CN107915948A - A kind of low smell sterilization reinforced ABS automobile rearview mirror frame material and preparation method - Google Patents
A kind of low smell sterilization reinforced ABS automobile rearview mirror frame material and preparation method Download PDFInfo
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- CN107915948A CN107915948A CN201711292322.8A CN201711292322A CN107915948A CN 107915948 A CN107915948 A CN 107915948A CN 201711292322 A CN201711292322 A CN 201711292322A CN 107915948 A CN107915948 A CN 107915948A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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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
Abstract
The invention discloses a kind of low smell sterilization reinforced ABS automobile rearview mirror frame material and preparation method.The automobile rearview mirror frame material is prepared by weight by ABS, short glass fiber, toughener, compatilizer, grafting and coating filler, heat stabilizer, low volatility materials adsorbent, bag shoe processing catabolic enzyme, nano photo-catalytic, antioxidant, ultraviolet absorber, the agent of anti-floating fibre, lubricant.The low volatility materials adsorbent that the present invention uses has very strong adsorption capacity, can effectively prevent the molding component of composite material from producing low volatility pernicious gas to external diffusion；Bag carries out processing catabolic enzyme and the micro low volatility pernicious gas of generation is resolved into harmless carbon dioxide and water by nano photo-catalytic, material of the present invention has good physical mechanical property, heat aging property and weather resistance, stress crack resistant, corrosion-resistant, vibration resistance, scratch-resistant, low smell, low TVOC contents, available for production automotive rear-view mirror holder.
Description
Technical field
The present invention relates to the technical field of modification of ABS material, and in particular to a kind of low smell sterilization reinforced ABS automotive rear-view
Mirror holder material and preparation method.
Background technology
ABS resin has excellent impact resistance, heat resistance, lower temperature resistance, chemical proofing, electric property, at the same time also
With it is easy to process, product size is stable, lustrous surface is good, easy application and coloring, easily carries out surface metallization and electricity
The features such as plating.Due to being largely used to manufacture automotive upholstery with good comprehensive performance, ABS material.
Rearview mirror bracket, which is arranged on, drives indoor middle part, and driver is looked behind by it；Rearview mirror for automobiles frame material one
As use glass fiber enhanced nylon, sail outdoor for frame.Benzene homologues and aldehyde system thing can be volatilized in ABS material, the TVOC of ABS is put down
In 30-50, emission belongs to medium, can jeopardize the physical and mental health of consumer, therefore reduces the odor properties of ABS material,
The regulation that country puts into effect in March, 2012 can be complied with --《Air Quality Evaluation guide in passenger car》To automotive interior material
Basic demand, it is really become a environment-friendly materials.
Chinese invention patent application CN102532792A discloses a kind of low smell, antibacterial ABS material and preparation method thereof,
It is mentioned that with diatomite, zeolite and magnesia composition odor suppressing agents, with cupric oxide and zinc oxide make antiseptic.Smell presses down
Preparation is that low waving property small molecule is adsorbed by itself huge specific surface area, but absorption has saturability, which makes
Antiseptic is inorganic antiseptic, and efficiency is low, and to effect of the sterilizing rate up to 99.9%, addition needs very big, this is by shadow
Ring the physical mechanical property of base material.
Chinese invention patent application CN103724922A discloses a kind of low smell fiber glass reinforced ABS composition and its preparation
Method, this application use the jellyfish grain using high flux foaming PP as carrier to be used as stripping agent；The small molecule volatilized in ABS material
Material mainly includes benzene homologues and aldehyde system thing, after water enters resin, can take away the aldehyde system thing in ABS, and benzene homologues do not dissolve in
Water, it is impossible to removed with the evaporation of water, though can be by foaming PP absorption, the specific surface area of the material is relatively small, if to increase
Strong adsorption effect, dosage requirement is very big, so has a great influence to the mechanical property of materials, which has certain limitation
Property.
The content of the invention
Existing in the prior art in order to solve the problems, such as, it is an object of the invention to propose a kind of low smell sterilization reinforced ABS
Automobile rearview mirror frame material and preparation method；The material has good physical mechanical property, heat aging property and weatherability
Energy, stress crack resistant, corrosion-resistant, vibration resistance, scratch-resistant, low smell, low TVOC contents, sterilizing function, good processing performance,
The features such as appearance is bright and clean beautiful.
In inventive formulation nano photo-catalytic can adsorb and decomposing material in itself and material peripheral Environment release go out it is low
VOC pernicious gases, including the organic compound such as aldehydes, benzene class, ammonia, TVOC, doped compound nano silver in nano photo-catalytic, therefore
With very strong bactericidal effect, but nano material common feature is to be easy to reunite, and addition is restricted, present invention adds
Micron order bag carries out processing catabolic enzyme, and dispersion effect is significantly better than nanometer light catalyst, becomes the capable helper of nano photo-catalytic, can
Greatly improve the effect for decomposing low VOC pernicious gases and organic pollution.
The present invention sails indoor rearview mirror bracket using fiber glass reinforced ABS composite material to make frame, low with cost, weather-proof
And good mechanical performance, dimensionally stable, low smell and there is sterilizing function.
In order to complete the purpose of the present invention, the technical solution that uses for：
A kind of low smell sterilization reinforced ABS automobile rearview mirror frame material, in terms of weight fraction, raw material composition includes：
The grafting and coating filler is by the calcium sulfate crystal whiskers of AS grafting and coatings and the calcium sulfate of AS-co-SBR grafting and coatings
Whisker in mass ratio 2:1-1:1 mixing gained；
The bag carries out the catabolic enzyme that processing catabolic enzyme is ECO Co., Ltd. of Japan model ECO-E；
The nano photo-catalytic is Co., Ltd. Lang Jinusi model KV-1N photocatalysts.
What the component that the present invention carries out processing catabolic enzyme, nano photo-catalytic using bag and can form the material into produced micro low waves
The low volatility pernicious gas that hair property pernicious gas and the member perimeter environment produce resolves into harmless carbon dioxide and water, receives
Nano silver in rice photocatalyst can also kill bacterium and decomposing organic pollutant, and organic pollution is resolved into free of contamination water
And carbon dioxide；The present invention uses grafting and coating filler so that the physical mechanical property of fiber glass reinforced ABS material obtains substantially
Improve, it is more preferable more resistant to stress cracking, dimensional stability higher, that resist warping deformation；This three can ensure purpose of the present invention reality
It is existing；And preferable ABS, short glass fiber, toughener, compatilizer, heat stabilizer, low volatile matter adsorbent, the agent of anti-floating fibre,
Antioxidant, uvioresistant auxiliary agent and lubricant contribute to the performance of respective function, and have certain synergistic effect, can be preferably
Realize the object of the invention.
The bag carries out processing catabolic enzyme and is purchased from ECO Co., Ltd. of Japan, and model ECO-E, is that one kind can be with resistance to 350 DEG C
The micron order complex compound of above high temperature, main ingredient are micron order phosphoric acid titanium dioxide, are handled through special parcel, scattered, no
Easily reunite, do not influence using effect, can have light or it is unglazed under conditions of water in catalytic air and oxygen oxidation occurs also
Original reaction, produces hydroxyl free radical and negative oxygen ion with Strong oxdiative, causes the associative key of organic compound gas intramolecular
Fracture, is broken down into harmless carbon dioxide and water and long-term negative ion release.Bag is carried out processing catabolic enzyme and can effectively be decomposed
The organic compounds such as formaldehyde, benzene, ammonia, TVOC, to environment non-secondary pollution.Bag carries out the portion that processing catabolic enzyme can form the material into
The low volatility materials that part and the member perimeter environment produce resolve into harmless carbon dioxide and water, and bag, which carries out processing catabolic enzyme, is
The important synergist of nano photo-catalytic.
The nano photo-catalytic is purchased from Co., Ltd. Lang Jinusi, and trade name LONGINUS, model KV-1N, makes
Smaller than general nano-titanium dioxide with 1-3nm grade titanium dioxides, particle diameter, specific surface area bigger, reactivity higher, urges light
Change performance to greatly promote, while doped compound nano silver, rare earth element in titanium dioxide, and it is unique using international advanced doping
Technology, doping metals cation and anionic part, greatly promote photocatalysis performance, spectral response range lifting to full light
Spectrum.Redox reaction can occurs in the water in catalytic air under conditions of full spectrum and oxygen in it, and generation has Strong oxdiative
Hydroxyl free radical and negative oxygen ion, cause the associative key of organic compound gas intramolecular to be broken, can effectively decompose aldehydes,
The organic compounds such as benzene class, ammonia, TVOC, are broken down into harmless carbon dioxide and water and long-term negative ion release, to environment
Non-secondary pollution.The composite nano silver adulterated in titanium dioxide, can destroy the cell membrane of bacterium and cure the protein of virus, can
Bacterium and decomposing organic pollutant are killed, organic pollution is resolved into free of contamination water (H2) and carbon dioxide (CO O2), thus
Closing can be effectively purified with extremely strong sterilization, deodorization, mould proof, anti-fouling and self-cleaning, air purification function, therefore nano photo-catalytic
Air in space.
Further to realize the object of the invention, it is preferable that the ABS (acrylonitrile-butadiene-styrene copolymer) is
One kind in medium impact strength or high impact strength.Medium impact strength type ABS is preferably that Taiwan is strange beautiful
PA757。
Preferably, the short glass fiber is E type short glass fibers.E type short glass fibers are preferably megalith
ECS13-4.5-534A types, the short glass fiber had been subjected to before dispatching from the factory silane coupling agent processing.
Preferably, the toughener is Methyl Methacrylate-Butadiene-Styrene Copolymer (MBS).MBS is one
Kind nucleocapsid structure toughener, good with ABS compatibilities, room temperature toughening effect and low temperature toughening effect are excellent, do not interfere with resistance to
It is hot, it is small on weatherability influence, and there are low odor characteristics.The EXL 2602 of the preferred model ROHM AND HAASs of MBS.
Preferably, the compatilizer is acrylonitrile, maleic anhydride and polystyrene ternary random copolymer, is had high resistance to
Heat, compatibility is excellent, good environmental stress crack resistance, good fluidity, can effectively improve the physical mechanical property of reinforced ABS；
The SMA800 of the preferred Shanghai Hua Wen of compatilizer.
Preferably, the anti-floating fibre agent is the hydroxyl telechelic polyester with dissaving structure.The preferably hyperbranched tree in Wuhan
The Hyper C100 of fat Science and Technology Ltd.；Such anti-floating fibre agent contains the new of " hyperbranched " (specific functional groups dendroid) structure
Generation high molecular weight, non-volatile, the fabulous energy conservation and environmental protection resin with various plastics, filler compatibility, in space chondritic, tool
There are smaller hydrodynamic radius, show notable lubricity low melt viscosity characteristic, its special construction can be penetrated into strand
Portion, reduces the active force of molecule interchain, drives strand quickly to move, reduces processing temperature, improves melt index, improves filler
Dosage easily realizes thin-walled, the injection of long flow, few addition to reduce cost, eliminate " sharkskin " phenomenon, floating fine phenomenon
Amount, it is possible to the mobility of resin is increased substantially, for floating fine improvement, significant effect.
Preferably, the low volatile matter adsorbent be nano silicon dioxide, zeolite molecular sieve, calcined diatomite it is (flat
Equal particle diameter is 5-10 μm) it is (0.5-1.5) in mass ratio：(1‐3)：(0.5-1.5) is formed.Nano silicon dioxide, zeolite molecules
Sieve, calcined diatomite suffer from very big specific surface area, and adsorption capacity is strong, and combining effectively to produce in sorbing material
Raw low volatility pernicious gas, the average grain diameter of calcined diatomite is 5-10 μm；But the adsorbent only helps out.
Preferably, the antioxidant is the Winox of Irganox1076 and Irganox168 and the Mu Nan chemical industry of vapour bar
GS antioxidant in mass ratio 2：1：1 mixing gained.Winox GS antioxidant coordinates with other antioxidant, can effectively prevent ABS
This kind of macromolecule degraded containing double bond.
Preferably, the heat stabilizer for acrylonitrile with styrol copolymer connecing with glycidyl methacrylate
Skill thing, grafting rate is 5% or so.Heat stabilizer is preferably preferred the SAG-005 easily held, and the heat stabilizer and antioxidant coordinate can be with
Effectively prevent high molecular material and other auxiliary materials from degrading and producing small-molecule substance, to reducing having for low volatility materials
Certain effect.
Preferably, the uvioresistant auxiliary agent is the combination of one or both of UV770 and UV5411；It is preferred that anti-purple
Outside line auxiliary agent presses 1 for UV770 and UV5411：1 mass ratio is used in mixed way.The lubricant is pentaerythrite hard acid esters.Profit
Lubrication prescription is preferably the Lonza in the U.S..
The preparation method of the low smell sterilization reinforced ABS automobile rearview mirror frame material, includes the following steps：
(1) ABS, short glass fiber, compatilizer, low volatile matter adsorbent, bag are first carried out into processing catabolic enzyme, nanometer light
Catalyst is respectively dried spare；
(2) in terms of weight fraction, by 23.6-62.7 parts ABS parts, 5-10 parts of toughener, 4-8 parts of compatilizer, heat stabilizer
0.1-0.3 parts, 5-15 parts of grafting and coating filler, 1-4 parts of the low volatile matter adsorbent dried, 0.1-0.5 parts of antioxidant,
0.3-0.6 parts of uvioresistant auxiliary agent, 0.5-1 parts of anti-floating fibre agent, 0.5-2 parts of lubricant, sequentially adds in high-speed mixer, mixing
5-10 minutes, obtain mixture component A；
(3) in terms of weight fraction, 20-30 parts of the short glass fiber dried is B component；
(3) bag dried shoe processing catabolic enzyme, nano photo-catalytic are mixed together uniformly, obtain mixture component C；
(4) component A is added from the main spout of double screw extruder, B component is fed from the first side of double screw extruder
Material mouth adds, and component C is added in the second side spout of double screw extruder, and 210 DEG C -240 is passed through in double screw extruder
DEG C melting mixing, water cooled, tie rod, air-dries, pelletizing, and low smell sterilization reinforced ABS automobile rearview mirror frame material is made；
The grafting and coating filler is prepared via a method which：
1) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches more than 110 DEG C, by the water in whisker
Divide and remove, then add acrylonitrile, styrene and copolymer-maleic anhydride in high-speed mixer, maintain temperature to be not less than 100
DEG C, it is blended 20-40 minutes, is cooled to less than 40 DEG C, the calcium sulfate crystal whiskers of AS grafting and coatings is made；Calcium sulfate crystal whiskers and propylene
Nitrile, the mass ratio of styrene and maleic anhydride (SMA800 of Shanghai Hua Wen) are 100:2；
2) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches more than 110 DEG C, by the water in whisker
Divide and remove, then add acrylonitrile, styrene, butadiene-styrene rubber and copolymer-maleic anhydride in high-speed mixer, maintain temperature
Not less than 100 DEG C, it is blended 20-40 minutes, is cooled to 40 DEG C, is made as the calcium sulfate crystal whiskers of AS-co-SBR grafting and coatings；Sulphur
The mass ratio of sour calcium pyroborate and acrylonitrile, styrene, butadiene-styrene rubber and copolymer-maleic anhydride (HW-100M of Shanghai Hua Wen) is
100:2；
3) in use, the calcium sulfate crystal whiskers of the calcium sulfate crystal whiskers of AS grafting and coatings and AS-co-SBR grafting and coatings are pressed matter
Measure ratio 2:1‐1:1 mixing.
Grafting and coating filler of the present invention is grafting and coating calcium sulfate crystal whiskers, including two kinds, first, acrylonitrile and styrene
The calcium sulfate crystal whiskers of copolymer (AS) grafting and coating, second, the sulphur that acrylonitrile is coated with styrene and butadiene-styrene rubber copolymer grafted
Sour calcium pyroborate (AS-co-SBR).The calcium sulfate crystal whiskers of AS grafting and coatings press one with the calcium sulfate crystal whiskers of AS-co-SBR grafting and coatings
The mixture of certainty ratio composition is filled ABS, can further improve the heat resistance of material, tensile strength, impact flexibility,
Bending modulus, corrosion resistance and resistance to warping, improve its dimensional stability, improve surface smoothness.With common silane coupling agent
The calcium sulfate crystal whiskers of processing are compared, and scattered to be more uniformly distributed, its tensile strength, impact strength are significantly improved.
Calcium sulfate crystal whiskers are fibrous monocrystal, have high intensity, high-modulus, high tenacity, high-insulativity, abrasion performance, resistance to
High temperature, it is anticorrosive, be easy to surface treatment, easily with compound, nontoxic, the inexpensive many excellent reasons of polymer (such as rubber, plastics)
Change performance, can be as the toughened and reinforced material of plastic cement.Calcium sulfate crystal whiskers are preferably the NP-S04 of Jiangxi peak Zhu.
The present invention has the advantages that：
This ABS material through modification, have good physical mechanical property, heat aging property and weather resistance, it is resistance to should
Power cracking, corrosion-resistant, vibration resistance, scratch-resistant, low smell, low TVOC contents, sterilizing function, good processing performance, outer mass color
Clean beauty, can be used for the car stand room of sailing and manufactures rearview mirror bracket.
It is 0.7 in mass ratio by nano silicon dioxide, zeolite molecular sieve, calcined diatomite (average grain diameter is 5-10 μm)：
2.2：The low volatile matter adsorbent of 1.3 compositions, adsorption capacity is strong, combines, and has cooperative effect, can effectively adsorb
The low volatility pernicious gas produced in material.
The special packet that is added in ABS material carries out the catabolic enzyme of processing, it be it is a kind of can be with the micron of resistance to more than 350 DEG C high temperature
Level complex compound, is easily dispersed, is not easy to reunite, and can produce the molding component of low smell ABS material and the member perimeter environment
Low volatility materials resolve into harmless carbon dioxide and water.Bag carries out the important synergistic that processing catabolic enzyme is nano photo-catalytic
Agent.
The micro nano photo-catalytic being mixed with ABS material, it can be in the water in catalytic air under conditions of full spectrum
Redox reaction occurs with oxygen, produces hydroxyl free radical and negative oxygen ion with Strong oxdiative, causes organic compound gas
The associative key fracture of body intramolecular, can effectively decompose the organic compounds such as aldehydes, benzene class, ammonia, TVOC, be broken down into harmless
Carbon dioxide and water and long-term negative ion release, to environment non-secondary pollution.The composite nano silver adulterated in titanium dioxide, energy
Destroy the cell membrane of bacterium and cure the protein of virus, bacterium and decomposing organic pollutant can be killed, organic pollution point
Solution is into free of contamination water (H2) and carbon dioxide (CO O2), thus with extremely strong sterilization, deodorization, mould proof, anti-fouling and self-cleaning, purification
Air function, therefore nano photo-catalytic can effectively purify the air on inside-automobile rear mirror frame periphery.
Catabolic enzyme, the nano photo-catalytic that addition low volatile matter adsorbent, special packet shoe are handled in material form compound
Air purifying preparation, can effectively purify the air in the material components surrounding enviroment.
1st, preparation method simple process and low cost provided by the invention, it is easily operated.
2nd, the present invention, which provides low smell, has the judgment criteria of the odor profiles qualitative and quantitative of the ABS material of sterilizing function,
Smell is tested and smell judges that grade performs the PV3900 standards of Volkswagen, and the total volatile organic compounds quantitatively detected contains
The PV3341 standards that (TVOC) performs Volkswagen are measured, the accuracy and precision of TVOC contents evaluation can be improved, are killed thin
Bacterium effect performs GB15981 testing standards.
Embodiment
To be best understood from the present invention, with reference to embodiment, the invention will be further described, and following embodiments are only pair
The present invention illustrates rather than it is limited.The embodiment of the present invention is only limitted to solved further to the present invention
Release and illustrate, be not intended to limit protection scope of the present invention.
Embodiment 1
(1) production method of grafting and coating filler：
1) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches 110 DEG C, and the moisture in whisker is gone
Fall, then add acrylonitrile, styrene and copolymer-maleic anhydride (SMA800 of Shanghai Hua Wen) in high-speed mixer, maintain
Temperature is not less than 100 DEG C, is blended 26 minutes, is cooled to 40 DEG C, you can taking-up is spare, and the calcium sulfate for being known as AS grafting and coatings is brilliant
Palpus.
2) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches 110 DEG C, and the moisture in whisker is gone
Fall, then add acrylonitrile and styrene and butadiene-styrene rubber at a high speed with copolymer-maleic anhydride (HW-100M of Shanghai Hua Wen)
In mixer, maintain temperature to be not less than 100 DEG C, be blended 25 minutes, be cooled to 40 DEG C, you can take out spare, referred to as AS-co-
The calcium sulfate crystal whiskers of SBR grafting and coatings.
3) in use, being needed to be grafted calcium sulfate crystal whiskers in mass ratio 3 by two kinds according to performance:2 mixing.
(2) main material making step：
(1) first by ABS (PA757), short glass fiber (ECS13-4.5-534A types), compatilizer SMA800, low volatilization
(nano silicon dioxide, zeolite molecular sieve, calcined diatomite (average grain diameter is 5-10 μm) are 1 in mass ratio to substance adsorber：2：
1 composition；The average grain diameter of calcined diatomite be 5-10 μm), bag carry out processing catabolic enzyme (be purchased from ECO Co., Ltd. of Japan, model
ECO-E), nano photo-catalytic (being purchased from Co., Ltd. Lang Jinusi, trade name LONGINUS, model KV-1N) is respectively dried
It is spare.
(2) in terms of weight fraction, by 67.45 parts of PA757, toughener EXL 2602 is 4 parts, and compatilizer SMA800 is 3 parts,
Heat stabilizer SAG-005 is 0.2 part, 5 parts of grafting and coating calcium sulfate crystal whiskers (3 parts of the calcium sulfate crystal whiskers of AS grafting and coatings, AS-co-
2 parts of the calcium sulfate crystal whiskers of SBR grafting and coatings), 2 parts of the low volatile matter adsorbent dried, 0.4 part of antioxidant, uvioresistant
0.3 part of auxiliary agent (UV770 is 0.15 part, and UV5411 is 0.15 part), anti-floating fibre agent Hyper C100 are 0.6 part, lubricant (season penta
Tetrol hard acid esters) 0.5 part, sequentially add in high-speed mixer, mix 6 minutes, obtain mixture component A.
(3) it is B component by 15 parts of the short glass fiber dried in terms of weight fraction.
(4) in terms of weight fraction, dried 0.95 part of bag is carried out into processing catabolic enzyme, 0.6 part of nano photo-catalytic mixes together
Close uniformly, obtain mixture component C.
(5) component A is added from the main spout of double screw extruder, B component is fed from the first side of double screw extruder
Material mouth adds, and component C is added in the second side spout of double screw extruder, and 210 DEG C -240 is passed through in double screw extruder
DEG C melting mixing, water cooled tie rod air-dries pelletizing and is made.The particle injection molding sample preparation on injection molding machine after drying.
Embodiment 2
(1) production method of grafting and coating filler
1) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches 110 DEG C, and the moisture in whisker is gone
Fall, then add acrylonitrile, styrene and copolymer-maleic anhydride in high-speed mixer, maintain temperature to be not less than 100 DEG C, altogether
It is 20 minutes mixed, it is cooled to 40 DEG C, you can taking-up is spare, is known as the calcium sulfate crystal whiskers of AS grafting and coatings.
2) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches 110 DEG C, and the moisture in whisker is gone
Fall, then add acrylonitrile and styrene and butadiene-styrene rubber at a high speed with copolymer-maleic anhydride (HW-100M of Shanghai Hua Wen)
In mixer, maintain temperature to be not less than 100 DEG C, be blended 30 minutes, be cooled to 40 DEG C, you can take out spare, referred to as AS-co-
The calcium sulfate crystal whiskers of SBR grafting and coatings.
(3) in use, being needed to be grafted calcium sulfate crystal whiskers in mass ratio 4 by two kinds according to performance:3 mixing.
(2) main material making step：
(1) first by ABS (PA757), short glass fiber (ECS13-4.5-534A types), compatilizer SMA800, low volatilization
(nano silicon dioxide, zeolite molecular sieve, calcined diatomite (average grain diameter is 5-10 μm) are 0.7 in mass ratio to substance adsorber：
2.2：1.3 composition；The average grain diameter of calcined diatomite be 5-10 μm), bag carry out processing catabolic enzyme (be purchased from ECO Co., Ltd. of Japan,
Model ECO-E), nano photo-catalytic (being purchased from Co., Ltd. Lang Jinusi, trade name LONGINUS, model KV-1N) point
It is not dried for standby.
(2) in terms of weight fraction, by 58.05 parts ABS parts, toughener EXL 2602 is 5 parts, and compatilizer SMA800 is 4 parts,
Heat stabilizer SAG-005 is 0.2 part, 7 parts of grafting and coating calcium sulfate crystal whiskers (4 parts of the calcium sulfate crystal whiskers of AS grafting and coatings, AS-co-
3 parts of the calcium sulfate crystal whiskers of SBR grafting and coatings), 2.2 parts of the low volatile matter adsorbent dried, 0.4 part of antioxidant, uvioresistant
0.3 part of line auxiliary agent (UV770 is 0.15 part, and UV5411 is 0.15 part), anti-floating fibre agent Hyper C100 are 0.7 part, lubricant (season
Penta tetrol hard acid esters) 0.5 part, sequentially add in high-speed mixer, mix 10 minutes, obtain mixture A, abbreviation component A.
(3) in terms of weight fraction, 20 parts of the short glass fiber dried is B component.
(4) in terms of weight fraction, dried 1 part of bag is carried out into processing catabolic enzyme, 0.65 part of nano photo-catalytic is mixed together
Uniformly, mixture C, abbreviation component C are obtained.
(5) component A is added from the main spout of double screw extruder, B component is fed from the first side of double screw extruder
Material mouth adds, and component C is added in the second side spout of double screw extruder, and 210 DEG C -240 is passed through in double screw extruder
DEG C melting mixing, water cooled tie rod air-dries pelletizing and is made.The particle injection molding sample preparation on injection molding machine after drying.
Embodiment 3
(1) production method of grafting and coating filler
1) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches 110 DEG C, and the moisture in whisker is gone
Fall, then add acrylonitrile, styrene and copolymer-maleic anhydride in high-speed mixer, maintain temperature to be not less than 100 DEG C, altogether
It is 30 minutes mixed, it is cooled to 40 DEG C, you can taking-up is spare, is known as the calcium sulfate crystal whiskers of AS grafting and coatings.
2) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches 110 DEG C, and the moisture in whisker is gone
Fall, then add acrylonitrile, styrene, butadiene-styrene rubber and copolymer-maleic anhydride (HW-100M of Shanghai Hua Wen) mixed at a high speed
In conjunction machine, maintain temperature to be not less than 100 DEG C, be blended 20 minutes, be cooled to 40 DEG C, you can take out spare, referred to as AS-co-SBR
The calcium sulfate crystal whiskers of grafting and coating.
3) in use, being needed to be grafted calcium sulfate crystal whiskers in mass ratio 1 by two kinds according to performance:1 mixing.
(2) main material making step：
(1) first by ABS (PA757), short glass fiber (ECS13-4.5-534A types), compatilizer (EXL 2602), low
Volatile substance adsorbent, bag shoe processing catabolic enzyme, nano photo-catalytic are respectively dried spare.
(2) in terms of weight fraction, by 46.2 parts ABS parts, toughener EXL 2602 is 7 parts, and compatilizer SMA800 is 5 parts,
Heat stabilizer SAG-005 is 0.2 part, 10 parts of grafting and coating calcium sulfate crystal whiskers (5 parts of the calcium sulfate crystal whiskers of AS grafting and coatings, AS-
5 parts of the calcium sulfate crystal whiskers of co-SBR grafting and coatings), 2.4 parts of the low volatile matter adsorbent dried, 0.4 part of antioxidant, anti-purple
0.3 part of outside line auxiliary agent (UV770 is 0.15 part, and UV5411 is 0.15 part), anti-floating fibre agent Hyper C100 are 0.8 part, lubricant
0.7 part of (pentaerythrite hard acid esters), sequentially adds in high-speed mixer, mixes 5 minutes, obtains mixture component A.
(3) in terms of weight fraction, 25 parts of the short glass fiber dried is B component.
(4) in terms of weight fraction, dried 1.2 parts of bags are carried out into processing catabolic enzyme, 0.8 part of nano photo-catalytic is mixed together
Uniformly, mixture C, abbreviation component C are obtained.
(5) component A is added from the main spout of double screw extruder, B component is fed from the first side of double screw extruder
Material mouth adds, and component C is added in the second side spout of double screw extruder, and 210 DEG C -240 is passed through in double screw extruder
DEG C melting mixing, water cooled tie rod air-dries pelletizing and is made.The particle injection molding sample preparation on injection molding machine after drying.
Comparative example 1
(1) production method of grafting and coating filler：With embodiment 1
(2) main material making step：
(1) first ABS (PA757), short glass fiber (ECS13-4.5-534A types), compatilizer SMA800 are respectively dried
It is spare.
(2) in terms of weight fraction, by 61.9 parts ABS parts, toughener EXL 2602 is 5 parts, and compatilizer SMA800 is 4 parts,
Heat stabilizer SAG-005 is 0.2 part, 7 parts of grafting and coating calcium sulfate crystal whiskers (4 parts of the calcium sulfate crystal whiskers of AS grafting and coatings, AS-co-
3 parts of the calcium sulfate crystal whiskers of SBR grafting and coatings), 0.4 part of antioxidant, (UV770 is 0.15 part to uvioresistant auxiliary agent, and UV5411 is
0.15 part) 0.3 part, anti-floating fibre agent Hyper C100 are 0.7 part, and 0.5 part of lubricant (pentaerythrite hard acid esters), sequentially adds
In high-speed mixer, mix 6 minutes, obtain mixture component A.
(3) it is B component by 20 parts of the short glass fiber dried in terms of weight fraction.
(4) component A is added from the main spout of double screw extruder, B component is fed from the first side of double screw extruder
Material mouth adds, and 210 DEG C -240 DEG C of melting mixing is passed through in double screw extruder, and water cooled tie rod air-dries pelletizing and is made.Grain
The sub injection molding sample preparation on injection molding machine after drying.
Comparative example 2
(1) production method of grafting and coating filler：
Calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches 110 DEG C, by the removing moisture in whisker,
Then silane coupling A -172 is added in high-speed mixer, maintains temperature to be not less than 100 DEG C, be blended 20 minutes, be cooled to
40 DEG C, silane coupling agent grafting and coating calcium sulfate crystal whiskers are obtained, are taken out spare.
(2) main material making step：
(1) first by ABS (PA757), short glass fiber (ECS13-4.5-534A types), compatilizer SMA800, low volatilization
(nano silicon dioxide, zeolite molecular sieve, calcined diatomite (average grain diameter is 5-10 μm) are 1 in mass ratio to substance adsorber：2：
1 composition；The average grain diameter of calcined diatomite be 5-10 μm), bag carry out processing catabolic enzyme (be purchased from ECO Co., Ltd. of Japan, model
ECO-E), nano photo-catalytic (being purchased from Co., Ltd. Lang Jinusi, trade name LONGINUS, model KV-1N) is respectively dried
It is spare.
(2) in terms of weight fraction, by 58.05 parts ABS parts, toughener EXL 2602 is 5 parts, and compatilizer SMA800 is 4 parts,
Heat stabilizer SAG-005 is 0.2 part, and 7 parts of the silane coupling agent grafting and coating filler prepared with step (1), what is dried is low
2.2 parts of volatile substance adsorbent, 0.4 part of antioxidant, (UV770 is 0.15 part to 0.3 part of uvioresistant auxiliary agent, UV5411 0.15
Part), anti-floating fibre agent Hyper C100 are 0.7 part, and 0.5 part of lubricant (pentaerythrite hard acid esters), sequentially adds mixed at high speed
In machine, mix 6 minutes, obtain mixture component A.
(3) it is B component by 20 parts of the short glass fiber dried in terms of weight fraction.
(4) in terms of weight fraction, dried 1 part of bag is carried out into processing catabolic enzyme, 0.65 part of nano photo-catalytic is mixed together
Uniformly, mixture C, abbreviation component C are obtained.
(5) component A is added from the main spout of double screw extruder, B component is fed from the first side of double screw extruder
Material mouth adds, and component C is added in the second side spout of double screw extruder, and 210 DEG C -240 is passed through in double screw extruder
DEG C melting mixing, water cooled tie rod air-dries pelletizing and is made.The particle injection molding sample preparation on injection molding machine after drying.
The test method of the embodiment of the present invention is as follows：Physical property detection uses ASTM methods of test.Oder levels judge
Perform the PV3900 standards of Volkswagen.TVOC：The total volatile organic compounds content (TVOC) quantitatively detected performs masses
The PV3341 standards of automobile.Anti-microbial property：Kill antibacterial effect and perform GB15981 testing standards.
From comparative example 2 as can be seen that the positive effect that calcium sulfate crystal whiskers are handled with silane coupling agent is not so good as grafting and coating sulphur
Sour calcium pyroborate, is mainly reflected in tensile strength, impact strength and heat resistance, this explanation uses grafting and coating sulfuric acid of the present invention
Calcium pyroborate fills ABS so that the physical mechanical property of material is remarkably reinforced.
Table 1
Table 2
| Sequence number | Oder levels (level) | TVOC(μg/g) | Anti-microbial property |
| Examination criteria | PV3900 | PV3341 | GB15981 |
| Embodiment 1 | 1 | 7 | 99.9 |
| Embodiment 2 | 1 | 6 | 99.9 |
| Embodiment 3 | 1 | 6 | 99.9 |
| Comparative example 1 | >4 | 85.9 | Without antibiotic property |
| Comparative example 2 | 1 | 6 | 99.9 |
Low volatility materials adsorbent, bag shoe processing catabolic enzyme and nano photo-catalytic are not dosed in comparative example 1, material
Oder levels and TVOC numerical value are sharply increased, and are no longer complies with automobile and use standard and environmental requirement, and do not have antibiotic property substantially.Bag
The use for carrying out processing catabolic enzyme, nano photo-catalytic had not only eliminated the bad smell produced in material and its surrounding enviroment, but also made material
Material and surrounding enviroment have superpower antibiotic property, reach national antibacterial standard requirement.
Low volatility materials absorption is dosed in the material, bag carries out processing catabolic enzyme and nano photo-catalytic so that the gas of material
Taste grade has reached level-one, and TVOC (μ g/g) numerical value has reached units value, and TVOC has great lifting, and oder levels are significantly
The index in prior art CN103724922A is exceeded：3 grades, and prior art CN103724922A does not possess antibiotic property, and
Prior art CN102532792A patent oder levels highest indexs are also only 3 grades, and antibiotic property is up to 97.5%, is not reached
99.9%.
Oder levels and TVOC of the present invention obtain greatly lifting, reason and are the reduction of nanometer addition of photodissociation matchmaker, together
When add bag carry out processing catabolic enzyme number so that the nano material agglomeration of addition declines to a great extent, dispersiveness it is stronger, with
The micron order bag of the favorable dispersibility of addition carries out the result that processing catabolic enzyme has given play to synergistic effect.
From Table 1 and Table 2, the present invention uses homemade grafting and coating filler so that the thing of fiber glass reinforced ABS material
Reason mechanical performance is improved significantly, more preferable more resistant to stress cracking, dimensional stability higher, that resist warping deformation, combined type taste removal
The addition of agent so that material up to standard, significant effect in smell processing and anti-microbial property.
In general, the material that the present invention obtains has good physical mechanical property, heat aging property (thermal deformation temperature
Degree is high) and weather resistance, stress crack resistant (being stress crack resistant without floating fibre), corrosion-resistant, vibration resistance, scratch-resistant (fiberglass reinforced
And add whisker after, natural scratch-resistant, corrosion-resistant, vibration resistance), low smell, low TVOC contents, sterilizing function, good processing
The features such as performance (high melt index), bright and clean beauty of appearance, nothing floats fine phenomenon, it can be completely applied to conduct in car steering room
Rearview mirror bracket material.
Claims (10)
- A kind of 1. low smell sterilization reinforced ABS automobile rearview mirror frame material, it is characterised in that in terms of weight fraction, raw material composition Including：The grafting and coating filler is by the calcium sulfate crystal whiskers of AS grafting and coatings and the calcium sulfate crystal whiskers of AS-co-SBR grafting and coatings In mass ratio 2:1-1:1 mixing gained；The bag carries out the catabolic enzyme that processing catabolic enzyme is ECO Co., Ltd. of Japan model ECO-E；The nano photo-catalytic is Co., Ltd. Lang Jinusi model KV-1N photocatalysts.
- 2. reinforced ABS automobile rearview mirror frame material is sterilized according to the low smell described in claim 1, it is characterised in that：It is described ABS be one kind in medium impact strength or high impact strength.
- 3. reinforced ABS automobile rearview mirror frame material is sterilized according to the low smell described in claim 1, it is characterised in that：It is described Short glass fiber be E type short glass fibers.
- 4. reinforced ABS automobile rearview mirror frame material is sterilized according to the low smell described in claim 1, it is characterised in that：It is described Toughener be Methyl Methacrylate-Butadiene-Styrene Copolymer.
- 5. reinforced ABS automobile rearview mirror frame material is sterilized according to the low smell described in claim 1, it is characterised in that：It is described Compatilizer be acrylonitrile, maleic anhydride and polystyrene ternary random copolymer.
- 6. reinforced ABS automobile rearview mirror frame material is sterilized according to the low smell described in claim 1, it is characterised in that：It is described The agent of anti-floating fibre be the hydroxyl telechelic polyester with dissaving structure.
- 7. reinforced ABS automobile rearview mirror frame material is sterilized according to the low smell described in claim 1, it is characterised in that：It is described Low volatile matter adsorbent be that nano silicon dioxide, zeolite molecular sieve, calcined diatomite (average grain diameter is 5-10 μm) press matter It is (0.5-1.5) to measure ratio：(1-3)：(0.5-1.5) is formed.Nano silicon dioxide, zeolite molecular sieve, calcined diatomite suffer from Very big specific surface area, adsorption capacity is strong, and the low volatility that combining effectively to produce in sorbing material is harmful to gas Body.The average grain diameter of calcined diatomite is 5-10 μm.
- 8. reinforced ABS automobile rearview mirror frame material is sterilized according to the low smell described in claim 1, it is characterised in that：It is described Antioxidant be Irganox1076, Irganox168 and Winox GS antioxidant in mass ratio 2：1：1 mixing gained；Described Heat stabilizer connects skill thing with styrol copolymer for acrylonitrile with glycidyl methacrylate.
- 9. reinforced ABS automobile rearview mirror frame material is sterilized according to the low smell described in claim 1, it is characterised in that：It is described Uvioresistant auxiliary agent for one or both of UV770 and UV5411 combination；The lubricant is pentaerythrite hard Acid esters.
- 10. the preparation method of the low smell sterilization reinforced ABS automobile rearview mirror frame material of claim 1-9 any one of them, its It is characterized in that including the following steps：(1) ABS, short glass fiber, compatilizer, low volatile matter adsorbent, bag are first carried out into processing catabolic enzyme, nano photo-catalytic It is respectively dried spare；(2) in terms of weight fraction, by 23.6-62.7 parts ABS parts, 5-10 parts of toughener, 4-8 parts of compatilizer, heat stabilizer 0.1- 0.3 part, 5-15 parts of grafting and coating filler, 1-4 parts of the low volatile matter adsorbent dried, 0.1-0.5 parts of antioxidant, anti-purple 0.3-0.6 parts of outside line auxiliary agent, 0.5-1 parts of anti-floating fibre agent, 0.5-2 parts of lubricant, sequentially adds in high-speed mixer, mixes 5-10 Minute, obtain mixture component A；(3) in terms of weight fraction, 20-30 parts of the short glass fiber dried is B component；(3) bag dried shoe processing catabolic enzyme, nano photo-catalytic are mixed together uniformly, obtain mixture component C；(4) component A is added from the main spout of double screw extruder, first side spout of the B component from double screw extruder Add, component C is added in the second side spout of double screw extruder, by 210 DEG C -240 DEG C in double screw extruder Melting mixing, water cooled, tie rod, air-dries, pelletizing, and low smell sterilization reinforced ABS automobile rearview mirror frame material is made；The grafting and coating filler is prepared via a method which：1) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches more than 110 DEG C, and the moisture in whisker is gone Fall, then add acrylonitrile, styrene and copolymer-maleic anhydride in high-speed mixer, maintain temperature to be not less than 100 DEG C, altogether It is 20-40 minutes mixed, less than 40 DEG C are cooled to, the calcium sulfate crystal whiskers of AS grafting and coatings are made；Calcium sulfate crystal whiskers and acrylonitrile, benzene The mass ratio of copolymer from ethylene and maleie anhydride is 100:2；2) calcium sulfate crystal whiskers are added into high-speed mixer, high-speed stirred, temperature reaches more than 110 DEG C, and the moisture in whisker is gone Fall, then add acrylonitrile, styrene, butadiene-styrene rubber and copolymer-maleic anhydride in high-speed mixer, maintain temperature not low In 100 DEG C, it is blended 20-40 minutes, is cooled to 40 DEG C, is made as the calcium sulfate crystal whiskers of AS-co-SBR grafting and coatings；Calcium sulfate The mass ratio of whisker and acrylonitrile, styrene, butadiene-styrene rubber and copolymer-maleic anhydride is 100:2；3) in use, by the calcium sulfate crystal whiskers of the calcium sulfate crystal whiskers of AS grafting and coatings and AS-co-SBR grafting and coatings in mass ratio 2:1‐1:1 mixing.
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| CN109651777A (en) * | 2018-12-27 | 2019-04-19 | 华润化学材料科技有限公司 | The dedicated impregnant of thermoplastic composite polyester |
| CN109810301A (en) * | 2019-02-16 | 2019-05-28 | 齐齐哈尔大学 | A kind of multipurpose memory type side mirror material |
| CN112480611A (en) * | 2020-11-27 | 2021-03-12 | 上海金发科技发展有限公司 | Low-emission long glass fiber reinforced PCBT material and preparation method thereof |
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| CN114672098A (en) * | 2022-05-05 | 2022-06-28 | 界首市亚鑫塑业科技有限公司 | Low-VOC (volatile organic compound) modified polypropylene composite material |
| CN115895210A (en) * | 2022-11-29 | 2023-04-04 | 金发科技股份有限公司 | Low-VOC low-odor biodegradable material and preparation method and application thereof |
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