Toughener composition, method for preparing the same, and use thereof, abs resin and method for preparing the same

Abstract

The present application relates to the field of styrene resin, and discloses a toughening agent composition, a preparation method and application thereof, and ABS resin and a preparation method thereof.The toughening agent composition comprises low-cis polybutadiene rubber and linear butadiene-styrene copolymer, wherein the molecular weight of the low-cis polybutadiene rubber is bimodal distribution, the Mn1 of the low-molecular-weight component in the bimodal distribution is 30,000-40,000, and the ratio Mn2 / Mn1 of the high-molecular-weight component Mn2 to the low-molecular-weight component Mn1 is 5-6; the molecular weight of the linear butadiene-styrene copolymer is unimodal distribution, the number-average molecular weight is 100,000-140,000, and the weight ratio of the styrene segment to the butadiene segment in the linear butadiene-styrene copolymer is 0.53-0.82:1.The 5% styrene solution viscosity of the composition at 25 DEG C is extremely low, the Mooney viscosity is high, and the gel content is low, and ABS resin with good impact resistance and higher gloss and flowability can be obtained.

Description

Technical Field

[0001] This invention relates to the field of styrene resins, specifically to a toughening agent composition, its preparation method and application, and an ABS resin and its preparation method. Background Technology

[0002] Continuous bulk ABS resin is obtained by adding toughening agents to styrene and acrylonitrile monomers in a certain proportion, and then initiating the process using thermal or free radical initiation in the presence of a small amount of ethylbenzene solvent. Low-cis polybutadiene rubber and linear block styrene-butadiene copolymers have low gel content, are free of transition metals, have good color, exhibit random cis-trans distribution, no crystallization tendency, good low-temperature impact resistance, freely adjustable molecular weight, moderate 1,2-structural unit content, and high grafting and crosslinking reactivity, making them the preferred toughening rubbers for modifying continuous bulk ABS resin. ABS resin prepared using low-cis polybutadiene rubber as a single component as a toughening agent exhibits poor interfacial compatibility between the rubber particles and the styrene-acrylonitrile matrix resin, resulting in unsatisfactory impact resistance and gloss. ABS resin prepared using linear styrene-butadiene copolymer as a single component as a toughening agent demonstrates good interfacial compatibility and gloss, but the excessively high styrene content limits its impact resistance. To balance impact resistance and gloss, a two-component toughening process using low-cis polybutadiene rubber and linear styrene-butadiene copolymer is generally employed to improve the interfacial compatibility between the rubber and the matrix resin, while simultaneously increasing the rubber particle size distribution.

[0003] Low-cis polybutadiene rubber (LPB) employs branching technology to reduce its viscosity in a 5% styrene solution at 25°C. In existing technologies, the lower limit of the viscosity of LPB in a 5% styrene solution at 25°C is 20 centipoise; otherwise, the Mooney viscosity is too low for processing. To obtain ABS resin with high gloss, the viscosity of the 5% styrene solution of LPB and linear styrene-butadiene copolymer (LSB) should generally be as low as possible. To control the viscosity of the 5% styrene solution of LSB at 25°C, the styrene content of LSB is generally high. However, excessively high styrene content leads to excessively high Mooney viscosity, making feeding difficult during extrusion dehydration and expansion drying, resulting in long residence times, increased gel content, and difficulty in molding during briquetting, causing severe pulverization and compromising product quality.

[0004] CN109503900A discloses a toughening agent composition and its preparation method, as well as a styrene-based resin and its preparation method. The composition has a viscosity of 15-35 centipoise in a 5% by weight styrene solution at 25°C and a Mooney viscosity of 60-90 at 100°C. The low-cis polybutadiene rubber in the composition has a viscosity of 20-30 centipoise in a 5% by weight styrene solution at 25°C, and the linear styrene-butadiene copolymer in the composition has a viscosity of 15-35 centipoise in a 5% styrene solution.

[0005] CN107722402A discloses a toughening agent composition and ABS resin and its preparation method. The composition contains low-cis polybutadiene rubber and linear styrene-butadiene copolymer. The molecular weight of the low-cis polybutadiene rubber is bimodal, with the bimodal number-average molecular weights ranging from 40,000 to 75,000 and from 125,000 to 250,000, respectively. The number-average molecular weight of the linear styrene-butadiene copolymer is 70,000 to 200,000.

[0006] The toughening agent compositions disclosed in CN109503900A and CN107722402A have a number-average molecular weight ratio of less than 4 for the high molecular weight component to the low molecular weight component in the bimodal low-cis polybutadiene rubber. In order to achieve a balance between Mooney viscosity and solution viscosity, the viscosity of a 5% by weight styrene solution at 25°C is maintained above 20 centipoise, which still cannot meet the flowability requirements of high-performance ABS resin. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of existing technologies where the viscosity of a 5% styrene solution with toughening agents at 25°C is high, making it impossible to achieve a balance between solution viscosity and Mooney viscosity, and thus difficult to prepare ABS resins with higher flowability and gloss. This invention provides a toughening agent composition, its preparation method, its application, and ABS resin. This toughening agent composition features extremely low viscosity, high Mooney viscosity, and low gel content in a 5% styrene solution at 25°C. When used to prepare ABS resin, this toughening agent composition can produce ABS resins with good impact resistance, higher gloss, and better flowability.

[0008] Through in-depth research, the inventors of this invention discovered that the viscosity of a 5% styrene solution of toughening agent at 25°C is closely related to the particle size of the rubber particles formed during the phase inversion process, thus affecting the impact resistance, gloss, and melt flow index of ABS resin. The viscosity of a 5% styrene solution of low-cis polybutadiene rubber at 25°C is closely related to its molecular weight, degree of branching, and number of branched arms. The viscosity of a 5% styrene solution of linear styrene-butadiene copolymer at 25°C is closely related to its molecular weight, bound styrene content, and styrene sequence distribution. If the toughening rubber particle size is too small, it is not conducive to the termination of crazes and the induction of shear bands, resulting in poor impact resistance of the prepared ABS resin. If the toughening rubber particle size is too large, the number of rubber molecules per unit weight decreases, the probability of encountering cracks is low, the improvement in impact resistance is small, and the gloss of the ABS resin is also affected. By using the low-cis polybutadiene rubber with a specific number-average molecular weight and a bimodal distribution, and the linear styrene-butadiene copolymer with a specific number-average molecular weight, as a toughening agent, ABS resin can be prepared, thereby obtaining ABS resin with good impact resistance, higher gloss and flowability, thus completing the present invention.

[0009] To achieve the above objectives, the first aspect of the present invention provides a toughening agent composition, characterized in that the composition comprises low-cis polybutadiene rubber and linear styrene-butadiene copolymer, wherein the molecular weight of the low-cis polybutadiene rubber exhibits a bimodal distribution, wherein the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000-40,000, and the ratio Mn2 / Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is 5-6;

[0010] The linear styrene-butadiene copolymer has a unimodal molecular weight distribution with a number average molecular weight in the range of 100,000-140,000. In the linear styrene-butadiene copolymer, the weight ratio of styrene segments to butadiene segments is 0.53-0.82:1.

[0011] A second aspect of the present invention provides a method for preparing the above-mentioned toughening agent composition, the method comprising:

[0012] (1) In the presence of a first organic solvent, a first structure regulator and a first initiator, anionic solution polymerization of butadiene is carried out until butadiene is completely polymerized. After a coupling reaction is carried out by adding a 6-functional compound, a first terminator and a first antioxidant are added to obtain a low-cis polybutadiene solution.

[0013] (2) In the presence of a second organic solvent, a second initiator and optionally a second structure modifier, styrene and butadiene are subjected to a second anionic solution polymerization until styrene and butadiene are completely polymerized. Then, a second terminator and a second antioxidant are added to obtain a linear styrene-butadiene copolymer solution.

[0014] (3) The low-cis polybutadiene solution and the linear styrene-butadiene copolymer solution are mixed to obtain a composition solution;

[0015] (4) Remove the solvent from the composition solution to obtain colloidal particles, and dry the colloidal particles to obtain the composition.

[0016] A third aspect of the present invention provides a toughening agent composition prepared by the above-described preparation method.

[0017] A fourth aspect of the present invention provides the use of the above-described toughening agent composition in the preparation of ABS resin.

[0018] The fifth aspect of the present invention provides a method for preparing ABS resin, characterized in that styrene and acrylonitrile are copolymerized in the presence of a toughening agent composition to obtain the ABS resin;

[0019] The toughening agent composition is the toughening agent composition described above.

[0020] A sixth aspect of the present invention provides an ABS resin prepared by the above-described preparation method.

[0021] Through the above technical solutions, the toughening agent composition, its preparation method and application, and the ABS resin and its preparation method provided by the present invention achieve the following beneficial effects:

[0022] The toughening agent composition provided by the present invention contains low cis polybutadiene rubber with a specific number-average molecular weight and a bimodal distribution, and linear styrene-butadiene copolymer with a specific number-average molecular weight. When this toughening agent composition is used to prepare ABS resin, ABS resin with good impact resistance, gloss and higher flowability can be obtained. Detailed Implementation

[0023] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] In this invention, low-cis polybutadiene rubber refers to a polymer with a low content of structural units obtained by cis-1,4-polymerization, typically referring to polybutadiene rubber with a cis-1,4-structural unit content of 30-40% by weight. In this invention, linear styrene-butadiene copolymer refers to styrene-butadiene rubber with a linear molecular chain that simultaneously contains styrene blocks and random copolymer segments of styrene and butadiene.

[0025] The first aspect of the present invention provides a toughening agent composition, characterized in that the composition comprises low-cis polybutadiene rubber and linear styrene-butadiene copolymer, wherein the molecular weight of the low-cis polybutadiene rubber is bimodal, the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000-40,000, and the ratio of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution, Mn2 / Mn1, is 5-6;

[0026] The linear styrene-butadiene copolymer has a unimodal molecular weight distribution with a number average molecular weight in the range of 100,000-140,000. In the linear styrene-butadiene copolymer, the weight ratio of styrene segments to butadiene segments is 0.53-0.82:1.

[0027] In this invention, the toughening agent composition contains a low-cis polybutadiene rubber with a specific number-average molecular weight and a bimodal distribution, and a linear styrene-butadiene copolymer with a specific number-average molecular weight. The toughening system containing the above two components can obtain a toughened rubber with a wider particle size distribution and can improve the interfacial compatibility between the rubber and the resin. When this toughening agent composition is used to prepare ABS resin, it can significantly improve the overall performance of ABS resin. In particular, it can obtain ABS resin with good impact resistance, higher gloss and flowability.

[0028] According to the present invention, in the toughening agent composition, the weight ratio of styrene segments to butadiene segments is 0.13-0.39:1.

[0029] In this invention, when the weight ratio of styrene segments to butadiene segments is controlled to meet the above-mentioned range, the toughening agent composition can have a suitable Mooney viscosity and a styrene solution viscosity of 5% by weight at 25°C. When used to prepare ABS resin, the resulting ABS resin can have both excellent impact resistance and gloss.

[0030] In this invention, the butadiene segments in the toughening agent composition include butadiene segments from low-cis polybutadiene rubber and butadiene segments from linear styrene-butadiene copolymers.

[0031] Furthermore, in the toughening agent composition, the weight ratio of styrene segments to butadiene segments is 0.15-0.35:1, preferably 0.18-0.32:1.

[0032] According to the present invention, the toughening agent composition has a Mooney viscosity ML at 100°C. 1+4 Within the range of 50-100.

[0033] In this invention, the Mooney viscosity ML of the toughening agent composition at 100°C is controlled. 1+4Meeting the above-mentioned range ensures that the toughening agent composition has excellent processing properties, which in turn facilitates the extrusion dehydration and expansion drying of the toughening agent composition. When the Mooney viscosity of the toughening agent composition is too low, it is not conducive to the expansion during the drying process; when the Mooney viscosity of the toughening agent composition is too high, it is not conducive to processing and molding.

[0034] Furthermore, the toughening agent composition has a Mooney viscosity ML at 100°C. 1+4 Within the range of 55-95, more preferably within the range of 60-90.

[0035] According to the present invention, the viscosity of the toughening agent composition at 25°C as a 5% by weight styrene solution is in the range of 8-20 centipoise.

[0036] In this invention, when the viscosity of the toughening agent composition at 25°C is controlled to meet the above-mentioned range at 5% by weight of styrene solution, it can be ensured that the toughening agent composition has a smaller rubber particle size, thereby making the ABS resin made from the toughening agent composition have excellent gloss and flowability.

[0037] Furthermore, the viscosity of the toughening agent composition at 25°C as a 5% by weight styrene solution is in the range of 9-19 centipoise, preferably in the range of 10-18.

[0038] According to the present invention, the volatile content of the toughening agent composition is less than or equal to 1 wt%.

[0039] Furthermore, the volatile content of the toughening agent composition is less than or equal to 0.75 wt%, preferably less than or equal to 0.5 wt%.

[0040] According to the present invention, the gel content of the toughening agent composition is 0-150 ppm.

[0041] In this invention, when the gel content of the toughening agent composition is controlled to meet the above-mentioned range, the prepared ABS resin has higher gloss and better mechanical properties.

[0042] Furthermore, the gel content of the toughening agent composition is 0-100 ppm, preferably 0-75 ppm.

[0043] According to the present invention, the weight ratio of the low-cis polybutadiene rubber to the linear styrene-butadiene copolymer is 0.42-2.33:1.

[0044] In this invention, when the weight ratio of low-cis polybutadiene rubber to linear styrene-butadiene copolymer in the toughening agent composition meets the above-mentioned range, the toughening agent composition can have a more reasonable rubber particle size distribution. When used to prepare ABS resin, it can produce ABS resin with better overall performance.

[0045] Furthermore, the weight ratio of the low-cis polybutadiene rubber to the linear styrene-butadiene copolymer is 0.6-1.5:1.

[0046] Low cis polybutadiene rubber

[0047] In this invention, the molecular weight of the low-cis polybutadiene rubber exhibits a bimodal distribution, with the number-average molecular weight Mn1 of the low molecular weight component in the bimodal distribution ranging from 30,000 to 40,000, and the ratio of the number-average molecular weight Mn2 of the high molecular weight component to the number-average molecular weight Mn1 of the low molecular weight component in the bimodal distribution, Mn2 / Mn1, being 5-6.

[0048] In this invention, when the number-average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is controlled to meet the above-mentioned range, it can be ensured that the low cis polybutadiene rubber has the viscosity of a 5% by weight styrene solution at 25°C as described in this invention; when the ratio Mn2 / Mn1 of the number-average molecular weight Mn2 of the high molecular weight component and the number-average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is controlled to meet the above-mentioned range, it can be ensured that the low cis polybutadiene rubber has the Mooney viscosity as described in this invention.

[0049] According to the present invention, the molecular weight distribution index Mw1 / Mn1 of the low molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 1-1.1.

[0050] According to the present invention, the molecular weight distribution index Mw2 / Mn2 of the high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 1-1.1.

[0051] According to the present invention, the molecular weight distribution of the low cis polybutadiene rubber is 1.1-1.5, preferably 1.15-1.45.

[0052] According to the present invention, the weight ratio of the low molecular weight component to the high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 0.01-0.25:1.

[0053] In this invention, when the weight ratio of the low molecular weight component to the high molecular weight component of the low cis polybutadiene rubber is controlled to meet the above-mentioned range, it can be ensured that the low cis polybutadiene rubber has a suitable degree of branching and that the low cis polybutadiene rubber has excellent processing performance.

[0054] Furthermore, the weight ratio of the low molecular weight component to the high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 0.04-0.18:1.

[0055] According to the present invention, the 1,2-structure content is 6-16 wt% based on the total weight of the low cis polybutadiene rubber.

[0056] In this invention, the term "1,2-structural unit" refers to a structural unit formed by the 1,2-polymerization of butadiene, and the content of 1,2-structural units can also be referred to as vinyl content. In this invention, when the 1,2-structural unit content of the low-cis polybutadiene rubber is controlled to meet the above-mentioned range, using the low-cis polybutadiene rubber containing the above-mentioned vinyl content to prepare ABS resin can yield ABS resin with suitable grafting efficiency and rubber phase volume fraction, thereby improving the overall performance of the ABS resin.

[0057] Furthermore, based on the total weight of the low-cis polybutadiene rubber, the 1,2-structure content is 8-14 wt%.

[0058] According to the present invention, the Mooney viscosity ML of the low cis polybutadiene rubber at 100°C is... 1+4 Within the range of 38-58.

[0059] In this invention, when the Mooney viscosity of the low-cis polybutadiene rubber is controlled to meet the above-mentioned range, the low-cis polybutadiene rubber can have excellent processing properties, thereby enabling the ABS resin made from the toughening agent composition containing the low-cis polybutadiene rubber to have excellent gloss and flowability.

[0060] Furthermore, the Mooney viscosity ML of the low cis polybutadiene rubber at 100°C 1+4 Within the range of 42-54.

[0061] According to the present invention, the viscosity of the low-cis polybutadiene rubber in a 5% by weight styrene solution at 25°C is in the range of 8-20 centipoise.

[0062] In this invention, when the viscosity of a 5% by weight styrene solution of low-cis polybutadiene rubber at 25°C is controlled to meet the above-mentioned range, the low-cis polybutadiene rubber can have a smaller particle size, thereby enabling the ABS resin made from the toughening agent composition containing the low-cis polybutadiene rubber to have excellent gloss and flowability.

[0063] Furthermore, the viscosity of the low-cis polybutadiene rubber in a 5% by weight styrene solution at 25°C is in the range of 9-19 centipoise, preferably in the range of 10-18 centipoise.

[0064] Linear styrene-butadiene copolymer

[0065] In this invention, the linear styrene-butadiene copolymer has a unimodal molecular weight distribution with a number average molecular weight in the range of 100,000-140,000, and the weight ratio of styrene segments to butadiene segments in the linear styrene-butadiene copolymer is 0.53-0.82:1.

[0066] According to the present invention, in the linear styrene-butadiene copolymer, the weight ratio of styrene block to styrene non-block is 1.2-4:1.

[0067] In this invention, styrene block refers to the content of six or more consecutive styrene structural units in the styrene-butadiene copolymer molecular chain. In this invention, the weight ratio of styrene blocks to non-block styrene is determined by proton nuclear magnetic resonance spectroscopy.

[0068] In this invention, when the weight ratio of styrene blocks to styrene non-blocks in the linear styrene-butadiene copolymer meets the above-mentioned range, the linear styrene-butadiene copolymer can have both excellent Mooney viscosity and the viscosity of a styrene solution with 5% by weight at 25°C.

[0069] Furthermore, in the linear styrene-butadiene copolymer, the weight ratio of styrene block to styrene non-block is 1.4-3:1.

[0070] According to the present invention, the 1,2-structure content is 6-16 wt%, based on the total weight of the butadiene segments of the linear styrene-butadiene copolymer.

[0071] In this invention, the term "1,2-structural unit" refers to a structural unit formed by the 1,2-polymerization of butadiene, and the content of 1,2-structural units can also be referred to as vinyl content. By controlling the 1,2-structural unit content in the linear styrene-butadiene copolymer to meet the above-mentioned range, using a low-cis polybutadiene rubber containing the above-mentioned vinyl content to prepare ABS resin can yield an ABS resin with suitable grafting efficiency and rubber phase volume fraction, thereby improving the overall performance of the ABS resin.

[0072] Furthermore, based on the total weight of butadiene segments in the linear styrene-butadiene copolymer, the 1,2-structure content is 8-14 wt%.

[0073] According to the present invention, the molecular weight distribution of the linear styrene-butadiene copolymer is 1-1.1.

[0074] According to the present invention, the Mooney viscosity ML of the linear styrene-butadiene copolymer at 100°C is... 1+4 Within the range of 80-120.

[0075] In this invention, when the Mooney viscosity of the linear styrene-butadiene copolymer is controlled to meet the above-mentioned range, it can be ensured that the linear styrene-butadiene copolymer has excellent processing properties, thereby enabling the ABS resin made from the toughening agent composition containing the linear styrene-butadiene copolymer to have excellent gloss and flowability.

[0076] Furthermore, the Mooney viscosity ML of the linear styrene-butadiene copolymer at 100°C 1+4 Within the range of 90-110.

[0077] According to the present invention, the viscosity of the linear styrene-butadiene copolymer in a 5% by weight styrene solution at 25°C is in the range of 8-20 centipoise.

[0078] In this invention, when the viscosity of a 5% by weight styrene solution of linear styrene-butadiene copolymer at 25°C is controlled to meet the above-mentioned range, it can be ensured that the linear styrene-butadiene copolymer has a smaller particle size, thereby making the ABS resin made from the toughening agent composition containing the linear styrene-butadiene copolymer have excellent gloss and flowability.

[0079] Furthermore, the viscosity of the linear styrene-butadiene copolymer in a 5% by weight styrene solution at 25°C is in the range of 9-19 centipoise, more preferably in the range of 10-18 centipoise.

[0080] A second aspect of the present invention provides a method for preparing a toughening agent composition, characterized in that the preparation method includes the following steps:

[0081] (1) In the presence of a first organic solvent, a first structure regulator and a first initiator, butadiene is polymerized in a first anionic solution until butadiene is completely polymerized. Then, a 6-functional compound is added for coupling reaction. Finally, a first terminator and a first antioxidant are added to obtain a low-cis polybutadiene solution.

[0082] (2) In the presence of a second organic solvent, a second initiator and optionally a second structure modifier, styrene and butadiene are subjected to a second anionic solution polymerization until styrene and butadiene are completely polymerized. Then, a second terminator and a second antioxidant are added to obtain a linear styrene-butadiene copolymer solution.

[0083] (3) The low-cis polybutadiene solution and the linear styrene-butadiene copolymer solution are mixed to obtain a composition solution;

[0084] (4) Remove the solvent from the composition solution to obtain colloidal particles, and dry the colloidal particles to obtain the composition.

[0085] In this invention, the toughening agent composition described in the first aspect of this invention can be obtained by using the above preparation method.

[0086] According to the present invention, in step (1), the molecular weight of the low-cis polybutadiene rubber in the low-cis polybutadiene solution exhibits a bimodal distribution.

[0087] In the bimodal distribution, the number-average molecular weight Mn1 of the low molecular weight component is in the range of 30,000-40,000; the ratio of the number-average molecular weight Mn2 of the high molecular weight component to the number-average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is 5-6.

[0088] According to the present invention, the Mooney viscosity ML of the low-cis polybutadiene rubber in the low-cis polybutadiene solution at 100°C is... 1+4 Within the range of 38-58.

[0089] According to the present invention, the viscosity of the low-cis polybutadiene rubber in the low-cis polybutadiene solution at 25°C and 5% by weight of styrene solution is in the range of 8-20 centipoise.

[0090] According to the present invention, the number average molecular weight of the linear styrene-butadiene copolymer is in the range of 100,000-140,000, and the weight ratio of styrene segments to butadiene segments in the linear styrene-butadiene copolymer is 0.53-0.82:1.

[0091] According to the present invention, the Mooney viscosity ML of the linear styrene-butadiene copolymer at 100°C is... 1+4 Within the range of 80-120.

[0092] According to the present invention, the viscosity of the linear styrene-butadiene copolymer in a 5% by weight styrene solution at 25°C is in the range of 8-20 centipoise.

[0093] Low cis polybutadiene solution

[0094] According to the present invention, in step (1), the method for preparing the low-cis polybutadiene solution includes the following steps:

[0095] (a) In a first organic solvent, in the presence of a first initiator and a first structure modifier, 1,3-butadiene is subjected to a first anionic solution polymerization reaction until the conversion rate of 1,3-butadiene is above 99%, thereby obtaining polybutadiene active chains; wherein the molar ratio of 1,3-butadiene to the first initiator is 550-750:1.

[0096] (b) The active polybutadiene chain is coupled in the presence of a 6-functional coupling agent.

[0097] (c) After terminating the product of the coupling reaction in the presence of a first terminator, a first antioxidant is added to obtain the low-cis polybutadiene solution.

[0098] In this invention, the low-cis polybutadiene solution is prepared using the above method, and the low-cis polybutadiene rubber as described in this invention can be obtained.

[0099] According to the present invention, in step (a), the first anionic solution polymerization reaction causes 1,3-butadiene to polymerize into polybutadiene active chains with a number average molecular weight of 30,000-40,000, and in particular, the molecular weight distribution index of the polybutadiene active chains is 1-1.1.

[0100] According to the present invention, in step (a), the first organic solvent is an inert nonpolar solvent, preferably an alkane solvent and / or a cycloalkane solvent. Specifically, the alkane solvent is preferably at least one of C4-C8 alkane solvents, more preferably one or more of n-pentane, n-hexane, n-heptane, and isooctane. The cycloalkane solvent is preferably one or more of C4-C8 cycloalkane solvents, more preferably one or more of cyclopentane and / or cyclohexane.

[0101] In this invention, the amount of the first organic solvent can vary within a wide range. Preferably, based on the total weight of the first organic solvent and 1,3-butadiene, the content of 1,3-butadiene is 10-20% by weight.

[0102] In one specific embodiment of the present invention, the first organic solvent is a mixed solvent of cyclohexane and hexane, wherein the weight ratio of cyclohexane to hexane is 4-19:1.

[0103] In this invention, there is no particular limitation on the type of the first initiator; various organolithium initiators conventionally used in the preparation of polybutadiene rubber can be used. Preferably, the first initiator is of formula R. 1 The organolithium compound represented by Li, wherein R 1 The initiator is selected from C1-C10 alkyl groups; more preferably, the first initiator is one or more of n-butyllithium, sec-butyllithium, isobutyllithium, and tert-butyllithium, more preferably n-butyllithium and / or sec-butyllithium, and even more preferably n-butyllithium. The first initiator is added to the polymerization system in solution form. The solvent used to dissolve the first initiator can be one or more of hexane, cyclohexane, heptane, etc. There is no particular limitation on the amount of the solvent used. Preferably, the amount of solvent used results in a concentration of the first initiator solution of 0.1-1.0 mol / L.

[0104] According to the present invention, the amount of the first initiator can be reasonably selected according to the amount of monomer and the number average molecular weight of the low cis polybutadiene rubber to be obtained. The amount can vary within a wide range. Preferably, when the molar ratio of 1,3-butadiene to the first initiator is 550-750:1, the polybutadiene active chain obtained in step (a) can have the number average molecular weight described in the present invention, thereby making the obtained low cis polybutadiene rubber have the number average molecular weight required by the present invention.

[0105] According to the present invention, there is no particular limitation on the type of the first structure modifier, and conventional structure modifiers in the art can be used. Preferably, the first structure modifier is selected from ether compound structure modifiers and / or amine compound structure modifiers.

[0106] Preferably, the ether compound structure modifier is one or more of aliphatic monoethers, aliphatic polyethers, aromatic ethers, and cyclic ethers.

[0107] More preferably, the aliphatic monoether is one or more of aliphatic symmetrical monoether and aliphatic asymmetric monoether, the aliphatic symmetrical monoether is one or more of methyl ether, diethyl ether, propyl ether and butyl ether, and the aliphatic asymmetric monoether is methyl ethyl ether.

[0108] More preferably, the aliphatic polyether is one or more of aliphatic symmetrical polyether and aliphatic asymmetric polyether, the aliphatic symmetrical polyether is one or more of ethylene glycol diC1-C4 alkyl ether, diethylene glycol diC1-C4 alkyl ether and diethylene glycol diC1-C4 alkyl ether, preferably one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, and the aliphatic asymmetric polyether is ethylene glycol methyl ethyl ether and / or diethylene glycol methyl ethyl ether.

[0109] Preferably, the aromatic ether is anisole and / or diphenyl ether.

[0110] Preferably, the cyclic ether is one or more of tetrahydrofuran, tetrahydrofurfuryl C1-C4 alkyl ether, and 1,4-dioxane, and more preferably one or more of tetrahydrofuran, tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl propyl ether, tetrahydrofurfuryl isopropyl ether, tetrahydrofurfuryl butyl ether, and 1,4-dioxane.

[0111] Preferably, the amine compound structure modifier is one or more selected from N,N,N',N'-tetramethylethylenediamine, N,N-dimethyltetrahydrofurfurylamine, triethylamine, and tripropylamine.

[0112] In a preferred embodiment of the present invention, the structure modifier is one or more of tetrahydrofuran, tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl propyl ether, tetrahydrofurfuryl isopropyl ether, tetrahydrofurfuryl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol diethyl ether, more preferably one or more of tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, and tetrahydrofurfuryl propyl ether, and particularly preferably tetrahydrofurfuryl ethyl ether.

[0113] In this invention, in order to ensure that the vinyl content in the obtained low-cis polybutadiene rubber meets the range required by this invention while increasing the reaction rate of the toughening agent composition for preparing ABS resin, preferably, the molar ratio of the first structure adjustment to the first initiator is 0.02-2:1.

[0114] According to the present invention, in step (a), the first anionic solution polymerization reaction results in a conversion rate of 1,3-butadiene of 99% or more, for example, 99-100%; preferably, the conditions for the anionic solution polymerization reaction include: a temperature of 40-100°C, preferably 50-90°C; a time of 20-100 min, preferably 30-60 min; and a gauge pressure of 0.1-1 MPa, preferably 0.2-0.5 MPa.

[0115] According to the present invention, in step (b), the active chain of the polybutadiene is coupled in the presence of a 6-functional coupling agent, which enables the molecular weight of the obtained low-cis polybutadiene rubber to exhibit a bimodal distribution, wherein the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000-40,000, and the ratio Mn2 / Mn1 of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is 5-6.

[0116] Furthermore, the weight ratio of the low molecular weight component to the high molecular weight component in the bimodal distribution of the prepared low cis polybutadiene rubber is 0.01-0.25:1; and the molecular weight distribution of the low cis polybutadiene rubber is 1.1-1.5.

[0117] According to the present invention, the 6-functional group coupling agent is selected from at least one of hexachlorosilane, hexachloroethane, 1,1,1,3,3,3-hexachloropropane, triethyl glycerol, and trimethyl glycerol. To further improve the stability and reproducibility of the coupling reaction, preferably, the 6-functional group coupling agent is selected from hexachlorosilane and / or hexachloroethane.

[0118] According to the present invention, in step (b), the molar ratio of the coupling agent to the first initiator is 0.14-0.19:1.

[0119] In this invention, when the molar ratio of the coupling agent to the first initiator meets the above-mentioned range, the resulting low-cis polybutadiene rubber can have a more superior degree of branching, thereby obtaining an ideal Mooney viscosity.

[0120] Furthermore, the molar ratio of the coupling agent to the first initiator is 0.15-0.18:1.

[0121] According to the present invention, in step (b), the conditions for the coupling reaction include: a temperature of 40-100°C, a time of 15-40 min, and a gauge pressure of 0.1-1 MPa.

[0122] Further, in step (b), the conditions for the coupling reaction include: a temperature of 60-100℃, a time of 20-40 min, and a gauge pressure of 0.1-0.5 MPa.

[0123] In this invention, preferably, steps (a) and (b) are carried out in a protective atmosphere provided by one or more inert gases selected from nitrogen, neon and argon.

[0124] According to the present invention, in step (c), the coupling reaction and the polymerization reaction can be terminated by using a first terminator, thereby obtaining a polymerization solution of low cis polybutadiene rubber.

[0125] According to the present invention, in step (c), the first terminator is selected from one or more of C1-C4 alcohols, organic acids, and carbon dioxide, preferably one or more of isopropanol, stearic acid, citric acid, and carbon dioxide, and more preferably carbon dioxide. Using carbon dioxide to terminate the reaction allows it to react with metal ions in the polymerization system to form carbonates and separate from the polymer, thereby avoiding the color reaction of the metal ions and resulting in a product with lower color intensity. The carbon dioxide can be introduced into the reaction system in the form of a gas (e.g., carbon dioxide gas with a gauge pressure of 0.2-1 MPa (e.g., 0.3-0.6 MPa)) or in the form of a dry ice aqueous solution (e.g., a concentration of 0.1-5% by weight).

[0126] According to the present invention, preferably, the amount of the first terminator is 0.1-0.2 parts by weight relative to 100 parts by weight of 1,3-butadiene monomer.

[0127] In this invention, in order to improve the antioxidant properties of the obtained low-cis polybutadiene rubber, preferably, the method further includes: mixing the product obtained at the end of step (c) with a first antioxidant.

[0128] In this invention, there is no particular limitation on the type of the first antioxidant. Conventional antioxidants in the art can be used. For example, the first antioxidant is selected from one or more of the following: 4,6-di(octylthiomethyl)o-cresol (trade name: Antioxidant 1520), β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester (trade name: Antioxidant 1076), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (trade name: Antioxidant 4020), N-isopropylphenyl-N'-phenyl-p-phenylenediamine (trade name: Antioxidant 4010NA), and N-phenyl-2-naphthylamine (trade name: Antioxidant D). It is preferably a mixture of antioxidant 1520 and antioxidant 1076, especially a combination of antioxidant 1520 and antioxidant 1076 with a weight ratio of 0.5-5:1, preferably 1:1.

[0129] In this invention, the amount of the first antioxidant can vary within a wide range. Preferably, in step (c), the amount of the first antioxidant is 0.1-0.3 parts by weight relative to 100 parts by weight of 1,3-butadiene monomer.

[0130] Linear styrene-butadiene copolymer solution

[0131] According to the present invention, in step (2), the method for preparing the linear styrene-butadiene copolymer solution includes the following steps:

[0132] (i) In a second organic solvent, in the presence of a second initiator and optionally a second structure modifier, 1,3-butadiene and styrene are subjected to a second anionic solution polymerization reaction until the conversion rate of 1,3-butadiene and styrene is above 99%, to obtain an active chain of butadiene-styrene copolymer; preferably, the number average molecular weight of the active chain of butadiene-styrene copolymer is 100,000-140,000;

[0133] (ii) In the presence of a second terminator, after terminating the product of the second polymer anionic reaction, a second antioxidant is added to obtain a linear styrene-butadiene copolymer solution.

[0134] According to the present invention, the method for preparing the linear styrene-butadiene copolymer can obtain the linear styrene-butadiene copolymer of the present invention, and therefore the method is limited to a method that can obtain the above-mentioned linear styrene-butadiene copolymer of the present invention.

[0135] According to the present invention, the second anionic solution polymerization reaction in step (i) will yield an active chain of 1,3-butadiene and styrene copolymer, and the reaction process will be controlled to obtain a linear styrene-butadiene copolymer active chain with a number average molecular weight of 100,000-140,000, and in particular, the molecular weight distribution index of the linear styrene-butadiene copolymer active chain is 1.0-1.1.

[0136] According to the present invention, in step (i), the weight ratio of styrene to 1,3-butadiene is 0.53-0.82:1.

[0137] In this invention, in step (i), the type of the second initiator is not particularly limited, and various organolithium initiators conventionally used in the preparation of polybutadiene rubber in the art can be used. Preferably, the first initiator is of formula R. 1 The organolithium compound represented by Li, wherein R 1The first initiator is selected from C1-C10 alkyl groups; more preferably, it is one or more of n-butyllithium, sec-butyllithium, isobutyllithium, and tert-butyllithium, more preferably n-butyllithium and / or sec-butyllithium, and even more preferably n-butyllithium. The second initiator is added to the polymerization system in solution form. The solvent used to dissolve the second initiator can be one or more of hexane, cyclohexane, heptane, etc. There is no particular limitation on the amount of the solvent used, but preferably, the amount of solvent is such that the concentration of the second initiator solution is preferably 0.1-1.0 mol / L.

[0138] According to the present invention, the amount of the second initiator can be reasonably selected according to the amount of monomer and the number-average molecular weight of the linear styrene-butadiene copolymer to be obtained. The amount can vary within a wide range. Preferably, when the total molar amount of 1,3-butadiene and styrene is 1300-1900:1 with the molar amount of the first initiator, the butadiene-styrene active chain obtained in step (i) can have the number-average molecular weight described in the present invention, thereby making the obtained linear styrene-butadiene copolymer have the number-average molecular weight required by the present invention.

[0139] In this invention, the first initiator and the second initiator may be the same or different.

[0140] According to the present invention, there is no particular limitation on the type of the first structure modifier, and conventional structure modifiers in the art can be used. Preferably, the first structure modifier is selected from ether compound structure modifiers and / or amine compound structure modifiers.

[0141] Preferably, the ether compound structure modifier is one or more of aliphatic monoethers, aliphatic polyethers, aromatic ethers, and cyclic ethers.

[0142] More preferably, the aliphatic monoether is one or more of aliphatic symmetrical monoether and aliphatic asymmetric monoether, the aliphatic symmetrical monoether is one or more of methyl ether, diethyl ether, propyl ether and butyl ether, and the aliphatic asymmetric monoether is methyl ethyl ether.

[0143] More preferably, the aliphatic polyether is one or more of aliphatic symmetrical polyether and aliphatic asymmetric polyether, the aliphatic symmetrical polyether is one or more of ethylene glycol diC1-C4 alkyl ether, diethylene glycol diC1-C4 alkyl ether and diethylene glycol diC1-C4 alkyl ether, preferably one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, and the aliphatic asymmetric polyether is ethylene glycol methyl ethyl ether and / or diethylene glycol methyl ethyl ether.

[0144] Preferably, the aromatic ether is anisole and / or diphenyl ether.

[0145] Preferably, the cyclic ether is one or more of tetrahydrofuran, tetrahydrofurfuryl C1-C4 alkyl ether, and 1,4-dioxane, and more preferably one or more of tetrahydrofuran, tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl propyl ether, tetrahydrofurfuryl isopropyl ether, tetrahydrofurfuryl butyl ether, and 1,4-dioxane.

[0146] Preferably, the amine compound structure modifier is one or more selected from N,N,N',N'-tetramethylethylenediamine, N,N-dimethyltetrahydrofurfurylamine, triethylamine, and tripropylamine.

[0147] In a preferred embodiment of the present invention, the structure modifier is one or more of tetrahydrofuran, tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl propyl ether, tetrahydrofurfuryl isopropyl ether, tetrahydrofurfuryl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol diethyl ether, more preferably one or more of tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, and tetrahydrofurfuryl propyl ether, and particularly preferably tetrahydrofurfuryl ethyl ether.

[0148] In this invention, in order to ensure that the content of 1,2-structure and styrene block in the obtained linear styrene-butadiene copolymer meets the range required by this invention while improving the reaction rate of the toughening agent composition for preparing ABS resin, preferably, the molar ratio of the first structure modifier to the first initiator is 0.02-2:1.

[0149] In this invention, the first structure modifier and the second structure modifier may be the same or different.

[0150] According to the present invention, in step (i), the second organic solvent is an inert nonpolar solvent, preferably an alkane solvent and / or a cycloalkane solvent. Specifically, the alkane solvent is preferably at least one of C4-C8 alkane solvents, more preferably one or more of n-pentane, n-hexane, n-heptane, and isooctane. The cycloalkane solvent is preferably one or more of C4-C8 cycloalkane solvents, more preferably cyclopentane and / or cyclohexane.

[0151] In this invention, the amount of the second organic solvent can vary within a wide range. Preferably, based on the total weight of the second organic solvent, 1,3-butadiene, and styrene, the content of 1,3-butadiene and styrene is 10-20% by weight.

[0152] In this invention, the first organic solvent and the second organic solvent may be the same or different.

[0153] In one specific embodiment of the present invention, the second organic solvent is a mixed solvent of cyclohexane and hexane, wherein the weight ratio of cyclohexane to hexane is 4-19:1.

[0154] According to the present invention, in step (i), the second anionic solution polymerization reaction results in a conversion rate of 1,3-butadiene and styrene of 99% or more, for example, 99-100%; preferably, the conditions for the anionic solution polymerization reaction include: a temperature of 40-100°C, preferably 50-100°C; a time of 30-80 min, preferably 40-60 min; and a gauge pressure of 0.1-1 MPa, preferably 0.2-0.5 MPa.

[0155] In this invention, preferably, steps (i) and (ii) are carried out in a protective atmosphere provided by one or more inert gases selected from nitrogen, neon and argon.

[0156] According to the present invention, in step (ii), the polymerization reaction can be terminated by using a second terminator to obtain a polymerization solution of linear styrene-butadiene copolymer.

[0157] According to the present invention, in step (ii), the second terminator is selected from one or more of C1-C4 alcohols, organic acids, and carbon dioxide, preferably one or more of isopropanol, stearic acid, citric acid, and carbon dioxide, and more preferably carbon dioxide. Using carbon dioxide to terminate the reaction allows it to react with metal ions in the polymerization system to form carbonates and separate from the polymer, thereby avoiding the color reaction of the metal ions and resulting in a product with lower color intensity. The carbon dioxide can be introduced into the reaction system in the form of a gas (e.g., carbon dioxide gas with a gauge pressure of 0.2-1 MPa (e.g., 0.3-0.6 MPa)) or in the form of a dry ice aqueous solution (e.g., a concentration of 0.1-5% by weight).

[0158] According to the present invention, preferably, the amount of the second terminator is 0.1-0.2 parts by weight relative to the total amount of 1,3-butadiene monomer and styrene monomer used.

[0159] In this invention, the first terminator and the second terminator may be the same or different.

[0160] In this invention, in order to improve the antioxidant properties of the obtained linear styrene-butadiene rubber, preferably, the method further includes: mixing the product obtained at the end of step (ii) with a second antioxidant.

[0161] In this invention, there is no particular limitation on the type of the second antioxidant. Conventional antioxidants in the art can be used. For example, the second antioxidant is selected from one or more of the following: 4,6-bis(octylthiomethyl)o-cresol (trade name: Antioxidant 1520), β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester (trade name: Antioxidant 1076), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (trade name: Antioxidant 4020), N-isopropylphenyl-N'-phenyl-p-phenylenediamine (trade name: Antioxidant 4010NA), and N-phenyl-2-naphthylamine (trade name: Antioxidant D). It is preferably a mixture of antioxidant 1520 and antioxidant 1076, especially a combination of antioxidant 1520 and antioxidant 1076 with a weight ratio of 0.5-5:1, preferably 1:1.

[0162] In this invention, the amount of the second antioxidant can vary within a wide range. Preferably, in step (ii), the amount of the second antioxidant is 0.1-0.3 parts by weight relative to the total amount of 100 parts by weight of 1,3-butadiene and styrene.

[0163] In this invention, the first antioxidant and the second antioxidant may be the same or different.

[0164] According to the present invention, in step (3), the amount of the low cis polybutadiene solution and the linear styrene-butadiene copolymer solution is such that the weight ratio of the low cis polybutadiene rubber and the linear styrene-butadiene copolymer in the composition is 0.42-2.33:1, preferably 0.6-1.5:1.

[0165] According to the present invention, in step (4), the moisture content of the colloid particles is 40-60 wt%.

[0166] In this invention, there are no particular limitations on the method for removing the solvent from the composition solution; for example, steam condensation can be used.

[0167] According to the present invention, the volatile matter content of the toughening agent composition is less than or equal to 1 wt%.

[0168] A third aspect of the present invention provides a toughening agent composition prepared by the above-described preparation method.

[0169] A fourth aspect of the present invention provides the use of the above-described plasticizer composition in the preparation of ABS resin.

[0170] The fifth aspect of the present invention provides a method for preparing ABS resin, characterized in that styrene and acrylonitrile are copolymerized in the presence of a toughening agent composition to obtain the ABS resin;

[0171] The toughening agent composition is the toughening agent composition described above.

[0172] A sixth aspect of the present invention provides an ABS resin prepared by the above-described preparation method.

[0173] The present invention will be described in detail below through embodiments.

[0174] In the following examples and comparative examples, the monomer conversion rate was determined by gravimetric method, which is the weight percentage of the polymer after solvent removal to the theoretical polymer yield.

[0175] The contents of 1,2-polymeric structural units, 1,4-polymeric structural units, styrene content, styrene block content, and styrene non-block content in low-cis polybutadiene rubber and linear styrene-butadiene copolymer were measured using a Bruker AVANCE400 superconducting nuclear magnetic resonance spectrometer (1H-NMR). The resonance frequency of the 1H nucleus was 300.13 MHz, the spectral width was 2747.253 Hz, the pulse width was 5.0 μs, the data point was 16 K, the sample tube diameter was 5 mm, the solvent was deuterated chloroform (CDCl3), the sample concentration was 15% (W / V), the test temperature was room temperature, the number of scans was 16, and the chemical shift of tetramethylsilane was 0 ppm for calibration.

[0176] Molecular weight and molecular weight distribution were determined using an HLC-8320 gel permeation chromatograph from Tosoh Corporation, Japan. The test conditions included: TSKgel SuperMultipore HZ-N column, TSKgel SuperMultipore HZ standard column, chromatographic grade THF solvent, polystyrene as calibration standard, sample concentration of 1 mg / ml, injection volume of 10.00 μl, flow rate of 0.35 ml / min, and test temperature of 40.0 °C.

[0177] The viscosity of a styrene solution containing 5% by weight of rubber at 25℃ was determined using the enterprise standard Q / SH3155.SXL.C26-2019 of Beijing Yanshan Petrochemical Company, and was measured at a constant temperature of 25℃ using a Finch viscometer.

[0178] Mooney viscosity was measured using a GT-7080-S2 Mooney viscometer manufactured by Gotech Corporation of Taiwan, in accordance with GB / T1232.1 standard. The preheating time was 1 min, the rotation time was 4 min, and the test temperature was 100℃.

[0179] The melt flow index of ABS resin was measured according to GB / T3682.1-2018 standard, the notched impact strength of cantilever beam (23℃) was measured according to GB / T1843-2018 standard, and the 60° gloss was determined according to GB / T8807-2018 standard.

[0180] All pressures of carbon dioxide listed below refer to gauge pressure.

[0181] Cyclohexane and hexane were provided by Sinopharm Reagent Company, polymer grade, and soaked in molecular sieves until the water content was below 10 ppm; butadiene was provided by Yanshan Petrochemical, polymer grade; THF was provided by Sinopharm Reagent Company, chromatographic grade, and soaked in molecular sieves for more than 15 days after being diluted 10 times with hexane, and the amount used in the system was based on the pure substance; tetrahydrofurfuryl ether was provided by Sinopharm Reagent Company, analytical grade, and soaked in molecular sieves for more than 15 days after being diluted 20 times with hexane, and the amount used in the system was based on the pure substance; n-butyllithium was provided by Bailingwei Reagent Co., Ltd., 1.6 mol.L -1 Dilute to 0.4 mol / L -1 Hexachloroethane was provided by Inokai Reagents, analytical grade, diluted to 0.1 mol / L. -1 Antioxidants 1520 and 1076 were provided by Sinopharm Reagent Company and diluted to a mass concentration of 10%. The amount used in the system was calculated based on the pure substance.

[0182] Polybutadiene rubber 720AX was purchased from Asahi Kasei Corporation of Japan. Structural parameters are detailed in Table 2.

[0183] Linear styrene-butadiene copolymer 1322 was purchased from Dynasol in Mexico. Its structural parameters are detailed in Table 4.

[0184] Example 1

[0185] This embodiment illustrates the toughening agent composition and its preparation method of the present invention.

[0186] (1) Under nitrogen protection, nonpolar hydrocarbon solvents, 1,3-butadiene monomers, and structure modifiers (types and amounts are shown in Table 1, all amounts listed in the table are measured as pure compounds) are added to the reactor. After heating to the specified temperature, an organolithium initiator (types and amounts are shown in Table 1, all amounts listed in the table are measured as pure compounds) is added. Then, anionic solution polymerization is carried out at the specified temperature and pressure (reaction temperature 90℃, time 30min, pressure 0.3MPa) until the 1,3-butadiene monomer is completely converted. Then, a coupling agent (type of...) is added to the product of the anionic solution polymerization reaction. The types and amounts of the compounds are shown in Table 1 (all amounts listed in the table are measured as pure compounds). The coupling reaction was carried out at a specified temperature and pressure (coupling reaction temperature 80℃, time 30min, pressure 0.3MPa). The coupling reaction was terminated by a terminator (the types and amounts of which are shown in Table 1). Then, an antioxidant (1.2g of a combination of 1520 and 1076 in a weight ratio of 1:1) was added and mixed to obtain a low-cis polybutadiene rubber polymerization solution LCBR1. A portion of the obtained LCBR1 polymerization solution was subjected to steam condensation desolventizing treatment and dried. The structure and properties were then determined, and the results are shown in Table 2.

[0187] (2) Under nitrogen protection, nonpolar hydrocarbon solvent, 1,3-butadiene monomer, styrene monomer and structure modifier (type and amount are shown in Table 3, and the amounts listed in the table are all measured by pure compounds) were added to the reactor. After heating to the specified temperature, an organolithium initiator (type and amount are shown in Table 3, and the amounts listed in the table are all measured by pure compounds) was added. Then, anionic solution polymerization reaction was carried out at the specified temperature and reaction pressure (polymerization temperature is 90℃, polymerization time is 60min, polymerization pressure is 0.3MPa) until the 1,3-butadiene and styrene monomers were completely converted. The polymerization reaction was terminated by a terminator (type and amount are shown in Table 3). Then, an antioxidant (1.2g of a combination antioxidant of 1520 and 1076 in a weight ratio of 1:1) was added and mixed to obtain the linear styrene-butadiene copolymer polymerization solution LBS1. Part of the obtained LBS1 polymerization solution was subjected to steam condensation desolventizing treatment and dried. The structure and properties were measured, and the results are shown in Table 4.

[0188] (3) The LCBR1 solution and LBS1 solution were mixed at a weight ratio of 1:1 to obtain the toughening agent composition solution ZHW1. The obtained ZHW1 polymerization solution was subjected to steam condensation desolventizing treatment and dried, and its structure and properties were measured. The results are shown in Table 5.

[0189] Examples 2-9

[0190] This embodiment illustrates the toughening agent composition and its preparation method.

[0191] According to the method described in Example 1, except that the parameters shown in Tables 1 and 3 were used for the reaction to obtain LCBR2, LCBR3, LBS2, LBS3, LBS4, and LBS5, respectively. The structure and properties of the obtained polymers were measured, and the results are shown in Tables 2 and 4. Then, LCBR and LBS were mixed according to the weight ratio shown in Table 5 to obtain the toughening agent composition ZHW2-9. The obtained ZHW1 polymerization solution was subjected to steam condensation desolventizing treatment and dried, and the structure and properties were measured, and the results are shown in Table 5.

[0192] Table 1 (Low cis polybutadiene rubber)

[0193] Solvent cyclohexane / g 2300 2300 2300 1,3-Butadiene / g 374 374 374 n-Butyllithium / nmol 10.5 12.0 9.5 Butadiene / n-Butyllithium 660 577 729 Structure modifier / g 0.2% tetrahydrofurfuryl alcohol ethyl ether 0.2% tetrahydrofurfuryl alcohol ethyl ether 0.2% tetrahydrofurfuryl alcohol ethyl ether Structure modifier / n-butyllithium 0.15 0.13 0.16 Coupling agent hexachloroethane / nmol 1.83 2.18 1.59 Coupling agent / n-butyllithium 0.17 0.18 0.17 Terminator: carbon dioxide, g 0.5 0.5 0.5

[0194] Table 2 (Low cis polybutadiene rubber)

[0195] Low molecular weight component Mn1 / 10,000 3.6 3.1 4.0 4.8 Low molecular weight components Mw1 / Mn1 1.03 1.03 1.03 1.03 Low molecular weight components / wt% 4 2 8 8 Polymer component Mn2 / 10,000 19.1 16.5 21.1 15.8 High molecular weight component Mw2 / Mn2 1.04 1.04 1.05 1.04 High molecular weight component / wt% 96 98 92 92 Mn2 / Mn1 5.31 5.32 5.28 3.29 Low molecular weight component weight / high molecular weight component weight 0.042 0.020 0.087 0.087 Mw / Mn 1.17 1.12 1.19 1.24 1,2-Structure Content / wt% 12.2 12.1 12.6 12.4 5% styrene solution viscosity / cp 15.4 11.7 15.8 24.6 Mooney viscosity 52 46 49 37 Gel content / ppm 28 41 47 54

[0196] Table 3 (Linear styrene-butadiene copolymer)

[0197] Cyclohexane / g 2300 2300 2300 2300 2300 1,3-Butadiene / g 225 225 225 240 210 Styrene / g 150 150 150 135 165 n-Butyllithium / nmol 3.2 3.7 2.8 3.2 3.2 Structure modifier / g Tetrahydrofuran 0.2 Tetrahydrofuran 0.2 0.1% Tetrahydrofurfuryl alcohol ethyl ether - 0.1% Tetrahydrofurfuryl alcohol ethyl ether Carbon dioxide / g 0.2 0.2 0.2 0.2 0.2

[0198] Table 4 (Linear styrene-butadiene copolymer)

[0199] Number average molecular weight / 10,000 11.9 10.2 13.6 12.0 12.1 14.8 Molecular weight distribution 1.07 1.06 1.05 1.08 1.08 1.17 Styrene content / wt% 40.2 40.1 40.2 36.2 44.3 31.3 Styrene segment / butadiene segment 0.67 0.67 0.67 0.57 0.80 0.46 Block styrene content / wt% 28.4 28.8 23.9 25.7 28.1 23.8 Styrene non-block content / wt% 11.8 11.3 16.3 10.5 16.2 7.5 Styrene block / styrene non-block 2.41 2.55 1.47 2.45 1.73 3.17 1,2-Structure Content / wt% 9.8 9.6 12.8 7.8 12.6 8.2 Mooney viscosity 98 86 107 83 117 131 5% styrene solution viscosity / cp 13.7 10.4 17.2 14.8 11.3 24.2

[0200] Table 5

[0201]

[0202] Application Example 1

[0203] This application example illustrates the ABS resin and its preparation method of the present invention.

[0204] 25g of toughening agent composition ZHW1 was mixed with 130g of styrene, 50g of acrylonitrile, 20g of ethylbenzene and 0.02g of benzoyl peroxide and polymerized at 110℃ for 2h, 120℃ for 2h, 140℃ for 2h and 160℃ for 2h. The reaction product was then subjected to vacuum flash evaporation to remove unreacted monomers and solvents to obtain ABS1 resin. The structure and properties were then determined, and the results are shown in Table 6.

[0205] Application Example 2-9

[0206] ABS resin was prepared using the method shown in Application Example 1, except that ZHW2-ZHW9 was used instead of ZHW1 as a toughening agent to prepare ABS2-ABS9 resin. The structure and properties were then measured, and the results are shown in Table 6.

[0207] Comparative Application Example 1

[0208] ABS resin was prepared using the method shown in Application Example 1. LCBR1 prepared in Example 1 was used instead of ZHW1 as a toughening agent to prepare DABS1 resin. The structure and properties were then measured, and the results are shown in Table 6.

[0209] Comparative Application Example 2

[0210] ABS resin was prepared using the method shown in Application Example 1. LBS1 prepared in Example 1 was used instead of ZHW1 as a toughening agent to prepare DABS2 resin. The structure and properties were then measured, and the results are shown in Table 6.

[0211] Comparative Application Example 3

[0212] ABS resin was prepared using the method shown in Application Example 1. 720AX manufactured by Asahi Kasei (test data shown in Table 2) was used instead of LCBR1 and LBS1 in Example 1 to prepare toughening agent composition DZHW3 in a 1:1 ratio, thereby obtaining DABS3 resin. The structure and properties were then measured, and the results are shown in Table 6.

[0213] Comparative Application Example 4

[0214] ABS resin was prepared using the method shown in Application Example 1. Dynasol 1322 (test data shown in Table 4) was used instead of LBS1 and LCBR1 in Example 1 to prepare toughening agent composition DZHW4 in a 1:1 ratio, thereby obtaining DABS4 resin. The structure and properties were then determined, and the results are shown in Table 6.

[0215] Comparative Application Example 5

[0216] ABS resin was prepared using the method shown in Application Example 1. Asahi Kasei's 720AX (test data shown in Table 2) was used instead of LCBR1 in Example 1, and Dynasol's 1322 (test data shown in Table 4) was used instead of LBS1 in Example 1. Toughening agent composition DZHW5 was prepared by mixing 720AX and 720AX in a 1:1 ratio to obtain DABS5 resin. The structure and properties were measured, and the results are shown in Table 6.

[0217] Table 6

[0218] ABS1 32.8 20.6 98 ABS2 33.4 20.2 99 ABS3 30.6 21.1 96 ABS4 31.5 20.8 97 ABS5 32.9 19.8 96 ABS6 33.8 19.3 98 ABS7 30.8 20.7 98 ABS8 32.1 19.1 98 ABS9 32.3 20.4 95 DABS1 31.5 16.4 92 DABS2 34.5 14.7 94 DABS3 29.8 18.9 88 DABS4 30.4 19.6 86 DABS5 26.8 18.4 82

[0219] As can be seen from Table 6, by using the toughening agent composition containing the present invention as the toughening agent, a melt flow rate of over 30 g / 10 min and a cantilever beam impact strength of 19 KJ / m can be obtained. 2 ABS resin with a gloss level of 95° or higher and a gloss level of 60° or higher.

[0220] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A toughening agent composition, characterized in that, The composition comprises low-cis polybutadiene rubber and linear styrene-butadiene copolymer, wherein the molecular weight of the low-cis polybutadiene rubber exhibits a bimodal distribution, the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000-40,000, and the ratio of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution, Mn2 / Mn1, is 5-6. The linear styrene-butadiene copolymer has a unimodal molecular weight distribution with a number average molecular weight in the range of 100,000-140,000. In the linear styrene-butadiene copolymer, the weight ratio of styrene segments to butadiene segments is 0.53-0.82:

1. The weight ratio of the low-cis polybutadiene rubber to the linear styrene-butadiene copolymer is 0.42-2.33:1, and the weight ratio of the low molecular weight component to the high molecular weight component in the bimodal distribution of the low-cis polybutadiene rubber is 0.01-0.25:

1. The preparation method of the low-cis polybutadiene rubber includes: in the presence of a first organic solvent, a first structure modifier and a first initiator, performing a first anionic solution polymerization of butadiene until the butadiene is completely polymerized, adding a 6-functional compound for a coupling reaction, and then adding a first terminator and optionally a first antioxidant.

2. The toughening agent composition according to claim 1, wherein, In the toughening agent composition, the weight ratio of styrene segments to butadiene segments is 0.13-0.39:

1.

3. The toughening agent composition according to claim 2, wherein, In the toughening agent composition, the weight ratio of styrene segments to butadiene segments is 0.15-0.35:

1.

4. The toughening agent composition according to claim 3, wherein, In the toughening agent composition, the weight ratio of styrene segments to butadiene segments is 0.18-0.32:

1.

5. The toughening agent composition according to claim 1, wherein, The toughening agent composition has a Mooney viscosity (ML) at 100°C. 1+4 Within the range of 50-100; And / or, the viscosity of the toughening agent composition in a 5% by weight styrene solution at 25°C is in the range of 8-20 centipoise; And / or, the content of volatile matter in the toughening agent composition is less than or equal to 1 wt%; And / or, the gel content of the toughening agent composition is 0-150 ppm.

6. The toughening agent composition according to claim 5, wherein, The toughening agent composition has a Mooney viscosity (ML) at 100°C. 1+4 Within the range of 55-95; And / or, the viscosity of the toughening agent composition at 25°C as a 5% by weight styrene solution is in the range of 9-19 centipoise; And / or, the gel content of the toughening agent composition is 0-100 ppm.

7. The toughening agent composition according to claim 6, wherein, The toughening agent composition has a Mooney viscosity (ML) at 100°C. 1+4 Within the range of 60-90; And / or, the viscosity of the toughening agent composition at 25°C as a 5% by weight styrene solution is in the range of 10-18.

8. The toughening agent composition according to claim 1, wherein, The weight ratio of the low-cis polybutadiene rubber to the linear styrene-butadiene copolymer is 0.6-1.5:

1.

9. The toughening agent composition according to claim 1, wherein, The molecular weight distribution index Mw1 / Mn1 of the low molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 1-1.

1. And / or, the molecular weight distribution index Mw2 / Mn2 of the high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 1-1.1; And / or, the molecular weight distribution of the low cis polybutadiene rubber is 1.1-1.

5.

10. The toughening agent composition according to claim 9, wherein, The molecular weight distribution of the low-cis polybutadiene rubber is 1.15-1.

45.

11. The toughening agent composition according to claim 1, wherein, The weight ratio of the low molecular weight component to the high molecular weight component in the bimodal distribution of the low cis polybutadiene rubber is 0.04-0.18:

1. And / or, based on the total weight of the low-cis polybutadiene rubber, the 1,2-structure content is 6-16 wt%; And / or, the Mooney viscosity ML of the low cis polybutadiene rubber at 100°C 1+4 Within the range of 38-58; And / or, the viscosity of the low-cis polybutadiene rubber in a 5% by weight styrene solution at 25°C is in the range of 8-20 centipoise.

12. The toughening agent composition according to claim 11, wherein, Based on the total weight of the low-cis polybutadiene rubber, the 1,2-structure content is 8-14 wt%; And / or, the Mooney viscosity ML of the low cis polybutadiene rubber at 100°C 1+4 Within the range of 42-54; And / or, the viscosity of the low-cis polybutadiene rubber in a 5% by weight styrene solution at 25°C is in the range of 9-19 centipoise.

13. The toughening agent composition according to claim 12, wherein, The viscosity of the low-cis polybutadiene rubber in a 5% by weight styrene solution at 25°C is in the range of 10-18 centipoise.

14. The toughening agent composition according to claim 1, wherein, In the linear styrene-butadiene copolymer, the weight ratio of styrene blocks to styrene non-blocks is 1.2-4:1; And / or, based on the total weight of butadiene segments in the linear styrene-butadiene copolymer, the 1,2-structure content is 6-16 wt%; And / or, the linear styrene-butadiene copolymer has a molecular weight distribution of 1-1.1; And / or, the Mooney viscosity ML of the linear styrene-butadiene copolymer at 100°C 1+4 Within the range of 80-120; And / or, the viscosity of the linear styrene-butadiene copolymer in a 5% by weight styrene solution at 25°C is in the range of 8-20 centipoise.

15. The toughening agent composition according to claim 14, wherein, In the linear styrene-butadiene copolymer, the weight ratio of styrene blocks to styrene non-blocks is 1.4-3:1; And / or, based on the total weight of butadiene segments in the linear styrene-butadiene copolymer, the 1,2-structure content is 8-14 wt%; And / or, the Mooney viscosity ML of the linear styrene-butadiene copolymer at 100°C 1+4 Within the range of 90-110; And / or, the viscosity of the linear styrene-butadiene copolymer in a 5% by weight styrene solution at 25°C is in the range of 9-19 centipoise.

16. The toughening agent composition according to claim 15, wherein, The viscosity of the linear styrene-butadiene copolymer in a 5% by weight styrene solution at 25°C is in the range of 10-18 centipoise.

17. A method for preparing a toughening agent composition according to any one of claims 1-16, characterized in that, The preparation method includes the following steps: (1) In the presence of a first organic solvent, a first structure regulator and a first initiator, butadiene is polymerized in a first anionic solution until butadiene is completely polymerized. After a coupling reaction is carried out by adding a 6-functional compound, a first terminator and optionally a first antioxidant are added to obtain a low-cis polybutadiene solution. (2) In the presence of a second organic solvent, a second initiator and optionally a second structure modifier, a second anionic solution polymerization of styrene and butadiene is carried out until styrene and butadiene are completely polymerized. Then, a second terminator and optionally a second antioxidant are added to obtain a linear styrene-butadiene copolymer solution. (3) The low-cis polybutadiene solution and the linear styrene-butadiene copolymer solution are mixed to obtain a composition solution; (4) Remove the solvent from the composition solution to obtain colloidal particles, and dry the colloidal particles to obtain the composition.

18. The preparation method according to claim 17, wherein, In step (1), the molecular weight of the low-cis polybutadiene rubber in the low-cis polybutadiene solution exhibits a bimodal distribution. Among them, the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is in the range of 30,000-40,000; the ratio of the number average molecular weight Mn2 of the high molecular weight component to the number average molecular weight Mn1 of the low molecular weight component in the bimodal distribution is 5-6. And / or, the Mooney viscosity ML of the low-cis polybutadiene rubber in the low-cis polybutadiene solution at 100°C. 1+4 The viscosity of a 5% by weight styrene solution at 25°C is 8-20 centipoise in the range of 38-58°C. And / or, the number average molecular weight of the linear styrene-butadiene copolymer is in the range of 100,000-140,000, and the weight ratio of styrene segments to butadiene segments in the linear styrene-butadiene copolymer is 0.53-0.82:1; And / or, the Mooney viscosity ML of the linear styrene-butadiene copolymer at 100°C 1+4 Within the range of 80-120; And / or, the viscosity of the linear styrene-butadiene copolymer in a 5% by weight styrene solution at 25°C is in the range of 8-20 centipoise.

19. The preparation method according to claim 17, wherein, In step (1), the preparation method of the low-cis polybutadiene solution includes the following steps: (a) In a first organic solvent, in the presence of a first initiator and a first structure modifier, 1,3-butadiene is subjected to a first anionic solution polymerization reaction until the conversion rate of 1,3-butadiene is above 99%, thereby obtaining polybutadiene active chains; wherein the molar ratio of 1,3-butadiene to the first initiator is 550-750:1; (b) In the presence of a 6-functional coupling agent, the polybutadiene active chains are subjected to a coupling reaction. (c) After terminating the product of the coupling reaction in the presence of the first terminator, the first antioxidant is added to obtain the low-cis polybutadiene solution.

20. The preparation method according to claim 19, wherein, The number-average molecular weight of the polybutadiene active chain is 30,000-40,000; And / or, in step (a), the conditions for the polymerization reaction of the first anionic solution include: a temperature of 40-100°C, a time of 20-100 min, and a gauge pressure of 0.1-1 MPa; And / or, in step (a), the molar ratio of the first structure modifier to the first initiator is 0.02-2:1; And / or, in step (b), the 6-functional coupling agent is selected from at least one of hexachlorosilane, hexachloroethane, 1,1,1,3,3,3-hexachloropropane, triethyl glycerol and trimethyl glycerol; And / or, in step (b), the molar ratio of the coupling agent to the first initiator is 0.14-0.19:

1.

21. The preparation method according to claim 20, wherein, In step (a), the conditions for the polymerization reaction of the first anionic solution include: a temperature of 50-90℃, a time of 30-60 min, and a gauge pressure of 0.2-0.5 MPa. And / or, in step (b), the 6-functional coupling agent is selected from hexachlorosilane and / or hexachloroethane; And / or, in step (b), the molar ratio of the coupling agent to the first initiator is 0.15-0.18:

1.

22. The preparation method according to claim 17, wherein, In step (2), the preparation method of the linear styrene-butadiene copolymer solution includes the following steps: (i) In a second organic solvent, in the presence of a second initiator and optionally a second structure modifier, 1,3-butadiene and styrene are subjected to a second anionic solution polymerization reaction until the conversion of 1,3-butadiene and styrene is above 99%, to obtain an active chain of butadiene-styrene copolymer; (ii) In the presence of a second terminator, after terminating the product of the second anionic solution polymerization reaction, a second antioxidant is added to obtain a linear styrene-butadiene copolymer solution.

23. The preparation method according to claim 22, wherein, The number-average molecular weight of the active chain of the butadiene-styrene copolymer is 100,000-140,000. And / or, in step (i), the weight ratio of the styrene to the 1,3-butadiene is 0.53-0.82:1; And / or, in step (i), the ratio of the total molar amount of the 1,3-butadiene and styrene to the molar amount of the second initiator is 1300-1900:1; And / or, in step (i), the molar ratio of the second structure modifier to the second initiator is 0.02-1:1; And / or, in step (ii), the conditions for the second anionic solution polymerization reaction include: a temperature of 40-100°C, a time of 30-80 min, and a gauge pressure of 0.1-1 MPa; And / or, in step (ii), the amount of the second terminator is 0.02-0.8 parts by weight relative to the total amount of 100 parts by weight of 1,3-butadiene and styrene; And / or, in step (ii), the amount of the second antioxidant is 0.1-0.3 parts by weight relative to the total amount of 1,3-butadiene and styrene used in 100 parts by weight.

24. The preparation method according to claim 23, wherein, In step (ii), the conditions for the polymerization reaction of the second anionic solution include: a temperature of 50-100℃, a time of 40-60 min, and a gauge pressure of 0.2-0.5 MPa.

25. The preparation method according to claim 17, wherein, The first initiator and the second initiator are each independently of formula R. 1 The organolithium compound represented by Li, wherein R 1 Alkyl groups selected from C1-C10; And / or, the first organic solvent and the second organic solvent are each independently an inert nonpolar organic solvent; And / or, the first terminator and the second terminator are each independently selected from at least one of C1-C4 alcohols, organic acids and carbon dioxide.

26. The preparation method according to claim 25, wherein, The first initiator and the second initiator are each independently selected from at least one of n-butyllithium, sec-butyllithium, isobutyllithium and tert-butyllithium; And / or, the first organic solvent and the second organic solvent are each independently a mixed solvent of cyclohexane:hexane in a weight ratio of 4-19:1; And / or, the first terminator and the second terminator are each independently selected from at least one of isopropanol, stearic acid, citric acid and carbon dioxide.

27. The preparation method according to claim 26, wherein, The first initiator and the second initiator are each independently selected from n-butyllithium and / or sec-butyllithium; And / or, the first terminator and the second terminator are each independently carbon dioxide.

28. The preparation method according to claim 17, wherein, In step (3), the amounts of the low-cis polybutadiene solution and the linear styrene-butadiene copolymer solution are such that the weight ratio of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer in the composition is 0.42-2.33:1; And / or, in step (4), the moisture content of the granules is 40-60 wt%; And / or, the volatile content of the toughening agent composition is less than or equal to 1 wt%.

29. The preparation method according to claim 28, wherein, In step (3), the amounts of the low-cis polybutadiene solution and the linear styrene-butadiene copolymer solution are such that the weight ratio of the low-cis polybutadiene rubber and the linear styrene-butadiene copolymer in the composition is 0.6-1.5:

1.

30. A toughening agent composition prepared by any one of claims 17-29.

31. Use of the toughening agent composition according to any one of claims 1-16 and 30 in the preparation of ABS resin.

32. A method for preparing ABS resin, characterized in that, In the presence of a toughening agent composition, styrene and acrylonitrile are copolymerized to obtain the ABS resin; The toughening agent composition is any one of the toughening agent compositions according to claims 1-16 and 30.

33. The ABS resin prepared by the preparation method according to claim 32.

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