A graft copolymer composition, an ABS resin, and a preparation method and application thereof

Abstract

The present invention discloses a graft copolymer composition, an ABS resin, and their preparation methods and applications, belonging to the technical field of polymer materials. The graft copolymer is prepared by introducing phenyl organosilane monomers and organosilane polymers into monomers. The phenyl organosilane monomers can polymerize within the butadiene rubber, and there are a small number of silane segments on its periphery. In addition, organosilane polymers are introduced into the graft shell. Combining that the graft base contains organosilicon components and the outside contains organosilicon extended branches. At the same time, during the graft polymerization process, the polymerization monomers are pre-emulsified in advance, which can greatly reduce the content of 1,3,5-triphenylcyclohexane in the graft copolymer and the final ABS resin. The finally prepared ABS resin can maintain the mechanical properties unchanged while also having strong anti-high-speed impact and puncture resistance, and is particularly suitable for applications in fields such as the protection around automotive batteries, automotive pedestrian protection devices, and safety helmets for industries such as motorcycles.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a graft copolymer composition, an ABS resin, and a preparation method and application thereof. Background Art

[0002] The most critical technologies for electric vehicles are the "three electrics", namely batteries, electronic controls, and motors. The general structure of a lithium battery is: battery cell - module - battery pack. The battery cell technology is the cornerstone of the battery system. The process of assembling lithium battery cells into a group is called PACK. One of the most critical technologies in PACK structure design is battery thermal management. Battery thermal management is a technology that, based on the influence of temperature on battery performance, solves the problems of heat dissipation or thermal runaway caused by the operation of lithium batteries at too high or too low temperatures through reasonable design to improve the overall performance of the battery. The high-voltage insulation performance is one of the most important technical performance requirements for the battery pack structure design. Plastics have good high-voltage insulation properties. Another significant advantage of plastics is that they can reduce the weight of the battery pack, increase the weight-specific energy density of the storage battery, and increase the driving range of electric vehicles.

[0003] ABS resin is one of the potential material choices for the PACK module housing. The main preparation methods of ABS resin are emulsion polymerization and bulk polymerization. The rubber design of ABS resin prepared by emulsion polymerization is diverse and more suitable for applications in multiple scenarios. However, the disadvantages of ABS resin prepared by emulsion polymerization are also relatively obvious. First, ABS resin mostly uses butadiene rubber and styrene-butadiene rubber as energy-absorbing impact toughening agents, and its crosslinking degree is relatively high. Although it has a certain impact resistance, its protection ability against puncture damage caused by high-speed impact is insufficient. Second, if we blindly increase the toughness and impact strength of the material, a large amount of rubber needs to be added for toughening, resulting in a significant decrease in tensile strength, making it difficult to maintain the strength of the overall battery module, exposing the battery components, and posing a large safety hazard. Finally, in the prior art, PC / ABS alloys are mostly used to solve the above problems, but the introduction of polycarbonate has negative impacts on weight reduction, cost, etc., so it cannot meet the technical requirements of comprehensively improving multiple defects. Therefore, the present invention provides a graft copolymer composition and an ABS resin to solve the above problems from the production technology, thereby increasing the variety of ABS resins. Summary of the Invention

[0004] The purpose of the present invention is to overcome the deficiencies or defects in the prior art that the puncture performance and the high-speed impact resistance of ABS resin prepared by emulsion polymerization are not high enough, and to provide a graft copolymer composition and an ABS resin.

[0005] Another purpose of the present invention is to provide a preparation method of the graft copolymer composition.

[0006] Another purpose of the present invention is to provide a preparation method of the ABS resin.

[0007] Another object of the present invention is to provide the application of the ABS resin.

[0008] To achieve the above object, the present invention is realized by the following technical solutions:

[0009] A graft copolymer composition, the graft copolymer composition comprising:

[0010] A: 95 to 99.9 wt% of at least one graft copolymer A, which comprises:

[0011] Based on the graft copolymer A, 50 to 80 wt% of at least one graft base A1 obtained by emulsion polymerization of the following components:

[0012] A11: Based on the graft base A1, 60 to 99.8 wt% of butadiene monomer;

[0013] A12: Based on the graft base A1, 0 to 39.7 wt% of at least one aromatic vinyl monomer;

[0014] A13: Based on the graft base A1, 0.1 to 1 wt% of phenyl organosilane monomer;

[0015] A14: Based on the graft base A1, 0 to 1 wt% of alkyl organosilane monomer;

[0016] A15: Based on the graft base A1, 0.1 to 2 wt% of organosilane poly-mer;

[0017] wherein the sum of the weight percentages of A11, A12, A13, A14 and A15 is 100%; and

[0018] Based on the graft copolymer A, 20 to 50 wt% of at least one graft shell A2, which is obtained by emulsion polymerization of the following components in the presence of at least one graft base A1:

[0019] A21: Based on the graft shell A2, 40 to 99.9 wt% of at least one aromatic vinyl monomer;

[0020] A22: Based on the graft shell A2, 0 to 50 wt% of acrylonitrile-based monomer;

[0021] A23: Based on the graft shell A2, 0.1 to 2 wt% of organosilane poly-mer;

[0022] wherein the sum of the weight percentages of A21, A22 and A23 is 100%;

[0023] The sum of the weight percentages of A1 and A2 is 100%, and

[0024] C1: at least one other component C1 of 0.1 to 5 wt%;

[0025] The content of 1,3,5 - triphenylcyclohexane in the graft copolymer composition is not higher than 5000 ppm.

[0026] In the graft copolymer composition prepared in the present invention, first, a phenylsilane monomer and a polysilane are introduced into the graft base A1; a polysilane is introduced during the preparation of both the graft base and the graft shell. Combining that the graft base A1 contains a silicone component and has silicone extended side chains outside, the polysilane is enriched at the position of the graft copolymer due to similar solubility. Eventually, a silicone / butadiene / styrene / acrylonitrile composite rubber with a special phase state is formed in the prepared ABS resin. At the same time, the graft polymerization monomers are pre - emulsified in advance to improve the mass transfer efficiency of the reaction substances, greatly reducing the content of 1,3,5 - triphenylcyclohexane in the graft copolymer composition, making this kind of rubber prone to cavitation when subjected to an impact force and thus absorbing a large amount of energy; The ABS resin prepared from the graft copolymer composition obtained by the present invention has unchanged mechanical properties while having very strong anti - high - speed impact and puncture resistance.

[0027] It should be noted that 1,3,5 - triphenylcyclohexane comes from the side reaction during the emulsion polymerization of the graft shell. Specifically, it can be adjusted by adjusting the types and contents of monomers, increasing the stirring speed in the emulsion polymerization, or by pre - emulsifying the raw materials in the graft shell. At the same time, the content of 1,3,5 - triphenylcyclohexane can also be adjusted by post - treatment, such as washing the graft copolymer a large number of times.

[0028] It should be noted that the content of 1,3,5 - triphenylcyclohexane in the graft copolymer composition described in the present invention is not higher than 5000 ppm. For example, but not limited to, not higher than 5000 ppm, 4500 ppm, 4000 ppm, 3500 ppm, 3000 ppm, 2500 ppm, 2000 ppm, 1500 ppm, 1000 ppm, 900 ppm, 800 ppm, 700 ppm, 600 ppm, 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm or 10 ppm, etc. can all achieve the present invention.

[0029] It should be noted that A15 and A23 can be the same or different. Preferably, A15 and A23 are the same.

[0030] Furthermore, the at least one graft base A1 is obtained by the following emulsion polymerization:

[0031] A11: 60 to 99.8 wt% of butadiene monomers based on graft base A1; preferably 65 to 98 wt%, preferably 70 to 96.5 wt%, preferably 75 to 95 wt%, more preferably 80 to 90 wt%;

[0032] A12: 0 to 39.8 wt% of at least one aryl vinyl monomer based on graft base A1; preferably 1.5 to 31.6 wt%, preferably 2.5 to 27.3 wt%, preferably 3.55 to 22.7 wt%, more preferably 8.3 to 17.9 wt%;

[0033] A13: 0.1 to 1 wt% of phenyl organosilane monomer based on graft base A1; preferably 0.2 to 0.8 wt%, preferably 0.3 to 0.6 wt%, preferably 0.35 to 0.55 wt%, more preferably 0.4 to 0.5 wt%;

[0034] A14: 0 to 1 wt% of alkyl organosilane monomer based on graft base A1; preferably 0.1 to 0.8 wt%, preferably 0.2 to 0.6 wt%, preferably 0.3 to 0.55 wt%, more preferably 0.4 to 0.5 wt%;

[0035] A15: 0.1 to 2 wt% of organosilane polymer based on graft base A1; preferably 0.2 to 1.8 wt%, preferably 0.5 to 1.5 wt%, preferably 0.8 to 1.2 wt%; more preferably 0.9 to 1.1 wt%;

[0036] wherein the sum of the weight percentages of A11, A12, A13, A14 and A15 is 100%.

[0037] Furthermore, the at least one graft shell A2 is obtained by emulsion polymerization of the following components in the presence of at least one graft base A1:

[0038] A21: 40 to 99.9 wt% of at least one aryl vinyl monomer based on graft shell A2; preferably 45 to 95 wt%, preferably 50 to 90 wt%, preferably 55 to 85 wt%, more preferably 60 to 80 wt%;

[0039] A22: 0 to 50 wt% of acrylonitrile-based monomers based on graft shell A2; preferably 4.8 to 53.2 wt%, preferably 9.5 to 48 wt%, preferably 14.4 to 43.5 wt%, more preferably 19.2 to 38.8 wt%;

[0040] A23: 0.1 to 2 wt% of organosilane polymer based on graft base A2; preferably 0.2 to 1.8 wt%, preferably 0.5 to 1.6 wt%, preferably 0.6 to 1.5 wt%, more preferably 0.8 to 1.2 wt%.

[0041] Further, the phenyl organosilane monomer is one or more of dimethylphenylvinylsilane, trimethoxy(4-vinylphenyl)silane, and trimethyl(4-vinylphenyl)silane.

[0042] Further, the organosilane polymer is polymethylsiloxane; preferably AFE TM 7610, AFE TM 1520, AFE TM 0020 and AFE TM One or several of 1410. In some preferred specific embodiments, the organosilane polymer is a polyether-modified organosilane polymer. Preferably, the polyether-modified organosilane polymer is AFE TM 7610 and / or AFE TM 1520. The ABS resin prepared by its application has better puncture resistance.

[0043] Further, the alkyl organosilane monomer is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriisopropoxysilane, γ-methacryloxypropyltrimethoxysilane.

[0044] Specifically, the aryl vinyl monomer is one or several of styrene, α-methylstyrene, or p-methylstyrene.

[0045] The acrylonitrile monomer is one or several of acrylonitrile and / or methacrylonitrile.

[0046] Optionally, one or more optional other components C1 are added. For example, the at least one other component C1 can be selected from one or several of an emulsifier, a reducing agent, a chain transfer agent, or an electrolyte.

[0047] In the present invention, common emulsifiers can be selected according to the prior art, such as but not limited to one or several of potassium disproportionated rosin, potassium fatty acid, sodium dodecylsulfonate, or sodium dodecylbenzenesulfonate.

[0048] In the present invention, common chain transfer agents can be selected according to the prior art, such as but not limited to n-dodecyl mercaptan and / or tert-dodecyl mercaptan.

[0049] In the present invention, common electrolytes can be selected according to the prior art, such as but not limited to one or several of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, or potassium hydroxide.

[0050] In the present invention, common reducing agents can be selected according to the prior art, such as but not limited to Rongalite, sugars, vitamin C, etc.

[0051] The present invention also provides a method for preparing the above graft copolymer composition, comprising the following steps:

[0052] S1. Before preparing at least one graft base A1, an initiator is added, and then A11, A12, A13, A14, and A15 are emulsion polymerized in the presence of C1 to obtain the graft base A1.

[0053] S2. In the presence of at least one graft base A1 and C1 described in step S1, A23, pre-emulsified A21, and A22 are added for emulsion polymerization. After the polymerization is completed, the graft copolymer composition is obtained by high-temperature coagulation.

[0054] In the present invention, common initiators can be selected with reference to the prior art, such as, but not limited to, one or more of persulfate initiators, azo initiators, or peroxide initiators.

[0055] Specifically, the persulfate initiator includes one or more of potassium persulfate, sodium persulfate, and ammonium persulfate; the azo initiator includes one or more of azobisisobutyronitrile, azobisisovaleronitrile, or azobisisoheptonitrile; the peroxide initiator includes one or more of cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, and benzoyl peroxide.

[0056] Specifically, the pre-emulsified A21 and A22 are obtained by uniformly mixing A21, A22, an emulsifier, and demineralized water.

[0057] Specifically, the temperature of the emulsion polymerization is 50-85°C, and the time of the emulsion polymerization is 24-40 h.

[0058] Specifically, the temperature of the high-temperature coagulation is 65-100°C.

[0059] Specifically, the emulsion polymerization in step S1 is stepwise temperature-rising polymerization.

[0060] More specifically, the stepwise temperature-rising polymerization is specifically that the temperature is raised to 50-60°C and kept at a constant temperature for reaction for 6-10 h as the first-stage polymerization reaction, and the stirring speed is controlled at 90-120 rpm; after the first-stage polymerization reaction is completed, the temperature of the system is raised to 65-72°C and kept at a constant temperature for reaction for 10-15 h as the second-stage polymerization reaction, and the stirring speed is 110-130 rpm; after the second-stage polymerization reaction is completed, the temperature is raised to 75-85°C and kept at a constant temperature for reaction for 10-14 h as the third-stage reaction, and the stirring speed is controlled at 120-180 rpm.

[0061] In a preferred embodiment, the graft copolymer obtained is in powder form, i.e., the graft copolymer in the drying step S2 without adding other polymer components. The residual moisture of the obtained graft copolymer powder is less than or equal to 20 wt%, preferably less than or equal to 10 wt%, more preferably less than or equal to 8 wt%.

[0062] Specifically, the residual moisture refers to the weight percentage of water based on the undehydrated graft copolymer composition obtained in step S2. Specifically, the residual moisture is determined by means of a suitable analytical device (such as drying and weighing equipment), and the sample is dried until a constant sample weight is reached within a specified time. For example, the residual moisture of the graft copolymer can be determined in a halogen moisture analyzer HR73 of Mettler Toledo at 180 °C until the weight is constant within 30 seconds.

[0063] In a specific embodiment, the preparation method includes the following steps:

[0064] S1. Add water, initiator, electrolyte, chain transfer agent, and emulsifier into a reaction kettle (kettle-type reaction kettle), stir at room temperature until completely dissolved and mixed evenly; introduce nitrogen into the reaction kettle to displace air so that the oxygen content is lower than 10 ppm, and then add A11, A12, A13, A14, and A15 in proportion;

[0065] The reaction kettle is heated to 50 - 60 °C and kept at a constant temperature for 6 - 10 h for the first-stage polymerization reaction, and the stirring speed is controlled at 90 - 120 rpm; after the first-stage polymerization reaction is completed, the system is heated to 65 - 72 °C and kept at a constant temperature for 10 - 15 h for the second-stage polymerization reaction, and the stirring speed is 110 - 130 rpm; after the second-stage polymerization reaction is completed, it is heated to 75 - 85 °C and kept at a constant temperature for 10 - 14 h for the third-stage reaction, and the stirring speed is controlled at 120 - 180 rpm. After the reaction is completed, it is cooled and discharged to obtain the graft base A1;

[0066] S2. Heat the graft base A1 in step S1 to 50 - 60 °C, continuously dropwise add the initiator, chain transfer agent, reducing agent, electrolyte, A23, pre-emulsified A21, and A22 (obtained by mixing A21, A22, emulsifier, and demineralized water evenly) for 1.5 - 2.5 h. After heating, continue the reaction for 2 - 4 h, and then raise the temperature to 63 - 68 °C and continue the reaction for 1.5 - 2.5 h to obtain the graft latex; take the graft latex and add it to the coagulation reaction kettle, heat it to 70 - 80 °C, gradually add sulfuric acid thereto, add it up in 1.5 - 2.5 h, and raise the temperature to 90 - 99 °C and keep the temperature for 1.5 - 3 h. The suspension of water and the graft copolymer composition powder is centrifugally dehydrated to obtain a wet powder with a water content of 25 - 40%, and after washing and drying, a graft copolymer composition with a water content < 1% is obtained.

[0067] The present invention also provides an ABS resin, which comprises:

[0068] D: 65 to 85 wt% of a styrene-acrylonitrile copolymer;

[0069] B: 15 to 35 wt% of the graft copolymer composition as described above or the graft copolymer composition prepared by the above preparation method;

[0070] F: 0 to 20 wt% of at least one other polymer component F, and

[0071] C2: 0 to 10 wt% of at least one other component C2.

[0072] Specifically, the weight content of styrene in the styrene-acrylonitrile copolymer is 72 to 78 wt%.

[0073] In a specific embodiment, the other polymer component F is selected from polycarbonate, polyamide, and polyester.

[0074] In a specific embodiment, the other component C2 includes, but is not limited to, one or more of a filler, a reinforcing agent, a dye, a lubricant, a mold release agent, a stabilizer, an antioxidant, a UV absorber, a plasticizer, an impact modifier, an antistatic agent, a flame retardant, a fungicide, or a foaming agent.

[0075] Specifically, the filler or the reinforcing agent includes, but is not limited to, one or more of silicate, amorphous silica, calcium silicate, quartz, mica, metal oxide, metal hydroxide, graphite, barium sulfate, calcium carbonate, magnesium carbonate, talc, kaolin, carbon fiber, or glass fiber.

[0076] Specifically, the pigment includes, but is not limited to, one or more of titanium dioxide, phthalocyanine, ultramarine, iron oxide, or carbon black.

[0077] Specifically, the stabilizer includes, but is not limited to, one or more of m-phenylene diphenol, salicylate, benzotriazole, or benzophenone.

[0078] Specifically, the mold release agent includes, but is not limited to, fatty acids having 12 to 30 carbon atoms, their salts, and their derivatives, such as stearic acid, stearate, palmitic acid, palmitate, stearyl alcohol, amide wax, and polyolefin wax.

[0079] In the present invention, common antioxidants can be selected according to the prior art, such as, but not limited to, one or more of hindered phenol antioxidants, phosphite antioxidants, or thioester antioxidants.

[0080] Specifically, the hindered phenol antioxidant is one or more of N, N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or spiroglycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0081] Specifically, the phosphite antioxidant is 2,4-di-tert-butylphenol and / or pentaerythritol bis(2,6-di-tert-butyl-4-methylphenyl) phosphite.

[0082] Specifically, the thioester antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate, or pentaerythritol tetrakis(3-laurylthiopropionate).

[0083] In the present invention, common lubricants can be selected according to the prior art, such as but not limited to at least one of amide lubricants, stearate lubricants, ester lubricants, or silicone lubricants.

[0084] The present invention also provides a method for preparing the ABS resin, comprising the following steps:

[0085] Mix the above graft copolymer composition, styrene-acrylonitrile copolymer other polymerization component F, and other component C2 evenly, and obtain the ABS resin by extrusion granulation.

[0086] Further, the extrusion granulation is carried out using a twin-screw extruder.

[0087] Further, the extrusion temperature is 200~300 °C.

[0088] Further, the screw rotation speed of the twin-screw extruder is 200~300 rpm.

[0089] Further, the length-diameter ratio of the screw of the twin-screw extruder is 18:1.

[0090] The present invention relates to the use of the above ABS resin for preparing household items, electronic components, household appliances, gardening equipment, medical technology equipment, motor vehicle parts, and vehicle body parts. In particular, the above ABS resin can be used to make articles with puncture resistance (such as molded products). In particular, it can be used to prepare safety helmets for industries such as automotive battery perimeter protection, automotive pedestrian protection devices, and motorcycles.

[0091] Compared with the prior art, the present invention has the following beneficial effects:

[0092] The present invention provides a graft copolymer composition. By introducing a phenyl organosilane monomer, on the one hand, an organosilane phase region is formed inside the rubber during the polymerization process, and on the other hand, an organosilane chain segment is formed on the periphery of the rubber. In combination with an externally added organosilane polymer, a special-phase organosilicon / butadiene / styrene / acrylonitrile composite rubber is formed in the ABS system. The ABS resin prepared from this rubber has very strong puncture resistance in addition to maintaining its high mechanical properties, and can be widely used in fields such as the protection around automotive batteries, automotive pedestrian protection devices, and safety helmets for industries such as motorcycles. Detailed Embodiments

[0093] The following further elaborates on the present invention in combination with specific embodiments. The embodiments are only used to explain the present invention and are not used to limit the scope of the present invention. The test methods used in the following embodiments are all conventional methods unless otherwise specified; the materials, reagents, etc. used are all reagents and materials that can be obtained from commercial channels unless otherwise specified.

[0094] Raw materials used in each embodiment and comparative example:

[0095] A11: Butadiene monomer, industrial-grade butadiene, purity greater than 96%, Huarui Chemical Industry;

[0096] A12: Aryl vinyl monomer, styrene, purity greater than or equal to 99%, purchased from Aladdin Reagent Company;

[0097] A13: Phenyl organosilane monomer

[0098] A13-1: Trimethoxy(4-vinylphenyl)silane, purity greater than or equal to 99%, purchased from Aladdin Reagent Company;

[0099] A13-2: Dimethylphenylvinylsilane, purity greater than or equal to 99%, purchased from Aladdin Reagent Company;

[0100] A13-3: Trimethyl(4-vinylphenyl)silane, purity greater than or equal to 99%, purchased from Aladdin Reagent Company;

[0101] A14: Alkyl organosilane monomer, vinyltrimethoxysilane, purity greater than or equal to 99%, purchased from Aladdin Reagent Company;

[0102] A15: Organosilane polymer

[0103] A15-1: AFE TM 7610, purchased from Dow Chemical Company;

[0104] A15-2: AFE TM 1520, purchased from Dow Chemical Company;

[0105] A15-3: AFE TM 0120, purchased from Dow Chemical Company;

[0106] Other surfactant S-1: Polyvinyl alcohol ether surfactant, ABEX DBR-Z, purchased from Solvay;

[0107] Other surfactant S-2: 2,5,8,11-Tetramethyl-6-dodecyn-5,8-diol, with a purity of greater than or equal to 99%, purchased from Aladdin Reagent Company;

[0108] A21: Styrene monomer, industrial-grade styrene, with a purity of greater than 96%, Baolai Chemical Industry;

[0109] A22: Acrylonitrile monomer, acrylonitrile, with a purity of greater than or equal to 99%, purchased from Aladdin Reagent Company;

[0110] A23: Organosilane polymer

[0111] A23-1: AFE TM 7610, purchased from Dow Chemical Company;

[0112] A23-2: AFE TM 1520, purchased from Dow Chemical Company;

[0113] A23-3: AFE TM 0120, purchased from Dow Chemical Company;

[0114] Other surfactant S-3: Organosiloxane surfactant, TEGOPREN 5840, purchased from Evonik;

[0115] Other surfactant S-4: 2,5,8,11-Tetramethyl-6-dodecyn-5,8-diol, with a purity of greater than or equal to 99%, purchased from Aladdin Reagent Company;

[0116] Initiator: Sodium persulfate, commercially available;

[0117] Other component C1

[0118] Electrolyte: Sodium carbonate, commercially available;

[0119] Emulsifier: Potassium disproportionated rosin, commercially available;

[0120] Chain transfer agent: tert-Dodecyl mercaptan, commercially available;

[0121] Reducing agent: Rongalite, commercially available;

[0122] Styrene-acrylonitrile copolymer: PN-118, with a styrene content of 75%, purchased from Chi Mei, Taiwan, China;

[0123] Other component C2:

[0124] Antioxidants: Pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (hindered phenolic antioxidant) and tris(2,4-di-tert-butylphenyl) phosphite (phosphite antioxidant) are compounded at a weight ratio of 1:1 and are commercially available;

[0125] Lubricant: Ethylene bisstearamide, commercially available; It should be noted that the raw materials used in the parallel experiments of the examples and comparative examples are all the same commercially available products.

[0126] Examples 1 to 11 and Comparative Examples 1 to 8

[0127] In the examples and comparative examples, the graft copolymer composition is prepared by the following method according to the formulations in Tables 1 to 2, and includes the following steps:

[0128] S1. Based on graft base A1, 100 wt% of water, 1 wt% of initiator, 0.6 wt% of chain transfer agent, 0.4 wt% of electrolyte and 0.4 wt% of emulsifier are added to a reaction kettle (kettle-type reaction kettle), and stirred at room temperature until completely dissolved and mixed evenly; Nitrogen is introduced into the reaction kettle to displace the air so that the oxygen content is lower than 10 ppm, and then A11, A12, A13, A14 and A15 are added in proportion;

[0129] The reaction kettle is heated to 55 °C and kept at a constant temperature for 9 h for the first-stage polymerization reaction, and the stirring speed is controlled at 105 rpm; After the first-stage polymerization reaction is completed, the system is heated to 70 °C and kept at a constant temperature for 12 h for the second-stage polymerization reaction, and the stirring speed is controlled at 120 rpm; After the second-stage polymerization reaction is completed, it is heated to 75 °C and kept at a constant temperature for 12 h for the third-stage reaction, and the stirring speed is controlled at 130 rpm. After the third-stage reaction, it is cooled and discharged to obtain graft base A1;

[0130] S2. Heat the grafting base A1 in step S1 to 55 °C, add 0.7 wt% initiator, 0.6 wt% chain transfer agent, 0.8% reducing agent, 0.2% electrolyte, A23, pre-emulsified A21 and A22 (obtained by uniformly mixing A21, A22, 0.4 wt% emulsifier based on graft copolymer A and 120 wt% deionized water) and continuously drip-feed for 2 h. After heating is completed, continue the reaction for 3 h, then raise the temperature to 65 °C and react for 2 h to obtain the graft latex. Take the graft latex and add it to the coagulation reactor, heat it to 75 °C, gradually add sulfuric acid thereto, finish adding in 2 h, and raise the temperature to 95 °C and maintain the temperature for 2 h to obtain a suspension of water and the powder of the graft copolymer composition. After centrifugal dehydration, a wet powder with a moisture content of 25% - 40% is obtained. Then add water twice the weight of the wet powder for washing, perform centrifugal dehydration again after washing, and repeat the cycle 3 times. Then dry the washed wet powder in a fluidized bed dryer at 60 °C for 2 h to obtain a graft copolymer composition with a moisture content < 1%.

[0131] Determination of the content of 1,3,5-triphenylcyclohexane in the graft copolymer composition: Take 5 mg of the graft copolymer composition prepared in each of the examples and comparative examples and put it into 20 mL of absolute ethanol, shake for 5 hours, let it stand and then filter with filter paper. Take the clarified filtrate for gas chromatography test. Chromatographic column: Aglient HP-1 column (50 m * 0.25 mm, 0.5 μm, Agilent Technologies, USA); carrier gas: nitrogen; column flow rate: 1.0 mL / min; column oven temperature programming: initial temperature 40 °C, hold for 5 min, rise to 150 °C at 10 °C / min, and then rise to 220 °C at 15 °C / min; vaporization chamber temperature: 280 °C; detector temperature 300 °C; split ratio 50:1; injection volume: 1 μL; cylinder pressure: 0.5 - 1.5 MPa; quantitative method: external standard method of chromatographic peak area, calculate the concentration of 1,3,5-triphenylcyclohexane in the graft copolymer composition, and the result is calculated in ppm.

[0132] Table 1 Dosages of each component in the graft copolymer composition in Examples 1 - 10 (unit: weight percentage)

[0133]

[0134] Note: The weight percentages of A1 and A2 are both based on graft copolymer A, and graft copolymer A accounts for more than 95 wt% of the graft copolymer composition.

[0135] Table 2 Dosages of each component in the graft copolymer composition in Comparative Examples 1 - 7 (unit: weight percentage)

[0136]

[0137] Note: The weight percentages of A1 and A2 are both based on the graft copolymer A, and the graft copolymer A accounts for more than 95 wt% of the graft copolymer composition.

[0138] The preparation of the graft copolymer composition in Comparative Example 8 was the same as that in Example 1, except that in step S2, A21, A22, the emulsifier, and demineralized water were directly added without pre-emulsification, and the content of 1,3,5-triphenylcyclohexane was 5102 ppm.

[0139] The graft copolymer composition described in Example 11 was a suspension of water and the graft copolymer composition powder obtained by coagulating and dehydrating the graft latex obtained in step S2 of Comparative Example 8. After centrifugal dehydration, a wet powder with a wet content of 25% - 40% was obtained. Then, water 12 times the weight of the wet powder was added for washing. After washing, centrifugal dehydration was carried out again. After 5 cycles, the washed wet powder was dried in a fluidized bed dryer at 60 °C for 2 h to obtain a graft copolymer composition with a water content < 1%; the content of 1,3,5-triphenylcyclohexane was 4428 ppm.

[0140] Specifically, the dosage of each component in A1 and A2 is shown in Tables 3 - 4.

[0141] Table 3 Dosage of each component in A1 (unit: weight percentage)

[0142]

[0143] Note: The weight percentages of A11, A12, A13, A14, A15, S-1, and S-2 are based on A1.

[0144] Table 4 Dosage of each component in A2 (unit: weight percentage)

[0145]

[0146] Note: The weight percentages of A21, A22, A23, S-3, and S-4 are based on A2.

[0147] Examples 12 - 24 and Comparative Examples 9 - 16

[0148] In the examples and comparative examples, the ABS resin was prepared according to the formulations in Tables 5 - 6 by the following method, including the following steps:

[0149] The above graft copolymer composition, styrene-acrylonitrile copolymer, and other component C2 were mixed uniformly and extruded and pelletized by a twin-screw extruder to obtain the ABS resin; the extrusion temperature was 200 - 300 °C, the screw speed was 250 rpm, and the screw length-diameter ratio was 18:1.

[0150] Table 5 Formulation of ABS resin in Examples 12 - 24 (unit: weight percentage)

[0151]

[0152] Table 6 Formulations of ABS resins in Comparative Examples 9 - 16 (unit: weight percentage)

[0153]

[0154] Performance testing

[0155] The ABS resins prepared in the above - mentioned examples and comparative examples were subjected to performance testing. The specific test items and test methods are as follows:

[0156] 1. Test method:

[0157] (1) Mechanical property testing: The ABS resin was dried in an 80 o °C oven for 2 hours. Then, using a KraussMaffei injection molding machine, an ISO standard mechanical mold was selected to perform injection molding at 220 o °C, medium - high pressure and speed to obtain tensile specimens and impact specimens that meet the ISO standard. The specimens were conditioned at room temperature of 23 o °C and constant humidity of RH 50% for 24 hours. Then, a tensile strength test was carried out according to ISO 527 - 2:2012, with a tensile speed of 50 mm / min; a notched impact strength test was carried out according to ISO 178:2010.

[0158] (2) Anti - puncture property testing: Evaluated by multi - axial impact strength testing (MAI), measured according to ISO 6603 - 2023 using test specimens with a thickness of 3.2 mm and a diameter of 10 cm. The drop hammer diameter is 12.5 mm and the measurement speed is 4.4 m / s. The results are characterized by the ductility in % and the absorbed energy value. This method provides a means to characterize the amount of energy absorbed by the material under multi - axial deformation conditions and the form of material failure. The applied deformation is high - speed puncture. If the material shows 0% ductility, that is, 100% brittleness and absorbs less energy, it cannot be applied in protective components such as battery packs and helmets. The final test result is calculated as the average test result of 5 test specimens.

[0159] 2. Test results

[0160] The test results are shown in Table 7.

[0161] Table 7 Experimental results of each example and comparative example

[0162]

[0163] As can be seen from Table 7, the content of 1,3,5-triphenylcyclohexane in the graft copolymer composition prepared by the present invention is not higher than 5000 ppm, and the mechanical properties and puncture resistance of the ABS resin prepared by mixing and extruding with styrene-acrylonitrile copolymer are both good.

[0164] As can be seen from Comparative Examples 9 to 11, if no organosilane polymer is added to the graft shell or other surfactants are used to replace the organosilane polymer in the present invention, the content of 1,3,5-triphenylcyclohexane in the prepared graft copolymer composition increases, and the mechanical properties of the finally prepared ABS resin slightly decrease, but the puncture resistance significantly decreases.

[0165] As can be seen from Comparative Examples 12 to 15, if other substances are used to replace the phenylalkylsilane monomer in the graft base or no organosilane polymer is added to the graft base or other surfactants are used to replace the organosilane polymer in the present invention, the content of 1,3,5-triphenylcyclohexane in the graft copolymer composition increases, and the mechanical properties of the finally prepared ABS resin slightly decrease, but the puncture resistance significantly decreases.

[0166] As can be seen from Comparative Example 16, if A21 and A22 in the graft shell are not pre-emulsified, the content of 1,3,5-triphenylcyclohexane increases, and the mechanical properties of the ABS resin do not meet the expectations, and there is an obvious gap in puncture resistance compared with the examples.

[0167] Obviously, the above embodiments of the present invention are merely examples for clearly explaining the present invention, and are not intended to limit the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to enumerate all the implementation manners here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A graft copolymer composition, characterized in that The graft copolymer composition comprises: A: 95 to 99.9 wt% of at least one graft copolymer A, which comprises: Based on the graft copolymer A, 50 to 80 wt% of at least one graft base A1 obtained by emulsion polymerization of the following components: A11: 60 to 99.8 wt% of butadiene monomer based on the graft base A1; A12: 0 to 39.8 wt% of at least one aryl vinyl monomer based on the graft base A1; A13: 0.1 to 1 wt% of phenyl organosilane monomer based on the graft base A1; A14: 0 to 1 wt% of alkyl organosilane monomer based on the graft base A1; A15: 0.1 to 2 wt% of organosilane poly-mer based on the graft base A1; wherein the sum of the weight percentages of A11, A12, A13, A14 and A15 is 100%; and Based on the graft copolymer A, 20 to 50 wt% of at least one graft shell A2, which is obtained by emulsion polymerization of the following components in the presence of at least one graft base A1: A21: 40 to 99.9 wt% of at least one aryl vinyl monomer based on the graft shell A2; A22: 0 to 50 wt% of acrylonitrile-based monomer based on the graft shell A2; A23: 0.1 to 2 wt% of organosilane poly-mer based on the graft shell A2; wherein the sum of the weight percentages of A21, A22 and A23 is 100%; the sum of the weight percentages of A1 and A2 is 100%, and C1: 0.1 to 5 wt% of at least one other component C1; the other component C1 includes one or several of emulsifier, reducing agent, chain transfer agent or electrolyte; The content of 1,3,5-triphenylcyclohexane in the graft copolymer composition is not higher than 5000 ppm.

2. The graft copolymer composition according to claim 1, wherein The phenyl organosilane monomer is one or more of dimethylphenylvinylsilane, trimethoxy(4-vinylphenyl)silane and trimethyl(4-vinylphenyl)silane.

3. The graft copolymer composition according to claim 1, characterized in that, The organosilane poly-mer is polymethylsiloxane.

4. The graft copolymer composition according to claim 1, wherein The alkyl organosilane monomer is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, vinyltriisopropoxysilane, γ-methacryloxypropyltrimethoxysilane.

5. The graft copolymer composition according to claim 1, characterized in that, The aryl vinyl monomer is one or several of styrene, α-methylstyrene or p-methylstyrene.

6. The graft copolymer composition according to claim 1, characterized in that, The acrylonitrile-based monomer is one or several of acrylonitrile and / or methacrylonitrile.

7. A method for preparing the graft copolymer composition according to any one of claims 1 to 6, characterized in that, Comprises the following steps: S1. Before preparing at least one graft base A1, an initiator is added, and then A11, A12, A13, A14 and A15 are emulsion polymerized in the presence of C1 to obtain the graft base A1; S2. A23, pre-emulsified A21 and A22 are added in the presence of at least one graft base A1 obtained in step S1 and C1 for emulsion polymerization, and after polymerization is completed, high-temperature coagulation is carried out to obtain the graft copolymer composition; the temperature of the high-temperature coagulation is 65-100 °C.

8. The preparation method according to claim 7, wherein The emulsion polymerization in step S1 is stepwise temperature-rising polymerization.

9. The preparation method according to claim 8, characterized in that, The stepwise temperature-rising polymerization specifically includes: heating to 50-60°C for isothermal reaction for 6-10 hours as the first-stage polymerization reaction, with the stirring speed controlled at 90-120 rpm; after the first-stage polymerization reaction is completed, heating the system to 65-72°C for isothermal reaction for 10-15 hours as the second-stage polymerization reaction, with the stirring speed being 110-130 rpm; after the second-stage polymerization reaction is completed, heating to 75-85°C for isothermal reaction for 10-14 hours as the third-stage reaction, and controlling the stirring speed to be 120-180 rpm.

10. An ABS resin, characterized in that, The ABS resin comprises: D: 65 to 85 wt% of styrene-acrylonitrile copolymer; B: 15 to 35 wt% of the graft copolymer composition described in any one of claims 1-6 or the graft copolymer composition prepared by the preparation method of the graft copolymer composition described in any one of claims 8-9; F: 0 to 20 wt% of at least one other polymerization component F, and C2: 0 to 10 wt% of at least one other component C2; The other polymerization component F is selected from polycarbonate, polyamide and polyester; the other component C2 includes one or several of filler, reinforcing agent, dye, lubricant, demolding agent, stabilizer, antioxidant, UV absorber, plasticizer, impact modifier, antistatic agent, flame retardant, fungicide or foaming agent.

11. A method for preparing an ABS resin, characterized in that, It includes the following steps: Mix the styrene-acrylonitrile copolymer, the graft copolymer composition described in any one of claims 1-6 or the graft copolymer composition prepared by the preparation method of the graft copolymer composition described in any one of claims 8-9, the other polymerization component F and the other component C2 evenly, and obtain the ABS resin through extrusion granulation.

12. Application of the ABS resin described in claim 11 in preparing the peripheral protection of automobile batteries, automobile pedestrian protection devices and safety helmets for the motorcycle industry.

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