CN106065171A - A kind of high durable PC ASA alloy material and preparation method thereof - Google Patents
A kind of high durable PC ASA alloy material and preparation method thereof Download PDFInfo
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- CN106065171A CN106065171A CN201610696701.2A CN201610696701A CN106065171A CN 106065171 A CN106065171 A CN 106065171A CN 201610696701 A CN201610696701 A CN 201610696701A CN 106065171 A CN106065171 A CN 106065171A
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- alloy material
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- asa
- pmma
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of high durable PC ASA alloy material and preparation method thereof, PC ASA alloy material includes the recipe ingredient of following parts by weight: PC resin 30 70 parts, ASA resin 10 30 parts, PMMA resin 5 25 parts, the block copolymer of the methyl methacrylate mutual-phenenyl two acid bromide two alcohol ester containing GMA functional group 5 15 parts, the present invention proposes a kind of high durable PC ASA alloy material, has weather resistance light feature excellent, high, overcomes and adds the problem that PMMA can produce pearly-lustre in PC and its alloy；On the other hand, the preparation method that the present invention proposes, can effectively control the phase of PMMA, operation is simple.
Description
Technical field
The present invention relates to polymer blended, Polymer Processing technical field, particularly relate to a kind of high durable PC-ASA
Alloy material and preparation method thereof.
Background technology
PC-ASA alloy material, due to the shock resistance of its excellence, thermostability, weather resistance, is widely used and automobile and electricity
The fields such as sub-product.Along with the development of automobile, exempt from primary coat environment-friendly materials and will become a kind of trend.
When PC-ASA uses as exterior trim, the highest to weather-proof requirement.Common PC-ASA cannot meet exterior trim use to be wanted
Ask.PMMA, as the resin of weather-proof excellence, improves weather resistance usually through adding PMMA.But owing to PMMA and PC refractive power refers to
Number difference is too big, causes adding PMMA in PC and its alloy and produces pearly-lustre, it is impossible to meets outward appearance demand.
Summary of the invention
It is an object of the invention to propose a kind of high durable PC-ASA alloy material, there is weather resistance excellence, Gao Guangte
Point, overcomes and adds the problem that PMMA can produce pearly-lustre in PC and its alloy.
It is an object of the invention to propose the preparation method of a kind of high durable PC-ASA alloy material, method can effectively be controlled
The phase of PMMA processed, operation is simple.
For reaching this purpose, the present invention by the following technical solutions:
A kind of high durable PC-ASA alloy material, including the recipe ingredient of following parts by weight:
PC resin 30-70 part,
ASA resin 10-30 part,
PMMA resin 5-25 part,
Block copolymer 5-15 part of methyl methacrylate mutual-phenenyl two acid bromide two alcohol ester containing GMA functional group.
By the weather resistance adding raising PC-ASA alloy material of PMMA resin in formula, further, also
The block copolymer adding the methyl methacrylate mutual-phenenyl two acid bromide two alcohol ester containing GMA functional group (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.
The excellent compatibility of PBT and PC resin, after particularly there is ester exchange in processing, it is possible to obtain fully compatible body
System.In PC resin and alloy thereof, there was added the block copolymer of the PBT-PMMA of GMA, further improve PMMA Yu PC resin
The compatibility, due to PBT and PC occur ester exchange obtain the extraordinary compatibility so that the phase of PBT-PMMA is that outer layer is
PBT, internal layer are the spherical of PMMA.The phase of PMMA is controlled so that PMMA phase dimension is less than visible light wave by the method
Long half, solves the pearly-lustre problem that PMMA causes.
Further description, also includes the recipe ingredient of following parts by weight: weather resisting agent 0.1-1 part, antioxidant 0.1-1
Part, lubricant 0.1-1 part, colored particles 2-5 part.
Further description, described colored particles is black masterbatch, described black masterbatch be content of carbon black be 30-70%
Master batch, master batch carrier is PE wax.
Further description, the described methyl methacrylate mutual-phenenyl two acid bromide two alcohol ester containing GMA functional group
Block copolymer, the content of its mutual-phenenyl two acid bromide two alcohol ester is 30～70%, and GMA functional group content is 1～5%.
Further description, described weather resisting agent includes one or both in benzotriazole and triazine.
Further description, described antioxidant is the double [β-(3-tertiary butyl-4-hydroxy-5-methylbenzene of triethylene-glycol
Base) propionic ester] (i.e. antioxidant 245), four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propanoic acid] pentaerythritol ester (i.e. antioxidant
1010), three (2,4-di-tert-butyl-phenyl) phosphite ester (i.e. irgasfos 168), double stearyl alcohol tetramethylolmethane diphosphorous acid
The mixing of one or more in ester (i.e. antioxidant 618).
Further description, described lubricant is silane polymer, hard paraffin, liquid paraffin, soap, tristearin
Acid 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 in acid amide.
Further description, the weight average molecular weight of described PMMA resin is 50,000-250,000.
Further description, the weight average molecular weight of described PC resin is 10000～30000g/mol.
Further description, described ASA resin is the graft copolymer of Acrylate-styrene bipolymer-acrylonitrile composition, rubber
Glue content is at 30-80%.
A kind of method preparing above-mentioned high durable PC-ASA alloy material that the present invention proposes, comprises the following steps:
A () weighs PC resin, ASA resin, PMMA resin, PMMA processing aid, adjuvant and colored particles, and by above-mentioned
Raw material carries out mix and blend；
B the mixture of step a gained is carried out extruding pelletization by (), obtain PC-ASA alloy material.
Further description, the mixture of step a gained is blended pelletize by double screw extruder, wherein extrusion temperature
For 240-260 DEG C.
Compared with prior art, the device have the advantages that into: by PMMA improve weather resistance, added by PMMA
Work auxiliary agent improves the compatibility of PMMA Yu PC so that the phase of PMMA-PBT be outer layer be PBT internal layer be the spherical of PMMA.Logical
Cross the method and control the phase of PMMA so that PMMA phase dimension, less than the half of visible wavelength, solves PMMA and causes
Pearly-lustre problem, it is thus achieved that high light high durable PC-ASA alloy material.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.
The PC resin L-1250WS of Di Ren Asahi Chemical Industry selected in following example and comparative example, ASA resin Korea S
The XC-400 of kumho company, PMMA resin uses strange beautiful PMMA205；Antioxidant be Ciba company Irganox 1070,
Irganox 168, Irganox628 and Irganox 245；Lubricant is commercially available tetramethylolmethane stearic acid, weather resisting agent be
The Kemisorb 102 of Basf company, black masterbatch is the I-940 of Cabot.
Comparative example 1
A kind of PC-ASA alloy material and preparation method thereof, the method comprises 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, lubricant 0.3 part, weather resisting agent 0.5 part.
(2) (a) will mix in all raw materials addition mixing and blending machine；B step a gained mixture is passed through double spiral shells by ()
Bar extruder is blended pelletize, and extrusion temperature is 260 DEG C, and through melt extruding, pelletize i.e. obtains product.
Comparative example 2
A kind of PC-ASA alloy material and preparation method thereof, the method comprises the following steps:
(1) weighing each component by weight: PC resin: 65 parts, ASA resin: 10 parts, PMMA resin: 25 parts, white carbon black is female
Grain: 5 parts；Antioxidant 1010: 0.1 part, irgasfos 168: 0.1 part, lubricant 0.3 part, weather resisting agent 0.5 part.
(2) (a) will mix in all raw materials addition mixing and blending machine；B step a gained mixture is passed through double spiral shells by ()
Bar extruder is blended pelletize, and extrusion temperature is 260 DEG C, and through melt extruding, pelletize i.e. obtains product.
Embodiment 1
A kind of high durable PC-ASA alloy material and preparation method thereof, the method comprises the following steps:
(1) each component is weighed by weight: PC resin: 50 parts, ASA resin: 20 parts, PMMA resin: 20 parts, containing GMA
The block copolymer (wherein PBT content is 70%, and GMA content is 5%) of PMMA-PBT: 10 parts；Black masterbatch: 4 parts；Antioxygen
Agent 1010:0.1 part, irgasfos 168: 0.1 part, lubricant 0.3 part, weather resisting agent 1 part.
(2) (a) will mix in all raw materials addition mixing and blending machine；B step a gained mixture is passed through double spiral shells by ()
Bar extruder is blended pelletize, and extrusion temperature is 260 DEG C, and through melt extruding, pelletize i.e. obtains product.
Embodiment 2
A kind of high durable PC-ASA alloy material and preparation method thereof, the method comprises the following steps:
(1) each component is weighed by weight: PC resin: 30 parts, ASA resin: 30 parts, PMMA resin: 25 parts, containing GMA
The block copolymer (wherein PBT content is 30%, and GMA content is 1%) of PMMA-PBT: 15 parts, black masterbatch: 4 parts, antioxygen
Agent 1010:0.1 part, irgasfos 168: 0.1 part, lubricant 0.3 part, weather resisting agent 1 part.
(2) (a) will mix in all raw materials addition mixing and blending machine；B step a gained mixture is passed through double spiral shells by ()
Bar extruder is blended pelletize, and extrusion temperature is 260 DEG C, and through melt extruding, pelletize i.e. obtains product.
Embodiment 3
A kind of high durable PC-ASA alloy material and preparation method thereof, the method comprises the following steps:
(1) each component is weighed by weight: PC resin: 60 parts, ASA resin: 20 parts, PMMA resin: 5 parts, containing GMA's
The block copolymer (wherein PBT content is 30%, and GMA content is 1%) of PMMA-PBT: 5 parts, black masterbatch: 4 parts, antioxidant
1010:0.1 part, irgasfos 168: 0.1 part, lubricant 0.3 part, weather resisting agent 1 part.
(2) (a) will mix in all raw materials addition mixing and blending machine；B step a gained mixture is passed through double spiral shells by ()
Bar extruder is blended pelletize, and extrusion temperature is 260 DEG C, and through melt extruding, pelletize i.e. obtains product.
Embodiment 4
A kind of high durable PC-ASA alloy material and preparation method thereof, the method comprises the following steps:
(1) each component is weighed by weight: PC resin: 60 parts, ASA resin: 15 parts, PMMA resin: 20 parts, containing GMA
The block copolymer (wherein PBT content is 70%, and GMA content is 5%) of PMMA-PBT: 5 parts, black masterbatch: 5 parts, antioxygen
Agent 1010:0.1 part, irgasfos 168: 0.1 part, lubricant 0.3 part, weather resisting agent 1 part.
(2) (a) will mix in all raw materials addition mixing and blending machine；B step a gained mixture is passed through double spiral shells by ()
Bar extruder is blended pelletize, and extrusion temperature is 260 DEG C, and through melt extruding, pelletize i.e. obtains product.
Implementation result comparison
Before preparing batten, fully it is dried the product pellet obtained, tests after placing 24h after preparing batten；
1) injection machine is used to carry out injecting all kinds of test bars and specular plate；
2) Izod impact strength is carried out according to ISO-180 standard, and temperature is 23 DEG C；
3) xenon lamp aging experiment is carried out according to SAE2527 standard, and energy is 1025KJ, measuring colour difference and color fastness after illumination.
Table 1 embodiment 1～4 and comparative example 1～2 product test result
As shown in Table 1, embodiment 1 impacts excellence, and high bright finish is without pearly-lustre, and weather resistance is excellent.Improved weather-proof by PMMA
Performance, improves the compatibility of PMMA Yu PC by PMMA processing aid so that the phase of PMMA-PBT be outer layer be PBT internal layer
Spherical for PMMA.The phase of PMMA is controlled so that PMMA phase dimension is less than the half of visible wavelength by the method,
Solve the pearly-lustre problem that PMMA causes, it is thus achieved that high light high durable PC-ASA alloy material.
Embodiment 5
A kind of high durable PC-ASA alloy material and preparation method thereof, the method comprises the following steps:
(1) each component is weighed by weight: PC resin: 70 parts, ASA resin: 30 parts, PMMA resin: 25 parts, containing GMA
The block copolymer (wherein PBT content is 70%, and GMA content is 5%) of PMMA-PBT: 15 parts；Black masterbatch: 5 parts；Antioxygen
Agent 618:0.1 part, antioxidant 245:0.1 part, lubricant 0.3 part, weather resisting agent 1 part.
(2) (a) will mix in all raw materials addition mixing and blending machine；B step a gained mixture is passed through double spiral shells by ()
Bar extruder is blended pelletize, and extrusion temperature is 240 DEG C, and through melt extruding, pelletize i.e. obtains product.
Embodiment 6
A kind of high durable PC-ASA alloy material and preparation method thereof, the method comprises the following steps:
(1) each component is weighed by weight: PC resin: 50 parts, ASA resin: 20 parts, PMMA resin: 20 parts, containing GMA
The block copolymer (wherein PBT content is 70%, and GMA content is 5%) of PMMA-PBT: 10 parts；Black masterbatch: 4 parts；Antioxygen
Agent 1010:0.3 part, lubricant 0.3 part, weather resisting agent 1 part.
(2) (a) will mix in all raw materials addition mixing and blending machine；B step a gained mixture is passed through double spiral shells by ()
Bar extruder is blended pelletize, and extrusion temperature is 260 DEG C, and through melt extruding, pelletize i.e. obtains product.
The know-why of the present invention is described above in association with specific embodiment.These describe and are intended merely to explain the present invention's
Principle, and limiting the scope of the invention can not be construed to by any way.Based on explanation herein, the technology of this area
Personnel need not pay performing creative labour can associate other detailed description of the invention of the present invention, and these modes fall within
Within protection scope of the present invention.
Claims (10)
1. a high durable PC-ASA alloy material, it is characterised in that: include the recipe ingredient of following parts by weight:
PC resin 30-70 part,
ASA resin 10-30 part,
PMMA resin 5-25 part,
Block copolymer 5-15 part of methyl methacrylate mutual-phenenyl two acid bromide two alcohol ester containing GMA functional group.
A kind of high durable PC-ASA alloy material the most according to claim 1, it is characterised in that: also include following weight portion
The recipe ingredient of number: weather resisting agent 0.1-1 part, antioxidant 0.1-1 part, lubricant 0.1-1 part, colored particles 2-5 part.
A kind of high durable PC-ASA alloy material the most according to claim 2, it is characterised in that: described colored particles is charcoal
Black masterbatch, described black masterbatch be content of carbon black be the master batch of 30-70%, master batch carrier is PE wax.
A kind of high durable PC-ASA alloy material the most according to claim 1, it is characterised in that: described containing GMA official's energy
The block copolymer of the methyl methacrylate mutual-phenenyl two acid bromide two alcohol ester of group, the content of its mutual-phenenyl two acid bromide two alcohol ester
30～70%, GMA functional group content is 1～5%.
A kind of high durable PC-ASA alloy material the most according to claim 2, it is characterised in that: described weather resisting agent includes
One or both in benzotriazole and triazine.
A kind of high durable PC-ASA alloy material the most according to claim 2, it is characterised in that: described antioxidant is two contractings
Triethylene glycol double [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], four [β-(3,5-di-t-butyl 4-hydroxy benzeness
Base) propanoic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) phosphite ester, double stearyl alcohol tetramethylolmethane diphosphorous acid
The mixing of one or more in ester.
A kind of high durable PC-ASA alloy material the most according to claim 2, it is characterised in that: described lubricant is silane
Polymer, hard paraffin, liquid paraffin, soap, calcium stearate fatty acid amide, calcium stearate, zinc stearate, stearic acid
The mixing of one or more in amide, methylene bis stearic amide and N, N-ethylene bis stearic acid amide.
A kind of high durable PC-ASA alloy material the most according to claim 1, it is characterised in that: described PMMA resin
Weight average molecular weight is 50,000-250,000.
A kind of high durable PC-ASA alloy material the most according to claim 1, it is characterised in that: described ASA resin is third
The graft copolymer of olefin(e) acid ester-styrene-acrylonitrile composition, rubber content is at 30-80%.
10. prepare the method for high durable PC-ASA alloy material described in claim 1 for one kind, it is characterised in that: include following step
Rapid:
A () weighs PC resin, ASA resin, PMMA resin, PMMA processing aid, adjuvant and colored particles, and by above-mentioned raw materials
Carry out mix and blend；
B the mixture of step a gained is carried out extruding pelletization by (), obtain PC-ASA alloy material.
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| CN106674967A (en) * | 2016-12-28 | 2017-05-17 | 上海锦湖日丽塑料有限公司 | High-gloss spray-free environment-friendly flame-retardant polycarbonate (PC) material and preparation method thereof |
| CN106854353A (en) * | 2016-12-28 | 2017-06-16 | 上海锦湖日丽塑料有限公司 | A kind of polycarbonate compositions of friction resistant noise and preparation method thereof |
| CN113956598A (en) * | 2021-09-27 | 2022-01-21 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106674967A (en) * | 2016-12-28 | 2017-05-17 | 上海锦湖日丽塑料有限公司 | High-gloss spray-free environment-friendly flame-retardant polycarbonate (PC) material and preparation method thereof |
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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 |
| CN113956598A (en) * | 2021-09-27 | 2022-01-21 | 武汉金发科技有限公司 | Glass fiber reinforced ASA/PBT alloy material and preparation method and application thereof |
| 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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| CN106065171B (en) | 2018-08-10 |
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