CN114605804A - High-abrasion-resistance PC + PBT (Poly carbonate + polybutylene terephthalate) polymer resin and preparation process thereof - Google Patents

High-abrasion-resistance PC + PBT (Poly carbonate + polybutylene terephthalate) polymer resin and preparation process thereof Download PDF

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CN114605804A
CN114605804A CN202210314014.5A CN202210314014A CN114605804A CN 114605804 A CN114605804 A CN 114605804A CN 202210314014 A CN202210314014 A CN 202210314014A CN 114605804 A CN114605804 A CN 114605804A
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pbt
polybutylene terephthalate
polycarbonate
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polymeric resin
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谢玉辉
童大山
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Guangzhou Souliao Information Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/42—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

The invention belongs to the technical field of resin modification, and particularly relates to a high-abrasion-resistance PC + PBT polymer resin and a preparation process thereof. The prepared toughening auxiliary agent is prepared by dispersing nano molybdenum disulfide powder by using a dispersing agent, and then mixing the nano molybdenum disulfide powder with fluorine-containing silane to form a wrapping structure of molybdenum disulfide, and the formed polycarbonate, polybutylene terephthalate and hydroxyl-terminated polybutadiene are subjected to physical combination on a phase interface under the reaction of the toughening auxiliary agent and a cross-linking agent, so that the physical binding force of the phase interface of the polycarbonate and the polybutylene terephthalate is improved, the toughness and the friction resistance of the PC + PBT polymeric resin are improved, the tensile capability and the fatigue resistance of the polycarbonate are enhanced on the basis that the polycarbonate and the polybutylene terephthalate have high heat resistance, chemical resistance, weather resistance, excellent dimensional stability and mechanical properties, and the prepared PC + PBT polymeric resin can be applied to parts outside automobiles.

Description

High-abrasion-resistance PC + PBT (Poly carbonate + polybutylene terephthalate) polymer resin and preparation process thereof
Technical Field
The invention belongs to the technical field of resin modification, and particularly relates to high-abrasion-resistance PC + PBT polymer resin and a preparation process thereof.
Background
Polycarbonate is also called PC plastic, is colorless and transparent, heat-resistant, impact-resistant and flame-retardant at BI level, and has good mechanical properties at common use temperature. The main performance defects of the PC are that the PC has the defects of insufficient hydrolysis resistance stability, sensitivity to gaps, poor organic chemical resistance and poor scratch resistance, and can yellow after being exposed to ultraviolet rays for a long time. Like other resins, PC is susceptible to attack by certain organic solvents. And the abrasion resistance of polycarbonate is relatively poor compared to most plastic materials, at a moderate or low level, some polycarbonate devices for wear-prone applications require special surface treatment.
The combination of the polycarbonate and the polybutylene terephthalate has the characteristics of complementary advantages and disadvantages, the blend has stronger chemical resistance and mechanical property, and in order to fully exert the combination capability of the polycarbonate and the polybutylene terephthalate, the invention provides the blend of the polycarbonate and the polybutylene terephthalate with enhanced friction resistance.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a high-abrasion-resistance PC + PBT polymer resin and a preparation process thereof, which improve the physical bonding force of a phase interface of polycarbonate and polybutylene terephthalate, thereby improving the toughness and the abrasion resistance of the PC + PBT polymer resin.
The technical content of the invention is as follows:
the invention provides a preparation process of high-abrasion-resistance PC + PBT polymeric resin, which comprises the following steps:
1) pretreatment of the surface of a raw material: respectively carrying out surface pretreatment on polycarbonate and polybutylene terephthalate; the melt flow rate of the polycarbonate is 15-20 g/10 min;
the melt flow rate of the polybutylene terephthalate is 75-85 g/10 min.
The surface pretreatment of the polycarbonate comprises the following steps: mixing polycarbonate and sodium gluconate, heating to 240-250 ℃, uniformly stirring, adding hexadecyltrimethylammonium chloride, feeding into a double-screw extruder, mixing at 240-250 ℃, and finally extruding into granules;
the surface pretreatment of the polybutylene terephthalate comprises the following steps: mixing polybutylene terephthalate and sodium gluconate, heating to 250-260 ℃, uniformly stirring, adding hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at the temperature of 250-260 ℃, and finally extruding into granules;
2) preparing a toughening auxiliary agent: mixing nano molybdenum disulfide powder, a dispersing agent and fluorine-containing silane, heating to 100-125 ℃, carrying out ultrasonic stirring treatment, stopping ultrasonic stirring at constant temperature, heating to 135-155 ℃, adding a lubricating agent, continuously stirring at constant temperature to obtain a homogeneous material, cooling to 100-110 ℃, adding triphenylmethane triisocyanate, adjusting the pH to 7-9, and cooling to normal temperature after stirring to obtain a modified toughening agent;
the dispersing agent comprises one or more of glyceryl monostearate, glyceryl monolaurate and glyceryl monooleate;
the fluorine-containing silane comprises one or more of tridecafluorooctyl triethoxysilane, tridecafluorooctyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, and heptadecafluorodecyl trimethoxysilane;
the lubricant comprises zinc stearate, calcium stearate or aluminum stearate;
in the toughening auxiliary agent, by mass, 38-58% of nano molybdenum disulfide powder, 10-15% of a dispersing agent, 8-15% of fluorine-containing silane, 10-15% of a lubricating agent and 14-20% of triphenylmethane triisocyanate;
3) PC + PBT polymeric resin: drying the polycarbonate, polybutylene terephthalate, hydroxyl-terminated polybutadiene, toughening auxiliary agent and cross-linking agent which are subjected to surface pretreatment, mixing, uniformly stirring at a high speed, sequentially feeding into a double-screw extruder at a feeding speed of 230-260 r/min, setting temperatures of 7 temperature zones of 200 ℃, 220 ℃, 250 ℃, 260 ℃, 240 ℃, 230 ℃ and 210 ℃ respectively, and finally extruding and molding to obtain the PC + PBT polymeric resin;
the cross-linking agent comprises 1, 3-butanediol dimethacrylate or 1, 6-hexanediol butyl dimethacrylate;
in the PC + PBT polymeric resin, by mass, 40-50% of polycarbonate, 20-30% of polybutylene terephthalate, 15-20% of hydroxyl-terminated polybutadiene, 5-8% of toughening aid and 6-10% of cross-linking agent are used.
The high-abrasion-resistance PC + PBT polymer resin prepared by the preparation method is applied to the field of preparation of automobile outer parts.
The invention has the following beneficial effects:
in the preparation process of the PC + PBT polymeric resin, 1) in the surface pretreatment of polycarbonate and polybutylene terephthalate, sodium gluconate is adopted to clean and activate the surface of the resin, and then cetyl trimethyl ammonium chloride is adopted to activate ester groups on the surface of the resin, so that the modification capacity of the resin is enhanced; 2) in the prepared toughening auxiliary agent, dispersing nano molybdenum disulfide powder by using a dispersing agent, mixing the nano molybdenum disulfide powder with fluorine-containing silane to form a molybdenum disulfide wrapping structure, and enabling triphenylmethane triisocyanate and the fluorine-containing silane to perform a coupling reaction by using a lubricating agent for enhancing the lubricity of the wrapping structure to obtain molybdenum disulfide included in the grafted resin, so that the toughening performance of the resin is enhanced; 3) the formed polycarbonate, polybutylene terephthalate and hydroxyl-terminated polybutadiene form physical combination on a phase interface under the reaction of a toughening auxiliary agent and a cross-linking agent, so that the physical combination force of the phase interface of the polycarbonate and the polybutylene terephthalate is improved, the toughness and the friction resistance of the PC + PBT polymeric resin are improved, the tensile capability and the fatigue resistance of the polycarbonate are enhanced on the basis that the polycarbonate and the polybutylene terephthalate have high heat resistance, chemical resistance, weather resistance, excellent dimensional stability and mechanical properties, and the prepared PC + PBT polymeric resin can be applied to automobile exterior parts.
Drawings
FIG. 1 is an SEM scan of a cross-section of a PC + PBT polymeric resin prepared by the present invention;
FIG. 2 is an electron microscope scan of a cross-section of the PC + PBT polymeric resin prepared in comparative example 2.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
In the preparation of the PC + PBT polymeric resin, the melt flow rate of the adopted polycarbonate is 15-20 g/10min, and the melt flow rate of the polybutylene terephthalate is 75-85 g/10 min.
Example 1
Preparation process of high-abrasion-resistance PC + PBT (Poly carbonate + polybutylene terephthalate) polymer resin
1) Pretreatment of the surface of a raw material:
mixing polycarbonate with 30 wt% of sodium gluconate, heating to 250 ℃, uniformly stirring, adding 25 wt% of hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at the temperature of 250 ℃, and finally extruding into granules;
mixing polybutylene terephthalate and 30 wt% of sodium gluconate, heating to 260 ℃, uniformly stirring, adding 30 wt% of hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at 260 ℃, and finally extruding into granules;
2) preparing a toughening auxiliary agent: mixing 40% of nano molybdenum disulfide powder, 13% of glycerol monooleate and 13% of tridecafluorooctyltriethoxysilane, heating to 125 ℃ for ultrasonic stirring treatment, stopping ultrasonic stirring at constant temperature, heating to 155 ℃, adding 14% of calcium stearate, continuously stirring at constant temperature to obtain a homogeneous material, cooling to 110 ℃, adding 20% of triphenylmethane triisocyanate, adjusting the pH to 9, uniformly stirring, and cooling to normal temperature to obtain a modified toughening agent;
3) PC + PBT polymeric resin: 42 percent of polycarbonate, 30 percent of polybutylene terephthalate, 15 percent of hydroxyl-terminated polybutadiene, 7 percent of toughening auxiliary agent and 6 percent of propyl trimethoxy after surface pretreatment are dried, mixed, stirred uniformly at a high speed, and then sequentially fed into a double-screw extruder at a feeding speed of 260r/min, the set temperatures of 7 temperature zones are respectively 200 ℃, 220 ℃, 250 ℃, 260 ℃, 240 ℃, 230 ℃ and 210 ℃, and finally extruded and molded to obtain the PC + PBT polymeric resin.
Example 2
Preparation process of high-abrasion-resistance PC + PBT (Poly carbonate + polybutylene terephthalate) polymer resin
1) Pretreatment of the surface of a raw material:
mixing polycarbonate with 30 wt% of sodium gluconate, heating to 240 ℃, uniformly stirring, adding 25 wt% of hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at 240 ℃, and finally extruding into granules;
mixing polybutylene terephthalate and 30 wt% of sodium gluconate, heating to 250 ℃, uniformly stirring, adding 30 wt% of hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at the temperature of 250 ℃, and finally extruding into granules;
2) preparing a toughening auxiliary agent: mixing 38% of nano molybdenum disulfide powder, 15% of glyceryl monooleate and 15% of tridecafluorooctyltriethoxysilane, heating to 100 ℃ for ultrasonic stirring treatment, stopping ultrasonic stirring at constant temperature, heating to 135 ℃, adding 15% of zinc stearate, continuously stirring at constant temperature to obtain a homogeneous material, cooling to 100 ℃, adding 17% of triphenylmethane triisocyanate, adjusting the pH to 7, uniformly stirring, and cooling to normal temperature to obtain a modified toughening agent;
3) PC + PBT polymeric resin: 47% of polycarbonate, 21% of polybutylene terephthalate, 20% of hydroxyl-terminated polybutadiene, 5% of toughening auxiliary agent and 7% of propyl trimethoxy after surface pretreatment are dried, mixed, stirred uniformly at a high speed, and then sequentially fed into a double-screw extruder at a feeding speed of 230r/min, wherein the set temperatures of 7 temperature zones are 200 ℃, 220 ℃, 250 ℃, 260 ℃, 240 ℃, 230 ℃ and 210 ℃, respectively, and finally extruded and molded to obtain the PC + PBT polymeric resin.
Example 3
Preparation process of high-abrasion-resistance PC + PBT (Poly carbonate + polybutylene terephthalate) polymer resin
1) Pretreatment of the surface of a raw material:
mixing polycarbonate with 30 wt% of sodium gluconate, heating to 245 ℃, uniformly stirring, adding 25 wt% of hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at the temperature of 245 ℃, and finally extruding into granules;
mixing polybutylene terephthalate and 30 wt% of sodium gluconate, heating to 255 ℃, uniformly stirring, adding 30 wt% of hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at the temperature of 255 ℃, and finally extruding into granules;
2) preparing a toughening auxiliary agent: mixing 42% of nano molybdenum disulfide powder, 14% of glycerol monolaurate and 14% of heptadecafluorodecyltrimethoxysilane, heating to 110 ℃, carrying out ultrasonic stirring treatment, stopping ultrasonic stirring at constant temperature, heating to 140 ℃, adding 15% of zinc stearate, continuously stirring at constant temperature to obtain a homogeneous material, cooling to 105 ℃, adding 15% of triphenylmethane triisocyanate, adjusting the pH to 8, uniformly stirring, and cooling to normal temperature to obtain a modified toughening agent;
3) PC + PBT polymeric resin: 50% of polycarbonate, 20% of polybutylene terephthalate, 15% of hydroxyl-terminated polybutadiene, 5% of toughening auxiliary agent and 10% of propyl trimethoxy after surface pretreatment are dried, mixed, stirred uniformly at a high speed, and then sequentially fed into a double-screw extruder at a feeding speed of 250r/min, set temperatures of 7 temperature zones of 200 ℃, 220 ℃, 250 ℃, 260 ℃, 240 ℃, 230 ℃ and 210 ℃, and finally extruded and molded to obtain the PC + PBT polymeric resin.
Example 4
Preparation process of high-abrasion-resistance PC + PBT (Poly carbonate + polybutylene terephthalate) polymer resin
1) Pretreatment of the surface of a raw material:
mixing polycarbonate with 30 wt% of sodium gluconate, heating to 245 ℃, uniformly stirring, adding 25 wt% of hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at the temperature of 250 ℃, and finally extruding into granules;
mixing polybutylene terephthalate and 30 wt% of sodium gluconate, heating to 250 ℃, uniformly stirring, adding 30 wt% of hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at 255 ℃, and finally extruding into granules;
2) preparing a toughening auxiliary agent: mixing 58% of nano molybdenum disulfide powder, 10% of glycerol monooleate and 8% of tridecafluorooctyl trimethoxysilane, heating to 120 ℃ for ultrasonic stirring treatment, stopping ultrasonic stirring at constant temperature, heating to 140 ℃, adding 10% of aluminum stearate, continuously stirring at constant temperature to obtain a homogeneous material, cooling to 108 ℃, adding 14% of triphenylmethane triisocyanate, adjusting the pH to 7, uniformly stirring, and cooling to normal temperature to obtain a modified toughening agent;
3) PC + PBT polymeric resin: drying 40% of polycarbonate, 30% of polybutylene terephthalate, 15% of hydroxyl-terminated polybutadiene, 8% of toughening aid and 7% of propyl trimethoxy after surface pretreatment, mixing, uniformly stirring at high speed, sequentially feeding into a double-screw extruder at a feeding speed of 240r/min, setting the temperature of 7 temperature zones to be 200 ℃, 220 ℃, 250 ℃, 260 ℃, 240 ℃, 230 ℃ and 210 ℃, and finally extruding and molding to obtain the PC + PBT polymeric resin.
Comparative example 1
As a control for example 3, the surface treatment of polycarbonate and polybutylene terephthalate was eliminated in the preparation of PC + PBT polymer resin of comparative example 1, and the other steps were unchanged.
Comparative example 2
As a control of example 3, in the preparation process of PC + PBT polymer resin of comparative example 2, the preparation of toughening aid was cancelled, and then step 3) was to mix 50% polycarbonate, 20% polybutylene terephthalate, 18% hydroxyl-terminated polybutadiene, and 12% propyltrimethoxy, which had undergone surface pretreatment, and extrude to obtain PC + PBT polymer resin.
As shown in fig. 1, which is an electron microscope scanning image of the cross section of the PC + PBT polymeric resin prepared by the present invention, fig. 2 is an electron microscope scanning image of the cross section of the PC + PBT polymeric resin prepared by the comparative example 2, and compared with the comparative example 2, the PC + PBT polymeric resin prepared by the present invention has the advantages of uniform internal particle distribution, compact structure and uniform particle distribution direction, which indicates that the adopted toughening aid has obvious effect, and can improve fatigue resistance and friction resistance.
The PC + PBT polymer resins prepared in the examples and comparative examples were tested for mechanical properties and impact properties, and the results are shown below.
TABLE 1 mechanical and impact Property testing
Figure BDA0003568281600000091
Therefore, the PC + PBT polymer resin prepared by the invention enhances the impact resistance and fatigue resistance of the stretching ability and improves the friction resistance, and the prepared PC + PBT polymer resin can be applied to automobile outer parts.

Claims (9)

1. A preparation process of high abrasion-resistant PC + PBT polymeric resin is characterized by comprising the following steps:
1) pretreatment of the surface of a raw material: respectively carrying out surface pretreatment on polycarbonate and polybutylene terephthalate;
2) preparing a toughening auxiliary agent: mixing nano molybdenum disulfide powder, a dispersing agent and fluorine-containing silane, heating to 100-125 ℃, carrying out ultrasonic stirring treatment, stopping ultrasonic stirring at constant temperature, heating to 135-155 ℃, adding a lubricating agent, continuously stirring at constant temperature to obtain a homogeneous material, cooling to 100-110 ℃, adding triphenylmethane triisocyanate, adjusting the pH to 7-9, and cooling to normal temperature after stirring to obtain a modified toughening agent;
3) PC + PBT polymeric resin: the method comprises the steps of drying and mixing polycarbonate, polybutylene terephthalate, hydroxyl-terminated polybutadiene, toughening auxiliary agent and cross-linking agent which are subjected to surface pretreatment, uniformly stirring at a high speed, sequentially feeding into a double-screw extruder at a feeding speed of 230-260 r/min, setting temperatures of 7 temperature zones of 200 ℃, 220 ℃, 250 ℃, 260 ℃, 240 ℃, 230 ℃ and 210 ℃, and finally extruding and molding to obtain the PC + PBT polymeric resin.
2. The preparation process of the high abrasion-resistant PC + PBT polymer resin according to claim 1, wherein the melt flow rate of the polycarbonate in the step 1) is 15-20 g/10min, and the melt flow rate of the polybutylene terephthalate is 75-85 g/10 min.
3. The process for preparing the high abrasion-resistant PC + PBT polymeric resin according to claim 1, wherein the surface pretreatment of the polycarbonate in the step 1) is as follows: mixing polycarbonate and sodium gluconate, heating to 240-250 ℃, uniformly stirring, adding hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at the temperature of 240-250 ℃, and finally extruding into granules;
the surface pretreatment of the polybutylene terephthalate comprises the following steps: mixing polybutylene terephthalate and sodium gluconate, heating to 250-260 ℃, uniformly stirring, adding hexadecyl trimethyl ammonium chloride, feeding into a double-screw extruder, mixing at the temperature of 250-260 ℃, and finally extruding into granules.
4. The process for preparing the high abrasion-resistant PC + PBT polymer resin according to claim 1, wherein the dispersant in the step 2) comprises one or more of glycerol monostearate, glycerol monolaurate and glycerol monooleate.
5. The process for preparing PC + PBT polymer resin with high abrasion resistance according to claim 1, wherein the fluorine-containing silane of step 2) comprises one or more of tridecafluorooctyl triethoxysilane, tridecafluorooctyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, and heptadecafluorodecyl trimethoxysilane.
6. The process for preparing a highly abrasion resistant PC + PBT polymeric resin of claim 1, wherein the lubricant of step 2) comprises zinc stearate, calcium stearate or aluminum stearate.
7. The preparation process of the high abrasion-resistant PC + PBT polymeric resin according to claim 1, wherein in the toughening assistant in step 2), the nano molybdenum disulfide powder accounts for 38-58%, the dispersant accounts for 10-15%, the fluorine-containing silane accounts for 8-15%, the lubricant accounts for 10-15%, and the triphenylmethane triisocyanate accounts for 14-20% by mass.
8. The preparation process of the highly abrasion-resistant PC + PBT polymeric resin according to claim 1, wherein in the PC + PBT polymeric resin of step 3), the polycarbonate accounts for 40-50%, the polybutylene terephthalate accounts for 20-30%, the hydroxyl-terminated polybutadiene accounts for 15-20%, the toughening agent accounts for 5-8%, and the crosslinking agent accounts for 6-10% by mass.
9. The preparation method of any one of claims 1-8 is used for obtaining a high-abrasion-resistance PC + PBT polymer resin.
CN202210314014.5A 2022-03-28 2022-03-28 High-abrasion-resistance PC + PBT (Poly carbonate + polybutylene terephthalate) polymer resin and preparation process thereof Withdrawn CN114605804A (en)

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