CN105462092A - High performance, anti-static and antibacterial glass fiber reinforced AS composite material and preparation method thereof - Google Patents
High performance, anti-static and antibacterial glass fiber reinforced AS composite material and preparation method thereof 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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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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
- C08L2201/04—Antistatic
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Abstract
The invention provides a high performance, anti-static and antibacterial glass fiber reinforced AS composite material. The high performance, anti-static and antibacterial glass fiber reinforced AS composite material comprises, by weight percentage, 48-86% of AS resin, 10-28% of glass fiber, 1-10% of compatilizer, 0.1-1% of coupling agent, 8-12% of anti-static agent, 0.5-2% of antibacterial agent and 0.1-2.5% of adjuvant, wherein the compatilizer is one or mixture of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer and styrene-acrylonitrile-methyl methacrylate copolymer. The antibacterial agent is quaternary ammonium salt, and a general formula is R4NX, wherein four alkyl radicals R are identical or different, and X is halogen anions or acid radical. The high performance, anti-static and antibacterial glass fiber reinforced AS composite material effectively changes the interface state of the glass fiber and the resin, improve the adhesive force of the interface and improve the performance of the composite material, The prepared glass fiber reinforced AS composite material has excellent antibacterial effect and can be utilized as anti-bacterial materials to be used in car, refrigerator and television industries.
Description
Technical field
The present invention relates to modified plastics field, be specifically related to a kind of high performance antistatic antibacterial fiberglass reinforced AS matrix material and preparation method thereof.
Background technology
Acrylonitrile-styrene (AS) resin is that material copolymerization closes obtained a kind of thermoplastics by vinylbenzene (St), vinyl cyanide (AN) two kinds of monomers.AS resin has excellent performance, has fabulous dimensional stability, electrical property, wear resistance, chemical proof, dyeability, and forming process and mechanical workout better, are a kind of important engineering plastics.
Fiberglass reinforced plastics have the advantages such as specific tenacity is high, corrosion-resistant, heat insulation, molding shrinkage is little.In addition, utilize fiberglass reinforced that the tensile property of plastics can be made to increase substantially.Add intensity and thermal deformation resistant ability that glass fibre can strengthen AS resin in AS resin, also can reduce the thermal expansivity of AS resin.
Glass fiber reinforcement AS has good using value because it has good processing characteristics, dimensional stability and tensile strength in household appliance technical field, as the axial flow in air-conditioning, through-flow and centrifugal fan leaf etc.The performance of fiberglass reinforced AS product directly has influence on the quality of conditioner, closely bound up with everybody daily life.
The performance requriements of household appliance technical field to fiberglass reinforced AS matrix material is generally: tensile strength >100MPa, modulus in flexure >6500MPa, heat-drawn wire >100 DEG C, glass weight content 19-22%, notched Izod impact strength >6.0kJ/m2.
The mechanical property of glass fiber reinforcement AS depends on the cohesive strength of AS and glass fibre to a great extent, because the bonding interface of resin and glass is poor, the enhancement of glass can not be given full play to, the composite material strength of formation, toughness, the poor-performings such as thermotolerance.
Klumperman etc. (W091/15543) once with styrene-maleic anhydride copolymer (SMA), ABS, AS and glass for raw material, the ABS mixture of blended system.This mixture improves vicat softening temperature, but modulus in flexure is too low, only has 5000MPa; And owing to adding a large amount of ABS and SMA, manufacturing cost rises.Chinese patent CN201110138482 with AS, glass, coupling agent is raw material, combined by adjusting screw(rod), prepared density and strengthened AS matrix material comparatively uniformly, but its matrix material tensile strength prepared is at 100-110MPa, shock strength is at 5.5-6.5kJ/m2, and performance is also lower.Compatilizer system relatively more conventional in current resin and fiberglass reinforced system is the multipolymer of vinylbenzene and maleic anhydride.
And, due to the poor conductor that AS material is electricity, easy accumulate static charge in processing and use procedure, when accumulation of electrostatic charge to a certain extent, electrostatic can cause materials adsorption dust, and causes material damage, also may produce static sparking electric discharge, cause Chemicals storehouse etc. on fire from explosion, cause great fatal accident.
In addition, the requirement of antibiosis also should be had for material.Along with the submission of people's living standard, one of the focus that product hommization, health will be competition.
At present, there has been an industrial standards in China to the antibacterial of plastics.Antibacterial standard is: antibacterium rate meets the antibiotic plastic of I >=99% can as strong antibiotic plastic, and antibacterium rate meets the antibiotic plastic of I >=90% can as there being anti-microbial effect plastics.At present polypropylene material is concentrated on to the report of anti-biotic material, as patent CN1017255771A adopts interpolation carrying silver ion antiseptic-germicide to reach anti-microbial effect.
Therefore, develop a kind of excellent in mechanical performance, and have antistatic, the fiberglass reinforced AS matrix material of antibacterial seems particularly important, has the huge market space.
Summary of the invention
In view of this, the present invention is intended to propose a kind of high performance antistatic antibacterial fiberglass reinforced AS matrix material, to overcome the deficiencies in the prior art, interfacial state between effective change glass fibre and resin, improves the cohesive force at its interface, thus improves the performance of matrix material, the fiberglass reinforced AS matrix material of preparation has excellent antibacterial effect, automobile can be used for, refrigerator, televisor industry as anti-biotic material.
For achieving the above object, technical scheme of the present invention is achieved in that
A kind of high performance antistatic antibacterial fiberglass reinforced AS matrix material, is characterized in that: by weight percentage, comprises following component:
Wherein, described compatilizer is methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, MBS terpolymer, the one in styrene-acrylonitrile-methyl methacrylate ter-polymers or its mixture, glass fiber reinforced materials is because be the complex body be made up of glass fibre and synthetic resins, two kinds of materials differ greatly, compatible problem is there is after being mixed with each other, utilize methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), MBS terpolymer (MBS) or ethylene-propylene nitrile-methyl methacrylate ter-polymers (ASA) have the feature of high polarity, add this type of compatilizer in formula and can change interfacial state between glass fibre and resin, improve the cohesive force at its interface, thus improve the performance of matrix material.
Described antiseptic-germicide is quarternary ammonium salt, general formula R 4NX, and wherein four alkyl R are identical or different, and X is halogen anion or acid group, and preferably, X is halogen anion F
-, Cl
-, Br
-, I
-or acid group HSO4
-, RCOO
-in a kind of bacterial cell surface generally electronegative, the positive charge of quarternary ammonium salt attracts the negative charge on bacterial cell membrane surface, stops the movement of bacterium, makes it lose nutrition and dead, or cytomorphosis is broken dead because content oozes out, thus reach antibacterial effect.
Described auxiliary agent is at least one in thermo-stabilizer, photostabilizer, processing aid, pigment.
Further, described AS resin is vinyl cyanide, cinnamic multipolymer.
Further, described glass fibre is the mixing of long glass fibres and short glass fiber.
Further, described long glass fibres is alkali free glass fibre, and diameter is 10-16 μm; The length of described short glass fiber is 0.2-10mm, and diameter is 8-20 μm.
Further, described coupling agent is silane coupling agent, use silane coupling agent, utilize its have can with some radical reaction of fiberglass surfacing, again can with the feature of resin reaction, an interfacial layer is formed between glass fibre and resin matrix, interfacial layer can transmit stress, thus enhances bond strength between glass fibre and resin, forms stable structure, make disperse phase and external phase evenly, the compatibilized both namely realizing.
Especially, described silane coupling agent is amino-type silane coupling agent.
Especially, the number of amino groups that described amino-type silane coupling agent contains is more than 2 or 2.
This is because silane coupling agent (YSiX3), its hydrolysis rate is taken at silicon can roll into a ball X, is then taken at carbon functional group Y with the reactive behavior of organic polymer.In the group of two class performance inequalities of silane coupling agent, the difference of X base can only affect hydrolysis rate, on the essentially no impact of the performance of matrix material; Y group then directly determines the effect of silane coupling agent.Only have when Y group can react with corresponding matrix resin, could bonding strength be improved.General requirement Y group can mix with resin and can play linked reaction, so, for different substrate materials or handling object, select applicable silane coupling agent most important.
For fiberglass reinforced AS system, select amino-type silane coupling agent proper, this is because amino is polarity, can also AS resin compatible, and amino can play linked reaction with vinyl cyanide.In addition, the silane coupling agent of two amino-type or polyamino type, its catalytic activity is higher, advantageously in the mechanical property improving matrix material.Further, described static inhibitor is permanent antistatic agent, comprises metal-salt and polyoxyethylene in its composition.
Further, because the present invention is automotive trim AS matrix material, can be used alone above-mentioned auxiliary agent according to the structure of different automotive trim, technical requirements etc., or compound use.Described thermo-stabilizer is selected from one or more in phenols, phosphorous acid esters, monothioester class, and thermo-stabilizer can improve the heat aging property of material in processing and use procedure; Described photostabilizer is hindered amines or UV light absorber, and photostabilizer can improve material light aging resisting property in use; Described processing aid is one or more in low molecule ester class stearic acid, metallic soap, stearic acid complex ester or amides.
Another object of the present invention is to the preparation method proposing a kind of high performance antistatic antibacterial fiberglass reinforced AS matrix material, comprise the following steps:
(1) take AS resin, compatilizer, static inhibitor, antiseptic-germicide, coupling agent and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend;
(2) Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying, to obtain final product.
The described condition melt extruded is: a district temperature 180-210 DEG C, two district temperature 190-220 DEG C, three district temperature 190-230 DEG C, four district temperature 190-240 DEG C, five district temperature 190-240 DEG C, six district temperature 190-240 DEG C, seven district temperature 190-240 DEG C, eight district temperature 190-240 DEG C, nine district temperature 190-240 DEG C, engine speed 250-600 rev/min; The length-to-diameter ratio of twin screw extruder is 40:1.
Relative to prior art, the present invention has following advantage:
1) the present invention uses MABS, MBS or ASA as compatilizer, utilizes it to have the feature of high polarity, effectively can change the interfacial state between glass fibre and resin, improve the cohesive force at its interface, thus improves the performance of matrix material.
In addition, by adding silane coupling agent, utilize its have can with some radical reaction of fiberglass surfacing, again can with the feature of resin reaction, between glass fibre and resin matrix formed an interfacial layer, interfacial layer can transmit stress, thus enhance bond strength between glass fibre and resin, form stable structure, make disperse phase and external phase evenly, the compatibilized both namely realizing.
2) silane coupling agent that the present invention uses is amino-type silane coupling agent, especially the amino-type silane coupling agent containing 2 amino or multiple amino is used, its activity is higher, more effectively enhance the bond strength between glass fibre and resin, thus the mechanical property of matrix material is significantly improved.
3) the present invention is by adding static inhibitor, and the surface resistivity of AS composition can be made to be reduced to 108 Ω from 1016 Ω, and antistatic effect is good.
4) after the present invention adds antiseptic-germicide, the fiberglass reinforced AS matrix material of preparation has excellent antibacterial effect, can be used for automobile, refrigerator, televisor industry as anti-biotic material.
Embodiment
Unless otherwise indicated, term used herein all has the implication that those skilled in the art's routine is understood, and for the ease of understanding the present invention, terms more used herein has been carried out following definitions.
All Digital IDs, such as pH, temperature, time, concentration, comprise scope, is all approximation.Understand, although not always clear and definite describe all Digital IDs before all add term " about ".Also will understand, describe although always not clear and definite, reagent described herein is only example, and its Equivalent is known in the art simultaneously.
The present invention is described in detail below in conjunction with embodiment.
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
In following examples and comparative example, the processing conditions that forcing machine melt extrudes is as follows: a district temperature 180-210 DEG C, two district temperature 190-220 DEG C, three district temperature 190-230 DEG C, four district temperature 190-240 DEG C, five district temperature 190-240 DEG C, six district temperature 190-240 DEG C, seven district temperature 190-240 DEG C, eight district temperature 190-240 DEG C, nine district temperature 190-240 DEG C, engine speed 250-600 rev/min; The length-to-diameter ratio of twin screw extruder is 40:1.
AS resin is selected from the NF2200 of Taiwan, and roving glass fiber is selected from the ER13-2000-988A of megalith group, and its Fibre diameter is 13 μm, and linear density is 2000tex; Short glass fiber is selected from the ECS-13-4.5 series of ShenzhenYataida company, and the length of its glass fibre is 4.5mm, and diameter is 13 μm; Compatilizer is selected from the strange beautiful PMMACM-207 in Taiwan; ; Silane coupling agent is selected from the KH-550 of the Chinese Academy of Sciences, KH-560 and KH-602.Static inhibitor is selected from the PELESTAT6500 that Sanyo changes into.Antiseptic-germicide is various quaternary antiseptic-germicides commercially available at present.
Embodiment 1-6, comparative example 6
A fiberglass reinforced AS matrix material for excellent in mechanical performance, its composition of raw materials is as shown in table 1, and its preparation method comprises the following steps:
Take AS resin, compatilizer, silane coupling agent, static inhibitor, antiseptic-germicide and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend; Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying.Measure its performance, concrete data list in table 3.
Comparative example 1-3
A fiberglass reinforced AS matrix material for excellent in mechanical performance, its composition of raw materials is as shown in table 1, and its preparation method comprises the following steps:
Take AS resin, compatilizer and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend; Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying.Measure its performance, concrete data list in table 3.
Comparative example 4
A fiberglass reinforced AS matrix material for excellent in mechanical performance, its composition of raw materials is as shown in table 1, and its preparation method comprises the following steps:
Take AS resin, silane coupling agent and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend; Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying.Measure its performance, concrete data list in table 3.
Comparative example 5
A fiberglass reinforced AS matrix material for excellent in mechanical performance, its composition of raw materials is as shown in table 1, and its preparation method comprises the following steps:
Take AS resin, static inhibitor by weight percentage, antiseptic-germicide and auxiliary agent mix 1-3min in high mixer; Mix, obtain Preblend; Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying.Measure its performance, concrete data list in table 3.
The fiberglass reinforced AS matrix material that embodiment and comparative example obtain adopts iso standard to test its correlated performance.Its antibiotic rate measures, and adopts Chinese light industry standard QB/T2591-2003 " antibiotic plastic---anti-microbial property evaluation and testing method thereof " standard.Experimental strain is intestinal bacteria, streptococcus aureus.
The composition of raw materials (by weight percentage) of the fiberglass reinforced AS matrix material of table 1 embodiment and comparative example
Silane coupling agent specification used in table 2 embodiment and comparative example
The performance data of the fiberglass reinforced AS matrix material of table 3 embodiment and comparative example
By embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, embodiment 3 and comparative example 3, contrast can be found out, after adding silane coupling agent, the mechanical property of matrix material significantly improves, this is because by using silane coupling agent, the bond properties of glass fibre and resin can be improved, thus improve the performance of matrix material.This phenomenon can be explained with theory of chemical bonds, this theory is thought: silane coupling agent contains two kinds of different chemical functional groups, its one end (X group) and inorganic materials, the silanol groups reaction as surfaces such as glass fibre, silicate, metal oxides generates covalent linkage; The other end (Y group) generates covalent linkage with superpolymer base-material or resin again, thus erects between inorganic substance and the interface of organic substance " molecular bridge ", and then two kinds of inconsistent material couplings is got up.In addition, with suitable silane coupling agent process fiberglass surfacing, its surface tension can be improved, thus impel organic resin in the infiltration of mineral surfaces and expansion, convergency and the processing characteristics of glass can be improved.
Contrasted can be seen by embodiment 3 and embodiment 4 and embodiment 5, use amino-type silane coupling agent, its coupling effect wants excellent in the coupling effect of medium-sized silane coupling agent, specifically, use two amino-type silane coupling agent, the better excellence of its coupling effect, is more conducive to improving composite materials property.
By embodiment 4 and comparative example 4, embodiment 5 and comparative example 5, contrast can be found out: add the performance that compatilizer effectively can improve matrix material in formula, this is because glass fiber reinforced materials is because be the complex body be made up of glass fibre and synthetic resins, two kinds of materials differ greatly, and there is compatible problem after being mixed with each other.And polymethylmethacrylate (PMMA) has high polarity, the interfacial state between glass fibre and resin can be changed, improve the cohesive force at its interface, thus improve the performance of matrix material.And using silane coupling agent and the composite mode of compatilizer, the mechanical property of composite performance is more excellent.
In addition, can see from embodiment 6 and comparative example 6 contrast, when coupling agent consumption is excessive, the comprehensive mechanical property of matrix material is in a slight decrease on the contrary.This is because what really play action of coupling agents in GFAS matrix material is the unimolecular layer that coupling agent molecule is formed at fiberglass surfacing, therefore too much interpolation coupling agent is unnecessary.When coupling agent consumption is less, along with the increase of consumption, tensile strength and shock strength can be improved to some extent; When the consumption of coupling agent is excessive, this excessive interpolation is unnecessary, and can cause negative impact to the performance of material, causes the performance of material to occur declining.
In addition, by adding static inhibitor, the surface resistivity of composition can be made to be reduced to 108 Ω from 1016 Ω, and antistatic effect is good.After adding antiseptic-germicide, the matrix material of preparation has excellent antibacterial effect.
As can be seen from embodiment, use the antistatic fiberglass reinforced AS matrix material that the present invention produces, its mechanical property and antistatic effect are very excellent.As part fiberglass reinforced AS matrix material of 20 in embodiment 5, its tensile strength has risen to 130-140MPa than material on the market from 100-110MPa, its shock strength than the material on market from 5.5-6.5KJ/m
2rise to 8-9KJ/m
2etc..
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a high performance antistatic antibacterial fiberglass reinforced AS matrix material, is characterized in that: by weight percentage, comprises following component:
Wherein, described compatilizer is methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, MBS terpolymer, the one in styrene-acrylonitrile-methyl methacrylate ter-polymers or its mixture;
Described antiseptic-germicide is quarternary ammonium salt, general formula R 4NX, and wherein four alkyl R are identical or different, and X is halogen anion or acid group;
Described auxiliary agent is at least one in thermo-stabilizer, photostabilizer, processing aid, pigment.
2. a kind of high performance antistatic according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: described AS resin is vinyl cyanide, cinnamic multipolymer.
3. a kind of high performance antistatic according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: described glass fibre is the mixing of long glass fibres and short glass fiber.
4. a kind of high performance antistatic according to claim 3 antibacterial fiberglass reinforced AS matrix material, it is characterized in that: described long glass fibres is alkali free glass fibre, diameter is 10-16 μm; The length of described short glass fiber is 0.2-10mm, and diameter is 8-20 μm.
5. a kind of high performance antistatic according to claim 1 antibacterial fiberglass reinforced AS matrix material, it is characterized in that: described coupling agent is amino-type silane coupling agent, the number of amino groups that described amino-type silane coupling agent contains is more than 2 or 2.
6. a kind of high performance antistatic according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: described static inhibitor is permanent antistatic agent, comprises metal-salt and polyoxyethylene in its composition.
7. a kind of high performance antistatic according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: described thermo-stabilizer is selected from one or more in phenols, phosphorous acid esters, monothioester class; Described photostabilizer is hindered amines or UV light absorber; Described processing aid is one or more in low molecule ester class stearic acid, metallic soap, stearic acid complex ester or amides.
8. a kind of high performance antistatic according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: in described quarternary ammonium salt, and X is halogen anion F
-, Cl
-, Br
-, I
-or acid group HSO4
-, RCOO
-in one.
9. the preparation method of a kind of high performance antistatic according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: (1) takes AS resin, compatilizer, static inhibitor, antiseptic-germicide, coupling agent and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend;
(2) Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying, to obtain final product.
The described condition melt extruded is: a district temperature 180-210 DEG C, two district temperature 190-220 DEG C, three district temperature 190-230 DEG C, four district temperature 190-240 DEG C, five district temperature 190-240 DEG C, six district temperature 190-240 DEG C, seven district temperature 190-240 DEG C, eight district temperature 190-240 DEG C, nine district temperature 190-240 DEG C, engine speed 250-600 rev/min; The length-to-diameter ratio of twin screw extruder is 40:1.
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Application publication date: 20160406 |