CN112080120A - Polycarbonate alloy material and preparation method and application thereof - Google Patents
Polycarbonate alloy material and preparation method and application thereof Download PDFInfo
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- CN112080120A CN112080120A CN202010867740.0A CN202010867740A CN112080120A CN 112080120 A CN112080120 A CN 112080120A CN 202010867740 A CN202010867740 A CN 202010867740A CN 112080120 A CN112080120 A CN 112080120A
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses a polycarbonate alloy material and a preparation method and application thereof, wherein the polycarbonate alloy material comprises the following components: 52-75 parts of PC resin; 15-30 parts of acrylonitrile-styrene copolymer SAN; 10-15 parts of ABS high rubber powder; 1-3 parts of a compatilizer; wherein the lanthanum element is present in an amount of 5ppm to 120ppm by weight, based on the total weight of the polycarbonate alloy material. The polycarbonate alloy material prepared by the invention can obviously reduce the glossiness of the alloy material and greatly improve the humidity resistance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polycarbonate alloy material, and a preparation method and application thereof.
Background
The polycarbonate alloy material is an engineering plastic with excellent comprehensive performance, has the advantages of high impact strength, good creep resistance and dimensional stability, heat resistance, transparency, low water absorption, no toxicity, excellent dielectric property and the like, and is widely applied in the automobile industry. In the automotive industry, materials are often required to have low gloss, reduce interference with drivers and passengers, and upgrade trim parts. Meanwhile, since PC is not water-resistant and is easily hydrolyzed in a humid environment, and thus the performance is greatly reduced, it is required to improve the moist heat resistance of the alloy material.
In order to reduce the glossiness of the material, the industry generally adds inorganic filler or organic flatting agent, because need add the part to reach better effect, this often produces negative effects to mechanical properties, processing mobility of material etc.. In addition, the moisture and heat resistance of the polycarbonate resin can be improved by preparing the polycarbonate resin by a special polymerization method, but the cost is too high.
According to the invention, through the unexpected research, the lanthanum compound is added into the polycarbonate alloy material, and the content of lanthanum in the polycarbonate alloy material is controlled within the range of 5-120ppm, so that the glossiness of the alloy material can be obviously reduced on the premise of basically not influencing the mechanical property, and the humidity resistance can be greatly improved.
Disclosure of Invention
The invention aims to provide a polycarbonate alloy material, which can obviously reduce the glossiness of the alloy material and greatly improve the humidity resistance on the premise of basically not influencing the mechanical property.
The invention also aims to provide a preparation method of the polycarbonate alloy material.
The invention is realized by the following technical scheme:
the polycarbonate alloy material comprises the following components in parts by weight:
preferably, the lanthanum element is present in an amount of 5 to 120ppm by weight, preferably 10 to 60ppm by weight, based on the total weight of the polycarbonate alloy material.
The method for testing the weight content of the lanthanum element comprises the following steps: 2g of particles of a polycarbonate alloy material are accurately weighed in an analytical balance, poured into a 100ml digestion bottle, then added with 5ml of 97% concentrated sulfuric acid, heated in an iron plate heating instrument at a preset temperature of 300 ℃ for 10 minutes, then added with 5ml of 68% nitric acid, kept heated for 20 minutes, cooled to room temperature after the particles are completely decomposed, added with 20ml of hydrogen peroxide to neutralize the acidity until the pH value is 7, diluted with deionized water, and introduced into an ICP detection instrument through a sample inlet pipe to measure the concentration of lanthanum.
Preferably, the lanthanum element is derived from a lanthanum compound, and the lanthanum compound is one or more of lanthanum oxide, lanthanum hydroxide or lanthanum chloride.
The PC resin can be prepared by a phosgene method or an ester exchange method in the industry, and can also be obtained in a commercially available mode.
The polycarbonate of the present invention may be one or a mixture of several selected from aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branched polycarbonate, and siloxane copolycarbonate. According to the invention, researches show that SAN with different AN contents has certain influence on the humidity resistance in the alloy material, the higher the AN content is, the better the humidity resistance is, but the too high AN content can obviously reduce the fluidity of the material. Therefore, it is preferable that the content of acrylonitrile AN in the acrylonitrile-styrene copolymer SAN is 21% to 32%, preferably 30% to 32%, based on the total weight of the acrylonitrile-styrene copolymer SAN.
The ABS high-rubber powder is an acrylonitrile-butadiene-styrene terpolymer with high rubber content and polymerized by an emulsion method. According to the invention, researches show that the grain size of the high-rubber ABS powder has a certain influence on the glossiness of the alloy material, and the toughening effect of the high-rubber ABS powder can be greatly reduced if the grain size is too small; the larger the particle size, the lower the glossiness of the material, but the too large particle size easily causes agglomeration, thereby affecting the mechanical properties of the material. Preferably, the ABS high-rubber powder is one or a mixture of two of ABS high-rubber powder with the particle size of butadiene rubber D50 of 100-400nm or ABS high-rubber powder with the particle size of butadiene rubber D50 of 500-800nm, and more preferably ABS high-rubber powder with the particle size of butadiene rubber D50 of 500-800 nm.
Preferably, the compatilizer is one or a mixture of two of styrene-acrylonitrile-glycidyl methacrylate terpolymer, styrene-nitryl phenyl maleimide-maleic anhydride terpolymer or styrene-maleic anhydride.
The invention also provides a preparation method of the polycarbonate alloy material, which comprises the following steps:
(1) weighing the components according to the proportion, mixing the components in a high-speed mixer for 1-5min, and adding the mixture into a double-screw extruder at a first section after uniformly mixing;
(2) adding a lanthanum compound in a side feed of a double screw;
(3) and (3) performing melt extrusion, granulation and drying to obtain the polycarbonate alloy material.
Preferably, in the step (3), the melt extrusion conditions are as follows: the temperature of the first zone is 200-; the length-diameter ratio of the double-screw extruder is 32:1-42: 1.
the invention also provides application of the polycarbonate alloy material in the automobile industry.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, through the unexpected research, the lanthanum compound is added into the polycarbonate alloy material, and the content of lanthanum in the polycarbonate alloy material is controlled within the range of 5-120ppm, so that the glossiness of the alloy material can be obviously reduced on the premise of basically not influencing the mechanical property, and the humidity resistance can be greatly improved.
(2) The invention can further reduce the glossiness of the alloy material and improve the humidity resistance by the synergistic effect of the PC resin, the SAN and the ABS high rubber powder and the optimization of the SAN and ABS high rubber powder.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
PC resin, commercially available;
acrylonitrile-styrene copolymer SAN:
SAN 350, AN content of 32%, korean brocade lake;
SAN 335, AN content of 26% AN, brocade lake korea;
SAN 320, AN content of 24.5%, korean brocade lake;
SAN 310, AN content of 21%, brocade lake korea;
1, ABS high-rubber powder, wherein the particle size of the butadiene rubber D50 is 100-400 nm;
2, ABS high-rubber powder, wherein the particle size of the butadiene rubber D50 is 500-800 nm;
a compatilizer: styrene-acrylonitrile-glycidyl methacrylate terpolymer, RAS-302, Jiaxing Hua Wen, Inc.
Compounds of lanthanum: lanthanum oxide, lanthanum hydroxide, lanthanum chloride, commercially available;
examples 1 to 11 and comparative examples 1 to 2:
(1) weighing the components according to the proportion in the table 1, mixing the components in a high-speed mixer for 5min, and adding the mixture into a double-screw extruder at a first section after uniformly mixing;
(2) lanthanum compound is added in the third section side feed of the double screw;
(3) and (3) performing melt extrusion, granulation and drying to obtain the polycarbonate alloy material.
Wherein the conditions of melt extrusion are as follows: the temperature of the first zone is 200-; the length to diameter ratio of the twin-screw extruder was 38: 1.
The content of the lanthanum element in the polycarbonate alloy materials of the examples and the comparative examples is controlled by adding a lanthanum compound to the polycarbonate alloy material and adjusting the adding amount of the lanthanum compound.
Each performance test condition:
the method for testing the weight content of the lanthanum element comprises the following steps: accurately weighing 2g of particles of an alloy material in an analytical balance, pouring the particles into a 100ml digestion bottle, adding 5ml of 97% concentrated sulfuric acid, heating the particles in an iron plate heating instrument at a preset temperature of 300 ℃ for 10 minutes, then adding 5ml of 68% nitric acid, keeping heating for 20 minutes, cooling the particles to room temperature after completely decomposing the particles, adding 20ml of hydrogen peroxide to neutralize the particles until the pH value is 7, diluting the liquid with deionized water, and introducing the liquid into an ICP (inductively coupled plasma) detection instrument through a sample inlet pipe to measure the concentration of lanthanum;
gloss: carrying out a 60-degree angle test by adopting a BYK4560 type gloss instrument according to ISO 2813, and recording a gloss value;
moisture and heat resistance: placing the material at 85 ℃ and 85% humidity for 500 hours, testing the notched impact strength of the cantilever beam before and after placement according to ISO 180, and calculating the retention rate, wherein the higher the retention rate is, the better the moisture and heat resistance is;
tensile strength: ISO 527, units MPa;
bending strength: ISO 178, units MPa.
TABLE 1 concrete compounding ratio (parts by weight) of each component in each example and comparative example
TABLE 1
As can be seen from the data of the examples and the comparative examples 1-2, the content of lanthanum element in the polycarbonate alloy material is controlled within the range of 5-120ppm by adding the lanthanum compound in the polycarbonate alloy material, so that the glossiness of the polycarbonate alloy can be obviously reduced on the premise of ensuring that the mechanical property is not affected basically, and the humidity resistance can be greatly improved; in comparative examples 1 to 2, when the lanthanum element content in the polycarbonate alloy material was less than 5ppm or more than 120ppm, the polycarbonate alloy material had high gloss and poor wet heat resistance.
As can be seen from examples 1 and 6-8, SAN with different AN contents has a certain influence on the moist heat resistance in the alloy material, and the higher the AN content is, the better the moist heat resistance is. This is because the higher the AN content, the higher the polarity, and the more uniform the dispersion of the rubber particles of the ABS high rubber powder in the matrix.
As can be seen from the data of examples 1 and 5, the glossiness of example 1 is obviously lower than that of example 5, which shows that the grain size of ABS high rubber powder has a certain influence on the glossiness of the alloy material, and the larger the grain size is, the lower the glossiness of the material is.
Claims (10)
1. The polycarbonate alloy material is characterized by comprising the following components in parts by weight:
52-75 parts of polycarbonate resin;
15-30 parts of acrylonitrile-styrene copolymer SAN;
10-15 parts of ABS high rubber powder;
1-3 parts of a compatilizer.
2. The polycarbonate alloy material of claim 1, wherein the lanthanum element is present in an amount of 5 to 120ppm, preferably 10 to 60ppm, by weight, based on the total weight of the polycarbonate alloy material.
3. The polycarbonate alloy material of claim 2, wherein the lanthanum element is measured by the method comprising: 2g of particles of a polycarbonate alloy material are accurately weighed in an analytical balance, poured into a 100ml digestion bottle, then added with 5ml of 97% concentrated sulfuric acid, heated in an iron plate heating instrument at a preset temperature of 300 ℃ for 10 minutes, then added with 5ml of 68% nitric acid, kept heated for 20 minutes, cooled to room temperature after the particles are completely decomposed, added with 20ml of hydrogen peroxide to neutralize the acidity until the pH value is 7, diluted with deionized water, and introduced into an ICP detection instrument through a sample inlet pipe to measure the concentration of lanthanum.
4. The polycarbonate alloy material of claim 2, wherein the lanthanum element is derived from a lanthanum compound, and the lanthanum compound is one or more of lanthanum oxide, lanthanum hydroxide or lanthanum chloride.
5. The polycarbonate alloy material of claim 1, wherein the acrylonitrile-styrene copolymer has AN acrylonitrile AN content of 21% to 32%, preferably 30% to 32%, based on the total weight of the acrylonitrile-styrene copolymer SAN.
6. The polycarbonate alloy material as claimed in claim 1, wherein the ABS high-rubber powder is one or a mixture of two of ABS high-rubber powder with a butadiene rubber D50 particle size of 100-400nm and ABS high-rubber powder with a butadiene rubber D50 particle size of 500-800nm, preferably ABS high-rubber powder with a butadiene rubber D50 particle size of 500-800 nm.
7. The polycarbonate alloy material of claim 1, wherein the compatibilizer is one or a mixture of two of styrene-acrylonitrile-glycidyl methacrylate terpolymer, styrene-nitophenylmaleimide-maleic anhydride terpolymer, or styrene-maleic anhydride.
8. The method for preparing the polycarbonate alloy material according to any one of claims 1 to 7, comprising the following steps:
(1) weighing the components according to the proportion, mixing the components in a high-speed mixer for 1-5min, and adding the mixture into a double-screw extruder at a first section after uniformly mixing;
(2) adding a lanthanum compound in a side feed of a double screw;
(3) and (3) performing melt extrusion, granulation and drying to obtain the polycarbonate alloy material.
9. The method for preparing a polycarbonate alloy material according to claim 8, wherein in the step (3), the melt extrusion conditions are as follows: the temperature of the first zone is 200-; the length-diameter ratio of the twin-screw extruder is 32:1-42: 1.
10. Use of the polycarbonate alloy material according to any one of claims 1 to 7 in automotive materials.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113462142A (en) * | 2021-06-28 | 2021-10-01 | 武汉金发科技有限公司 | High-weather-resistance PC/AES alloy and preparation method thereof |
| CN113969049A (en) * | 2021-12-13 | 2022-01-25 | 重庆华众新型材料有限公司 | Preparation method of solvent stress cracking resistant PC alloy |
| CN115232459A (en) * | 2022-07-28 | 2022-10-25 | 金发科技股份有限公司 | Ultraviolet-resistant PC/ABS alloy and preparation method and application thereof |
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| CN113462142A (en) * | 2021-06-28 | 2021-10-01 | 武汉金发科技有限公司 | High-weather-resistance PC/AES alloy and preparation method thereof |
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| CN113969049A (en) * | 2021-12-13 | 2022-01-25 | 重庆华众新型材料有限公司 | Preparation method of solvent stress cracking resistant PC alloy |
| CN115232459A (en) * | 2022-07-28 | 2022-10-25 | 金发科技股份有限公司 | Ultraviolet-resistant PC/ABS alloy and preparation method and application thereof |
| CN115232459B (en) * | 2022-07-28 | 2023-11-07 | 金发科技股份有限公司 | Ultraviolet-resistant PC/ABS alloy and preparation method and application thereof |
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