CN101906234A - Polymethylmethacrylate composition and preparation method thereof - Google Patents
Polymethylmethacrylate composition and preparation method thereof Download PDFInfo
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- CN101906234A CN101906234A CN201010252197XA CN201010252197A CN101906234A CN 101906234 A CN101906234 A CN 101906234A CN 201010252197X A CN201010252197X A CN 201010252197XA CN 201010252197 A CN201010252197 A CN 201010252197A CN 101906234 A CN101906234 A CN 101906234A
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- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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Abstract
The invention provides a polymethylmethacrylate composition and a preparation method thereof. The polymethylmethacrylate composition comprises the following components in percentage by weight: 20-70% of polymethylmethacrylate resin, 5-25% of flexibilizer, 0.2-2% of compatilizer, 0.05-5% of flame retardant, 0.1-1% of lubricant, 0.1-1% of UV absorbent and 0.15-2% of antioxygen. The preparation method of the polymethylmethacrylate composition comprises the following steps: weighing the components of the polymethylmethacrylate composition according to the weight proportion; mixing the polymethylmethacrylate, the compatilizer and the flame retardant for 10-30 minutes, then adding the flexibilizer and mixing for 10-30 minutes, and finally adding the lubricant, the UV absorbent and the antioxygen and mixing for 10-30 minutes; and melting, mixing, extruding and granulating the well mixed raw materials in the eight regions of a twin-screw extruder. The polymethylmethacrylate composition of the invention has high processing yield, high light transmittance, high surface hardness, favorable toughness, chemical stability, weather resistance and fire resistance.
Description
Technical field
The present invention relates to a kind of polymethylmethacrylacomposition composition and preparation method thereof, relate in particular to a kind of on toughness, the transparency, flame retardant resistance improved polymethylmethacrylacomposition composition and preparation method thereof.
Background technology
Polymethylmethacrylate (PMMA) plastic material uncoloured is transparent, chemical stability and weathering resistance is good, the high scrape resistant of surface hardness, but it has the shortcoming that notch sensitivity is big, impelling strength is low and the goods residualinternal stress is big, thereby in the course of processing and use the broken and defective that occurs turning white of easy fracture, be not suitable for making baroque goods.
Adopt the toughening modifying technology can improve its toughness for the PMMA plastic material, thereby enlarge its range of application.But the selection of flexibilizer additive and product producing process design improper meeting reduces its performance of item in addition simultaneously, as causes decline, the decline of weathering resistance and the following degradation of flame retardant resistance of the transparency.The toughner that employing has a nucleocapsid structure generally can farthest guarantee the multinomial performance of material, however, but often still can not satisfy all use properties requirements in the practical application.For example, at the PMMA plastic basis material, the methyl methacrylate (MMA) that the shell constituent material of this nucleocapsid structure toughner can be good with the base material consistency and specific refractory power is close, played the transparent effect that does not also influence surface hardness of neither influence, but then, thereby its nuclear constituent material is generally to play and absorbs the toughness reinforcing rubber phase of impact energy effect, and it belongs to inflammable material, thereby this class is added the toughness reinforcing flame retardant properties that generally can reduce material.For the PMMA plastics, simple PMMA has certain flame retardant resistance, can reach the substandard flame retardant resistance HB level of UL94, and has added the PMMA of nucleocapsid structure toughner, will make material not have flame retardant resistance under the flexible addition guaranteeing to improve; Simultaneously, the nuclear constituent material will be if divinyl rubber etc. also will reduce the weathering resistance of material.
On the other hand, directly add toughner in the product molding process and also have additive and disperse shortcoming uneven and that easily reunite, thereby the defective of white point also can appear in the toughening effect that had both influenced final finished in finished product.In addition, consistency and the favorable dispersity of toughner in PMMA can also reduce the consumption of toughner, avoids other mechanical properties, hot loss of energy too many.
Summary of the invention
Problem at the prior art existence, the purpose of this invention is to provide a kind of polymethylmethacrylacomposition composition and preparation method thereof, described polymethylmethacrylacomposition composition has high processed finished products rate, high transmission rate, high surface hardness, good toughness and chemical stability, weathering resistance and flame retardant resistance.
At purpose of the present invention, in a first aspect of the present invention, the invention provides a kind of polymethylmethacrylacomposition composition, by percentage to the quality, described polymethylmethacrylacomposition composition comprises: plexiglass, 20～70%; Toughner, 5～25%; Compatilizer, 0.2～2%; Fire retardant, 0.05～5%; Lubricant, 0.1～1%; The UV absorption agent, 0.1～1%; And oxidation inhibitor, 0.15～2%.
At purpose of the present invention, in a second aspect of the present invention, the invention provides a kind of preparation method of polymethylmethacrylacomposition composition, comprise step: take by weighing according to the component in the polymethylmethacrylacomposition composition described in a first aspect of the present invention according to mass ratio; Polymethylmethacrylate, compatilizer and fire retardant were mixed 10～30 minutes; Dropping into toughner subsequently mixed 10～30 minutes; Dropping into lubricant, UV absorption agent and oxidation inhibitor at last again mixed 10～30 minutes; Through twin screw extruder eight district's melting mixing, extruding pelletization, wherein, the residence time of mixing raw material in twin screw extruder was controlled at 1～4 minute with mixed raw materials; The temperature of twin screw extruder is controlled to be: 1 district is 170～180 ℃, 2 districts are 180～240 ℃, 3 districts are 180～240 ℃, 4 districts are 180～240 ℃, and 5 districts are 180～240 ℃, and 6 districts are 180～240 ℃, 7 districts are 180～240 ℃, 8 districts are 180～240 ℃, and head temperature is 180～240 ℃, and melt temperature is 180～240 ℃.
By the present invention, described polymethylmethacrylacomposition composition has high processed finished products rate, high transmission rate, high surface hardness, good toughness and chemical stability, weathering resistance and flame retardant resistance.
Embodiment
Describe in detail according to polymethylmethacrylacomposition composition of the present invention and preparation method thereof below.
At first, illustrate according to polymethylmethacrylacomposition composition of the present invention.
The present invention adopts interpolation toughner toughness reinforcing, and toughner adopts nucleocapsid structure, and the specific refractory power of its specific refractory power and PMMA base material is close, does not influence the transparency of material.The shell constituent material is the MMA material, to reach the effect compatible with base material PMMA; The nuclear constituent material is acrylic rubber and vinylbenzene etc., absorbs impact energy to reach, improves toughness and weathering resistance, and the effect that reduces defective such as breaking of moulding process, raising yield rate.
According to polymethylmethacrylacomposition composition of the present invention, by percentage to the quality, described polymethylmethacrylacomposition composition comprises:
Plexiglass, 20～70%;
Toughner, 5～25%;
Compatilizer, 0.2～2%;
Fire retardant, 0.05～5%;
Lubricant, 0.1～1%;
The UV absorption agent, 0.1～1%;
Oxidation inhibitor, 0.15～2%.
According in the polymethylmethacrylacomposition composition of the present invention, melting index the polymethylmethacrylate powder material 1.2～4.0g/10min between of described plexiglass under 230 ℃, 3.8KG test condition, recording according to ASTM D1238 standard.
In foundation polymethylmethacrylacomposition composition of the present invention, described toughner is the nucleocapsid structure material, wherein, the main component of nuclear is acrylic rubber and vinylbenzene, rubber phase content is 70%, shell is the MMA material, absorbs impact energy to reach, improves toughness and weathering resistance, and reduce defective such as breaking of moulding process, improve the effect of yield rate.The specific refractory power of described toughner is close with the specific refractory power of PMMA, thereby does not influence the transparency of polymethylmethacrylacomposition composition.The shell constituent material is the MMA material, to reach the effect compatible with base material PMMA.
In foundation polymethylmethacrylacomposition composition of the present invention, described compatilizer is liquid compatilizer, comprises γ-An Jibingjisanyiyangjiguiwan, γ-glycidyl ether oxygen propyl three silicomethanes, γ-methacryloxypropyl trimethoxy silane.
In foundation polymethylmethacrylacomposition composition of the present invention, described fire retardant is tricresyl phosphate (2-chloroethyl) ester, trichloropropyl phosphate is a kind of or their mixture.Described fire retardant does not influence the transparency of polymethylmethacrylacomposition composition, has remedied the infringement of toughner to the flame retardant resistance of polymethylmethacrylacomposition composition.
According in the polymethylmethacrylacomposition composition of the present invention, described lubricant is an ethylene bis stearamide, and described lubricant helps further reducing that the demoulding causes after the polymethylmethacrylacomposition composition moulding breaks and defective such as stress whitening.
In foundation polymethylmethacrylacomposition composition of the present invention, described UV absorption agent is a hydroxybenzotriazole class UV light absorber.When flame-retardant additive of the present invention for for tricresyl phosphate (2-chloroethyl) ester, trichloropropyl phosphate is a kind of or during their mixture, this based flame retardant belongs to halogen flame, weathering resistance to product is influential, but the UV absorption agent that herein adds has remedied the influence of fire retardant to weathering resistance.
In foundation polymethylmethacrylacomposition composition of the present invention, described oxidation inhibitor is one or more mixtures that comprise phosphorous acid ester, triphenyl phosphite, hindered phenol.
Secondly, provide the preparation method of polymethylmethacrylacomposition composition of the present invention.
The preparation method of polymethylmethacrylacomposition composition of the present invention may further comprise the steps:
Take by weighing according to the component in the aforementioned polymethylmethacrylacomposition composition according to mass ratio;
Polymethylmethacrylate was mixed 10～30 minutes with compatilizer, fire retardant;
Dropping into toughner subsequently mixed 10～30 minutes;
Dropping into lubricant, UV absorption agent and oxidation inhibitor at last again mixed 10～30 minutes;
With mixed raw materials through twin screw extruder eight district's melting mixing, extrude, granulation, wherein, the residence time of mixing raw material in twin screw extruder was controlled at 1～4 minute; The temperature of twin screw extruder is controlled to be: 1 district is 170～180 ℃, 2 districts are 180～240 ℃, 3 districts are 180～240 ℃, 4 districts are 180～240 ℃, and 5 districts are 180～240 ℃, and 6 districts are 180～240 ℃, 7 districts are 180～240 ℃, 8 districts are 180～240 ℃, and head temperature is 180～240 ℃, and melt temperature is 180～240 ℃.
At last, provide embodiments of the invention and Comparative Examples, so that the performance of polymethylmethacrylacomposition composition of the present invention to be described.
Table 1 has been listed the ratio of each component in embodiments of the invention and the comparative example.Wherein, toughner is selected the nucleocapsid structure material for use, and the nuclear main component is acrylic rubber and vinylbenzene, and rubber phase content 70%, shell are MMA, and specific refractory power and PMMA are close; Compatilizer is a γ-An Jibingjisanyiyangjiguiwan; Fire retardant is a trichloropropyl phosphate; The UV absorption agent is a hydroxybenzotriazole class UV light absorber; Lubricant is an ethylene bis stearamide; Oxidation inhibitor is the mixture of phosphorous acid ester and hindered phenol, and the ratio of the two is 1: 1.In table 1, each components contents is unit with the kilogram.
Table 2 has provided the The performance test results of embodiments of the invention and comparative example.Wherein, the manufacture craft of test sample is: with the particle of finishing granulation in the above-mentioned example in 70 ℃ hot air drier dry 4 hours, be injection molded into the performance test batten subsequently on the 80T injection moulding machine, the injection mould temperature remains on below 50 ℃.Testing standard is: the socle girder notched Izod impact strength is with ASTM D256 standard testing, the J/m of unit; Transmittance is with ASTM D1003 standard testing; Flame retardant resistance is with the UL94 standard testing; The goods white point is judged to observe 50mm * 50mm * 1.5mm thin slice.
Table 1
Table 2
Illustrate by embodiment and comparative example: the present invention adds in the polymethylmethacrylacomposition composition by selecting suitable toughner and compatilizer, improve the shock resistance of polymethylmethacrylacomposition composition, well kept the transparency of polymethylmethacrylacomposition composition simultaneously; By adding a certain amount of fire retardant, make polymethylmethacrylacomposition composition after toughness reinforcing can reach the fire-retardant rank of HB in the UL94 standard.In addition, adopt little addition and suitable technology, prevented the white-spot defects that goods are reunited and occurred because of toughner.
Claims (9)
1. polymethylmethacrylacomposition composition, by percentage to the quality, described polymethylmethacrylacomposition composition comprises:
Plexiglass, 20～70%;
Toughner, 5～25%;
Compatilizer, 0.2～2%;
Fire retardant, 0.05～5%;
Lubricant, 0.1～1%;
The UV absorption agent, 0.1～1%; And
Oxidation inhibitor, 0.15～2%.
2. polymethylmethacrylacomposition composition according to claim 1, it is characterized in that melting index the polymethylmethacrylate powder material 1.2～4.0g/10min between of described plexiglass under 230 ℃, 3.8KG test condition, recording according to ASTM D1238 standard.
3. polymethylmethacrylacomposition composition according to claim 1 is characterized in that, described toughner is the nucleocapsid structure material, specific refractory power and PMMA are close, and wherein, the nuclear main component is acrylic rubber and vinylbenzene, rubber phase content is 70%, and shell is the MMA material.
4. polymethylmethacrylacomposition composition according to claim 1, it is characterized in that, described compatilizer is liquid compatilizer, comprises γ-An Jibingjisanyiyangjiguiwan, γ-glycidyl ether oxygen propyl three silicomethanes, γ-methacryloxypropyl trimethoxy silane.
5. polymethylmethacrylacomposition composition according to claim 1 is characterized in that, described fire retardant is a kind of in tricresyl phosphate (2-chloroethyl) ester, the trichloropropyl phosphate or their mixture.
6. polymethylmethacrylacomposition composition according to claim 1 is characterized in that, described lubricant is an ethylene bis stearamide.
7. polymethylmethacrylacomposition composition according to claim 1 is characterized in that, described UV absorption agent is a hydroxybenzotriazole class UV light absorber.
8. polymethylmethacrylacomposition composition according to claim 1 is characterized in that, described oxidation inhibitor is one or more mixtures that comprise phosphorous acid ester, triphenyl phosphite, hindered phenol.
9. the preparation method of a polymethylmethacrylacomposition composition comprises step:
Take by weighing according to the component in each described polymethylmethacrylacomposition composition in the claim 1～8 according to mass ratio;
Polymethylmethacrylate, compatilizer and fire retardant were mixed 10～30 minutes;
Dropping into toughner subsequently mixed 10～30 minutes;
Dropping into lubricant, UV absorption agent and oxidation inhibitor at last again mixed 10～30 minutes;
Through twin screw extruder eight district's melting mixing, extruding pelletization, wherein, the residence time of mixing raw material in twin screw extruder was controlled at 1～4 minute with mixed raw materials; The temperature of twin screw extruder is controlled to be: 1 district is 170～180 ℃, 2 districts are 180～240 ℃, 3 districts are 180～240 ℃, 4 districts are 180～240 ℃, and 5 districts are 180～240 ℃, and 6 districts are 180～240 ℃, 7 districts are 180～240 ℃, 8 districts are 180～240 ℃, and head temperature is 180～240 ℃, and melt temperature is 180～240 ℃.
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| CN201010252197XA CN101906234A (en) | 2010-08-12 | 2010-08-12 | Polymethylmethacrylate composition and preparation method thereof |
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| CN201010252197XA CN101906234A (en) | 2010-08-12 | 2010-08-12 | Polymethylmethacrylate composition and preparation method thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190846A (en) * | 2011-01-28 | 2011-09-21 | 上海锦湖日丽塑料有限公司 | Antiscratch resin and preparation method thereof |
| CN103265782A (en) * | 2013-05-06 | 2013-08-28 | 广东华声电器股份有限公司 | PMMA/MBS surface layer co-extrusion material and preparation method thereof |
| WO2014032231A1 (en) * | 2012-08-29 | 2014-03-06 | 深圳市毅彩鸿翔塑料有限公司 | Pmma composite material, co-extrusion molded plastic product and plastic product |
| CN104045955A (en) * | 2014-07-10 | 2014-09-17 | 苏州新区华士达工程塑胶有限公司 | Flame-retardant polymethyl methacrylate |
| CN104403250A (en) * | 2014-11-28 | 2015-03-11 | 上海锦湖日丽塑料有限公司 | Methyl methacrylate resin with excellent thermal stability |
| CN104945815A (en) * | 2015-07-28 | 2015-09-30 | 张家港市德力特新材料有限公司 | Anti-aging organic glass |
| CN105001575A (en) * | 2015-07-28 | 2015-10-28 | 张家港市德力特新材料有限公司 | Fireproof flame-retardant organic glass |
| CN106700371A (en) * | 2015-07-27 | 2017-05-24 | 季叶俊 | Preparation method for acrylic press bar |
| CN106749804A (en) * | 2016-08-23 | 2017-05-31 | 安阳工学院 | A kind of synthetic method of fire-retardant polymethyl methacrylate |
| CN108102272A (en) * | 2017-12-21 | 2018-06-01 | 郑州源冉生物技术有限公司 | A kind of transparent toughened polymethyl methacrylate (PMMA) material and preparation method thereof |
| CN108329633A (en) * | 2018-03-16 | 2018-07-27 | 湖州知维技术服务有限公司 | A kind of durable organic glass processing technology |
| CN109810441A (en) * | 2019-01-22 | 2019-05-28 | 重庆鑫翎创福光电科技股份有限公司 | Outdoor light conducting plate made from a kind of anti-aging polymethylmethacrylacomposition composition, preparation method and combinations thereof |
| CN113388218A (en) * | 2021-06-21 | 2021-09-14 | 广东欧派斯润滑科技有限公司 | Preparation method of polymethacrylate composition |
| CN113881178A (en) * | 2021-09-28 | 2022-01-04 | 江苏金发科技新材料有限公司 | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof |
| CN114213708A (en) * | 2021-11-15 | 2022-03-22 | 金发科技股份有限公司 | Application of phenol compound as heat stabilizer in preparation of polymethyl methacrylate composition |
| CN115353702A (en) * | 2022-08-26 | 2022-11-18 | 万敬新材料(上海)有限公司 | Polymethyl methacrylate composition |
| WO2024067453A1 (en) * | 2022-09-30 | 2024-04-04 | 成都金发科技新材料有限公司 | Ultraviolet-resistant, highly tough pmma composition, preparation method therefor, and use thereof |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190846A (en) * | 2011-01-28 | 2011-09-21 | 上海锦湖日丽塑料有限公司 | Antiscratch resin and preparation method thereof |
| WO2014032231A1 (en) * | 2012-08-29 | 2014-03-06 | 深圳市毅彩鸿翔塑料有限公司 | Pmma composite material, co-extrusion molded plastic product and plastic product |
| CN103265782A (en) * | 2013-05-06 | 2013-08-28 | 广东华声电器股份有限公司 | PMMA/MBS surface layer co-extrusion material and preparation method thereof |
| CN104045955A (en) * | 2014-07-10 | 2014-09-17 | 苏州新区华士达工程塑胶有限公司 | Flame-retardant polymethyl methacrylate |
| CN104403250A (en) * | 2014-11-28 | 2015-03-11 | 上海锦湖日丽塑料有限公司 | Methyl methacrylate resin with excellent thermal stability |
| CN106700371A (en) * | 2015-07-27 | 2017-05-24 | 季叶俊 | Preparation method for acrylic press bar |
| CN104945815A (en) * | 2015-07-28 | 2015-09-30 | 张家港市德力特新材料有限公司 | Anti-aging organic glass |
| CN105001575A (en) * | 2015-07-28 | 2015-10-28 | 张家港市德力特新材料有限公司 | Fireproof flame-retardant organic glass |
| CN106749804A (en) * | 2016-08-23 | 2017-05-31 | 安阳工学院 | A kind of synthetic method of fire-retardant polymethyl methacrylate |
| CN108102272A (en) * | 2017-12-21 | 2018-06-01 | 郑州源冉生物技术有限公司 | A kind of transparent toughened polymethyl methacrylate (PMMA) material and preparation method thereof |
| CN108329633A (en) * | 2018-03-16 | 2018-07-27 | 湖州知维技术服务有限公司 | A kind of durable organic glass processing technology |
| CN109810441A (en) * | 2019-01-22 | 2019-05-28 | 重庆鑫翎创福光电科技股份有限公司 | Outdoor light conducting plate made from a kind of anti-aging polymethylmethacrylacomposition composition, preparation method and combinations thereof |
| CN113388218A (en) * | 2021-06-21 | 2021-09-14 | 广东欧派斯润滑科技有限公司 | Preparation method of polymethacrylate composition |
| CN113881178A (en) * | 2021-09-28 | 2022-01-04 | 江苏金发科技新材料有限公司 | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof |
| CN114213708A (en) * | 2021-11-15 | 2022-03-22 | 金发科技股份有限公司 | Application of phenol compound as heat stabilizer in preparation of polymethyl methacrylate composition |
| CN114213708B (en) * | 2021-11-15 | 2023-09-26 | 金发科技股份有限公司 | Application of phenol compound as heat stabilizer in preparation of polymethyl methacrylate composition |
| CN115353702A (en) * | 2022-08-26 | 2022-11-18 | 万敬新材料(上海)有限公司 | Polymethyl methacrylate composition |
| WO2024067453A1 (en) * | 2022-09-30 | 2024-04-04 | 成都金发科技新材料有限公司 | Ultraviolet-resistant, highly tough pmma composition, preparation method therefor, and use thereof |
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