CN113801277A - Star block copolymer (SBR-BR) n-C HIPS resin with ultrahigh impact strength and preparation method thereof - Google Patents
Star block copolymer (SBR-BR) n-C HIPS resin with ultrahigh impact strength and preparation method thereof Download PDFInfo
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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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Abstract
The invention belongs to the technical field of functionalized high polymer materials, and provides an ultrahigh impact strength HIPS resin of a star block copolymer (SBR-BR) n-C in order to solve the problem of low impact strength of the HIPS resin in the prior art, wherein the HIPS resin is styrene/(SBR-BR) n-C copolymer resin, the mass content of (SBR-BR) n-C is 3-35% by taking the HIPS resin as 100%, and the number average molecular weight range of the HIPS resin is 5 multiplied by 104‑80×104g/mol. Wherein: SBR is a butadiene and styrene copolymer block, BR is a butadiene homopolymer block, C is a polyfunctional alkyl lithium initiator residue, and n is more than or equal to 3; the butadiene content in the SBR block is 5-85 percent calculated by the mass of the butadiene-styrene copolymer SBR block as 100 percent; butadiene, styrene copolymer SBR BlockThe mass ratio of the segment to the polybutadiene BR block is 1: 9-9: 1.
Description
Technical Field
The invention belongs to the technical field of functionalized high polymer materials, and particularly relates to a star block copolymer (SBR-BR) n-C polystyrene resin (HIPS resin) with ultrahigh impact strength and a preparation method thereof.
Background
In recent years, as petroleum resources are increasingly tense, the automobile industry is striving to develop novel tread rubber for saving energy, which can reduce rolling resistance, reduce internal consumption caused by heat generation, save fuel, improve wet-skid resistance and wear resistance, and ensure durability and running safety of tires. At present, relevant researchers have gradually changed the research focus from "physical blending" to "chemical blending", that is, various block copolymers are continuously developed to enable polymers to achieve segment-level blending, thereby endowing materials with more perfect properties.
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. In the research of multi-lithium system star block copolymer, Beijing Yanshan petrochemical company applies for a plurality of patents, one or a mixture of a plurality of multi-functional group initiators in the multi-functional group lithium initiators initiates conjugated dienes such as styrene, isoprene, butadiene and the like to copolymerize to obtain a series of star block copolymers, and the star polymer has the following structure: (SBR-BR) n-C, (SBR-IR) n-C, (SBR-IBR) n-C, and the like.
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.
Disclosure of Invention
In order to solve the problem that the impact strength of the resin prepared by adopting the classical polybutadiene rubber or butadiene and styrene copolymer rubber as a toughening agent in the prior art is low, the invention provides a high impact strength HIPS resin of a star block copolymer (SBR-BR) n-C and a preparation method thereof.
In a first aspect, the invention provides a type of ultra-high impact strength HIPS resin of a star block copolymer (SBR-BR) n-C, wherein the HIPS resin is styrene/(SBR-BR) n-C copolymer resin which is a graft copolymer of (SBR-BR) n-C and monomer styrene;
wherein (SBR-BR) n-C is a butadiene and styrene star block copolymer, wherein SBR is a butadiene and styrene copolymer block, and BR is a butadiene homopolymer block; c is a polyfunctional alkyl lithium initiator residue, n is an initiator functionality, n is a natural number and ranges from 3 to 50;
the content of (SBR-BR) n-C is 3-35 percent based on the mass of the HIPS resin as 100 percent; the HIPS resin has a number average molecular weight in the range of 5X 104-80×104g/mol; the number average molecular weight of the (SBR-BR) n-C is in the range of 4 x 104-50×104g/mol；
The butadiene content in the SBR block is 5-86 percent calculated by the mass of the butadiene-styrene copolymer SBR block as 100 percent; the mass ratio of the butadiene-styrene copolymer SBR block to the polybutadiene BR is 9: 1-1: 9.
furthermore, the mass fraction of the butadiene in the SBR block is 15-65 percent based on 100 percent of the total mass of the SBR block of the butadiene and styrene copolymer.
Further, the ratio of the butadiene-styrene copolymer SBR block to the polybutadiene BR block is SBR/BR mass ratio ranging from 3:7 to 7: 3.
Further, the mass ratio of (SBR-BR) n-C is 5-25% based on 100% of the mass of the HIPS resin; the HIPS resin has a number average molecular weight of 10 x 104-50×104g/mol; the number average molecular weight of the (SBR-BR) n-C is in the range of 5 x 104-30×104g/mol。
Further, the content of the (SBR-BR) n-C is 15-20% based on 100% of the mass of the HIPS resin.
Further, the mass percentage of the butadiene in the SBR block is 5-86 percent based on 100 percent of the total mass of the SBR block of the butadiene and styrene copolymer; the ratio of the SBR block of the butadiene-styrene copolymer to the BR block of the polybutadiene is 9:1-81 by mass ratio of SBR/BR.
Further, the mass percentage of the butadiene in the SBR block is 70-85 percent based on 100 percent of the total mass of the butadiene and styrene copolymer SBR block; the mass ratio of the butadiene-styrene copolymer SBR block to the polybutadiene BR block is 9: 3-6.
Further, the content of the (SBR-BR) n-C is 15-20 percent, preferably 16 percent, 17 percent and 18 percent based on 100 percent of the mass of the HIPS resin.
Further, the mass fraction of the butadiene in the SBR block is 25-50 percent based on 100 percent of the total mass of the SBR block of the butadiene and styrene copolymer; the ratio of the SBR block to the polybutadiene BR block of the butadiene-styrene copolymer is 21:20-40 by mass ratio of SBR/BR.
In a second aspect, the invention provides a preparation method of a high impact strength HIPS resin with ultrahigh impact strength of a star block copolymer (SBR-BR) n-C, which comprises the following steps:
step one, preparing a star block copolymer (SBR-BR) n-C: adding a first batch of butadiene monomer and a polar additive into a reactor according to the monomer ratio in a nonpolar hydrocarbon solvent, and adding a polyfunctional group lithium initiator when the initiation reaction temperature reaches 10-90 ℃ to prepare a butadiene homopolymer block BR;
and after the butadiene is completely reacted, adding a second batch of butadiene and styrene monomers containing polar additives into the reactor at one time according to the monomer ratio to start to prepare the butadiene and styrene copolymer block SBR, and after the butadiene and styrene are completely reacted, terminating the reaction to obtain the (SBR-BR) n-C star block copolymer.
Preparing HIPS resin, and supplementing styrene to adjust the concentration of the glue solution according to the requirement of the n-C content of (SBR-BR) in the HIPS resin; selecting a chain transfer agent to adjust the molecular weight of the HIPS resin; adding a free radical initiator to initiate polymerization reaction by adopting a free radical polymerization method, wherein the initiation reaction temperature is 100-120 ℃, and after the reaction is finished, performing post-treatment on the polymer to obtain HIPS resin;
the free radical initiator is peroxide or azodicarbonitrile compound, and the dosage of the free radical initiator is 150ppm-600 ppm;
the chain transfer agent is selected from ethylbenzene, and the dosage of the ethylbenzene is 5-20% of the total mass of the reaction monomers;
the azodicarbonitrile compound is at least one of azodiisobutyronitrile and azodiisoheptanonitrile.
Further, the peroxide is generally selected from at least one of diacyl peroxide, peroxydicarbonate, peroxycarboxylate, alkyl hydroperoxide, and dialkylene peroxide; preferably at least one selected from dibenzoyl peroxide, di-o-methylbenzoyl peroxide, acetyl isobutyryl peroxide, diisolactone peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-tert-butylcyclohexyl peroxydicarbonate, tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, 1-bis (tert-butyl peroxy) cyclohexane and dicumyl peroxide.
Further, adding an anti-aging agent after the reaction is finished, carrying out post-treatment on the polymer by adopting a traditional method, and carrying out analysis and test after the product is dried; the free radical polymerization initiation method comprises thermal initiation and initiator initiation.
Further, the anti-aging agent is hindered phenol or a mixture of hindered phenol and phosphite ester.
Further, the multifunctional lithium initiator is selected from one or a mixture of several multifunctional lithium initiators in RLin and T (RLi) n, wherein: r is a hydrocarbon group with 4-20 carbon atoms, and T is a metal atom of Sn, Si, Pb, Ti and Ge; c is a polyfunctional alkyl lithium initiator residue, n is the initiator functionality, n is a natural number and ranges from 3 to 50, and the most preferred range is from 3 to 10.
Further, the multifunctional lithium initiator RLin is selected from various polychelated organic lithium initiators obtained by reacting divinylbenzene with alkyl lithium.
Further, the method can be used for preparing a novel materialThe multifunctional lithium initiator T (RLi) n is selected from Sn-containing, Si-type multifunctional organic lithium initiators Sn (RLi) n, Si (RLi) n, and the optimal range is Sn (RLi)4、Si(RLi)4。
Further, the polar additive is selected from one or a mixture of oxygen-containing, nitrogen-containing, sulfur-containing and phosphorus-containing polar compounds and metal alkoxide compounds, and the optimal range is at least one of diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, hexamethylphosphoric triamide and tetramethylethylenediamine.
Further, the nonpolar hydrocarbon solvent is selected from one of benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed xylene, and raffinate oil.
The invention has the beneficial effects that:
the preparation of the HIPS resin with ultrahigh impact strength is realized by adopting methods such as a bulk method, a bulk-suspension method, a solution method, a suspension method and the like, and the continuous bulk method is the best implementation process route. 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 performance test instrument used in the embodiment of the present invention:
the microstructure is tested by nuclear magnetic resonance spectroscopy, the molecular weight and the molecular weight distribution thereof are tested by Gel Permeation Chromatography (GPC), the notched Izod impact strength (Izod) is tested according to ISO180:2000 standard, and the tensile yield strength, the tensile breaking strength and the bending strength are tested by a universal tester.
The polyfunctional group lithium initiator used in the following examples is a polychelated 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 polychelate organic lithium initiator solution, wherein the initiator concentration is measured by adopting a double titration method.
(SBR-BR) n-C radial block copolymer: s is the amount of styrene, B1 is the amount of butadiene used in the first batch (for the preparation of the BR block), B2 is the amount of butadiene used in the second batch (for the preparation of the SBR block), S/B2 is the ratio by weight of styrene to butadiene monomers in the SBR block, and SBR/BR is the ratio by weight of the SBR block to the BR block.
Example 1
Preparation of (SBR-BR) n-C radial Block copolymer: adding 3.5 liters of cyclohexane 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 175g of butadiene and 35g of styrene containing the polar additives THF (THF/Li molar ratio) were added, the reaction was continued for 60 minutes, and after the polymerization of butadiene and styrene was completed, a terminator was added to terminate the reaction.
(SBR-BR) n-C radial block copolymer: b1 represents 140g of the first butadiene charge (used for preparing the BR block); b2 shows 175g of butadiene in the second batch (used for preparing SBR block), S shows 35g of styrene, S/B2 shows the ratio (weight ratio) of styrene to butadiene in SBR block, the butadiene content in SBR block is 83% (weight percent), and the styrene content is 17% (weight percent); the ratio of SBR block to BR block, SBR/BR, was 60/40 (weight ratio); the number average molecular weight was 18.5 ten thousand and the molecular weight distribution index was 1.36.
In a 2 liter stainless steel stirred tank reactor, 1141 grams of styrene were added first, followed by 245 grams of toughener (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 380J/m, the tensile yield strength is 27.9MPa, the tensile breaking strength is 27.7MPa, and the bending strength is 40.6 MPa; the styrene content in the product was 83.0% (by weight), (SBR-BR) n-C content was 17.0% (by weight), number average molecular weight was 25.2 ten thousand, and molecular weight distribution index was 2.32.
Example 2
(SBR-BR) n-C radial block copolymer: adding 3.5 liters of cyclohexane and 210 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 105g of butadiene and 35g of styrene containing the polar additives THF, the THF/Li molar ratio being 35, were added and the reaction was continued for 60 minutes, and after the polymerization of butadiene and styrene had been completed, the reaction was terminated by adding a terminating agent. (SBR-BR) n-C radial block copolymer: b1 represents 210g of the first butadiene charge (used for preparing the BR block); b2 is 105g of butadiene in the second batch (used for preparing SBR block), S is 35g of styrene, S/B2 is the ratio (weight ratio) of styrene to butadiene monomers in the SBR block, the butadiene content in the SBR block is 86 percent (weight percent), and the styrene content is 14 percent (weight percent); the ratio of SBR block to BR block, SBR/BR, was 40/60 (weight ratio); the number average molecular weight was 22.0 ten thousand and the molecular weight distribution index was 1.35.
A2 liter stainless steel stirred tank reactor was charged first with 1211 grams of styrene and then with 175 grams of toughener (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 450ppm, 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 216J/m, the tensile yield strength is 29.1MPa, the tensile breaking strength is 31.7MPa, and the bending strength is 49.0 MPa; the styrene content in the product was 88.0% (by weight), (SBR-BR) n-C content was 12.0% (by weight), number average molecular weight was 27.5 ten thousand, and molecular weight distribution index was 2.43.
Example 3
(SBR-BR) n-C radial block copolymer: adding 3.5 liters of cyclohexane 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 140g of butadiene and 70g of styrene containing the polar additive THF, the THF/Li molar ratio being 35, were added and the reaction was continued for 60 minutes, and after the polymerization of butadiene and styrene had been completed, the reaction was terminated by adding a terminating agent. (SBR-BR) n-C radial block copolymer: 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 preparing SBR block) 140g, S is the amount of styrene used in the second batch 70g, S/B2 is the ratio of styrene to butadiene monomers in the SBR block (weight ratio), the butadiene content in the SBR block is 67% (weight percent), the styrene content is 33% (weight percent); the ratio of SBR block to BR block, SBR/BR, was 60/40 (weight ratio); the number average molecular weight was 15.6 ten thousand and the molecular weight distribution index was 1.32.
In a 2 liter stainless steel stirred tank reactor, 1281 grams of styrene was first added, followed by 105 grams of toughener (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 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: the Izod impact strength is 179J/m, the tensile breaking strength is 30.8MPa, and the bending strength is 51.4 MPa; the styrene content in the product was 93.0% (by weight), (SBR-BR) n-C content was 7.0% (by weight), number average molecular weight was 22.8 ten thousand, and molecular weight distribution index was 2.38.
Example 4
(SBR-BR) n-C radial block copolymer: adding 3.5 liters of cyclohexane and 105 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 140g of butadiene and 105g of styrene containing the polar additive THF, the THF/Li molar ratio being 35, were added and the reaction was continued for 60 minutes, and after the polymerization of butadiene and styrene had been completed, the reaction was terminated by adding a terminating agent. (SBR-BR) n-C radial block copolymer: b1 is 105g of the first butadiene charge (used for preparing the BR block); b2 is the amount of butadiene used in the second batch (for preparing SBR block) 140g, S is the amount of styrene used 105g, S/B2 is the ratio of styrene to butadiene monomers in the SBR block (weight ratio), the butadiene content in the SBR block is 58% (weight percent), the styrene content is 42% (weight percent); the ratio of SBR block to BR block, SBR/BR, was 70/30 (weight ratio); the number average molecular weight was 15.6 ten thousand and the molecular weight distribution index was 1.45.
In a 2 liter stainless steel stirred tank reactor, 1246 grams of styrene were first added, followed by 140 grams of toughener (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 200ppm, 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 195J/m, the tensile breaking strength is 29.2Mpa, and the bending strength is 50.8 Mpa; the styrene content in the product was 90.0% (by weight), (SBR-BR) n-C content was 10.0% (by weight), number average molecular weight was 23.5 ten thousand, and molecular weight distribution index was 2.25.
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 star block copolymer (SBR-BR) n-C HIPS resin with ultrahigh impact strength is characterized in that the HIPS resin is styrene/(SBR-BR) n-C copolymer resin which is a graft copolymer of (SBR-BR) n-C and monomer styrene;
wherein (SBR-BR) n-C is a butadiene and styrene star block copolymer, wherein SBR is a butadiene and styrene copolymer block, and BR is a butadiene homopolymer block; c is a polyfunctional alkyl lithium initiator residue, n is an initiator functionality, n is a natural number and ranges from 3 to 50;
the content of (SBR-BR) n-C is 3-35 percent based on the mass of the HIPS resin as 100 percent; the HIPS resin has a number average molecular weight in the range of 5X 104-80×104g/mol; the number average molecular weight of the (SBR-BR) n-C is in the range of 4 x 104-50×104g/mol；
The butadiene content in the SBR block is 5-86 percent calculated by the mass of the butadiene-styrene copolymer SBR block as 100 percent; the mass ratio of the butadiene-styrene copolymer SBR block to the polybutadiene BR is 9: 1-1: 9.
2. ultra-high impact strength HIPS resin of radial block copolymer (SBR-BR) n-C according to claim 1, characterized in that the mass fraction of butadiene in the SBR block is 15-65% in terms of 100% of the total mass of the SBR blocks of butadiene-styrene copolymer.
3. An ultra high impact strength HIPS resin of radial block copolymer (SBR-BR) n-C as claimed in claim 1 wherein the ratio of butadiene, styrene copolymer SBR block to polybutadiene BR block SBR/BR mass ratio ranges from 3:7 to 7: 3.
4. The ultra-high impact strength HIPS resin of a radial block copolymer (SBR-BR) n-C according to claim 1, wherein the proportion of (SBR-BR) n-C is 5 to 25% by mass based on 100% by mass of the HIPS resin; the HIPS resin has a number average molecular weight of 10 x 104-50×104g/mol; the number average molecular weight of the (SBR-BR) n-C is in the range of 5 x 104 to 30 x 104g/mol。
5. Ultra-high impact strength HIPS resin of a radial block copolymer (SBR-BR) n-C according to any of claims 1 to 4, wherein the content of (SBR-BR) n-C is 15 to 20% based on 100% by mass of the HIPS resin.
6. The preparation method of the star block copolymer (SBR-BR) n-C HIPS resin with ultrahigh impact strength is characterized by comprising the following steps:
step one, preparing (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, and adding a polyfunctional group lithium initiator when the initiation reaction temperature reaches 10-90 ℃ to prepare a butadiene homopolymer block BR;
after the butadiene is completely reacted, adding a second batch of butadiene and styrene monomers containing polar additives into the reactor at one time according to the monomer ratio to start to prepare a butadiene and styrene copolymer block SBR, and after the butadiene and styrene are completely reacted, terminating the reaction to obtain a (SBR-BR) n-C star-shaped block copolymer;
step two, preparing HIPS resin: supplementing styrene to adjust the concentration of the glue solution according to the requirement of the n-C content of (SBR-BR) in the HIPS resin; selecting a chain transfer agent to adjust the molecular weight of the HIPS resin; adding a free radical initiator to initiate polymerization reaction by adopting a free radical polymerization method, wherein the initiation reaction temperature is 100-120 ℃, and after the reaction is finished, performing post-treatment on the polymer to obtain HIPS resin;
the free radical initiator is a peroxide initiator and an azodicarbonitrile compound, and the dosage of the free radical initiator is 150ppm-600 ppm;
the chain transfer agent is selected from ethylbenzene, and the dosage of the ethylbenzene is 5-20% of the total mass of the reaction monomers;
the peroxide is selected from at least one of diacyl peroxide, peroxydicarbonate, peroxycarboxylic ester, alkyl hydroperoxide and dialkyl peroxide; the azodicarbonitrile compound is at least one of azodiisobutyronitrile and azodiisoheptanonitrile.
7. The process for preparing ultra high impact strength HIPS resin of radial block copolymer (SBR-BR) n-C according to claim 6, wherein: the peroxide is at least one selected from dibenzoyl peroxide, di-o-methylbenzoyl peroxide, acetyl isobutyryl peroxide, diisolactone peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-tert-butylcyclohexyl peroxydicarbonate, tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, 1-di (tert-butyl peroxide) cyclohexane and dicumyl peroxide.
8. The method for preparing an ultra-high impact strength HIPS resin of a radial block copolymer (SBR-BR) n-C as claimed in claim 6, wherein the multifunctional lithium initiator is selected from one or a mixture of several multifunctional lithium initiators of RLin, T (RLi) n, wherein: r is a hydrocarbon group with 4-20 carbon atoms, and T is a metal atom of Sn, Si, Pb, Ti and Ge; c is a polyfunctional alkyllithium initiator residue, n is the initiator functionality, and n is a natural number and ranges from 3 to 50.
9. 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.
10. The method for preparing an ultra-high impact strength HIPS resin of radial block copolymer (SBR-BR) n-C as claimed in any of claims 6 to 9, wherein said non-polar hydrocarbon solvent is one selected from the group consisting of benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, xylene mixture, raffinate oil.
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