CN115537006A - Preparation method and application of high-impact low-linear-expansion-coefficient PC/ABS alloy material - Google Patents
Preparation method and application of high-impact low-linear-expansion-coefficient PC/ABS alloy material Download PDFInfo
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- CN115537006A CN115537006A CN202110734384.XA CN202110734384A CN115537006A CN 115537006 A CN115537006 A CN 115537006A CN 202110734384 A CN202110734384 A CN 202110734384A CN 115537006 A CN115537006 A CN 115537006A
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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
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- 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
- C08K2201/002—Physical properties
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a preparation method and application of a high-impact low-linear-expansion-coefficient PC/ABS alloy material, wherein the material comprises the following raw materials in parts by weight based on 100 parts by weight of the total raw materials: 25-65 parts of Polycarbonate (PC) resin, 15-40 parts of ABS resin, 10-30 parts of wollastonite, 2-5 parts of compatilizer, 3-5 parts of flexibilizer, 0.3-1 part of antioxidant and 0.2-1 part of lubricant; the wollastonite is subjected to multiple coating treatment by adopting long-chain octadecyl silane, monoalkoxy titanate and maleic anhydride grafted polyethylene wax. The preparation method comprises the following steps: the raw materials are uniformly mixed according to the proportion, the obtained mixed material is fed through a main feeding port of a double-screw extruder, wollastonite is fed through a side feeding port, and the PC/ABS alloy material with high impact and low linear expansion coefficient is obtained after extrusion, granulation and drying. The material has extremely high impact toughness and low linear expansion coefficient, can be applied to preparing middle and front frames of large-size televisions, and simultaneously has better sprayability than glass fiber reinforced PC/ABS materials.
Description
Technical Field
The invention relates to the technical field of modification of PC/ABS alloy compositions, in particular to a preparation method and application of a high-impact low-linear-expansion-coefficient PC/ABS alloy material.
Background
The PC/ABS alloy material is a thermoplastic polymer alloy material formed by blending Polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS), combines the excellent characteristics of the two materials, has very excellent comprehensive performance, and is widely applied to the industrial fields of automobiles, household appliances, mobile phone communication and the like.
In the aspect of household appliance application, the middle and front frames of a television are mostly made of PC/ABS alloy materials, the requirements of large size, narrow frame and the like are met along with the design requirements of the frame of the television, and in order to meet the requirements of assembly size matching and falling prevention of cracking of the large-size and thin-walled frame, the frame material is required to have lower linear expansion coefficient and higher impact performance, and the PC/ABS material filled with minerals or reinforced by glass fibers is mostly adopted in the industry at present to carry out injection molding on the frame of the television.
Chinese patent document CN103224699A discloses a PC/ABS alloy composition with low linear expansion coefficient and a preparation method thereof, and the composition comprises the following components in parts by mass: 40-80 parts of PC resin, 15-55 parts of ABS resin, 5-20 parts of inorganic mineral, 0.1-1 part of antioxidant and 0.1-1 part of lubricant. The preparation method comprises the following steps: step 1: adding the PC resin, the ABS resin, the antioxidant and the lubricant into a mixing stirrer for mixing to obtain a mixture; step 2: and (3) feeding the mixture through a main feeding way and the inorganic mineral through a side feeding way, and adding the mixture into a double-screw extruder for mixing and granulating. The composite material prepared by the invention has the advantages of simple preparation process, low linear expansion coefficient of the material, and good dimensional stability and toughness, and can meet the requirements of certain parts with high dimensional stability and toughness on automobiles, such as automobile empennages, automobile tail door handles and the like. The invention utilizes the characteristic of higher impact toughness of the PC/ABS alloy, the prepared alloy material has certain impact toughness, but the incompatibility problem of inorganic mineral and polymer matrix is not fully considered, and particularly when the inorganic mineral filling amount is larger, the impact toughness of the composition is sharply reduced.
Chinese patent document CN101469116A discloses a mineral filled, high-toughness, ultraviolet-resistant polycarbonate composition and a preparation method thereof, wherein the composition comprises the following components in parts by mass: 40-85 parts of polycarbonate resin, 10-50 parts of ABS mixture, 2-10 parts of inorganic filler, 0.2-2 parts of titanium dioxide or carbon black and 0.3-1 part of antioxidant stabilizer. The PC composition prepared by the invention has high toughness, high heat-resistant dimensional stability and long-term ultraviolet radiation resistance, and can be used for various automobile internal and external plastic parts. According to the invention, inorganic minerals and ABS resin are required to be prepared into master batches in advance, although the dispersion effect of the mineral filler can be enhanced, the complexity of the production process is increased by preparing the master batches, and meanwhile, the length-diameter ratio of the wollastonite filler can be damaged, so that the strength and other properties of the material are influenced; on the other hand, since the content of the mineral component in the master batch is limited, the mineral filling amount of the final alloy composition is also limited, and thus an alloy composition having a high filling content cannot be prepared.
Disclosure of Invention
Aiming at the requirements of large size and narrow side thin wall of a television shell, the invention provides a preparation method of a PC/ABS alloy material with high impact and low linear expansion coefficient, wollastonite filler with proper length-diameter ratio is preferably selected as the modified alloy material, and the compatibility of the modified alloy material and a PC/ABS resin matrix is improved by a method of multi-coating wollastonite, and the prepared alloy combination has extremely high impact toughness and low linear expansion coefficient, can be applied to preparation of middle and front frames of large-size televisions, and has better sprayability than a glass fiber reinforced PC/ABS material.
A high-impact low-linear-expansion-coefficient PC/ABS alloy material is characterized by comprising the following raw materials in parts by weight based on 100 parts of the total weight of the raw materials:
25-65 parts of polycarbonate PC (polycarbonate),
15-40 parts of ABS resin,
10-30 parts of wollastonite,
2-5 parts of a compatilizer,
3-5 parts of a toughening agent,
0.3 to 1 portion of antioxidant,
0.2-1 part of lubricant;
the wollastonite is multiply coated by long-chain octadecyl silane, monoalkoxy titanate and maleic anhydride grafted polyethylene wax, and the length-diameter ratio of the wollastonite is 13-20. The long-chain octadecylsilane is adopted for coating, so that the damage of alkalescence of wollastonite to molecular chains of the PC material in the extrusion processing process can be weakened, and the moisture and heat resistance of the material can be improved; the compatibility of wollastonite and PC/ABS alloy can be improved by the monoalkoxy titanate and the maleic anhydride grafted polyethylene wax, the impact toughness of the material is greatly improved, the filling amount of the filler can be increased, and the material cost is further reduced.
Preferably, the polycarbonate PC is bisphenol A aromatic polycarbonate, and the melt flow rate of the polycarbonate PC under the conditions of 300 ℃ and 1.2 Kg is 15-25g/10min.
Preferably, the ABS resin is a terpolymer composed of acrylonitrile-butadiene-styrene, wherein the weight percentage of butadiene is 10-20%.
Preferably, the melt flow rate of the ABS resin at 220 ℃ and 10 Kg is 20-35g/10min.
Preferably, the compatilizer is one or two of maleic anhydride grafted acrylonitrile-styrene or maleic anhydride grafted styrene.
Preferably, the toughening agent is one or two of methacrylate-butadiene-styrene core-shell structure copolymer or polymethyl methacrylate-acrylate-organosilicon core-shell copolymer.
Preferably, the antioxidant is a compound of an antioxidant 1076 and an antioxidant 168 according to a weight ratio of 1.
Preferably, the lubricant is at least one of calcium stearate, pentaerythritol stearate and silicone powder.
The invention also provides a preparation method of the PC/ABS alloy material with high impact and low linear expansion coefficient, which is characterized by comprising the following steps:
step 1, stirring 100 parts by mass of wollastonite at a medium-low rotating speed of 200-300 revolutions per minute, simultaneously adding 1 part by mass of long-chain octadecyl silane and 1 part by mass of monoalkoxy titanate into the wollastonite in a spray manner according to sequence for coating, and finally adding 2 parts by mass of maleic anhydride grafted polyethylene wax into the wollastonite and uniformly stirring the mixture;
step 2, uniformly mixing the PC resin, the ABS resin, the compatilizer, the flexibilizer, the antioxidant and the lubricant according to the proportion; feeding the obtained mixed material through a main feeding port of a double-screw extruder, feeding wollastonite through side feeding, and obtaining the high-impact low-linear expansion coefficient PC/ABS alloy material after extrusion, granulation and drying;
the temperature of each temperature zone from feeding to extruding and discharging of the double-screw extruder is set as follows: a first area: 225 to 245 ℃ and two to nine areas: 230 to 250 ℃, and a die head: at 250 ℃ to obtain a mixture.
The invention also provides application of the PC/ABS alloy material with high impact and low linear expansion coefficient in preparing television middle frames or front frame products.
Compared with the prior art, the invention has the main advantages that: according to the high-impact low-linear-expansion-coefficient PC/ABS alloy material, wollastonite filler with a proper length-diameter ratio is used for filling the PC/ABS polymer, so that the linear expansion coefficient of the alloy composition is reduced to a certain extent, and the dimensional stability of the material is improved; on the other hand, the compatibility of the mineral filler and a PC/ABS alloy system is greatly improved by a method of carrying out multiple coating on the long-chain octadecylsilane, the monoalkoxy titanate and the maleic anhydride grafted polyethylene wax, the notch impact toughness of the prepared material is greatly improved, the maximum filling amount of the filler can reach 30% based on the good compatibility of the coated filler and a resin matrix, and the cost of the whole material is further reduced. The finally prepared alloy composition has extremely high impact toughness, lower linear expansion coefficient and higher cost performance, is particularly suitable for middle and front frame parts of large-size television sets by injection molding, and has excellent dimensional stability and better drop resistance. The invention adopts a melt mixing extrusion process, has simple and convenient production flow, simple operation and high industrial production efficiency.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
In the following examples and comparative examples, the following brands of raw materials were specifically selected:
the PC resin adopts the Taiwan light IR1900, and the melt flow rate under the conditions of 300 ℃ and 1.2 Kg is 19 g/10min.
The ABS is high petrochemical 8391, and the melt flow rate is 27 g/10min at 220 deg.C and 10 Kg.
The wollastonite is coated by using raw powder with the length-diameter ratio of 13-20.
The compatibilizer was selected from Shanghai Wen SMA700.
The toughening agent is Rohm and Haas EXL-2620.
The antioxidant is a compound consisting of an antioxidant 1076 and an antioxidant 168 according to the weight ratio of 1.
The lubricant is pentaerythritol stearate (PETS).
In the following examples and comparative examples, the addition amounts are in parts by weight unless otherwise specified, and the specific preparation process is as follows:
step 1, stirring 100 parts by mass of wollastonite at a medium-low rotating speed of 200-300 revolutions per minute, simultaneously adding 1 part by mass of long-chain octadecyl silane and 1 part by mass of monoalkoxyl titanate into the wollastonite in a spray form according to a sequence for coating, and finally adding 2 parts by mass of maleic anhydride grafted polyethylene wax into the wollastonite and uniformly stirring the mixture;
step 2, uniformly mixing the PC resin, the ABS resin, the compatilizer, the flexibilizer, the antioxidant and the lubricant according to the proportion; feeding the obtained mixed material through a main feeding port of a double-screw extruder, feeding wollastonite through side feeding, and obtaining the high-impact low-linear expansion coefficient PC/ABS alloy material after extrusion, granulation and drying;
the temperature of each temperature zone from feeding to extruding and discharging of the double-screw extruder is set as follows: a first region: 225 to 245 ℃ and two to nine areas: 230 to 250 ℃, die head: at 250 deg.c.
The test method for testing the performance of the materials prepared in the examples and the comparative examples is as follows:
physical and mechanical properties: the tensile property test refers to GB/T1040.2-2006 standard, and the tensile rate is 10mm/min; the bending property test refers to the GB/T9341-2008 standard, and the bending speed is 2mm/min; the notch impact performance test refers to GB/T1043.1-2008 standard; the heat distortion temperature is referred to GB/T1634.2-2004 standard. The linear expansion coefficient refers to the GB/T1036-2008 standard, and the test range is-30 ℃ to 30 ℃.
Examples 1 to 4 and comparative examples 1 to 4
The addition amounts of the raw material components of the PC/ABS alloy compositions of examples 1 to 4 and comparative examples 1 to 4 are shown in Table 1, and the results of the material performance tests are shown in Table 2. The purpose of comparative examples 1 to 4 is to study the influence of wollastonite on the linear expansion coefficient of PC/ABS alloy materials and the influence of a proper coating mode of wollastonite on the impact toughness of an alloy system, wherein in comparative examples 2 to 3, wollastonite is not coated, and in comparative example 4, only wollastonite is coated by a monoalkoxy titanate coupling agent.
TABLE 1
TABLE 2
* Humid heat aging conditions: 85 ℃/85RH% for 500 hours
As can be seen from the data related to the examples 1 to 4 in tables 1 and 2, the alloy material prepared by filling wollastonite into a PC/ABS alloy material and coating the wollastonite in a multilayer manner has excellent impact toughness and low linear expansion coefficient. With the continuous increase of the filling content of the wollastonite, the notch impact property and the linear expansion coefficient of the alloy material are reduced, the fluidity of the material is also reduced, and the material is more difficult to inject.
Comparing the data of examples 1-2 and comparative example 1, it can be seen that the linear expansion coefficient of the materials of examples 1-2 is obviously reduced along with the increase of the content of wollastonite compared with the system of comparative example 1 without wollastonite, but the introduction of wollastonite does not obviously improve the material strength of the PC/ABS alloy system, and the tensile bending strength of the materials is reduced to a small extent even along with the increase of the addition amount of wollastonite.
The comparative examples 2 to 3 adopt the non-coated wollastonite to fill the PC/ABS alloy, the notch impact strength of the material is obviously reduced, and the higher the wollastonite content is compared with the melt flow rate of the material, the higher the melt flow rate of the material is, which is completely different from the rules of the examples 1 to 3, and probably caused by the degradation of the PC material due to the weak alkalinity of the non-coated wollastonite.
Comparative example 4 only adopts the conventional titanate coupling agent coating method, compared with example 4, the notched impact strength is obviously lower, and the notched impact performance retention rate is also obviously reduced after the moist heat aging, so that wollastonite and PC/ABS alloy cannot form a good compatible system by adopting the conventional coupling agent treatment method; on the other hand, the melt flow rate of comparative example 4 was also higher than the multilayer coating method used in example 4, probably also due to the basicity of wollastonite leading to degradation of the PC material.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A high-impact low-linear-expansion-coefficient PC/ABS alloy material is characterized by comprising the following raw materials in parts by weight based on 100 parts of the total weight of the raw materials:
25-65 parts of polycarbonate PC (polycarbonate),
15-40 parts of ABS resin,
10-30 parts of wollastonite,
2-5 parts of a compatilizer,
3-5 parts of a toughening agent,
0.3 to 1 portion of antioxidant,
0.2-1 part of a lubricant;
the wollastonite is multiply coated by long-chain octadecyl silane, monoalkoxy titanate and maleic anhydride grafted polyethylene wax, and the length-diameter ratio of the wollastonite is 13-20.
2. The high impact, low linear expansion coefficient PC/ABS alloy material according to claim 1, wherein the polycarbonate PC is bisphenol A aromatic polycarbonate and has a melt flow rate of 15-25g/10min at 300 ℃ and 1.2 Kg.
3. The high impact, low linear expansion coefficient PC/ABS alloy material of claim 1, wherein the ABS resin is a terpolymer of acrylonitrile-butadiene-styrene, wherein the weight percentage of butadiene is 10-20%.
4. The high impact, low linear expansion coefficient PC/ABS alloy material of claim 1, wherein the melt flow rate of the ABS resin is 20-35g/10min at 220 ℃ and 10 Kg.
5. The high impact, low linear expansion coefficient PC/ABS alloy material of claim 1, wherein the compatibilizer is one or both of maleic anhydride grafted acrylonitrile-styrene or maleic anhydride grafted styrene.
6. The high-impact low-linear-expansion-coefficient PC/ABS alloy material according to claim 1, wherein the toughening agent is one or two of a methacrylate-butadiene-styrene core-shell structure copolymer or a polymethyl methacrylate-acrylate-organosilicon core-shell copolymer.
7. The high-impact low-linear-expansion-coefficient PC/ABS alloy material as claimed in claim 1, wherein the antioxidant is a compound of antioxidant 1076 and antioxidant 168 in a weight ratio of 1.
8. The high impact, low linear expansion coefficient PC/ABS alloy material of claim 1, wherein the lubricant is at least one of calcium stearate, pentaerythritol stearate, silicone powder.
9. The preparation method of the high-impact low-linear-expansion-coefficient PC/ABS alloy material as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
step 1, stirring 100 parts by mass of wollastonite at a medium-low rotating speed of 200-300 revolutions per minute, simultaneously adding 1 part by mass of long-chain octadecyl silane and 1 part by mass of monoalkoxy titanate into the wollastonite in a spray manner according to sequence for coating, and finally adding 2 parts by mass of maleic anhydride grafted polyethylene wax into the wollastonite and uniformly stirring the mixture;
step 2, uniformly mixing the PC resin, the ABS resin, the compatilizer, the flexibilizer, the antioxidant and the lubricant according to the proportion; feeding the obtained mixed material through a main feeding port of a double-screw extruder, feeding wollastonite through side feeding, and obtaining the high-impact low-linear expansion coefficient PC/ABS alloy material after extrusion, granulation and drying;
the temperature of each temperature zone from feeding to extruding discharging of the double-screw extruder is set as follows: a first region: 225 to 245 ℃ and two to nine areas: 230 to 250 ℃, die head: at 250 deg.c.
10. Use of the high-impact low-linear-expansion-coefficient PC/ABS alloy material according to any one of claims 1-8 in the preparation of a television middle frame or a front frame part.
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| CN101367991A (en) * | 2008-09-25 | 2009-02-18 | 上海交通大学 | Method of manufacturing polycarbonate/vinyl cyanide-butadiene-styrol copolymer alloy |
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| CN106905683A (en) * | 2017-04-21 | 2017-06-30 | 桑德（天津）再生资源投资控股有限公司 | A kind of HI high impact heat-resistant halogen-free flame-retardant PC/ABS alloy materials and preparation method thereof |
| CN107541044A (en) * | 2017-09-01 | 2018-01-05 | 品诚塑胶科技（上海）有限公司 | Poly carbonate resin composition and preparation method thereof |
| CN111154247A (en) * | 2019-12-27 | 2020-05-15 | 会通新材料股份有限公司 | High-toughness low-linear-expansion-coefficient PC/ABS composite material and preparation method thereof |
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- 2021-06-30 CN CN202110734384.XA patent/CN115537006A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367991A (en) * | 2008-09-25 | 2009-02-18 | 上海交通大学 | Method of manufacturing polycarbonate/vinyl cyanide-butadiene-styrol copolymer alloy |
| CN103224699A (en) * | 2013-04-27 | 2013-07-31 | 上海锦湖日丽塑料有限公司 | Low linear expansion coefficient PC/ABS alloy composition and preparation method thereof |
| CN106905683A (en) * | 2017-04-21 | 2017-06-30 | 桑德（天津）再生资源投资控股有限公司 | A kind of HI high impact heat-resistant halogen-free flame-retardant PC/ABS alloy materials and preparation method thereof |
| CN107541044A (en) * | 2017-09-01 | 2018-01-05 | 品诚塑胶科技（上海）有限公司 | Poly carbonate resin composition and preparation method thereof |
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