CN109251264B - Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof - Google Patents
Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof Download PDFInfo
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- CN109251264B CN109251264B CN201710573911.7A CN201710573911A CN109251264B CN 109251264 B CN109251264 B CN 109251264B CN 201710573911 A CN201710573911 A CN 201710573911A CN 109251264 B CN109251264 B CN 109251264B
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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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
Abstract
The invention relates to the field of synthetic rubber and resin, in particular to low cis-polybutadiene rubber and a preparation method thereof, and HIPS resin and a preparation method thereof. The preparation method of the low cis-polybutadiene rubber comprises the following steps: (1) continuously introducing 1, 3-butadiene into a reaction vessel in an organic solvent in the presence of an organolithium initiator, a retarder, and optionally a structure modifier to effect an anionic solution polymerization reaction; (2) continuously introducing the product of the anionic solution polymerization reaction into another reaction vessel in the presence of a coupling agent to effect a coupling reaction; (3) terminating the product of the coupling reaction in the presence of a terminating agent. The low cis-polybutadiene rubber prepared by the invention has high Mooney viscosity, low solution viscosity and wide molecular weight distribution, can be used as a toughening agent in HIPS resin synthesis, and the obtained HIPS resin has higher glossiness and impact resistance.
Description
Technical Field
The invention relates to the field of synthetic rubber and resin, in particular to low cis-polybutadiene rubber and a preparation method thereof, and HIPS resin and a preparation method thereof.
Background
In the preparation of HIPS resin (i.e., high impact polystyrene), the rubber conventionally selected as the toughening agent may be low cis-polybutadiene rubber, high cis-polybutadiene rubber, butadiene-isoprene copolymer, solution polymerized styrene-butadiene rubber, styrene-butadiene-styrene copolymer, and particularly, low cis-polybutadiene rubber and high cis-polybutadiene rubber are the most preferable. For low-temperature toughness resin, low cis-polybutadiene rubber and its derivative block styrene-butadiene rubber are generally selected for toughening. However, the molecular weight and the distribution of the toughened rubber have obvious influence on the impact resistance of the continuous bulk HIPS resin, and generally, the rubber molecular weight is too small, so that the toughening effect is poor; the rubber has too high molecular weight, and the HIPS resin has poor glossiness. The low cis-polybutadiene rubber can be divided into continuous polymerization and intermittent polymerization according to a polymerization process, the production quality of the continuous polymerization process is stable, the product quality fluctuation is small, but most products of the existing process have linear structures, the viscosity of a 5% styrene solution is large, and the balance of the impact strength and the glossiness of the HIPS prepared by the method is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defect that the existing toughening agent for HIPS resin is difficult to obtain a HIPS resin product with high glossiness and high impact resistance, and provides a low cis-polybutadiene rubber serving as the toughening agent and capable of obtaining the HIPS resin with high glossiness and high impact strength, a preparation method of the low cis-polybutadiene rubber, the HIPS resin and a preparation method of the HIPS resin.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a low-cis polybutadiene rubber, comprising:
(1) continuously introducing 1, 3-butadiene into a reaction vessel in an organic solvent in the presence of an organolithium initiator, a retarder, and optionally a structure modifier to effect anionic solution polymerization, to a 1, 3-butadiene conversion of greater than 99%; wherein the retarder is selected from one or more of metal alkyl compounds; the content of 1, 3-butadiene is more than 20 wt% based on the total weight of the organic solvent and the 1, 3-butadiene;
(2) continuously introducing the product of the anionic solution polymerization reaction into another reaction vessel in the presence of a coupling agent to effect a coupling reaction;
(3) terminating the product of the coupling reaction in the presence of a terminating agent;
wherein the number average molecular weight of the low cis-polybutadiene rubber obtained by the method is 70,000-130,000; the molecular weight distribution coefficient is 1.6-2.2.
In a second aspect, the present invention provides a low cis-polybutadiene rubber obtained by the above-mentioned process.
In a third aspect, the present invention provides a process for preparing a HIPS resin, the process comprising: in benzene solvent, in the presence of free radical initiator, styrene and toughening agent are polymerized; wherein the toughening agent contains the low cis-polybutadiene rubber; wherein the benzene solvent is one or more of unsubstituted or C1-C4 alkyl substituted benzene.
In a fourth aspect, the present invention provides a HIPS resin prepared by the above process.
The low cis-polybutadiene rubber prepared by the invention has high Mooney viscosity, low solution viscosity and wide molecular weight distribution, can be used as a toughening agent in HIPS resin synthesis, and the obtained HIPS resin has higher glossiness and impact resistance.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect, the present invention provides a method for preparing a low cis-polybutadiene rubber, comprising:
(1) continuously introducing 1, 3-butadiene into a reaction vessel in an organic solvent in the presence of an organolithium initiator, a retarder, and optionally a structure modifier to effect an anionic solution polymerization reaction to a conversion of 1, 3-butadiene of 99% or greater; wherein the retarder is selected from one or more of metal alkyl compounds; the content of 1, 3-butadiene is more than 20 wt% based on the total weight of the organic solvent and the 1, 3-butadiene;
(2) continuously introducing the product of the anionic solution polymerization reaction into another reaction vessel in the presence of a coupling agent to effect a coupling reaction;
(3) terminating the product of the coupling reaction in the presence of a terminating agent;
wherein the number average molecular weight of the low cis-polybutadiene rubber obtained by the method is 70,000-130,000; the molecular weight distribution coefficient is 1.6-2.2.
According to the present invention, the above-mentioned process for producing a low-cis polybutadiene rubber is carried out in a continuous reaction manner, and in order to realize the continuous reaction, the production process may be carried out in a plurality of reactors connected in series, and the number, capacity design and reaction in the reactors may be appropriately adjusted according to the reaction time required for each step, for example, the process for producing a low-cis polybutadiene rubber of the present invention may be carried out in a system of three reactors connected in series and followed by a buffer vessel, wherein the first reactor and the second reactor are used for carrying out the anionic solution polymerization reaction described in the step (1), the third reactor is used for carrying out the coupling reaction of the step (2), and the buffer vessel is used for carrying out the termination treatment of the step (3). Thus, the reaction materials continuously enter the first reaction vessel, and the product materials and the unreacted materials in the first reaction vessel continuously flow into the second reaction vessel to continue the anionic solution polymerization reaction; then continuously introducing the product of the anionic solution polymerization reaction from the second reactor into a third reactor and continuously introducing a coupling agent and the like; the product of the coupling reaction in the third reactor is also continuously introduced into a buffer vessel for termination.
In the present invention, the butadiene monomer forming the low-cis polybutadiene rubber mainly refers to 1, 3-butadiene unless otherwise specified. Wherein the polymerized form of 1, 3-butadiene generally comprises a 1, 2-polymerized form, thereby forming said1, 2-polymeric structural unit (- [ CH)2-CH2(CH＝CH2)]-) also includes a 1, 4-polymerized form, thereby forming a 1, 4-polymerized structural unit (- [ CH)2-CH＝CH-CH2]-). Among them, the above-mentioned production method of the present invention is preferable to make the content of 1, 2-polymerization structural unit in the resulting low cis-polybutadiene rubber 6 to 20% by weight, so that the grafting reaction of the continuous bulk HIPS resin can be ensured. When the content of the 1, 2-polymeric structural unit is less than 6% by weight, the progress of the subsequent grafting reaction in the preparation of the post HIPS resin will be unfavourable; when the content of the 1, 2-polymerized structural unit is more than 20% by weight, crosslinking points are easily formed, which is disadvantageous in improvement of impact resistance. Preferably, the low cis-polybutadiene rubber has a 1, 2-polymerized structural unit content of 8 to 16 wt%, more preferably 9 to 13 wt%. In the case where the above-mentioned content range of the 1, 2-polymeric constitutional unit is satisfied, the content of the 1, 4-polymeric constitutional unit is preferably 80 to 94% by weight, more preferably 84 to 92% by weight, and still more preferably 87 to 91% by weight.
According to the present invention, the low-cis polybutadiene rubber has a relatively high number average molecular weight, a molecular weight distribution coefficient in a certain range, and a molecular weight distribution in a single peak, so as to be set in a suitable range for the purpose of controlling the Mooney viscosity and the particle size; wherein, when the number average molecular weight of the low-cis polybutadiene rubber is not within 70,000-130,000, the Mooney viscosity and the rubber particle diameter of the obtained low-cis polybutadiene rubber are not within the control range, and the processability thereof is deteriorated and the toughening effect is deteriorated; preferably, the number average molecular weight of the low-cis polybutadiene rubber is 72,000-125,000, preferably 85,000-115,000, more preferably 90,000-110,000.
The low cis-polybutadiene rubber prepared by the method has a molecular weight distribution coefficient in a certain range, so that the impact resistance and the glossiness of the continuous body HIPS resin are improved. Among them, the low cis-polybutadiene rubber obtained by the method of the present invention preferably has a molecular weight distribution coefficient of 1.7 to 2.1, more preferably 1.9 to 2.1.
According to the invention, the low-cis polybutadiene obtained by the above-mentioned process of the inventionMooney viscosity ML of rubber at 100 ℃1+4Preferably 40 to 80, preferably 50 to 70, more preferably 55 to 70. The low cis-polybutadiene rubber with the Mooney viscosity range can ensure better processing performance.
According to the present invention, the low cis-polybutadiene rubber obtained by the above-mentioned process of the present invention has a viscosity of a 5 wt% styrene solution at 25 ℃ of preferably 70cp or less, preferably 65cp or less, more preferably 25 to 60cp, still more preferably 40 to 60 cp. Controlling the viscosity of a 5 wt.% styrene solution of low cis polybutadiene rubber at 25 ℃ in the above range and preferred ranges allows the resulting HIPS resin to achieve higher gloss and processability.
According to the present invention, the low cis-polybutadiene rubber of the present invention can obtain a low gel content, and preferably, the gel content of the low cis-polybutadiene rubber is 100ppm or less, preferably 50ppm or less. The retarder adopted by the invention can effectively avoid the accumulation of active macromolecular chains in the reactor and avoid the generation of gel in the polymerization stage.
According to the invention, the low-cis polybutadiene rubber of the invention can obtain a lower color, preferably a color of less than 10APHA, preferably less than 8APHA, preferably less than 5APHA, for example 1-5APHA, in a 5% by weight styrene solution of the low-cis polybutadiene rubber.
According to the present invention, the production of the low-cis polybutadiene rubber of the present invention can be carried out at a relatively high concentration, wherein the content of 1, 3-butadiene is 20 wt% or more, preferably 20 to 60 wt%, more preferably 30 to 50 wt%, based on the total weight of the organic solvent and 1, 3-butadiene. The organic solvent may be any of various organic solvents conventionally used in the art, and preferably, the organic solvent is one or more of an alkane solvent and a cycloalkane solvent. Wherein the alkane solvent is preferably one or more of C4-C8 alkane solvents, and more preferably one or more of n-pentane, n-hexane, n-heptane and isooctane. Wherein, the naphthenic solvent is preferably one or more of C4-C8 naphthenic solvents, and more preferably one or more of cyclopentane, cyclohexane and cycloheptane.
According to the present invention, the organolithium initiator is not particularly limited, and various organolithium initiators conventionally used in the preparation of polybutadiene rubber in the art may be used, and preferably, the organolithium initiator is of the formula R1A compound represented by Li, wherein R1Alkyl selected from C1-C10; more preferably, the organolithium initiator is one or more of n-butyllithium, sec-butyllithium, iso-butyllithium, and tert-butyllithium, more preferably n-butyllithium and/or sec-butyllithium, and still more preferably n-butyllithium. Wherein, the organic lithium initiator is added into the polymerization system in the form of solution, the solvent of the organic lithium initiator can be one or more of hexane, cyclohexane, heptane and the like, and the concentration is preferably 0.04-0.2 mol/L.
The amount of the initiator used in the present invention can be reasonably selected according to the amount of the monomer and the molecular weight of the low cis-polybutadiene rubber to be obtained, and the amount can vary within a wide range, and preferably, the molar ratio of 1, 3-butadiene to the organolithium initiator is 700-: 1, preferably 750-: 1, more preferably 800-: 1, more preferably 900-: 1.
according to the present invention, the anionic solution polymerization reaction of the present invention further incorporates a retarder selected from one or more metal alkyl compounds, which forms an intermediate capable of frequently switching between an active species and a dormant species by complexing with PBLi when one or more selected from the metal alkyl compounds (for example, one or more selected from the group consisting of an organoaluminum compound, an organomagnesium compound and an organozinc compound, particularly, one or more selected from the group consisting of an organoaluminum compound and an organomagnesium compound) is introduced as a retarder into the reaction system, thereby reducing the concentration of the active species and thus allowing the polymerization reaction to proceed more smoothly. Preferably, the retarder is selected from one or more of an organoaluminum compound, an organomagnesium compound, and an organozinc compound.
Preferably, the organoaluminum compound is of the formula (R)2)3A compound represented by Al, wherein eachR is2Each independently selected from C1-C8 alkyl; more preferably, the organoaluminum compound is one or more of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum and triisobutylaluminum, and still more preferably triethylaluminum and/or triisobutylaluminum.
Preferably, the organomagnesium compound is of formula (R)3)2A compound represented by Mg, wherein each R3Each independently selected from C1-C8 alkyl; more preferably, the organomagnesium compound is one or more of di-n-butylmagnesium, di-sec-butylmagnesium, di-isobutylmagnesium, di-tert-butylmagnesium, and n-sec-butylmagnesium, and still more preferably di-n-butylmagnesium and/or n-sec-butylmagnesium.
Preferably, the organozinc compound is of formula (R)4)2Zn, wherein each R is4Each independently selected from C1-C8 alkyl; more preferably, the organozinc compound is one or more of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-sec-butyl zinc, diisobutyl zinc and di-tert-butyl zinc, and still more preferably diethyl zinc and/or di-n-butyl zinc.
Wherein, the polymerization rate and the polymerization heat can be adjusted by controlling the proportion of the retarder and the organolithium initiator, thereby realizing the controllable adjustment of the polymerization process. Preferably, when an organoaluminum compound is used as the retarder, the organoaluminum compound and the organolithium initiator are used in such amounts that the molar ratio of the Al element to the Li element is from 0.7 to 0.9: 1, more preferably 0.75 to 0.85: 1.
preferably, when an organomagnesium compound is used as the retarder, the organomagnesium compound and the organolithium initiator are used in amounts such that the molar ratio of Mg element and Li element is 1 to 6: 1, more preferably 2 to 4: 1.
preferably, when an organoaluminum compound and an organomagnesium compound are employed as the retarder, the organoaluminum compound, the organomagnesium compound, and the organolithium initiator are used in amounts such that the molar ratio of Al element, Mg element, and Li element is from 0.5 to 2: 1-5: 1, more preferably 0.8 to 1: 1.5-3: 1.
preferably, when an organozinc compound is used as the retarder, the organozinc compound and the organolithium initiator are used in such amounts that the molar ratio of Zn element and Li element is 1 to 6: 1, more preferably 2 to 4: 1.
according to the present invention, the anionic solution polymerization may be performed in the presence of a structure modifier, which may be conventionally selected in the art, and preferably, the structure modifier is one or more of an ether compound structure modifier and an amine compound structure modifier.
Preferably, the ether compound structure regulator is one or more of aliphatic monoethers, aliphatic polyethers, aromatic ethers and cyclic ethers.
More preferably, the aliphatic monoether is one or more of aliphatic symmetrical monoether and aliphatic asymmetrical monoether, the aliphatic symmetrical monoether is one or more of methyl ether, ethyl ether, propyl ether and butyl ether, and the aliphatic asymmetrical monoether is methyl ethyl ether.
More preferably, the aliphatic polyether is one or more of aliphatic symmetrical polyether and aliphatic asymmetrical polyether, the aliphatic symmetrical polyether is one or more of ethylene glycol di-C1-C4 alkyl ether, diethylene glycol di-C1-C4 alkyl ether and diethylene glycol di-C1-C4 alkyl ether, preferably one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether, and the aliphatic asymmetrical polyether is ethylene glycol methyl ethyl ether and/or diethylene glycol methyl ethyl ether.
Preferably, the aromatic ether is anisole and/or diphenyl ether.
Preferably, the cyclic ether is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol C1-C4 alkyl ether and 1, 4-dioxycyclohexane, preferably one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol isopropyl ether, tetrahydrofurfuryl alcohol butyl ether and 1, 4-dioxycyclohexane.
Preferably, the amine compound structure regulator is one or more of N, N' -tetramethylethylenediamine, N-dimethyltetrahydrofurfuryl amine, triethylamine and tripropylamine.
In a preferred embodiment of the present invention, the structure modifier is one or more of tetrahydrofuran, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol isopropyl ether, tetrahydrofurfuryl alcohol butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether, more preferably one or more of tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether and tetrahydrofurfuryl alcohol propyl ether, and particularly preferably tetrahydrofurfuryl alcohol ethyl ether.
Wherein the molar ratio of the amounts of the structure regulator and the organolithium initiator is preferably 0.01 to 2: 1, more preferably 0.01 to 1: 1, more preferably 0.01 to 0.5: 1. this allows the resulting low cis-polybutadiene rubber to maintain a certain vinyl content while increasing the reaction rate.
According to the invention, the anionic solution polymerization reaction of step (1) will result in a conversion of 1, 3-butadiene of more than 98%; preferably, the anionic solution polymerization conditions include: the temperature is 0-120 deg.C, preferably 50-120 deg.C (e.g. 70-120 deg.C), preferably 80-110 deg.C; the time (i.e. residence time) is 80-150min, preferably 90-120 min; the gauge pressure is 0.1 to 2MPa, preferably 0.2 to 0.8 MPa. It is worth mentioning that the anionic solution polymerization reaction of the invention has higher controllability, and the polymerization temperature is easy to control, so that the performance of the obtained product is easy to control.
According to the present invention, the number average molecular weight of the polymer in the obtained polymer reaction product can reach 40,000-80,000, preferably 50,000-70,000, by the anionic solution polymerization of the above step (1). Then coupled in step (2) to obtain a polybutadiene rubber with a further provided molecular weight.
According to the present invention, the coupling agent is not particularly limited as long as the low cis-polybutadiene rubber of the present invention can be obtained. Preferably, the coupling agent is one or more of silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, 1, 8-dibromooctane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, more preferably silicon tetrachloride and/or methyltrichlorosilane. The amount of the coupling agent to be used is not particularly limited as long as the low-cis polybutadiene rubber of the present invention having a unimodal distribution with a number average molecular weight in the range of 70,000-130,000, preferably 72,000-125,000, more preferably 85,000-115,000, still more preferably 90,000-110,000 and in the range of the molecular weight distribution coefficient, respectively, can be obtained. However, in order to obtain a butadiene-isoprene copolymer with a more suitable branching area for higher impact properties in HIPS, it is preferred that the molar ratio of the coupling agent to the organolithium initiator is in the range of 0.05 to 0.5: 1, preferably 0.08 to 0.3: 1, more preferably 0.09 to 0.25: 1. wherein the coupling agent is added into the polymerization system in the form of solution, the solvent of the coupling agent can be one or more of hexane, cyclohexane, heptane and the like, and the concentration is preferably 0.02-0.2 mol/L.
According to the present invention, preferably, the conditions of the coupling reaction include: the temperature is 60-120 deg.C (preferably 70-110 deg.C), the time is 30-80min (i.e. residence time, preferably 45-80min), and the gauge pressure is 0.1-2MPa (preferably 0.3-0.6 MPa).
Preferably, steps (1) and (2) are carried out in an inert atmosphere provided by a non-reactive gas selected from one or more of nitrogen, neon and argon.
According to the present invention, in the step (3), the polymerization solution of the low cis-polybutadiene rubber can be obtained by terminating the living polymer chain with a terminator, and in order to extract the low cis-polybutadiene rubber, the low cis-polybutadiene rubber can be extracted by removing the solvent or the like (for example, by vapor condensation desolvation treatment) after termination.
Preferably, the terminating agent is one or more of a C1-C4 alcohol, an organic acid, and carbon dioxide, preferably one or more of isopropanol, stearic acid, citric acid, and carbon dioxide, more preferably carbon dioxide. The carbon dioxide is adopted for termination reaction, and the carbon dioxide can form carbonate with metal ions (Li, Mg, Al, Fe and Zn) in a polymerization system, so that the color development reaction of the metal ions is avoided, and the product has lower chroma. The carbon dioxide herein may be introduced into the reaction system in the form of a gas (for example, carbon dioxide gas having a gauge pressure of 0.2 to 1MPa (for example, 0.3 to 0.6MPa) or may be introduced into the reaction system in the form of an aqueous dry ice solution (for example, having a concentration of 0.1 to 5% by weight).
The amount of the terminator to be used is not particularly limited, but is preferably 0.05 to 0.2 parts by weight per 100 parts by weight of the 1, 3-butadiene monomer.
In order to achieve the oxidation resistance of the low cis-polybutadiene rubber obtained, an antioxidant may be further introduced into the low cis-polybutadiene rubber, and preferably, after the termination in step (3), an antioxidant is introduced into the reaction system obtained by the termination, so that the polymerization solution of the low cis-polybutadiene rubber obtained may contain the antioxidant, and if it is desired to extract the low cis-polybutadiene rubber, the desolvation treatment may be performed after the introduction of the antioxidant. The antioxidant of the present invention is not particularly limited, and may be any of various antioxidants conventionally used in the art. For example, the antioxidant is one or more of 4, 6-bis (octylthiomethyl) o-cresol (trade name: antioxidant 1520), N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: antioxidant 1076), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (trade name: antioxidant 4020), N-cumyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010NA), and N-phenyl-2-naphthylamine (trade name: antioxidant D), preferably a combination of antioxidant 1520 and antioxidant 1076, more preferably a combination of antioxidant 1076 in a weight ratio of 1: 1-3 of 1520 antioxidant and 1076 antioxidant.
Preferably, the weight ratio of the antioxidant to the 1, 3-butadiene is 0.1-0.4: 100, preferably 0.2 to 0.3: 100.
in a second aspect, the present invention provides a low cis-polybutadiene rubber obtained by the above-mentioned process.
Wherein the low cis-polybutadiene rubber has the properties as described above, and the present invention is not described herein again.
In a third aspect, the present invention provides a process for preparing a HIPS resin, the process comprising: in benzene solvent, in the presence of free radical initiator, styrene and toughening agent are polymerized; wherein the toughening agent contains the low cis-polybutadiene rubber; wherein the benzene solvent is one or more of unsubstituted or C1-C4 alkyl substituted benzene.
The benzene solvent is one or more of unsubstituted or C1-C4 alkyl substituted benzene. Among them, the C1-C4 alkyl group may be, for example, one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, etc., and the C1-C4 alkyl-substituted benzene as the benzene-based solvent may be either single-or multi-substituted, and preferably, the benzene-based solvent is one or more of benzene, toluene, ethylbenzene, and xylene. The benzene solvent may be used in an amount conventionally used in the art for preparing HIPS resin, and preferably, the benzene solvent is used in an amount of 6 to 18% by weight, based on the total weight of the styrene, the benzene solvent and the toughening agent.
According to the present invention, although the toughening agent contains the low cis-polybutadiene rubber obtained by the above method of the present invention, the HIPS resin with high gloss and high impact resistance can be obtained, in order to obtain the HIPS resin with more excellent performance, the weight ratio of styrene to the toughening agent on a dry basis is preferably 550-1900: 100, preferably 600-: 100, more preferably 800-: 100, more preferably 900-: 100.
according to the present invention, the radical initiator may be various initiators conventionally used in the art for preparing HIPS resins, for example, the radical initiator may be one or more of thermal decomposition type initiators, preferably one or more selected from peroxide type initiators and azobisnitrile type compound initiators, more preferably one or more selected from t-butyl peroxy-2-ethylhexyl tert-carbonate, diacyl peroxide, peroxydicarbonate, peroxycarboxylate, alkyl peroxide and azobisnitrile type compounds, still more preferably one or more selected from dibenzoyl peroxide, di-o-toluyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile. Preferably, the weight ratio of the amount of the styrene to the amount of the radical initiator is 2500-: 1, more preferably 3000-: 1, more preferably 4000-: 1, more preferably 5000-: 1.
according to the present invention, the polymerization reaction may incorporate various additives to provide a better balance of properties to the HIPS. The additive is preferably mineral oil. Preferably, the mineral oil is used in an amount of 2 to 5 parts by weight, relative to 100 parts by weight of styrene.
According to the present invention, preferably, the polymerization conditions include: the polymerization conditions include: the temperature is 100 ℃ and 150 ℃, and the time is 7-9 h. The polymerization reaction may be carried out with stirring, for example, with stirring at 100-400 rpm.
In another preferred embodiment of the present invention, according to the present invention, the polymerization conditions comprise: first reacting at 100-110 ℃ for 1-3h, then reacting at 115-125 ℃ for 1-3h (e.g. 1-2h), then reacting at 130-140 ℃ for 1-3h (e.g. 1-2h), and finally reacting at 145-155 ℃ for 1-3h (e.g. 1-2.5 h). More preferably, the polymerization conditions include: firstly reacting at 110 ℃ for 1.5-2.5h, then reacting at 125 ℃ for 1.5-2.5h, then reacting at 135 ℃ for 1.5-2.5h, and finally reacting at 155 ℃ for 1.5-2.5 h. The polymerization reaction may be carried out with stirring, for example, with stirring at 100-400 rpm.
In a fourth aspect, the invention provides a HIPS resin made by the above process.
Preferably, the HIPS resin of the present invention has a styrene content of from 85 to 95% by weight, preferably from 88 to 94% by weight (it being understood that the remaining content is mainly structural units provided for butadiene, i.e. the content of said butadiene structural units is from 5 to 15% by weight, preferably from 6 to 12% by weight); the weight average molecular weight of the HIPS resin is 150,000-400,000g/mol, more preferably 200,000-300,000 g/mol; the molecular weight distribution coefficient is 2-2.5.
HIPS prepared by the method of the inventionThe resin has high impact resistance and high glossiness. Preferably, the HIPS resin has an Izod impact strength of 10kJ/m2Above, preferably 12kJ/m2Above, preferably 13 to 15.5kJ/m2(ii) a The 60 ℃ surface gloss is 70 or more, preferably 75 or more, for example, 75 to 81.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the monomer conversion was determined gravimetrically, i.e.the weight of polymer after removal of solvent as a percentage of the theoretical polymer production.
Mooney viscosity was measured by means of a Mooney viscometer without a rotor, model SMV-201SK-160, manufactured by Shimadzu corporation, in which the preheating time was 1min, the rotation time was 4min, and the measurement temperature was 100 ℃.
The content of 1, 2-polymerized structural units in the low-cis polybutadiene rubber is measured by an AVANCEDRX400MHz type nuclear magnetic resonance apparatus produced by BRUKER, wherein the frequency is 400MHz, the solvent is deuterated chloroform, and the built-in standard is tetramethylsilane.
The molecular weight and the molecular weight distribution were measured by using a gel permeation chromatograph model HLC-8320 from Tosoh corporation, Japan, wherein the test conditions included: the chromatographic column was TSKgel SuperMultiporeHZ-N, the standard column was TSKgel SuperMultiporeHZ, the solvent was chromatographically pure THF, the calibration standard was polystyrene, the sample mass concentration was 1mg/ml, the sample amount was 10.00. mu.l, the flow rate was 0.35ml/min, and the test temperature was 40.0 ℃.
The viscosity of a 5% by weight rubber solution at 25 ℃ was measured at a constant temperature of 25 ℃ using a capillary viscometer.
HIPS mechanical properties were tested using an INSTRON 5567 Universal Material testing machine, UK. Wherein the notched Izod impact Strength is measured in accordance with GB/T1843-1996 (kj/m)2) (ii) a The 60 ℃ gloss was measured according to ASTM D526(60 ℃).
Experimental device and process: the experiment was carried out in three polymerization reactors connected in series (the residence time in each reactor being substantially equal), operating at full load with a feed pattern of bottom in top out. Solvent, monomer, initiator, structure regulator and retarder are added from the bottom of the first reactor, and after the materials stay in the first reactor for a period of time, the materials overflow from the top of the first reactor to the bottom of the second reactor. Adding the coupling agent from the bottom of the third reactor, removing the coupling agent from the top, then carrying out termination reaction in a buffer container, and finally adding the antioxidant to obtain the polymer glue solution.
The pressure of carbon dioxide is hereinafter referred to as gauge pressure.
Antioxidant 1520 was purchased from national pharmaceutical agents; antioxidant 1076 was purchased from enokay reagent.
Tetrahydrofurfuryl alcohol ether is available from carbofuran reagent.
Silicon tetrachloride, analytically pure, supplied by enokay reagent company, diluted to 0.04mol/L with hexane.
Methyltrichlorosilane, analytically pure, supplied by enoka reagent company, diluted to 0.06mol/L with hexane.
N-butyllithium and sec-butyllithium were supplied from carbofuran reagent company, and each was diluted with hexane to a 0.07mol/L hexane solution,
triisobutylaluminum and triethylaluminum were supplied from carbofuran reagent company, and were each diluted with hexane to a 0.05mol/L hexane solution.
Dibutylmagnesium, supplied by carbofuran reagents, was diluted to 0.2mol/L in hexane.
Example 1
This example illustrates the low cis polybutadiene rubber of the present invention and its preparation.
(1) Continuously adding an organic solvent, a 1, 3-butadiene monomer, an organic lithium initiator, a retarder and a structure regulator into a first reactor under the protection of nitrogen; and carrying out an anionic solution polymerization reaction at a specified temperature and reaction pressure (the conditions are shown in Table 1, the flow rates listed in the table are all measured as pure compounds), and overflowing into a second reactor to continue the reaction, so as to obtain the monomer conversion rate shown in Table 2;
(2) introducing the product of the anionic solution polymerization into a third reactor, and adding a coupling agent (the type and the amount of the coupling agent are shown in Table 2, and the flow rates listed in the table are all measured as pure compounds) from the bottom of the third reactor to perform the coupling reaction at the specified temperature and pressure (the conditions are shown in Table 2);
(3) introducing a product of the coupling reaction into a buffer container, terminating by using a terminating agent (the type and the amount of which are shown in table 2), adding an antioxidant (the type and the amount of which are shown in table 2), mixing to finally obtain a low cis-polybutadiene rubber polymerization solution, wherein the content of the low cis-polybutadiene rubber is 30 wt%, and performing steam coagulation desolventizing treatment on the obtained polymerization solution to obtain the low cis-polybutadiene rubber PB 1. The resulting polymer was subjected to structural and property measurements, and the results are shown in Table 3.
Examples 2 to 6
This example illustrates the low cis polybutadiene rubber of the present invention and its preparation.
According to the method described in example 1, except that the reactions were carried out using the parameters shown in tables 1 and 2, to obtain low cis-polybutadiene rubbers PB2-PB6, respectively, wherein the low cis-polybutadiene rubber content in the respective low cis-polybutadiene rubber solutions was: PB 2: 40 wt%; PB 3: 40 wt%; PB 4: 30% by weight; PB 5: 30% by weight; PB 6: 30% by weight. The resulting polymer was subjected to structural and property measurements, and the results are shown in Table 3.
Example 7
This example illustrates the low cis polybutadiene rubber of the present invention and its preparation.
According to the process described in example 1, except that isopropanol was used in place of the aqueous carbon dioxide solution as the terminator in the step (3) and the amount of isopropanol was 0.32g per 100g of 1, 3-butadiene, low-cis polybutadiene rubber PB7 was obtained, wherein the low-cis polybutadiene rubber content in the polymerization solution of the low-cis polybutadiene rubber was 30% by weight. The resulting polymer was subjected to structural and property measurements, and the results are shown in Table 3.
Comparative example 1
The process of example 1 except that no silicon tetrachloride was used in step (2) so that the product of the anionic solution polymerization was continuously introduced into the third reactor for anionic solution polymerization (i.e., the polymerization was continued under the coupling conditions of example 1), wherein the monomer conversion prior to coupling was 99.6%; thus, low cis-polybutadiene rubber DPB1 was obtained, in which the content of low cis-polybutadiene rubber in the polymerization solution of low cis-polybutadiene rubber was 30% by weight. The resulting polymer was subjected to structural and property measurements, and the results are shown in Table 3.
Comparative example 2
The process of example 1 was followed except that in step (1), the anionic solution polymerization was carried out without the addition of triisobutylaluminum as a retarder, but butadiene was imploded during the polymerization, the polymerization temperature was not controlled, and the maximum temperature reached 323 ℃; wherein the monomer conversion rate before coupling is 100%; thereby obtaining low cis-polybutadiene rubber DPB2 in which a large amount of gel appeared in the polymerization solution, wherein the content of the low cis-polybutadiene rubber in the polymerization solution of the low cis-polybutadiene rubber was 30% by weight. The resulting polymer was subjected to structural and property measurements, and the results are shown in Table 3.
Comparative example 3
The process of example 1 was followed except that the flow rate of n-butyllithium was 1.06g/h and the amount of triisobutylaluminum was 1.64g/h, wherein the monomer conversion before coupling was 99.2%; thus, low cis-polybutadiene rubber DPB3 was obtained, in which the content of low cis-polybutadiene rubber in the polymerization solution of low cis-polybutadiene rubber was 30% by weight. The resulting polymer was subjected to structural and property measurements, and the results are shown in Table 3.
Comparative example 4
The process of example 1, except that the residence time for the anionic solution polymerization reaction was 40min and the residence time for the coupling reaction was 20min, where the monomer conversion before coupling was 63.8%; thus, low-cis polybutadiene rubber DPB4 was obtained, in which the content of low-cis polybutadiene rubber in the polymerization solution of low-cis polybutadiene rubber was 19.2% by weight. The resulting polymer was subjected to structural and property measurements, and the results are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3
As can be seen from Table 3, the preparation method provided by the invention can be used for obtaining the low cis-polybutadiene rubber with high Mooney viscosity and low styrene solution viscosity of 5%, and is extremely low in gel content and low in chroma, so that the preparation method is particularly suitable for modifying continuous bulk HIPS.
Example 9
This example illustrates the HIPS resin of the present invention and the method of preparing the same.
Mixing 100g of low cis-polybutadiene rubber PB1, 150g of ethylbenzene and 1100g of styrene monomer, adding 45g of mineral oil (provided by Beijing Yanshan petrochemical company, chemical industry and factory, density 0.85-0.88g/ml, the same below) and 0.1g of tert-butyl peroxy-2-ethylhexyl carbonate, mixing, polymerizing for 2h at a stirring speed of 300rpm and a polymerization temperature of 105 ℃, and then heating to 120 ℃ for polymerizing for 2 h; heating to 135 ℃ at the stirring speed of 100rpm, polymerizing for 2h, finally heating to 150 ℃, polymerizing for 2h, and carrying out vacuum flash evaporation on the reaction product to remove unreacted monomers and solvent to obtain the HIPS resin P1.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
Example 10
This example illustrates the HIPS resin of the present invention and the method of preparing the same.
Mixing 120g of low cis-polybutadiene rubber PB2, 150g of xylene and 1100g of styrene monomer, adding 50g of mineral oil and 0.2g of azobisisobutyronitrile, mixing, polymerizing for 1.5h at the stirring speed of 350rpm and the polymerization temperature of 110 ℃, and then heating to 120 ℃ for polymerizing for 2.5 h; heating to 130 ℃ under the stirring speed of 200rpm, polymerizing for 1.5h, finally heating to 155 ℃ for polymerizing for 2h, and carrying out vacuum flash evaporation on the reaction product to remove unreacted monomers and solvent to obtain the HIPS resin P2.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
Examples 11 to 16
This example illustrates the HIPS resin of the present invention and the method of preparing the same.
According to the method described in example 9, except that low cis-polybutadiene rubber PB3-PB7 is used instead of low cis-polybutadiene rubber PB1, respectively, the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvent, so as to obtain HIPS resins P3-P7, respectively.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
Comparative examples 1 to 4
According to the method described in example 9, except that the low cis-polybutadiene rubber PB1 was replaced by low cis-polybutadiene rubber DPB1-DPB4, respectively, the reaction product was subjected to vacuum flash evaporation to remove unreacted monomers and solvent to obtain HIPS resins DP1-DP4, respectively.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
Comparative examples 5 to 6
According to the method described in example 9, except that low cis polybutadiene rubber PB1 was replaced by linear products 35AE and 55AE (solvent removed) from the Japanese Asahi continuous polymerization process, respectively, the reaction product was subjected to vacuum flash evaporation to remove unreacted monomers and solvent to obtain HIPS resins DP5-DP6, respectively.
The HIPS resin was dried and subjected to structural and performance measurements, the results of which are shown in Table 4.
TABLE 4
As can be seen from Table 4, by using the low cis-polybutadiene of the present invention as a toughening agent, it is possible to obtain a HIPS resin having more excellent properties, particularly impact resistance and gloss, and the HIPS resin obtained by the present invention has a great improvement in impact resistance and gloss as compared with the HIPS resin obtained by using a commercially popular toughening agent.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (63)
1. A method for preparing a low cis-polybutadiene rubber, comprising:
(1) continuously introducing 1, 3-butadiene into a reaction vessel in an organic solvent in the presence of an organolithium initiator, a retarder, and optionally a structure modifier to effect an anionic solution polymerization reaction to a conversion of 1, 3-butadiene of 99% or greater; wherein the retarder is selected from one or more of metal alkyl compounds; the content of 1, 3-butadiene is more than 20 wt% based on the total weight of the organic solvent and the 1, 3-butadiene;
(2) continuously introducing the product of the anionic solution polymerization reaction into another reaction vessel in the presence of a coupling agent to effect a coupling reaction;
(3) terminating the product of the coupling reaction in the presence of a terminating agent;
wherein the number average molecular weight of the low cis-polybutadiene rubber obtained by the method is 70,000-130,000; the molecular weight distribution coefficient is 1.9-2.2; and the molecular weight is unimodal.
2. The process as claimed in claim 1, wherein the low-cis polybutadiene rubber obtained by the process has a number average molecular weight of 72,000-125,000.
3. The process as claimed in claim 2, wherein the low-cis polybutadiene rubber obtained by the process has a number average molecular weight of 85,000-115,000.
4. The process as claimed in claim 3, wherein the low-cis polybutadiene rubber obtained by the process has a number average molecular weight of 90,000-110,000.
5. The process of claim 3, wherein the low cis polybutadiene rubber obtained by the process has a molecular weight distribution coefficient of 1.9-2.1.
6. The process according to claim 3, wherein the Mooney viscosity ML of the low-cis polybutadiene rubber obtained by the process at 100 ℃1+4Is 40-80.
7. The process according to claim 6, wherein the Mooney viscosity ML of the low-cis polybutadiene rubber obtained by the process at 100 ℃1+4Is 50-70.
8. The process according to claim 7, wherein the Mooney viscosity ML of the low-cis polybutadiene rubber obtained by the process at 100 ℃1+4Is 55-70.
9. The process according to claim 3, wherein the low-cis polybutadiene rubber obtained by the process has a viscosity of 70cp or less in a 5 wt% styrene solution at 25 ℃.
10. The process according to claim 9, wherein the low-cis polybutadiene rubber obtained by the process has a viscosity of 65cp or less in a 5 wt% styrene solution at 25 ℃.
11. The process of claim 10 wherein the low cis polybutadiene rubber obtained by the process has a 5 wt% styrene solution viscosity at 25 ℃ of 25-60 cp.
12. The process of claim 11 wherein the low cis polybutadiene rubber obtained by the process has a 5 wt% styrene solution viscosity of 40-60cp at 25 ℃.
13. The process of any of claims 1-11, wherein the organolithium initiator is of formula R1A compound represented by Li, wherein R1Selected from C1-C10 alkyl groups.
14. The process of claim 13, wherein the organolithium initiator is one or more of n-butyllithium, sec-butyllithium, iso-butyllithium, and tert-butyllithium.
15. The process of claim 14, wherein the organolithium initiator is n-butyllithium and/or sec-butyllithium.
16. The method as claimed in claim 13, wherein the molar ratio of 1, 3-butadiene to the organolithium initiator is 700-: 1.
17. the process as claimed in claim 16, wherein the molar ratio of 1, 3-butadiene to the organolithium initiator is 750-1300: 1.
18. the process as claimed in claim 17, wherein the molar ratio of 1, 3-butadiene to the organolithium initiator is 800-: 1.
19. the process as claimed in claim 18, wherein the molar ratio of 1, 3-butadiene to the organolithium initiator is 900-: 1.
20. the method of any of claims 1-11 and 14-19, wherein the retarder is selected from one or more of an organoaluminum compound, an organomagnesium compound, and an organozinc compound.
21. The process of claim 20, wherein the organoaluminum compound is of formula (R)2)3A compound represented by Al, wherein each R is2Each independently selected from C1-C8 alkyl.
22. The process of claim 21, wherein the organoaluminum compound is one or more of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, and triisobutylaluminum.
23. The process according to claim 22, wherein the organoaluminum compound is triethylaluminum and/or triisobutylaluminum.
24. The method of claim 20, wherein the organomagnesium compound is of formula (R)3)2A compound represented by Mg, wherein each R3Each independently selected from C1-C8 alkyl.
25. The process of claim 24, wherein the organomagnesium compound is one or more of di-n-butylmagnesium, di-sec-butylmagnesium, di-isobutylmagnesium, di-tert-butylmagnesium, and n-sec-butylmagnesium.
26. The process of claim 25, wherein the organomagnesium compound is di-n-butylmagnesium and/or n-sec-butylmagnesium.
27. The method of claim 20 wherein the organozinc compound is of formula (R)4)2Zn, wherein each R is4Each independently selected from C1-C8 alkyl.
28. The method of claim 27, wherein the organozinc compound is one or more of diethylzinc, dipropylzinc, di-n-butylzinc, di-sec-butylzinc, diisobutylzinc, di-tert-butylzinc.
29. The process of claim 28, wherein the organozinc compound is diethyl zinc and/or di-n-butyl zinc.
30. The process according to claim 20, wherein, when an organoaluminum compound is employed as the retarder, the organoaluminum compound and the organolithium initiator are used in such amounts that the molar ratio of Al element to Li element is from 0.7 to 0.9: 1; when an organomagnesium compound is used as the retarder, the organomagnesium compound and the organolithium initiator are used in amounts such that the molar ratio of Mg element to Li element is 1 to 6: 1; when an organoaluminum compound and an organomagnesium compound are used as the retarder, the organoaluminum compound, the organomagnesium compound, and the organolithium initiator are used in amounts such that the molar ratio of the Al element, the Mg element, and the Li element is from 0.5 to 2: 1-5: 1; when an organozinc compound is used as the retarder, the organozinc compound and the organolithium initiator are used in such amounts that the molar ratio of Zn element to Li element is 1 to 6: 1.
31. the process according to claim 30, wherein, when an organoaluminum compound is employed as the retarder, the organoaluminum compound and the organolithium initiator are used in such amounts that the molar ratio of Al element to Li element is from 0.75 to 0.85: 1; when an organomagnesium compound is used as the retarder, the organomagnesium compound and the organolithium initiator are used in amounts such that the molar ratio of Mg element to Li element is 2 to 4: 1; when an organoaluminum compound and an organomagnesium compound are used as the retarder, the organoaluminum compound, the organomagnesium compound, and the organolithium initiator are used in amounts such that the molar ratio of the Al element, the Mg element, and the Li element is from 0.8 to 1: 1.5-3: 1; when an organozinc compound is used as the retarder, the organozinc compound and the organolithium initiator are used in such amounts that the molar ratio of Zn element to Li element is 2 to 4: 1.
32. the method of claim 20, wherein the anionic solution polymerization conditions comprise: the temperature is 0-120 ℃; the time is 80-150 min; gauge pressure is 0.1-2 MPa.
33. The method of claim 32, wherein the anionic solution polymerization conditions comprise: the temperature is 50-120 ℃; the time is 90-120 min; gauge pressure is 0.2-0.8 MPa.
34. The process of claim 33, wherein the anionic solution polymerization temperature is 80-110 ℃.
35. The method of any one of claims 1-11, 14-19, and 21-34, wherein the coupling agent is one or more of silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, 1, 8-dibromooctane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
36. The method of claim 35, wherein the coupling agent is silicon tetrachloride and/or methyltrichlorosilane.
37. The process of claim 35, wherein the molar ratio of coupling agent to organolithium initiator is from 0.05 to 0.5: 1.
38. the process of claim 37, wherein the molar ratio of coupling agent to organolithium initiator is from 0.08 to 0.3: 1.
39. the process of claim 38, wherein the molar ratio of coupling agent to organolithium initiator is from 0.09 to 0.25: 1.
40. the method of claim 35, wherein the conditions of the coupling reaction comprise: the temperature is 60-120 deg.C, the time is 30-80min, and the gauge pressure is 0.1-2 MPa.
41. The method of any one of claims 1-11, 14-19, 21-34, and 36-40, wherein the terminating agent is one or more of a C1-C4 alcohol, an organic acid, and carbon dioxide.
42. The method of claim 41, wherein the terminating agent is one or more of isopropanol, stearic acid, citric acid, and carbon dioxide.
43. The method of claim 42, wherein the terminating agent is carbon dioxide.
44. A low cis polybutadiene rubber obtained by the process of any one of claims 1-43.
45. A method of preparing a HIPS resin, the method comprising: in benzene solvent, in the presence of free radical initiator, styrene and toughening agent are polymerized; wherein the toughening agent comprises the low cis polybutadiene rubber of claim 44; wherein the benzene solvent is one or more of unsubstituted or C1-C4 alkyl substituted benzene.
46. The method of claim 45, wherein the benzene-based solvent is used in an amount of 6 to 18 wt%, based on the total weight of the styrene, the benzene-based solvent, and the toughening agent.
47. The preparation method as claimed in claim 46, wherein the weight ratio of styrene to the toughening agent on a dry basis is 550-1900: 100.
48. the method as claimed in claim 47, wherein the weight ratio of styrene to the toughening agent is 600-1600: 100.
49. the method as claimed in claim 48, wherein the weight ratio of styrene to the toughening agent is 800-1400: 100.
50. the method as claimed in claim 49, wherein the weight ratio of styrene to the toughening agent on a dry basis is 900-1300: 100.
51. the production method according to any one of claims 45 to 50, wherein the radical initiator is one or more of diacyl peroxide, peroxydicarbonate, peroxycarboxylate, alkyl peroxide, and azobisnitrile compounds.
52. The method of claim 51, wherein the free radical initiator is one or more of t-butyl peroxy-2-ethylhexyl tert-carbonate, dibenzoyl peroxide, di-o-methylbenzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile.
53. The method of claim 52, wherein the free radical initiator is one or more of t-butyl peroxy-2-ethylhexyl tert-carbonate, dibenzoyl peroxide, di-o-methylbenzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile.
54. The preparation method as claimed in claim 51, wherein the weight ratio of the styrene to the free radical initiator is 2500-12000: 1.
55. the preparation method as claimed in claim 54, wherein the weight ratio of the styrene to the radical initiator is 3000-9500: 1.
56. the preparation method as claimed in claim 55, wherein the weight ratio of the styrene to the free radical initiator is 4000-9000: 1.
57. the preparation method as claimed in claim 56, wherein the weight ratio of the amount of styrene to the amount of the radical initiator is 5000-8500: 1.
58. the production method according to any one of claims 45 to 50 and 52 to 57, wherein the polymerization conditions include: the temperature is 100-150 ℃, and the time is 7-9 h;
alternatively, the polymerization conditions include: firstly reacting at 110 ℃ for 1-3h, then reacting at 125 ℃ for 1-3h, then reacting at 140 ℃ for 1-3h, and finally reacting at 155 ℃ for 1-3 h.
59. The method of claim 58, wherein the polymerization conditions comprise: firstly reacting at 110 ℃ for 1.5-2.5h, then reacting at 125 ℃ for 1.5-2.5h, then reacting at 135 ℃ for 1.5-2.5h, and finally reacting at 155 ℃ for 1.5-2.5 h.
60. HIPS resin produced by the method of any one of claims 45 to 59.
61. The HIPS resin of claim 60, wherein the content of structural units of styrene in the HIPS resin is 85 to 95% by weight; the weight average molecular weight of the HIPS resin was 150,000-400,000 g/mol.
62. The HIPS resin of claim 61, wherein the HIPS resin has a styrene structural unit content of 88 to 94% by weight; the weight average molecular weight of the HIPS resin was 200,000-300,000 g/mol.
63. The HIPS resin of claim 61, wherein the HIPS resin has a surface gloss of 70 or more at 60 °.
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