High-gloss, high-hardness and high-impact ABS (Acrylonitrile Butadiene Styrene) resin as well as preparation method and application thereof

Abstract

The invention relates to the field of styrene resin materials, in particular to high-gloss, high-hardness and high-impact-resistance ABS (acrylonitrile butadiene styrene) resin as well as a preparation method and application thereof. The preparation method comprises the following steps: 1, contacting basic latex, emulsion, styrene I, acrylonitrile I, a molecular weight regulator and an initiator, and performing first-stage reaction to obtain a first-stage product; 2, styrene II and acrylonitrile II are added into the first-stage product for a second-stage reaction, and a second-stage product is obtained; 3, methyl methacrylate I is added into the second-section product for a third-section reaction, and a third-section product is obtained; 4, adding a coagulant into the third-section product for coagulation to obtain grafting powder; 5, styrene III, acrylonitrile III and methyl methacrylate II are subjected to bulk polymerization, and modified SAN resin is obtained; and 6, mixing the grafting powder, the modified SAN resin, the antioxidant and the lubricant, and carrying out extrusion granulation. According to the method disclosed by the invention, the ABS resin with high gloss, high hardness and high impact resistance can be prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of styrene-based resin materials, and particularly relates to a high-gloss, high-hardness, and high-impact-resistant ABS resin and its preparation method and application. Background Art

[0002] ABS resin (acrylonitrile-butadiene-styrene copolymer) has good dimensional stability, chemical resistance, impact resistance, and excellent processability, so it is widely used in the fields of household appliances, electronic appliances, automobiles, etc. With the improvement of people's work and living standards, the requirements for the performance of household appliances, automobiles, and office supplies are getting higher and higher, and the material requirements are becoming increasingly specialized. Now, high-gloss, high-hardness, and high-impact resistance requirements are put forward for such products.

[0003] The gloss of ordinary ABS resin is about 80, the Rockwell hardness is about 108, and the impact strength is 18 - 20 KJ / m 2 . To improve the impact strength, a larger graft particle size is required, but a larger graft particle size will cause a decrease in the gloss of ABS resin. When the impact strength is high, the Rockwell hardness will decrease. Therefore, it is difficult for ABS resin to simultaneously have high gloss, high hardness, and high impact resistance, which greatly limits the application of ABS resin.

[0004] The gloss of ABS resin is not only related to the surface shape of the material but also related to the composition of the material. To improve the gloss of ABS resin, it can be achieved by blending a gloss improver or blending a high-gloss substance. However, the method of blending a gloss improver has the problem of being unable to maintain high gloss for a long time, and the method of blending a high-gloss substance has a high cost.

[0005] CN202310939941.0 discloses a high-flowability, high-toughness, and high-gloss ABS resin and its preparation method, which uses small-particle-size polystyrene latex as the core to graft polybutadiene latex and adds SAN for blending, and uses polystyrene as the core to improve the flowability and gloss of ABS resin. However, the hardness of the ABS resin with good flowability is low.

[0006] Therefore, there is an urgent need to develop an ABS resin that can simultaneously have high gloss, high hardness, and high impact resistance, has high comprehensive performance and good balance. Summary of the Invention

[0007] The purpose of the present invention is to overcome the problem that existing ABS resin is difficult to simultaneously have high gloss, high hardness, and high impact resistance, and to provide a high-gloss, high-hardness, and high-impact-resistant ABS resin and its preparation method and application.

[0008] To achieve the above object, a first aspect of the present invention provides a method for preparing a high-gloss, high-hardness, and high-impact-resistant ABS resin, and the method comprises the following steps:

[0009] (1) Contact a base latex, an emulsion, styrene I, acrylonitrile I, a molecular weight regulator, and an initiator and then carry out a first-stage reaction to obtain a first-stage product;

[0010] (2) Add styrene II and acrylonitrile II to the first-stage product and carry out a second-stage reaction to obtain a second-stage product;

[0011] (3) Add methyl methacrylate I to the second-stage product and carry out a third-stage reaction to obtain a third-stage product;

[0012] (4) Add a coagulant to the third-stage product to carry out coagulation to obtain a graft powder;

[0013] (5) Carry out bulk polymerization on styrene III, acrylonitrile III, and methyl methacrylate II to obtain a modified SAN resin;

[0014] (6) Mix the graft powder, the modified SAN resin, an antioxidant, and a lubricant and then carry out extrusion granulation to obtain a high-gloss, high-hardness, and high-impact-resistant ABS resin.

[0015] A second aspect of the present invention provides a high-gloss, high-hardness, and high-impact-resistant ABS resin prepared by the preparation method described in the first aspect of the present invention.

[0016] A third aspect of the present invention provides an application of the high-gloss, high-hardness, and high-impact-resistant ABS resin described in the second aspect of the present invention in the fields of automobiles, electrical appliances, and building materials.

[0017] Through the above technical solutions, the beneficial technical effects obtained by the present invention are as follows:

[0018] 1) In the method for preparing a high-gloss, high-hardness, and high-impact-resistant ABS resin provided by the present invention, grafting a styrene-acrylonitrile copolymer inside the base latex can play a supporting role inside the base latex, thereby improving the impact resistance of the prepared ABS resin;

[0019] 2) In the method for preparing a high-gloss, high-hardness, and high-impact-resistant ABS resin provided by the present invention, adding a small amount of methyl methacrylate when preparing the SAN resin can significantly improve the glossiness of the prepared ABS resin;

[0020] 3) In the method for preparing a high-gloss, high-hardness, and high-impact-resistant ABS resin provided by the present invention, forming a styrene-acrylonitrile copolymer graft shell layer outside the first-stage product helps to significantly improve the impact strength and hardness of the ABS resin;

[0021] 4) The preparation method of the high-gloss, high-hardness, and high-impact ABS resin provided in the present invention forms a methyl methacrylate grafted shell layer outside the secondary product, which can improve the gloss of the ABS resin;

[0022] 5) The preparation method of the high-gloss, high-hardness, and high-impact ABS resin provided in the present invention has a simple and efficient process, the prepared product has stable quality and good repeatability;

[0023] 6) The high-gloss, high-hardness, and high-impact ABS resin provided in the present invention not only has good surface gloss, hardness, and impact resistance, but also has the advantages of convenient processing, high cost performance, and good balance, and can be widely used in the fields of automobiles, electrical appliances, and building materials. Detailed Embodiments

[0024] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values and individual point values of each range, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0025] The first aspect of the present invention provides a preparation method of a high-gloss, high-hardness, and high-impact ABS resin, wherein the method comprises the following steps:

[0026] (1) Contact the base latex, emulsion, styrene I, acrylonitrile I, molecular weight regulator, and initiator and carry out a primary reaction to obtain a primary product;

[0027] (2) Add styrene II and acrylonitrile II to the primary product and carry out a secondary reaction to obtain a secondary product;

[0028] (3) Add methyl methacrylate I to the secondary product and carry out a tertiary reaction to obtain a tertiary product;

[0029] (4) Add a coagulant to the tertiary product and carry out coagulation to obtain a grafted powder;

[0030] (5) Carry out bulk polymerization on styrene III, acrylonitrile III, and methyl methacrylate II to obtain a modified SAN resin;

[0031] (6) Mix the grafted powder, the modified SAN resin, an antioxidant, and a lubricant and carry out extrusion granulation to obtain a high-gloss, high-hardness, and high-impact ABS resin.

[0032] In step (1):

[0033] In one embodiment of the present invention, the base latex is a large-particle-size polybutadiene latex, and the particle size of the large-particle-size polybutadiene latex is 250 - 350 nm, preferably 280 - 300 nm; the solid content is 20 - 50 wt%, preferably 30 - 40 wt%.

[0034] Among them, the polybutadiene latex in the present invention is a large-particle-size polybutadiene latex obtained by expanding the particle size of the small-particle-size polybutadiene latex prepared according to the "Preparation Method of a Small-Particle-Size Polybutadiene Latex" disclosed in CN1313504C. The operation of expanding the particle size includes: mixing the small-particle-size polybutadiene latex and acetic acid with a mass ratio of 100:1.2 - 1.5, preferably 100:1.3 - 1.4, and stirring at room temperature for 20 - 40 mim, and then adding potassium hydroxide for neutralization.

[0035] In one embodiment of the present invention, the emulsion is an aqueous solution of an emulsifier. Among them, the emulsifier is selected from one or more of potassium oleate, potassium disproportionated rosin, and sodium dodecyl sulfate, preferably potassium oleate.

[0036] In one embodiment of the present invention, the content of the emulsifier in the emulsion is 5 - 15 wt%, preferably 8 - 12 wt%.

[0037] In one embodiment of the present invention, the molecular weight regulator is selected from dodecyl mercaptan, preferably n-dodecyl mercaptan and / or tert-dodecyl mercaptan.

[0038] In one embodiment of the present invention, the initiator is selected from one or more of cumene hydroperoxide, diisopropylbenzene hydroperoxide, and potassium persulfate, preferably cumene hydroperoxide.

[0039] In one embodiment of the present invention, based on 100 parts by weight of the base latex, the addition amount of the emulsion is 2 - 3.6 parts by weight, the addition amount of styrene I is 0.5 - 5 parts by weight, the addition amount of acrylonitrile I is 0.1 - 3 parts by weight, the addition amount of the molecular weight regulator is 0.1 - 0.4 parts by weight, and the addition amount of the initiator is 0.1 - 0.3 parts by weight.

[0040] In one embodiment of the present invention, based on 100 parts by weight of the base latex, the addition amount of the emulsion is 2.3 - 3 parts by weight, the addition amount of styrene I is 1.5 - 2.5 parts by weight, the addition amount of acrylonitrile I is 0.5 - 1 part by weight, the addition amount of the molecular weight regulator is 0.2 - 0.3 parts by weight, and the addition amount of the initiator is 0.15 - 0.25 parts by weight.

[0041] In one embodiment of the present invention, the operating conditions of the first-stage reaction include: the first-stage reaction temperature is 40-70°C, preferably 45-65°C; the first-stage reaction time is 10-50 min, preferably 20-40 min.

[0042] Among them, in the present invention, the first-stage reaction is carried out under normal pressure, and the normal pressure in the present invention has a well-known meaning, and the present invention does not make special limitations on it. Through the first-stage reaction, styrene I and acrylonitrile I can be grafted into the interior of the base latex to form a support inside the base latex, thereby improving the impact resistance of the prepared high-gloss, high-hardness, and high-impact ABS resin.

[0043] In step (2):

[0044] In one embodiment of the present invention, based on 100 parts by weight of the base latex, the addition amount of styrene II is 10-25 parts by weight, and the addition amount of acrylonitrile II is 2-8 parts by weight.

[0045] In a preferred embodiment of the present invention, based on 100 parts by weight of the base latex, the addition amount of styrene II is 13-16 parts by weight, and the addition amount of acrylonitrile II is 4-5.5 parts by weight.

[0046] Among them, in the invention, when the amounts of styrene II and acrylonitrile II are within the preferred ranges, the impact resistance and hardness properties of the prepared high-gloss, high-hardness, and high-impact ABS resin are better.

[0047] In one embodiment of the present invention, the addition method of styrene II and acrylonitrile II is dropwise addition, preferably dropwise addition after mixing styrene II and acrylonitrile II together. Among them, the dropwise addition time is the second-stage reaction time.

[0048] In one embodiment of the present invention, the operating conditions of the second-stage reaction include: the second-stage reaction temperature is 50-70°C, preferably 60-65°C; the second-stage reaction time is 120-180 min, preferably 130-150 min.

[0049] Among them, in the present invention, through the second-stage reaction, a styrene-acrylonitrile copolymer grafted shell layer can be formed outside the first-stage product. The styrene-acrylonitrile copolymer grafted shell layer can improve the compatibility between the graft powder and the continuous-phase modified SAN resin, and can further balance the impact strength and hardness.

[0050] In step (3):

[0051] In one embodiment of the present invention, based on 100 parts by weight of the base latex, the addition amount of methyl methacrylate I is 0.8-3 parts by weight, preferably 1.2-1.6 parts by weight.

[0052] In one embodiment of the present invention, the methyl methacrylate I is added dropwise, and the dropping time of the methyl methacrylate I is 15 - 35 min, preferably 20 - 30 min. Preferably, the second-stage product is first heated to 55 - 95 °C, preferably 65 - 75 °C, and then the methyl methacrylate I is added dropwise.

[0053] In one embodiment of the present invention, the operating conditions of the third-stage reaction include: the third-stage reaction temperature is 60 - 80 °C, preferably 65 - 70 °C; the third-stage reaction time is 0.2 - 0.8 h, preferably 0.3 - 0.5 h. Among them, in the present invention, the third-stage reaction time is timed from the end of the dropping of the methyl methacrylate I.

[0054] Among them, in the present invention, through the third-stage reaction, a methyl methacrylate grafted shell layer can be formed on the outside of the second-stage product. The methyl methacrylate grafted shell layer is relatively sparse, which helps to improve the gloss of the ABS resin.

[0055] In step (4):

[0056] In one embodiment of the present invention, the coagulant is selected from one or more of magnesium sulfate, sulfuric acid, and acetic acid, preferably acetic acid and / or magnesium sulfate.

[0057] In one embodiment of the present invention, based on 100 parts by weight of the base latex, the addition amount of the coagulant is 1 - 8 parts by weight, preferably 3 - 4 parts by weight.

[0058] In one embodiment of the present invention, the operating conditions of the coagulation include: the coagulation temperature is 40 - 100 °C, preferably 50 - 95 °C; the coagulation time is 1 - 5 h, preferably 2 - 3 h.

[0059] Among them, in the present invention, the third-stage product is flocculated under the action of the coagulant and transformed into a solid. The flocculated solid is dried to obtain the grafted powder.

[0060] In step (5):

[0061] In one embodiment of the present invention, based on 100 parts by weight of styrene III, the addition amount of acrylonitrile III is 20 - 40 parts by weight, preferably 29 - 37 parts by weight; the addition amount of methyl methacrylate II is 4 - 21 parts by weight, preferably 8 - 10 parts by weight.

[0062] Among them, in the present invention, the inventors have found through research that adding a small amount of methyl methacrylate during the preparation of SAN resin can significantly improve the gloss of the prepared high-gloss, high-hardness, and high-impact ABS resin.

[0063] In one embodiment of the present invention, the operating conditions for bulk polymerization include: the bulk polymerization temperature is 120 - 180 °C, preferably 145 - 160 °C; the bulk polymerization pressure is 0.05 - 0.45 MPa, preferably 0.1 - 0.3 MPa; the bulk polymerization time is 2 - 8 h, preferably 3 - 5 h.

[0064] In step (6):

[0065] In one embodiment of the present invention, the antioxidant includes a hindered phenol antioxidant and / or a phosphite antioxidant, preferably a hindered phenol antioxidant and a phosphite antioxidant.

[0066] In one embodiment of the present invention, the hindered phenol antioxidant is selected from antioxidant 1010 and / or antioxidant 1076, preferably antioxidant 1076; the phosphite antioxidant is selected from antioxidant 168 and / or antioxidant 618, preferably antioxidant 168.

[0067] In one embodiment of the present invention, the lubricant is selected from one or more of ethylene bisstearamide (EBS), ethylene bisoleamide, and zinc stearate, preferably ethylene bisstearamide.

[0068] In one embodiment of the present invention, based on 100 parts by weight of the graft powder, the addition amount of the modified SAN resin is 240 - 320 parts by weight, preferably 240 - 280 parts by weight; the addition amount of the antioxidant is 0.5 - 4 parts by weight, preferably 1.5 - 3 parts by weight; the addition amount of the lubricant is 1 - 4 parts by weight, preferably 1.5 - 2.5 parts by weight.

[0069] In one embodiment of the present invention, the extrusion granulation is carried out in a twin - screw extruder. The present invention does not make special limitations on the operating conditions of the twin - screw extruder, and the extrusion granulation can be carried out according to the conventional operations in the art.

[0070] The second aspect of the present invention provides a high - gloss, high - hardness, and high - impact - resistance ABS resin prepared by the method described in the first aspect of the present invention.

[0071] Among them, the ABS resin provided in the present invention has a core - shell structure. The core is polybutadiene, and a styrene - acrylonitrile polymer is grafted inside the core; the shell includes a first - layer shell disposed on the core and a second - layer shell disposed on the first - layer shell. Among them, the first - layer shell is a styrene - acrylonitrile polymer, and the second - layer shell is a methyl methacrylate polymer. The unique core - shell structure enables the ABS resin provided in the present invention to have both high gloss, high hardness, and high impact resistance, and has excellent comprehensive performance.

[0072] In a preferred embodiment of the present invention, the Charpy impact strength of the high-gloss, high-hardness, and high-impact ABS resin is 20-30 KJ / m 2 , preferably 23-27 KJ / m 2 ; the Rockwell hardness is 110-120 HRC, preferably 114-116 HRC; the glossiness is 90-100 GU, preferably 97-100 GU.

[0073] The third aspect of the present invention provides an application of the high-gloss, high-hardness, and high-impact ABS resin described in the second aspect of the present invention in the fields of automobiles, electrical appliances, and building materials.

[0074] Among them, the high-gloss, high-hardness, and high-impact ABS resin prepared in the present invention can be used to prepare products such as household appliances, automobile and motorcycle parts, office supplies, tools, sanitary wares, daily necessities, toys, and modifications. For example, it can be used to produce high-gloss black household appliance panels.

[0075] The present invention will be described in detail below through examples.

[0076] ① Basic latex: Refer to Example 3 disclosed in CN1313504C to prepare small-particle-size polybutadiene latex. Mix small-particle-size polybutadiene latex and acetic acid with a mass ratio of 100:1.3 and stir at room temperature for 30 minutes, and then neutralize with potassium hydroxide to obtain large-particle-size polybutadiene latex with a particle size of 300 nm and a solid content of 34 wt%.

[0077] ② Styrene, purchased from Daqing Petrochemical Company;

[0078] ③ Acrylonitrile, purchased from Daqing Petrochemical Company;

[0079] ④ Methyl methacrylate, commercially available;

[0080] ⑤ Initiators, cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, commercially available;

[0081] ⑥ The emulsion is an aqueous solution of an emulsifier. Among them, the content of the emulsifier is 10 wt%, and the emulsifiers are oleic acid potassium, disproportionated rosin potassium, and sodium dodecyl sulfate;

[0082] ⑦ Molecular weight regulator, tert-dodecyl mercaptan, commercially available;

[0083] ⑧ Coagulant, magnesium sulfate, commercially available;

[0084] ⑨ Antioxidant HG-107E, a mixture of hindered phenol antioxidant 1076 and phosphite antioxidant 168, commercially available;

[0085] ⑩ The lubricant is EBS, commercially available.

[0086] Example 1

[0087] (1) Add 1000 g of base latex, 30 g of emulsion (aqueous solution of potassium oleate), 20 g of styrene I, 7 g of acrylonitrile I, 2 g of molecular weight regulator and 2 g of initiator cumene hydroperoxide into the grafting kettle, and react at 50 °C for 30 min to obtain a first-stage product;

[0088] (2) Heat up the grafting kettle to 65 °C, and dropwise add a mixture of 144 g of styrene II and 48 g of acrylonitrile II within 140 min. After the dropping is completed, a second-stage product is obtained;

[0089] (3) Heat up the grafting kettle to 68 °C again, and dropwise add 14 g of methyl methacrylate I within 22 min. After the dropping is completed, react at 75 °C for 0.3 h, and then unload the material to obtain a third-stage product;

[0090] (4) Add 35 g of coagulant into the above third-stage product, coagulate at 60 °C for 2 h, and then dry to obtain grafted powder;

[0091] (5) Mix 1000 g of styrene III, 333 g of acrylonitrile III and 100 g of methyl methacrylate II, and carry out bulk polymerization at 155 °C and 0.2 MPa for 4 h to obtain modified SAN resin;

[0092] (6) Add 1000 g of the above grafted powder, 2800 g of the above modified SAN resin, 22 g of antioxidant and 21 g of lubricant into a twin-screw extruder. The extruded strip is cooled by a water bath and then pelletized to obtain high-gloss, high-hardness and high-impact ABS resin.

[0093] Example 2

[0094] (1) Add 1000 g of base latex, 23 g of emulsion (aqueous solution of potassium oleate), 25 g of styrene I, 6 g of acrylonitrile I, 3 g of molecular weight regulator and 1.5 g of initiator cumene hydroperoxide into the grafting kettle, and react at 50 °C for 30 min to obtain a first-stage product;

[0095] (2) Heat up the grafting kettle to 65 °C, and dropwise add a mixture of 139 g of styrene II and 52 g of acrylonitrile II within 135 min. After the dropping is completed, a second-stage product is obtained;

[0096] (3) Heat up the grafting kettle to 68 °C again, and dropwise add 12 g of methyl methacrylate I within 20 min. After the dropping is completed, react at 60 °C for 0.5 h, and then unload the material to obtain a third-stage product;

[0097] (4) Add 30 g of coagulant into the above third-stage product, coagulate at 60 °C for 2 h, and then dry to obtain grafted powder;

[0098] (5) After mixing 1000 g of styrene III, 370 g of acrylonitrile III, and 80 g of methyl methacrylate II, bulk polymerization was carried out at 155 °C and 0.2 MPa for 4 h to obtain a modified SAN resin;

[0099] (6) 1000 g of the above graft powder, 2600 g of the above modified SAN resin, 18 g of antioxidant, and 18 g of lubricant were added to a twin-screw extruder. The extruded strip was cooled in a water bath and then pelletized to obtain a high-gloss, high-hardness, and high-impact ABS resin.

[0100] Example 3

[0101] (1) 1000 g of base latex, 28 g of emulsion (aqueous solution of potassium oleate), 15 g of styrene I, 10 g of acrylonitrile I, 2.5 g of molecular weight regulator, and 2.5 g of initiator cumene hydroperoxide were added to a grafting kettle and reacted at 50 °C for 30 min to obtain a first-stage product;

[0102] (2) The temperature of the grafting kettle was raised to 65 °C, and a mixture of 153 g of styrene II and 45 g of acrylonitrile II was added dropwise within 145 min. After the addition was completed, a second-stage product was obtained;

[0103] (3) The temperature of the grafting kettle was raised to 68 °C again, and 16 g of methyl methacrylate I was added dropwise within 24 min. After the addition was completed, the reaction was carried out at 65 °C for 0.4 h, and then the material was unloaded to obtain a third-stage product;

[0104] (4) 40 g of coagulant was added to the above third-stage product, and coagulation was carried out at 60 °C for 2 h, followed by drying to obtain a graft powder;

[0105] (5) After mixing 1000 g of styrene III, 290 g of acrylonitrile III, and 100 g of methyl methacrylate II, bulk polymerization was carried out at 155 °C and 0.2 MPa for 4 h to obtain a modified SAN resin;

[0106] (6) 1000 g of the above graft powder, 2400 g of the above modified SAN resin, 26 g of antioxidant, and 25 g of lubricant were added to a twin-screw extruder. The extruded strip was cooled in a water bath and then pelletized to obtain a high-gloss, high-hardness, and high-impact ABS resin.

[0107] Example 4

[0108] (1) 1000 g of base latex, 20 g of emulsion (aqueous solution of potassium disproportionated rosin), 35 g of styrene I, 15 g of acrylonitrile I, 1.5 g of molecular weight regulator, and 1 g of initiator potassium persulfate were added to a grafting kettle and reacted at 70 °C for 15 min to obtain a first-stage product;

[0109] (2) Heat the grafting kettle to 70 °C, and dropwise add a mixture of 176 g of styrene II and 70 g of acrylonitrile II within 160 min. After the dropping is completed, a second-stage product is obtained;

[0110] (3) Heat the grafting kettle to 68 °C again, and dropwise add 20 g of methyl methacrylate I within 26 min. After the dropping is completed, react at 60 °C for 0.8 h, and then discharge the material to obtain a third-stage product;

[0111] (4) Add 50 g of a coagulant to the above third-stage product, coagulate at 50 °C for 4 h, and then perform drying to obtain grafted powder;

[0112] (5) Mix 1000 g of styrene III, 400 g of acrylonitrile III and 110 g of methyl methacrylate II, and carry out bulk polymerization at 135 °C and 0.4 MPa for 6 h to obtain a modified SAN resin;

[0113] (6) Add 1000 g of the above grafted powder, 3000 g of the above modified SAN resin, 10 g of an antioxidant and 30 g of a lubricant to a twin-screw extruder. The extruded strand is cooled in a water bath and then pelletized to obtain a high-gloss, high-hardness and high-impact ABS resin.

[0114] Example 5

[0115] (1) Add 1000 g of base latex, 36 g of an emulsion (sodium dodecyl sulfate aqueous solution), 45 g of styrene I, 20 g of acrylonitrile I, 4 g of a molecular weight regulator and 2.7 g of an initiator dicumyl peroxide to the grafting kettle, and react at 50 °C for 30 min to obtain a first-stage product;

[0116] (2) Heat the grafting kettle to 65 °C, and dropwise add a mixture of 118 g of styrene II and 30 g of acrylonitrile II within 120 min. After the dropping is completed, a second-stage product is obtained;

[0117] (3) Heat the grafting kettle to 68 °C again, and dropwise add 25 g of methyl methacrylate I within 30 min. After the dropping is completed, react at 80 °C for 0.2 h, and then discharge the material to obtain a third-stage product;

[0118] (4) Add 20 g of a coagulant to the above third-stage product, coagulate at 60 °C for 2 h, and then perform drying to obtain grafted powder;

[0119] (5) Mix 1000 g of styrene III, 250 g of acrylonitrile III and 210 g of methyl methacrylate II, and carry out bulk polymerization at 155 °C and 0.2 MPa for 4 h to obtain a modified SAN resin;

[0120] (6) Add 1000 g of the above grafted powder, 3200 g of the above modified SAN resin, 5 g of antioxidant and 15 g of lubricant into a twin-screw extruder. After the extruded strip is cooled by a water bath, it is pelletized to obtain a high-gloss, high-hardness and high-impact ABS resin.

[0121] Example 6

[0122] (1) Add 1000 g of base latex, 32 g of emulsion (sodium dodecyl sulfate aqueous solution), 8 g of styrene I, 3 g of acrylonitrile I, 3.5 g of molecular weight regulator and 3 g of initiator cumene hydroperoxide into a grafting kettle, and react at 40 °C for 40 min to obtain a first-stage product.

[0123] (2) Raise the temperature of the grafting kettle to 65 °C, and dropwise add a mixture of 215 g of styrene II and 80 g of acrylonitrile II within 150 min. After the dropping is completed, a second-stage product is obtained.

[0124] (3) Raise the temperature of the grafting kettle to 65 °C again, dropwise add 8 g of methyl methacrylate I within 18 min. After the dropping is completed, react at 60 °C for 0.8 h, and then unload the material to obtain a third-stage product.

[0125] (4) Add 65 g of coagulant to the above third-stage product, coagulate at 70 °C for 1 h, and then dry to obtain grafted powder.

[0126] (5) Mix 1000 g of styrene III, 380 g of acrylonitrile III and 40 g of methyl methacrylate II, and carry out bulk polymerization at 170 °C and 0.05 MPa for 2 h to obtain modified SAN resin.

[0127] (6) Add 1000 g of the above grafted powder, 2800 g of the above modified SAN resin, 305 g of antioxidant and 305 g of lubricant into a twin-screw extruder. After the extruded strip is cooled by a water bath, it is pelletized to obtain a high-gloss, high-hardness and high-impact ABS resin.

[0128] Comparative Example 1

[0129] Same as Example 2, except that styrene I and acrylonitrile I in the first-stage reaction are omitted.

[0130] (1) Add 1000 g of base latex, 23 g of emulsion (potassium oleate aqueous solution), 3 g of molecular weight regulator and 1.5 g of initiator cumene hydroperoxide into a grafting kettle, and react at 50 °C for 30 min to obtain a first-stage product.

[0131] (2) Raise the temperature of the grafting kettle to 65 °C, and dropwise add a mixture of 139 g of styrene II and 52 g of acrylonitrile II within 135 min. After the dropping is completed, a second-stage product is obtained.

[0132] (3) Reheat the grafting kettle to 68 °C again, and dropwise add 12 g of methyl methacrylate I within 20 min. After the addition is completed, react at 60 °C for 0.5 h, and then discharge the material to obtain a three-stage product;

[0133] (4) Add 30 g of flocculant to the above three-stage product, flocculate at 60 °C for 2 h, and then dry to obtain grafted powder;

[0134] (5) Mix 1000 g of styrene III, 370 g of acrylonitrile III and 80 g of methyl methacrylate II, and carry out bulk polymerization at 155 °C and 0.2 MPa for 4 h to obtain modified SAN resin;

[0135] (6) Add 1000 g of the above grafted powder, 2600 g of the above modified SAN resin, 18 g of antioxidant and 18 g of lubricant to a twin-screw extruder. The extruded strip is cooled by a water bath and then pelletized to obtain ABS resin.

[0136] Comparative Example 2

[0137] Same as Example 2, except that methyl methacrylate II in step (5) is omitted.

[0138] (1) Add 1000 g of base latex, 23 g of emulsion (aqueous solution of potassium oleate), 25 g of styrene I, 6 g of acrylonitrile I, 0.3 g of molecular weight regulator and 1.5 g of initiator cumene hydroperoxide to the grafting kettle, and react at 50 °C for 30 min to obtain a first-stage product;

[0139] (2) Heat the grafting kettle to 65 °C, and dropwise add a mixture of 139 g of styrene II and 52 g of acrylonitrile II within 135 min. After the addition is completed, obtain a second-stage product;

[0140] (3) Reheat the grafting kettle to 68 °C again, and dropwise add 12 g of methyl methacrylate I within 20 min. After the addition is completed, react at 60 °C for 0.5 h, and then discharge the material to obtain a three-stage product;

[0141] (4) Add 30 g of flocculant to the above three-stage product, flocculate at 60 °C for 2 h, and then dry to obtain grafted powder;

[0142] (5) Mix 1000 g of styrene III and 370 g of acrylonitrile III, and carry out bulk polymerization at 155 °C and 0.2 MPa for 4 h to obtain SAN resin;

[0143] (6) Add 1000 g of the above grafted powder, 2600 g of the above SAN resin, 18 g of antioxidant and 18 g of lubricant into a twin-screw extruder. After the extruded strip is cooled by a water bath, it is pelletized to obtain ABS resin.

[0144] Comparative Example 3

[0145] Same as Example 2, except that the second-stage reaction is omitted.

[0146] (1) Add 1000 g of base latex, 23 g of emulsion (potassium oleate aqueous solution), 25 g of styrene I, 6 g of acrylonitrile I, 3 g of molecular weight regulator and 1.5 g of initiator cumene hydroperoxide into a grafting kettle, and react at 50 °C for 30 min to obtain a first-stage product;

[0147] (2) Raise the temperature of the grafting kettle to 68 °C, and dropwise add 12 g of methyl methacrylate I within 20 min. After the dropping is completed, react at 60 °C for 0.5 h, and then discharge the material to obtain a reaction product;

[0148] (3) Add 30 g of coagulant to the above reaction product, coagulate at 60 °C for 2 h, and then dry to obtain grafted powder;

[0149] (4) Mix 1000 g of styrene III, 370 g of acrylonitrile III and 80 g of methyl methacrylate II, and carry out bulk polymerization at 155 °C and 0.2 MPa for 4 h to obtain modified SAN resin;

[0150] (5) Add 1000 g of the above grafted powder, 2600 g of the above modified SAN resin, 18 g of antioxidant and 18 g of lubricant into a twin-screw extruder. After the extruded strip is cooled by a water bath, it is pelletized to obtain ABS resin.

[0151] Comparative Example 4

[0152] Same as Example 2, except that the third-stage reaction is omitted.

[0153] (1) Add 1000 g of base latex, 23 g of emulsion (potassium oleate aqueous solution), 25 g of styrene I, 6 g of acrylonitrile I, 3 g of molecular weight regulator and 1.5 g of initiator cumene hydroperoxide into a grafting kettle, and react at 50 °C for 30 min to obtain a first-stage product;

[0154] (2) Raise the temperature of the grafting kettle to 65 °C, and dropwise add a mixture of 139 g of styrene II and 52 g of acrylonitrile II within 135 min. After the dropping is completed, obtain a second-stage product;

[0155] (3) Add 30 g of coagulant to the above second-stage product, coagulate at 60 °C for 2 h, and then dry to obtain grafted powder;

[0156] (4) After mixing 1000 g of styrene III, 370 g of acrylonitrile III, and 80 g of methyl methacrylate II, bulk polymerization was carried out at 155 °C and 0.2 MPa for 4 h to obtain a modified SAN resin;

[0157] (5) 1000 g of the above grafted powder, 2600 g of the above modified SAN resin, 18 g of antioxidant, and 18 g of lubricant were added to a twin-screw extruder. The extruded strip was cooled in a water bath and then pelletized to obtain an ABS resin.

[0158] Test Example 1

[0159] The high-gloss, high-hardness, and high-impact ABS resins prepared in Examples 1-6 and the ABS resins prepared in Comparative Examples 1-4 were dried in a forced-air oven at 80 °C for 4 h, and then injection molded into standard specimens and 80 mm * 10 mm * 4 mm specimens using a plastic injection molding machine, with an injection temperature of 240 °C; After the injection-molded specimens and specimens were placed in an environment with a relative humidity of 50% and a temperature of 23 °C for 24 h, performance tests were carried out, and the test results are shown in Tables 1-2.

[0160] Among them, the product performance test methods are as follows:

[0161] Charpy impact strength was tested at room temperature according to the GB / T1043.1 standard;

[0162] Rockwell hardness was tested according to the GB / T3398.2 standard;

[0163] Glossiness was tested according to the ISO 2813 standard.

[0164] Table 1

[0165]

[0166] Among them, as can be seen from Table 1, the Charpy impact strength of the ABS resin prepared in the present invention is above 20 KJ / m 2 , the Rockwell hardness ≥ 110 HRC, and the glossiness is between 90-100 GU, which can have both high gloss, high hardness, and high impact resistance.

[0167] Table 2

[0168]

[0169] As can be seen from Table 2, by comparing Example 2 and Comparative Example 1, grafting styrene-acrylonitrile copolymer inside the base latex can play a supporting role inside the base latex, thereby improving the impact resistance of the prepared ABS resin.

[0170] It can be seen by comparing Example 2 with Comparative Example 3 that forming a styrene-acrylonitrile copolymer grafted shell layer outside the primary product helps to significantly improve the impact strength and hardness of the ABS resin.

[0171] It can be seen by comparing Example 2 with Comparative Example 2 that adding a small amount of methyl methacrylate during the preparation of the SAN resin helps to improve the gloss of the obtained ABS resin. It can be seen by comparing Example 2 with Comparative Example 4 that forming a methyl methacrylate grafted shell layer outside the secondary product can significantly improve the gloss of the ABS resin. The combined action of the methyl methacrylate grafted shell layer and the modified SAN resin can greatly enhance the gloss of the ABS resin.

[0172] 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 technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A preparation method of a high-gloss, high-hardness and high-impact ABS resin, characterized in that, The method includes the following steps: (1) After contacting the base latex, the emulsion, styrene I, acrylonitrile I, molecular weight regulator, and initiator, perform a first-stage reaction to obtain a first-stage product; (2) Add styrene II and acrylonitrile II to the first-stage product to perform a second-stage reaction to obtain a second-stage product; (3) Add methyl methacrylate I to the second-stage product to perform a third-stage reaction to obtain a third-stage product; (4) Add a coagulant to the third-stage product to perform coagulation to obtain graft powder; (5) Perform bulk polymerization on styrene III, acrylonitrile III, and methyl methacrylate II to obtain a modified SAN resin; (6) Mix the graft powder, the modified SAN resin, an antioxidant, and a lubricant, and then perform extrusion granulation to obtain a high-gloss, high-hardness, and high-impact ABS resin.

2. The preparation method according to claim 1, wherein, The base latex is polybutadiene latex; the emulsion is selected from one or more of potassium oleate, potassium disproportionated rosin, and sodium dodecyl sulfate; the molecular weight regulator is selected from dodecyl mercaptan; the initiator is selected from one or more of cumene hydroperoxide, diisopropylbenzene hydroperoxide, and potassium persulfate; Based on 100 parts by weight of the base latex, the addition amount of the emulsion is 2-3.6 parts by weight, the addition amount of styrene I is 0.5-5 parts by weight, the addition amount of acrylonitrile I is 0.1-3 parts by weight, the addition amount of the molecular weight regulator is 0.1-0.4 parts by weight, and the addition amount of the initiator is 0.1-0.3 parts by weight; The operating conditions of the first-stage reaction include: the first-stage reaction temperature is 40-70 °C, and the first-stage reaction time is 10-50 min.

3. The preparation method according to claim 1, wherein, Based on 100 parts by weight of the base latex, the addition amount of styrene II is 10-25 parts by weight, and the addition amount of acrylonitrile II is 2-8 parts by weight; The operating conditions of the second-stage reaction include: the second-stage reaction temperature is 50-70 °C, and the second-stage reaction time is 120-180 min.

4. The preparation method according to claim 1, wherein, Based on 100 parts by weight of the base latex, the addition amount of methyl methacrylate I is 0.8-3 parts by weight; The operating conditions of the third-stage reaction include: the third-stage reaction temperature is 60-80 °C, and the third-stage reaction time is 0.2-0.8 h.

5. The preparation method according to claim 1, wherein, The coagulant is selected from one or more of magnesium sulfate, sulfuric acid, and acetic acid; Based on 100 parts by weight of the base latex, the addition amount of the coagulant is 1-8 parts by weight; The operating conditions of the coagulation include: the coagulation temperature is 40-100 °C, and the coagulation time is 1-5 h.

6. The preparation method according to claim 1, wherein, Based on 100 parts by weight of styrene III, the addition amount of acrylonitrile III is 20-40 parts by weight, and the addition amount of methyl methacrylate II is 4-21 parts by weight; The operating conditions of the bulk polymerization include: the bulk polymerization temperature is 120-180 °C, the bulk polymerization pressure is 0.05-0.45 MPa, and the bulk polymerization time is 2-8 h.

7. The preparation method according to claim 1, wherein The antioxidant includes a hindered phenol antioxidant and / or a phosphite antioxidant; Among them, the hindered phenol antioxidant is selected from antioxidant 1010 and / or antioxidant 1076; the phosphite antioxidant is selected from antioxidant 168 and / or antioxidant 618; The lubricant is selected from one or more of ethylene bisstearamide, ethylene bisoleamide, and zinc stearate; Based on 100 parts by weight of the grafted powder, the addition amount of the modified SAN resin is 240 - 320 parts by weight, the addition amount of the antioxidant is 0.5 - 4 parts by weight, and the addition amount of the lubricant is 1 - 4 parts by weight.

8. A high-gloss, high-hardness, and high-impact ABS resin prepared by the method according to any one of claims 1 - 7.

9. The ABS resin according to claim 8, wherein, The Charpy impact strength of the high-gloss, high-hardness, and high-impact ABS resin is 20 - 30 KJ / m 2 , the Rockwell hardness is 110 - 120 HRC, and the glossiness is 90 - 100 GU.

10. Use of the high-gloss, high-hardness, and high-impact ABS resin according to claim 8 or 9 in the fields of automobiles, electrical appliances, and building materials.

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