residue, n is initiator functionality, n is a natural number, and n is greater than or equal to 3; the star copolymer block [ (SN-SBR) -BR [ ]]n-C has a number average molecular weight of 5X 104-50×104(ii) a Based on 100% of the mass of the (SN-SBR) copolymer block, the (SN-SBR) block contains 30-80% of butadiene, 5-50% of styrene and 0.5-20% of DPE derivative; the mass ratio of the (SN-SBR) block to the BR block in the star copolymer block is 10/90-90/10;
the DPE derivative is selected from an amino group-containing group, a silicon group/amino group monomer 1, 1-diphenylethylene derivative; the amino group, the silicon group/the amino group are connected at the para position, the meta position or the ortho position of the phenyl in the 1, 1-diphenylethylene derivative.
Further, the content of [ (SN-SBR) -BR ] n-C is 5-25% based on 100% of the mass of the HIPS resin.
Further, the HIPS resin has a number average molecular weight in the range of 10X 104-50×104g/mol。
Further, the star copolymer block [ (SN-SBR) -BR-]n-C has a number average molecular weight of 10X 104-30×104。
Further, the value of the initiator functionality n ranges from 3 to 50.
Further, the value range of the initiator functionality n is 3-10.
Further, the (SN-SBR) block has a butadiene content of 50 to 60%, a styrene content of 25 to 35%, and a DPE derivative content of 5 to 15% based on 100% by mass of the (SN-SBR) block.
Further, the mass ratio of the (SN-SBR) block to the polybutadiene BR block in the radial copolymer block [ (SN-SBR) -BR ] n-C is 30/70-70/30.
Further, the DPE derivative is selected from the group consisting of amino group-containing group, silicon group/amino group monomer 1, 1-diphenylethylene derivatives, including but not limited to mono-amino group-containing group, mono-siloxy group, di-amino group, di-siloxy group, siloxy/amino group, and mono-siloxy/amino group monomer 1, 1-diphenylethylene derivatives.
Further, the amine group-containing group, silicon group/amine group monomer 1, 1-diphenylethylene derivatives (DPE derivatives) are selected from:
(1) the amine group DPE derivative monomers generally range from 1- [ (N, N-dimethylamino) phenyl ] -1-phenylethene, 1- [ (N, N-diethylamino) phenyl ] -1-phenylethene, 1- [ (N, N-di-tert-butylamino) phenyl ] -1-phenylethene, 1- [ (N, N-diphenylamino) phenyl ] -1-phenylethene; the general ranges of the diamine group DPE derivative monomers are 1, 1-bis [ (N, N-dimethylamino) phenyl ] ethylene, 1-bis [ (N, N-diethylamino) phenyl ] ethylene, 1-bis [ (N, N-di-tert-butylamino) phenyl ] ethylene and 1, 1-bis [ (N, N-diphenylamino) phenyl ] ethylene; the most preferable ranges are 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, 1-bis [4- (N, N-dimethylamino) phenyl ] ethene.
(2) Siloxy group DPE derivative monomers generally range from 1- [4- (trimethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (triethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (tri-tert-butoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylmethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (diethylmethoxysilyl) phenyl ] -1-phenylethene; the general ranges of disiloxyl DPE derivative monomers are 1,1 bis [4- (trimethoxysilyl) phenyl ] ethylene, 1 bis [4- (triethoxysilyl) phenyl ] ethylene, 1 bis [4- (triisopropoxysilyl) phenyl ] ethylene, 1 bis [4- (tri-tert-butoxysilyl) phenyl ] ethylene, 1 bis [4- (dimethylmethoxysilyl) phenyl ] ethylene, 1 bis [4- (diethylmethoxysilyl) phenyl ] ethylene; the most preferable ranges are 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1-bis [4- (triisopropoxysilyl) phenyl ] ethylene.
(3) Silyloxy DPE derivative monomers generally range from 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, 1[3- (dimethylsilyl) phenyl ] -1-phenylethene, 1[2- (dimethylsilyl) phenyl ] -1-phenylethene, 1[4- (diethylsilyl) phenyl ] -1-phenylethene, 1[4- (dipropylsilyl) phenyl ] -1-phenylethene, 1[4- (diisopropylsilyl) phenyl ] -1-phenylethene, 1[4- (di-tert-butylsilyl) phenyl ] -1-phenylethene; bis-silyl group DPE derivative monomers generally range from 1,1 bis [4 (dimethylsilyl) phenyl ] ethylene, 1 bis [3 (dimethylsilyl) phenyl ] ethylene, 1 bis [2 (dimethylsilyl) phenyl ] ethylene, 1 bis [3,4 (dimethylsilyl) phenyl ] ethylene, 1 bis [2,3 (dimethylsilyl) phenyl ] ethylene, 1 bis [4 (diethylsilyl) phenyl ] ethylene, 1 bis [4 (dipropylsilyl) phenyl ] ethylene, 1 bis [4 (diisopropylsilyl) phenyl ] ethylene, 1 bis [4 (di-tert-butylsilyl) phenyl ] ethylene; the most preferable ranges are 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, 1 bis [4 (dimethylsilyl) phenyl ] ethene.
(4) The siloxy group/amino group DPE derivative monomers typically range from 1- [4- (trimethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (triethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (tripropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, n-dimethylamino) phenyl ] ethylene, 1- [4- (monoisopropoxydimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene; the most preferable range is 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene.
(5) The silylhydride group/amine group DPE derivative monomers typically range from 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (diethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (dipropylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (diisopropylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (di-tert-butylsilyl) phenyl ] -1- [4- (N, n-dimethylamino) phenyl ] ethylene; the most preferable range is 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene.
Further, the DPE derivative monomerSelectingIs 1- [4- (N, N-dimethylamino) phenyl]-1-phenylethene, 1-bis [4- (N, N-dimethylamino) phenyl]Ethylene, 1- [4- (triisopropoxysilyl) phenyl]-1-phenylethene, 1-bis [4- (dimethylsilyl) phenyl]Ethylene, 1[4- (dimethylsilyl) phenyl]-1-phenylethene, 1-bis [4- (triisopropoxysilyl) phenyl]Ethylene, 1- [4- (triisopropoxysilyl) phenyl]-1- [4- (N, N-dimethylamino) phenyl]Ethylene, 1- [4- (dimethylsilyl) phenyl]-1- [4- (N, N-dimethylamino) phenyl]At least one of ethylene.
In a second aspect, the invention provides a method for preparing HIPS resin containing DPE derivatives, butadiene and styrene star copolymer blocks, which comprises the following steps,
step S1, preparing star copolymer block [ (SN-SBR) -BR ] n-C glue solution:
adding a first batch of butadiene monomer and a polar additive into a reactor according to the monomer ratio in a nonpolar hydrocarbon solvent, enabling the initiation reaction temperature to reach 10-90 ℃, and the reaction time to be 20-100min, and then adding a polyfunctional group organic lithium initiator to prepare a butadiene homopolymer block BR;
after the first batch of butadiene is completely reacted, adding a second batch of butadiene monomer containing a polar additive, a DPE derivative and styrene into the reactor at one time according to the monomer proportion, wherein the reaction time is 50-100min, and after the DPE derivative, the butadiene and the styrene are completely reacted, stopping the reaction to obtain [ (SN-SBR) -BR ] n-C star copolymer block glue solution;
step S2, preparing HIPS resin:
adding styrene into [ (SN-SBR) -BR ] n-C glue solution according to the content requirements of [ (SN-SBR) -BR ] n-C and styrene in the designed HIPS resin, and simultaneously selectively supplementing styrene to adjust the concentration of the glue solution according to needs; selecting a chain transfer agent to adjust the molecular weight of the HIPS resin, initiating a polymerization reaction by adopting a free radical polymerization method, wherein the reaction temperature is 80-120 ℃, the reaction time is not less than 30min, and after the reaction is finished, performing post-treatment on the polymer to obtain the HIPS resin;
the initiator of the free radical polymerization method is selected from peroxide and azodicarbonitrile compounds.
Further, the chain transfer agent is selected from ethylbenzene, and the dosage of ethylbenzene is 5% -20% of the mass sum of the reaction monomers.
Further, the radical polymerization initiation method may employ thermal initiation or initiator initiation; when the initiator is used for initiation, the dosage of the initiator is 150ppm-600 ppm.
Further, the peroxide initiator is selected from at least one of diacyl peroxide, peroxydicarbonate, peroxycarboxylate, alkyl hydroperoxide, and dialkyl peroxide, preferably dibenzoyl peroxide, bis-o-methylbenzoyl peroxide, acetylisobutyryl peroxide, diisolactone peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-tert-butylcyclohexyl peroxydicarbonate, tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, 1-bis (tert-butyl peroxide) cyclohexane, and dicumyl peroxide; the azobisnitrile initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Further, the multifunctional organolithium initiator is selected from one or a mixture of several multifunctional organolithium initiators, including but not limited to multi-chelate organolithium initiator RLin or metal-based multifunctional organolithium initiator t (rli) n, wherein: r is a hydrocarbon group having 4 to 20 carbon atoms, R may be an alkane group or an aromatic hydrocarbon group, and T is a metal atom, and is generally a metal element such as tin Sn, silicon Si, lead Pb, titanium Ti, germanium Ge, or the like.
Further, the multifunctional organic lithium initiator T (RLi) n is generally selected from the group consisting of Sn-containing, Si-based multifunctional organic lithium initiators Sn (RLi) n, Si (RLi) n, wherein n is the initiator functionality and n is 3 to 50; the most preferred range is selected from Sn (RLi)4、Si(RLi)4。
Further, the polar additive is selected from one or a mixture of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and metal alkoxide compounds, such as: (1) an oxygenate, typically selected from: diethyl ether, tetrahydrofuran, R1OCH2CH2OR2(wherein: R1、R2Is an alkyl group having 1 to 6 carbon atoms, R1、R2May be the same or different, with R1、R2The difference is preferably as follows: ethylene glycol dimethyl ether, ethylene glycol diethyl ether), R1OCH2CH2OCH2CH2OR2(wherein: R1、R2Is an alkyl radical R having 1 to 6 carbon atoms1、R2May be the same or different, with R1、R2Preferably different, such as diethylene glycol dimethyl ether, diethylene glycol dibutyl ether), crown ethers; (2) a nitrogen-containing compound, generally selected from: triethylamine, Tetramethylethylenediamine (TMEDA), dipiperidine ethane (DPE), preferably TMEDA; (3) a phosphorus-containing compound, which is generally selected from hexamethylphosphoric triamide (HMPA); (4) the metal alkoxide compound is generally selected from the group consisting of ROMs, wherein: r is an alkyl group having 1 to 6 carbon atoms, O is an oxygen atom, M is a metal ion sodium Na or potassium K, preferably selected from: potassium tert-butoxide, potassium tert-pentoxide.
The non-polar organic solvent used in the present invention is selected from one or a mixture of several hydrocarbon solvents selected from non-polar aromatic hydrocarbons and non-polar aliphatic hydrocarbons, and is generally selected from: benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons (e.g. mixed xylenes), mixed aliphatic hydrocarbons (e.g. raffinate), preferably from: benzene, toluene, pentane, hexane, cyclohexane.
Further, after the reaction in step S2 is completed, an anti-aging agent (hindered phenol or a mixture of hindered phenol and phosphite) is added, the polymer is post-treated by a conventional method, and the product is dried and then subjected to an analytical test.
Further, it is determined whether to use the polar additive in step S1 depending on the polybutadiene microstructure requirement.
Further, the mass concentration of all monomers added in the step S1 is 5% to 25%, depending on the kind of the polar compound.
Further, the method comprises a step S1-1 of adding a terminator after the reaction of the step S1 is finished to terminate the polymerization reaction; the terminator is a terminator which can be used for anionic polymerization reaction, such as water, methanol, ethanol or isopropanol and the like.
The invention has the beneficial effects that:
the invention starts from high molecular design, adopts a polyfunctional group organic lithium initiator to firstly carry out the polymerization of a butadiene homopolymer block BR, and then carry out the polymerization of a DPE derivative, butadiene and a styrene copolymer (SN-SBR) block to prepare a [ (SN-SBR) -BR ] n-C star copolymer block, and prepares the HIPS resin with ultrahigh impact strength on the basis. The invention really realizes the chemical compounding of the DPE derivative, the butadiene and the styrene copolymer rubber and the polybutadiene rubber, and has the technical effects of simplicity, convenience and practicability and better effect compared with the traditional rubber compounding method which adopts a mode of physically mixing various rubbers on an open mill or an internal mixer; on the basis, the prepared HIPS resin with ultrahigh impact strength can be realized by adopting a bulk method, a bulk-suspension method, a solution method, a suspension method and other methods, and compared with the common HIPS resin, the impact strength of the obtained product is obviously improved.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental methods and calculation methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The polyfunctional organic lithium initiator used in the following examples is a polychelating organic lithium initiator, and the synthesis method is as follows: under the protection of high-purity nitrogen, adding 160 g of cyclohexane, 11 g of butadiene, 80mmol of Tetrahydrofuran (THF) and 100mmol of Divinylbenzene (DVB) into a 500 ml dry saline bottle according to the ratio, uniformly mixing, adding 100mmol of n-butyllithium by using a syringe, reacting at 70 ℃ for 30 minutes to generate a deep red homogeneous polychelating type organolithium initiator solution, wherein the initiator concentration is measured by adopting a double titration method. [ (SN-SBR) -BR ] n-C radial copolymer block: b1 is the first butadiene amount (for preparing BR block), B2 is the second butadiene amount [ for preparing (SN-SBR) block ], I is isoprene amount, SN is DPE derivative, S is styrene amount, the monomer ratio of butadiene B2, DPE derivative SN and styrene S in (SN-SBR) block, (SN-SBR)/BR is the weight ratio of (SN-SBR) block and BR block.
Example 1
[ (SN-SBR) -BR ] n-C radial copolymer block: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; 157.5 g of butadiene, 52.5 g of styrene and 4.5 g of 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene (DPE-2SiH) containing the polar additive THF were added, the reaction was continued for 60 minutes at a THF/Li molar ratio of 35, and after the polymerization of 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, butadiene and styrene had been completed, a terminator was added to terminate the reaction. [ (SN-SBR) -BR ] n-C radial copolymer block: b1 is the first butadiene (used to make the BR block); b2 is the second butadiene [ used for preparing (SN-SBR) block ], styrene, 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, (1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, butadiene, styrene monomer ratio (weight ratio) in SN-SBR) block, (butadiene content 70.2% (weight percent) in SN-SBR) block, styrene content 23.2% (weight percent), 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene content 6.6% (weight percent); the (SN-SBR) block to BR block ratio (SN-SBR)/BR was 60/40 (weight ratio); the number average molecular weight was 30.6 ten thousand and the molecular weight distribution index was 1.08.
Preparation of HIPS resin: in a 2 liter stainless steel reactor with agitation, 1150 grams of styrene were first added, followed by 245 grams of toughener [ (SN-SBR) -BR ] n-C. The initiation reaction temperature is 110 ℃, the polymerization is carried out by adopting a method initiated by a free radical initiator, the initiator adopts 1, 1-di (tert-butyl peroxide) cyclohexane, the dosage of the initiator is 350ppm, and the dosage of ethylbenzene accounts for 15 percent (weight percent) of the total amount of reaction monomers. The product was dried and then analyzed, and the structure and properties of the sample were tested using the classical method, with the following results: izod impact strength is 365J/m, tensile yield strength is 29.5MPa, tensile breaking strength is 28.8MPa, and bending strength is 45.2 MPa; the styrene content in the product was 83.5% (by weight), [ (SN-SBR) -BR ] n-C content was 16.5% (by weight), number average molecular weight was 25.6 ten thousand, and molecular weight distribution index was 2.28.
Example 2
[ (SN-SBR) -BR ] n-C radial copolymer block: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; 157.5 g of butadiene, 52.5 g of styrene and 4.4 g of 1[4- (dimethylsilyl) phenyl ] -1-phenylethene (DPE-SiH) containing the polar additive THF were then added, the reaction was continued for 60 minutes at a THF/Li molar ratio of 35, and after the polymerization of 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, butadiene and styrene had been completed, a terminator was added to terminate the reaction. [ (SN-SBR) -BR ] n-C radial copolymer block: b1 is the first butadiene (used to make the BR block); b2 is a second butadiene [ used for preparing (SN-SBR) block ], styrene, 1[4- (dimethylsilyl) phenyl ] -1-phenylethylene, (weight ratio of 1[4- (dimethylsilyl) phenyl ] -1-phenylethylene, butadiene, styrene monomer in SN-SBR) block, (butadiene content in SN-SBR) block is 70.1% (weight percentage), styrene content is 24.2% (weight percentage), 1[4- (dimethylsilyl) phenyl ] -1-phenylethylene content is 5.7% (weight percentage); the (SN-SBR) block to BR block ratio (SN-SBR)/BR was 60/40 (weight ratio); the number average molecular weight was 30.5 ten thousand and the molecular weight distribution index was 1.08.
Preparation of HIPS resin: a2 liter stainless steel stirred tank reactor was charged first with 1210 grams of styrene and then with 175 grams of toughener [ (SN-SBR) -BR ] n-C. The initiation reaction temperature is 110 ℃, the polymerization is carried out by adopting a method initiated by a free radical initiator, the initiator adopts 1, 1-di (tert-butyl peroxide) cyclohexane, the dosage of the initiator is 400ppm, and the dosage of ethylbenzene accounts for 15 percent (weight percentage) of the total amount of reaction monomers. The product was dried and then analyzed, and the structure and properties of the sample were tested using the classical method, with the following results: the Izod impact strength is 215J/m, the tensile yield strength is 30.5MPa, the tensile breaking strength is 31.6MPa, and the bending strength is 49.5 MPa; the styrene content in the product was 88.5% (by weight), [ (SN-SBR) -BR ] n-C content was 11.5% (by weight), number average molecular weight was 28.6 ten thousand, and molecular weight distribution index was 2.25.
Example 3
[ (SN-SBR) -BR ] n-C radial copolymer block: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 155 g of butadiene and 55 g of styrene containing a polar additive THF, 55 g of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene (DPE-N) with a THF/Li molar ratio of 35 were added, the reaction was continued for 60 minutes, and when the polymerization of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, butadiene and styrene was completed, a terminator was added to terminate the reaction. [ (SN-SBR) -BR ] n-C radial copolymer block: b1 is the first butadiene (used to make the BR block); b2 is butadiene [ used for preparing (SN-SBR) block ], styrene, 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethylene, (1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethylene, butadiene, styrene monomer ratio (weight ratio) in SN-SBR) block, (butadiene content 75.4% (weight percentage) in SN-SBR) block, styrene content 17.8% (weight percentage), 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethylene content 6.8% (weight percentage); the (SN-SBR) block to BR block ratio (SN-SBR)/BR was 60/40 (weight ratio); the number average molecular weight was 39.8 ten thousand and the molecular weight distribution index was 1.11.
Preparation of HIPS resin: in a 2 liter stainless steel reactor with agitation, 1245 grams of styrene were first added, followed by 140 grams of toughener [ (SN-SBR) -BR ] n-C. The initiation reaction temperature is 115 ℃, the polymerization is carried out by adopting a method initiated by a free radical initiator, the initiator adopts 1, 1-di (tert-butyl peroxide) cyclohexane, the dosage of the initiator is 250ppm, and the dosage of ethylbenzene accounts for 15 percent (weight percent) of the total amount of reaction monomers. The product was dried and then analyzed, and the structure and properties of the sample were tested using the classical method, with the following results: izod impact strength is 225J/m, tensile breaking strength is 31.2Mpa, and bending strength is 50.5 Mpa; the styrene content in the product was 90.5% (by weight), [ (SN-SBR) -BR ] n-C was 9.5% (by weight), the number average molecular weight was 25.2 ten thousand, and the molecular weight distribution index was 2.25.
Example 4
[ (SN-SBR) -BR ] n-C radial copolymer block: adding 3.5L of toluene and 140g of butadiene into a 5L stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; 178.5 g of butadiene, 31.5 g of styrene and 55 g of 1- [4- (triisopropoxysido) phenyl ] -1-phenylethene (DPE-SiO) containing the polar additive THF were then added, the reaction was continued for 60 minutes at a THF/Li molar ratio of 35, and after the polymerization of 1- [4- (triisopropoxysido) phenyl ] -1-phenylethene, butadiene and styrene had been completed, a terminator was added to terminate the reaction. [ (SN-SBR) -BR ] n-C radial copolymer block: b1 is the first butadiene (used to make the BR block); b2 is a second butadiene [ used for preparing (SN-SBR) block ], styrene, 1- [4- (triisopropoxysilicone-based) phenyl ] -1-phenylethene, (weight ratio) of 1- [4- (triisopropoxysilicone-based) phenyl ] -1-phenylethene, butadiene, styrene monomer in SN-SBR) block, (butadiene content 69.2% (weight percent) in SN-SBR block, styrene content 11.7% (weight percent) in SN-SBR block, 1- [4- (triisopropoxysilicone-based) phenyl ] -1-phenylethene content 19.1% (weight percent); the (SN-SBR) block to BR block ratio (SN-SBR)/BR was 60/40 (weight ratio); the number average molecular weight was 35.5 ten thousand and the molecular weight distribution index was 1.09.
Preparation of HIPS resin: a2 liter stainless steel stirred tank reactor was charged first with 1210 grams of styrene and then with 175 grams of toughener [ (SN-SBR) -BR ] n-C. The initiation reaction temperature is 110 ℃, the polymerization is carried out by adopting a method initiated by a free radical initiator, the initiator adopts 1, 1-di (tert-butyl peroxide) cyclohexane, the dosage of the initiator is 400ppm, and the dosage of ethylbenzene accounts for 15 percent (weight percentage) of the total amount of reaction monomers. The product was dried and then analyzed, and the structure and properties of the sample were tested using the classical method, with the following results: the Izod impact strength is 238J/m, the tensile yield strength is 31.4MPa, the tensile breaking strength is 33.8MPa, and the bending strength is 48.5 MPa; the styrene content in the product was 88.5% (by weight), [ (SN-SBR) -BR ] n-C content was 11.5% (by weight), number average molecular weight was 26.2 ten thousand, and molecular weight distribution index was 2.28.
Example 5
[ (SN-SBR) -BR ] n-C radial copolymer block: adding 3.5L of toluene and 140g of butadiene into a 5L stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 150g of butadiene containing THF as a polar additive, 60g of styrene, 20g of 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene (DPE-N/SiO) in a molar ratio of THF/Li of 35 were added, the reaction was continued for 60 minutes, and after the polymerization of 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene and styrene had been completed, a terminator was added to terminate the reaction. Obtaining [ (SN-SBR) -BR ] n-C star copolymer block: b1 represents 140g of the first butadiene charge (used for preparing the BR block); b2 is the amount of butadiene used in the second batch [ for the preparation of the (SN-SBR) block ]150g, styrene 60g, 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene 20g, B1 is the amount of butadiene used in the first batch (for the preparation of the BR block); b2 is a second batch of butadiene [ used for preparing (SN-SBR) blocks ], styrene, 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, the proportions (by weight) of 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, butadiene and styrene in the (SN-SBR) block were 67.3% by weight of butadiene and 26.5% by weight of styrene in the (SN-SBR) block, and the 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene was 6.2% by weight; the (SN-SBR) block to BR block ratio (SN-SBR)/BR was 60/40 (weight ratio); the number average molecular weight was 35.5 ten thousand and the molecular weight distribution index was 1.09.
Preparation of HIPS resin: a2 liter stainless steel stirred tank reactor was charged first with 1210 grams of styrene and then with 175 grams of toughener [ (SN-SBR) -BR ] n-C. The initiation reaction temperature is 105 ℃, the polymerization is carried out by adopting a method initiated by a free radical initiator, the initiator adopts 1, 1-di (tert-butyl peroxide) cyclohexane, the dosage of the initiator is 400ppm, and the dosage of ethylbenzene accounts for 20 percent (weight percent) of the total amount of reaction monomers. The product was dried and then analyzed, and the structure and properties of the sample were tested using the classical method, with the following results: the Izod impact strength is 265J/m, the tensile yield strength is 29.5MPa, the tensile breaking strength is 32.8MPa, and the bending strength is 46.8 MPa; the styrene content in the product was 89.5% (by weight), [ (SN-SBR) -BR ] n-C content was 10.5% (by weight), number average molecular weight was 26.5 ten thousand, and molecular weight distribution index was 2.26.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. HIPS resin containing DPE derivative, butadiene and styrene star copolymer blockWherein the HIPS resin is styrene/[ (SN-SBR) -BR]The n-C copolymer resin is [ (SN-SBR) -BR]Graft copolymers of n-C with styrene monomers; the [ (SN-SBR) -BR ] is calculated by taking the mass of the HIPS resin as 100 percent]The content of n-C is 3-35%; the HIPS resin has a number average molecular weight in the range of 5 x 104-80×104g/mol；
Wherein the [ (SN-SBR) -BR]n-C is a DPE derivative, butadiene, styrene star copolymer block, (SN-SBR) is a DPE derivative, butadiene, styrene copolymer block, BR is a butadiene homopolymer block; c is a polyfunctional alkyl lithium initiator residue, n is initiator functionality, n is a natural number, and n is 3-50; the [ (SN-SBR) -BR]The mass ratio of the (SN-SBR) block in the n-C to the BR block is 10/90-90/10; the [ (SN-SBR) -BR]n-C has a number average molecular weight of 5X 104-50×104(ii) a Based on 100 percent of the mass of the (SN-SBR) copolymer block, the content of butadiene is 30 to 80 percent, the content of styrene is 5 to 50 percent, and the content of DPE derivatives is 0.5 to 20 percent;
the DPE derivative is selected from an amino group-containing group, a silicon group/amino group monomer 1, 1-diphenylethylene derivative; the amino group, the silicon group/the amino group are connected at the para position, the meta position or the ortho position of the phenyl in the 1, 1-diphenylethylene derivative.
2. The HIPS resin of claim 1, wherein the [ (SN-SBR) -BR ] n-C content ranges from 5% to 25% based on 100% by mass of the HIPS resin; based on 100% of the mass of the (SN-SBR) block, the (SN-SBR) block contains 50-60% of butadiene, 25-35% of styrene and 5-15% of DPE derivatives.
3. The HIPS resin of claim 2, wherein the mass ratio of the (SN-SBR) block to the BR block in the star copolymer block is 30/70-70/30.
4. The HIPS resin of claim 3, wherein the HIPS resin has a number average molecular weight of10×104-50×104g/mol; the [ (SN-SBR) -BR]The number average molecular weight of the n-C block is 10X 104-30×104。
5. The HIPS resin of claim 1, wherein the DPE derivative is selected from the group consisting of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylsilyl) phenyl ] -1-phenylethene, 1-bis [4- (N, N-dimethylamino) phenyl ] ethene, 1-bis [4- (triisopropoxysilyl) phenyl ] ethene, 1-bis [4- (dimethylsilyl) phenyl ] ethene, 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, and mixtures thereof, 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene.
6. A process for the preparation of HIPS resin containing a DPE derivative, butadiene, isoprene, styrene star copolymer blocks as claimed in any of claims 1 to 5, comprising the steps of:
step S1, preparing star copolymer block [ (SN-SBR) -BR ] n-C glue solution:
adding a first batch of butadiene monomer and a polar additive into a reactor according to the monomer ratio in a nonpolar hydrocarbon solvent, enabling the initiation reaction temperature to reach 10-90 ℃, and the reaction time to be 20-100min, and then adding a polyfunctional group organic lithium initiator to prepare a butadiene homopolymer block BR;
after the first batch of butadiene is completely reacted, adding a second batch of butadiene monomer containing a polar additive, a DPE derivative and styrene into the reactor at one time according to the monomer proportion, wherein the reaction time is 50-100min, and after the DPE derivative, the butadiene and the styrene are completely reacted, stopping the reaction to obtain a [ (SN-SBR) -BR ] n-C star copolymer block;
step S2, preparing HIPS resin:
according to the content requirements of [ (SN-SBR) -BR ] n-C and styrene in the designed HIPS resin, adding styrene into the [ (SN-SBR) -BR ] n-C glue solution, selecting a chain transfer agent to adjust the molecular weight of the HIPS resin, initiating a polymerization reaction by adopting a free radical polymerization method, wherein the reaction temperature is 80-120 ℃, the reaction time is not less than 30min, and performing post-treatment on a polymer after the reaction is finished to obtain the HIPS resin;
the multifunctional organic lithium initiator is selected from one multifunctional organic lithium initiator or a mixture of several multifunctional organic lithium initiators, including but not limited to a multi-chelate organic lithium initiator RLin or a metal multifunctional organic lithium initiator T (RLi) n, wherein: r is a hydrocarbon group with 4-20 carbon atoms, R can be an alkane group or an aromatic hydrocarbon group, T is a metal atom and is selected from tin Sn, silicon Si, lead Pb, titanium Ti and germanium Ge, n is initiator functionality, and n is 3-50;
the initiator of the free radical polymerization method is selected from peroxide and azodicarbonitrile compounds.
7. The method of claim 6, wherein the chain transfer agent is selected from ethylbenzene in an amount of 5% to 20% by weight of the total amount of reactive monomers.
8. The method of claim 6, wherein the multi-functional organolithium initiator of the group consisting of Sn, Si and Sn is selected from Sn (RLi)4、Si(RLi)4。
9. The method of claim 7, wherein the peroxide initiator is selected from the group consisting of dibenzoyl peroxide, di-o-methylbenzoyl peroxide, acetyl isobutyryl peroxide, diisolactone peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-t-butylcyclohexyl peroxydicarbonate, t-butyl peroxypivalate, t-butyl peroxybenzoate, t-butyl hydroperoxide, cumene hydroperoxide, 1-bis (t-butyl peroxy) cyclohexane, dicumyl peroxide; the azobisnitrile initiator is selected from azobisisobutyronitrile and azobisisoheptonitrile.
10. The method of claim 6, wherein the polar additive is at least one selected from the group consisting of diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, hexamethylphosphoric triamide, and tetramethylethylenediamine.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1350011A (en) * 2000-10-19 2002-05-22 中国石油化工股份有限公司 Star-shaped butadiene-styrene block copolymer and its prepn
US20020120069A1 (en) * 2000-10-19 2002-08-29 Yang Li Star-block interpolymers and preparation of the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1350011A (en) * 2000-10-19 2002-05-22 中国石油化工股份有限公司 Star-shaped butadiene-styrene block copolymer and its prepn
US20020120069A1 (en) * 2000-10-19 2002-08-29 Yang Li Star-block interpolymers and preparation of the same

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