CN107501829A - A kind of automobile-used resistance to thermal level exempts to spray PMMA/ASA alloys - Google Patents
A kind of automobile-used resistance to thermal level exempts to spray PMMA/ASA alloys Download PDFInfo
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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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- 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
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
A kind of automobile-used resistance to thermal level exempts to spray PMMA/ASA alloys, belongs to technical field of novel materials.The present invention provides a kind of automobile-used heat resistant type and exempts to spray PMMA/ASA alloys in parts by weight, including following component：50~70 parts of PMMA resins, 10~20 parts of SAN resins, 1~5 part of inorganic nano-particle, 5~25 parts of toughener, 15 parts of boron nitride fiber, 5~15 parts of heat-resistant agent, 0.5~1 part of light diffusing agent, 10 20 parts of compatilizer, 1~5 part of processing aid.The present invention solves the problems, such as that PMMA/ASA alloys excellent mechanical performances and heat resistance can not have both.Compatibility of the present invention is reasonable, and preparation technology simple mechanisms obtain excellent and heat-resist automobile-used of tool performance and exempt to spray PMMA/ASA alloys.
Description
Technical field
The present invention relates to alloy resin, more particularly to a kind of automobile-used resistance to thermal level to exempt to spray PMMA/ASA alloys, belongs to new
Field of material technology.
Background technology
Currently, " lightweight ", " green " one word are visible everywhere in automobile industry, therefore have derived plated item and replaced
Substituting metal part, exempt from spraying substitute coated article neonatal material, these new materials also constantly promote auto parts and components it is low into
This change so that the design of whole auto parts and components field becomes more flexible.
Radiator grid is generally described as " preceding face " before automobile, therefore its outward appearance one of is judged as key, at present
Grid part is commonplace using application money ABS and dermatoglyph money ASA, and it is then the novel-section to grow up in the recent period to exempt from sprayed on material
Material, such as PMMA/ASA alloys.PMMA resins are by the polymer obtained by acrylicacidandesters Type of Collective, are commonly called as lucite,
Lucite is macromolecule transparent material most excellent at present, and light transmittance reaches 92%, and high mechanical strength, relative molecular mass
About 2,000,000, it is in light weight, there is good scraping and wiping resistance performance, in automotive field, it is widely used in glass pane, cover lid, instrument
The parts such as watch crystal, car light, label.ASA resin is by ter-polymers combined polymerizations such as styrene, acrylonitrile and acryl rubber
A kind of Resin Used As Impact Modifier formed, has good mechanical and physical performance, and not containing unsaturated double-bond in ASA can not only resist
Degraded, aging, colour fading caused by ultraviolet irradiation, it is greatly improved the anti-aging and weathering performance of material.But PMMA trees
Fat category fragile material, impact property is low, and ASA resin case hardness is inadequate, and scratch resistance, rub resistance, wear resistance are bad.
Chinese patent application (publication number：105419205A) disclose the PMMA/ASA alloy trees that a kind of high glaze exempts from spraying
Oil/fat composition and preparation method thereof, by the way that PMMA resins and ASA resin are blended, introducing compatilizer improves the phase of the two for the invention
Capacitive, introduces the shock resistance that toughener improves co-mixing system, exempts from spraying, Physical Mechanical with high glaze so as to prepare
The excellent PMMA/ASA alloy resin compositions of energy, but the heat resistance of its material is bad.Automobile radiator grille generally will now
Ask material that there is higher heat resistance to deposit unchanged, existing PMMA/ASA alloys after 24h in 90 DEG C ± 2 DEG C of baking oven
Material can not meet the heat resistant requirements of grid product, or material is up to standard in heat resistance, but its in mechanical performance significantly
Decline.
The content of the invention
The purpose of the present invention is to be directed to the above-mentioned problems in the prior art, proposes that a kind of mechanical performance is excellent and heat resistance
Well automobile-used exempts to spray PMMA/ASA alloy materials.
The purpose of the present invention can be realized by following technical proposal：A kind of automobile-used heat resistant type exempts to spray PMMA/ASA materials
In parts by weight, including following component：
PMMA resins：50~70 parts,
SAN resins：10~20 parts,
Inorganic nano-particle：1~5 part,
Toughener：5~25 parts,
Boron nitride fiber：1-5 parts,
Heat-resistant agent：5~15 parts,
Light diffusing agent：0.5~1 part,
Compatilizer：10-20 parts,
Processing aid：1~5 part.
Heat resistant type of the present invention exempts to spray PMMA/ASA resin alloys, mainly using PMMA resins as main base resin,
The resin has good transparency, weatherability, wearability and performance easy to process in itself, adds SAN resins in the base, both made
For the melt blending matrix of PMMA/ASA resin alloys, and can improves the glass transition temperature of PMMA resins and strengthens its toughness
And intensity.Contain large volume phenyl and highly polar cyano group in SAN strands, large volume phenyl can increase PMMA strand internal rotations
Resistance, raise PMMA glass transition temperature, i.e. the addition of SAN resins can improve PMMA heat resistance；Highly polar cyano group energy
Increase the interaction force of PMMA strands, improve PMMA crystallinity and reduce free volume, make PMMA strands soft
Pliable variation, modulus of elasticity improve, and improve hardness, that is, improve the toughness of PMMA resins and slight.
Inorganic nano-particle, toughener, boron nitride fiber, resistance to is also added into PMMA/ASA resin alloys system of the present invention
Thermit powder, light diffusing agent, compatilizer, processing aid, so as to get alloy have higher heat resistance, scratch resistance, toughness strong etc.
A series of condition of vehicle materials, and in appearance it is attractive in appearance, be comfortably also improved.The inorganic nano-particle that the present invention adds,
Its particle is minimum, is easily scattered in high molecular polymer, and its strengthening and toughening acts in PMMA/ASA resin alloy systems, by
In rigid particles itself be present, particle and resin matrix Interface adhesive strength are good, in favor of the transmission of power, effectively strengthen
The impact resistance of resin alloy.Boron nitride fiber in the present invention is in itself by borazine polymer, through melt spinning into fibre
After dimensionization, the high-temperature region more than 1400 DEG C is burnt till.So it is a kind of exotic material.Will in PMMA/ASA alloy moltens
, can be as the skeleton structure of resin alloy with spinning fractions distribution in the cross-linked network of resin, and its crystal orients in an orderly manner
Orientation, the tensile strength and elastic strength of fiber can be greatly improved, so as to improve the mechanical property of resin.Boron nitride fiber is not
Luminous energy improves the heat resistance of PMMA/ASA resin alloys, moreover it is possible to substantially improve tensile strength and modulus of elasticity, but boron nitride
Fiber is fragile material, and general and toughener is used cooperatively.This kind of resinae heat-proof modifier of heat-resistant agent is also added in the present invention
It is splendid with PMMA/ASA resin compatibles, and the mechanics of alloy system is not interfered with while resin alloy heat resistance is increased yet
Performance.
In addition, the present invention also added micro light diffusing agent, it is microcosmic on be spheroid that light can not pass through, particle diameter is in 2-
4 μm or so, so the scattering and transmission of light can be increased, light emitting source and glare are covered, while whole resin alloy is seemed
It is bright and attractive in appearance.
Wherein, described PMMA resins pencil hardness is 5~9H, and Vicat softening point is 90~100 under the conditions of 50N is loaded
℃。
Described SAN resins melt index is 10-20g/10min under the conditions of 220 DEG C/10kg.
Described PMMA resins and SAN weight resins ratio is 4-5:1.Although in SAN strands containing large volume phenyl and
Highly polar cyano group, can improve the heat resistance and mechanical strength of PMMA resins, but when SAN is added to a certain degree, on PMMA strands
Cyano group polar group increases, and the electrostatic repulsion between cyano group is more than attraction, intermolecular interaction reduces, so that anti-impact
Hit ability reduction.
Described inorganic nano-particle is the mixing material of nano SiC and nano aluminium oxide, nano SiC and nano aluminium oxide
Mass ratio be 2-4：1.In melt blending, both can combine, and make structure finer and close, and mobility is more preferable, PMMA be present
In resin and SAN resin boundary surface layers, stabilization is played, the effect of strengthening and toughening can be produced to alloy.Both compare in different matching somebody with somebody
Its binding ability has an impact, and too many inorganic material is added in resin, can also influence the binding ability of resin alloy in itself.
Described nano SiC is the nano SiC after vinyl silicone oil couples processing.SiC fusing points are again high, are mixed in tree
Also heat resistance can be further improved in fat alloy, and can be acted synergistically with coupling agent, two kinds are contained in coupling agent molecule
Group, one be close inorganic matter group, easily with mineral surfaces chemically reactive；Another is organophilic group, energy
Chemical reaction occurs with synthetic resin or generation hydrogen bond is dissolved in wherein.Between nano SiC energy and resin matrix through coupling processing
A boundary layer is formed, so as to enhance bonding strength between reinforcing material and resin, improves the performance of composite, simultaneously
Layer protecting film can also be formed on surface prevents other media from, to contacting permeation, improving interface state, being advantageous to resin conjunction
Ageing-resistant, the proof stress of gold.Both are acted synergistically in PMMA/ASA resin alloy systems, and both modifying functions can obtain
To enhancing.
Described toughener is the esters of acrylic acid rubber graft of gel content 30~60%, and toughener is that have to reduce again
Condensation material fragility and the analog assistant for improving composite shock resistance, the present invention select esters of acrylic acid rubber graft,
It belongs to the impact modifying agent of core shell structure, the shell of methyl methacrylate-ethyl acrylate high polymer composition, with acrylic acid
The rubber elastomer that butyl ester class is cross-linked to form is distributed in internal granular layer for the segment of core, so as to ensure that it is higher heat-resisting that material possesses
Property after impact flexibility slightly improve.
Preferably, described boron nitride fiber nitrogen content is more than 52%.Because nitrogen content is too low, when illustrating synthetic fibers
Desalination degree is inadequate, and fibrous inside can form many spaces under the condition of high temperature so that crystal is too grown up, so as to influence mechanical property
Energy.
Described toughener and boron nitride fiber mass ratio are 8-10：1.
Described heat-resistant agent is in maleimide, alpha-alkyl phenylethylene copolymer, styrene-maleic anhydride copolymer
At least one.The present invention is heat resistance modified auxiliary agent preferably with maleimide amine type heat-resistant agent, because such heat-resistant agent possesses pole
Property stronger N-phenylmaleimide group, cause steric hindrance increase to lift intermolecular work in overall molecule structure
Firmly, to reach Tg=196 DEG C very high of heat resistance, outstanding heat endurance, and a small amount of maleic anhydride is contained, energy and hydroxyl groups
Reaction, alloy strength can be improved as the compatilizer of high-molecular compound alloy.
Described light diffusing agent is organosilicon diffusant, be one kind with silica key connection, the polymer of 3-D solid structure
Microballoon, this light diffusing agent sheet are added in the resin of unlike material as a kind of white powder, can be with a kind of trickle transparent
Glass spheres are uniformly dispersed in matrix, and by the difference of the refractive index with different substrate materials, light source penetration reflect,
Change the course of light, reach the purpose of even light and printing opacity.And it does not also melt weightlessness under conditions of up to 400 DEG C,
It is more preferable with fabulous heat resisting performance.
Described processing aid includes antioxidant, ultra-violet absorber, light stabilizer, color masterbatch.Wherein, antioxidant is to be obstructed
The one or more of which of phenolic antioxidant or phosphite ester kind antioxidant, ultra-violet absorber are benzotriazole absorbent,
Light stabilizer is hindered amine light stabilizer, and color masterbatch is the special color masterbatch of PMMA/ASA alloys, and its content of carbon black is 40~70%, and
Using ASA materials as color masterbatch carrier, integral material dyeing and it is scattered on be better than in general colouring aid.
The processing method that above-mentioned heat resistant type exempts to spray PMMA/ASA alloys comprises the following steps：
(1) raw material are weighed according to following proportioning：PMMA resins：50~70 parts, SAN resins：10~20 parts, inorganic nano
Particle：1~5 part, toughener：5~25 parts, boron nitride fiber：1-5 parts, heat-resistant agent：5~15 parts, light diffusing agent：0.5~1 part,
Compatilizer：10-20 parts, processing aid：1~5 part.
(2) raw material weighed are uniformly mixed using mixing equipment, blending on the twin screw extruder is granulated.Extruder
Set technique as：200~240 DEG C of temperature, 300~350r/min of rotating speed；The strip of extrusion is molded through the pelletizing of tank cooling water.
Prior art is compared, and the present invention has following beneficial effect：
1st, the present invention will be in PMMA/ASA alloy systems, and matrix resin PMMA and ASA resin adding proportion are 4-5：1,
Enable the heat resistance of SAN reinforced PMMA resins, and therefore the mechanical property such as hardness, shock resistance does not decline.
2nd, the present invention adds inorganic nano-particle, and nano SiC and nano aluminium oxide are compounded, further through vinyl silicone oil
Coupling processing is carried out to nano SiC, so that the rub of alloy material, wear resistance and case hardness obtain further
Raising, and itself fusing point is high, and heat resistance is also fabulous, can also lift the heat resistance of PMMA/ASA alloys.
3rd, the addition of boron nitride fiber, the heat resistance of PMMA/ASA alloys and firm alloy structure are further lifted,
Enhance the tensile strength and modulus of elasticity of resin alloy.
4th, the addition of organosilicon light diffusing agent so that PMMA/ASA alloy light diffuser efficiency more preferably, brightness it is higher, it is constant
Color, not only lift aesthetics and further lift heat resistance simultaneously.
5th, the particular/special requirement of the invention based on Auto front grille material, further adds heat-resistant agent and toughener, with exploitation
A kind of high brilliant black, exempt from spraying and high heat-resisting PMMA/ASA alloys, and assign the heat resistance of material higher level.
6th, the technological means of materials'use melt blending of the present invention, preparation method technical process is simple, cost is low, obtained
PMMA/ASA alloy resins are particularly suitable for fields such as automobile exteriors.
Embodiment
It is the specific embodiment of the present invention below, technical scheme is further described, but the present invention is simultaneously
It is not limited to these embodiments.
In the examples below that, PMMA resins select the beautiful positive IRD70 of Mitsubishi；D- of the SAN resins from strange beautification work
168；Boron nitride fiber nitrogen content is more than 52%；Ultra-violet absorber and light stabilizer select BASF UV-234 and 770, described
Color masterbatch content of carbon black 50%, the self-control black masterbatch using small particle esters of acrylic acid rubber powder as carrier.
Embodiment 1, toughener are the esters of acrylic acid rubber graft of gel content 30%, and heat-resistant agent selects alpha-alkyl second
Alkene copolymer.
Embodiment 2, toughener are the esters of acrylic acid rubber graft of gel content 40%, and heat-resistant agent selects alpha-alkyl second
10 parts of alkene copolymer and the mixture of 5 parts of maleimide heat-proof agent.
Embodiment 3, toughener are the esters of acrylic acid rubber graft of gel content 50%, and heat-resistant agent maleimide is resistance to
Thermit powder.
Embodiment 4, toughener are the esters of acrylic acid rubber graft of gel content 55%, and heat-resistant agent selects maleimide
5 parts of 5 parts of class, 5 parts of alpha-alkyl phenylethylene copolymer and styrene-maleic anhydride copolymer three's mixtures.
Embodiment 5, toughener are the esters of acrylic acid rubber graft of gel content 60%, and heat-resistant agent selects styrene-horse
Carry out acid anhydride copolymer.
Comparative example 1, toughener are the esters of acrylic acid rubber graft of gel content 50%, and heat-resistant agent selects alpha-alkyl second
Alkene copolymer.
Comparative example 2, toughener are the esters of acrylic acid rubber graft of gel content 50%, and heat-resistant agent selects styrene-horse
Carry out acid anhydride copolymer.
Comparative example 3, toughener are the esters of acrylic acid rubber graft of gel content 50%.
Table 1：Embodiment 1-5 and comparative example 1-3PMMA/ASA alloying components and parts by weight
Specific preparation and its method of evaluating performance：
Raw material in embodiment 1~5 and comparative example 1~3 are uniformly mixed using mixing equipment, in double screw extruder
Upper blending is granulated.And carry out melting extrusion with extruder；The strip of extrusion is molded through the pelletizing of tank cooling water.Drying at room temperature 24h
After carry out performance measurement.
Extruder technique initialization：
Embodiment 1,200 DEG C of temperature, rotating speed 300r/min.
Embodiment 2,210 DEG C of temperature, rotating speed 310r/min.
Embodiment 3,220 DEG C of temperature, rotating speed 320r/min.
Embodiment 4,230 DEG C of temperature, rotating speed 330r/min.
Embodiment 5,240 DEG C of temperature, rotating speed 350/min.
Comparative example 1,220 DEG C of temperature, rotating speed 320r/min.
Comparative example 2,220 DEG C of temperature, rotating speed 320r/min.
Comparative example 3,220 DEG C of temperature, rotating speed 320r/min.
Melt index：Carried out according to ISO 1133-1 standards, test condition is：220 DEG C, load 10kg；
Tensile strength：Carried out according to ISO 527-2 standards, test condition is：Draw speed 50mm/min；
Bending strength：Carried out according to the standards of ISO 178, test condition is：Rate of bending 2mm/min；
Bending modulus：Carried out according to the standards of ISO 178, test condition is：Rate of bending 2mm/min；
Heat distortion temperature：Carried out according to ISO 75-2 standards, test condition is：Load 0.45MPa, 120 DEG C of heating rate/
min；
Izod notched impact strength：Carried out according to the standards of ISO 180, test condition is：Under normal temperature, 2mm breach；
Glossiness：Carried out according to ASTM D523 standards, test angle is 60 °；
Pencil hardness：Carried out according to the standards of GB/T 6739, test condition is：45° angle, HB pencils, speed：1cm/s；
Table 2：PMMA/ASA alloy performance tests in embodiment 1-5 and comparative example 1-3
It can be drawn by the test result of comparative example 3 of comparing embodiment 1,2,3, increased in PMMA/ASA formula systems
Maleimide heat-proof agent can be obviously improved materials hot deformation temperature, and comparative example 3,4,5 and comparative example 1 can be drawn
Glossiness raises, comparative example 1,3 with the increase of organosilicon photochemical catalyst, 4,5 and comparative example 2 it can be seen that
Boron nitride fiber is added in PMMA/ASA formula systems can strengthen tensile strength and bending modulus, comparative example 1,3,5 and right
Ratio 1 can be seen that the nano SiC of different proportion and nano aluminium oxide has an impact to material thermal resistance and mechanical property, not be
Add more or more few better.
Exempt to spray PMMA/ASA alloy materials the present invention is to provide a kind of heat resistant type, purport is directed to radiator grid before automobile
Product is changed into heat-resisting bloom is black by spraying level exempts to spray level.The material of invention is not limited to automobile grills product, for automobile
Other positions to exempt from sprayed on material equally applicable.Concrete application approach of the present invention is a lot, and described above is only the preferred of the present invention
Embodiment.In above-mentioned patent, the direction of the present invention certain journey can be subjected to by increasing fire retardant or antistatic additive
The extension of degree.Increasing appropriate fire retardant systems, the present invention can expanded and exempt to spray PMMA/ASA alloys for heat-proof combustion-resistant；
After the antistatic additive that suitably matches of addition, this invention also may extend away heat-resisting exempts to spray PMMA/ASA alloys to be antistatic.
It should be pointed out that above example is merely to illustrate the present invention, and the protection domain being not intended to limit the invention.It is right
For those skilled in the art, under the premise without departing from the principles of the invention, some improvement can also be made,
These improvement also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of automobile-used resistance to thermal level exempts to spray PMMA/ASA alloys, it is characterised in that described alloy includes following parts by weight
Component：
PMMA resins：50~70 parts,
SAN resins：10~20 parts,
Inorganic nano-particle：1~5 part,
Toughener：5~25 parts,
Boron nitride fiber：1-5 parts,
Heat-resistant agent：5~15 parts,
Light diffusing agent：0.5~1 part,
Compatilizer：10-20 parts,
Processing aid：1~5 part.
2. the automobile-used resistance to thermal level of one kind according to claim 1 exempts to spray PMMA/ASA alloys, it is characterised in that the PMMA
Resin pencil hardness is 5~9H, and Vicat softening point is 90~100 DEG C under the conditions of 50N is loaded.
3. the automobile-used resistance to thermal level of one kind according to claim 1 or 2 exempts to spray PMMA/ASA alloys, it is characterised in that described
PMMA resins and SAN weight resins ratio be 4-5:1.
4. the automobile-used resistance to thermal level of one kind according to claim 1 exempts to spray PMMA/ASA alloys, it is characterised in that described nothing
Machine nano-particle is the mixing material of nano SiC and nano aluminium oxide, and the mass ratio of nano SiC and nano aluminium oxide is 2-4：1.
5. a kind of automobile-used resistance to thermal level according to claim 1 or 4 exempts to spray PMMA/ASA alloys, it is characterised in that described
Nano SiC be through vinyl silicone oil couple processing after nano SiC.
6. the automobile-used resistance to thermal level of one kind according to claim 1 exempts to spray PMMA/ASA alloys, it is characterised in that the toughness reinforcing
Agent is the esters of acrylic acid rubber graft of gel content 30~60%.
7. the automobile-used resistance to thermal level of one kind according to claim 1 exempts to spray PMMA/ASA alloys, it is characterised in that described nitrogen
Change boron fibre nitrogen content and be more than 52%.
8. the automobile-used resistance to thermal level of one kind according to claim 1 exempts to spray PMMA/ASA alloys, it is characterised in that described heat-resisting
Agent is at least one of maleimide, alpha-alkyl phenylethylene copolymer, styrene-maleic anhydride copolymer.
9. the automobile-used resistance to thermal level of one kind according to claim 1 exempts to spray PMMA/ASA alloys, it is characterised in that described light
Diffusant is organosilicon light diffusing agent.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107778750A (en) * | 2017-11-08 | 2018-03-09 | 上海倍聚兰科技有限公司 | A kind of weather-proof intermingling material with high brightness metal-like of damage resistant |
| 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 |
| CN113136077A (en) * | 2021-04-01 | 2021-07-20 | 广州市聚赛龙工程塑料股份有限公司 | PMMA/ASA alloy material and preparation method and application thereof |
| CN113278240A (en) * | 2021-05-25 | 2021-08-20 | 贵州省材料产业技术研究院 | High-heat-resistance high-toughness light diffusion PMMA alloy material for vehicle and preparation method thereof |
| EP3778767A4 (en) * | 2019-02-19 | 2021-08-25 | Lg Chem, Ltd. | Thermoplastic resin composition and thermoplastic resin molded article |
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