CN105419203A - Gasoline-resistant toughening PMMA resin and preparation method therefor - Google Patents
Gasoline-resistant toughening PMMA resin and preparation method therefor Download PDFInfo
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- CN105419203A CN105419203A CN201510973742.7A CN201510973742A CN105419203A CN 105419203 A CN105419203 A CN 105419203A CN 201510973742 A CN201510973742 A CN 201510973742A CN 105419203 A CN105419203 A CN 105419203A
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- gasoline
- resistance
- pmma
- polymethyl methacrylate
- toughner
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three 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)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides gasoline-resistant toughening PMMA resin and a preparation method thereof, and belongs to the technical field of modified resin. The gasoline-resistant toughening PMMA resin comprises the following formula in parts by weight: 40-80 parts of PMMA; 5-30 parts of a gasoline-resistant modifier; 15-30 parts of a toughening agent; 0.1-1 part of an antioxidant; 0.1-1 part of a lubricant; and 0.1-1 part of a weather-resistant agent. Compared with the prior art, gasoline resistance of the gasoline-resistant toughening PMMA resin prepared by the present invention is improved greatly under a premise of guaranteeing the toughness. The PMMA resin can be applied to free-spraying workpieces that have requirements for appearance and gasoline resistance, such as an automotive rearview mirror, a B pillar and a grille, and the like.
Description
Technical field
The present invention relates to a kind of modified resin, especially relate to a kind of toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin and preparation method thereof.
Background technology
Polymethylmethacrylate (PMMA) has excellent weathering resistance, higher surface hardness, preferably high-temperature behavior, excellent tinctorial property and the transparency, is widely used in industries such as aviation, automobile, electronics, medical treatment, chemical industry, building materials, bathroom and billboards.But common PMMA is lower due to extensibility, easily splits, frangible, limits it and further apply.
Along with the enhancing of people's environmental protection consciousness, exempt from the application of spray material on automobile interior exterior decorations more and more extensive, toughened polymethyl methacrylate (PMMA) exempts from spraying exterior trimming parts as the main raw of rear vision mirror, B post and grid etc. because its special high light high black property, scratch resistance and weathering resistance become automobile gradually.These products are because the gasoline that likely can contact in concrete use procedure, so can there be clear and definite requirement in a lot of main engine plants to petrol-resistance.Have at present and much patent reports the toughness reinforcing method of PMMA.
CN101870794A can ensure to make impact obtain obvious lifting under transparent prerequisite as toughner by adding the MBS of specific refractory power between 1.483-1.489.But the interpolation of MBS has a certain impact to weather-proof, when being applied to the exterior trimming parts of exempting to spray, weather-proof problem may be had.
CN104497461A provides the scheme of heat-resisting scratch resistance high permeability PMMA as heat-resistant agent by interpolation maleic anhydride-styrene-methyl acrylate terpolymer, the method makes the heat-resisting of polymkeric substance obtain certain lifting.
But there is not the petrol-resistance problem of patent report toughened polymethyl methacrylate (PMMA).
Summary of the invention
For defect of the prior art, the object of this invention is to provide a kind of toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin and preparation method thereof, can be applicable to automobile and exempt from spraying exterior trimming parts as grid, B post and rear vision mirror etc.
The present invention is achieved by the following technical solutions:
The invention provides a kind of toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin, comprise following component and weight part content:
Described resistance to gasoline modified dose is acylamide polymer, and described toughner is the acrylic acid series toughner of nucleocapsid structure.
Described resistance to gasoline modified agent content is too low, then can not play a protective role preferably, petrol-resistance can not meet the demands; Resistance to gasoline modified agent content is too high, then can impact the outward appearance of material.Described toughner content is too low, then the Toughness Ratio of material is poor, and can not play the effect of compatilizer between PMMA and resistance to gasoline modified dose, and toughner too high levels, then can have a strong impact on rigidity and the outward appearance of material.
More preferably, the described toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin, comprises following component and weight part content:
Preferably, described resistance to gasoline modified dose is one or more in PA6, PA66, PA12, PA1010.
Preferably, the acrylic acid series toughner of described nucleocapsid structure, wherein stratum nucleare is siliceous acrylic resin, and shell is epoxide modified MMA multipolymer.
Preferably, described oxidation inhibitor is one or both the mixture in hindered phenol compound, bi-ester of phosphite.
Preferably, described lubricant is the mixture of one or more in silicone oil, white mineral oil, fatty acid amide, stearate, paraffin, polyethylene wax or ethylene bis stearamide.
Preferably, described weather resisting agent is the mixture of uv-absorbing agent and hindered amine.
Present invention also offers a kind of preparation method of the toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin, the method comprises the following steps:
(1) each component is taken respectively by the toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin formula;
(2) by the PMMA taken in step (1), resistance to gasoline modified dose, toughner, oxidation inhibitor, lubricant and weather resisting agent put into homogenizer stir 5-30min after discharging obtain mixture;
(3) mixture step (2) obtained is through twin screw extruder extruding pelletization, and the temperature of twin screw extruder is 180-210 DEG C, and screw speed is 180-600 rev/min, and vacuum tightness is greater than 0.09MPa.
Compared with prior art, the present invention has following beneficial effect:
The petrol-resistance of conventional toughened polymethyl methacrylate (PMMA) is poor, the introducing acylamide polymer of novelty of the present invention especially PA6 as resistance to gasoline modified dose, utilization has nucleocapsid structure, and (wherein stratum nucleare is siliceous acrylic resin, shell is epoxide modified MMA multipolymer) acrylate copolymer as toughner, shell because of this toughner is epoxide modified MMA multipolymer, epoxide group wherein can react with acylamide polymer, MMA and PMMA has good homogeny, reduction interfacial tension can be played between acylamide polymer and the interface of PMMA, increase interfacial layer thickness, reduce the effect of dispersed particle size, the consistency of acylamide polymer and PMMA can be significantly improved, acylamide polymer is dispersed in PMMA more uniformly.The oil-proofness of the toughened polymethyl methacrylate (PMMA) prepared by the method is greatly improved, and can meet the oil resistant experiment of Duo Jia main engine plants.The toughened polymethyl methacrylate (PMMA) of resistance to gasoline prepared by the method can be applied to automobile rearview mirror, B post and grid etc. to outward appearance and resistance to gasoline have requirement exempt from spray product.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
Below in conjunction with specific embodiment, the present invention is described in detail.
In following examples and comparative example, the raw material used is as follows:
PMMA: strange beautiful CM211
Resistance to gasoline modified dose: newly U.S.A can reach PA6
Toughner: the beautiful positive S-2200 of Mitsubishi
Conventional toughner: clock deep pool M-210
General SAN: strange beautiful SAN128
Oxidation inhibitor: Ciba:TG-1076
Lubricant: commercially available EBS (ethylene bis stearic acid amide)
Weather resisting agent: commercially available UVP and 770, ratio is 1:1
embodiment 1
Take (component by weight, lower same)
Above each raw material is put into homogenizer stir 5-30min after discharging obtain mixture;
By mixture through twin screw extruder extruding pelletization, wherein the temperature of twin screw extruder is 180-210 DEG C, and screw speed is 180-600 rev/min.By conveying, melting, shear extrusion cooling granulation, namely obtain product.
embodiment 2
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
embodiment 3
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
embodiment 4
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
embodiment 5
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
embodiment 6
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
comparative example 1
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
comparative example 2
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
comparative example 3
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
comparative example 4
Take (component by weight, lower same)
Product is obtained by the method for embodiment 1.
The impact batten that resin prepared by each embodiment and comparative example is injection molded into standard by iso standard is tested, as shown in table 1.
Table 1 physicals and testing method correspondence table
| Physicals | Testing method |
| IZOD notched Izod impact strength (3.2mm) | ISO 180 |
Injection moulding height tabula rasa at resin 240 DEG C prepared by each embodiment and comparative example, model is placed 30Min under the baking oven of 50 DEG C, immediately the 93# gasoline of 5ml is poured on sample surfaces after taking-up, then model is placed 24h at 23 DEG C, repeat above step 2 time, third time terminates rear placement 72h, evaluate product surface, petrol-resistance can be better, and surperficial white hair is more not obvious, petrol-resistance can be poorer, and surface is turned white more obvious.
Quantitative measurement result and injection moulding height tabula rasa do the surface condition after the experiment of resistance to gasoline in table 2.
Table 2 embodiment and comparative example performance and resistance to gasoline test after surface condition
| IZOD notched Izod impact strength | Turn white situation in surface | |
| Unit | kJ/m2 | |
| Embodiment 1 | 7.3 | Not obvious |
| Embodiment 2 | 8.6 | Not obvious |
| Embodiment 3 | 10.2 | Not obvious |
| Embodiment 4 | 13.5 | Not obvious |
| Embodiment 5 | 15 | Not obvious |
| Embodiment 6 | 6.5 | Slightly |
| Comparative example 1 | 4 | Obviously |
| Comparative example 2 | 4.5 | Obviously |
| Comparative example 3 | 3 | Obviously |
| Comparative example 4 | 2.5 | Obviously |
As seen from the results in Table 2, by selecting PA6 as resistance to gasoline modified dose, select and there is nucleocapsid structure (wherein stratum nucleare is siliceous acrylic resin, shell is epoxide modified MMA multipolymer) acrylate copolymer as toughner, impact can be made to obtain obvious lifting, and oil-proofness obtains obvious improvement, can be applied to automobile rearview mirror, B post and grid etc. to outward appearance and resistance to gasoline have requirement exempt from spray product.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (7)
1. the toughened polymethyl methacrylate (PMMA) of a resistance to gasoline resin, is characterized in that, comprises following component and weight part content:
Described resistance to gasoline modified dose is acylamide polymer, and described toughner is the acrylic acid series toughner of nucleocapsid structure.
2. the toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin according to claim 1, is characterized in that, described resistance to gasoline modified dose is one or more in PA6, PA66, PA12, PA1010.
3. the toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin according to claim 1, is characterized in that, the acrylic acid series toughner of described nucleocapsid structure, and wherein stratum nucleare is siliceous acrylic resin, and shell is epoxide modified MMA multipolymer.
4. the toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin according to claim 1, is characterized in that, described oxidation inhibitor is one or both the mixture in hindered phenol compound, bi-ester of phosphite.
5. the toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin according to claim 1, is characterized in that, described lubricant is the mixture of one or more in silicone oil, white mineral oil, fatty acid amide, stearate, paraffin, polyethylene wax or ethylene bis stearamide.
6. the toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin according to claim 1, is characterized in that, described weather resisting agent is the mixture of uv-absorbing agent and hindered amine.
7. a preparation method for the toughened polymethyl methacrylate (PMMA) of the resistance to gasoline resin according to any one of claim 1 ~ 6, it is characterized in that, the method comprises the following steps:
(1) each component is taken respectively by the toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin formula;
(2) by the PMMA taken in step (1), resistance to gasoline modified dose, toughner, oxidation inhibitor, lubricant and weather resisting agent put into homogenizer stir 5-30min after discharging obtain mixture;
(3) mixture step (2) obtained is through twin screw extruder extruding pelletization, and the temperature of twin screw extruder is 180-210 DEG C, and screw speed is 180-600 rev/min, and vacuum tightness is greater than 0.09MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510973742.7A CN105419203B (en) | 2015-12-21 | 2015-12-21 | A kind of toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510973742.7A CN105419203B (en) | 2015-12-21 | 2015-12-21 | A kind of toughened polymethyl methacrylate (PMMA) of resistance to gasoline resin and preparation method thereof |
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| CN105419203A true CN105419203A (en) | 2016-03-23 |
| CN105419203B CN105419203B (en) | 2018-05-04 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778379A (en) * | 2016-05-12 | 2016-07-20 | 广东东华光电科技有限公司 | Flexible mirror |
| CN107365470A (en) * | 2017-06-29 | 2017-11-21 | 上海金山锦湖日丽塑料有限公司 | A kind of high heat-resisting HI high impact PMMA resins and preparation method thereof |
| CN107903553A (en) * | 2017-12-04 | 2018-04-13 | 青岛岩康塑料机械有限公司 | Preparation method with toughness, the acrylic resin of hardness under a kind of low temperature |
| CN111349329A (en) * | 2020-03-23 | 2020-06-30 | 上海锦湖日丽塑料有限公司 | Fingerprint-resistant high-gloss resin material and preparation method thereof |
| CN112266563A (en) * | 2020-11-05 | 2021-01-26 | 广东天雄新材料科技股份有限公司 | Polyamide-polymethyl methacrylate alloy material and preparation method thereof |
| 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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| CN102719047A (en) * | 2012-06-08 | 2012-10-10 | 中国科学院化学研究所 | Alloy material of long carbon chain nylon and polymethylmethacrylate and preparation method thereof |
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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 |
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Patent Citations (4)
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| CN101463188A (en) * | 2008-11-28 | 2009-06-24 | 上海锦湖日丽塑料有限公司 | Spraying-free high weather resistance anti-scraping PA/PMMA alloy and preparation thereof |
| CN102719047A (en) * | 2012-06-08 | 2012-10-10 | 中国科学院化学研究所 | Alloy material of long carbon chain nylon and polymethylmethacrylate and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778379A (en) * | 2016-05-12 | 2016-07-20 | 广东东华光电科技有限公司 | Flexible mirror |
| CN107365470A (en) * | 2017-06-29 | 2017-11-21 | 上海金山锦湖日丽塑料有限公司 | A kind of high heat-resisting HI high impact PMMA resins and preparation method thereof |
| CN107365470B (en) * | 2017-06-29 | 2019-09-17 | 上海金山锦湖日丽塑料有限公司 | A kind of high heat resistance HI high impact PMMA resin and preparation method thereof |
| CN107903553A (en) * | 2017-12-04 | 2018-04-13 | 青岛岩康塑料机械有限公司 | Preparation method with toughness, the acrylic resin of hardness under a kind of low temperature |
| CN111349329A (en) * | 2020-03-23 | 2020-06-30 | 上海锦湖日丽塑料有限公司 | Fingerprint-resistant high-gloss resin material and preparation method thereof |
| CN112266563A (en) * | 2020-11-05 | 2021-01-26 | 广东天雄新材料科技股份有限公司 | Polyamide-polymethyl methacrylate alloy material and preparation method thereof |
| 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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| CN105419203B (en) | 2018-05-04 |
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