CN107365470A - A kind of high heat-resisting HI high impact PMMA resins and preparation method thereof - Google Patents
A kind of high heat-resisting HI high impact PMMA resins and preparation method thereof Download PDFInfo
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- CN107365470A CN107365470A CN201710517054.9A CN201710517054A CN107365470A CN 107365470 A CN107365470 A CN 107365470A CN 201710517054 A CN201710517054 A CN 201710517054A CN 107365470 A CN107365470 A CN 107365470A
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- resisting
- heat
- high impact
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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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a kind of high heat-resisting HI high impact PMMA resins and preparation method thereof, belong to modified resin technical field.Described resin includes each component of following parts by weight：60 80 parts of PMMA, 0.1 2 parts of nano-graphene, 20 40 parts of toughener, 0.1 1 parts of antioxidant, 0.1 1 parts of lubricant, 0.1 1 parts of weather resisting agent.Compared with prior art, the present invention with the addition of nano-graphene material in PMMA resins, and the epoxide modified MMA polymer of the acrylate containing silicone for adding core shell structure, as toughener, high warm baking or heat storage are indeformable on the premise of HI high impact is ensured；And because nano-graphene size is very small, PMMA translucency is not interfered with, do not interfere with the black and bright effect of the bloom of black product yet.It can apply to the automobile exterior trimming parts such as the grid higher to heat-resisting, impact and appearance requirement, column, rearview mirror.
Description
Technical field
The present invention relates to a kind of modified resin, more particularly, to a kind of high heat-resisting HI high impact PMMA resins and its preparation side
Method.
Background technology
Polymethyl methacrylate (PMMA) have excellent weatherability, higher case hardness, preferably it is high temperatures
Energy, excellent tinctorial property and the transparency, in the row such as aviation, automobile, electronics, medical treatment, chemical industry, building materials, bathroom and billboard
Industry is widely used.But common PMMA easily splits because extensibility is relatively low, be frangible, limit it and further should
With.
With the enhancing of the green consciousness of people, it is more and more extensive to exempt from application of the sprayed on material on automobile interior exterior decorations,
Toughened polymethyl methacrylate (PMMA) exempts to spray exterior trimming parts such as backsight because its special bloom high black property, scratch resistance and weatherability are increasingly becoming automobile
The main material of mirror, B posts and grid etc..These exterior trimming parts are generally based on black, due in the position of sun direct irradiation
Put, generally there is heat-resisting requirement.Improve PMMA in itself it is heat-resisting can by adjust molecular weight and Third monomer content come reality
It is existing, but heat-resisting PMMA adds a large amount of toughener and carries out heat-resisting after toughness reinforcings and can substantially reduce, and can significantly affect material plus
Work performance.If being further continued for adding the heat-proof modifier of maleic anhydride or maleimide, toughness and mobility can be caused again
Decline, such vicious circle.
CN101870794A, which is used as toughener by adding MBS of the refractive index between 1.483-1.489, to be ensured
Impact is obviously improved on the premise of transparent.But MBS addition has a certain impact to weather-proof, applied to exempting from
Weather-proof problem is might have during the exterior trimming parts of spraying.
CN201410770763 is used as heat-resistant agent by adding maleic anhydride-styrene-methyl acrylate terpolymer
Heat-resisting scratch resistance high transmittance PMMA scheme is provided, this method makes the heat-resisting of polymer obtain certain lifting.
But it is not related to improve that PMMA is heat-resisting and the relevant report of toughness simultaneously.
The content of the invention
A kind of the defects of purpose of the present invention is exactly to overcome above-mentioned prior art to exist, there is provided high heat-resisting HI high impact
PMMA resins and preparation method thereof, it can be applied to automobile grills, rearview mirror and column etc. and higher portion required to heat-resisting and impact
Part.
The purpose of the present invention is achieved through the following technical solutions：
The invention provides a kind of high heat-resisting HI high impact PMMA resins, including following components and parts by weight content：
Preferably, the thickness of described nano-graphene is 0.2-0.8nm, is the one of individual layer, bilayer or multi-layer graphene
Kind.
Preferably, described toughener is the acrylic acid series toughener of core shell structure, and wherein stratum nucleare is siliceous acrylic acid
Resin, shell are epoxide modified MMA copolymers.
Preferably, described antioxidant is one or both of hindered phenol compound, bi-ester of phosphite mixture.
Preferably, described lubricant be silicone oil, White Mineral Oil, fatty acid amide, stearate, paraffin, Tissuemat E or
One or more of mixtures in ethylene bis stearamide.
Preferably, described weather resisting agent is the mixture of ultraviolet absorber and hindered amine.
Present invention also offers a kind of preparation method of high heat-resisting HI high impact PMMA resins, this method comprises the following steps：
S1, by the heat-resisting HI high impact PMMA resin formulas of the height each component is weighed respectively；
S2, the PMMA weighed in step S1, nano-graphene, toughener, antioxidant, lubricant and weather resisting agent be put into
Discharging obtains mixture after 5-30min is stirred in homogenizer；
S3, the mixture for obtaining step S2 produce the resin by double screw extruder extruding pelletization；Double spiral shells
The temperature of bar extruder is 180-210 DEG C, and screw speed is 180-600 revs/min, and vacuum is more than 0.09MPa.
Compared with prior art, the present invention has following beneficial effect：
Conventional PMMA toughness is excessively poor, and improving toughness needs to add substantial amounts of toughener, the addition meeting again of toughener
Make heat-resisting significantly to decline.Novelty of the invention with the addition of nano-graphene material in PMMA resins, and add nucleocapsid knot
The acrylate containing silicone of structure-epoxide modified MMA polymer is total to as toughener, the shell of the toughener for epoxide modified MMA
Polymers, epoxide group therein can react with the oxygen-containing functional group of nano-graphene remained on surface, so graphene and
Toughener can be evenly distributed in PMMA resins.Because nano-graphene has very high heat conductivility, addition pole
Can rapidly goes out the energy conduction that black resin absorbs when few, and then can reduce resin inside and surface temperature,
High warm baking or heat storage are indeformable on the premise of other heat-resistant agents are not added.And because nano-graphene size is non-
Often small, only several nanometers of zero point does not interfere with PMMA translucency, does not interfere with the black and bright effect of the bloom of black product yet
Fruit.It can apply to the automobile exterior trimming parts such as the grid higher to heat-resisting, impact and appearance requirement, column, rearview mirror.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the common skill to this area
For art personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to this
The protection domain of invention.
Raw material used in each embodiment and comparative example are as follows：
PMMA：Strange beautiful CM205
Nano-graphene：Double-layer graphite structure, thickness 0.2-0.5nm
Toughener：The beautiful positive S-2200 of Mitsubishi
Conventional toughener：Clock deep pool M-210
Antioxidant：Ciba：TG-1076
Lubricant：Commercially available EBS (ethylene bis stearic acid amide)
Weather resisting agent：Commercially available UVP and 770, ratio 1:1
Embodiment 1-6
Embodiment 1-6 provides a kind of high heat-resisting HI high impact PMMA resin combinations, its each component and parts by weight such as table
Shown in 2.
The preparation method of the heat-resisting HI high impact PMMA resin combinations of height comprises the following steps：
PMMA, nano-graphene, toughener, antioxidant, lubricant and weather resisting agent are weighed by the parts by weight in table 2 to put
Discharging obtains mixture after entering to stir 5-30min in homogenizer, and being sent to double screw extruder extrusion through metering device makes
Grain, the temperature of double screw extruder is 180-210 DEG C, and screw speed is 180-600 revs/min, and vacuum is more than 0.09MPa,
Under conveying, shearing and the mixing of screw rod, material melting, compound, extruded, tie rod, cooling, pelletizing step again, that is, PMMA is obtained
Resin.
Comparative example 1-2
Comparative example 1-2 provides a kind of low gloss heat-proof ABS resin composition, its each component and the parts by weight such as institute of table 2
Show.Its preparation method is identical with embodiment.
Compliance test result：
The impact batten that resin prepared by each embodiment and comparative example is molded into standard by iso standard is tested, and is tested
Condition is as shown in table 1, and test result is as shown in table 2.
The physical property of table 1 and method of testing corresponding table
| Physical property | Method of testing |
| Vicat softening point | ISO 306 |
| IZOD notch impact strengths (3.2mm) | ISO 180 |
The embodiment of table 2 and comparative example
As seen from the results in Table 2,2 conventional toughener of addition of comparative example, compared with pure PMMA performance, notch shock is strong
Degree is improved to some extent, but heat-resisting reduction is obvious；Comparative example 1 is that 0.2 part is with the addition of on the basis of comparative example 2
Graphene, because dispersion effect is bad, its heat resistance lifts unobvious relative to pure PMMA.The present invention using graphene and
The acrylate containing silicone of core shell structure-epoxide modified MMA polymer toughening agent compounding uses is heat-resisting while impact is improved
Also increase substantially, do not deformed in 110 DEG C of heat storage experiment.It can apply to heat-resisting, impact and outward appearance
It is required that the automobile exterior trimming parts such as higher grid, column, rearview mirror.
Concrete application approach of the present invention is a lot, and described above is only the 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 limit the invention.For the common skill of the art
For art personnel, under the premise without departing from the principles of the invention, some improvement can also be made, these improvement also should be regarded as this
The protection domain of invention.
Claims (7)
1. a kind of high heat-resisting HI high impact PMMA resins, it is characterised in that including following components and parts by weight content：
2. the heat-resisting HI high impact PMMA resins of height according to claim 1, it is characterised in that the thickness of described nano-graphene
Spend for 0.2-0.8nm, be one kind in individual layer, bilayer or multi-layer graphene.
3. the heat-resisting HI high impact PMMA resins of height according to claim 1, it is characterised in that described toughener is nucleocapsid knot
The acrylic acid series toughener of structure, wherein stratum nucleare are siliceous acrylic resin, and shell is epoxide modified MMA copolymers.
4. the heat-resisting HI high impact PMMA resins of height according to claim 1, it is characterised in that described antioxidant is hindered phenol
One or both of compound, bi-ester of phosphite mixture.
5. the heat-resisting HI high impact PMMA resins of height according to claim 1, it is characterised in that described lubricant be silicone oil,
One or more of mixing in White Mineral Oil, fatty acid amide, stearate, paraffin, Tissuemat E or ethylene bis stearamide
Thing.
6. the heat-resisting HI high impact PMMA resins of height according to claim 1, it is characterised in that described weather resisting agent is ultraviolet suction
Receive the mixture of agent and hindered amine.
A kind of 7. preparation method of the heat-resisting HI high impact PMMA resins of height according to claim 1, it is characterised in that this method
Comprise the following steps：
S1, by the heat-resisting HI high impact PMMA resin formulas of the height each component is weighed respectively；
S2, the PMMA weighed in step S1, nano-graphene, toughener, antioxidant, lubricant and weather resisting agent be put into high-speed stirring
Mix discharging after 5-30min is stirred in machine and obtain mixture；
S3, the mixture for obtaining step S2 produce the resin by double screw extruder extruding pelletization；The twin-screw squeezes
The temperature for going out machine is 180-210 DEG C, and screw speed is 180-600 revs/min, and vacuum is more than 0.09MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710517054.9A CN107365470B (en) | 2017-06-29 | 2017-06-29 | A kind of high heat resistance HI high impact PMMA resin and preparation method thereof |
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|---|---|---|---|
| CN201710517054.9A CN107365470B (en) | 2017-06-29 | 2017-06-29 | A kind of high heat resistance HI high impact PMMA resin and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107365470A true CN107365470A (en) | 2017-11-21 |
| CN107365470B CN107365470B (en) | 2019-09-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251502A (en) * | 2018-08-01 | 2019-01-22 | 公牛集团股份有限公司 | A kind of polycarbonate based composites and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150240004A1 (en) * | 2013-03-06 | 2015-08-27 | Sekisui Chemical Co., Ltd. | Method for producing resin composite material, and resin composite material |
| CN104945878A (en) * | 2015-06-30 | 2015-09-30 | 常州工程职业技术学院 | Preparation method of high-light-transmittance high-thermal-conductivity LED (light-emitting diode) lens |
| CN105419203A (en) * | 2015-12-21 | 2016-03-23 | 上海锦湖日丽塑料有限公司 | Gasoline-resistant toughening PMMA resin and preparation method therefor |
| CN106398076A (en) * | 2016-11-09 | 2017-02-15 | 安徽新胜塑料科技有限公司 | Highly tenacious acrylic board |
| CN106566156A (en) * | 2016-11-02 | 2017-04-19 | 武汉理工大学 | Preparation method of graphene nanobelt/PMMA microcellular foam nanocomposite |
-
2017
- 2017-06-29 CN CN201710517054.9A patent/CN107365470B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150240004A1 (en) * | 2013-03-06 | 2015-08-27 | Sekisui Chemical Co., Ltd. | Method for producing resin composite material, and resin composite material |
| CN104945878A (en) * | 2015-06-30 | 2015-09-30 | 常州工程职业技术学院 | Preparation method of high-light-transmittance high-thermal-conductivity LED (light-emitting diode) lens |
| CN105419203A (en) * | 2015-12-21 | 2016-03-23 | 上海锦湖日丽塑料有限公司 | Gasoline-resistant toughening PMMA resin and preparation method therefor |
| CN106566156A (en) * | 2016-11-02 | 2017-04-19 | 武汉理工大学 | Preparation method of graphene nanobelt/PMMA microcellular foam nanocomposite |
| CN106398076A (en) * | 2016-11-09 | 2017-02-15 | 安徽新胜塑料科技有限公司 | Highly tenacious acrylic board |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251502A (en) * | 2018-08-01 | 2019-01-22 | 公牛集团股份有限公司 | A kind of polycarbonate based composites and its preparation method and application |
| CN109251502B (en) * | 2018-08-01 | 2021-04-13 | 公牛集团股份有限公司 | Polycarbonate-based composite material and preparation method and application thereof |
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| CN107365470B (en) | 2019-09-17 |
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