CN113817111B - Soluble polymerized A-DPE derivative SIBR star-shaped integrated rubber toughened HIPS resin and preparation method thereof - Google Patents

Soluble polymerized A-DPE derivative SIBR star-shaped integrated rubber toughened HIPS resin and preparation method thereof Download PDF

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CN113817111B
CN113817111B CN202111063647.5A CN202111063647A CN113817111B CN 113817111 B CN113817111 B CN 113817111B CN 202111063647 A CN202111063647 A CN 202111063647A CN 113817111 B CN113817111 B CN 113817111B
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phenyl
styrene
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CN113817111A (en
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冷雪菲
李杨
韩丽
王艳色
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Dalian University of Technology
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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    • 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
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    • 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
    • C08F297/046—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 and isoprene, optionally with other conjugated dienes
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Abstract

The invention belongs to the technical field of functionalized high polymer materials, and provides a soluble polymerized A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin and a preparation method thereof in order to solve the problem of lower impact strength of HIPS resin in the prior art, wherein the A-DPE derivative is a 1, 1-diphenylethylene derivative monomer containing a silicon-based group, an amino group and a silicon-based group/amino group; based on the mass of the HIPS resin as 100%, the content of the integrated rubber is 3% -35%, and the balance is the content of styrene; the HIPS resin has a number average molecular weight in the range of 10 x 10 4 ‑80×10 4 g/mol. According to the invention, functional sites are qualitatively, quantitatively and positionally introduced into the rubber phase by an anion polymerization method, so that the uniform dispersion of the rubber phase is facilitated, the star topology structure is introduced into the integrated rubber, the comprehensive performance of the integrated rubber can be greatly improved, the HIPS rubber has excellent impact resistance, and the associativity and compatibility of the material and the polar additive are greatly improved.

Description

Soluble polymerized A-DPE derivative SIBR star-shaped integrated rubber toughened HIPS resin and preparation method thereof
Technical Field
The invention belongs to the technical field of functionalized high polymer materials, and particularly relates to a solution polymerized A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin and a preparation method thereof.
Background
The high impact polystyrene resin HIPS is a mixture of a styrene polymer PS as a resin phase and a butadiene/styrene graft copolymer as a rubber phase. The high impact polystyrene resin HIPS is used as a toughening modification material of polystyrene resin PS and is widely applied to the fields of electronics, instruments, automobiles, building materials and the like. The prior production technology of high impact polystyrene resin mainly comprises the following steps: the bulk-suspension method, the bulk method, the solution method and the suspension method, wherein the continuous bulk method is increasingly emphasized by people because of high product purity and good performance.
The HIPS 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 a thermal initiation or initiator initiation method. After the rubber toughening agent is added, the impact resistance of the SAN resin is improved, but the HIPS resin with ultrahigh impact strength is difficult to obtain by adopting the general rubber as the toughening agent, and the use of the HIPS olefin resin is limited to a certain extent.
How to further improve the dispersibility of the rubber phase in the resin and improve the dispersibility of inorganic substances in the resin matrix so as to achieve the aim of improving the performance of HIPS is a technical problem to be solved urgently.
Disclosure of Invention
The invention provides a soluble poly A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin and a preparation method thereof.
In a first aspect, the invention provides a soluble poly A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin, which is a graft copolymer of an A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber and styrene, wherein the A-DPE derivative is a 1, 1-diphenylethylene derivative monomer containing a silicon-based group, an amine group and a silicon-based group/amine group, A is a functional group substituent and is directly connected to para position, ortho position or meta position of a double bond of the diphenylethylene derivative, and the functional group A is selected from the group consisting of-SiH structure n R 3-n ，-Si(OR) n R’ 3-n or-NRR 'or one or two functional groups, R and R' are selected from methyl, ethyl, propyl, isopropyl, tertiary butyl and phenyl, and n is selected from 1, 2 and 3.
Based on 100% of the mass of the star-shaped integrated rubber, the star-shaped integrated rubber contains 5-80% of butadiene, 5-80% of isoprene, 0.8-20% of A-DPE derivative and the balance of styrene; the number average molecular weight of the star-shaped integrated rubber is 5 multiplied by 10 4 -70×10 4 g/mol；
Based on the mass of the HIPS resin as 100%, the content of star-shaped integrated rubber is 3% -35%, and the balance is the content of styrene; the HIPS resin has a number average molecular weight in the range of 10 x 10 4 -80×10 4 g/mol。
Preferably, the HIPS resin has a number average molecular weight in the range of 15X 10 4 -60×10 4 g/mol; the number average molecular weight of the integrated rubber is 7 multiplied by 10 4 -40×10 4 g/mol。
Preferably, based on 100% of the mass of the star-shaped integrated rubber, the content of butadiene is 20-60%, the content of isoprene is 20-60%, the content of A-DPE derivative is 1-15%, and the balance is styrene.
Preferably, the content of the star-shaped integrated rubber is 5-25% based on 100% of the mass of the HIPS resin, and the balance is styrene.
Preferably, the amine group-containing group, the silicon group/amine group monomer 1, 1-diphenylethylene derivative (DPE derivative) is selected from a group consisting of a mono-amine group DPE derivative monomer, a di-amine group DPE derivative monomer, a mono-siloxy group DPE derivative monomer, a di-siloxy group DPE derivative monomer, a siloxy group/amine group DPE derivative monomer, and a siloxy group/amine group DPE derivative monomer.
Preferred monomers for the monoamino group DPE derivatives 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, 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.
Preferred monosiloxy 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 disiloxyl DPE derivative monomers generally range from 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.
Preferred monosilicon group 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; the general range of bis-silyl DPE derivative monomers is 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 [2,4- (dimethylsilyl) phenyl ] ethylene 1, 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.
Preferred, siloxy/amino group DPE derivative monomers generally 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 preferred range is 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene.
Preferred, typical ranges for the silylhydride group/aminide group DPE derivative monomer are 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (diethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (dipropylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (diisopropylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 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.
Preferably, the star-integrated rubber has a number average molecular weight in the range of 10 × 10 4 -15×10 4 g/mol; based on 100% of the mass of the star-shaped integrated rubber, the content of butadiene is 50-55%, the content of isoprene is 25-30%, the content of A-DPE derivatives is 4-6%, and the balance is styrene;
the HIPS resin has a number average molecular weight in the range of 20X 10 4 -25×10 4 g/mol; the mass of the HIPS resin is 100%, the content of the star-shaped integrated rubber is 10% -15%, and the balance is polystyrene resin.
In a second aspect, the invention provides a preparation method of a soluble poly A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin, which comprises the following steps:
s1, under the protection of nitrogen or argon, firstly adding an organic solvent and an A-DPE derivative into a first polymerization reactor, heating the reactor to the polymerization temperature of 30-100 ℃, adding a polyfunctional group alkyl lithium initiator, and initiating the polymerization reaction of the A-DPE derivative and styrene for more than 30 minutes;
s2, adding isoprene, butadiene and a quantitative polar additive into the first reactor, and continuously reacting for 6-24 h at the temperature of 30-100 ℃; after the reaction is finished, injecting isopropanol into the reaction solution to terminate polymerization, depositing rubber, and drying in a vacuum drying oven to constant weight to obtain the A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber;
s3, adding the star-shaped integrated rubber and styrene monomer prepared in the step S2 into a second reactor, simultaneously adding a certain amount of ethylbenzene as a diluent and a chain transfer agent, adding a free radical initiator, initiating a polymerization reaction by adopting a free radical polymerization method, carrying out post-treatment on a polymer by adopting a traditional method after the reaction is finished to obtain a bulk HIPS resin,
the dosage of the ethylbenzene is 5 to 20 percent of the total mass of the reaction monomers;
the free radical initiator is selected from peroxide and azo bis nitrile thermal decomposition type initiator;
the polyfunctional alkyl lithium initiator is selected from RLi n 、T(RLi) n One or a mixture of several polyfunctional alkyl lithium initiators in (a), wherein: r is a hydrocarbon group with 4-20 carbon atoms, and T is a metal atom of Sn, si, pb, ti, ge and Ge; n is the initiator functionality, n is a natural number and ranges from 3 to 50.
Preferably, the polyfunctional alkyl lithium initiator RLin is selected from various polychelated organic lithium initiators obtained by reacting divinylbenzene with alkyl lithium; polyfunctional alkyl lithium initiator T (RLi) n Selected from tin-containing Sn, silicon Si multi-functional group organic lithium initiator Sn (RLi) n 、Si(RLi) n 。
Preferably, the polar additive is selected from at least one of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds or metal alkoxide compounds; the organic solvent is at least one selected from non-polar aromatic hydrocarbon and non-polar aliphatic hydrocarbon, and the organic solvent includes but is not limited to benzene, toluene, hexane and cyclohexane.
Preferably, the A-DPE derivative is preferably selected from one or more of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, 1-bis [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1-bis [4- (triisopropoxysilyl) phenyl ] ethene, 1- [4- (dimethylsilyl) phenyl ] -1-phenylethene, 1-bis [4- (dimethylsilyl) phenyl ] ethene, 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene.
Preferably, the peroxide thermal decomposition type initiator is selected from one or a mixture of several initiators selected from diacyl peroxide, peroxydicarbonate, peroxycarboxylic ester, alkyl hydroperoxide, and dialkyl peroxide, preferably selected from dibenzoyl peroxide, di-o-methylbenzoyl peroxide, acetylisobutyryl peroxide, diisolactone peroxydicarbonate, di-tert-butylcyclohexyl peroxydicarbonate, tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, 1-di (tert-butyl peroxy) cyclohexane, dicumyl peroxide, 3, 6, 9-trimethyl-3, 6, 9-triethyl-1, 4, 7-trioxane; the azo thermal decomposition initiator is selected from one or a mixture of a plurality of initiators of azobisisobutyronitrile, dimethyl azobisisobutyrate, azoisobutyronitrile formamide and azobisisoheptonitrile; the initiator for free radical polymerization may be one or a mixture of several of the above initiators.
Preferably, the number average molecular weight of the functionalized HIPS ranges from 10 x 10 4 －50×10 4 g/mol; the number average molecular weight of the functionalized star-shaped integrated rubber is in the molecular weight range of 5 multiplied by 10 4 -40×10 4 g/mol。
The invention has the beneficial effects that:
the multifunctional sites in the chain are qualitatively, quantitatively and positionally introduced into the rubber phase by an anion polymerization method, and the star topology structure is introduced into the integrated rubber, so that the comprehensive performance of the star integrated rubber can be greatly improved, and the improvement of the solubility of the star integrated rubber in a polymerized monomer is facilitated. The functionalized HIPS is synthesized by adopting a bulk method, so that the uniform dispersion of a rubber phase can be realized, the material has excellent impact resistance, and the associativity and compatibility of the material and a polar additive are greatly improved.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, aspects 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 invention may be practiced otherwise than as 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.
In the embodiment of the invention, a nuclear magnetic resonance spectrometer and an infrared spectrometer are used for analyzing the composition sequence distribution and the microstructure of the copolymer, a gel permeation chromatograph is used for analyzing the molecular weight and the molecular weight distribution index (the ratio of the weight average molecular weight to the number average molecular weight) of the copolymer, and a universal tensile tester is adopted according to the ASTM D412 standard for measuring the mechanical property.
Example 1
Under the protection of argon, sequentially adding 100ml of solvent benzene, 260ml of cyclohexane and 4.2g of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene into a polymerization reactor which is dried and deaerated, heating to 50 ℃, opening and stirring until the amino DPE derivative is completely dissolved, adding 100kg/mol of initiator multi-chelate alkyl lithium according to the designed molecular weight, and reacting for 60min; then sequentially adding 0.093g of Tetramethylethylenediamine (TMEDA), 6.3g of styrene, 12g of isoprene and 24g of butadiene, and continuing to react for 24 hours to prepare the functionalized star-shaped integrated rubber, wherein the product structure analysis result is as follows: 13.1 percent of styrene, 4.8 percent of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, 27.2 percent of isoprene and 54.9 percent of butadiene; the number average molecular weight was 13.2kg/mol and the molecular weight distribution was 1.15.
1211 g of styrene is firstly added into a stainless steel reaction kettle with a stirrer, 165 g of star-shaped functionalized integrated rubber toughening agent is then added, the toughening agent is completely dissolved in the styrene, 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 200ppm, and the dosage of ethylbenzene accounts for 10 percent (weight percent) of the total amount of reaction monomers. After the reaction is finished, the polymer is post-treated by adopting a traditional method, and the product structure analysis result is as follows: the styrene content in the product is 88.0 percent (weight percentage), the functionalized integrated rubber content is 12.0 percent (weight percentage), the number average molecular weight is 24.8 ten thousand, the molecular weight distribution index is 2.41, the Izod impact strength is 231J/m, the tensile yield strength is 30.8MPa, the tensile breaking strength is 35.9MPa, and the bending strength is 51.8MPa.
Example 2
Under the protection of argon, sequentially adding 100ml of solvent benzene, 260ml of cyclohexane and 4.2g of 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene into a polymerization reactor which is dried and deaerated, heating to 50 ℃, opening and stirring until the amino DPE derivative is completely dissolved, adding initiator multi-chelate alkyl lithium according to the designed molecular weight of 100kg/mol, and reacting for 60min; then sequentially adding 0.093g of Tetramethylethylenediamine (TMEDA), 7g of styrene, 14.3g of isoprene and 21g of butadiene, and continuing to react for 24 hours to prepare the functionalized star-shaped integrated rubber, wherein the product structure analysis result is as follows: 15.7 percent of styrene, 4.7 percent of 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, 32.2 percent of isoprene and 47.4 percent of butadiene; the number average molecular weight was 12.8kg/mol and the molecular weight distribution was 1.17.
1211 g of styrene is firstly added into a stainless steel reaction kettle with a stirrer, 145 g of star-shaped functionalized integrated rubber toughening agent is then added, the toughening agent is completely dissolved in the styrene, 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 200ppm, and the dosage of ethylbenzene accounts for 10 percent (weight percent) of the total amount of reaction monomers. After the reaction is finished, the polymer is post-treated by adopting a traditional method, and the result of the structural analysis of the product is as follows: the styrene content in the product is 89.5% (weight percent), the functionalized integrated rubber content is 10.2% (weight percent), the number average molecular weight is 22.6 ten thousand, the molecular weight distribution index is 2.28, the Izod impact strength is 214J/m, the tensile yield strength is 32.4MPa, the tensile breaking strength is 36.1MPa, and the bending strength is 48.6MPa.
Example 3
Under the protection of argon, sequentially adding 100ml of solvent benzene, 260ml of cyclohexane and 4.7g of 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene into a polymerization reactor which is dried and deaerated, heating to 50 ℃, opening and stirring until the amino DPE derivative is completely dissolved, adding initiator multi-chelate alkyl lithium according to the designed molecular weight of 100kg/mol, and reacting for 60min; then sequentially adding 0.093g of Tetramethylethylenediamine (TMEDA), 7.3g of styrene, 10.0g of isoprene and 25g of butadiene, and continuing to react for 24 hours to prepare the functionalized star-shaped integrated rubber, wherein the product structure analysis result is as follows: 16.4 percent of styrene, 4.7 percent of 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, 22.3 percent of isoprene and 56.7 percent of butadiene; the number average molecular weight was 14.3kg/mol and the molecular weight distribution was 1.23.
1211 g of styrene is firstly added into a stainless steel reaction kettle with a stirrer, 185 g of star-shaped functionalized integrated rubber toughening agent is then added, the toughening agent is completely dissolved in the styrene, 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 300ppm, and the dosage of ethylbenzene accounts for 10 percent (weight percent) of the total amount of reaction monomers. After the reaction is finished, the polymer is post-treated by adopting a traditional method, and the product structure analysis result is as follows: the styrene content in the product is 85.69% (weight percent), the functionalized integrated rubber content is 14.31% (weight percent), the number average molecular weight is 23.8 ten thousand, the molecular weight distribution index is 2.21, the Izod impact strength is 208J/m, the tensile yield strength is 33.1MPa, the tensile breaking strength is 34.8MPa, and the bending strength is 49.7MPa.
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. A kind of solution polymerized A-DPE derivant/styrene/isoprene/butadiene star shape integrated rubber toughened HIPS resin, characterized by that, the HIPS resin is A-DPE derivant/styrene/isoprene/butadiene star shape integrated rubber, graft copolymer of styrene, it is a polystyrene resin toughened with A-DPE derivant/styrene/isoprene/butadiene copolymer star shape integrated rubber;
wherein the A-DPE derivative is a 1, 1-diphenylethylene derivative monomer containing a silicon-based group, an amino group and a silicon-based group/amino group, A is a functional group substituent group and is directly connected with para position, ortho position or meta position of a double bond of the diphenylethylene derivative, and the functional group A is selected from-SiH n R 3-n ，-Si(OR) n R’ 3-n or-NRR' is selected from methyl, ethyl, propyl, isopropyl, tertiary butyl and phenyl, and n is selected from 1, 2 and 3;
based on the mass of the star-shaped integrated rubber being 100%, the content of butadiene is 20-60%, the content of isoprene is 20-60%, and the content of A-DPE derivatives is1-15% of styrene; the number average molecular weight of the star-shaped integrated rubber is 5 multiplied by 10 4 -70×10 4 g/mol；
Based on 100% of the mass of the HIPS resin, the content of the star-shaped integrated rubber is 3% -35%, and the content of the polystyrene resin is 65% -97%; the HIPS resin has a number average molecular weight in the range of 10 x 10 4 -80×10 4 g/mol。
2. The solution polymerized A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin as claimed in claim 1, wherein the HIPS resin has a number average molecular weight in the range of 15 x 10 4 -60×10 4 g/mol; the number average molecular weight of the star-shaped integrated rubber is 7 multiplied by 10 4 -40×10 4 g/mol。
3. The solution polymerized A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin as claimed in claim 2, wherein the HIPS resin contains 5-25% star-shaped integrated rubber and the balance of polystyrene resin, based on 100% by mass of the HIPS resin.
4. The solution polymerized A-DPE derivative/styrene/isoprene/butadiene star integrated rubber toughened HIPS resin of claim 3,
the number average molecular weight of the star-shaped integrated rubber is 10 multiplied by 10 4 -15×10 4 g/mol; based on 100% of the mass of the star-shaped integrated rubber, the content of butadiene is 50-55%, the content of isoprene is 25-30%, the content of A-DPE derivatives is 4-6%, and the balance is styrene;
the HIPS resin has a number average molecular weight in the range of 20 x 10 4 -25×10 4 g/mol; the content of the star-shaped integrated rubber is 10-15% based on 100% of the mass of the HIPS resin, and the balance is polystyrene resin.
5. The solution polymerized a-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin according to any one of claims 1 to 4, wherein the amine group-containing group, silicon group/amine group monomer 1, 1-diphenylethylene derivative is selected from at least one of a mono-amine group DPE derivative monomer, a bis-amine group DPE derivative monomer, a mono-siloxy group DPE derivative monomer, a bis-siloxy group DPE derivative monomer, a siloxy group/amine group DPE derivative monomer.
6. The preparation method of the solution polymerized A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin as claimed in claim 1, comprising the following steps:
s1, under the protection of nitrogen or argon, adding an organic solvent and an A-DPE derivative into a first polymerization reactor, heating to the polymerization temperature of 30-100 ℃, adding a polyfunctional group alkyl lithium initiator, and initiating the polymerization reaction of the A-DPE derivative for more than 30 minutes;
s2, adding styrene, isoprene, butadiene and a quantitative polar additive into the first reactor, and continuously reacting for 6-24 h at the temperature of 30-100 ℃; after the reaction is finished, injecting isopropanol into the reaction liquid to terminate polymerization, depositing rubber, and drying in a vacuum drying oven to constant weight to obtain A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber;
s3, adding the star-shaped integrated rubber and the styrene monomer prepared in the step S2 into a second reactor, simultaneously adding a certain amount of ethylbenzene and a radical initiator, initiating a polymerization reaction by adopting a radical polymerization method, and obtaining HIPS resin after the reaction is finished;
the dosage of the ethylbenzene accounts for 5 to 20 percent of the total mass of the reaction monomers;
the polyfunctional alkyl lithium initiator is selected from RLi n 、T(RLi) n A multifunctional alkyl lithium initiator or a mixture of several multifunctional alkyl lithium initiators in (a), wherein: r is a hydrocarbon group with 4-20 carbon atoms, and T is a metal atom of Sn, si, pb, ti, ge and Ge; n is the initiator functionality, n is a natural number having a value of 3-50；
The polar additive is selected from at least one of oxygen-containing, nitrogen-containing, sulfur-containing and phosphorus-containing polar compounds or metal alkoxide compounds;
the free radical initiator is selected from peroxide thermal decomposition type initiators and azobisnitrile thermal decomposition type initiators.
7. The method for preparing the solution polymerized A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin according to claim 6, wherein the polyfunctional alkyl lithium initiator is selected from various polychelated organic lithium initiators obtained by reacting divinylbenzene with alkyl lithium.
8. The method of claim 6 wherein the A-DPE derivative is selected from at least one of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (triisopropoxysilicol) phenyl ] -1-phenylethene, 1-bis [4- (triisopropoxysilicol) phenyl ] ethylene, 1- [4- (dimethylsiloxy) phenyl ] -1-phenylethene, 1- [4- (dimethylsilo) phenyl ] -1-phenylethene, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, 1- [4- (triisopropoxysilicol) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (dimethylsilo) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene.
9. The method for preparing the solution polymerized A-DPE derivative/styrene/isoprene/butadiene star-shaped integrated rubber toughened HIPS resin according to any one of claims 6 to 8, wherein the organic solvent is selected from non-polar aromatic hydrocarbons and non-polar aliphatic hydrocarbons.
10. The method of claim 9 wherein the organic solvent is selected from the group consisting of benzene, toluene, hexane, cyclohexane.
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