ABS resin, preparation method thereof, and resin product

Abstract

The present invention relates to the technical field of building materials, and more particularly to an ABS resin, a preparation method thereof, and a resin product thereof. The ABS resin comprises an ABS graft copolymer whose raw materials, by weight, include 20-30 parts of poly(butadiene-acrylonitrile) latex, 4-18 parts of a styrene monomer, 1-10 parts of an acrylonitrile monomer, 0.001-2 parts of an initiator, and 5-65 parts of water. The acrylonitrile content in the styrene-acrylonitrile copolymer is less than 34% and greater than 25%. The electroplating-grade ABS resin is obtained by combining an ABS graft copolymer obtained by combining a specific ratio of poly(butadiene-acrylonitrile) latex, a styrene monomer, an acrylonitrile monomer, an initiator, and water with the styrene-acrylonitrile copolymer, and controlling the acrylonitrile content in the styrene-acrylonitrile copolymer to be less than 34% and greater than 25%. The resin has good compatibility and significantly improved mechanical properties, heat resistance, and electroplating properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material preparation, and in particular to ABS resin, a preparation method thereof, and a resin product. Background Art

[0002] Butadiene-styrene-acrylonitrile (ABS) resin is a thermoplastic engineering plastic widely used in industry. ABS resin is typically prepared by emulsion polymerization of ABS grafted onto a bulk styrene-acrylonitrile (SAN) copolymer. This method begins with the synthesis of polybutadiene (PB) latex via emulsion polymerization. This latex is then used as a seed emulsion for graft polymerization of styrene (St) and acrylonitrile (AN) to produce the ABS graft copolymer. This graft copolymer is then melt-blended with SAN resin prepared in bulk to yield ABS resin.

[0003] The market demand for ABS is increasing, and with it comes increased performance requirements for ABS, placing higher demands on the heat resistance and plating performance of electroplating-grade ABS. Existing ABS resins suffer from issues such as easy deformation under heat, substandard basic electroplating properties, or insufficient plating adhesion. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the defect of ABS resin in the prior art that it cannot have both good heat resistance and electroplating performance, thereby resulting in the problems of easy deformation when heated, unqualified basic electroplating properties or insufficient coating adhesion.

[0005] The present invention provides an ABS resin, comprising an ABS graft copolymer and a styrene-acrylonitrile copolymer. The raw materials of the ABS graft copolymer include, by weight, 20-30 parts of poly(butadiene-acrylonitrile) latex, 4-18 parts of a styrene monomer, 1-10 parts of an acrylonitrile monomer, 0.001-2 parts of an initiator, and 5-65 parts of water. The acrylonitrile content in the styrene-acrylonitrile copolymer is less than 34% and greater than 25%.

[0006] The term acrylonitrile content refers to the mass percentage of acrylonitrile in a styrene-acrylonitrile copolymer. The test is performed by elemental analysis to determine the nitrogen content in styrene-acrylonitrile copolymers.

[0007] The term styrene monomer refers to styrene and its derivatives, and the styrene derivatives may include but are not limited to styrene substituted with 1 to 6 alkyl groups.

[0008] The term acrylonitrile monomer refers to acrylonitrile and its derivatives, and the acrylonitrile derivatives may include but are not limited to acrylonitrile substituted with 1 to 6 alkyl groups.

[0009] Furthermore, the styrene monomer is selected from one or more of styrene, α-methylstyrene and p-methylstyrene; and / or the acrylonitrile monomer is selected from one or more of acrylonitrile, methacrylonitrile and ethacrylonitrile; and / or the initiator comprises an organic peroxide initiator; and / or the particle size of the poly(butadiene-acrylonitrile) latex is 280-400 nm.

[0010] The organic peroxide initiator comprises one or more of cumene hydroperoxide, benzoyl peroxide, tert-butyl benzoyl peroxide, and methyl ethyl ketone peroxide.

[0011] Furthermore, the raw materials of the ABS graft copolymer further include one or more of an activator, a molecular weight regulator and an emulsifier;

[0012] Preferably, the activator comprises one or more of sodium pyrophosphate, ferrous sulfate and glucose;

[0013] Preferably, the molecular weight regulator comprises an alkyl mercaptan containing 1 to 25 carbon atoms;

[0014] Preferably, the emulsifier comprises an anionic emulsifier, more preferably, the anionic emulsifier is selected from one or more of alkylbenzene sulfonates having an alkyl carbon number between 6 and 22, alkyl sulfates having an alkyl carbon number between 6 and 22, fatty acid salts having an alkyl carbon number between 6 and 22, and disproportionated rosin acid soap;

[0015] Preferably, based on 100 parts by weight of the raw material of the ABS graft copolymer, the activator accounts for 0.001-2 parts;

[0016] Preferably, based on 100 parts by weight of the raw material of the ABS graft copolymer, the molecular weight regulator accounts for 0.05-0.1 parts;

[0017] Preferably, based on 100 parts by weight of the raw materials of the ABS graft copolymer, the emulsifier accounts for 0.05-0.2 parts.

[0018] Wherein, the alkyl mercaptan containing 1 to 25 carbon atoms includes one or more of methyl mercaptan, n-dodecyl mercaptan, and n-hexadecyl mercaptan.

[0019] Alkyl sulfates having an alkyl carbon number between 6 and 22 include sodium lauryl sulfate.

[0020] Alkylbenzene sulfonates with an alkyl group carbon number between 6 and 22 include sodium dodecylbenzene sulfonate.

[0021] The fatty acid salts with an alkyl carbon number between 6 and 22 include oleate and / or octadecane dioic acid soap.

[0022] In certain preferred embodiments, the emulsifier comprises one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, oleate, disproportionated rosin acid soap, and octadecane dioic acid soap.

[0023] The oleate salt may be a potassium salt and / or a sodium salt. The disproportionated rosin acid soap comprises disproportionated rosin acid potassium soap and / or disproportionated rosin acid sodium soap. The octadecane dioic acid soap comprises 1,18-octadecane dioic acid potassium soap and / or 1,18-octadecane dioic acid sodium soap. More preferably, the emulsifier is 1,18-octadecane dioic acid soap.

[0024] Furthermore, the mass ratio of the ABS graft copolymer to the styrene-acrylonitrile copolymer is 70:30-30:70; and / or the acrylonitrile content in the styrene-acrylonitrile copolymer is 27-30%.

[0025] Furthermore, the raw materials of the poly(butadiene-acrylonitrile) latex include, by weight, 30-55 parts of butadiene, 2-10 parts of acrylonitrile, 0.05-0.5 parts of an initiator, and 40-110 parts of water;

[0026] Optionally, the initiator is an inorganic peroxide initiator.

[0027] The inorganic peroxide initiator includes one or more of a persulfate initiator and a perphosphate initiator. The persulfate initiator includes one or more of potassium persulfate and sodium persulfate. The superphosphate includes one or more of potassium superphosphate and sodium superphosphate.

[0028] Furthermore, the raw materials of the poly(butadiene-acrylonitrile) latex further include one or more of a cross-linking agent, a molecular weight regulator, an emulsifier, and an electrolyte;

[0029] Preferably, the cross-linking agent comprises an ester cross-linking agent and / or a divinyl cross-linking agent;

[0030] Preferably, the molecular weight regulator comprises an alkyl mercaptan containing 1 to 25 carbon atoms;

[0031] Preferably, the emulsifier comprises an anionic emulsifier, more preferably, the anionic emulsifier is selected from one or more of alkylbenzene sulfonates having an alkyl carbon number between 6 and 22, alkyl sulfates having an alkyl carbon number between 6 and 22, fatty acid salts having an alkyl carbon number between 6 and 22, and disproportionated rosin acid soaps, more preferably, the emulsifier is 1,18-octadecane dioic acid soap;

[0032] Preferably, the electrolyte comprises potassium salt and / or sodium salt;

[0033] Preferably, based on 100 parts by weight of the raw material of the poly(butadiene-acrylonitrile) latex, the cross-linking agent accounts for 0.01-0.3 parts;

[0034] Preferably, based on 100 parts by weight of the raw material of the poly(butadiene-acrylonitrile) latex, the molecular weight regulator accounts for 0.01-0.3 parts;

[0035] Preferably, based on 100 parts by weight of the raw material of the poly(butadiene-acrylonitrile) latex, the emulsifier accounts for 0.05-2.5 parts;

[0036] Preferably, based on 100 parts by weight of the raw material of the poly(butadiene-acrylonitrile) latex, the electrolyte accounts for 0.1-1 part.

[0037] The ester crosslinking agent includes one or more of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, hexanediol dimethacrylate, and trimethylolpropane trimethacrylate.

[0038] The divinyl crosslinking agent includes divinylbenzene.

[0039] The alkyl mercaptan containing 1 to 25 carbon atoms includes one or more of methyl mercaptan, n-dodecyl mercaptan, and n-hexadecyl mercaptan.

[0040] Alkyl sulfates having an alkyl carbon number between 6 and 22 include sodium lauryl sulfate.

[0041] Alkylbenzene sulfonates with an alkyl group carbon number between 6 and 22 include sodium dodecylbenzene sulfonate.

[0042] The fatty acid salts with an alkyl carbon number between 6 and 22 include oleate and / or octadecane dioic acid soap.

[0043] In certain preferred embodiments, the emulsifier comprises one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, oleate, octadecane dioic acid soap, and disproportionated rosin acid soap.

[0044] The oleate salt may be a potassium salt and / or a sodium salt. The disproportionated rosin acid soap includes disproportionated rosin acid potassium soap and / or disproportionated rosin acid sodium soap. The octadecane dioic acid soap includes 1,18-octadecane dioic acid potassium soap and / or 1,18-octadecane dioic acid sodium soap.

[0045] Wherein, the potassium salt is selected from one or more of potassium carbonate, potassium chloride, potassium nitrate and potassium sulfate.

[0046] The sodium salt is selected from one or more of sodium carbonate, sodium chloride, sodium nitrate and sodium sulfate.

[0047] Furthermore, the mass ratio of butadiene to acrylonitrile is 80-95:20-5.

[0048] On the other hand, the present invention also provides a method for preparing ABS resin, comprising: mixing an ABS graft copolymer and a styrene-acrylonitrile copolymer to prepare the ABS resin;

[0049] Optionally, the mixing is performed at a temperature of 180-250°C.

[0050] For example, a conventional twin-screw extruder can be used for mixing, followed by water cooling and granulation.

[0051] Furthermore, the preparation method of the ABS graft copolymer includes mixing poly(butadiene-acrylonitrile) latex, styrene monomer, acrylonitrile monomer, initiator and water, heating and polymerizing, and coagulating to obtain the ABS graft copolymer;

[0052] Optionally, the heating polymerization temperature is 50-90° C. and the time is 2-8 hours;

[0053] Optionally, the coagulation process uses a coagulant, which comprises an acid solution.

[0054] The coagulant can be a magnesium sulfate solution, for example, a magnesium sulfate aqueous solution with a concentration of 3-8 wt%.

[0055] Furthermore, the preparation method of the poly(butadiene-acrylonitrile) latex includes mixing butadiene, acrylonitrile, an initiator and water, heating and polymerizing to obtain the poly(butadiene-acrylonitrile) latex;

[0056] Optionally, the reaction temperature of the heating polymerization does not exceed 85° C., the reaction pressure does not exceed 0.9 MPa, and the heating polymerization time is 10-40 hours;

[0057] Optionally, after the thermal polymerization, a chemical agglomeration step is further included. For example, acetic acid is added for chemical agglomeration to increase the latex particle size to 350 nm-400 nm. Alkali is then added to adjust the pH to 8-11.

[0058] The present invention also provides a resin product, which is an ABS resin prepared from the above-mentioned ABS resin or the ABS resin prepared by the above-mentioned method for preparing the ABS resin.

[0059] The resin product of the present invention can be produced by conventional technical means, for example, ABS resin can be injection molded into various types of resin products through an injection molding process.

[0060] The technical solution of the present invention has the following advantages:

[0061] 1. The ABS resin provided by the present invention comprises an ABS graft copolymer and a styrene-acrylonitrile copolymer. The raw materials of the ABS graft copolymer include, by weight, 20-30 parts of poly(butadiene-acrylonitrile) latex, 4-18 parts of a styrene monomer, 1-10 parts of an acrylonitrile monomer, 0.001-2 parts of an initiator, and 5-65 parts of water. The acrylonitrile content of the styrene-acrylonitrile copolymer is less than 34% and greater than 25%. The electroplating-grade ABS resin is obtained by combining an ABS graft copolymer obtained by combining a specific ratio of poly(butadiene-acrylonitrile) latex, a styrene monomer, an acrylonitrile monomer, an initiator, and water with the styrene-acrylonitrile copolymer, and controlling the acrylonitrile content of the styrene-acrylonitrile copolymer to be less than 34% and greater than 25%. The resin has good compatibility, good heat resistance and electroplating performance, and excellent overall performance.

[0062] Among them, poly(butadiene-acrylonitrile) latex replaces polybutadiene latex, increasing the polarity of the rubber phase. This not only facilitates the grafting of styrene-acrylonitrile with an acrylonitrile content of less than 34% and greater than 25%, but also enhances the etch resistance of the rubber phase. By controlling the acrylonitrile content of styrene-acrylonitrile copolymer to less than 34% and greater than 25%, chemical resistance is improved, preventing excessive etching of ABS by chromic acid during the roughening process, thereby improving the coating adhesion and enhancing the heat resistance and electroplating properties of the ABS resin. Testing has shown that the ABS resin has high flexibility, meets basic electroplating requirements, and exhibits no surface defects such as dents or bulges after high-temperature testing at 100°C.

[0063] Furthermore, the ABS resin produced by the present invention has higher fluidity than conventional ABS resin. This high fluidity facilitates stress release during part molding, improves plating leakage, and helps enhance the bonding strength of the electroplated layer, significantly improving the peel strength of injection-molded parts.

[0064] 2. The ABS resin provided by the present invention, by employing an anionic emulsifier, particularly 1,18-octadecane dioic acid soap, exhibits higher adsorption, emulsion stability, and solubility than the emulsifiers commonly used in butadiene latex polymerization, such as disproportionated rosin soap or sodium lauryl sulfate. This allows for smooth polymerization of butadiene latex and graft polymerization of butadiene latex. The emulsifier's hydrophobic group is a long-chain alkyl group, which reduces the concentration of micelles and allows for a reduced usage. Furthermore, the low molecular surface area allows for effective adsorption, thereby enhancing dispersion stabilization. The hydrophilic group incorporates two carboxyl bases, which enhances dispersion stabilization and significantly improves solubility. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0066] Figure 1 This is a particle size distribution diagram of the nitrile latex before adding acetic acid in Example 1 of the present invention;

[0067] Figure 2 This is a particle size distribution diagram of the nitrile latex after adding acetic acid in Example 1 of the present invention;

[0068] Figure 3 This is a particle size distribution diagram of the nitrile latex before adding acetic acid in Example 2 of the present invention;

[0069] Figure 4 This is a particle size distribution diagram of the nitrile latex after adding acetic acid in Example 2 of the present invention;

[0070] Figure 5 This is a particle size distribution diagram of the nitrile latex before adding acetic acid in Example 3 of the present invention;

[0071] Figure 6 This is a particle size distribution diagram of the nitrile latex after adding acetic acid in Example 3 of the present invention;

[0072] in Figure 1-6 In the figure, the horizontal axis Size is the particle size, and the vertical axis Intensity (Percent) is the intensity (percentage). DETAILED DESCRIPTION

[0073] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0074] If specific experimental procedures or conditions are not specified in the examples, the procedures or conditions described in the literature in the field can be followed. Reagents or instruments used without manufacturer indication are commercially available conventional reagents. TSC is total solids content, determined according to GB / T8298-2017.

[0075] Example 1 Poly(butadiene-acrylonitrile) latex A

[0076] This example provides a method for synthesizing poly(butadiene-acrylonitrile) latex A, which is carried out in a 10 L high-pressure polymerization reactor under nitrogen protection.

[0077] To a reaction kettle were added 4400 g of deionized water, 95 g of 1,18-octadecanediol soap (purchased from Latemul ASK), 10.276 g of potassium persulfate, and 25.69 g of potassium carbonate. After stirring and mixing thoroughly, 2487.48 g of butadiene, 130.92 g of acrylonitrile, 5.24 g of divinylbenzene, and 12.8 g of dodecyl mercaptan were added.

[0078] Start heating. Heat to 65°C in 1 hour. Adiabatically react at 65°C, controlling the reaction temperature not to exceed 85°C and the reaction pressure not to exceed 0.9 MPa. React for about 25 hours until the conversion rate reaches 98%, then terminate the reaction to obtain nitrile latex. Particle size was measured using a laser particle size analyzer (Zetasizer Nano ZS90, Malvern, UK). Figure 1 As shown, the average particle size is 106.5 nm and the PDI is 0.251.

[0079] The prepared nitrile latex (pH = 10.5, particle size within the range of 106.5 nm) was gradually agglomerated by adding 10% acetic acid. When the particle size reached 350-400 nm, 10 wt% potassium hydroxide aqueous solution was added to pH = 10.5, and deionized water was added to adjust TSC = 30% to obtain poly (butadiene-acrylonitrile) latex A. The particle size was measured, see Figure 2 As shown, the average particle size is 352.4 nm, the PDI is 0.170, and the particle size distribution is uniform.

[0080] Example 2 Poly(butadiene-acrylonitrile) latex B

[0081] This example provides a method for synthesizing poly(butadiene-acrylonitrile) latex B, which is carried out in a 10 L high-pressure polymerization reactor under nitrogen protection.

[0082] Add 4400 g of deionized water, 95 g of 1.18-octadecane dioic acid soap, 10.276 g of potassium persulfate, and 25.69 g of potassium carbonate to the reactor and stir to mix thoroughly. Then, add 2356.56 g of butadiene, 261.84 g of acrylonitrile, 7.7 g of divinylbenzene, and 10.5 g of dodecyl mercaptan.

[0083] Start heating. When the temperature reaches 65℃ in 1 hour. Carry out adiabatic reaction at 65℃, control the reaction temperature not to exceed 85℃, and the reaction pressure not to exceed 0.9MPa. React for about 25 hours until the conversion rate reaches 98%, then end the reaction to obtain nitrile latex. Measure the particle size, see Figure 3As shown, the average particle size is 96.09 nm and the PDI is 0.192.

[0084] The nitrile latex (pH = 10, particle size 96.09 nm) prepared above was gradually agglomerated by adding 10% acetic acid. When the particle size was measured to be 350-400 nm, 10 wt% potassium hydroxide aqueous solution was added to pH = 10, and deionized water was added to adjust TSC = 30% to obtain poly (butadiene-acrylonitrile) latex B. The particle size was measured, see Figure 4 As shown, the average particle size is 361.9 nm, the PDI is 0.229, and the particle size distribution is uniform.

[0085] Example 3 Poly(butadiene-acrylonitrile) Latex C

[0086] This example provides a method for synthesizing poly(butadiene-acrylonitrile) latex C, which is carried out in a 10 L high-pressure polymerization reactor under nitrogen protection.

[0087] Add 4400 g of deionized water, 95 g of 1.18-octadecane dioic acid soap, 10.276 g of potassium persulfate, and 25.69 g of potassium carbonate to the reactor and stir to mix thoroughly. Then, add 2225.64 g of butadiene, 392.76 g of acrylonitrile, 10.47 g of divinylbenzene, and 6.55 g of dodecyl mercaptan.

[0088] Start heating. When the temperature reaches 65℃ in 1 hour. Carry out adiabatic reaction at 65℃, control the reaction temperature not to exceed 85℃, and the reaction pressure not to exceed 0.9MPa. React for about 25 hours until the conversion rate reaches 98%, then end the reaction to obtain nitrile latex. Measure the particle size, see Figure 5 As shown, the average particle size is 89.27 nm and the PDI is 0.131.

[0089] The nitrile latex (pH = 9.7, particle size 89.27 nm) prepared above was gradually agglomerated by adding 10% acetic acid. When the particle size was measured to be 350-400 nm, 10 wt% potassium hydroxide aqueous solution was added to pH = 10, and deionized water was added to adjust TSC = 30% to obtain poly (butadiene-acrylonitrile) latex C. The particle size was measured, see Figure 6 As shown, the average particle size is 377.2 nm, the PDI is 0.256, and the particle size distribution is uniform.

[0090] Example 4 Synthesis of ABS-2

[0091] This embodiment provides an ABS resin, comprising SAN (purchased from Kumho, South Korea, brand SAN-300N A, molecular weight M) in a mass ratio of 70:30. W 12.5×10 4, 28% acrylonitrile content) and an ABS graft copolymer. The raw materials for the ABS graft copolymer include: 1188 g of poly(butadiene-acrylonitrile) latex A prepared in Example 1 (TSC = 30%), 171.072 g of styrene, 66.528 g of acrylonitrile, 1.9 g of cumene hydroperoxide, 260 g of deionized water, 2.376 g of dodecanethiol, 4.2 g of 1.18-octadecane dioic acid soap, 1.9008 g of sodium pyrophosphite, 3.564 g of anhydrous glucose, and 0.0476 g of ferrous sulfate.

[0092] The preparation method comprises the following steps:

[0093] S1. Polymerization: Place poly(butadiene-acrylonitrile) latex in a polymerization reactor and purge with nitrogen. Add 1,18-octadecanediol soap and 200 g of deionized water and stir for 30 minutes. Mix sodium pyrophosphite, anhydrous glucose, and ferrous sulfate and dissolve them in 60 g of deionized water to prepare an activator solution. Mix dodecanethiol, cumene hydroperoxide, styrene, and acrylonitrile to obtain a mixed monomer. Add the activator solution all at once to the polymerization reactor and raise the temperature to 70°C. Add the mixed monomer dropwise for 4 hours. Allow to react for 2 hours. Stop the reaction when the conversion reaches over 98% to produce an emulsion.

[0094] S2. Coagulation and Drying: Dilute the above emulsion with deionized water to a TSC of approximately 25%, maintaining the temperature at 50°C. Gradually add approximately 60g of a 20% by mass magnesium sulfate solution while stirring until the polymer is completely coagulated. Wash the coagulated polymer with deionized water until the pH of the washings reaches 6-7. Dry in an oven at 80°C to produce an ABS graft copolymer.

[0095] S3. Mixing: SAN and ABS graft copolymers were added to the main feeder of a twin-screw extruder in a mass ratio of 70:30. The twin-screw extrusion process conditions are shown in Table 1. After extrusion, the mixture was water-cooled and pelletized to produce ABS resin (denoted as ABS-2).

[0096] Table 1 Process conditions of twin-screw extrusion

[0097]

[0098] The test specimens were prepared by injection molding machine and then tested for performance. The results are shown in Tables 4 and 5.

[0099] Example 5 Synthesis of ABS-5

[0100] This embodiment provides an ABS resin that is substantially the same as that of Example 4, differing only in the type of poly(butadiene-acrylonitrile) latex. In this embodiment, poly(butadiene-acrylonitrile) latex B prepared in Example 2 with TSC = 30% of the same mass is used instead of poly(butadiene-acrylonitrile) latex A. The remaining raw material amounts and processes are the same as those of Example 4.

[0101] Example 6 Synthesis of ABS-8

[0102] This embodiment provides an ABS resin that is substantially the same as that of Example 4, differing only in the type of poly(butadiene-acrylonitrile) latex. In this embodiment, poly(butadiene-acrylonitrile) latex C prepared in Example 3 with TSC = 30% of the same mass is used instead of poly(butadiene-acrylonitrile) latex A. The remaining raw material amounts and processes are the same as those of Example 4.

[0103] Comparative Example 1 Synthesis of ABS-1

[0104] This comparative example provides an ABS resin, including SAN (purchased from Kumho, South Korea, brand SAN-326NA, molecular weight M) with a mass ratio of 70:30. W 12.6×10 4 , 25% acrylonitrile content) and ABS graft copolymer. The raw materials for the ABS graft copolymer include: TSC (30% poly(butadiene-acrylonitrile) latex A: 1188g, styrene: 178.2g, acrylonitrile: 59.4g, cumene hydroperoxide: 1.42g, deionized water: 260g, dodecanethiol: 2.376g, 1.18-octadecane dioic acid soap: 4.2g, sodium pyrophosphite: 1.9008g, anhydrous glucose: 3.564g, and ferrous sulfate: 0.0476g.

[0105] The preparation method comprises the following steps:

[0106] S1. Polymerization: Place poly(butadiene-acrylonitrile) latex in a polymerization reactor and purge with nitrogen. Add 1,18-octadecanediol soap and 200 g of deionized water and stir for 30 minutes. Mix sodium pyrophosphite, anhydrous glucose, and ferrous sulfate and dissolve them in 60 g of deionized water to prepare an activator solution. Mix dodecanethiol, cumene hydroperoxide, styrene, and acrylonitrile to obtain a mixed monomer. Add the activator solution all at once to the polymerization reactor and raise the temperature to 70°C. Add the mixed monomer dropwise for 4 hours. Allow to react for 2 hours. Stop the reaction when the conversion reaches over 98% to produce an emulsion.

[0107] S2. Coagulation and Drying: Dilute the above emulsion with deionized water to a TSC of approximately 25%, maintaining the temperature at 50°C. Gradually add approximately 60g of a 20% by mass magnesium sulfate solution while stirring until the polymer is completely coagulated. Wash the coagulated polymer with deionized water until the pH of the washings reaches 6-7. Dry in an oven at 80°C to produce an ABS graft copolymer.

[0108] S3. Mixing: SAN and ABS graft copolymers were added to the main feeder of a twin-screw extruder at a mass ratio of 70:30. The twin-screw extrusion process conditions are shown in Table 2. After extrusion, the mixture was water-cooled and pelletized to produce ABS resin (denoted as ABS-1).

[0109] Table 2 Process conditions of twin-screw extrusion

[0110]

[0111] The test specimens were prepared by injection molding machine and then tested for performance. The results are shown in Table 4.

[0112] Comparative Example 2 Synthesis of ABS-3

[0113] This comparative example provides an ABS resin, including SAN (purchased from Kumho, South Korea, brand SAN-350N HM, molecular weight M) with a mass ratio of 70:30. W 15.5×10 4 , 34% acrylonitrile content) and ABS graft copolymer. The raw materials for the ABS graft copolymer include: TSC (30% poly(butadiene-acrylonitrile) latex A: 1188g, styrene: 156.816g, acrylonitrile: 80.784g, cumene hydroperoxide: 2.85g, deionized water: 260g, dodecanethiol: 2.376g, 1.18-octadecane dioic acid soap: 4.2g, sodium pyrophosphite: 1.9008g, anhydrous glucose: 3.564g, and ferrous sulfate: 0.0476g.

[0114] The preparation method comprises the following steps:

[0115] S1. Polymerization: Place poly(butadiene-acrylonitrile) latex in a polymerization reactor and purge with nitrogen. Add 1,18-octadecanediol soap and 200 g of deionized water and stir for 30 minutes. Mix sodium pyrophosphite, anhydrous glucose, and ferrous sulfate and dissolve them in 60 g of deionized water to prepare an activator solution. Mix dodecanethiol, cumene hydroperoxide, styrene, and acrylonitrile to obtain a mixed monomer. Add the activator solution all at once to the polymerization reactor and raise the temperature to 70°C. Add the mixed monomer dropwise for 4 hours. Allow to react for 2 hours. Stop the reaction when the conversion reaches over 98% to produce an emulsion.

[0116] S2. Coagulation and Drying: Dilute the above emulsion with deionized water to a TSC of approximately 25%, maintaining the temperature at 50°C. Gradually add approximately 60g of a 20% by mass magnesium sulfate solution while stirring until the polymer is completely coagulated. Wash the coagulated polymer with deionized water until the pH of the washings reaches 6-7. Dry in an oven at 80°C to produce an ABS graft copolymer.

[0117] S3. Mixing: SAN and ABS graft copolymers were added to the main feeder of a twin-screw extruder at a mass ratio of 70:30. The twin-screw extrusion process conditions are shown in Table 3. After extrusion, the mixture was water-cooled and pelletized to produce ABS resin (denoted as ABS-3).

[0118] Table 3 Process conditions of twin-screw extrusion

[0119]

[0120] The test specimens were prepared by injection molding machine and then tested for performance. The results are shown in Table 4.

[0121] Comparative Example 3 Synthesis of ABS-4

[0122] This comparative example provides an ABS resin that is substantially the same as that of comparative example 1, except that the type of poly(butadiene-acrylonitrile) latex is different. In this comparative example, poly(butadiene-acrylonitrile) latex B of the same mass is used instead of poly(butadiene-acrylonitrile) latex A. The remaining raw material amounts and processes are the same as those of comparative example 1.

[0123] Comparative Example 4 Synthesis of ABS-6

[0124] This comparative example provides an ABS resin that is substantially the same as that of comparative example 2, except that the type of poly(butadiene-acrylonitrile) latex is different. In this comparative example, poly(butadiene-acrylonitrile) latex B of the same mass is used instead of poly(butadiene-acrylonitrile) latex A. The remaining raw material amounts and processes are the same as those of comparative example 2.

[0125] Comparative Example 5 Synthesis of ABS-7

[0126] This comparative example provides an ABS resin that is substantially the same as that of comparative example 1, except that the type of poly(butadiene-acrylonitrile) latex is different. In this comparative example, poly(butadiene-acrylonitrile) latex C of the same mass is used instead of poly(butadiene-acrylonitrile) latex A. The remaining raw material amounts and processes are the same as those of comparative example 1.

[0127] Comparative Example 6 Synthesis of ABS-9

[0128] This comparative example provides an ABS resin that is substantially the same as that of comparative example 2, except that the type of poly(butadiene-acrylonitrile) latex is different. In this comparative example, poly(butadiene-acrylonitrile) latex C of the same mass is used instead of poly(butadiene-acrylonitrile) latex A. The remaining raw material amounts and processes are the same as those of comparative example 2.

[0129] Comparative Example 7 Synthesis of ABS-10

[0130] This comparative example provides an ABS resin, which is basically the same as that of comparative example 1, except that the type of ABS graft copolymer is different. This comparative example uses commercially available Korean Kumho ABS-181 of the same quality to replace the ABS graft copolymer in comparative example 1.

[0131] Comparative Example 8 Synthesis of ABS-11

[0132] This comparative example provides an ABS resin that is substantially the same as that of Example 4, except that the type of ABS graft copolymer is different. This comparative example uses commercially available Korean Kumho ABS-181 of the same quality instead of the ABS graft copolymer of Example 4.

[0133] Comparative Example 9 Synthesis of ABS-12

[0134] This comparative example provides an ABS resin that is substantially the same as that of comparative example 2, except that the type of ABS graft copolymer is different. This comparative example uses commercially available Korean Kumho ABS-181 of the same quality instead of the ABS graft copolymer of comparative example 2.

[0135] Experimental Example 1

[0136] The ABS resins prepared in the examples and comparative examples were electroplated, and the basic electroplating performance, high temperature resistance and electroplating bonding strength of the electroplated parts were tested.

[0137] Basic electroplating performance (appearance): If there are no obvious defects or pitting on the surface of the electroplated part, the basic electroplating performance is qualified; otherwise, it is unqualified. If the basic electroplating performance is unqualified, the next test will not be carried out.

[0138] High temperature resistance: Place the electroplated parts in a 100℃ high temperature test chamber for 6 hours, then take them out and cool them to room temperature. If there are no dents, bulges or other appearance defects on the surface of the product, the high temperature resistance is qualified; otherwise, it is unqualified.

[0139] Electroplating adhesion: The electroplated thermoplastic resin test piece was cut into 100mm*25mm specimens. The electroplated specimens were subjected to a 90° peel strength test on a universal tensile testing machine according to ASTM B533.

[0140] The results are shown in the following table:

[0141] Table 4 Electroplating performance test results

[0142]

[0143] Appendix: Products with unqualified basic electroplating performance will not be tested for electroplating adhesion

[0144] As shown in Table 4, the basic electroplating performance of Comparative Examples 1-7 and Comparative Example 9 was unsatisfactory, with obvious defects and / or pitting on the surface of the plated parts. Furthermore, the bonding strength of Comparative Example 8 was poor. The ABS resins produced in Examples 4-6 of the present invention exhibited good basic electroplating performance and high-temperature resistance, as well as significantly improved peel strength. In particular, the bonding strength of the coatings in Examples 4 and 5 was significantly improved.

[0145] Experimental Example 2

[0146] The ABS resin prepared in each embodiment was subjected to the following tests:

[0147] The melt index was tested using a melt flow rate tester (model: GT-7100-MI) from a high-speed rail inspection company. The impact strength test was conducted in accordance with GB / T1043.1-2008. The notched impact strength was tested using an izod impact tester (model: GT-HV2000A-C6W) from a high-speed rail inspection company. The tensile strength test was conducted in accordance with GB / T1040.2-2006. The flexural performance test was conducted in accordance with GB / T9341-2008. The tensile and flexural tests were conducted using a universal testing machine (model: GT-TCS-2000) from a high-speed rail inspection company. The Vicat softening point was tested using a Vicat deformation tester (model: GTHV2000A-C5W) from a high-speed rail inspection company. The dielectric constant and dissipation factor were tested using a dielectric impedance spectrometer at 100 Hz in accordance with IEC 6231-2-1, with the sample being a 20 mm × 2 mm disc. The volume resistivity and surface resistivity were tested using a high resistance meter in accordance with IEC 6231-3-1 test.

[0148] Comparative samples that fail the electroplating performance test will no longer be subject to basic performance testing.

[0149] Table 5 Basic performance test results

[0150]

[0151] As shown in Table 5, the ABS resins prepared in various embodiments of the present invention have high notched Izod impact strength, tensile strength, flexural strength, and elongation at break, indicating excellent mechanical properties. The melt index is between 15 and 30 g / 10 min, indicating good fluidity. The dielectric constant is between 3 and 4, and the low dielectric constant provides excellent insulation properties, reducing signal loss and interference. The soft point, dissipation factor, dielectric constant, and resistivity also meet basic electroplating performance requirements.

[0152] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. An ABS resin, characterized in that: The invention comprises an ABS graft copolymer and a styrene-acrylonitrile copolymer. The raw materials of the ABS graft copolymer include, by weight, 20-30 parts of polybutadiene-acrylonitrile latex, 4-18 parts of styrene monomers, 1-10 parts of acrylonitrile monomers, 0.001-2 parts of an initiator and 5-65 parts of water. The acrylonitrile content in the styrene-acrylonitrile copolymer is less than 34% and greater than 25%.

2. The ABS resin according to claim 1, characterized in that The styrene monomer is selected from one or more of styrene, α-methylstyrene and p-methylstyrene; and / or, the acrylonitrile monomer is selected from one or more of acrylonitrile, methacrylonitrile and ethacrylonitrile; and / or, the initiator comprises an organic peroxide initiator; and / or, the particle size of the polybutadiene-acrylonitrile latex is 280-400 nm.

3. The ABS resin according to claim 1 or 2, characterized in that The raw materials of the ABS graft copolymer further include one or more of an activator, a molecular weight regulator and an emulsifier.

4. The ABS resin according to claim 3, characterized in that The activator comprises one or more of sodium pyrophosphite, ferrous sulfate and glucose.

5. The ABS resin according to claim 3, wherein The molecular weight regulator comprises an alkyl mercaptan having 1 to 25 carbon atoms.

6. The ABS resin according to claim 3, characterized in that The emulsifier comprises an anionic emulsifier.

7. The ABS resin according to claim 6, characterized in that The anionic emulsifier is selected from one or more of alkylbenzene sulfonates with an alkyl carbon number of 6-22, alkyl sulfates with an alkyl carbon number of 6-22, fatty acid salts with an alkyl carbon number of 6-22, and disproportionated rosin acid soap.

8. The ABS resin according to claim 3, wherein The emulsifier is 1,18-octadecane dioic acid soap.

9. The ABS resin according to claim 3, wherein Based on 100 parts by weight of the raw materials of the ABS graft copolymer, the activator accounts for 0.001-2 parts.

10. The ABS resin according to claim 3, wherein Based on 100 parts by weight of the raw materials of the ABS graft copolymer, the molecular weight regulator accounts for 0.05-0.1 part.

11. The ABS resin according to claim 3, wherein Based on 100 parts by weight of the raw materials of the ABS graft copolymer, the emulsifier accounts for 0.05-0.2 parts.

12. The ABS resin according to claim 1 or 2, characterized in that The mass ratio of the ABS graft copolymer to the styrene-acrylonitrile copolymer is 70:30-30:70; and / or the acrylonitrile content in the styrene-acrylonitrile copolymer is 27-30%.

13. The ABS resin according to claim 1 or 2, characterized in that The raw materials of the polybutadiene-acrylonitrile latex include, by weight, 30-55 parts of butadiene, 2-10 parts of acrylonitrile, 0.05-0.5 parts of initiator and 40-110 parts of water.

14. The ABS resin according to claim 3, wherein The initiator is an inorganic peroxide initiator.

15. The ABS resin according to claim 1 or 2, characterized in that The raw materials of the polybutadiene-acrylonitrile latex further include one or more of a cross-linking agent, a molecular weight regulator, an emulsifier, and an electrolyte.

16. The ABS resin according to claim 15, characterized in that The cross-linking agent comprises an ester cross-linking agent and / or a divinyl cross-linking agent.

17. The ABS resin according to claim 15, wherein The molecular weight regulator comprises an alkyl mercaptan having 1 to 25 carbon atoms.

18. The ABS resin according to claim 15, wherein The emulsifier comprises an anionic emulsifier.

19. The ABS resin according to claim 18, wherein The anionic emulsifier is selected from one or more of alkylbenzene sulfonates with an alkyl carbon number of 6-22, alkyl sulfates with an alkyl carbon number of 6-22, fatty acid salts with an alkyl carbon number of 6-22, and disproportionated rosin acid soap.

20. The ABS resin according to claim 15, wherein The emulsifier is 1,18-octadecane dioic acid soap.

21. The ABS resin according to claim 15, wherein The electrolyte comprises potassium salt and / or sodium salt.

22. The ABS resin according to claim 15, wherein Based on 100 parts by weight of the raw material of the polybutadiene-acrylonitrile latex, the cross-linking agent accounts for 0.01-0.3 parts.

23. The ABS resin according to claim 15, wherein Based on 100 parts by weight of the polybutadiene-acrylonitrile latex raw material, the molecular weight regulator accounts for 0.01-0.3 parts.

24. The ABS resin according to claim 15, wherein Based on 100 parts by weight of the raw material of the polybutadiene-acrylonitrile latex, the emulsifier accounts for 0.05-2.5 parts.

25. The ABS resin according to claim 15, wherein Based on 100 parts by weight of the raw material of the polybutadiene-acrylonitrile latex, the electrolyte accounts for 0.1-1 part.

26. The ABS resin according to claim 15, wherein The mass ratio of butadiene to acrylonitrile is 80-95:20-5.

27. A method for preparing the ABS resin according to any one of claims 1 to 26, characterized in that: ABS resin is prepared by mixing ABS graft copolymer and styrene-acrylonitrile copolymer.

28. The method for preparing ABS resin according to claim 27, wherein: The mixing is carried out at a temperature of 180-250°C.

29. The method for preparing ABS resin according to claim 27, wherein: The preparation method of the ABS graft copolymer comprises the steps of mixing polybutadiene-acrylonitrile latex, styrene monomer, acrylonitrile monomer, initiator and water, heating and polymerizing the mixture, and coagulating the mixture to obtain the ABS graft copolymer.

30. The method for preparing ABS resin according to claim 29, wherein: The temperature of the heating polymerization is 50-90° C. and the time is 2-8 hours.

31. The method for preparing ABS resin according to claim 29, wherein: The coagulation process utilizes a coagulant comprising an acid solution.

32. The method for preparing ABS resin according to claim 29, wherein: The preparation method of the polybutadiene-acrylonitrile latex comprises the steps of mixing butadiene, acrylonitrile, an initiator and water, and heating and polymerizing the mixture to obtain the polybutadiene-acrylonitrile latex.

33. The method for preparing ABS resin according to claim 32, wherein: The reaction temperature of the heating polymerization does not exceed 85° C., the reaction pressure does not exceed 0.9 MPa, and the heating polymerization time is 10-40 hours.

34. The method for preparing ABS resin according to claim 32, wherein: The thermal polymerization is followed by a chemical agglomeration step.

35. A resin product, characterized in that The ABS resin is prepared from the ABS resin described in any one of claims 1 to 26 or the ABS resin prepared by the preparation method of the ABS resin described in any one of claims 27 to 34.

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