CN106065171B - A kind of high durable PC-ASA alloy materials and preparation method thereof - Google Patents

A kind of high durable PC-ASA alloy materials and preparation method thereof Download PDF

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Publication number
CN106065171B
CN106065171B CN201610696701.2A CN201610696701A CN106065171B CN 106065171 B CN106065171 B CN 106065171B CN 201610696701 A CN201610696701 A CN 201610696701A CN 106065171 B CN106065171 B CN 106065171B
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parts
alloy materials
asa
pmma
high durable
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CN106065171A (en
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柏莲桂
***
罗明华
辛敏琦
王正磊
李军宏
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GUANGDONG KUMBO SUNNY POLYMER MATERIAL CO Ltd
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GUANGDONG KUMBO SUNNY POLYMER MATERIAL 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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

Abstract

A kind of high durable PC ASA alloy materials and preparation method thereof, PC ASA alloy materials include the recipe ingredient of following parts by weight：30 70 parts of PC resin, 10 30 parts of ASA resin, 5 25 parts of PMMA resins, 5 15 parts of the block copolymer of methyl methacrylate-mutual-phenenyl two acid bromide two alcohol ester containing GMA functional groups, the present invention proposes a kind of high durable PC ASA alloy materials, have the characteristics that weather resistance is excellent, bloom, overcomes the problem of addition PMMA will produce pearly-lustre in PC and its alloy；On the other hand, preparation method proposed by the present invention, can effectively control the phase of PMMA, and operation is simple.

Description

A kind of high durable PC-ASA alloy materials and preparation method thereof
Technical field
The present invention relates to polymer blended, Polymer Processing technical field more particularly to a kind of high durable PC-ASA Alloy material and preparation method thereof.
Background technology
PC-ASA alloy materials are widely used and automobile and electricity due to its excellent shock resistance, heat resistance, weather resistance The fields such as sub- product.With the development of automobile, a kind of trend will be become by exempting from primary coat environment-friendly materials.
PC-ASA is as exterior trim in use, very high to weather-proof requirement.Common PC-ASA cannot be satisfied exterior trim use and want It asks.PMMA often improves weather resistance as weather-proof excellent resin by adding PMMA.But since PMMA and PC refractive powers refer to Number difference is too big, causes the addition PMMA in PC and its alloy to generate pearly-lustre, cannot be satisfied appearance demand.
Invention content
It is an object of the invention to propose a kind of high durable PC-ASA alloy materials, have that weather resistance is excellent, bloom is special Point overcomes the problem of addition PMMA will produce pearly-lustre in PC and its alloy.
It is an object of the invention to propose that a kind of preparation method of high durable PC-ASA alloy materials, method can be controlled effectively The phase of PMMA processed, operation are simple.
For this purpose, the present invention uses following technical scheme：
A kind of high durable PC-ASA alloy materials, include the recipe ingredient of following parts by weight：
30-70 parts of PC resin,
10-30 parts of ASA resin,
5-25 parts of PMMA resins,
5-15 parts of the block copolymer of methyl methacrylate-mutual-phenenyl two acid bromide two alcohol ester containing GMA functional groups.
The weather resistance of PC-ASA alloy materials is improved by the addition of PMMA resins in formula, further, also The block copolymer of methyl methacrylate-mutual-phenenyl two acid bromide two alcohol ester of the addition containing GMA functional groups (hereinafter referred to as contains There is the block copolymer of the PMMA-PBT of GMA).
It should be noted that GMA is the abbreviation of glycidyl methacrylate.
PBT and PC resin it is excellent in compatibility, after especially transesterification occurs for processing, fully compatible body can be obtained System.The block copolymer for the PBT-PMMA for having GMA is added in PC resin and its alloy, further improves PMMA and PC resin Compatibility, obtain extraordinary compatibility since transesterification occurs for PBT and PC so that the phase of PBT-PMMA is that outer layer is PBT, the spherical shape that internal layer is PMMA.The phase of PMMA is controlled by the method so that PMMA phase dimensions are less than visible light wave Long half solves the problems, such as pearly-lustre caused by PMMA.
Further description further includes the recipe ingredient of following parts by weight：0.1-1 parts of weather resisting agent, antioxidant 0.1-1 Part, 0.1-1 parts of lubricant, 2-5 parts of colored particles.
Further description, the colored particles are black masterbatch, and the black masterbatch is that content of carbon black is 30-70% Master batch, master batch carrier be PE waxes.
Further description, the methyl methacrylate-mutual-phenenyl two acid bromide two alcohol ester containing GMA functional groups Block copolymer, the content of mutual-phenenyl two acid bromide two alcohol ester is 1~5% in 30~70%, GMA functional group contents.
Further description, the weather resisting agent include one or both of benzotriazole and triazine.
Further description, the antioxidant are the bis- [β-(3- tertiary butyl-4-hydroxy -5- methylbenzenes of triethylene-glycol Base) propionic ester] (i.e. antioxidant 245), four [β-(3,5- di-t-butyl 4- hydroxy phenyls) propionic acid] pentaerythritol ester (i.e. antioxidant 1010), three (2,4- di-tert-butyl-phenyl) phosphite esters (i.e. irgasfos 168), double stearyl alcohol pentaerythrite diphosphorous acids The mixing of one or more of ester (i.e. antioxidant 618).
Further description, the lubricant are silane polymer, solid paraffin, atoleine, fatty acid salt, tristearin Sour calcium fatty acid amide, calcium stearate, zinc stearate, stearic amide, methylene bis stearic amide and N, N- ethylene are double stearic The mixing of one or more of sour amide.
The weight average molecular weight of further description, the PMMA resins is 50,000-250,000.
The weight average molecular weight of further description, the PC resin is 10000~30000g/mol.
Further description, the ASA resin are the graft copolymer of Acrylate-styrene bipolymer-acrylonitrile composition, rubber Glue content is in 30-80%.
A kind of method preparing above-mentioned high durable PC-ASA alloy materials proposed by the present invention, includes the following steps：
(a) PC resin, ASA resin, PMMA resins, PMMA processing aids, adjuvant and colored particles are weighed, and will be above-mentioned Raw material is mixed；
(b) mixture obtained by step a is subjected to extruding pelletization, obtains PC-ASA alloy materials.
Further description, the mixture obtained by step a, which passes through double screw extruder and is blended, to be granulated, wherein extrusion temperature It is 240-260 DEG C.
Compared with prior art, the device have the advantages that being：Improve weather resistance by PMMA, by PMMA plus Work auxiliary agent improves the compatibility of PMMA and PC so that the phase of PMMA-PBT is that outer layer is the spherical shape that PBT internal layers are PMMA.It is logical Cross the phase that the method controls PMMA so that PMMA phase dimensions are less than the half of visible wavelength, and solving PMMA causes Pearly-lustre problem, obtain bloom high durable PC-ASA alloy materials.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
The L-1250WS of the PC resin selected in following embodiment and comparative example Di Ren Asahi Chemical Industries, ASA resin South Korea The XC-400 of kumho companies, PMMA resin are using strange beautiful PMMA205；Antioxidant be Ciba companies Irganox 1070, Irganox 168, Irganox628 and Irganox 245；Lubricant is commercially available pentaerythrite stearic acid, and weather resisting agent is The Kemisorb 102 of Basf companies, black masterbatch be Cabot I-940.
Comparative example 1
A kind of PC-ASA alloy materials and preparation method thereof, this approach includes the following steps：
(1) each component is weighed by weight：PC resin：70 parts, ASA resin：30 parts, black masterbatch：2 parts；Antioxidant 1010：0.1 part, irgasfos 168：0.1 part, 0.3 part of lubricant, 0.5 part of weather resisting agent.
(2) all raw materials are added in mixing and blending machine and mix by (a)；(b) mixture obtained by step a is passed through into double spiral shells Bar extruder, which is blended, to be granulated, and extrusion temperature is 260 DEG C, by melting extrusion, is granulated and is obtained product.
Comparative example 2
A kind of PC-ASA alloy materials and preparation method thereof, this approach includes the following steps：
(1) each component is weighed by weight：PC resin：65 parts, ASA resin：10 parts, PMMA resins：25 parts, carbon black is female Grain：5 parts；Antioxidant 1010：0.1 part, irgasfos 168：0.1 part, 0.3 part of lubricant, 0.5 part of weather resisting agent.
(2) all raw materials are added in mixing and blending machine and mix by (a)；(b) mixture obtained by step a is passed through into double spiral shells Bar extruder, which is blended, to be granulated, and extrusion temperature is 260 DEG C, by melting extrusion, is granulated and is obtained product.
Embodiment 1
A kind of high durable PC-ASA alloy materials and preparation method thereof, this approach includes the following steps：
(1) each component is weighed by weight：PC resin：50 parts, ASA resin：20 parts, PMMA resins：20 parts, contain GMA PMMA-PBT block copolymer (wherein PBT contents be 70%, GMA contents be 5%)：10 parts；Black masterbatch：4 parts；Antioxygen Agent 1010：0.1 part, irgasfos 168：0.1 part, 0.3 part of lubricant, 1 part of weather resisting agent.
(2) all raw materials are added in mixing and blending machine and mix by (a)；(b) mixture obtained by step a is passed through into double spiral shells Bar extruder, which is blended, to be granulated, and extrusion temperature is 260 DEG C, by melting extrusion, is granulated and is obtained product.
Embodiment 2
A kind of high durable PC-ASA alloy materials and preparation method thereof, this approach includes the following steps：
(1) each component is weighed by weight：PC resin：30 parts, ASA resin：30 parts, PMMA resins：25 parts, contain GMA PMMA-PBT block copolymer (wherein PBT contents be 30%, GMA contents be 1%)：15 parts, black masterbatch：4 parts, antioxygen Agent 1010：0.1 part, irgasfos 168：0.1 part, 0.3 part of lubricant, 1 part of weather resisting agent.
(2) all raw materials are added in mixing and blending machine and mix by (a)；(b) mixture obtained by step a is passed through into double spiral shells Bar extruder, which is blended, to be granulated, and extrusion temperature is 260 DEG C, by melting extrusion, is granulated and is obtained product.
Embodiment 3
A kind of high durable PC-ASA alloy materials and preparation method thereof, this approach includes the following steps：
(1) each component is weighed by weight：PC resin：60 parts, ASA resin：20 parts, PMMA resins：5 parts, contain GMA's (1%) it is that wherein PBT contents are 30%, GMA contents to the block copolymer of PMMA-PBT：5 parts, black masterbatch：4 parts, antioxidant 1010：0.1 part, irgasfos 168：0.1 part, 0.3 part of lubricant, 1 part of weather resisting agent.
(2) all raw materials are added in mixing and blending machine and mix by (a)；(b) mixture obtained by step a is passed through into double spiral shells Bar extruder, which is blended, to be granulated, and extrusion temperature is 260 DEG C, by melting extrusion, is granulated and is obtained product.
Embodiment 4
A kind of high durable PC-ASA alloy materials and preparation method thereof, this approach includes the following steps：
(1) each component is weighed by weight：PC resin：60 parts, ASA resin：15 parts, PMMA resins：20 parts, contain GMA PMMA-PBT block copolymer (wherein PBT contents be 70%, GMA contents be 5%)：5 parts, black masterbatch：5 parts, antioxygen Agent 1010：0.1 part, irgasfos 168：0.1 part, 0.3 part of lubricant, 1 part of weather resisting agent.
(2) all raw materials are added in mixing and blending machine and mix by (a)；(b) mixture obtained by step a is passed through into double spiral shells Bar extruder, which is blended, to be granulated, and extrusion temperature is 260 DEG C, by melting extrusion, is granulated and is obtained product.
Implementation result compares
Before preparing batten, the fully dry product pellet obtained is prepared to place after batten and be tested afterwards for 24 hours；
1) it carries out injecting all kinds of test bars and bloom colour table using injection molding machine；
2) Izod impact strengths are carried out according to ISO-180 standards, and temperature is 23 DEG C；
3) xenon lamp aging experiment is carried out according to SAE2527 standards, energy 1025KJ, measuring colour difference and color fastness after illumination.
1~2 product test result of 1 Examples 1 to 4 of table and comparative example
As shown in Table 1, embodiment 1 is impacted excellent, and for high smooth surface without pearly-lustre, weather resistance is excellent.It is improved by PMMA weather-proof Performance improves the compatibility of PMMA and PC by PMMA processing aids so that the phase of PMMA-PBT is that outer layer is PBT internal layers For the spherical shape of PMMA.The phase of PMMA is controlled by the method so that PMMA phase dimensions are less than the half of visible wavelength, It solves the problems, such as pearly-lustre caused by PMMA, obtains bloom high durable PC-ASA alloy materials.
Embodiment 5
A kind of high durable PC-ASA alloy materials and preparation method thereof, this approach includes the following steps：
(1) each component is weighed by weight：PC resin：70 parts, ASA resin：30 parts, PMMA resins：25 parts, contain GMA PMMA-PBT block copolymer (wherein PBT contents be 70%, GMA contents be 5%)：15 parts；Black masterbatch：5 parts；Antioxygen Agent 618：0.1 part, antioxidant 245：0.1 part, 0.3 part of lubricant, 1 part of weather resisting agent.
(2) all raw materials are added in mixing and blending machine and mix by (a)；(b) mixture obtained by step a is passed through into double spiral shells Bar extruder, which is blended, to be granulated, and extrusion temperature is 240 DEG C, by melting extrusion, is granulated and is obtained product.
Embodiment 6
A kind of high durable PC-ASA alloy materials and preparation method thereof, this approach includes the following steps：
(1) each component is weighed by weight：PC resin：50 parts, ASA resin：20 parts, PMMA resins：20 parts, contain GMA PMMA-PBT block copolymer (wherein PBT contents be 70%, GMA contents be 5%)：10 parts；Black masterbatch：4 parts；Antioxygen Agent 1010：0.3 part, 0.3 part of lubricant, 1 part of weather resisting agent.
(2) all raw materials are added in mixing and blending machine and mix by (a)；(b) mixture obtained by step a is passed through into double spiral shells Bar extruder, which is blended, to be granulated, and extrusion temperature is 260 DEG C, by melting extrusion, is granulated and is obtained product.
The technical principle of the present invention is described above in association with specific embodiment.These descriptions are intended merely to explain the present invention's Principle, and it cannot be construed to limiting the scope of the invention in any way.Based on the explanation herein, the technology of this field Personnel would not require any inventive effort the other specific implementation modes that can associate the present invention, these modes are fallen within Within protection scope of the present invention.

Claims (7)

1. a kind of high durable PC-ASA alloy materials, it is characterised in that：Include the recipe ingredient of following parts by weight：
30-70 parts of PC resin,
10-30 parts of ASA resin,
5-25 parts of PMMA resins,
5-15 parts of the block copolymer of methyl methacrylate-mutual-phenenyl two acid bromide two alcohol ester containing GMA functional groups；
It further include the recipe ingredient of following parts by weight：0.1-1 parts of weather resisting agent, 0.1-1 parts of lubricant, 0.1-1 parts of antioxidant 2-5 parts of coloured particles；
The block copolymer of the methyl methacrylate-mutual-phenenyl two acid bromide two alcohol ester containing GMA functional groups, to benzene The content of dioctyl phthalate butanediol ester is 1~5% in 30~70%, GMA functional group contents；
The ASA resin is the graft copolymer of Acrylate-styrene bipolymer-acrylonitrile composition, and rubber content is in 30-80%.
2. a kind of high durable PC-ASA alloy materials according to claim 1, it is characterised in that：The colored particles are charcoal Black masterbatch, the black masterbatch are the master batch that content of carbon black is 30-70%, and master batch carrier is PE waxes.
3. a kind of high durable PC-ASA alloy materials according to claim 1, it is characterised in that：The weather resisting agent includes One or both of benzotriazole and triazine.
4. a kind of high durable PC-ASA alloy materials according to claim 1, it is characterised in that：The antioxidant is two contractings Triethylene glycol bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters], four [β-(3,5- di-t-butyl 4- hydroxy benzenes Base) propionic acid] pentaerythritol ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, double stearyl alcohol pentaerythrite diphosphorous acids The mixing of one or more of ester.
5. a kind of high durable PC-ASA alloy materials according to claim 1, it is characterised in that：The lubricant is silane Polymer, solid paraffin, atoleine, calcium stearate, zinc stearate, stearic amide, methylene bis stearic amide and N, N- The mixing of one or more of ethylene bis stearic acid amide.
6. a kind of high durable PC-ASA alloy materials according to claim 1, it is characterised in that：The PMMA resins Weight average molecular weight is 50,000-250,000.
7. a kind of method preparing high durable PC-ASA alloy materials described in claim 1, it is characterised in that：Including following step Suddenly：
(a) PC resin, ASA resin, PMMA resins, block copolymer, weather resisting agent, antioxidant, lubricant and colored particles are weighed, And above-mentioned raw materials are mixed；
(b) mixture obtained by step a is subjected to extruding pelletization, obtains PC-ASA alloy materials.
CN201610696701.2A 2016-08-19 2016-08-19 A kind of high durable PC-ASA alloy materials and preparation method thereof Active CN106065171B (en)

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CN106674967B (en) * 2016-12-28 2018-11-09 上海锦湖日丽塑料有限公司 A kind of bloom exempts from the environmental-protection flame-retardant makrolon material and preparation method thereof of spraying
CN106854353B (en) * 2016-12-28 2019-03-08 上海锦湖日丽塑料有限公司 A kind of polycarbonate compositions and preparation method thereof of anti-friction noise
CN113956598B (en) * 2021-09-27 2023-05-09 武汉金发科技有限公司 Glass fiber reinforced ASA/PBT alloy material, and preparation method and application thereof

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