CN111073242A - High-melt-strength halogen-free flame-retardant blow-molded PC/ABS alloy and preparation method thereof - Google Patents
High-melt-strength halogen-free flame-retardant blow-molded PC/ABS alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-melt-strength halogen-free flame-retardant blow molding PC/ABS alloy and a preparation method thereof, wherein polycarbonate A, polycarbonate B, acrylonitrile-butadiene-styrene (ABS), a flame retardant, a toughening agent, an antioxidant and a lubricant are placed in a high-speed mixer according to a formula ratio to be stirred, the mixture is uniformly mixed and then fed into a double-screw extruder through a metering device, the temperature of the double-screw extruder is controlled to be 230-270 ℃, materials are melted and compounded under the conditions of conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotation speed of 200-500 screws, and the mixture is cooled and granulated to obtain the high-melt-strength halogen-free flame-retardant blow molding PC/ABS alloy mixture. Compared with the prior art, the invention has simple process and low energy consumption, is very suitable for the large-scale production of the halogen-free flame-retardant blow-molded PC/ABS with high melt strength, and can be applied to household appliances such as television bases and the like.
Description
Technical Field
The invention relates to a PC/ABS alloy material, in particular to a high-melt-strength halogen-free flame-retardant blow molding PC/ABS alloy and a preparation method thereof.
Background
Polycarbonate (PC) has the advantages of heat resistance, transparency, low water absorption, no toxicity, good toughness, flame retardance (UL94V-2), creep resistance, dimensional stability, excellent dielectric property and the like, but has the defects of poor processing flow, sensitive thickness and notch, easy stress cracking, easy aging, poor wear resistance and the like. Can overcome the defects of PC after being blended and modified with acrylonitrile-butadiene-styrene copolymer (ABS), and provides the comprehensive performance of the PC. With the demand of light weight and rapid development in the industries of automobiles, household appliances and the like, a high-strength PC/ABS plastic will gradually replace metal materials, such as a television base, which is usually prepared by blow molding, and the PC/ABS used for such parts needs high melt strength and UL-94(V-0) flame retardant property in addition to good mechanical properties. Generally, the flame retardancy of PC/ABS is provided by adding flame retardants. In contrast, as the content of the flame retardant is increased, the melt strength is decreased, which tends to cause defects such as uneven wall thickness and insufficient strength of the blow-molded article.
Although the flame retardant property of the polycarbonate is UL94V-2 grade, the practical application often requires higher flame retardant property, and simultaneously, the flame retardant property of PC is reduced along with the increase of the content of ABS. Although the halogen flame retardant has the advantages of small addition amount, high flame retardant efficiency and the like in a PC/ABS system, once the halogen flame retardant catches fire, toxic and corrosive gas is released in the combustion process to corrode equipment such as a mould and the like, the halogen-free flame retardant is not beneficial to escape of personnel and brings difficulty to rescue, and the halogen-free flame retardant has the characteristics of high flame retardant efficiency, environmental protection and the like.
Patent CN108164960A discloses a method for preparing a blow molded PC/ABS composite material with high heat resistance and high melt strength, however, the material obtained by the method does not have flame retardant property of V-0 grade.
The technical scheme has the defects that the wide application of the blow molding PC/ABS alloy in the fields with flame retardant requirements of household appliances, electronics and the like is greatly limited. At present, no report is found about a high-melt-strength halogen-free flame-retardant blow molding PC/ABS alloy and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a halogen-free flame-retardant blow-molded PC/ABS alloy with high melt strength and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: the high-melt-strength halogen-free flame-retardant blow molding PC/ABS alloy is characterized by comprising the following components in parts by weight:
the melt flow rate of the polycarbonate A is 10-20g/10min under the conditions of 300 ℃ multiplied by 1.2 kg.
The melt flow rate of the polycarbonate B is 1-10g/10min under the conditions of 300 ℃ multiplied by 1.2 kg. At present, the melt flow rate of general PC sold is generally 3, 10, 20g/10min and other specifications, two kinds of PC are compounded, on one hand, the melt strength of the material in the actual blow molding process is ensured, the problems of melt fracture and the like in the blow molding process are avoided, on the other hand, the processing time is shortened, and the production efficiency is improved.
The weight-average relative molecular mass of the acrylonitrile-butadiene-styrene (ABS) is 100000-500000g/mol, the content of butadiene rubber is 40-60%, and the number-average particle diameter of the rubber is 0.2-1.0 um.
The toughening agent comprises one of methyl methacrylate/butadiene/styrene copolymer, methyl methacrylate/acrylic polymer, acrylic toughening agent, acrylic-silicon rubber toughening agent, ethylene-butyl acrylate and ethylene-acrylate-glycidyl methacrylate terpolymer.
The flame retardant comprises a phosphorus flame retardant, preferably bisphenol A-bis (diphenyl phosphate). Since the molecular weight of the component is small, the influence on the melt strength of the material is large, if the addition amount is too large, blow molding is not facilitated, therefore, the proportion of the component to be added needs to be properly controlled, theoretically, most flame retardants are available, but the types of halogen-free flame retardants used in the PC/ABS system at present are few, such as phosphorus flame retardants like BDP, RDP, TPP, etc., so that the applicability of the patent is relatively wide from another point of view. In addition, the preferable flame retardant has the characteristics of symmetrical structure, high relative molecular weight, high phosphorus content and the like, and the plasticity, the flame retardance and the thermal stability of the flame retardant are all superior to those of common phosphate.
The antioxidant comprises one or more of commercially available antioxidant 1076, antioxidant 168, antioxidant 245 and antioxidant 1010.
The lubricant comprises one or more of pentaerythritol ester, silicone powder and ethylene bis stearamide.
The preparation method of the high-melt-strength halogen-free flame-retardant blow-molding PC/ABS alloy is characterized by comprising the steps of placing polycarbonate A, polycarbonate B, acrylonitrile-butadiene-styrene (ABS), a flame retardant, a toughening agent, an antioxidant and a lubricant into a high-speed mixer according to a formula ratio, stirring, uniformly mixing, feeding into a double-screw extruder through a metering device, controlling the temperature of the double-screw extruder to be 230-270 ℃, melting and compounding materials under the conditions of conveying, shearing and mixing of screws, carrying out melt extrusion at a rotating speed of 200 and 500, cooling and granulating to obtain the high-melt-strength halogen-free flame-retardant blow-molding PC/ABS alloy mixture.
The stirring speed of the high-speed mixer is 600-800rpm/min, and the stirring time is 10-30 min.
Compared with the prior art, the invention has the following advantages:
1. the PC/ABS alloy prepared by the invention has high melt strength, the melt strength of the PC/ABS alloy can be improved by improving the molecular weight and the content of PC in a formula and adopting methods such as ABS with high crosslinking degree, and the melt flow rate is at least 14.8g/10min (260 ℃ is 5kg), so that various parts with complex structures can be formed by blow molding.
2. Compared with the prior art, the flame retardant used in the invention has the characteristics of symmetrical structure, high relative molecular mass, high phosphorus content and the like, not only has thermal stability superior to other common phosphate flame retardants, but also has high carbonization efficiency with PC during combustion, so that the flame retardant grade of the prepared PC/ABS alloy is not lower than UL94V 0(1.6mm) grade, the comprehensive performance is excellent, no halogen is contained, and the environmental pollution is small.
3. The method for preparing the halogen-free flame-retardant blow-molding PC/ABS alloy has simple process and low energy consumption, is very suitable for the large-scale production of the halogen-free flame-retardant blow-molding PC/ABS with high melt strength, and can be applied to household appliance products such as television bases and the like.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the mixture is fed into a double-screw extruder through a metering device after being uniformly mixed, the temperature of the double-screw extruder is controlled to be 245 ℃, the materials are melted and compounded under the conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotating speed of 400 screws, and the mixture is cooled and granulated, so that the halogen-free flame-retardant blow molding PC/ABS alloy mixture with high melt strength is obtained.
Example 2
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the mixture is fed into a double-screw extruder through a metering device after being uniformly mixed, the temperature of the double-screw extruder is controlled to be 245 ℃, the materials are melted and compounded under the conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotating speed of 400 screws, and the mixture is cooled and granulated, so that the halogen-free flame-retardant blow molding PC/ABS alloy mixture with high melt strength is obtained.
Example 3
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the mixture is fed into a double-screw extruder through a metering device after being uniformly mixed, the temperature of the double-screw extruder is controlled to be 245 ℃, the materials are melted and compounded under the conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotating speed of 400 screws, and the mixture is cooled and granulated, so that the halogen-free flame-retardant blow molding PC/ABS alloy mixture with high melt strength is obtained.
Example 4
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the mixture is fed into a double-screw extruder through a metering device after being uniformly mixed, the temperature of the double-screw extruder is controlled to be 245 ℃, the materials are melted and compounded under the conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotating speed of 400 screws, and the mixture is cooled and granulated, so that the halogen-free flame-retardant blow molding PC/ABS alloy mixture with high melt strength is obtained.
Example 5
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the mixture is fed into a double-screw extruder through a metering device after being uniformly mixed, the temperature of the double-screw extruder is controlled to be 245 ℃, the materials are melted and compounded under the conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotating speed of 400 screws, and the mixture is cooled and granulated, so that the halogen-free flame-retardant blow molding PC/ABS alloy mixture with high melt strength is obtained.
Example 6
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the mixture is fed into a double-screw extruder through a metering device after being uniformly mixed, the temperature of the double-screw extruder is controlled to be 245 ℃, the materials are melted and compounded under the conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotating speed of 400 screws, and the mixture is cooled and granulated, so that the halogen-free flame-retardant blow molding PC/ABS alloy mixture with high melt strength is obtained.
Example 7
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the mixture is fed into a double-screw extruder through a metering device after being uniformly mixed, the temperature of the double-screw extruder is controlled to be 245 ℃, the materials are melted and compounded under the conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotating speed of 400 screws, and the mixture is cooled and granulated, so that the halogen-free flame-retardant blow molding PC/ABS alloy mixture with high melt strength is obtained.
Comparative example 1
A high melt strength, blow molded PC/ABS alloy and a method for making the same, the method comprising the steps of:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the mixture is fed into a double-screw extruder through a metering device after being uniformly mixed, the temperature of the double-screw extruder is controlled to be 245 ℃, the materials are melted and compounded under the conveying, shearing and mixing of screws, the melting extrusion is carried out at the rotating speed of 400 screws, and the mixture is cooled and granulated, so that the halogen-free flame-retardant blow molding PC/ABS alloy mixture with high melt strength is obtained.
The components of the examples and comparative examples are shown in Table 1
TABLE 1
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | Comparative example 1 |
| Polycarbonate A | 70 | 60 | 50 | 40 | 30 | 20 | 10 | 10 |
| Polycarbonate B | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 70 |
| ABS | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 18 |
| Flame retardant | 12 | 12 | 12 | 12 | 12 | 12 | 12 | |
| Toughening agent | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Antioxidant agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant agent | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
The above examples were tested for performance according to the criteria of table 2:
TABLE 2
And the product properties of each example are shown in Table 3:
TABLE 3
The experimental results of comparative examples 1 to 7 show that the increase of the content of the polycarbonate B reduces the fluidity of the material, improves the melt strength performance of the material, and improves the impact strength; the experimental results of example 7 and comparative example 1 show that the flame retardant performance is improved from V-2 grade to V-0 grade by adding 12 parts of flame retardant.
Example 8
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to the formula and stirred, the stirring speed of the high-speed mixer is 800rpm/min, the stirring time is 10min, the raw materials are uniformly mixed and then are fed into a double-screw extruder through a metering device, the temperature of the double-screw extruder is controlled to be 230 ℃, the materials are melted and compounded under the conveying, shearing and mixing of a screw, the melting extrusion is carried out at the rotation speed of the screw being 200 ℃, and the mixture of the halogen-free flame-retardant blow molding PC/ABS alloy with high melt strength is obtained after cooling granulation.
Example 9
A high melt strength, halogen-free flame retardant blow molding PC/ABS alloy and a preparation method thereof, the method comprises the following steps:
(1) the alloy composition comprises the following raw materials in parts by weight:
wherein, the polycarbonate A is Letian PC 1100; the polycarbonate B is three-nutrient PC3030 PJ; ABS is Jinhu 181; the flame retardant is bisphenol A-bis (diphenyl phosphate); the toughening agent is methyl methacrylate/butadiene/styrene copolymer; the antioxidant is preferably antioxidant 1076 and antioxidant 168; a lubricant pentaerythritol ester;
(2) the raw materials are placed in a high-speed mixer according to a formula and stirred, the stirring speed of the high-speed mixer is 600rpm/min, the stirring time is 30min, the raw materials are uniformly mixed and then are fed into a double-screw extruder through a metering device, the temperature of the double-screw extruder is controlled to be 270 ℃, the materials are melted and compounded under the conveying, shearing and mixing of a screw, the melting extrusion is carried out under the condition of the rotating speed of the screw being 500 ℃, and the mixture of the halogen-free flame-retardant blow molding PC/ABS alloy with high melt strength is obtained after cooling granulation.
Claims (10)
1. The high-melt-strength halogen-free flame-retardant blow molding PC/ABS alloy is characterized by comprising the following components in parts by weight:
2. the high melt strength, halogen-free, flame retardant blow molded PC/ABS alloy of claim 1, wherein the melt flow rate of polycarbonate A is 10-20g/10min at 300 ℃ x 1.2 kg.
3. The high melt strength, halogen-free, flame retardant blow molded PC/ABS alloy of claim 1 wherein the melt flow rate of polycarbonate B is 1-10g/10min at 300 ℃ x 1.2 kg.
4. The high melt strength, halogen-free, flame retardant blow molded PC/ABS alloy as claimed in claim 1, wherein the acrylonitrile-butadiene-styrene (ABS) has a weight average relative molecular mass of 100000-500000g/mol, a butadiene rubber content of 40% -60%, and a number average particle size of 0.2-1.0 μm.
5. The high melt strength, halogen-free, flame retardant blow molded PC/ABS alloy of claim 1 wherein the toughening agent comprises one of a methyl methacrylate/butadiene/styrene copolymer, a methyl methacrylate/acrylic polymer, an acrylic toughening agent, an acrylic-silicone rubber based toughening agent, ethylene-butyl acrylate, ethylene-acrylate-glycidyl methacrylate terpolymer.
6. The high melt strength, halogen free, flame retardant blow molded PC/ABS alloy according to claim 1, wherein the flame retardant comprises a phosphorus based flame retardant, preferably bisphenol A-bis (diphenyl phosphate).
7. The high melt strength, halogen-free, flame retardant blow molded PC/ABS alloy of claim 1, wherein the antioxidant comprises one or more of commercially available antioxidants 1076, 168, 245, 1010.
8. The high melt strength, halogen-free, flame retardant blow molded PC/ABS alloy of claim 1, wherein the lubricant comprises one or more of pentaerythritol ester, silicone powder, ethylene bis stearamide.
9. The preparation method of the high melt strength halogen-free flame retardant blow molding PC/ABS alloy as claimed in claim 1, characterized in that the polycarbonate A, the polycarbonate B, the acrylonitrile-butadiene-styrene (ABS), the flame retardant, the toughening agent, the antioxidant and the lubricant are placed in a high speed mixer according to the formula proportion and stirred, and are fed into a double screw extruder through a metering device after being uniformly mixed, the temperature of the double screw extruder is controlled to be 230-270 ℃, the materials are melted and compounded under the conditions of conveying, shearing and mixing of a screw, the melting extrusion is carried out at the rotation speed of 200-.
10. The method for preparing the high melt strength halogen-free flame retardant blow molded PC/ABS alloy according to claim 8, wherein the stirring speed of the high-speed mixer is 600-800rpm/min, and the stirring time is 10-30 min.
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| CN112375359A (en) * | 2020-10-10 | 2021-02-19 | 南京金杉汽车工程塑料有限责任公司 | Halogen-free flame-retardant PC/ABS alloy and preparation method thereof |
| CN112538247A (en) * | 2020-10-21 | 2021-03-23 | 上海锦湖日丽塑料有限公司 | Antibacterial, mildewproof and flame-retardant PC alloy composition and preparation method thereof |
| CN112812533A (en) * | 2020-12-29 | 2021-05-18 | 会通新材料股份有限公司 | Halogen-free flame-retardant PC/ABS alloy material and preparation method thereof |
| CN113337094A (en) * | 2021-05-22 | 2021-09-03 | 宁波市威宏明实汽车零部件有限公司 | High-strength high-toughness PC/ABS composite material, preparation method thereof and automotive interior trim part |
| CN113801456A (en) * | 2021-09-08 | 2021-12-17 | 无锡赢同新材料科技有限公司 | Flame-retardant PC/ABS alloy material suitable for blow molding and preparation method and application thereof |
| CN113980418A (en) * | 2021-12-13 | 2022-01-28 | 东莞市千晋塑料科技有限公司 | PC/ABS composite material and preparation method thereof, blow molding die and blow molding method |
| CN114539755A (en) * | 2022-02-25 | 2022-05-27 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
| CN115286914A (en) * | 2022-08-30 | 2022-11-04 | 广东锦湖日丽高分子材料有限公司 | High-impact transparent low-temperature-formable PC alloy and preparation method thereof |
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| CN113337094A (en) * | 2021-05-22 | 2021-09-03 | 宁波市威宏明实汽车零部件有限公司 | High-strength high-toughness PC/ABS composite material, preparation method thereof and automotive interior trim part |
| CN113801456A (en) * | 2021-09-08 | 2021-12-17 | 无锡赢同新材料科技有限公司 | Flame-retardant PC/ABS alloy material suitable for blow molding and preparation method and application thereof |
| CN113801456B (en) * | 2021-09-08 | 2023-08-04 | 无锡赢同新材料科技有限公司 | Flame-retardant PC/ABS alloy material suitable for blow molding and preparation method and application thereof |
| CN113980418A (en) * | 2021-12-13 | 2022-01-28 | 东莞市千晋塑料科技有限公司 | PC/ABS composite material and preparation method thereof, blow molding die and blow molding method |
| CN113980418B (en) * | 2021-12-13 | 2022-06-24 | 东莞市千晋塑料科技有限公司 | PC/ABS composite material and preparation method thereof, blow molding die and blow molding method |
| CN114539755A (en) * | 2022-02-25 | 2022-05-27 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
| CN115286914A (en) * | 2022-08-30 | 2022-11-04 | 广东锦湖日丽高分子材料有限公司 | High-impact transparent low-temperature-formable PC alloy and preparation method thereof |
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Application publication date: 20200428 |