DE102017219342B4 - Linear butadiene-styrene copolymer, manufacturing method and composition thereof, and aromatic vinyl resin and manufacturing method thereof - Google Patents

Abstract

Linear butadiene-styrene copolymer, the molecular weight of the linear butadiene-styrene copolymer being a number average molecular weight of 70,000 to 160,000 and a molecular weight distribution index of 1.55 to 2 in a unimodal distribution, based on the total amount of the linear butadiene -Styrene copolymer, a styrene structural unit content is 10 to 45% by weight and a butadiene-styrene unit content is 55 to 90% by weight and a 1,2-structural unit content is 8 to 14% by weight.

Description

Field of invention

This invention relates to a linear butadiene-styrene copolymer and its method of preparation; this invention further relates to a composition containing the linear butadiene-styrene copolymer, this invention further relates to an aromatic vinyl resin using the composition as a toughening agent and a production method therefor.

Background of the invention

The traditional aromatic vinyl resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin) and high impact polystyrene (HIPS resin) is obtained from thermal initiation or initiation with radical initiators by adding the dried rubber toughening agent in a certain proportion to polymeric monomers , for the production of aromatic vinyl resin, also a small amount of ethylbenzene as a solvent. The rubber toughening agent used for aromatic vinyl resin may be polybutadiene rubber, solution polymerized butadiene-styrene rubber (SSBR), or styrene-butadiene-styrene copolymer.

Low cis polybutadiene rubber and linear butadiene-styrene copolymer are the best toughness agents for the aromatic vinyl resin which requires high low-temperature toughness and high gloss. Compared with other tough rubber, polybutadiene rubber with low cis content and linear butadiene-styrene copolymer have the following advantages: (1) high crosslinking reactivity and easy grafting with aromatic vinyl resin because their molecular chains contain vinyl side chains; (2) Transition metals excluding high purity, whereby an advantage in improving the aging resistance is obtained in the aromatic vinyl resin. However, the low-cis polybutadiene rubber and the linear butadiene-styrene copolymer are produced using the anionic polymerization and have the inherent characteristics of the active polymerization products, that is, generally narrow molecular weight distribution range and individual rubber particle size distribution (generally lower than 1.5 and in the range 1 to 1.2). This easily leads to deteriorated processability of the rubber and is also contrary to the improvement of the impact resistance of the resin.

The existing aromatic vinyl resin is generally produced by using the bulk polymerization method. The procedure is as follows: first, preparing solid particles as a toughening agent, then dissolving the toughening agent solid particles in a solvent and mixing with the polymeric monomer of aromatic vinyl resin to give a polymerization reaction to obtain the aromatic vinyl resin. However, the aromatic vinyl resin produced by this method is very difficult to meet the requirements of high gloss applications, and the causes thereof may be as follows. During extrusion pelletization of the polymer of the toughness agent using a twin screw extruder, a crosslinking reaction occurs because of the Heating and extrusion in the twin-screw extruder, which leads to an increased gel content in the solid particles produced as a toughening agent with deteriorated color, which speaks against an improvement in the gloss and impact resistance of the aromatic vinyl resin.

Content of the invention

It is an object of this invention to overcome the shortcomings of the prior art and to provide a linear butadiene-styrene copolymer. The linear butadiene-styrene copolymer has a wide range of molecular weight distribution. The aromatic vinyl resin using the low-linear butadiene-styrene copolymer as a toughening agent has apparently improved impact resistance.

According to the first aspect of this invention, this invention provides a linear butadiene-styrene copolymer having a number average molecular weight of the linear butadiene-styrene copolymer 70,000 to 160,000 and a molecular weight distribution index of 1.55 to 2 with a unimodal distribution, based on a total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit is 10 to 45% by weight, and a content of the butadiene structural unit is 55 to 90% by weight.

According to the second aspect of this invention, this invention provides a composition containing a linear butadiene-styrene copolymer and a low-cis polybutadiene rubber, wherein the linear butadiene-styrene copolymer is the linear butadiene-styrene copolymer according to the first Aspect of this invention is and the molecular weight of the low cis polybutadiene rubber has a bimodal distribution, the number average molecular weight of a low molecular weight component in the bimodal distribution is 42,000 to 90,000 with a molecular weight distribution index of 1.55 to 2, where the Number average molecular weight of a high molecular weight component in the bimodal distribution is 120,000 to 280,000 with a molecular weight distribution index of 1.55 to 2, based on a total content of the polybutadiene rubber with a low cis content, a content of the high molecular weight component 60 to 95 wt. % is.

• (1) unter einer Bedingung einer anionischen Initiierungsreaktion Durchführen einer Initiierungsreaktion mit Butadien und Styrol im Kontakt mit einem organischen Lithium-Initiator in Alkylbenzol;
• (2) Zugabe eines Blockiermittels zu einer Mischung, erhalten von der Initiierungsreaktion von Schritt (1) und Durchführen einer Polymerisationsreaktion mit der Mischung, die das Blockiermittel enthält, in einem Zustand einer anionischen Polymerisationsreaktion;
• (3) Kontaktieren einer Mischung, erhalten von der Polymerisationsreaktion, mit einem Terminierungsmittel, zur Durchführung einer Terminierungsreaktion, unter Erhalt der Polymerlösung, die lineares Butadien-Styrol-Copolymer enthält.

According to the third aspect of this invention, this invention provides a process for producing the linear butadiene-styrene copolymer according to the first aspect of this invention, comprising the following steps:

• (1) under a condition of an anionic initiation reaction, carrying out an initiation reaction with butadiene and styrene in contact with an organic lithium initiator in alkylbenzene;
• (2) adding a blocking agent to a mixture obtained from the initiation reaction of step (1) and performing a polymerization reaction on the mixture containing the blocking agent in a state of anionic polymerization reaction;
• (3) Contacting a mixture obtained from the polymerization reaction with a terminating agent to carry out a termination reaction to obtain the polymer solution containing linear butadiene-styrene copolymer.

According to the fourth aspect of this invention, this invention provides an aromatic vinyl resin containing a structural unit derived from an aromatic vinyl monomer and a structural unit derived from the toughening agent, wherein the toughening agent is the composition according to the second aspect of this invention.

1. (a) Durchführen einer Initiierungsreaktion mit Butadien im Kontakt mit einem organischen Lithium-Initiator in Alkylbenzol unter einer Bedingung einer anionischen Initiierungsreaktion;
2. (b) Zugabe eines Blockiermittels zu einer Mischung, erhalten von der Initiierungsreaktion von Schritt (a) und Durchführen einer Polymerisationsreaktion mit der Mischung, die das Blockiermittel enthält, in einem Zustand der anionischen Polymerisationsreaktion;
3. (c) Durchführen einer Kupplungsreaktion mit einer Mischung, erhalten von der Polymerisationsreaktion, durch Kontakt mit einem Kupplungsmittel;
4. (d) Kontaktieren einer Mischung, erhalten von der Kupplungsreaktion mit einem Terminierungsmittel, zur Durchführung einer Terminierungsreaktion, unter Erhalt einer Polymerlösung, die Polybutadien-Kautschuk mit niedrigem cis-Gehalt enthält.

According to the fifth aspect of this invention, this invention provides a method for producing an aromatic vinyl resin comprising the step of mixing polymeric monomers containing aromatic vinyl monomer with a solution containing a toughening agent to obtain a mixture and polymerizing the mixture ,
wherein the solution containing the toughening agent contains a solution of linear butadiene-styrene copolymer and a solution of polybutadiene rubber of low cis content,
wherein the linear butadiene-styrene copolymer solution is the polymer solution containing the linear butadiene-styrene copolymer obtained by the method according to the third aspect of this invention; and
the solution containing the low-cis polybutadiene rubber is a polymer solution with low-cis polybutadiene rubber prepared by a process including the steps of:

1. (a) performing an initiation reaction with butadiene in contact with an organic lithium initiator in alkylbenzene under a condition of an anionic initiation reaction;
2. (b) adding a blocking agent to a mixture obtained from the initiation reaction of step (a) and performing a polymerization reaction on the mixture containing the blocking agent in a state of anionic polymerization reaction;
3. (c) performing a coupling reaction on a mixture obtained from the polymerization reaction by contact with a coupling agent;
4. (d) contacting a mixture obtained from the coupling reaction with a terminating agent to carry out a termination reaction to obtain a polymer solution containing low-cis polybutadiene rubber.

The linear butadiene-styrene copolymer of this invention has a wide range of molecular weight distribution, which can effectively increase the impact resistance of the aromatic vinyl resin when it is used as a toughness agent. In contrast to the existing bulk polymerization process for producing an aromatic vinyl resin in which both polybutadiene rubber with a low cis content and linear butadiene-styrene copolymer are dry granulated and then redissolved, the process of this invention for producing an aromatic vinyl resin both the polymer solution of low-cis polybutadiene rubber and the polymer solution of linear butadiene-styrene copolymer mixed with the aromatic vinyl matrix monomers to conduct bulk polymerization to obtain the aromatic vinyl resin. The method of this invention simplifies the process operation, shortens the process flow, and is advantageous in reducing the overall Process energy consumption. It is more desirable that the aromatic vinyl resin produced by the process of the present invention exhibit markedly improved gloss and impact resistance.

Detailed description of the exemplary embodiments

Some embodiments of this invention are described in detail below. It is to be understood that the exemplary embodiments described herein are provided only to describe and explain this invention, but are not intended to represent a limitation of this invention.

The endpoints and any value within the ranges disclosed in this invention are not intended to limit the exact ranges or values; these ranges or values are intended to include those that are close to those ranges or values. For numerical ranges, the endpoints of the ranges, the endpoints of the ranges, and the concrete point values and the concrete point values can be combined to obtain one or more new numerical ranges that are believed to be disclosed in this document.

In accordance with the first aspect of this invention, this invention provides a linear butadiene-styrene copolymer.

According to the invention, the molecular weight of the linear butadiene-styrene copolymer in unimodal distribution, the number average molecular weight (i.e. Mn) of the linear butadiene-styrene copolymer is 70,000 to 160,000 with a molecular weight distribution index (i.e. Mw / Mn, where Mw is the Weight average molecular weight means from 1.55 to 2 (preferably 1.6 to 2, more preferably 1.8 to 2).

In this invention, the molecular weight and molecular weight distribution index of the low-cis polybutadiene rubber and the linear butadiene-styrene copolymer are measured by gel permeation chromatographic analysis using TOSH HLC-8320 gel permeation chromatograph using TSKgel SuperMultiporeHZ -N and TSKgel SuperMultiporeHZ standard columns and the solvent is chromatographically pure tetrahydrofuran (THF) using a narrowly distributed polystyrene as the standard sample, the polymer sample is prepared to a THF solution at 1 mg / ml, the injection amount of the sample Is 10.00 µl, the flow rate is 0.3 ml / min and the test temperature is 40.0 ° C.

According to the linear butadiene-styrene copolymer of this invention, based on a total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit can be 10 to 45% by weight, preferably 15 to 43% by weight, a content of the butadiene Structural unit can be 55 to 90% by weight, preferably 57 to 85% by weight.

According to the invention, the term “styrene structural unit” relates to the structural unit formed by polymerizing styrene monomers, and the term “butadiene structural unit” relates to the structural unit formed by polymerizing butadiene monomers. In this invention, the content of the styrene structural unit and the butadiene structural unit is determined by ¹ H-NMR analysis; during the test the solvent used is deuterated chloroform and tetramethylsilane is used as an internal standard substance.

According to the linear butadiene-styrene copolymer of this invention, based on the total amount of the linear butadiene-styrene copolymer, the content of the 1,2-structural unit may be 8 to 14% by weight, preferably 10 to 13.5% by weight.

In the linear butadiene-styrene copolymer of this invention, the Mooney viscosity of the linear butadiene-styrene copolymer can be 50 to 150, preferably 50 to 140, and more preferably 50 to 135.

According to the present invention, Mooney viscosity is determined using SHIMADZU SMV-201 SK-160 Mooney viscometer according to the method specified in Chinese National Standards GB / T1232-92, the test method including: ML (1 + 4) and a Test temperature of 100 ° C.

According to the linear butadiene-styrene copolymer of this invention, a gel content of the linear butadiene-styrene copolymer is below 20 ppm, preferably not more than 15 ppm, and more preferably not more than 10 ppm, as measured by weight.

According to the invention, the gel content is determined using the weight method. The specific procedure is as follows: adding a polymer sample to styrene and performing oscillation in an oscillator at 25 ° C for 16 hours to completely dissolve soluble substances, to obtain a styrene solution with 5% by weight of polymer content (the Mass of the rubber sample is denoted by C (in grams); Weigh a 360 mesh pure nickel screen and label this mass as B (in grams); then filtering the above solution with the nickel screen and washing the nickel screen with styrene after filtering; Drying the nickel screen at 150 ° C. and normal pressure for 30 minutes and then weighing the nickel screen and designating its mass as A (in grams); where the gel content is calculated from the following formula: $$\text{gel}-\text{Salary\%}=\left[\left(\text{A.}-\text{B.}\right)\text{/ C}\right]\times 100\%.$$

According to the linear butadiene-styrene copolymer of this invention, in a preferred embodiment, the number average molecular weight of the linear butadiene-styrene copolymer is 70,000 to 150,000, preferably 75,000 to 140,000, a molecular weight distribution index of the linear butadiene-styrene copolymer is 1 .6 to 2 and preferably 1.8 to 1.95; Based on the total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit can be 12 to 40% by weight, preferably 15 to 35% by weight; a content of the butadiene structural unit can be 60 to 88% by weight, preferably 65 to 85% by weight. In the preferred embodiment, a Mooney viscosity of the linear butadiene-styrene copolymer is 50 to 145, preferably 50 to 135. The linear butadiene-styrene copolymer in this embodiment is particularly suitable as a toughness agent of the ABS resin.

According to the linear butadiene-styrene copolymer of this invention, in another preferred embodiment, the number average molecular weight of the linear butadiene-styrene copolymer is 90,000 to 160,000, preferably 10,000 to 160,000; a molecular weight distribution index of the butadiene-styrene linear copolymer is 1.6 to 2, and preferably 1.8 to 2; Based on a total amount of the linear butadiene-styrene copolymer, a content of the styrene structural unit can be 12 to 45% by weight, preferably 15 to 42% by weight; a content of the butadiene structural unit can be 55 to 88% by weight, preferably 58 to 85% by weight. In the preferred embodiment, the Mooney viscosity of the linear butadiene-styrene copolymer is 80 to 140, preferably 90 to 130 and more preferably 100 to 135. The linear butadiene-styrene copolymer according to this embodiment is particularly suitable as a toughening agent for high impact polystyrene.

According to the second aspect of this invention, this invention provides a composition containing a linear butadiene-styrene copolymer and a low-cis polybutadiene rubber, wherein the linear butadiene-styrene copolymer is the linear butadiene-styrene copolymer according to the first Aspect of this invention is.

According to the composition of this invention, the molecular weight of the low cis polybutadiene rubber in the bimodal distribution, the number average molecular weight of the low molecular weight component in the bimodal distribution is 42,000 to 90,000 with a molecular weight distribution index of 1.55 to 2 (preferably 1 , 7 to 2); the number average molecular weight of the high molecular weight component in the bimodal distribution is 120,000 to 280,000 with a molecular weight distribution index of 1.55 to 2 (preferably 1.7 to 2) based on a total amount of the low cis polybutadiene rubber is a Content of the high molecular weight component 65 to 95% by weight.

With respect to the low-cis polybutadiene rubber, the low molecular component in the bimodal distribution is a linear polymer (i.e., uncoupled polymer) and the high molecular component in the bimodal distribution is a coupled polymer (i.e., a star-branched polymer). The coupled polymer includes coupling centers and the linear chains attached to the coupling centers, wherein the linear chains are derived from linear polymers. According to the present invention, the low-cis polybutadiene rubber can be obtained by coupling the linear polymers with coupling agents, and the obtained products contain uncoupled polymers (i.e., low molecular weight component) and coupled polymers (i.e., high molecular weight component).

With respect to the low cis polybutadiene rubber, the molecular weight distribution index of the low cis polybutadiene rubber is 1.9 to 2.5.

In the present invention, the molecular weight distribution index of the polybutadiene rubber having a low cis content is the entire molecular weight distribution index of rubber, that is, the Molecular weight distribution index is determined using the double peaks as a yardstick. The molecular weight distribution index of the high molecular component in the bimodal distribution refers to the molecular weight distribution index calculated by using the elution peak of the high molecular component as a yardstick; the molecular weight distribution index of the low molecular weight component in the bimodal distribution refers to the molecular weight distribution index calculated by using the elution peak of the low molecular weight component as a yardstick. The content of the high molecular weight component refers to the percentage of the elution peak area of the high molecular weight component to the total area of the double peaks.

With respect to the low cis polybutadiene rubber, with respect to the total amount of the low cis polybutadiene rubber, the content of the 1,2 structural unit in the low cis polybutadiene rubber can be 8 to 14 wt. % be; Based on the total amount of the low-cis polybutadiene rubber, the content of the cis-1,4 structural unit in the low-cis polybutadiene rubber is 30 to 40% by weight.

According to the invention, the expression “1,2-structural unit” relates to the structural unit formed in the 1,2-polymerization of butadiene, and the 1,2-structural unit content can also be known as the vinyl content. The term “cis-1,4 structural unit” relates to the structural unit that is formed during the 1,4-polymerization of butadiene and has a cis configuration, i.e. the structural unit with the formula I:

According to the invention, the content of the 1,2-structural unit and the cis-1,4-structural unit is determined by using ¹³ C-NMR; during the test the solvent is deuterated chloroform and tetramethylsilane is used as an internal standard substance.

In this invention, the Mooney viscosity of the low cis polybutadiene rubber of this invention is 30 to 70, preferably 40 to 70, and more preferably 45 to 70.

According to the invention, a gel content of the polybutadiene rubber with a low cis content is below 20 ppm, preferably not more than 15 ppm and more preferably not more than 10 ppm, measured as weight.

According to the invention, in a preferred embodiment, the number average molecular weight of the low molecular weight component in the bimodal distribution is 45,000 to 75,000 with a molecular weight distribution index of 1.7 to 2, the number average molecular weight of the high molecular weight component in the bimodal distribution is 140,000 to 190,000 with a molecular weight distribution index of 1.7 to 2. Based on the total amount of the polybutadiene rubber having a low cis content, the content of the high molecular weight component is 70 to 95% by weight. According to the preferred embodiment, the Mooney viscosity of the low-cis polybutadiene rubber is 40 to 65, preferably 45 to 60. The low-cis polybutadiene rubber according to this preferred embodiment is particularly suitable as the toughness agent of acrylonitrile-butadiene-styrene -Copolymers (i.e. ABS resin).

According to the invention, in another preferred embodiment, the number average molecular weight of the low molecular weight component in the bimodal distribution is 50,000 to 90,000 with a molecular weight distribution index of 1.7 to 2, the number average molecular weight of the high molecular weight component in the bimodal distribution is 150,000 to 270,000 , preferably 160,000 to 260,000 with a molecular weight distribution index of 1.7 to 2 (preferably 1.8 to 2). Based on a total amount of the polybutadiene rubber with a low cis content, the content of the high molecular weight component is 60 to 95% by weight, preferably 65 to 95% by weight. According to this preferred embodiment, the Mooney viscosity of the low cis polybutadiene rubber is 45 to 70, preferably 50 to 70. The low cis polybutadiene rubber according to this preferred embodiment is particularly useful as the toughness agent of the high impact polystyrene (the is called HIPS resin).

According to the composition of this invention, the weight ratio of the low cis polybutadiene rubber to the linear butadiene-styrene copolymer can be 0.3 to 6: 1. When the weight ratio of the low-cis polybutadiene rubber to the linear butadiene-styrene copolymer is within the above range, the composition is particularly useful as the toughening agent of the aromatic vinyl resin. The weight ratio of the low-cis polybutadiene rubber and the linear butadiene-styrene copolymer is preferably 0.3-6: 1, preferably 0.4-4: 1, more preferably 0.45-3: 1, and more preferably 0.5-2: 1.

In a preferred embodiment, the weight ratio of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer is 0.6-3: 1, preferably 0.8-2: 1, and more preferably 1-1.5: 1 . The composition according to this preferred embodiment is particularly useful as a toughening agent for ABS resin.

In another preferred embodiment, the weight ratio of the polybutadiene rubber with low cis content and the linear butadiene-styrene copolymer is 0.4-3: 1, preferably 0.45-2: 1 and more preferably 0.5-1, 5: 1. The composition according to this preferred embodiment is particularly suitable as a toughening agent for high-impact polystyrene.

• (1) Unter der Bedingung einer anionischen Initiierungsreaktion erfolgt eine Initiierungsreaktion von Butadien und Styrol im Kontakt mit einem organischen Lithium-Initiator in Alkylbenzol;
• (2) Zugabe eines Blockiermittels in eine Mischung, erhalten von der Initiierungsreaktion von Schritt (1) und Durchführen einer Polymerisationsreaktion mit der Mischung, die das Blockiermittel enthält, in einem Zustand einer anionischen Polymerisationsreaktion,
• (3) Kontaktieren einer Mischung, erhalten von der Polymerisationsreaktion mit einem Terminierungsmittel, zur Durchführung einer Terminierungsreaktion unter Erhalt der Polymerlösung, enthaltend lineares Butadien-Styrol-Copolymer.

According to the third aspect of this invention, this invention provides a process for producing the linear butadiene-styrene copolymer according to the first aspect of this invention, comprising the following steps:

• (1) Under the condition of an anionic initiation reaction, an initiation reaction of butadiene and styrene occurs in contact with an organic lithium initiator in alkylbenzene;
• (2) adding a blocking agent to a mixture obtained from the initiation reaction of step (1) and performing a polymerization reaction on the mixture containing the blocking agent in a state of anionic polymerization reaction,
• (3) Contacting a mixture obtained from the polymerization reaction with a terminating agent to carry out a termination reaction to obtain the polymer solution containing linear butadiene-styrene copolymer.

worin R₁ und R₂ gleich oder verschieden sind und unabhängig ausgewählt sind aus Wasserstoffatom oder C_1-5-Alkyl, zum Beispiel Wasserstoffatom, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek-Butyl, Isobutyl, tert-Butyl, n-Amyl, Isoamyl, tert-Amyl oder Neoamyl; zusätzlich sind R₁ und R₂ nicht Wasserstoffatom zur gleichen Zeit.The alkylbenzene is used as the polymerization solvent in step (1). The alkylbenzene can be one or more of monoalkylbenzene, dialkylbenzene and trialkylbenzene. Specifically, the alkylbenzene can be selected from compounds having the formula II.

wherein R ₁ and R _{2 are the} same or different and are independently selected from hydrogen atom or C _1-5 -alkyl, for example hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- Butyl, n-amyl, isoamyl, tert-amyl or neoamyl; in addition, R ₁ and R _{2 are} not hydrogen atoms at the same time.

The alkylbenzene is preferably one or more selected from the group consisting of toluene, ethylbenzene and dimethylbenzene. More preferably the alkylbenzene is ethylbenzene.

In step (1), the alkylbenzene is used as the polymerization solvent, and an amount may allow the total concentration of butadiene and styrene in the alkylbenzene to be 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more is more, more preferably 20% by weight or more, more preferably 25% by weight or more, particularly preferably 30% by weight or more. The amount of the alkylbenzene can enable the total concentration of butadiene and styrene in the alkylbenzene to be 70% by weight or less, preferably 65% by weight or less, more preferably 60% by weight or less. The total concentration of butadiene and styrene in the alkylbenzene is preferably 30 to 60% by weight, more preferably 35 to 55% by weight, and more preferably 40 to 55% by weight. The polymer solution obtained with the linear butadiene-styrene copolymer by polymerization at the above monomer concentration can directly with the polymer Monomers of the aromatic vinyl resin are mixed for bulk polymerization without solvent removal to produce aromatic vinyl resin such as ABS resin and HIPS resin.

In step (I), the amount of styrene and butadiene can be selected according to the intended linear butadiene-styrene copolymer based on the total amount of styrene and butadiene, a content of styrene can be 10 to 45% by weight, preferably 15 to 43% by weight .% be; the butadiene content can be 55 to 90% by weight, preferably 57 to 85% by weight.

In a preferred embodiment, based on the total amount of styrene and butadiene, a styrene content can be 12 to 40% by weight, preferably 15 to 35% by weight; a content of butadiene can be 60 to 88% by weight, preferably 65 to 85% by weight, and the obtained polymer solution with linear butadiene-styrene copolymer according to this embodiment is particularly suitable as a toughness agent of the ABS resin.

In another preferred embodiment, based on the total amount of styrene and butadiene, a content of styrene may be 12 to 45% by weight, preferably 15 to 42% by weight; a butadiene content can be 55 to 88% by weight, is preferably 58 to 85% by weight, and the polymer solution obtained with linear butadiene-styrene copolymer according to this exemplary embodiment is particularly suitable as a toughness agent for the impact-resistant polystyrene.

In the step (1), the initiation reaction is used to allow a contact reaction of styrene and butadiene with an organic lithium initiator and carry out the oligomerization to obtain an oligomer with an active end group, for example an oligomer with an active end group and a molecular weight of 100 to 200. In general, the initiation reaction can be carried out at 10 to 50 ° C, preferably 25 to 40 ° C, and more preferably 30 to 40 ° C. A time of the initiation reaction can be 1 to 8 minutes, preferably 1 to 5 minutes, preferably 2 to 4.5 minutes, and more preferably 3 to 4 minutes.

In step (1), the organic lithium initiator may be any typical organic lithium initiator which can initiate the polymerization of styrene and butadiene in the anionic polymerization field. The organic lithium initiator is preferably an organic mono-lithium compound, and more preferred is the compound having the formula III. R ₃ Li formula III, wherein R _{3 is} C _1-10 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), octyl (including the various isomers), nonyl (including the various isomers) or decyl (including the various isomers).

The specific examples of the organic lithium initiator may include, but are not limited to: one or more selected from the group consisting of lithium ethide, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and isobutyl lithium.

The organic lithium initiator is preferably one or more selected from the group consisting of n-butyllithium, sec-butyllithium, isobutyllithium and tert-butyllithium. More preferably the organic lithium initiator is n-butyllithium.

The amount of the organic lithium initiator can be selected according to the molecular weight of the aimed polymer. Preferably, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in the step (2) to be 70,000 to 160,000. In a preferred embodiment, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (2) to be 70,000 to 150,000 (preferably 75,000 to 140,000) and the polymer solution with the linear butadiene -Styrene copolymer in this exemplary embodiment is particularly suitable as a toughening agent for ABS resin. In another preferred embodiment, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (2) to be 90,000 to 160,000 (preferably 100,000 to 160,000) and the polymer solution, which contains the linear butadiene-styrene copolymer, in this preferred embodiment, is particularly suitable as a toughening agent for a high-impact polystyrene.

The method for determining the amount of initiator according to the molecular weight of the intended polymer is known to those skilled in the art and is thus not described in detail in this disclosure.

In the step (1), the organic lithium initiator is added to a polymerization system in the form of a solution. For example, a solvent in a solution of the organic lithium initiator can be one or more of hexane, cyclohexane and heptane, and a concentration of this solution is preferably 0.5 to 2 mol / l and preferably 0.8 to 1.5 mol / l.

In the step (2), the blocking agent is added to the mixture obtained from the initiation reaction to carry out the polymerization reaction. The blocking agent is selected from one or more metal alkyl compounds and one or more selected from the group consisting of organic aluminum compound, organic magnesium compound and organic zinc compound is preferred.

worin R₄, R₅ und R₆ identisch oder verschieden voneinander sind und unabhängig ausgewählt sind aus C_1-8-Alkyl, zum Beispiel Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tert-Butyl, n-Amyl, Isoamyl, tert-Amyl, Neoamyl, Hexyl (einschließlich den verschiedenen Isomeren), Heptyl (einschließlich den verschiedenen Isomeren), oder Octyl (einschließlich den verschiedenen Isomeren).The organic aluminum compound can be one or more of the compounds of the formula IV.

wherein R ₄ , R ₅ and R _{6 are} identical or different from one another and are independently selected from C _1-8 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n- Amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).

The specific examples of the organic aluminum compounds may include, but are not limited to: one or more selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum and triisobutyl aluminum, and preferably selected from triethyl aluminum and / or triisobutyl aluminum.

The organic magnesium compound can be one or more of the compounds of the formula V. R ₈ —Mg —— R ₇ Formula V wherein R ₇ and R _{8 are} identical or different and are independently selected from C _1-8 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n- Amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers) or octyl (including the various isomers).

The specific examples of the organic magnesium compound may include, without being limited to: one or more selected from the group consisting of di-n-butylmagnesium, di-sec-butylmagnesium, diisobutylmagnesium, di-tert-butylmagnesium, and n-butyl-sec -butylmagnesium and n-butyl-sec-butylmagnesium is preferred.

The organic zinc compound can be the compound having the formula VI. R ₁₀ - Zn - R ₉ formula VI wherein R ₉ and R _{10 are} identical or different and are independently selected from C _1-8 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n- Amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).

The specific examples of the organic zinc compound may include, but are not limited to: one or more selected from the group consisting of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-sec-butyl zinc, diisobutyl zinc and di-tert-butyl zinc and preferably selected from diethyl zinc and / or di-n-butyl zinc.

The blocking agent is preferably an organic aluminum compound and / or organic magnesium compound. More preferably, the blocking agent is one or more selected from the group consisting of triethyl aluminum, triisobutyl aluminum and n-butyl-sec-butyl magnesium.

The amount of the blocking agent can be selected according to the type.

In one embodiment, the blocking agent is the organic aluminum compound, and a molar ratio of the organic aluminum compound and the organic lithium initiator can be 0.6-0.95: 1, preferably 0.7-0.9: 1 , the organic aluminum compound is calculated by the aluminum element, and the organic lithium initiator is calculated by the lithium element.

In another embodiment, the blocking agent is the organic magnesium compound, and a molar ratio of the organic magnesium compound and the organic lithium initiator can be 1-6: 1, is preferably 2-4: 1, the organic magnesium compound becomes calculated by magnesium element, and the organic lithium initiator is calculated by lithium element.

In another exemplary embodiment, the blocking agent is a combination of the organic aluminum compound and the organic magnesium compound; a molar ratio of the organic aluminum compound to the organic magnesium compound to the organic lithium initiator can be 0.5-2: 1 -5: 1, is preferably 0.8-1: 1.5-3: 1, the organic aluminum compound being the aluminum element, the organic magnesium compound being the magnesium element and the organic lithium initiator being lithium Element are calculated.

In another embodiment, the blocking agent is an organic zinc compound, a molar ratio of the organic zinc compound to the organic lithium initiator can be 1-6: 1, preferably it is 2-4: 1, the organic zinc compound becomes Calculated by zinc element and the organic lithium initiator is calculated by lithium element.

In the step (2), the polymerization reaction can be carried out under a conventional condition of the anionic polymerization reaction. In general, the condition of the polymerization reaction may include: temperature of 50 to 140 ° C, preferably 70 to 130 ° C, and more preferably 80 to 120 ° C; a time of 60 to 150 minutes, preferably 70 to 120 minutes.

In step (3), the terminating agent is added to the mixture obtained from the polymerization reaction to inactivate active chains. The terminating agent can be one or more of C _1-4 alcohol, organic acid and carbon dioxide and is preferably one or more of isopropanol, geoceric acid, citric acid and carbon dioxide, and more preferred is carbon dioxide.

In a preferred embodiment, step (3) includes: carrying out a contact reaction with the mixture obtained from the polymerization reaction in step (2) with carbon dioxide. Carbon dioxide is used to carry out the termination reaction. Carbon dioxide can form carbonates with metal ions (Li, Mg, Al, Zn and Fe) in the polymerization system, so that the chromogenic reaction of metal ions is avoided and the polymer product produced is poor in color. The carbon dioxide can be injected into the reaction system in the form of a gas, for example, carbon dioxide gas is injected into the mixture at 0.2 to 1 MPa (gauge pressure), preferably 0.3 to 0.6 MPa (gauge pressure), resulting from the polymerization reaction is obtained. The carbon dioxide can also be introduced in a form of a water solution of dry ice into the mixture obtained by the polymerization reaction; for example, 0.5 to 2 mol / l of dry ice in water is introduced into the mixture obtained from the polymerization reaction.

In this embodiment, a condition of the termination reaction may include: temperature from 50 to 80 ° C., time from 10 to 40 minutes.

According to the method for producing the butadiene-styrene linear copolymer in this invention, the polymer solution obtained from the termination reaction in step (3) can be directly discharged or used in the subsequent processes without solvent removal treatment; for example, the polymer solution can be used directly for the preparation of the toughening agent of the aromatic vinyl resin prepared by a bulk polymerization method. Under a specific condition, the polymer solution obtained from the termination reaction in the step (3) can also be treated for solvent removal; for example, the evaporation process is used to remove some of the solvents to meet the requirements of subsequent process operations to meet. The polymer solution obtained from the termination reaction in step (3) can also be treated for solvent removal using conventional methods (e.g., coagulation), and is extruded and pelletized by an extruder (e.g., twin screw extruder) to obtain the corresponding polymer granules.

According to the method for producing the butadiene-styrene linear copolymer of this invention, the use of alkylbenzene as a polymerization solvent while a blocking agent is introduced during the polymerization reaction can effectively widen the molecular weight distribution range of the butadiene-styrene linear copolymer produced. The linear butadiene-styrene copolymer obtained by the production method of this invention generally has a molecular weight distribution index of 1.55 to 2, preferably 1.6 to 2, and more preferably 1.8 to 2. In addition, the method for producing the polybutadiene -Low cis rubber according to the invention greatly reduce the gel content of the polymer produced; for example, the gel content of the linear butadiene-styrene copolymer is below 20 ppm, preferably not more than 15 ppm, and more preferably not more than 10 ppm, as measured by weight. The linear butadiene-styrene copolymer produced by the process of the present invention is particularly useful as a toughness agent of the acrylonitrile-butadiene-styrene copolymer (i.e., ABS resin) and the impact-resistant polystyrene (i.e., HIPS resin).

According to the fourth aspect of this invention, this invention provides an aromatic vinyl resin containing a structural unit derived from aromatic vinyl monomer and a structural unit derived from the toughening agent, wherein the toughening agent is the composition according to the second aspect of this invention.

In this invention, the term "structure derived from vinyl aromatic monomer" refers to the structural unit formed by vinyl aromatic monomers, and the structural unit and vinyl aromatic monomers have the same atomic types and atomic numbers except for the electronic structure with some modification; the term "structural unit derived from the toughening agent" refers to the structural unit formed by the toughening agent, and the structural unit and the toughening agent have the same types of atoms and the same atomic number except for the electronic structure with some modification.

The aromatic vinyl monomer refers to the monomer containing both aryl (e.g. vinyl) and vinyl in the molecular structure. The specific examples of the vinyl aromatic monomer may include, but are not limited to: one or more selected from the group consisting of styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, p-ethyl styrene, and vinyl naphthalene . The aromatic vinyl monomer styrene is preferred.

The aromatic vinyl resin may contain only the structural unit derived from the aromatic vinyl monomers and the structural unit derived from the toughening agent, or may further contain another structural unit derived from other vinyl monomers. The specific examples of the other vinyl monomers may include, but are not limited to: one or more selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, and maleic acid.

In a preferred embodiment, the aromatic vinyl resin contains only the structural unit derived from the aromatic vinyl monomers and the structural unit derived from the toughening agent, and a preferred aromatic vinyl resin is a high impact polystyrene.

Based on the total amount of the high-impact polystyrene, a content of the styrene structural unit can be 80 to 95% by weight, is preferably 85 to 93% by weight and more preferably 88 to 92% by weight; a content of the butadiene structural unit can be 5 to 20% by weight, preferably 7 to 15% by weight and more preferably 8 to 12% by weight. The weight average molecular weight of the high impact polystyrene can be 150,000 to 350,000, is preferably 160,000 to 220,000, and more preferably is 170,000 to 300,000, and the molecular weight distribution index can be 1.8 to 3.8, preferably 2 to 3 .5 and more preferably 2.5 to 3.3.

In another embodiment, the aromatic vinyl matrix resin contains the structural unit derived from the aromatic vinyl monomers, the structural unit derived from the toughening agent, and the structural unit derived from acrylonitrile, and a preferred aromatic vinyl resin is acrylonitrile-butadiene-styrene- Copolymer. The composition of the acrylonitrile-butadiene-styrene copolymer can be selected routinely. In general, based on a total amount of the acrylonitrile-butadiene-styrene copolymer, a content of the butadiene structural unit can be 5 to 20% by weight, preferably 8 to 15% by weight. %; a content of the styrene structural unit can be 55 to 75%, preferably 60 to 72% by weight; a content of the acrylonitrile structural unit (that is to say the structural unit formed by acrylonitrile) can be 10 to 35% by weight, preferably 15 to 30% by weight. The weight average molecular weight of the acrylonitrile-butadiene-styrene copolymer can be 100,000 to 400,000, preferably 150,000 to 350,000 and more preferably 180,000 to 300,000, and the molecular weight distribution index can be 2 to 4, preferably 2. 2 to 3.5 and more preferred is 2.3 to 3.

The total amount of toughening agent can be routinely selected. With respect to the total content of the aromatic vinyl resin, the content of the toughening agent can preferably be 2 to 25% by weight, preferably 5 to 20% by weight. The amount of the toughening agent can be optimized according to the type of the aromatic vinyl resin.

In a preferred embodiment, the aromatic vinyl resin is acrylonitrile-butadiene-styrene resin; Based on a total content of the aromatic vinyl resin, a preferable content of the toughening agent is 5 to 20% by weight, and more preferably 6 to 15% by weight, and more preferably 8 to 13% by weight.

In another preferred embodiment, the aromatic vinyl matrix resin is high impact polystyrene; Based on a total amount of the aromatic vinyl resin, a preferable content of the toughening agent is 5 to 15%, and more preferable is 6 to 12% by weight.

1. (a) unter einer Bedingung einer anionischen Initiierungsreaktion wird Butadien im Kontakt mit einem organischen Lithium-Initiator in Alkylbenzol einer Initiierungsreaktion unterworfen;
2. (b) ein Blockiermittel wird in eine Lösung gegeben, erhalten von der Initiierungsreaktion von Schritt (a), und Polymerisationsreaktion wird mit der Mischung, die das Blockiermittel enthält, in einer Bedingung einer anionischen Polymerisationsreaktion durchgeführt;
3. (c) eine Mischung, erhalten von der Polymerisationsreaktion, wird einer Kupplungsreaktion durch Kontaktieren mit einem Kupplungsmittel unterworfen;
4. (d) eine Mischung, erhalten von der Kupplungsreaktion, wird mit einem Terminierungsmittel kontaktiert, zur Durchführung einer Terminierungsreaktion, unter Erhalt einer Polymerlösung, die Polybutadien-Kautschuk mit niedrigem cis-Gehalt enthält.

According to the fifth aspect of this invention, this invention provides a process for producing an aromatic vinyl resin comprising the steps of mixing the polymeric monomers containing aromatic vinyl monomer with a solution containing a toughening agent to obtain a mixture and polymerizing the • mixture,
wherein the solution containing the toughening agent contains a solution containing linear butadiene-styrene copolymer and a solution containing polybutadiene rubber having a low cis content,
the solution containing the linear butadiene-styrene copolymer is the polymer solution containing the linear butadiene-styrene copolymer obtained by the method according to the third aspect of this invention; and
the solution containing the low cis polybutadiene rubber is a polymer solution containing low cis polybutadiene rubber prepared by a method including the steps of:

1. (a) under an anionic initiation reaction condition, butadiene is subjected to an initiation reaction in contact with an organic lithium initiator in alkylbenzene;
2. (b) a blocking agent is put into a solution obtained from the initiation reaction of step (a), and polymerization reaction is carried out on the mixture containing the blocking agent in a condition of anionic polymerization reaction;
3. (c) a mixture obtained from the polymerization reaction is subjected to a coupling reaction by contacting it with a coupling agent;
4. (d) A mixture obtained from the coupling reaction is contacted with a terminating agent to conduct a terminating reaction to obtain a polymer solution containing polybutadiene rubber of low cis content.

worin R₁ und R₂ gleich oder verschieden voneinander sind und jeweils unabhängig ausgewählt sind aus Wasserstoff oder C_1-5-Alkyl, zum Beispiel Wasserstoffatom, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek-Butyl, Isobutyl, tert-Butyl, n-Amyl, Isoamyl, tert-Amyl oder Neoamyl; zusätzlich sind R₁ und R₂ nicht gleichzeitig Wasserstoffatom.The alkylbenzene is used as the polymerization solvent in step (a). The alkylbenzene can be one or more selected from the group consisting of monoalkylbenzene, dialkylbenzene and trialkylbenzene. Specifically, the alkylbenzene can be selected from the compounds having the formula II.

in which R ₁ and R _{2 are the} same or different from one another and are each independently selected from hydrogen or C _1-5 -alkyl, for example hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, tert-amyl or neoamyl; in addition, R ₁ and R _{2 are} not hydrogen atoms at the same time.

The alkylbenzene is preferably one or more selected from the group consisting of toluene, ethylbenzene and dimethylbenzene. More preferably the alkylbenzene is ethylbenzene.

In the step (a), the alkylbenzene is used as the polymerization solvent and its amount enables the concentration of butadiene in the alkylbenzene to be 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more preferably 20% by weight or more, more preferably 25% by weight or more, particularly preferably 30% by weight or more. The amount of the alkylbenzene can enable the concentration of butadiene in the alkylbenzene to be 70% by weight or less, preferably 65% by weight or less, more preferably 60% by weight or less. The concentration of butadiene in the alkylbenzene is preferably 30 to 60% by weight, more preferably 35 to 55% by weight, and more preferably 40 to 55% by weight. The obtained polymer solution containing polybutadiene rubber of low cis content and obtained by polymerization at the above monomer concentration can be mixed directly with the polymeric monomers of aromatic vinyl resin for bulk polymerization without solvent removal to produce an aromatic vinyl resin such as ABS resin and HIPS resin.

In step (a), the initiation reaction is used to allow butadiene to undergo a contact reaction with an organic lithium initiator and carry out oligomerization to obtain an oligomer with active end groups, for example an oligomer with active end groups and a molecular weight of 100 to 200. In general, the initiation reaction can be carried out at 10 to 50 ° C, preferably 25 to 40 ° C, and more preferably 30 to 40 ° C. A time of the initiation reaction may be 1 to 8 minutes, preferably 1 to 5 minutes, preferably 2 to 4.5 minutes, and more preferably 3 to 4 minutes.

In step (a) the organic lithium initiator can be any typical organic lithium initiator which can initiate the polymerization of butadiene in the anionic polymerization field. The organic lithium initiator is preferably an organic mono-lithium compound, and more preferred is the compound having the formula III. R ₃ Li formula III, wherein R _{3 is} C _1-10 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), octyl (including the various isomers), nonyl (including the various isomers) or decyl (including the various isomers).

The specific examples of the organic lithium initiator may include, but are not limited to: one or more selected from the group consisting of lithium ethide, n-propyllithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, and isobutyl lithium.

The organic lithium initiator is preferably one or more selected from the group consisting of n-butyllithium, sec-butyllithium, isobutyllithium and tert-butyllithium. More preferably the organic lithium initiator is n-butyllithium.

The amount of the organic lithium initiator can be selected according to the molecular weight of the expected polymer. Preferably, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (b) to be 42,000 to 90,000. In a preferred embodiment, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (b) to be 45,000 to 75,000 and the polymer solution containing low-cis polybutadiene rubber , in this preferred embodiment is particularly useful as a toughening agent for ABS resin. In another preferred embodiment, the amount of the organic lithium initiator enables the number average molecular weight of the polymer obtained from the polymerization reaction in step (b) to be 50,000 to 90,000 and the polymer solution containing low-cis polybutadiene rubber , in this preferred embodiment is particularly useful as a toughening agent of high impact polystyrene.

The method for determining the amount of initiator according to the molecular weight of the expected polymer is known to those skilled in the art and is thus not described in detail.

In step (a) the organic lithium initiator is added to a polymerization system in the form of a solution. For example, a solvent in a solution of the organic lithium initiator can be used or more of hexane, cyclohexane and heptane, and a concentration of this solution is preferably 0.5 to 2 mol / und, and more preferably 0.8 to 1.5 mol /.

In the step (b), the blocking agent is added to the mixture obtained from the initiation reaction to carry out the polymerization reaction. The blocking agent is selected from one or more metal alkyl compounds, and preferred is one or more selected from the group consisting of an organic aluminum compound, organic magnesium compound and organic zinc compound.

worin R₄, R₅ und R₆ identisch oder verschieden voneinander sind und unabhängig ausgewählt sind aus C_1-8-Alkyl, zum Beispiel Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tert-Butyl, n-Amyl, Isoamyl, tert-Amyl, Neoamyl, Hexyl (einschließlich den verschiedenen Isomeren), Heptyl (einschließlich den verschiedenen Isomeren), oder Octyl (einschließlich den verschiedenen Isomeren).The organic aluminum compound can be one or more of the compounds of the formula IV.

wherein R ₄ , R ₅ and R _{6 are} identical or different from one another and are independently selected from C _1-8 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n- Amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).

The specific examples of the organic aluminum compounds may include, but are not limited to: one or more selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum and triisobutyl aluminum, and preferably selected from triethyl aluminum and / or triisobutyl aluminum.

The organic magnesium compound can be one or more of the compounds of the formula V. R ₈ —Mg —— R ₇ Formula V wherein R ₇ and R _{8 are} identical or different and are independently selected from C _1-8 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n- Amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).

The specific of the organic magnesium compounds can include, without being limited to: one or more selected from the group consisting of di-n-butylmagnesium, di-sec-butylmagnesium, diisobutylmagnesium, di-tert-butylmagnesium and n-butyl-sec- butylmagnesium and preferred is n-butyl-sec-butylmagnesium.

The organic zinc compound can be the compound having the formula VI. R ₁₀ - Zn - R ₉ formula VI wherein R ₉ and R _{10 are} identical or different and are independently selected from C _1-8 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n- Amyl, isoamyl, tert-amyl, neoamyl, hexyl (including the various isomers), heptyl (including the various isomers), or octyl (including the various isomers).

The specific examples of the organic zinc compound may include, but are not limited to: one or more selected from the group consisting of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-sec-butyl zinc, diisobutyl zinc and di-tert-butyl zinc and preferably selected from diethyl zinc and / or di-n-butyl zinc.

The blocking agent is preferably an organic aluminum compound and / or organic magnesium compound. More preferably, the blocking agent is one or more selected from the group consisting of triethyl aluminum, triisobutyl aluminum and n-butyl-sec-butyl magnesium.

The amount of the blocking agent can be selected according to the type.

In one embodiment, the blocking agent is the organic aluminum compound, and a molar ratio of the organic aluminum compound and the organic lithium initiator can be 0.6-0.95: 1, preferably 0.7-0.9: 1 , the organic aluminum compound is calculated by the aluminum element, and the organic lithium initiator is calculated by the lithium element.

In another embodiment, the blocking agent is the organic magnesium compound, and a molar ratio of the organic magnesium compound and the organic lithium initiator can be 1-6: 1, is preferably 2-4: 1, the organic magnesium compound becomes calculated by magnesium element, and the organic lithium initiator is calculated by lithium element.

In another exemplary embodiment, the blocking agent is a combination of the organic aluminum compound and the organic magnesium compound; a molar ratio of the organic aluminum compound to the organic magnesium compound to the organic lithium initiator can be 0.5-2: 1 -5: 1, is preferably 0.8-1: 1.5-3: 1, the organic aluminum compound being the aluminum element, the organic magnesium compound being the magnesium element and the organic lithium initiator being lithium Element are calculated.

In another embodiment, the blocking agent is an organic zinc compound, a molar ratio of the organic zinc compound to the organic lithium initiator can be 1-6: 1, preferably it is 2-4: 1, the organic zinc compound becomes Calculated by zinc element and the organic lithium initiator is calculated by lithium element.

In the step (b), the polymerization reaction can be carried out under a conventional condition of the anionic polymerization reaction. In general, the condition of the polymerization reaction may include: temperature of 50 to 140 ° C, preferably 70 to 130 ° C, and more preferably 80 to 120 ° C; a time of 60 to 150 minutes, preferably 70 to 120 minutes.

In the step (c), a coupling agent is used to carry out the coupling of the mixture obtained from the polymerization reaction in the step (b), and part of the polymer chains are bonded to form multi-arm star polymers so that the molecular weight of the produced low cis polybutadiene rubber shows a bimodal distribution. The specific examples of the coupling agent may include, but are not limited to, one or more selected from the group consisting of tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, 1,8-octamethylene bromide, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γethoxysilane, and methyltrimethoxysilane, and γethoxysilane N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane. The coupling agent is preferably tetrachlorosilane and / or methyltrichlorosilane.

The amount of the coupling agent may be selected according to an introduction amount of the intended multi-arm star polymer of the low-cis polybutadiene rubber. The amount of coupling agent preferably enables the molecular weight of the polybutadiene rubber finally obtained with a low cis content to be in a bimodal distribution, the number average molecular weight of the high molecular weight component (i.e. polymer components formed by the coupling) in the bimodal distribution 120 000 to 280,000 and the content (also known as coupling efficiency) of the high molecular component is 65 to 95% by weight.

In a preferred embodiment, the amount of coupling agent enables the molecular weight of the finally produced polybutadiene rubber having a low cis content to be in a bimodal distribution, the number average molecular weight of the high molecular weight component in the bimodal distribution to be 140,000 to 190,000 and the content the high molecular weight component is 70 to 95% by weight. The polymer solution containing the low cis polybutadiene rubber according to this embodiment is particularly useful as a toughening agent for ABS resin.

In another preferred embodiment, the amount of coupling agent enables the molecular weight of the finally produced polybutadiene rubber with low cis content to be in the bimodal distribution, the number average molecular weight of the high molecular weight component in the bimodal distribution 150,000 to 270,000, preferably 160 000 to 260,000 and the content of the high molecular weight component is 60 to 95% by weight, preferably 65 to 95% by weight. The polymer solution containing polybutadiene rubber with a low cis content according to this exemplary embodiment is particularly suitable as a toughness agent for the high-impact polystyrene.

The amount of the coupling agent can be determined according to the expected coupling efficiency. In general, the molar ratio of the coupling agent to the organic lithium initiator is 0.1-0.5: 1, preferably 0.15-0.4: 1. The organic lithium initiator refers to the organic lithium initiator used in the initiation reaction in the step (a) and does not contain the organic lithium initiator which is added to remove the impurities in the reaction system before the addition of the polymeric monomers . The coupling agent can be added to the polymerization system in the form of a solution. For example, the solvent for dissolving the coupling agent may be one or more of hexane, cyclohexane and heptane, and the concentration of the coupling agent is preferably 0.05 to 1 mol / l, preferably 0.1 to 0.5 mol / l, and more preferably 0 , 1 to 0.2 mol / l.

The coupling reaction can be carried out under the conventional condition in step (c). In general, one condition of the coupling reaction may include: a temperature of 50 to 100 ° C., preferably 60 to 80 ° C., and a time of 20 to 150 minutes, preferably 30 to 120 minutes.

In step (d) the terminating agent is added to the mixture obtained from the coupling reaction to inactivate the active chains. The terminating agent can be one or more selected from the group consisting of C _1-4 alcohol, organic acid and carbon dioxide, and preferably one or more selected from the group consisting of isopropanol, geoceric acid, citric acid and carbon dioxide, and more preferred is carbon dioxide .

In a preferred embodiment, step (d) includes: carrying out a contact reaction with the mixture obtained from the coupling reaction in step (c) with carbon dioxide. Carbon dioxide is used to carry out the termination reaction. Carbon dioxide can form carbonates with metal ions (Li, Mg, Al, Zn and Fe) in the polymerization system, so that the chromogenic reaction of the metal ions is avoided and the polymer product produced has a lower color. The carbon dioxide can be injected into the reaction system in the form of a gas; for example, the carbon dioxide gas is injected at 0.2 to 1 MPa (gauge pressure), preferably 0.32 to 0.6 MPa (gauge pressure) into the mixture obtained from the coupling reaction. The carbon dioxide can also be introduced into the mixture in the form of a water solution of dry ice obtained from the coupling reaction; for example, 0.5 to 2 mol / l dry ice in water is introduced into the mixture obtained from the coupling reaction.

In this embodiment, a condition of the termination reaction may include: a temperature of 50 to 80 ° C, a time of 10 to 40 minutes.

The polymer solution obtained from the termination reaction in the step (d) can be used directly for the preparation of the toughening agent of the aromatic vinyl resin prepared by the bulk polymerization process.

The use of alkylbenzene as the polymerization solvent while the blocking agent is introduced during the polymerization reaction can effectively expand the molecular weight distribution range of the produced low cis polybutadiene rubber and the molecular weight of the low cis polybutadiene rubber in the polymer solution, containing low cis polybutadiene rubber obtained from the invention is in bimodal distribution. The molecular weight distribution range of the low molecular weight component in the bimodal distribution can be 1.55 to 2, preferably 1.7 to 2, the molecular weight distribution range of the high molecular weight component in the bimodal distribution can be 1.55 to 2, preferably 1.7 to 2. In addition, the polymer solution containing the low cis polybutadiene rubber obtained by this invention has a low gel content; for example, the gel content is below 20 ppm, preferably not more than 15 ppm and more preferably not more than 10 ppm, measured as weight.

According to the method for producing the aromatic vinyl resin of this invention, the polymer solution containing the toughening agent can be used directly to produce the aromatic vinyl resin without solvent removal treatment, thereby shortening the process route and reducing the operating power consumption. Moreover, this can effectively prevent the increase in gel content and the deterioration in coloration of the polymer, which may be caused by the solvent removal process, so as to affect the impact resistance and gloss of the finally obtained aromatic vinyl resin.

According to the method for producing the aromatic vinyl resin of this invention, the weight ratio of the polybutadiene rubber having a low cis content to the linear butadiene-styrene Copolymer 0.3-6: 1. When the weight ratio of the low cis polybutadiene rubber to the linear butadiene-styrene copolymer falls within the above range, the composition is particularly useful as a toughening agent of the aromatic vinyl resin. The weight ratio of the polybutadiene rubber having a low cis content to the linear butadiene-styrene copolymer is preferably 0.3-6: 1, more preferably 0.4-4: 1, more preferably 0.45-3: 1 and more 0.5-2: 1 is preferred.

According to the method for producing the aromatic vinyl resin of this invention, the specific examples of the aromatic vinyl monomer may include, but are not limited to: one or more of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m -Ethyl styrene, n-ethyl styrene and vinyl naphthalene. The aromatic vinyl monomer styrene is preferred.

The polymeric monomer can contain other vinyl monomers in addition to aromatic vinyl monomers. The specific examples of other vinyl monomers may include, but are not limited to: one or more selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, and maleic acid.

According to the method for producing the aromatic vinyl resin of this invention, the polymerization reaction can be carried out by free radical polymerization. The type of free radical initiator used in the free radical polymerization is not particularly limited and can be routinely selected; for example, the free radical initiator can be one or more of the free radical initiators for thermal decomposition. The free radical initiator is preferably one or more of the peroxide initiator and the azodinitrile initiator. The specific examples of the free radical initiator may include, but are not limited to: one or more selected from the group consisting of dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexyl carbonate, peroxydicarbonate, percarboxy ester, alkyl peroxide and azodinitrile compound (e.g. azodiisobutyl nitrile and azo -bis-isoheptonitrile). The free radical initiator is preferably one or more selected from the group consisting of dibenzoyl peroxide, di (o-methylbenzoyl) peroxide, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexyl carbonate.

The amount of the free radical initiator can be routinely selected so that the aromatic vinyl resin having the expected molecular weight can be obtained. The method for determining the amount of initiator according to the expected polymer molecular weight is known to the person skilled in the art and is therefore not described in detail.

According to the method for producing the aromatic vinyl resin of this invention, the polymerization reaction can be carried out under routine conditions. More preferably, a condition of the polymerization reaction includes: temperature of 100 to 155 ° C (e.g. 100 to 150 ° C) and time of 4 to 12 hours (e.g. 7 to 9 hours).

In a preferred example, one condition of the polymerization reaction includes: first reaction at 100 to 110 ° C for 1 to 3 hours, optionally reaction at 115 to 125 ° C for 1 to 3 hours (eg 1.5 to 2.5 hours), then Reaction at 130 to 140 ° C. for 1 to 3 hours (e.g. 1.5 to 2.5 hours) and finally reaction at 145 to 155 ° C. for 1 to 3 hours (e.g. 1.5 to 2.5 hours). One condition of the polymerization reaction preferably includes: first reaction at 105 to 110 ° C. for 1 to 2 hours, subsequent reaction at 120 to 125 ° C. for 1 to 2 hours, subsequent reaction at 130 to 135 ° C. for 1 to 2 hours and finally Reaction at 150 to 155 ° C for 1 to 2 hours.

In the following, this invention will be described in detail in some embodiments, but the scope of this invention is not limited.

In the examples below, the pressure of CO _{2 is} gauge pressure.

The following test procedures are used in the following examples:

(1) Molecular weight and molecular weight distribution index

The molecular weight and the molecular weight distribution index are determined using TOSOH HLC-8320 gel permeation chromatograph. The gel permeation chromatograph is equipped with TSKgel SuperMultiporeHZ-N and TSKgel SuperMultiporeHZ standard columns; the solvent is chromatographically pure THF and narrow partition polystyrene is used as the standard sample.

The test method for the molecular weight and molecular weight distribution index of low cis polybutadiene rubber and linear butadiene-styrene copolymer is as follows: the solvent is chromatographically pure THF and narrow distribution polystyrene is used as a standard sample; the polymer sample is made into a THF solution at 1 mg / ml; an injection amount of the sample is 10.00 µl; a flow rate is 0.35 ml / min and the test temperature is 40.0 ° C.

The molecular weight distribution index of the low cis polybutadiene rubber is the entire molecular weight distribution index of rubber, that is, the molecular weight distribution index is determined by using double peaks as a standard. The molecular weight distribution index of the high molecular weight component in the bimodal distribution refers to the molecular weight distribution index calculated by using the elution peak of the high molecular weight component as a yardstick. The molecular weight distribution index of the low molecular weight component in the bimodal distribution refers to the molecular weight distribution index calculated by using the elution peak of the low molecular weight component as a yardstick. The content of the high molecular weight component refers to the percentage of the area of the elution peak of the high molecular weight component to the total area of the double peaks.

The test method for the molecular weight and the molecular weight distribution index of ABS resin and HIPS resin is as follows: dissolving ABS resin and HIPS resin with toluene and performing centrifugal separation; after agglomeration of the upper clear solution with ethanol, the clear solution is dissolved with THF and then made into a 1 mg / l solution. THF is used as the mobile phase and the test temperature is 40 ° C.

(2) Microscopic structure of the polymer containing: content of each structural unit, content of 1,2-structural unit, and content of cis-1,4-structural unit.

The content is determined with an AVANCEDRX400MHz nuclear magnetic resonance system, produced by BRUKER, during the test the solvent used is deuterated chloroform and tetramethylsilane is used as the internal standard substance.

(3) Mooney viscosity

Mooney viscosity is determined using SHIMADZU SMV-201 SK-160 -Mooney viscometer according to the procedure given in GB / T1232-92 , the test method is ML (1 + 4), and the test temperature is 100 ° C.

(4) gel content

The gel content is determined using the weight method. The specific procedure is as follows: adding a polymer sample in styrene and performing oscillation in an oscillator at 25 ° C for 16 hours so as to completely dissolve soluble substances, thereby obtaining a styrene solution having 5% by weight of polymer content (the mass of Rubber sample is designated as C (in grams); weighing a 360 mesh pure nickel sieve and designating the mass as B (in grams); then filtering the above solution with the nickel sieve and washing the nickel sieve with styrene after filtering; drying the nickel sieve at 150 ° C and normal pressure for 30 minutes and then weighing the nickel sieve and designating the mass as A (in grams); the gel content is calculated using the following formula: $$\text{gel}-\text{Salary\%}=\left[\left(\text{A.}-\text{B.}\right)\text{/ C}\right]\times 100\%$$

(5) impact resistance

The impact strength of the ABS resin is determined by using a specific test method for impact strength with cantilevered beam (J / m) according to ASTMD256 and the dimension of the sample tape used is 63.5 mm x 12.7 mm x 6.4 mm.

The impact strength of HIPS resin is determined using a specific test method for the impact strength (in kJ / m ² ) of the cantilever beam in GB / T1843-1996 , and the dimension of the sample tape used is 80 mm x 10 mm x 4 mm.

(6) 60 ° gloss is determined using a method according to ASTM D526 (60 °)

example 1

• (1) 275 g Ethylbenzol werden mit 225 g Butadien vermischt und 5 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 40°C gegeben, während 3 min reagiert wird; dann werden 4 ml Methylbenzol-Lösung von Triisobutylaluminium (die Konzentration von Triisobutylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösungsmittel wird auf 90°C erhöht und die Mischung wird bei dieser Temperatur 120 min reagiert; 6,5 ml n-Hexan-Lösung von Siliciumtetrachlorid (die Konzentration von Siliciumtetrachlorid ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 80°C reduziert und die Mischung bei dieser Temperatur 40 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A1 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 45 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 1 angegeben.
• (2) 275 g Ethylbenzol, 67,5 g Styrol und 157,5 g Butadien werden gemischt und 1,8 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 3 min zugegeben; 1,5 ml Methylbenzol-Lösung von Triisobutylaluminium (Konzentration von Triisobutylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 90°C erhöht und die Mischung bei dieser Temperatur 120 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B1 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 45 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 2 angegeben.
• (3) Die Lösung A1 und die Lösung B1 werden bei einem Gewichtsverhältnis von 1:1 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C1. 40 g Zähigkeitsmittel C1, 140 g Styrol, 40 g Acrylnitril und 0,02 g Dibenzoylperoxid werden gemischt und die Mischung bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von ABS-Harz P1, und die Eigenschaften davon sind in Tabelle 3 angegeben.

This method is provided to describe this invention.

• (1) 275 g of ethylbenzene are mixed with 225 g of butadiene and 5 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C. over 3 min is responded; then 4 ml of a methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solvents is raised to 90 ° C. and the mixture is reacted at this temperature for 120 minutes; 6.5 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 40 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A1 with polybutadiene rubber with a low cis content (the concentration of the polymers is 45% by weight). The molecular weight of the low-cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
• (2) 275 g of ethylbenzene, 67.5 g of styrene and 157.5 g of butadiene are mixed, and 1.8 ml of n-hexane solution of n-butyl lithium (concentration of n-butyl lithium is 1 mol / l) is added to the mixture added at 40 ° C for reaction for 3 min; 1.5 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 90 ° C. and the mixture is reacted at this temperature for 120 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being kept at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B1 of the linear butadiene-styrene copolymer (concentration of the polymers is 45% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in a unimodal distribution, and the specific properties are given in Table 2.
• (3) The solution A1 and the solution B1 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as a toughening agent C1. 40 g of toughening agent C1, 140 g of styrene, 40 g of acrylonitrile and 0.02 g of dibenzoyl peroxide are mixed and the mixture is polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product was subjected to vacuum flashing to remove unreacted monomers and the solvent to obtain ABS resin P1, and the properties thereof are shown in Table 3.

Reference example 1

According to step (3) of the method of Example 1, i.e. during the production of ABS resin, the toughening agent C1 is not used, and the amount of polymerized monomers and the solvent is adjusted as follows: 140 g styrene, 40 g acrylonitrile, 16 g of butadiene and 22 g of ethylbenzene to obtain ABS resin R1, and the properties are shown in Table 3.

Example 2

• (1) 275 g Ethylbenzol werden mit 275 g Butadien vermischt und 5,2 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 40°C gegeben, während 3 min reagiert wird; dann werden 4,4 ml Methylbenzol-Lösung von Triisobutylaluminium (die Konzentration von Triisobutylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösung wird auf 90°C erhöht und die Mischung wird bei dieser Temperatur 120 min reagiert; 5,8 ml n-Hexan-Lösung von Siliciumtetrachlorid (die Konzentration von Siliciumtetrachlorid ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 70°C reduziert und die Mischung bei dieser Temperatur 30 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,5 MPa eingeführt, während bei dieser Temperatur 20 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A2 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 55 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 1 angegeben.
• (2) 225 g Ethylbenzol, 69 g Styrol und 206 g Butadien werden gemischt und 2,3 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 3 min zugegeben; 1,9 ml Methylbenzol-Lösung von Triisobutylaluminium (Konzentration von Triisobutylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 90°C erhöht und die Mischung bei dieser Temperatur 120 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B2 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 55 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 2 angegeben.
• (3) Die Lösung A2 und die Lösung B2 werden bei einem Gewichtsverhältnis von 1:0,8 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C2. 50 g Zähigkeitsmittel C2, 130 g Styrol, 50 g Acrylnitril und 0,03 g Di-o-methylbenzoylperoxid werden gemischt und die Mischung bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von ABS-Harz P2, und die Eigenschaften davon sind in Tabelle 3 angegeben.

This method is provided to describe this invention.

• (1) 275 g of ethylbenzene are mixed with 275 g of butadiene, and 5.2 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while 3 min reacts; then 4.4 ml of a methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solution is increased to 90 ° C. and the mixture is reacted at this temperature for 120 minutes; 5.8 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 70 ° C and the mixture is at this Temperature 30 min reacts. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.5 MPa while maintaining at that temperature for 20 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A2 with polybutadiene rubber with a low cis content (the concentration of the polymers is 55% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
• (2) 225 g of ethylbenzene, 69 g of styrene and 206 g of butadiene are mixed and 2.3 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C added for reaction for 3 min; 1.9 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 90 ° C. and the mixture is reacted at this temperature for 120 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being kept at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B2 of the linear butadiene-styrene copolymer (concentration of the polymers is 55% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in a unimodal distribution, and the specific properties are given in Table 2.
• (3) The solution A2 and the solution B2 are mixed at a weight ratio of 1: 0.8 to obtain a mixed solution as a toughening agent C2. 50 g toughening agent C2, 130 g styrene, 50 g acrylonitrile and 0.03 g di-o-methylbenzoyl peroxide are mixed and the mixture is polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product was subjected to vacuum flashing to remove unreacted monomers and the solvent to obtain ABS resin P2, and the properties thereof are shown in Table 3.

Example 3

• (1) 250 g Ethylbenzol werden mit 250 g Butadien vermischt und 4,2 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 30°C gegeben, während 4 min reagiert wird; dann werden 3,6 ml Methylbenzol-Lösung von Triisobutylaluminium (die Konzentration von Triisobutylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösung wird auf 80°C erhöht und die Mischung wird bei dieser Temperatur 100 min reagiert; 3,8 ml n-Hexan-Lösung von Siliciumtetrachlorid (die Konzentration von Siliciumtetrachlorid ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 80°C reduziert und die Mischung bei dieser Temperatur 30 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,4 MPa eingeführt, während bei dieser Temperatur 13 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A3 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 50 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 1 angegeben.
• (2) 250 g Ethylbenzol, 50 g Styrol und 200 g Butadien werden gemischt und 1,8 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 35°C für eine Reaktion für 5 min zugegeben; 1,5 ml Methylbenzol-Lösung von Triisobutylaluminium (Konzentration von Triisobutylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 80°C erhöht und die Mischung bei dieser Temperatur 110 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 70°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B3 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 50 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 2 angegeben.
• (3) Die Lösung A3 und die Lösung B3 werden bei einem Gewichtsverhältnis von 1:1 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C3. 40 g Zähigkeitsmittel C3, 120 g Styrol, 50 g Acrylnitril und 0,02 g Dibenzoylperoxid werden gemischt und die Mischung bei einer Temperatur von 105°C 1,5 h polymerisiert; die Temperatur der Reaktionslösung wird auf 125°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 155°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von ABS-Harz P3, und die Eigenschaften davon sind in Tabelle 3 angegeben.

This method is provided to describe this invention.

• (1) 250 g of ethylbenzene are mixed with 250 g of butadiene, and 4.2 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 30 ° C while 4 min reacts; then 3.6 ml of a methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solution is increased to 80 ° C. and the mixture is reacted at this temperature for 100 minutes; 3.8 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.4 MPa while maintaining at that temperature for 13 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A3 with polybutadiene rubber with a low cis content (the concentration of the polymers is 50% by weight). The molecular weight of the low-cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
• (2) 250 g of ethylbenzene, 50 g of styrene and 200 g of butadiene are mixed and 1.8 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 35 ° C added for reaction for 5 min; 1.5 ml of a methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 80 ° C. and the mixture is reacted at this temperature for 110 minutes. Finally, the temperature of the reaction solution is reduced to 70 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B3 of the linear butadiene-styrene copolymer (concentration of the polymers is 50% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in a unimodal distribution, and the specific properties are given in Table 2.
• (3) The solution A3 and the solution B3 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as a toughening agent C3. 40 g of toughening agent C3, 120 g of styrene, 50 g of acrylonitrile and 0.02 g of dibenzoyl peroxide are mixed and the mixture is polymerized at a temperature of 105 ° C. for 1.5 hours; the temperature of the reaction solution is increased to 125 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 155 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product is subjected to vacuum flashing to remove unreacted monomers and the solvent to obtain ABS resin P3, and the properties thereof are shown in Table 3.

Example 4

• (1) 250 g Ethylbenzol werden mit 250 g Butadien vermischt und 3,7 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 40°C gegeben, während 3 min reagiert wird; dann werden 3 ml Methylbenzol-Lösung von Triethylaluminium (die Konzentration von Triethylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösung wird auf 90°C erhöht und die Mischung wird bei dieser Temperatur 120 min reagiert; 7 ml n-Hexan-Lösung von Methyltrichlorsilan (die Konzentration von Methyltrichlorsilan ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 80°C reduziert und die Mischung bei dieser Temperatur 30 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,4 MPa eingeführt, während bei dieser Temperatur 13 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A4 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 50 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 1 angegeben.
• (2) 250 g Ethylbenzol, 40 g Styrol und 210 g Butadien werden gemischt und 3,4 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 5 min zugegeben; 2,7 ml Methylbenzol-Lösung von Triethylaluminium (Konzentration von Triethylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 80°C erhöht und die Mischung bei dieser Temperatur 120 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B4 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 50 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 2 angegeben.
• (3) Die Lösung A4 und die Lösung B4 werden bei einem Gewichtsverhältnis von 1:1 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C4. 40 g Zähigkeitsmittel C4, 130 g Styrol, 50 g Acrylnitril und 0,03 g tert-Butylperoxybenzoat werden gemischt und die Mischung bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von ABS-Harz P4, und die Eigenschaften davon sind in Tabelle 3 angegeben.

This method is provided to describe this invention.

• (1) 250 g of ethylbenzene are mixed with 250 g of butadiene, and 3.7 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while 3 min reacts; then 3 ml of methylbenzene solution of triethylaluminum (the concentration of triethylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 90 ° C. and the mixture is reacted at this temperature for 120 minutes; 7 ml of n-hexane solution of methyltrichlorosilane (the concentration of methyltrichlorosilane is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.4 MPa while maintaining at that temperature for 13 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A4 with polybutadiene rubber with a low cis content (the concentration of the polymers is 50% by weight). The molecular weight of the low-cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
• (2) 250 g of ethylbenzene, 40 g of styrene and 210 g of butadiene are mixed and 3.4 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C added for reaction for 5 min; 2.7 ml of methylbenzene solution of triethylaluminum (concentration of triethylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 80 ° C. and the mixture reacts at this temperature for 120 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being kept at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B4 of the linear butadiene-styrene copolymer (concentration of the polymers is 50% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in a unimodal distribution, and the specific properties are given in Table 2.
• (3) The solution A4 and the solution B4 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as the toughening agent C4. 40 g of toughening agent C4, 130 g of styrene, 50 g of acrylonitrile and 0.03 g of tert-butyl peroxybenzoate are mixed and the mixture is polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to obtain ABS resin P4, and the properties thereof are shown in Table 3.

Example 5

• (1) 250 g Ethylbenzol werden mit 250 g Butadien vermischt und 4,4 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 40°C gegeben, während 3 min reagiert wird; dann werden 3,5 ml Methylbenzol-Lösung von Triisobutylaluminium (die Konzentration von Triisobutylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösungsmittel wird auf 90°C erhöht und die Mischung wird bei dieser Temperatur 120 min reagiert; 4,4 ml n-Hexan-Lösung von Siliciumtetrachlorid (die Konzentration von Siliciumtetrachlorid ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 80°C reduziert und die Mischung bei dieser Temperatur 30 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A5 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 50 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 1 angegeben.
• (2) 250 g Ethylbenzol, 87,5 g Styrol und 162,5 g Butadien werden gemischt und 2 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 3 min zugegeben; 1,6 ml Methylbenzol-Lösung von Triisobutylaluminium (Konzentration von Triisobutylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 80°C erhöht und die Mischung bei dieser Temperatur 120 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B5 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 50 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 2 angegeben.
• (3) Die Lösung A5 und die Lösung B5 werden bei einem Gewichtsverhältnis von 1:1 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C5. 40 g Zähigkeitsmittel C5, 150 g Styrol, 40 g Acrylnitril und 0,02 g Dibenzoylperoxid werden gemischt und die Mischung bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von ABS-Harz P5, und die Eigenschaften davon sind in Tabelle 3 angegeben.

This method is provided to describe this invention.

• (1) 250 g of ethylbenzene are mixed with 250 g of butadiene, and 4.4 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while 3 min reacts; then 3.5 ml of a methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solvents is increased to 90 ° C. and the mixture is reacted at this temperature for 120 minutes; 4.4 ml of n-hexane solution of Silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A5 with polybutadiene rubber with a low cis content (the concentration of the polymers is 50% by weight). The molecular weight of the low-cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.
• (2) 250 g of ethylbenzene, 87.5 g of styrene and 162.5 g of butadiene are mixed and 2 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C added for reaction for 3 min; 1.6 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 80 ° C. and the mixture is reacted at this temperature for 120 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being kept at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B5 of the linear butadiene-styrene copolymer (concentration of the polymers is 50% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in a unimodal distribution, and the specific properties are given in Table 2.
• (3) The solution A5 and the solution B5 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as a toughening agent C5. 40 g of toughening agent C5, 150 g of styrene, 40 g of acrylonitrile and 0.02 g of dibenzoyl peroxide are mixed and the mixture is polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to obtain ABS resin P5, and the properties thereof are shown in Table 3.

Example 6

This example is given to describe this invention.

Following the procedure of Example 1, the difference being that in steps (1) and (2) carbon dioxide is replaced with isopropanol as a terminating agent, i.e. 0.2 g of isopropanol is added to the reaction system and held for 15 minutes .

An ethylbenzene polymer solution A6 of polybutadiene rubber having a low cis content (concentration of the polymer is 45% by weight) is obtained in step (1); and the molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the properties are shown in Table 1.

An ethylbenzene polymer solution B6 of the linear butadiene-styrene copolymer (concentration of the polymer is 45% by weight) is obtained in step (2); and the molecular weight of the linear butadiene-styrene copolymer is in unimodal distribution, and the properties are shown in Table 2.

ABS resin P6 is obtained in step (3) and the properties are shown in Table 3.

Comparative example 1

Following the procedure of Example 1, the difference being that in step (3) the toughening agent is only 40 g of solution A1 and that the amount of styrene is increased to 145 ° g in step (3) and after vacuum flashing ABS resin DP1 is obtained to remove the unreacted monomer and the solvent. The properties are given in Table 3.

Comparative example 2

Following the procedure of Example 1, the difference being that in step (3) the toughening agent is only 40 g of solution B1 and that the amount of styrene is increased to 135 g in step (3), and after vacuum flashing to Removal of the unreacted monomer and the solvent gives ABS resin DP1. The properties are given in Table 3.

Comparative example 3

Following the procedure of Example 1, the difference being that silicon tetrachloride is not added, to carry out a coupling reaction in step (1), whereby a polymer ethylbenzene solution DA1 of polybutadiene rubber having a low cis content (concentration of the polymer is 45% by weight) is obtained, and the molecular weight of the polybutadiene rubber having a low cis content in the solution is in a unimodal distribution. The specific properties are given in Table 1.

In step (3), A1 in the toughness agent is replaced with DA1, and thereby ABS resin DP3 is obtained; its properties are given in Table 3.

Comparative example 4

According to the method of Example 1, the difference being that in step (1) 275 g of ethylbenzene are mixed with 225 g of butadiene and 7.5 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 35 ° C while reacting for 3 minutes; 6.4 ml of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) are then added, and the temperature of the reaction solution is increased to 80 ° C. and the mixture is reacted at this temperature for 120 minutes; 9.2 ml of n-hexane solution of silicon tetrachloride (concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution DA2 made from polybutadiene rubber with a low cis content (the concentration of the polymers is 45% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.

In step (3), A1 is replaced with DA2, and thereby ABS resin DP4 is obtained. Its properties are given in Table 3.

Comparative example 5

According to the method of Example 1, the difference being that in step (1) 275 g of ethylbenzene are mixed with 225 g of butadiene and 2.7 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while reacting for 4 minutes; 2.2 ml of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) are then added, and the temperature of the reaction solution is increased to 90 ° C. and the mixture is reacted at this temperature for 80 minutes; 3.3 ml of n-hexane solution of silicon tetrachloride (concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 30 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution DA3 made of polybutadiene rubber with a low cis content (the concentration of the polymers is 45% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.

In step (3), A1 is replaced with DA3, and thereby ABS resin DP5 is obtained. Its properties are given in Table 3.

Comparative example 6

Following the procedure of Example 1, the difference being that in step (2) 275 g of ethylbenzene, 67.5 g of styrene and 157.5 g of butadiene are mixed and 4.7 ml of n-hexane solution of n-butyllithium (Concentration of n-butyllithium is 1 mol / l) is added into the mixture at 40 ° C while reacting for 3 minutes; then 4 ml of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) are added, and the temperature of the reaction solution is increased to 60 ° C. and the mixture is reacted at this temperature for 80 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution DB1 of linear butadiene-styrene copolymer (the concentration of the polymer is 45% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in unimodal distribution, and the specific properties are shown in Table 2.

In step (3), B1 is replaced with DB1, and thereby ABS resin DP6 is obtained. Its properties are given in Table 3.

Comparative example 7

Following the procedure of Example 1, the difference being that in step (2) 275 g of ethylbenzene are mixed with 67.5 g of styrene and 157.5 g of butadiene and 1.3 ml of n-hexane solution of n-butyllithium (Concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while reacting for 4 minutes; then 1 ml of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added, and the temperature of the reaction solution is increased to 90 ° C. and the mixture is reacted at this temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution DB2 of linear butadiene-styrene copolymer (the concentration of the polymer is 45% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in a unimodal distribution, and the specific properties are given in Table 2.

In step (3), B1 is replaced with DB2, and thereby ABS resin DP6 is obtained. Its properties are given in Table 3.

Comparative example 8

Following the procedure of Example 1 with the difference that in step (1) triisobutylaluminum is not used during the polymerization and the polymerization rate and the polymerization temperature cannot be controlled in the polymerization process; explosive polymerization occurs while a large amount of gel is generated. The supernatant is separated from the polymerization reaction system to obtain a polymeric ethylbenzene solution DA4 of the low cis polybutadiene rubber (concentration of the polymer is 45% by weight) and the molecular weight of the low cis polybutadiene rubber in the solution is in trimodal distribution and the properties are given in Table 1.

In step (3), A1 is replaced with DA4, and thereby ABS resin DP8 is obtained. The property parameters are given in Table 3.

Comparative example 9

Following the procedure of Example 1 with the difference that in step (1) ethylbenzene is replaced by the same amount of n-hexane. The reaction solution obtained is polymeric n-hexane solution DA5 made of polybutadiene rubber with a low cis content (concentration of the polymer is 45% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 1.

In step (3), the solvent is removed from DA5 via steam coagulation, the residue therein is dried in a plasticator and dissolved in ethylbenzene to obtain 45% by weight of ethylbenzene solution to replace A1 and ABS resin DP9 is obtained. The properties are given in Table 3.

Comparative example 10

Following the procedure of Example 1 with the difference that in step (2) triisobutylaluminum is not used during the polymerization and the polymerization rate and the polymerization temperature cannot be controlled in the polymerization process; explosive polymerization occurs while a large amount of gel is generated. The supernatant is separated from the polymerization reaction system to obtain a polymeric ethylbenzene solution DB3 of linear butadiene-styrene copolymer (concentration of the polymer is 45% by weight). The linear butadiene-styrene copolymer in the solution is in bimodal distribution and the properties are given in Table 2.

In step (3), B1 is replaced with DB3, and thereby ABS resin DP10 is obtained. The property parameters are given in Table 3.

Comparative Example 11

Following the procedure of Example 1 with the difference that in step (2) ethylbenzene is replaced by the same amount of n-hexane. The reaction solution obtained is polymer n-hexane solution DB4 made of linear butadiene-styrene copolymer (concentration of the polymer is 45% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in a unimodal distribution, and the specific properties are shown in Table 2.

In step (3), the solvent is removed from DB4 by steam coagulation, the residue therein is dried in a plasticator and dissolved in ethylbenzene to obtain 45% by weight of ethylbenzene solution to replace B1 and ABS resin DP11 is obtained. The properties are given in Table 3.

Comparative example 12

Following the procedure of Example 1 except that in step (3) A1 is replaced with DA4 made in Comparative Example 8, B1 is replaced with DB3 made in Comparative Example 10, and thereby ABS resin DP12 is obtained; the properties are given in Table 3.

Comparative example 13

Following the procedure of Example 1 with the difference that in step (3) the solvent is removed from DA5 and DB4 by steam coagulation, the rest therein is dried in the plasticizer, and dissolved in ethylbenzene to obtain 45% ethylbenzene solution, to replace A1 and B1 and ABS resin DP13 is obtained. The properties are given in Table 3. Table 1 No. High molecular weight component Low molecular weight component M _n M _w / M _n Content (wt.%) M _n M _w / M _n Content (wt.%) example 1 147000 1.76 92 46000 1.71 8th Example 2 173000 1.96 81 54000 1.92 19th Example 3 188000 1.90 72 59000 1.86 28 Example 4 185000 1.93 94 71000 1.89 6th Example 5 182000 1.89 74 57000 1.85 26th Example 6 147000 1.76 92 46000 1.71 8th Comparative example 3 / / / 46000 1.71 100 Comparative example 4 102000 1.76 91 32000 1.67 9 Comparative example 5 291000 2.03 93 91000 1.96 7th Comparative example 8 102000 + 155000 1.69 + 1.72 37 + 59 49000 1.64 4th Comparative example 9 165000 1.37 92 51000 1.32 7th Table 1 (continued) No. Polybutadiene rubber with a low cis content Content of the 1,2 structural unit (wt.%) Content of the cis-1,4 structural unit (% by weight) Mooney viscosity Gel content (ppm) M _w / M _n example 1 10.8 33.6 47 2 1.98 Example 2 11.2 34.1 52 6th 2.23 Example 3 10.7 33.8 58 2 2.36 Example 4 10.9 34.8 59 6th 2.08 Example 5 11.4 34.6 54 3 2.33 Example 6 10.8 33.6 47 0 1.98 Comparative example 3 10.8 33.6 17th 3 1.71 Comparative example 4 10.4 33.8 31 8th 1.91 Comparative example 5 10.6 33.8 92 4th 2.21 Comparative example 8 18.2 32.8 67 649 2.94 Comparative example 9 8.6 35.2 43 44 1.56 Table 2 No. M _n M _w / M _n Content of the styrene structural unit (wt.%) Content of the butadiene structural unit (wt.%) Content of the 1,2 structural unit (wt.%) Mooney viscosity Gel content (ppm) example 1 134000 1.84 29.9 70.1 10.2 131 3 Example 2 122000 1.94 25.1 74.9 10.9 117 0 Example 3 138000 1.93 20.2 79.8 10.1 108 0 Example 4 77000 1.87 16.1 83.9 10.3 51 3 Example 5 132000 1.92 34.9 65.1 10.7 126 2 Example 6 134000 1.84 29.9 70.1 10.2 131 2 Comparative example 6 52000 1.82 30.1 69.9 10.2 46 4th Comparative example 7 184000 1.99 30.2 69.8 10.8 162 2 Comparative example 10 136,000 (content 84 wt.%) +273,000 (content 16 wt.%) 1.69 + 1.71 (M _{w /} M _n of linear butadiene-styrene copolymer 1.99) 29.8 70.2 17.4 127 577 Comparative Example 11 147000 1.36 29.9 70.1 9.6 133 27 Table 3 No. Content of the butadiene structural unit (wt.%) Content of the styrene structural unit (wt.%) Content of the acrylonitrile structural unit (wt.%) M _w M _w / M _n Izod (J / m) (60 °) gloss example 1 9.4 69.2 21.4 282000 2.33 286 98 Reference example 1 8.6 70.3 21.1 246000 3.12 94 92 Example 2 14.1 62.6 23.3 226000 2.39 383 91 Example 3 11.5 61.5 27.0 259000 2.46 334 93 Example 4 11.6 63.9 24.5 214000 2.41 248 88 Example 5 11.0 70.2 18.8 184000 2.54 218 89 Example 6 9.4 69.2 21.4 276000 2.68 254 91 Comparative example 1 9.6 69.3 21.1 287000 2.41 213 74 Comparative example 2 9.1 69.4 21.5 163000 2.46 104 93 Comparative example 3 9.0 68.7 22.3 297000 2.51 127 92 Comparative example 4 8.9 69.4 21.7 267000 2.54 164 91 Table 3 (continued) No. Content of the butadiene structural unit (wt.%) Content of the styrene structural unit (wt.%) Content of the acrylonitrile structural unit (wt.%) M _w M _w / M _n Izod (J / m) (60 °) gloss Comparative example 5 9.6 69.1 21.3 194000 2.48 214 78 Comparative example 6 9.6 68.3 22.1 265000 2.64 139 88 Comparative example 7 9.3 69.6 21.1 238000 2.72 156 82 Comparative example 8 8.3 70.4 21.3 197000 2.92 114 82 Comparative example 9 9.1 69.7 21.2 251000 2.92 193 82 Comparative example 10 9.0 69.4 21.6 223000 3.17 173 79 Comparative Example 11 9.0 69.5 21.5 267000 2.86 194 77 Comparative example 12 7.2 71.2 21.6 178000 3.44 88 73 Comparative example 13 9.2 69.7 21.1 236000 2.91 151 72

Comparing Example 1 with Comparative Examples 1 to 7 and 12 to 13 and Reference Example 1, it can be seen that ABS resin using a combination of low cis polybutadiene rubber and linear butadiene-styrene copolymer as the toughness agent has improved impact resistance and has gloss.

Comparing Example 1 with Comparative Examples 8-11, it can be seen that the processes for making the low cis polybutadiene rubber and the linear butadiene-styrene copolymer of this invention show a well-controlled polymerization process and the polymer produced has a low gel strength. Has salary. The ABS resin using a combination of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer as a toughness agent has improved high impact strength and gloss. The prepared polymer solution from the polybutadiene rubber with low cis content and the prepared polymer solution from the linear butadiene-styrene copolymer can be used directly as a toughening agent for mixing with the polymeric monomers for the production of the ABS resin by free-radical polymerization reaction without solvent removal and again Dissolution can be used prior to carrying out the free radical polymerization reaction, obtaining in situ formation of the ABS resin.

Example 7

• (1) 300 g Ethylbenzol werden mit 200 g Butadien vermischt und 3,7 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 40°C gegeben, während 3 min reagiert wird; dann werden 3,1 ml Methylbenzol-Lösung von Triisobutylaluminium (die Konzentration von Triisobutylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösungsmittel wird auf 100°C erhöht und die Mischung wird bei dieser Temperatur 90 min reagiert; 4,6 ml n-Hexan-Lösung von Siliciumtetrachlorid (die Konzentration von Siliciumtetrachlorid ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 80°C reduziert und die Mischung bei dieser Temperatur 80 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 70°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A7 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 40 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 4 angegeben.
• (2) 300 g Ethylbenzol, 60 g Styrol und 140 g Butadien werden gemischt und 1,6 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 3 min zugegeben; 1,3 ml Methylbenzol-Lösung von Triisobutylaluminium (Konzentration von Triisobutylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 90°C erhöht und die Mischung bei dieser Temperatur 90 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B7 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 40 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 5 angegeben.
• (3) Die Lösung A7 und die Lösung B7 werden bei einem Gewichtsverhältnis von 1:1 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C7. 35 g Zähigkeitsmittel C7, 150 g Styrol und 0,02 g tert-Butylperoxy-2-ethylhexylcarbonat werden gemischt und die Mischung bei 300 Upm gerührt und bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei 100 Upm gerührt und bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von HIPS-Harz P7, und die Eigenschaften davon sind in Tabelle 6 angegeben.

This method is provided to describe this invention.

• (1) 300 g of ethylbenzene are mixed with 200 g of butadiene, and 3.7 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while 3 min reacts; then 3.1 ml of a methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solvents is increased to 100 ° C. and the mixture is reacted at this temperature for 90 minutes; 4.6 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 80 minutes. Finally, the temperature of the reaction solution is reduced to 70 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A7 with polybutadiene rubber with a low cis content (the concentration of the polymers is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
• (2) 300 g of ethylbenzene, 60 g of styrene and 140 g of butadiene are mixed and 1.6 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C added for reaction for 3 min; 1.3 ml of a methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 90 ° C. and the mixture is reacted at this temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being kept at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B7 of the linear butadiene-styrene copolymer (concentration of the polymers is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution, and the specific properties are shown in Table 5.
• (3) The solution A7 and the solution B7 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as a toughening agent C7. 35 g of toughening agent C7, 150 g of styrene and 0.02 g of tert-butylperoxy-2-ethylhexyl carbonate are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to obtain HIPS resin P7, and the properties thereof are shown in Table 6.

Reference example 2

According to step (3) of the procedure of Example 7, that is, during the production of HIPS resin, the toughening agent C7 is not used, and the amount of polymerized monomers and the solvent is adjusted as follows: 150 g of styrene, 14 g of butadiene and 18 g of ethylbenzene to obtain HIPS resin R2, and the properties are shown in Table 6.

Example 8

• (1) 275 g Ethylbenzol werden mit 225 g Butadien vermischt und 2,9 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 40°C gegeben, während 3 min reagiert wird; dann werden 2,4 ml Methylbenzol-Lösung von Triisobutylaluminium (die Konzentration von Triisobutylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösungsmittel wird auf 100°C erhöht und die Mischung wird bei dieser Temperatur 90 min reagiert; 2,4 ml n-Hexan-Lösung von Siliciumtetrachlorid (die Konzentration von Siliciumtetrachlorid ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 70°C reduziert und die Mischung bei dieser Temperatur 80 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 70°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,5 MPa eingeführt, während bei dieser Temperatur 20 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A8 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 45 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 4 angegeben.
• (2) 275 g Ethylbenzol, 56,2 g Styrol und 168,8 g Butadien werden gemischt und 2,6 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 3 min zugegeben; 2,2 ml Methylbenzol-Lösung von Triisobutylaluminium (Konzentration von Triisobutylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 100°C erhöht und die Mischung bei dieser Temperatur 90 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 70°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B8 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 45 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 5 angegeben.
• (3) Die Lösung A8 und die Lösung B8 werden bei einem Gewichtsverhältnis von 1:2 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C8. 40 g Zähigkeitsmittel C8, 170 g Styrol und 0,02 g tert-Butylperoxy-2-ethylhexylcarbonat werden gemischt und die Mischung bei 300 Upm gerührt und bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei 100 Upm gerührt und bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von HIPS-Harz P8, und die Eigenschaften davon sind in Tabelle 6 angegeben.

This method is provided to describe this invention.

• (1) 275 g of ethylbenzene are mixed with 225 g of butadiene and 2.9 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while 3 min reacts; then 2.4 ml of a methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solvents is increased to 100 ° C. and the mixture is reacted at this temperature for 90 minutes; 2.4 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 70 ° C. and the mixture is reacted at that temperature for 80 minutes. Finally, the temperature of the reaction solution is reduced to 70 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.5 MPa while maintaining at that temperature for 20 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A8 with polybutadiene rubber with a low cis content (the concentration of the polymers is 45% by weight). The molecular weight of the polybutadiene rubber with low cis in the solution is in bimodal distribution, and the specific properties are given in Table 4.
• (2) 275 g of ethylbenzene, 56.2 g of styrene and 168.8 g of butadiene are mixed, and 2.6 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture added at 40 ° C for reaction for 3 min; 2.2 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 100 ° C. and the mixture is reacted at this temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 70 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B8 of the linear butadiene-styrene copolymer (concentration of the polymers is 45% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution, and the specific properties are shown in Table 5.
• (3) The solution A8 and the solution B8 are mixed at a weight ratio of 1: 2 to obtain a mixed solution as a toughening agent C8. 40 g toughening agent C8, 170 g styrene and 0.02 g tert-butylperoxy-2-ethylhexyl carbonate are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to obtain HIPS resin P8, and the properties thereof are shown in Table 6.

Example 9

• (1) 250 g Ethylbenzol werden mit 250 g Butadien vermischt und 5,0 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 30°C gegeben, während 4 min reagiert wird; dann werden 10 ml Methylbenzol-Lösung von n-Butyl-sek-butylmagnesium (die Konzentration von n-Butyl-sek-butylmagnesium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösung wird auf 80°C erhöht und die Mischung wird bei dieser Temperatur 120 min reagiert; 6 ml n-Hexan-Lösung von Siliciumtetrachlorid (die Konzentration von Siliciumtetrachlorid ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 80°C reduziert und die Mischung bei dieser Temperatur 90 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,4 MPa eingeführt, während bei dieser Temperatur 13 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A9 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 50 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 4 angegeben.
• (2) 250 g Ethylbenzol, 50 g Styrol und 200 g Butadien werden gemischt und 1,5 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 3 min zugegeben; 3 ml Methylbenzol-Lösung von n-Butyl-sek-butylmagnesium (Konzentration von n-Butyl-sek-butylmagnesium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 100°C erhöht und die Mischung bei dieser Temperatur 90 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B9 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 50 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 5 angegeben.
• (3) Die Lösung A9 und die Lösung B9 werden bei einem Gewichtsverhältnis von 1:0,8 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C9. 40 g Zähigkeitsmittel C9, 170 g Styrol und 0,02 g Dibenzoylperoxid werden gemischt und die Mischung bei 300 Upm gerührt und bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei 100 Upm gerührt und bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von HIPS-Harz P9, und die Eigenschaften davon sind in Tabelle 6 angegeben.

This method is provided to describe this invention.

• (1) 250 g of ethylbenzene are mixed with 250 g of butadiene, and 5.0 ml of a n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 30 ° C while 4 min reacts; then 10 ml of methylbenzene solution of n-butyl-sec-butylmagnesium (the concentration of n-butyl-sec-butylmagnesium is 1 mol / l) is added and the temperature of the reaction solution is increased to 80 ° C and the mixture is at this Temperature reacts 120 min; 6 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.4 MPa while maintaining at that temperature for 13 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A9 with polybutadiene rubber with a low cis content (the concentration of the polymers is 50% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
• (2) 250 g of ethylbenzene, 50 g of styrene and 200 g of butadiene are mixed and 1.5 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C added for reaction for 3 min; 3 ml of methylbenzene solution of n-butyl-sec-butylmagnesium (concentration of n-butyl-sec-butylmagnesium is 1 mol / l) is added and the temperature of the reaction solution is increased to 100 ° C. and the mixture is kept at this temperature for 90 min responds. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being kept at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B9 of the linear butadiene-styrene copolymer (concentration of the polymers is 50% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution, and the specific properties are shown in Table 5.
• (3) The solution A9 and the solution B9 are mixed at a weight ratio of 1: 0.8 to obtain a mixed solution as a toughening agent C9. 40 g toughening agent C9, 170 g styrene and 0.02 g dibenzoyl peroxide are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to obtain HIPS resin P9, and the properties thereof are shown in Table 6.

Example 10

• (1) 300 g Ethylbenzol werden mit 200 g Butadien vermischt und 2,4 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 40°C gegeben, während 4 min reagiert wird; dann werden 2 ml Methylbenzol-Lösung von Triethylaluminium (die Konzentration von Triethtylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösung wird auf 100°C erhöht und die Mischung wird bei dieser Temperatur 90 min reagiert; 3,2 ml n-Hexan-Lösung von Methyltrichlorsilan (die Konzentration von Trichlorsilan ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 80°C reduziert und die Mischung bei dieser Temperatur 90 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A10 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 40 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 4 angegeben.
• (2) 300 g Ethylbenzol, 30 g Styrol und 170 g Butadien werden gemischt und 1,3 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 3 min zugegeben; 1 ml Methylbenzol-Lösung von Triisobutylaluminium (Konzentration von Triisobutylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 90°C erhöht und die Mischung bei dieser Temperatur 100 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 70°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B10 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 40 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 5 angegeben.
• (3) Die Lösung A10 und die Lösung B10 werden bei einem Gewichtsverhältnis von 1:1 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C10. 35 g Zähigkeitsmittel C10, 170 g Styrol und 0,02 g tert-Butylperoxy-2-ethylhexylcarbonat werden gemischt und die Mischung bei 300 Upm gerührt und bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei 100 Upm gerührt und bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von HIPS-Harz P10, und die Eigenschaften davon sind in Tabelle 6 angegeben.

This method is provided to describe this invention.

• (1) 300 g of ethylbenzene are mixed with 200 g of butadiene, and 2.4 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while 4 min reacts; then 2 ml of a methylbenzene solution of triethylaluminum (the concentration of triethylaluminum is 1 mol / l) is added and the temperature of the reaction solution is raised to 100 ° C. and the mixture is reacted at this temperature for 90 minutes; 3.2 ml of n-hexane solution of methyltrichlorosilane (the concentration of trichlorosilane is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C., and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain of the reaction solution as a polymeric ethylbenzene solution A10 with polybutadiene rubber having a low cis content (the concentration of the polymers is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
• (2) 300 g of ethylbenzene, 30 g of styrene and 170 g of butadiene are mixed and 1.3 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C added for reaction for 3 min; 1 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 90 ° C. and the mixture is reacted at this temperature for 100 minutes. Finally, the temperature of the reaction solution is reduced to 70 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B10 of the linear butadiene-styrene copolymer (concentration of the polymers is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution, and the specific properties are shown in Table 5.
• (3) The solution A10 and the solution B10 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as the toughening agent C10. 35 g of toughening agent C10, 170 g of styrene and 0.02 g of tert-butylperoxy-2-ethylhexyl carbonate are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to obtain HIPS resin P10, and the properties thereof are shown in Table 6.

Example 11

• (1) 300 g Ethylbenzol werden mit 200 g Butadien vermischt und 3,9 ml n-Hexan-Lösung von n-Butyllithium (die Konzentration von n-Butyllithium ist 1 mol/l) wird zu der Mischung bei 40°C gegeben, während 3 min reagiert wird; dann werden 3,1 ml Methylbenzol-Lösung von Triisobutylaluminium (die Konzentration von Triisobutylaluminium ist 1 mol/l) zugegeben und die Temperatur der Reaktionslösungsmittel wird auf 120°C erhöht und die Mischung wird bei dieser Temperatur 70 min reagiert; 4,3 ml n-Hexan-Lösung von Siliciumtetrachlorid (die Konzentration von Siliciumtetrachlorid ist 0,2 mol/l) wird zum Reaktionssystem gegeben, dann wird die Temperatur der Reaktionslösung auf 80°C reduziert und die Mischung bei dieser Temperatur 80 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 60°C reduziert und Kohlendioxidgas in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird das Einführen von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung A11 mit Polybutadien-Kautschuk mit niedrigem cis-Gehalt (die Konzentration der Polymere ist 40 Gew.%). Das Molekulargewicht des Polybutadien-Kautschuks mit niedrigem cis-Gehalt in der Lösung ist in bimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 4 angegeben.
• (2) 300 g Ethylbenzol, 80 g Styrol und 120 g Butadien werden gemischt und 2,0 ml n-Hexan-Lösung von n-Butyllithium (Konzentration von n-Butyllithium ist 1 mol/l) wird in die Mischung bei 40°C für eine Reaktion für 3 min zugegeben; 1,7 ml Methylbenzol-Lösung von Triisobutylaluminium (Konzentration von Triisobutylaluminium ist 1 mol/l) wird zugegeben und die Temperatur der Reaktionslösung wird auf 100°C erhöht und die Mischung bei dieser Temperatur 90 min reagiert. Schließlich wird die Temperatur der Reaktionslösung auf 70°C reduziert und Kohlendioxidgas wird in das Reaktionssystem bei einem Druck von 0,3 MPa eingeführt, während bei dieser Temperatur 15 min gehalten wird, und dann wird die Einfuhr von Kohlendioxid gestoppt, unter Erhalt der Reaktionslösung als polymere Ethylbenzol-Lösung B11 des linearen Butadien-Styrol-Copolymers (Konzentration der Polymere ist 40 Gew.%). Das Molekulargewicht des linearen Butadien-Styrol-Copolymers in der Lösung ist in unimodaler Verteilung, und die spezifischen Eigenschaften sind in Tabelle 5 angegeben.
• (3) Die Lösung A11 und die Lösung B11 werden bei einem Gewichtsverhältnis von 1:1 gemischt, unter Erhalt einer gemischten Lösung als Zähigkeitsmittel C11. 40 g Zähigkeitsmittel C11, 170 g Styrol und 0,02 g tert-Butylperoxy-2-ethylhexylcarbonat werden gemischt und die Mischung bei 300 Upm gerührt und bei einer Temperatur von 105°C 2 h polymerisiert; die Temperatur der Reaktionslösung wird auf 120°C erhöht und dann wird die Mischung bei dieser Temperatur 2 h polymerisiert, die Temperatur der Reaktionslösung wird auf 135°C erhöht und dann wird die Mischung bei 100 Upm gerührt und bei dieser Temperatur 2 h polymerisiert. Schließlich wird die Temperatur der Reaktionslösung auf 150°C erhöht und dann wird die Mischung bei dieser Temperatur für 2 h polymerisiert. Nach der Polymerisation wird mit dem Reaktionsprodukt ein Vakuum-Flashen durchgeführt, zur Entfernung von nicht-reagierten Monomeren und des Lösungsmittels, unter Erhalt von HIPS-Harz P11, und die Eigenschaften davon sind in Tabelle 6 angegeben.

This method is provided to describe this invention.

• (1) 300 g of ethylbenzene are mixed with 200 g of butadiene, and 3.9 ml of n-hexane solution of n-butyllithium (the concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C while 3 min reacts; then 3.1 ml of a methylbenzene solution of triisobutylaluminum (the concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solvents is raised to 120 ° C. and the mixture is reacted at this temperature for 70 minutes; 4.3 ml of n-hexane solution of silicon tetrachloride (the concentration of silicon tetrachloride is 0.2 mol / l) is added to the reaction system, then the temperature of the reaction solution is reduced to 80 ° C. and the mixture is reacted at that temperature for 80 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to obtain the reaction solution as polymeric Ethylbenzene solution A11 with polybutadiene rubber with a low cis content (the concentration of the polymers is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the specific properties are shown in Table 4.
• (2) 300 g of ethylbenzene, 80 g of styrene and 120 g of butadiene are mixed and 2.0 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40 ° C added for reaction for 3 min; 1.7 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is added and the temperature of the reaction solution is increased to 100 ° C. and the mixture is reacted at this temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 70 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while maintaining at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution B11 of the linear butadiene-styrene copolymer (concentration of the polymers is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in unimodal distribution, and the specific properties are shown in Table 5.
• (3) The solution A11 and the solution B11 are mixed at a weight ratio of 1: 1 to obtain a mixed solution as the toughening agent C11. 40 g of toughening agent C11, 170 g of styrene and 0.02 g of tert-butyl peroxy-2-ethylhexyl carbonate are mixed and the mixture is stirred at 300 rpm and polymerized at a temperature of 105 ° C. for 2 hours; the temperature of the reaction solution is increased to 120 ° C. and then the mixture is polymerized at this temperature for 2 hours, the temperature of the reaction solution is increased to 135 ° C. and then the mixture is stirred at 100 rpm and polymerized at this temperature for 2 hours. Finally, the temperature of the reaction solution is increased to 150 ° C. and then the mixture is polymerized at this temperature for 2 hours. After the polymerization, the reaction product is vacuum flashed to remove unreacted monomers and the solvent to obtain HIPS resin P11, and the properties thereof are shown in Table 6.

Comparative example 14

Following the procedure of Example 7 with the difference that in step (3) the toughening agent is only solution A7 and the amount of styrene is increased to 160 g in step (3) and after vacuum flashing to remove the unreacted monomer and the solvent is obtained HIPS resin DP14. The properties are given in Table 6.

Comparative example 15

Following the procedure of Example 7 with the difference that in step (3) the toughening agent is only solution B7 and the amount of styrene is reduced to 145 g in step (3) and after vacuum flashing to remove the unreacted monomer and the solvent is obtained HIPS resin DP15. The properties are given in Table 6.

Comparative example 16

Following the procedure of Example 7 except that silicon tetrachloride is not added to carry out a coupling reaction in step (1), thereby producing a polymeric ethylbenzene solution DA6 with polybutadiene rubber having a low cis content (the concentration of the polymer is 40% % By weight), and the molecular weight of the low-cis polybutadiene rubber is unimodal and the properties are shown in Table 4.

In step (3), A7 is replaced with DA7, and thereby HIPS resin DP16 is obtained. The property parameters are given in Table 6.

Comparative example 17

Following the procedure of Example 7 with the difference that in step (1) 5.0 ml of n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is added to the mixture at 40.degree while reacting for 5 min; then 4.2 ml of methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) are added and the temperature of the reaction solution is increased to 100 ° C .; and the mixture is reacted at this temperature for 80 minutes; 5.5 ml n-hexane solution of Silicon tetrachloride (concentration of silicon tetrachloride is 0.2 mol / l) is added into the reaction system, then the temperature of the reaction solution is reduced to 70 ° C. and the mixture is reacted at that temperature for 90 minutes. Finally, the temperature of the reaction solution is reduced to 60 ° C, and carbon dioxide gas is introduced into the reaction system at a pressure of 0.3 MPa while being held at that temperature for 15 minutes, and then the introduction of carbon dioxide is stopped to keep the reaction solution as polymeric ethylbenzene solution DA7 made of polybutadiene rubber with a low cis content (concentration of the polymers is 40% by weight). The molecular weight of the low-cis polybutadiene rubber in the solution in bimodal distribution and the specific properties are shown in Table 4.

In step (3), A7 is replaced with DA7, and thereby HIPS resin DP17 is obtained. The property parameters are given in Table 6.

Comparative example 18

Following the procedure of Example 7 except that in step (1) the amount of the n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is 2.2 ml, the amount of methylbenzene -Solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is 1.9 ml, the amount of n-hexane solution of silicon tetrachloride (concentration of silicon tetrachloride is 0.2 mol / l) is 2.2 ml and the obtained Reaction solution is polymeric ethylbenzene solution DA8 made of polybutadiene rubber with a low cis content (concentration of the polymer is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution in the solution, and the properties are shown in Table 4.

In step (3), A7 is replaced with DA8, and thereby HIPS resin DP18 is obtained. The property parameters are given in Table 6.

Comparative example 19

Following the procedure of Example 7 except that in step (2) the amount of the n-hexane solution of n-butyllithium (concentration of n-butyl lithium is 1 mol / l) is 4 ml, the amount of the methylbenzene solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is 3.5 ml and the resulting reaction solution is polymeric ethylbenzene solution DB5 made of linear butadiene-styrene copolymer (concentration of butadiene-styrene copolymer in the solution is 40% by weight) is. The molecular weight of the linear butadiene-styrene copolymer is in unimodal distribution in the solution and the properties are given in Table 5.

In step (3), B7 is replaced with DB5, and thereby HIPS resin DP19 is obtained. The property parameters are given in Table 6.

Comparative example 20

Following the procedure of Example 7 except that in step (2) the amount of the n-hexane solution of n-butyllithium (concentration of n-butyllithium is 1 mol / l) is 1.1 ml, the amount of methylbenzene Solution of triisobutylaluminum (concentration of triisobutylaluminum is 1 mol / l) is 0.85 ml and the resulting reaction solution is polymeric ethylbenzene solution DB6 of linear butadiene-styrene copolymer (concentration of butadiene-styrene copolymer in the solution is 40 wt. %) is. The molecular weight of the linear butadiene-styrene copolymer is in unimodal distribution in the solution and the properties are given in Table 5.

In step (3), B1 is replaced with DB6, and thereby HIPS resin DP20 is obtained. The property parameters are given in Table 6.

Comparative Example 21

Following the procedure of Example 7 except that in step (1) triisobutylaluminum is not used during the polymerization, and in the polymerization process the polymerization rate and the polymerization temperature cannot be controlled; explosive polymerization occurs while a large amount of gel is generated. The supernatant is separated from the polymerization reaction system to obtain a polymeric ethylbenzene solution DA9 of polybutadiene rubber having a low cis content (concentration of the polymer is 40% by weight). The molecular weight of the polybutadiene Rubber with low cis content in the solution is in trimodal distribution and the properties are given in Table 4.

In step (3), A7 is replaced with DA9, and thereby HIPS resin DP21 is obtained. The property parameters are given in Table 6.

Comparative Example 22

Following the procedure of Example 7 with the difference that in step (1) ethylbenzene is replaced by the same amount of n-hexane. The reaction solution obtained is polymeric n-hexane solution DA10 made of polybutadiene rubber with a low cis content (the concentration of the polymer is 40% by weight). The molecular weight of the low cis polybutadiene rubber in the solution is in bimodal distribution, and the properties are shown in Table 4.

In step (3), the solvent is removed from DA10 via steam coagulation, the residue therein is dried in the plasticizer and dissolved in ethylbenzene to obtain 40% by weight of ethylbenzene solution to replace A7, and HIPS resin DP22 is obtained. The property parameters are given in Table 6.

Comparative example 23

Following the procedure of Example 7 except that in step (2) triisobutylaluminum is not used during the polymerization, and in the polymerization process the polymerization rate and the polymerization temperature cannot be controlled; explosive polymerization occurs while a large amount of gel is generated. The supernatant is separated from the polymerization reaction system to obtain an ethylbenzene polymer solution DB7 of linear butadiene-styrene copolymer (concentration of the polymer is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in bimodal distribution and the properties are shown in Table 5.

In step (3), B7 is replaced with DB7, and thereby HIPS resin DP23 is obtained. The property parameters are given in Table 6.

Comparative example 24

Following the procedure of Example 7 with the difference that in step (2) ethylbenzene is replaced by the same amount of n-hexane. The reaction solution obtained is n-hexane polymer solution DB8 made of linear butadiene-styrene copolymer (the concentration of the polymer is 40% by weight). The molecular weight of the linear butadiene-styrene copolymer in the solution is in a unimodal distribution and the properties are shown in Table 5.

In step (3), the solvent is removed from DB8 by steam coagulation, the residue therein is dried in the plasticator and dissolved in ethylbenzene to obtain 40% by weight ethylbenzene solution to replace B7, and HIPS resin DP24 is obtained. The property parameters are given in Table 6.

Comparative Example 25

Following the procedure of Example 7 except that in step (3) A7 is replaced with DA9 made in Comparative Example 21, B7 is replaced with DB7 made in Comparative Example 23, and thereby HIPS resin DP25 is obtained. The properties are given in Table 6.

Comparative Example 26

Following the procedure of Example 7 with the difference that in step (3) the solvent of DA10, prepared in Comparative Example 22, and DB8, prepared in Comparative Example 24, is removed via steam coagulation, dried in a plasticizer and dissolved in ethylbenzene, under A 40% strength by weight benzene solution is obtained to replace A7 and B7, and HIPS resin DP26 is obtained. The properties are given in Table 6. Table 4 No. High molecular weight component Low molecular weight component M _n M _w / M _n Content (wt.%) M _n M _w / M _n Content (wt.%) Example 7 182000 1.82 93 57000 1.74 7th Example 8 259000 1.95 66 81000 1.91 34 Example 9 234000 1.97 84 73000 1.92 16 Example 10 229000 1.94 78 88000 1.89 22nd Example 11 169000 1.86 82 53000 1.81 18th Comparative example 16 / / / 57000 1.74 100 Comparative example 17 128000 1.73 82 40000 1.68 18th Comparative example 18 305000 1.97 72 95000 1.92 28 Comparative Example 21 187000+ 155000 1.79 + 1.72 34 + 58 58000 1.74 8th Comparative Example 22 197000 1.33 94 62000 1.27 6th Table 4 (continued) No. Polybutadiene rubber with a low cis content Content of the 1,2 structural unit (wt.%) Content of the cis-1,4 structural unit (% by weight) Mooney viscosity Gel content (ppm) M _w / M _n Example 7 12.1 36.4 59 4th 2.03 Example 8 12.3 35.8 62 7th 2.39 Example 9 9.7 35.3 59 6th 2.23 Example 10 12.7 35.9 66 0 2.26 Example 11 13.7 34.8 54 2 2.21 Comparative example 16 12.1 36.4 29 4th 1.74 Comparative example 17 12.8 35.6 31 2 1.97 Comparative example 18 13.3 35.4 78 6th 2.34 Comparative Example 21 17.8 34.1 72 588 2.91 Comparative Example 22 9.2 35.4 43 44 1.59 Table 5 No. M _n M _w / M _n Content of the styrene structural unit (wt.%) Content of the butadiene structural unit (wt.%) Content of the 1,2 structural unit (wt.%) Mooney viscosity Gel content (ppm) Example 7 136000 1.87 30.1 69.9 11.8 129 3 Example 8 124000 1.91 25.0 75.0 12.7 119 4th Example 9 147000 1.96 20.1 79.9 13.1 127 8th Example 10 158000 1.84 15.1 84.9 11.2 101 0 Example 11 106000 1.83 40.3 59.7 13.1 114 4th Comparative example 19 53000 1.67 30.1 69.9 11.2 57 0 Comparative example 20 214000 1.95 30.1 69.9 13.5 178 2 Comparative example 23 136,000 (content 82% by weight) +273,000 (content 18% by weight) 1.69 + 1.71 (M _w / M _n of linear butadiene-styrene copolymer 2.19) 30.2 69.8 17.4 148 613 Comparative example 24 144000 1.31 30.1 69.9 9.4 121 25th Table 6 No. Content of the butadiene structural unit (wt.%) Content of the styrene structural unit (wt.%) M _w M _w / M _n Impact strength (kJ / m ² ) (60 °) gloss Example 7 9.1 90.9 286000 2.56 14.6 86 Reference example 2 8.7 91.3 174000 3.21 8.1 66 Example 8 10.1 89.9 247000 2.48 15.4 84 Example 9 11.8 88.2 265000 2.66 16.7 82 Example 10 8.7 91.3 238000 2.61 12.2 71 Example 11 8.6 91.4 218000 2.57 11.3 82 Comparative example 14 9.9 90.1 196000 2.72 10.2 58 Comparative example 15 7.8 92.2 245000 2.48 7.6 82 Comparative example 16 9.0 91.0 252000 2.64 8.1 79 Comparative example 17 8.9 91.1 261000 2.56 9.7 77 Comparative example 18 9.2 90.8 273000 2.73 11.8 58 Table 6 (continued) No. Content of the butadiene structural unit (wt.%) Content of the styrene structural unit (wt.%) M _w M _w / M _n Impact strength (kJ / m ² ) (60 °) gloss Comparative example 19 8.9 91.1 221000 2.49 7.9 77 Comparative example 20 9.2 90.8 294000 2.69 9.1 67 Comparative Example 21 7.9 92.1 208000 3.04 7.1 62 Comparative Example 22 8.9 91.1 243000 2.84 11.8 69 Comparative example 23 8.4 91.6 244000 2.94 8.7 66 Comparative example 24 9.2 69.8 271000 2.73 12.1 62 Comparative Example 25 7.1 92.9 164000 3.47 5.4 48 Comparative Example 26 8.6 91.4 215000 2.91 10.3 58

Comparing Example 7 with Comparative Examples 15-20 and 25-26 and Reference Example 2, it can be seen that HIPS resin using a combination of low cis polybutadiene rubber and linear butadiene-styrene copolymer as the toughness agent apparently improved impact resistance and Has gloss.

Comparing Example 7 with Comparative Examples 21 to 24, it can be seen that the processes for making the low cis polybutadiene rubber and the butadiene-styrene linear copolymer of the invention exhibit a well controlled polymerization process and the polymer produced exhibits a low gel -Has content. The HIPS resin using a combination of the low cis polybutadiene rubber and the linear butadiene-styrene copolymer as a toughness agent has improved impact resistance and gloss. The polymer solution prepared from the polybutadiene rubber with low cis content and the polymer solution prepared from the linear butadiene-styrene copolymer can be used directly as a toughening agent for mixing with the polymeric monomers for the production of the HIPS resin by free-radical polymerization reaction without solvent removal and redissolution can be used before carrying out the free radical polymerization reaction, with in situ formation of the HIPS resin.

While this invention has been described in detail in some preferred embodiments, this invention is not limited thereto. Various simple variations, including combinations of the technical features in any appropriate manner, can be made in the technical scheme of this invention within the scope of the technical concept of this invention, and these simple variations and combinations are to be regarded as disclosures of this invention, which is within the scope of the invention belongs.

Claims (25)

Linear butadiene-styrene copolymer, the molecular weight of the linear butadiene-styrene copolymer being a number average molecular weight of 70,000 to 160,000 and a molecular weight distribution index of 1.55 to 2 in a unimodal distribution, based on the total amount of the linear butadiene -Styrene copolymer, a styrene structural unit content is 10 to 45% by weight and a butadiene-styrene unit content is 55 to 90% by weight and a 1,2-structural unit content is 8 to 14% by weight. Linear butadiene-styrene copolymer according to Claim 1 wherein, based on the total amount of the linear butadiene-styrene copolymer, a content of the 1,2 structural unit is 10 to 13.5% by weight. Linear butadiene-styrene copolymer according to Claim 1 or 2 wherein a Mooney viscosity of the butadiene-styrene linear copolymer is 50 to 150. Linear butadiene-styrene copolymer according to one of the Claims 1 to 3 wherein a gel content of the linear butadiene-styrene copolymer is below 20 ppm, preferably not more than 15 ppm, and preferably not more than 10 ppm, as measured by weight. A composition containing a linear butadiene-styrene copolymer and a low-cis polybutadiene rubber, wherein the linear butadiene-styrene copolymer is the linear butadiene-styrene copolymer according to any one of Claims 1 to 4th and the molecular weight of the low cis polybutadiene rubber in bimodal distribution is, the number average molecular weight of a low molecular weight component in the bimodal distribution is 42,000 to 90,000, a molecular weight distribution index is 1.55 to 2, the number average molecular weight is one The high molecular weight component in the bimodal distribution is 120,000 to 280,000 with a molecular weight distribution index of 1.55 to 2, with a content of the high molecular weight component being 60 to 95% by weight based on the total amount of the polybutadiene rubber with a low cis content. Composition according to Claim 5 wherein a molecular weight distribution index of the low cis polybutadiene rubber is 1.9 to 2.5. Composition according to Claim 5 or 6th wherein with respect to the total amount of the low cis polybutadiene rubber, a content of the 1,2 structural unit in the low cis polybutadiene rubber is 8 to 14% by weight. Composition according to one of the Claims 5 to 7th wherein a gel content of the low cis polybutadiene rubber is below 20 ppm, preferably not higher than 15 ppm, and more preferably not higher than 10 ppm, as measured by weight. Composition according to one of the Claims 5 to 8th wherein a Mooney viscosity of the low cis polybutadiene rubber is 30 to 70, preferably 40 to 70, and more preferably 45 to 70. Composition according to one of the Claims 5 to 9 wherein the low molecular weight component in the bimodal distribution is a linear polymer and the high molecular weight component in the bimodal distribution is a coupled polymer. Composition according to one of the Claims 5 to 10 wherein a weight ratio of the low cis polybutadiene rubber and the butadiene-styrene linear copolymer is 0.3-6: 1, preferably 0.4-5: 1, and more preferably 0.5-2: 1. Process for the preparation of the linear butadiene-styrene copolymer according to Claim 1 Containing the following steps: (1) under a condition of anionic initiation reaction, butadiene and styrene are subjected to initiation reaction in contact with an organic lithium initiator in alkylbenzene, (2) adding a blocking agent to a mixture obtained from the initiation reaction of step ( 1), and carrying out a polymerization reaction with the mixture containing the blocking agent in a condition of an anionic polymerization reaction, (3) contacting a mixture obtained from the polymerization reaction with a terminating agent to carry out a termination reaction to obtain the polymer solution, the linear Contains butadiene-styrene copolymer. Procedure according to Claim 12 wherein the total concentration of butadiene and styrene in the alkylbenzene is 30 to 60 wt%, preferably 35 to 55 wt%, and more preferably 40 to 55 wt%. Procedure according to Claim 12 or 13th wherein the alkylbenzene is one or more selected from the group consisting of methylbenzene, ethylbenzene and xylene. Method according to one of the Claims 12 to 14th , wherein the blocking agent is selected from one or more selected from the group consisting of an organic aluminum compound, organic magnesium compound and organic zinc compound, the organic aluminum compound preferably being one or more of compounds with the formula IV,

wherein R ₄ , R ₅ and R _{6 are} independently selected from C _1-8 alkyl; more preferably the organic aluminum compound is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum and triisobutylaluminum and is preferably selected from triethylaluminum and / or triisobutylaluminum, in which preferred the organic magnesium compound is one or more compounds with the formula V, R ₈ —Mg —— R ₇ Formula V wherein R ₇ and R _{8 are} independently selected from C _1-8 alkyl, more preferably the organic magnesium compound is one or more selected from the group consisting of di-n-butylmagnesium, di-sec-butylmagnesium, diisobutylmagnesium, di -tert-butylmagnesium and n-butyl-sec-butylmagnesium and preferably n-butyl-sec-butylmagnesium, in which the organic zinc compound is preferably one or more of compounds with the formula VI, R ₁₀ - Zn - R ₉ formula VI wherein R ₉ and R _{10 are} independently selected from C _1-8 alkyl, more preferably the organic zinc compound is one or more selected from the group consisting of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-secbutyl zinc, diisobutyl zinc and di-tert-butyl zinc and is preferably selected from diethyl zinc and / or di-n-butyl zinc, wherein the blocking agent is preferably the organic aluminum compound and the amount of the organic aluminum compound and the organic lithium initiator is a molar ratio of Al Element to Li element of 0.6-0.95: 1, preferably 0.7: 0.9: 1, preferably the blocking agent is the organic magnesium compound and the amount of the organic magnesium compound and the organic lithium Initiator enables a molar ratio of Mg element to Li element of 1-6: 1, preferably 2-4: 1, wherein the blocking agent is preferably a combination of the organic aluminum compound and the organic magnesium compound and the amount of the organic aluminum compound, the organic magnesium compound and the organic lithium initiator is a molar ratio of Al element to Mg element to Li element of 0.5-2: 1-5: 1, preferably 0.8-1: 1.5-3: 1, in which the blocking agent is preferably the organic zinc compound and the amount of organic zinc Compound and the organic lithium initiator allows a molar ratio of the Zn element to Li element of 1-6: 1, preferably 2-4: 1. Method according to one of the Claims 12 to 15th , wherein in step (1) the initiation reaction at 10 to 50 ° C, preferably 25 to 40 ° C and more preferably 30 to 40 ° C, at a time of the initiation reaction of 1 to 8 min, preferably 1 to 5 min, preferably 2 to 4.5 minutes and more preferably 3 to 4 minutes, in step (2) a temperature of the polymerization reaction 50 to 140 ° C, preferably 70 to 130 ° C and more preferably 80 to 120 ° C, a time of the polymerization reaction 60 to 150 min and preferably 70 to 120 min, in step (3) the terminating agent is carbon dioxide. An aromatic vinyl resin containing a structural unit derived from aromatic vinyl monomer and a structural unit derived from the toughening agent, wherein the toughening agent has the composition of any of Claims 5 to 11 is. Aromatic vinyl resin after Claim 17 wherein the aromatic vinyl resin is acrylonitrile-butadiene-styrene resin or high impact styrene resin. A method for producing an aromatic vinyl resin, comprising steps of mixing polymeric monomers containing aromatic vinyl monomer with a solution containing toughening agent to obtain a mixture and polymerizing the mixture, wherein the solution containing the toughening agent is a solution of linear butadiene-styrene Copolymer and a solution with polybutadiene rubber having a low cis content, the solution with linear butadiene-styrene copolymer being the polymer solution with linear butadiene-styrene copolymer obtained from the method according to one of the Claims 12 to 16 ; and the low-cis polybutadiene rubber solution is a low-cis polybutadiene rubber polymer solution prepared by a method including the steps of: (a) performing an initiation reaction of butadiene under a condition of an anionic initiation reaction Contacting with an organic lithium initiator in alkylbenzene, (b) adding a blocking agent to a mixture obtained from the initiation reaction of step (a) and performing a polymerization reaction on the mixture containing the blocking agent in a state of anionic polymerization reaction, (c ) Carrying out a coupling reaction on a mixture obtained from the polymerization reaction by contacting with a coupling agent; (d) contacting a mixture obtained from the coupling reaction with a terminating agent to carry out a termination reaction to obtain a polymer solution containing polybutadiene-Ka uchuk with low cis content. Procedure according to Claim 19 wherein in step (a) the concentration of butadiene in the alkylbenzene is 30 to 60% by weight, preferably 35 to 55% by weight, and more preferably 40 to 55% by weight. Procedure according to Claim 19 or 20th wherein in step (a) the alkylbenzene is one or more selected from the group consisting of methylbenzene, ethylbenzene and xylene. Method according to one of the Claims 9 to 21st , wherein in step (2) the blocking agent is one or more selected from the group consisting of organic aluminum compound, organic magnesium compound and organic zinc compound, the organic aluminum compound preferably being one or more of compounds having the formula IV is

wherein R ₄ , R ₅ and R _{6 are} independently selected from C _1-8 alkyl; more preferably the organic aluminum compound is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum and triisobutylaluminum and is preferably selected from triethylaluminum and / or triisobutylaluminum, in which preferred the organic magnesium compound is one or more compounds with the formula V, R ₈ —Mg —— R ₇ Formula V wherein R ₇ and R _{8 are} independently selected from C _1-8 alkyl, more preferably the organic magnesium compound is one or more selected from the group consisting of di-n-butylmagnesium, di-sec-butylmagnesium, diisobutylmagnesium, di -tert-butylmagnesium and n-butyl-sec-butylmagnesium and preferably n-butyl-sec-butylmagnesium, in which the organic zinc compound is preferably one or more of compounds with the formula VI, R ₁₀ - Zn - R ₉ formula VI wherein R ₉ and R _{10 are} independently selected from C _1-8 alkyl, more preferably the organic zinc compound is one or more selected from the group consisting of diethyl zinc, dipropyl zinc, di-n-butyl zinc, di-secbutyl zinc, diisobutyl zinc and di-tert-butyl zinc and is preferably selected from diethyl zinc and / or di-n-butyl zinc, wherein the blocking agent is preferably the organic aluminum compound and the amount of the organic aluminum compound and the organic lithium initiator is a molar ratio of Al Element to Li element of 0.6-0.95: 1, preferably 0.7: 0.9: 1, preferably the blocking agent is the organic magnesium compound and the amount of the organic magnesium compound and the organic lithium Initiator allows a molar ratio of Mg element to Li element of 1-6: 1, preferably 2-4: 1, wherein the blocking agent is preferably a combination of the organic aluminum compound and the organic magnesium compound and the Amount of the organic aluminum compound, the organic magnesium compound and the organic lithium initiator a molar ratio of Al element to Mg element to Li element of 0.5-2: 1-5: 1, preferably 0.8 -1: 1.5-3: 1 enables, in which the blocking agent is preferably the organic zinc compound and the amount of the organic zinc compound and the organic lithium initiator has a molar ratio of the Zn element to Li element of 1- 6: 1, preferably 2-4: 1. Method according to one of the Claims 19 to 22nd , wherein in step (a) the initiation reaction at 10 to 50 ° C, preferably 25 to 40 ° C and more preferably 30 to 40 ° C, at a time of the initiation reaction of 1 to 8 min, preferably 1 to 5 min, preferably 2 to 4.5 minutes and more preferably 3 to 4 minutes, in step (2) a temperature of the polymerization reaction 50 to 140 ° C, preferably 70 to 130 ° C and more preferably 80 to 120 ° C, a time of the polymerization reaction 60 to 150 min and preferably 70 to 120 min, in step (c) the coupling agent is tetrachlorosilane and / or methyltrichlorosilane, a temperature of the coupling reaction is 50 to 100 ° C and preferably 60 to 80 ° C, a time of the coupling reaction is 20 to 150 min and preferably 30 to 120 min is in step (d) the terminating agent is carbon dioxide. Method according to one of the Claims 19 to 23 wherein a weight ratio of the low cis polybutadiene rubber and the butadiene-styrene linear copolymer is 0.3-6: 1, preferably 0.4-5: 1, and more preferably 0.5-2: 1. Method according to one of the Claims 19 to 24 wherein the aromatic vinyl resin is acrylonitrile-butadiene-styrene resin or high impact styrene resin.