High-transparency ABS resin and preparation method thereof

Abstract

The invention provides high-transparency ABS (acrylonitrile butadiene styrene) resin and a preparation method thereof.The high-transparency ABS resin is prepared from, by weight, 30-60 parts of ABS resin, 5-16 parts of methyl methacrylate monomer, 2-20 parts of modifier and 0.4-1 part of antioxidant. According to the method, a modifier system composed of hydrogenated rosin and derivatives thereof is mainly adopted to be blended with an ABS system, and the high-transparency ABS resin is prepared. And the ABS resin with excellent mechanical properties and high transparency can be obtained through twin-screw melt extrusion. The obtained ABS resin product has the characteristics of excellent mechanical property and high transparency, the preparation process is simple, the production cost is reduced, the application range of the product is wide, the problems of single raw material, limited resin transparency improvement, complex production process and high production cost of the existing transparent ABS resin are solved, and the method is suitable for industrial production. The market popularization and application of the high-end transparent ABS resin are promoted, and a new thought is provided for the development of the high-performance high-transparency ABS resin.

Description

Technical Field

[0001] The present invention relates to the field of ABS resins, and particularly relates to a highly transparent ABS resin and a preparation method thereof. Background Art

[0002] ABS resin is a copolymer synthesized from three monomers: acrylonitrile, butadiene, and styrene. Transparent ABS resin is obtained by adding methyl methacrylate (MMA) on this basis, and has characteristics such as high transparency, high hardness, high rigidity, and high impact strength. It is widely used in fields such as electronic appliances, vacuum cleaners, smoking machines, toys, furniture, and medical products. By researching highly transparent ABS resin, not only can the application fields of ABS be broadened, but also the requirements for transparent materials in special industrial fields can be met, promoting the innovation and development of related industries. At the same time, by optimizing the preparation process and formula, its performance can be improved, the cost can be reduced, and its wider application can be promoted.

[0003] The existing patent CN119101197A reports a highly tough and rigid transparent ABS resin and a preparation method thereof. The invention uses a binary or ternary copolymer of styrene, acrylonitrile, and methyl methacrylate as the innermost core (this core is a plastic core), and then constructs an outer core of polybutadiene or styrene-butadiene rubber on the surface of this plastic core (this layer is a rubber phase), and finally grafts a shell layer of a binary or ternary copolymer of styrene, acrylonitrile, and methyl methacrylate on the surface of the outer core, and finally prepares an ABS graft copolymer with a three-layer structure. This technology prepares a transparent ABS resin with good impact performance and tensile strength by regulating the refractive indices of the three layers of polymers. However, this technology has high requirements for materials, complicated processes, high production costs, and general impact resistance of the product. Patents CN106699981B and CN106221114B disclose a transparent ABS resin composition with a large phase region size. By weight percentage, it includes 6-12% of rubber-like copolymer particles in the dispersed phase and 88-94% of the copolymer continuous phase; the number average molecular weight of the copolymer continuous phase is 40,000-150,000, and the weight average molecular weight is 50,000-300,000. A transparent ABS resin is prepared by bulk polymerization technology. This technology controls the particle size of rubber particles by controlling the phase inversion in bulk polymerization, and finally prepares a transparent ABS resin with high impact strength and few residual monomers. The transparent ABS resin prepared by this method has relatively high impact strength, but poor tensile strength, and the bulk polymerization preparation process is relatively complicated, with high requirements for equipment and high production costs. In addition, for patent CN1172120A, according to the method provided by this patent, the optimal range of the number average molecular weight of the resin phase is controlled to be 15×10 4 ~35×10 4, while using a styrene-butadiene copolymer with a styrene content of 60-95% as a toughening agent. The finally prepared transparent resin has excellent transparency, up to 90% at most, but its impact resistance is poor and needs to be further improved. Patent CN104136530B prepares an acrylonitrile-butadiene-styrene graft (g-ABS) copolymer (A) by graft copolymerizing a monomer mixture (a2) based on acrylate monomers, styrene-based monomers, and acrylonitrile-based monomers onto a butadiene-based rubber polymer (a1). The g-ABS copolymer (A) is preferably polymerized at a grafting rate of 55 to 80% to prepare a transparent ABS resin, which has good product strength and high hardness, but its impact strength is not satisfactory.

[0004] In summary, the preparation of transparent ABS resin currently mainly realizes by adding the modified raw material MMA, or further improving the synthesis process after adding MMA to adjust the size ratio of the polyacrylonitrile-styrene and polybutadiene blend phase. Not only is the raw material single, the improvement of resin transparency is limited, but also the complex production process greatly increases the production cost of transparent ABS resin, hindering the application of high-end transparent ABS resin. Therefore, developing a new type of high-transparency ABS resin is of great significance for meeting the market demand of high-end transparent ABS resin. Summary of the Invention

[0005] To improve the transparency of ABS resin while maintaining its original mechanical properties and reducing the production cost of transparent ABS resin, the present invention provides a high-transparency ABS resin and its preparation method. This method mainly uses a modifier system composed of hydrogenated rosin and its derivatives to blend with the ABS system, and excellent mechanical properties and high-transparency ABS resin can be obtained through twin-screw melt extrusion, which is beneficial to promoting the market promotion and application of high-end transparent ABS resin.

[0006] The present invention is realized through the following technical solutions:

[0007] A high-transparency ABS resin comprises the following raw materials in parts by weight: 30-60 parts of ABS resin, 5-16 parts of methyl methacrylate monomer, 5-20 parts of modifier, and 0.4-1 part of antioxidant.

[0008] Specifically, the light transmittance of the ABS resin is greater than or equal to 80%, and preferably the ABS product of CT2010 brand of Guangxi Changke New Materials Co., Ltd.

[0009] Specifically, the modifier is one or a mixture of hydrogenated rosin, hydrogenated rosin alcohol, hydrogenated rosin alcohol derivatives, epoxy resin, polyisobutylene, methyl silicone oil, vinyl silicone oil.

[0010] Furthermore, the hydrogenated rosin alcohol derivative can be prepared by using hydrogenated rosin or abietic acid as raw materials and reacting with epichlorohydrin under the promotion of tetrabutylammonium bromide or tetrabutylammonium chloride.

[0011] Specifically, the antioxidant is one or a mixture of antioxidants 168, 1076, and 1010. Among them, preferably, the hindered phenol antioxidant with model 1010 is used as the main antioxidant, and the hindered phenol antioxidant with model 168 is used as the auxiliary antioxidant. The main antioxidant 1010 and the auxiliary antioxidant 168 are configured in a weight ratio of 3:1.

[0012] A preparation method of a highly transparent ABS resin includes the following steps: (1) Accurately weigh the raw materials of ABS resin, methyl methacrylate monomer, modifier, and antioxidant in proportion; (2) Add the raw materials in step (1) to a mixer in turn, and mix at a rotation speed of 1200 - 1800 r / min for 40 - 100 min to obtain mixture A; (3) Add mixture A to a twin-screw extruder for reaction, and melt and extrude through the following temperature sections in turn. The temperature of the first zone of the twin-screw extruder is 165 - 175 °C, the temperature of the second zone is 175 - 190 °C, the temperature of the third zone is 190 - 210 °C, the temperature of the fourth zone is 180 - 200 °C. Control the head temperature to be 220 - 230 °C, the residence time is 2 - 3 min, and the pressure is 13 - 18 MPa to obtain reaction product B; (4) Pelletize and dry reaction product B to obtain the finished product.

[0013] The beneficial effects of the present invention are as follows: The present invention provides a highly transparent ABS resin and its preparation method. This technology mainly blends a modifier system composed of hydrogenated rosin and its derivatives with the ABS system. During the twin-screw melt extrusion process, the carboxyl or hydroxyl group in the structure of hydrogenated rosin and its derivatives in the modifier system interacts with the polar components in the ABS resin, and the tricyclic phenanthrene structure in its structure interacts with the non-polar components in the ABS resin, not only improving the compatibility between polyacrylonitrile-styrene and polybutadiene in the ABS resin, but also the large-volume tricyclic phenanthrene structure maintaining the mechanical strength of the ABS resin. Therefore, the ABS resin product obtained by the present invention has both excellent mechanical properties and high transparency, and moreover, the preparation process is simple, the production cost is reduced, the product has a wide range of applications, solving the problems of single raw materials of existing transparent ABS resins, limited improvement in resin transparency, complex production processes, and high production costs. It not only helps to promote the market promotion and application of high-end transparent ABS resins, but also provides a new idea for the development of high-performance and highly transparent ABS resins. Specific embodiments

[0014] The technical solution of the present invention will be described clearly and completely below. Obviously, the embodiments described herein are only a part rather than all of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention.

[0015] The hydrogenated rosin alcohol derivative in the present invention can be prepared by the following method: Dissolve hydrogenated rosin or abietic acid resin in solvents such as toluene, xylene, dichloromethane, etc., add epichlorohydrin and mix evenly, add tetrabutylammonium bromide or tetrabutylammonium chloride as a promoter, and react at 60-110 °C for 0.5-8 h. After the reaction is completed, add deionized water, shake well, let it stand for layering, remove the water layer, and perform high-vacuum rotary evaporation on the oil-soluble layer liquid to obtain the hydrogenated rosin alcohol derivative. Specifically, the amount of epichlorohydrin added, in terms of the amount of substance, is 1.1-1.3 times the amount of carboxyl groups in hydrogenated rosin or abietic acid resin.

[0016] The preparation of abietic acid in the present invention is carried out according to the literature (Wan Guoyun, Wang Zhenguo, Su Jianxiong. Preparation of acrylic rosin polyester fiberglass from rosin [J]. Plastics Industry, 1987, (01): 30-32+2.). Add rosin and acrylic acid to a three-necked flask at a mass ratio of 4:25, heat to 170 °C under nitrogen protection and react for 2 h to isomerize the abietic acid-type resin acid in rosin to form levopimaric acid. Then raise the temperature to 225 °C and react for 2 h. Since the conjugated double bond of levopimaric acid belongs to S-cis, its reaction activity is relatively high, and it undergoes a Diels-Alder reaction with the dienophile - acrylic acid to obtain abietic acid as a pale yellow transparent solid.

[0017] Example 1 By mass, take 30 parts of ABS resin of grade CT2010, 5 parts of methyl methacrylate monomer, 1 part of hydrogenated rosin, 1 part of hydrogenated rosin alcohol derivative, and 0.4 part of antioxidant 168. Add the above raw materials to a high-speed mixer in sequence, and mix at a speed of 1200 r / min for 40 min to obtain mixture A; add mixture A to a twin-screw extruder for reaction, and melt and extrude through the following temperature sections in sequence. The temperature of the first zone of the twin-screw extruder is 170 °C, the second zone is 180 °C, the third zone is 190 °C, the fourth zone is 200 °C, control the head temperature to be 230 °C, the residence time is 2-3 min, and the pressure is 15 MPa to obtain reaction product B; perform water cooling, strand cutting, and drying on reaction product B to obtain high-transparency ABS resin pellets.

[0018] Example 2 By mass, take 40 parts of ABS resin with the brand CT2010, 8 parts of methyl methacrylate monomer, 6 parts of hydrogenated rosin alcohol, and 0.7 part of antioxidant 1010. Add the above raw materials into a high-speed mixer in sequence. At a rotation speed of 1300 r / min, mix for 50 min to obtain mixture A; add mixture A into a twin-screw extruder for reaction, and melt and extrude through the following temperature sections in sequence. The temperature of the first zone of the twin-screw extruder is 175 °C, the second zone is 190 °C, the third zone is 210 °C, the fourth zone is 200 °C. Control the head temperature to be 220 °C, the residence time is 2 - 3 min, and the pressure is 18 MPa to obtain reaction product B; carry out water-cooled strand drawing, pelletizing, and drying on reaction product B to obtain high-transparency ABS resin pellets.

[0019] Example 3 By mass, take 50 parts of ABS resin with the brand CT2010, 12 parts of methyl methacrylate monomer, 4 parts of hydrogenated rosin alcohol derivative, 1.5 parts of epoxy resin, 0.5 part of polyisobutene, 0.2 part of antioxidant 1076, and 0.4 part of antioxidant 1010. Add the above raw materials into a high-speed mixer in sequence. At a rotation speed of 1400 r / min, mix for 80 min to obtain mixture A; add mixture A into a twin-screw extruder for reaction, and melt and extrude through the following temperature sections in sequence. The temperature of the first zone of the twin-screw extruder is 175 °C, the second zone is 190 °C, the third zone is 210 °C, the fourth zone is 200 °C. Control the head temperature to be 220 °C, the residence time is 2 - 3 min, and the pressure is 14 MPa to obtain reaction product B; carry out water-cooled strand drawing, pelletizing, and drying on reaction product B to obtain high-transparency ABS resin pellets.

[0020] Example 4 By mass, take 60 parts of ABS resin with the brand CT2010, 16 parts of methyl methacrylate monomer, 5 parts of hydrogenated rosin, 12 parts of hydrogenated rosin alcohol derivative, 2.5 parts of epoxy resin, 0.5 part of methyl silicone oil, 0.2 part of antioxidant 168, 0.2 part of antioxidant 1076, and 0.6 part of antioxidant 1010. Add the above raw materials into a high-speed mixer in sequence. At a rotation speed of 1800 r / min, mix for 100 min to obtain mixture A; add mixture A into a twin-screw extruder for reaction, and melt and extrude through the following temperature sections in sequence. The temperature of the first zone of the twin-screw extruder is 175 °C, the second zone is 180 °C, the third zone is 200 °C, the fourth zone is 180 °C. Control the head temperature to be 220 °C, the residence time is 2 - 3 min, and the pressure is 18 MPa to obtain reaction product B; carry out water-cooled strand drawing, pelletizing, and drying on reaction product B to obtain high-transparency ABS resin pellets.

[0021] Example 5 By mass, take 45 parts of ABS resin with the grade of CT2010, 12 parts of methyl methacrylate monomer, 7.5 parts of hydrogenated rosin alcohol derivative, 0.5 part of vinyl silicone oil, 0.2 part of antioxidant 168, and 0.6 part of antioxidant 1010. Add the above raw materials into a high-speed mixer in sequence, and mix at a speed of 1500 r / min for 100 min to obtain mixture A; add mixture A into a twin-screw extruder for reaction, and melt and extrude through the following temperature sections in sequence. The temperature of the first zone of the twin-screw extruder is 170 °C, the temperature of the second zone is 185 °C, the temperature of the third zone is 200 °C, the temperature of the fourth zone is 195 °C, control the head temperature to be 220 °C, the residence time is 2 - 3 min, and the pressure is 13 MPa to obtain reaction product B; carry out water-cooling drawing, pelletizing, and drying on reaction product B to obtain high-transparency ABS resin pellets.

[0022] Take the ABS resin with the grade of CT2010 as a comparative example, and compare its performance with the high-transparency ABS resins prepared in Examples 1 to 4. Rectangular specimens with a thickness of 4 mm and a width of 10 mm are respectively made for tensile property characterization, and the tensile rate is 50 mm / min; circular specimens with a thickness of 4 mm and a diameter of 60 mm are made for transparency characterization.

[0024] Those skilled in the art will readily conceive of other embodiments of the present invention after considering the specification and practicing the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the present invention, which follow the general principles of the present invention and include the known common knowledge or conventional technical means in the technical field not disclosed by the present invention. The specification and examples are only regarded as exemplary, and the true scope and spirit of the present invention are pointed out by the following claims.

[0025] It should be understood that the present invention is not limited to the content described above and can be modified and changed without departing from its scope. The scope of the present invention is only limited by the appended claims.

Claims

1. A highly transparent ABS resin, characterized in that, The raw materials include the following weight ratios: 30 - 60 parts of ABS resin, 5 - 16 parts of methyl methacrylate monomer, 2 - 20 parts of modifier, and 0.4 - 1 part of antioxidant.

2. A highly transparent ABS resin according to claim 1, characterized in that, The modifier is one or a mixture of hydrogenated rosin, hydrogenated rosin alcohol, hydrogenated rosin alcohol derivatives, polyisobutylene, methyl silicone oil, vinyl silicone oil, and epoxy resin.

3. A highly transparent ABS resin according to claim 1, characterized in that, The light transmittance of the ABS resin is greater than or equal to 80%, and preferably the ABS product of CT2010 grade.

4. A highly transparent ABS resin according to claim 1, wherein The antioxidant is one or a mixture of antioxidant 168, antioxidant 1076, and antioxidant 1010. Preferably, the hindered phenol antioxidant with the model 1010 is used as the main antioxidant, and the hindered phenol antioxidant with the model 168 is used as the auxiliary antioxidant. The main antioxidant 1010 and the auxiliary antioxidant 168 are configured in a weight ratio of 3:

1.

5. A preparation method of a highly transparent ABS resin, characterized in that, It includes the following steps: (1) Weigh accurately the ABS resin, methyl methacrylate monomer, modifier, and antioxidant according to the ratio. (2) Add the raw materials in step (1) into a mixer in sequence, and mix at a speed of 1200 - 1800 r / min for 40 - 100 min to obtain mixture A. (3) Add mixture A into a twin - screw extruder for reaction, and melt - extrude it successively through the following temperature sections. The temperature of the first zone of the twin - screw extruder is 165 - 175 °C, the second zone is 175 - 190 °C, the third zone is 190 - 210 °C, the fourth zone is 180 - 200 °C. Control the head temperature to be 220 - 230 °C, the residence time is 2 - 3 min, and the pressure is 13 - 18 MPa to obtain reaction product B. (4) Pelletize and dry the reaction product B to obtain the finished product.