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CN-122011722-A - Low-warpage PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) high-gloss plastic and compatibilization modification preparation method thereof

CN122011722ACN 122011722 ACN122011722 ACN 122011722ACN-122011722-A

Abstract

The invention discloses a low-warpage PC/ABS (polycarbonate/acrylonitrile butadiene styrene) highlight plastic and a compatibilization modification preparation method thereof, belonging to the technical field of high-molecular modified engineering plastics. The high-gloss plastic comprises 60-80 parts of polycarbonate, 20-40 parts of ABS resin, 1-5 parts of styrene-maleic anhydride copolymer, 0.5-2 parts of dynamic covalent cross-linking agent, 0.1-0.5 part of antioxidant and 0.2-1 part of lubricant, wherein the dynamic covalent cross-linking agent has a multi-arm core-reversible dynamic covalent bond-amphiphilic chain segment structure, and can realize transient homogenization of PC and ABS at a processing temperature. The invention suppresses phase separation and molding warpage of PC/ABS alloy through the synergistic effect of SMA static compatibilization and dynamic covalent cross-linking agent, realizes excellent high gloss and high comprehensive mechanical property and processing fluidity, is suitable for the existing industrial production line, and can be widely applied to high-end fields such as automobile interior and exterior trim, electronic and electrical appliance housing, aerospace interior trim and the like.

Inventors

  • CHEN YAN
  • CHEN JIAHENG
  • Shi Biaobiao

Assignees

  • 浙江汇晶新材料股份有限公司

Dates

Publication Date
20260512
Application Date
20260413

Claims (9)

  1. 1. The low-warpage PC/ABS highlight plastic is characterized by comprising, by weight, 60-80 parts of polycarbonate, 20-40 parts of acrylonitrile-butadiene-styrene terpolymer resin, 1-5 parts of styrene-maleic anhydride copolymer, 0.5-2 parts of dynamic covalent cross-linking agent, 0.1-0.5 part of antioxidant and 0.2-1 part of lubricant; the dynamic covalent cross-linking agent has a structure of a multi-arm core-reversible dynamic covalent bond-affinity chain segment; Wherein the multi-arm core is of a pentaerythritol derivative four-arm structure with 4 reaction sites, the reversible dynamic covalent bond is a hindered urea bond, the affinity chain segment comprises a polycarbonate affinity chain segment and an acrylonitrile-butadiene-styrene terpolymer resin affinity chain segment, the polycarbonate affinity chain segment is bisphenol A type epoxy oligomer, and the acrylonitrile-butadiene-styrene terpolymer resin affinity chain segment is styrene-acrylonitrile copolymer oligomer; The dynamic covalent cross-linking agent can be reversibly dissociated by hindered urea bond at processing temperature, so that transient homogenization of the polycarbonate and the acrylonitrile-butadiene-styrene terpolymer resin is realized.
  2. 2. The low warp PC/ABS high gloss plastic according to claim 1, wherein the polycarbonate is bisphenol a type polycarbonate having a number average molecular weight of 15000 to 40000.
  3. 3. The low-warpage PC/ABS high-gloss plastic according to claim 1, wherein the ABS resin is synthesized by a bulk method or an emulsion method, and the mass content of acrylonitrile is 20% -30%.
  4. 4. The low-warpage PC/ABS high-gloss plastic according to claim 1, wherein the antioxidant is a compound of hindered phenol antioxidants and phosphite antioxidants, and the lubricant is pentaerythritol stearate or ethylene bis-stearamide.
  5. 5. The low warp PC/ABS high gloss plastic according to claim 1, wherein the preparation process of the dynamic covalent cross-linker comprises the following steps: ① Under the protection of dry nitrogen, pentaerythritol is dissolved in N, N-dimethylformamide, dibutyl tin dilaurate is added, diisocyanate is added, the reaction temperature is controlled at 60-70 ℃, the temperature is kept for 4-6 hours, and the four-arm isocyanate end-capped intermediate is obtained through post treatment; Wherein the molar ratio of pentaerythritol to diisocyanate is 1:4-4.2, and the dosage of dibutyltin dilaurate is 0.1% -0.15% of the total mass of pentaerythritol and diisocyanate; ② Dissolving a four-arm isocyanate end-capped intermediate in N, N-dimethylformamide, adding 2, 6-tetramethylpiperidine amine according to the molar ratio of NCO groups to amino groups of 1:1.05-1.1, stirring and reacting for 8 hours at 50 ℃ until the NCO groups completely react, and carrying out post treatment to obtain the four-arm core intermediate modified by the hindered urea bonds; ③ Grafting of an affinity chain segment, namely dissolving a four-arm core intermediate modified by hindered urea bonds in a solvent, firstly adding bisphenol A type epoxy oligomer and dibutyl tin dilaurate, reacting for 6 hours at 90 ℃ to complete grafting of the affinity chain segment of polycarbonate, then adding end group functionalized styrene-acrylonitrile copolymer oligomer and a condensing agent/catalyst, reacting for 12 hours at 80 ℃ to complete grafting of the affinity chain segment of ABS, and performing aftertreatment to obtain the dynamic covalent cross-linking agent; The dosage of the dibutyl tin dilaurate is 0.1-0.15% of the total mass of the four-arm core intermediate modified by the hindered urea bond and the bisphenol A type epoxy oligomer.
  6. 6. The low warp PC/ABS high gloss plastic according to claim 5, wherein the diisocyanate is toluene diisocyanate or isophorone diisocyanate; The epoxy equivalent of the bisphenol A type epoxy oligomer is 180-220g/eq, the number average molecular weight of the bisphenol A type epoxy oligomer is 1000-2000, the number average molecular weight of the styrene-acrylonitrile copolymer oligomer is 1500-3000, the mass content of acrylonitrile is 25%, the end group of the acrylonitrile is carboxyl or hydroxyl, and the grafting mole ratio of the polycarbonate affinity chain segment to the acrylonitrile-butadiene-styrene terpolymer resin affinity chain segment is 1:1.
  7. 7. A method for preparing the low-warpage PC/ABS highlight plastic by compatibilization modification according to any one of claims 1 to 5, comprising the steps of: S1, drying raw materials, namely drying polycarbonate, ABS resin, styrene-maleic anhydride copolymer, dynamic covalent cross-linking agent, antioxidant and lubricant; s2, mixing the dried raw materials uniformly according to a proportion to obtain a premix; S3, melt blending granulation, namely adding the premix into a double-screw extruder, and obtaining composite granules through melt blending, extrusion, cooling and granulating; s4, injection molding, namely drying the composite granules again, and performing injection molding, cooling and demoulding to obtain the low-warpage PC/ABS highlight plastic product.
  8. 8. The method for preparing the compatibilizer modifier according to claim 7, wherein in the step S3, the temperature of each region of the twin-screw extruder is 190-240 ℃, the screw speed is 200-300rpm, and in the step S4, the temperature of the injection molding barrel is 220-240 ℃ and the temperature of the mold is 50-80 ℃.
  9. 9. Use of the low warp PC/ABS high gloss plastic according to any one of claims 1 to 5 in automotive interiors and exteriors, electrical and electronic housings or aerospace interiors.

Description

Low-warpage PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) high-gloss plastic and compatibilization modification preparation method thereof Technical Field The invention relates to the technical field of macromolecule modified engineering plastics, in particular to a low-warpage PC/ABS (polycarbonate/acrylonitrile butadiene styrene) highlight plastic and a compatibilization modification preparation method thereof. Background The Polycarbonate (PC)/acrylonitrile-butadiene-styrene copolymer (ABS) alloy has the advantages of high impact resistance, heat resistance, easy processing of ABS, high fluidity and the like of PC, is one of the engineering plastic alloys which are most widely applied at present, and is widely applied to the fields of automobile inner and outer decorations, electronic and electric appliance shells, household appliance parts and the like. However, PC and ABS belong to a partially compatible system, the bonding force of two-phase interfaces is weak, phase separation is easy to occur in the processes of melt processing and cooling forming, so that the internal stress concentration and the warp deformation of a product are serious, the surface glossiness and the mechanical property of a material are influenced, and the use requirements of a high-gloss product and a high-precision structural member cannot be met. At present, the compatibility of PC/ABS alloy is mainly improved by adding a compatibilizer in the industry, and most of the commonly used compatibilizer is a traditional nonreactive or irreversible reactive compatibilizer such as maleic anhydride grafted polyolefin, styrene-maleic anhydride copolymer (SMA) and the like. The compatibilizer can improve the compatibility of two phases to a certain extent, but has the obvious defects that firstly, the compatibilizer and a matrix are combined into an irreversible structure, the flowability in the processing process and the structural stability after molding cannot be balanced, the viscosity of the system is high during processing, the flowability is poor, the problems of melt fracture, surface flow marks and the like are easy to occur, the highlight effect is influenced, secondly, the compatibilizer has limited compatibilizer efficiency, the effect can be achieved only by needing a higher additive amount, the heat resistance and the mechanical property of a material are easy to be reduced, thirdly, the internal stress in the product molding process cannot be effectively eliminated, and the buckling deformation problem is difficult to be fundamentally solved, so that the dimensional stability requirement of a high-precision product cannot be met. The dynamic covalent bond has the stability of the covalent bond and the reversibility of the non-covalent bond, can be reversibly dissociated and rebuilt at a specific temperature, and provides a new thought for the compatibilization and modification of the polymer alloy. The hindered urea bond is used as a typical dynamic covalent bond, the dissociation temperature of the hindered urea bond is adapted to the processing temperature range of PC/ABS, no additional catalyst is required to be introduced, the dissociation-reconstruction process has good reversibility, no side reaction is generated, and the hindered urea bond is very suitable for processing modification of PC/ABS alloy. However, at present, a hindered urea bond is not combined with a multi-arm amphiphilic segment, and a special dynamic covalent cross-linking agent is designed for a related mature technology of PC/ABS alloy low-warpage high-light modification. Therefore, developing a PC/ABS alloy material with high compatibilization efficiency, low warpage, high gloss and excellent mechanical properties, and simultaneously matching with a simple and easy-to-industrialize preparation process becomes a technical problem to be solved in the field. Disclosure of Invention The invention aims to solve the defects in the prior art, and provides a low-warpage PC/ABS high-gloss plastic and a compatibilization modification preparation method thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: The invention firstly provides a low-warpage PC/ABS (polycarbonate/acrylonitrile butadiene styrene) highlight plastic which comprises, by weight, 60-80 parts of Polycarbonate (PC), 20-40 parts of acrylonitrile-butadiene-styrene copolymer (ABS) resin, 1-5 parts of styrene-maleic anhydride copolymer (SMA), 0.5-2 parts of dynamic covalent cross-linking agent, 0.1-0.5 part of antioxidant and 0.2-1 part of lubricant; The dynamic covalent cross-linking agent has a multi-arm core-reversible dynamic covalent bond-affinity chain segment structure, and can be reversibly dissociated at the processing temperature to realize transient homogenization of PC and ABS; The affinity chain segment comprises a PC affinity chain segment and an ABS affinity chain segment, wherein the PC affinity chain segment is bi