CN111234443A - Yellowing-resistant PMMA/ABS spraying-free resin and preparation method thereof - Google Patents
Yellowing-resistant PMMA/ABS spraying-free resin and preparation method thereof Download PDFInfo
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- CN111234443A CN111234443A CN202010067491.7A CN202010067491A CN111234443A CN 111234443 A CN111234443 A CN 111234443A CN 202010067491 A CN202010067491 A CN 202010067491A CN 111234443 A CN111234443 A CN 111234443A
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- abs
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- 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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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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
Abstract
The invention discloses a yellowing-resistant PMMA/ABS spraying-free resin and a preparation method thereof; the spraying-free resin comprises: 5-80 parts of PMMA, 5-80 parts of bulk ABS, 0.5-20 parts of EEA-MAH, 0.1-20 parts of pearlescent effect pigment, 0-2 parts of magnesium oxide, 0.4-2 parts of light stabilizer, 0.05-2 parts of antioxidant and 0.1-2 parts of lubricant. According to the invention, through the introduction of EEA-MAH, on the basis of ensuring the impact property of the material, the problems of darkroom yellowing and thermal yellowing of the material are effectively improved; the thermal yellowing performance of the material is improved by adding magnesium oxide, and the weather resistance of the material is improved by blending PMMA and ABS in a bulk method and introducing a light stabilizer; by side feeding of the pearlescent effect pigment, the material degradation yellowing possibly caused by the pearlescent effect pigment is reduced, the shearing process of the pearlescent pigment is reduced, and the appearance effect of the spraying-free material is ensured.
Description
Technical Field
The invention belongs to the field of high polymer materials and engineering, and particularly relates to yellowing-resistant PMMA/ABS spraying-free resin and a preparation method thereof.
Background
Along with low carbon and environmental protection, the green sustainable development is more and more emphasized by people, and various new technologies for low carbon and environmental protection are more and more popular with consumers. The spraying-free aesthetic plastic can realize beautiful appearance special color effect through one-step forming, avoids post-processing procedures such as spraying, electroplating and the like, greatly improves the production efficiency, reduces the production cost and energy consumption, reduces the environmental pollution, obtains more and more enterprise attention, and is widely applied to the fields of household appliances, automobiles, OA and the like.
PMMA/ABS has the comprehensive properties of scratch resistance, light resistance, high gloss, impact improvement and easy processing and forming, has higher permeability, is used for spraying-free aesthetic plastic substrates, can obtain more beautiful appearance effect, and is popular with consumers.
However, in order to achieve transparent and beautiful appearance effects, the existing spray-free aesthetic plastics, especially the PMMA/ABS material added with the pearlescent effect pigment, cannot be added with too much hiding toner, which causes yellowing phenomena such as darkroom yellowing, thermal yellowing, photoaging yellowing and the like during storage, injection molding and use of the material to be more remarkable, and the introduction of the pearlescent effect pigment may further aggravate the yellowing behavior of the material, bring great instability to the management and control of the color appearance standard of the material, cause project failure, and limit the popularization and application of the aesthetic plastics. Therefore, the development of the spraying-free aesthetic plastic with beautiful appearance and yellowing resistance has important commercial value and scientific value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a yellowing-resistant PMMA/ABS spraying-free resin and a preparation method thereof; the problems of darkroom yellowing, thermal yellowing and photoaging yellowing of the spraying-free material while realizing beautiful appearance are comprehensively improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention relates to a yellowing-resistant PMMA/ABS spraying-free resin composition which is prepared from the following components in parts by weight: 5-80 parts of PMMA, 5-80 parts of bulk ABS, 0.5-20 parts of maleic anhydride grafted ethylene acrylate (EEA-MAH), 0.1-20 parts of pearlescent pigment, 0-2 parts of magnesium oxide, 0.4-2 parts of light stabilizer, 0.05-2 parts of antioxidant and 0.1-2 parts of lubricant.
As a class of embodiments of the present invention, the resin composition is made from the following components in parts by weight: 20-40 parts of PMMA, 40-70 parts of bulk ABS, 10-15 parts of maleic anhydride grafted ethylene acrylate ester (EEA-MAH), 10-15 parts of pearlescent effect pigment, 0.2-1 part of magnesium oxide, 0.6-1 part of light stabilizer, 0.05-0.3 part of antioxidant and 0.1-2 parts of lubricant.
Preferably, the PMMA has a weight average molecular weight of 25000-200000 g/mol.
Preferably, the weight-average molecular weight of the bulk ABS resin is 80000-200000g/mol, the rubber content of the bulk ABS resin is 10-25%, and the number-average particle size of the rubber is 0.2-3.0 μm.
Preferably, the maleic anhydride grafted ethylene ethyl acrylate has a maleic anhydride content of 0.1% to 3%; the content of ethyl acrylate is 10-35%, and the melt index under the condition of 190 deg.C and 2.16kg is 2-20g/10 min. Furthermore, EEA, if used, is poorly compatible in the formulation of the present invention, making impact performance unacceptable.
Preferably, the particle size of the pearlescent effect pigment is 1-500 μm; the pearlescent effect pigment is one or more selected from bismuth oxychloride crystalline metal pigment, mica coated metal pigment, silicon dioxide coated metal pigment, aluminum borate salt coated metal pigment, artificial mica coated metal pigment, aluminum oxide coated metal pigment and bismuth oxide coated metal pigment.
Preferably, the magnesium oxide has a particle size of 0.5-5 μm and a purity of more than 99%.
The light stabilizer is one or a mixture of more of benzophenone ultraviolet absorbent, benzotriazole ultraviolet absorbent and hindered amine free radical scavenger.
The antioxidant is selected from one or more of aromatic amine antioxidant, hindered phenol antioxidant, phosphite antioxidant, thioester antioxidant, aromatic phosphate and pentaerythritol ester.
The lubricant is selected from one or more of silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, paraffin, polyethylene wax, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer and aromatic phosphate.
The invention also relates to a preparation method of the yellowing-resistant PMMA/ABS spray-free resin composition, which comprises the following steps:
s1, placing the PMMA, the bulk ABS, the maleic anhydride grafted ethylene acrylate ester, the magnesium oxide, the light stabilizer, the antioxidant and the lubricant in a high-speed mixer and stirring for 10-20 min;
s2, feeding the mixture obtained in the step S1 from the main feed of a double-screw extruder, and simultaneously adding the pearlescent effect pigment into the melt of the double-screw extruder in a side feeding manner to perform extrusion to obtain the resin composition.
The temperature of the double-screw extruder is 190-240 ℃, the length-diameter ratio of the screw is 25-45, and the rotating speed of the screw is 400-600 r/min.
Compared with the prior art, the invention has the following beneficial effects:
1. through the introduction of EEA-MAH, on the basis of ensuring the impact property of the material, the problems of darkroom yellowing and thermal yellowing of the material are effectively improved; the heat-resistant yellowing performance of the material is improved by adding magnesium oxide, and the weather resistance of the material is improved by blending PMMA and ABS in a bulk method and introducing a light stabilizer;
2. by side feeding of the pearlescent effect pigment, the material degradation yellowing possibly caused by the pearlescent effect pigment is reduced, the shearing process of the pearlescent pigment is reduced, and the appearance effect of the spraying-free material can be ensured;
3. the invention can comprehensively improve the problems of dark chamber yellowing, thermal yellowing and photoaging yellowing of the material caused by the fact that the spraying-free material is beautiful in appearance and too much covering color powder cannot be added, and can be widely applied to household appliance appearance pieces such as air conditioners, refrigerators, washing machines, massage chairs and the like.
Detailed Description
The present invention will be described in detail with reference to 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 it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Examples 1 to 5
The components and the contents thereof used in examples 1 to 5 are shown in table 1, and the materials were prepared according to the components and the contents of the examples in table 1.
Then, the mixture of the PMMA/ABS spray-free resin composition raw materials which do not contain the pearlescent effect pigment is pre-mixed in a mixer according to the proportion in the table 1, then the premix is blended by a double screw, and the pearlescent effect pigment is added into the melt in a side feeding mode. Wherein the temperature of the extruder is 220 ℃, the length-diameter ratio of the screw is 35, the rotating speed of the screw is 500 r/min, and cooling granulation is carried out to obtain the yellowing-resistant PMMA/ABS spray-free resin composition.
Comparative examples 1 to 2
The components and the contents thereof used in comparative examples 1-2 are shown in table 1, and the materials were prepared according to the components and the contents of each proportion in table 1.
Then, the mixture of the PMMA/ABS spray-free resin composition raw materials which do not contain the pearlescent effect pigment is pre-mixed in a mixer according to the proportion in the table 1, then the premix is blended by a double screw, and the pearlescent effect pigment is added into the melt in a side feeding mode. Wherein the temperature of the extruder is 220 ℃, the length-diameter ratio of the screw is 35, the rotating speed of the screw is 500 r/min, and the PMMA/ABS spray-free resin composition is obtained after cooling granulation.
The components and characteristics referred to in the above examples and comparative examples are as follows:
PMMA 1: weight average molecular weight 60000.
PMMA 2: weight average molecular weight 80000.
ABS 1: the ABS prepared by the bulk method has the butadiene rubber content of 15 percent, the number average particle diameter of 0.3 mu m and the weight average molecular weight of 80000.
ABS 2: the ABS prepared by the bulk method has the butadiene rubber content of 20 percent, the number average particle size of 1.5 mu m and the weight average molecular weight of 100000.
ABS 3: emulsion ABS, butadiene rubber content 50%, number average particle diameter 0.3 μm, weight average molecular weight 120000.
SAN 1: the AN content was 24%, and the weight-average molecular mass was 120000.
EEA-MAH 1: the MAH content was 1.5%, the EA content was 30%, and the melt index at 190 ℃ under 2.16kg was 7g/10 min.
EEA-MAH 2: the MAH content was 2.5%, the EA content was 17%, and the melt index at 190 ℃ under 2.16kg was 3g/10 min.
Pearlescent effect pigment 1: the aluminum borate salt coated metal pigment has a particle size of 100-500 μm.
Pearlescent effect pigment 1: the silica-coated metal pigment has a particle size of 20 to 70 μm.
Magnesium oxide: the grain diameter is 1 μm, and the purity is more than 99.9%.
Light stabilizer: 770DF from Ciba.
Antioxidant: irganox 1076 and Irganox 168 from Ciba, at a weight ratio of 1: 1.
Lubricant: commercially available pentaerythritol stearic acid.
TABLE 1 ingredient and content table
The performance test method comprises the following steps:
notched Izod impact strength IS: tested according to ASTM D256-10, units J/m.
Testing a dark room yellowing value: molding a color plate with a thickness of 8cm × 12cm × 3mm at 240 deg.C, cooling to room temperature, testing b value with D65 light source color difference meter, sealing in a black plastic bag, taking out after 30 days, testing b value with D65 light source color difference meter, and calculating the difference Db of b values.
Testing the thermal yellowing value: respectively injecting and molding color plates with the thickness of 8cm multiplied by 12cm multiplied by 3mm at the temperature of 240 ℃, then injecting and molding the color plates after 10min of hot dwell, respectively testing the b values of the non-hot dwell color plates and the hot dwell color plates by using a D65 light source color difference meter after completely cooling to the room temperature, and calculating the difference Db of the b values.
And (3) testing the light aging yellowing resistance value: plaques of 8 cm. times.12 cm. times.3 mm were injection molded at 240 ℃ and the change in b value of the plaques Db was tested according to ASTM D4329 method A.
The results are shown in Table 2.
Table 2 results of performance testing
Note: the more it is, the more excellent the appearance is.
Experimental results show that the yellowing-resistant PMMA/ABS spray-free resin composition prepared by the invention can greatly improve darkroom yellowing, thermal yellowing and photoaging yellowing of materials under the condition of ensuring the impact strength and appearance effect of the materials.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. The yellowing-resistant PMMA/ABS spraying-free resin composition is characterized by comprising the following components in parts by weight: 5-80 parts of PMMA, 5-80 parts of bulk ABS, 0.5-20 parts of maleic anhydride grafted ethylene acrylate ester, 0.1-20 parts of pearlescent effect pigment, 0-2 parts of magnesium oxide, 0.4-2 parts of light stabilizer, 0.05-2 parts of antioxidant and 0.1-2 parts of lubricant.
2. The yellowing-resistant PMMA/ABS spray-free resin composition of claim 1, wherein the weight average molecular weight of PMMA is 25000-200000 g/mol; the weight average molecular weight of the bulk ABS is 80000-200000g/mol, and in the bulk ABS, the rubber content is 10-25%, and the number average particle size of the rubber is 0.2-3.0 μm.
3. The yellowing-resistant PMMA/ABS spray-free resin composition of claim 1, wherein the maleic anhydride grafted ethylene ethyl acrylate has a maleic anhydride content of 0.1% -3%; the content of ethyl acrylate is 10-35%, and the melt index under the condition of 190 deg.C and 2.16kg is 2-20g/10 min.
4. The yellowing-resistant PMMA/ABS spray-free resin composition of claim 1, wherein the particle size of the pearlescent effect pigment is 1 μm to 500 μm; the pearlescent effect pigment is one or more selected from bismuth oxychloride crystalline metal pigment, mica coated metal pigment, silicon dioxide coated metal pigment, aluminum borate salt coated metal pigment, artificial mica coated metal pigment, aluminum oxide coated metal pigment and bismuth oxide coated metal pigment.
5. The yellowing-resistant PMMA/ABS spray-free resin composition of claim 1, wherein the magnesium oxide particle size is 0.5-5 μm and the purity is more than 99%.
6. The yellowing-resistant PMMA/ABS spray-free resin composition of claim 1, wherein the light stabilizer is one or a mixture of benzophenone ultraviolet absorber, benzotriazole ultraviolet absorber and hindered amine radical scavenger.
7. The yellowing-resistant PMMA/ABS spray-free resin composition of claim 1, wherein the antioxidant is selected from one or more of aromatic amine antioxidant, hindered phenol antioxidant, phosphite antioxidant, thioester antioxidant, aromatic phosphate ester, pentaerythritol ester.
8. The yellowing-resistant PMMA/ABS spray-free resin composition according to claim 1, wherein the lubricant is selected from one or more of silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, paraffin wax, polyethylene wax, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer and aromatic phosphate.
9. A method for preparing a PMMA/ABS spray-free resin composition with yellowing resistance according to claim 1, comprising the steps of:
s1, placing the PMMA, the bulk ABS, the maleic anhydride grafted ethylene acrylate ester, the magnesium oxide, the light stabilizer, the antioxidant and the lubricant in a high-speed mixer and stirring for 10-20 min;
s2, feeding the mixture obtained in the step S1 from the main feed of a double-screw extruder, and simultaneously adding the pearlescent effect pigment into the melt of the double-screw extruder in a side feeding manner to perform extrusion to obtain the resin composition.
10. The method for preparing the yellowing-resistant PMMA/ABS spray-free resin composition as claimed in claim 9, wherein the temperature of the twin-screw extruder is 190-240 ℃, the length-diameter ratio of the screw is 25-45, and the rotation speed of the screw is 400-600 rpm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN111234443B CN111234443B (en) | 2022-09-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111849115A (en) * | 2020-07-15 | 2020-10-30 | 海信（山东）空调有限公司 | Novel high polymer material and display mask of cabinet air conditioner prepared from same |
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| CN103756238A (en) * | 2013-12-27 | 2014-04-30 | 吴江市东泰电力特种开关有限公司 | Enhanced ABS (Acrylonitrile Butadiene Styrene)/PMMA (Polymethyl Methacrylate) alloy material |
| WO2016105162A1 (en) * | 2014-12-24 | 2016-06-30 | 삼성에스디아이 주식회사 | Polyamide resin composition and moulded article produced from same |
| CN106589768A (en) * | 2016-12-06 | 2017-04-26 | 上海锦湖日丽塑料有限公司 | PC/ABS free-spraying resin composition improving silver wire problem in injection molding and preparation method of PC/ABS free-spraying resin composition |
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2020
- 2020-01-20 CN CN202010067491.7A patent/CN111234443B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756238A (en) * | 2013-12-27 | 2014-04-30 | 吴江市东泰电力特种开关有限公司 | Enhanced ABS (Acrylonitrile Butadiene Styrene)/PMMA (Polymethyl Methacrylate) alloy material |
| WO2016105162A1 (en) * | 2014-12-24 | 2016-06-30 | 삼성에스디아이 주식회사 | Polyamide resin composition and moulded article produced from same |
| CN106589768A (en) * | 2016-12-06 | 2017-04-26 | 上海锦湖日丽塑料有限公司 | PC/ABS free-spraying resin composition improving silver wire problem in injection molding and preparation method of PC/ABS free-spraying resin composition |
Non-Patent Citations (1)
| Title |
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| 刘瑞雪等: "《高分子材料》", 30 September 2018, 河南大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111849115A (en) * | 2020-07-15 | 2020-10-30 | 海信（山东）空调有限公司 | Novel high polymer material and display mask of cabinet air conditioner prepared from same |
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