CN106046643B - High-compatibility PMMA/ASA alloy resin compositions and preparation method thereof - Google Patents
High-compatibility PMMA/ASA alloy resin compositions and preparation method thereof Download PDFInfo
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- CN106046643B CN106046643B CN201610414293.7A CN201610414293A CN106046643B CN 106046643 B CN106046643 B CN 106046643B CN 201610414293 A CN201610414293 A CN 201610414293A CN 106046643 B CN106046643 B CN 106046643B
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of high-compatibility PMMA/ASA alloy resin compositions and preparation method thereof, and the composition includes following components and content：Polymethyl methacrylate (PMMA) resin 65-80 parts by weight, acrylonitrile-styrene-butyl acrylate (ASA) resin 15-25 parts by weight, compatilizer 8-15 parts by weight, processing aid 0.5-1.5 parts by weight；Above-mentioned raw material are premixed 3-10 minutes in high-speed mixer, then premix obtains PMMA/ASA alloy resin compositions through double screw extruder extruding pelletization.The PMMA/ASA alloy resins of the present invention have outstanding compatibility, therefore physical mechanical property is excellent, there is good impact flexibility and weather resistance simultaneously, the spray painting post-processing process that can omit previous and direct staining injection molding product, the alloy resin composition are highly suitable to be applied for the automobile exterior trimming parts such as grid, pillar panel, backsight mirror shell.
Description
Technical field
The present invention relates to a kind of alloy resin compositions and preparation method thereof, more particularly, to a kind of high-compatibility PMMA/
ASA alloy resin compositions and preparation method thereof.
Background technology
There is excellent optical property, transparency may be up to 92% for PMMA resins, also referred to as acrylic or organic glass.
In addition to this, with splendid weatherability, mechanical strength, good heat-insulating sound-insulating insulating properties, gloss is high, strong coloring force and resistance to
It scratches.In automotive field, PMMA resins can be applicable to the components such as glass pane, the cover, apparatus glass, car light, label.ASA resin
It is the terpolymer of acrylonitrile, acrylate, styrene, without unsaturated double-bond in structure, therefore weatherability is far superior to
ABS resin.In addition, ASA resin has good shock resistance, coloring, chemical-resistant.ASA resin is on automobile
Using mainly in exterior trimming parts, such as grid, corner block, pillar panel.It is worth noting that, the high glaze of automobile exterior trimming parts, black
It is again bright to have become a kind of fashion, and this effect is difficult to be realized by the direct injection molding of plastics, it usually needs spraying process, and
Spraying not only increases cost and also generates serious pollution to environment.Based on this, exploitation design exempt from spraying etc. after-processing technologies and can
The material of direct Injection moulded part application is of great significance, and PMMA/ASA alloys are exactly such a material, resistance to ag(e)ing and
Scratch resistance.But since the compatibility of PMMA and ASA are bad, its comprehensive mechanical property is caused to be difficult to meet especially automobile industry
Standard requirement.
Patent CN201010578693.4 discloses a kind of high gloss spraying-free ABS resin and preparation method thereof, the hair
Bright is to be prepared for high glaze spraying-free ABS resin using the polymer of substituted phenylethylene, polymethyl methacrylate as brightener.
Patent CN201310652729.2 discloses a kind of high glaze, exempts to spray PTT/PMMA rearview mirrors PP Pipe Compound and its life
Production. art, the invention use maleic anhydride grafting ethylene propylene diene rubber to be adjusted by adjusting the ratio of PTT/PMMA as compatilizer
Whole processing temperature and mold temperature, to prepare compatibility, good high glaze exempts to spray PTT/PMMA resins.
Patent CN201110410738.1 discloses a kind of high glaze ABS/PMMA alloy materials and preparation method thereof and answers
With.The invention selects core-shell tougheners MBS to carry out toughening, while increasing the compatibility between substrate interface so that different
Base material preferably mutually contains, and significantly increases the impact strength of alloy material, and the phenolic antioxidant of selection makes preparation
ABS/PMMA alloy materials have environmental-protecting performance, reduce the environmental of product.
However, these above-mentioned technical solutions often exist, such as impact property deficiency, hardness, rigidity is low, thermal level is low, resistance to
The defects of time property cannot reach automobile exterior requirement, and PMMA/ASA resins have excellent weather resistance, reasonably select simultaneously
PMMA and ASA resin, and the proportioning by regulating and controlling PMMA and ASA resin, introduce best compatilizer, can prepare comprehensive mechanics
Performance, hardness, heat resistance, ageing-resistant performance it is excellent exempt spraying etc. after-processing technologies and directly Injection moulded part application
Resin alloy.
Invention content
For the defects in the prior art, the object of the present invention is to provide a kind of high-compatibility PMMA/ASA alloy resin groups
Close object and preparation method thereof.Provide that a kind of compatibility is excellent, technical process is simple, physical mechanical property is excellent, can exempt
The PMMA/ASA alloy resin compositions and preparation method thereof of the post-processings such as spray painting and direct Injection moulded part application.
The purpose of the present invention is what is be achieved through the following technical solutions：
The present invention provides a kind of high-compatibility PMMA/ASA alloy resin compositions, combined object includes following parts by weight
Several each components：
Preferably, the average weight-molecular mass of the PMMA resins is 150,000-350,000, vicat softening temperature
>=105 DEG C, molecular weight is too low, and alloy resin is partially crisp and heat-resisting insufficient and limits its application, excessively high, is difficult to be molded.
Preferably, the average weight-molecular mass of the ASA resin is 100,000-500,000g/mol, rubber content
In 40%-70%, too low rubber content is difficult to play the role of toughened polymethyl methacrylate (PMMA), excessively high to reduce the rigid and heat-resisting of alloy resin
Property.
Preferably, the compatilizer is at least one of MMA-SAN, SMA, AS-g-MAH.
Preferably, in the MMA-SAN, S (styrene), AN (acrylonitrile), MMA (methyl methacrylate) quality hundred
Divide than being 27:25:48 (optimal proportions for obtaining three kinds of monomer components of compatilizer used in good workability, biocompatible alloy),
The ratio of stringent control three can active balance processability and increase-volume PMMA and ASA resin.
Preferably, in the SMA, the mass percent of S (styrene) and MA (maleic anhydride) is 92:8.
Preferably, in the AS-g-MAH, the grafting amount of MAH is 2-3%.
Preferably, the processing aid includes antioxidant, lubricant and releasing agent.
Preferably, the antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant, and the lubricant is
Pentaerythritol stearate or ethylene bis stearic acid amide, the releasing agent are silicone releasing agent.
The present invention also provides a kind of preparation method of high-compatibility PMMA/ASA alloy resin compositions, this method includes
Following steps：
(1) it presses following components and content is stocked up：PMMA resin 65-80 parts by weight, ASA resin 15-25 parts by weight, compatilizer
8-15 parts by weight, processing aid 0.5-1.5 parts by weight；
(2) material got ready in step (1) is premixed in super mixer；
(3) by the premix obtained in step (2) by double screw extruder, in 200-240 DEG C of extrusion temperature and 200-
Melting extrusion is carried out under the conditions of 500 revs/min of screw speed, cooling granulation obtains the excellent PMMA/ASA alloys of compatibility
Resin combination.
The prior art is compared, and the present invention has following advantageous effect：
1, the present invention uses the technological means of blending and modifying, selects specific PMMA and ASA resin, and by PMMA resins with
ASA resin is blended, and introduces the compatibility that unique compatilizer both improves, to prepare with toughness, rigid, heat-resisting, hard
The PMMA/ASA alloy resin compositions spent and had excellent weather resistance；
2, preparation method technical process of the invention is simple, at low cost, and PMMA/ASA alloy resins obtained are particularly suitable for
Applied to fields such as automobile exteriors.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
A kind of high-compatibility PMMA/ASA alloy resin compositions that following embodiment provides, including following parts by weight
Each component：
The average weight-molecular mass of the PMMA resins is 150,000-350,000, vicat softening temperature >=105
℃。
The average weight-molecular mass of the ASA resin is 100,000-500,000, and rubber content is in 40%-70%.
The compatilizer is that MMA-SAN (S/AN/MMA=27/25/48), SMA (S/MA=92/8) AS-g-MAH (connect
At least one of the amount of branch MAH is 2-3%).
The processing aid includes antioxidant, lubricant and releasing agent.
The antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant, and the lubricant is pentaerythrite
Stearate or ethylene bis stearic acid amide, the releasing agent are silicone releasing agent.
The preparation method of high-compatibility PMMA/ASA alloy resin compositions described in following embodiment, including following step
Suddenly：
(1) it presses following components and content is stocked up：PMMA resin 65-80 parts by weight, ASA resin 15-25 parts by weight, compatilizer
8-15 parts by weight, processing aid 0.5-1.5 parts by weight；
(2) material got ready in step (1) is premixed in super mixer；
(3) by the premix obtained in step (2) by double screw extruder, in 200-240 DEG C of extrusion temperature and 200-
Melting extrusion is carried out under the conditions of 500 revs/min of screw speed, cooling granulation obtains the excellent PMMA/ASA alloys of compatibility
Resin combination.
Embodiment 1
High-compatibility PMMA/ASA alloy resin compositions described in the present embodiment, include each group of following parts by weight
Point：
Embodiment 2
High-compatibility PMMA/ASA alloy resin compositions described in the present embodiment, include each group of following parts by weight
Point：
Embodiment 3
High-compatibility PMMA/ASA alloy resin compositions described in the present embodiment, include each group of following parts by weight
Point：
Embodiment 4
High-compatibility PMMA/ASA alloy resin compositions described in the present embodiment, include each group of following parts by weight
Point：
Embodiment 5
High-compatibility PMMA/ASA alloy resin compositions described in the present embodiment, include each group of following parts by weight
Point：
Comparative example 1
High-compatibility PMMA/ASA alloy resin compositions described in the present embodiment, include each group of following parts by weight
Point：
70 parts of PMMA resins,
20 parts of ASA resin,
1.0 parts of processing aid.
Comparative example 2
High-compatibility PMMA/ASA alloy resin compositions described in this comparative example, include each group of following parts by weight
Point：
Comparative example 3
High-compatibility PMMA/ASA alloy resin compositions described in this comparative example, include each group of following parts by weight
Point：
Comparative example 4
High-compatibility PMMA/ASA alloy resin compositions described in this comparative example, with differing only in for embodiment 4：This
The mass percent of S, AN, MMA of the compatilizer MMA-SAN that comparative example uses is 40:35:25.
Performance evaluation mode and its implementation standard
Mechanical performance and hardness test：
The PMMA/ASA resin combination excellent to the compatibility obtained by embodiment 1-5 and comparative example 1-4 carries out machinery
Performance test, the results are shown in Table 1：
Charpy notch impact strengths：According to ISO 179-1:2010 (E) standard testings, impact energy 4J；
Vicat softening point：According to ISO 306:2013 (E) standard testings, test condition 5Kg, 50 DEG C/h；
Bending modulus：According to ISO 178:2010 (E) standard testings, test speed 2mm/min；
Melt index：According to ISO 1133-1:2011 (E) standard testings, test condition are 220 DEG C of * 10Kg；
Pencil hardness：According to ISO 15184-2012 standard testings, test condition is 23 DEG C, relative humidity 50%.
1 mechanical performance of table and hardness test
According to the test result in table 1, after introducing compatilizer, the comprehensive performance of alloy resin system is obviously improved, especially
It is impact property and hardness.In addition, comparing embodiment 4,5 and embodiment 1,3, using MMA-SAN as obtained by compatilizer
The comprehensive performance of PMMA/ASA alloy resins, be better than SMA and AS-g-MAH, i.e. MMA-SAN be PMMA/ASA alloy resins most
Good compatilizer.By adjusting the ratio and the suitable MMA-SAN compatilizers of combination of PMMA and ASA, different automobile marks can be prepared
The PMMA/ASA alloy resins of alignment request.
In conclusion the present invention uses the technological means of blending and modifying, specific PMMA and ASA resin are selected, and will
PMMA resins are blended with ASA resin, and introducing unique compatilizer improves the compatibility of the two, to prepare with toughness, just
Property, heat-resisting, hardness and the PMMA/ASA alloy resin compositions having excellent weather resistance；The preparation method technical process letter of the present invention
Single, at low cost, PMMA/ASA alloy resins obtained are particularly suitable for fields such as automobile exteriors.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection domain being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection domain.
Claims (3)
1. a kind of PMMA/ASA alloy resin compositions, which is characterized in that the composition by following parts by weight each component
Composition：
The average weight-molecular mass of the PMMA resins is 150,000-350,000；
The average weight-molecular mass of the ASA resin is 100,000-500,000, and rubber quality content is in 40%-70%；
The compatilizer is at least one of MMA-SAN, SMA, AS-g-MAH；
In the MMA-SAN, the mass percent of S, AN, MMA are 27:25:48；
In the SMA, the mass percent of S and MA are 92:8；
In the AS-g-MAH, the grafting amount of MAH is 2-3%；
The processing aid includes antioxidant, lubricant and releasing agent.
2. PMMA/ASA alloy resin compositions according to claim 1, which is characterized in that the antioxidant is to be obstructed
Phenolic antioxidant or phosphite ester kind antioxidant, the lubricant are pentaerythritol stearate or the double stearic acid acyls of ethylene
Amine, the releasing agent are silicone releasing agent.
3. a kind of preparation method of PMMA/ASA alloy resin compositions as described in claim 1, which is characterized in that this method
Include the following steps：
(1) it presses following components and content is stocked up：PMMA resin 65-80 parts by weight, ASA resin 15-25 parts by weight, compatilizer 8-15
Parts by weight, processing aid 0.5-1.5 parts by weight；
(2) material got ready in step (1) is premixed in super mixer；
(3) by the premix obtained in step (2) by double screw extruder, in 200-240 DEG C of extrusion temperature and 200-500
Rev/min screw speed under the conditions of carry out melting extrusion, cooling granulation obtains the excellent PMMA/ASA alloy resins of compatibility
Composition.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118480A (en) * | 2017-05-05 | 2017-09-01 | 安徽科聚新材料有限公司 | PMMA/ASA composites and preparation method thereof |
| CN107841077B (en) * | 2017-11-09 | 2020-04-21 | 银禧工程塑料（东莞）有限公司 | Heat-resistant transparent PMMA/ASA alloy material and preparation method thereof |
| CN109337272A (en) * | 2018-09-13 | 2019-02-15 | 广东锦湖日丽高分子材料有限公司 | A kind of PMMA/ASA alloy resin composition and preparation method thereof |
| CN112745615B (en) * | 2019-10-29 | 2023-08-15 | 合肥杰事杰新材料股份有限公司 | PMMA/ASA material and preparation method thereof |
| CN111690222B (en) * | 2020-07-09 | 2022-05-10 | 东莞市奥能工程塑料有限公司 | High-heat-resistance high-brightness PMMA/ASA alloy material and preparation method and application thereof |
| CN112745620B (en) * | 2020-12-29 | 2022-07-01 | 江阴市羽项汽车饰件有限公司 | Environment-friendly paint-spraying-free highlight AES/PMMA alloy grid and preparation method thereof |
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