CN104448600A - Antibacterial glass fiber reinforced AS (acrylonitrile-styrene copolymer) composite material and preparation method thereof - Google Patents
Antibacterial glass fiber reinforced AS (acrylonitrile-styrene copolymer) composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an antibacterial glass fiber reinforced AS (acrylonitrile-styrene copolymer) composite material and a preparation method thereof. The composite material comprises the following components by weight percent: 55.4-88.4% of AS resin, 10-30% of glass fibers, 1-5% of compatilizer, 0.1-1% of coupling agent, 0.5-2% of antibacterial agent and 0.1-3% of auxiliaries, wherein the compatilizer is PMMA (polymethyl methacrylate); the coupling agent is a silane coupling agent. The composite material has the advantages and positive effects that with the AS resin as the matrix, the composite material has the advantages of excellent properties, low cost, simple preparation process, and the like; used as the compatilizer, PMMA is not only limited to reinforcing the binding forces between the glass fibers and the AS resin but is also suitable for reinforcing fiber and resin composite material systems with similar properties.
Description
Technical field
The invention belongs to modified plastics field, especially relate to a kind of antibacterial fiberglass reinforced AS matrix material and preparation method thereof.
Background technology
Acrylonitrile styrene resin (AS) and AS resin, be that material copolymerization closes obtained a kind of thermoplastics with vinylbenzene (St), vinyl cyanide (AN) two kinds of monomers, AS resin has excellent performance, there are fabulous dimensional stability, electrical property, wear resistance, chemical proof, dyeability, 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, utilize fiberglass reinforced that the tensile property of plastics can be made to increase substantially.In AS resin, add intensity and thermal deformation resistant ability that glass fibre can strengthen 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 axial flow, through-flow and centrifugal fan leaf etc. for making in air-conditioning, the performance of fiberglass reinforced AS resin 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 resin 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/m
2.
The mechanical property of glass fiber reinforcement AS resin depends on the cohesive strength of AS resin 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 poor-performings such as the composite material strength formed, toughness, thermotolerance.
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 CN 1017255771A adopts interpolation carrying silver ion antiseptic-germicide to reach anti-microbial effect.
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.In Chinese patent CN1362443A and CN1352212A, have employed Methacrylate-butadiene-styrene (MBS), AS, SMA, ABS and glass as raw material, the AS mixture of blended system, but which increase glass dip treating step, complex process and cost promote further.In addition, Chinese patent CN201110138482, is combined by adjusting screw(rod) for raw material with AS, glass, coupling agent, has prepared density and has strengthened AS matrix material comparatively uniformly, but its matrix material tensile strength prepared is at 100-110MPa, and shock strength is at 5.5-6.5kJ/m
2, performance is also lower.
To sum up, because glass-fibre reinforced resin matrix material has broad application prospects, therefore urgently develop a kind of excellent in mechanical performance, antibacterial preparation technology simple, lower-cost fiberglass reinforced AS matrix material.
Summary of the invention
The invention provides a kind of antibacterial fiberglass reinforced AS matrix material and preparation method thereof, there is the advantages such as excellent performance, with low cost, preparation technology is simple.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of high performance antistatic antibacterial fiberglass reinforced AS matrix material, is characterized in that, comprises following component by weight percentage:
Described compatilizer is polymethylmethacrylate, and polymethylmethacrylate is also called PMMA; In the complex body be made up of glass fibre and synthetic resins AS, the material of glass and this bi-material of AS resin differs greatly, compatible problem is there is after being mixed with each other, the present invention utilizes polymethylmethacrylate to have the feature of high polarity, the interfacial state between glass fibre and AS resin is changed by PMMA, cohesive force between both raisings interface, thus the performance improving fiberglass reinforced AS matrix material.
Described coupling agent is silane coupling agent; Silane coupling agent have can with some radical reaction of fiberglass surfacing, again can with the feature of AS resin reaction, an interfacial layer is formed between glass fibre and AS resin matrix, coupling agent defines stable interface structure between glass fibre and AS resin, make disperse phase and external phase evenly, the compatibilized both namely realizing; This interface structure has the ability transmitting stress, enhances bond strength between glass fibre and AS resin, also improves the mechanical property of fiberglass reinforced AS matrix material.
Further, described glass fibre is at least one in long glass fibres or 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 silane coupling agent is amino-type silane coupling agent.
Further, described amino-type silane coupling agent contains two or three above amino:
Its general formula of silane coupling agent is YSiX
3, its hydrolysis rate is taken at functionalized silicon group 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 composite system, preferred amino-type silane coupling agent because amino is polar group, can with AS resin compatible, and amino can play linked reaction with vinyl cyanide.In addition, the catalytic activity of the silane coupling agent of two amino-type or polyamino type is higher, advantageously in the mechanical property improving matrix material.
Further, described auxiliary agent comprises any one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment; Described antiseptic-germicide is by photocatalitic germicide and silver-based inorganic antibacterial agent is composite forms.
Described antiseptic-germicide is the composite antiseptic-germicide of photocatalitic germicide and silver-based inorganic antibacterial agent, and to be preferably weight percent be that 1:1 is composite forms.Adopt photocatalitic germicide and the composite antiseptic-germicide of silver-based inorganic antibacterial agent, the limitation of single antiseptic-germicide can be overcome; Its Antibacterial Mechanism is: absorb the outside energy such as UV-light, visible ray, by excitation electron transition, activates the oxygen around antiseptic-germicide and water molecules, becomes active oxygen and hydroxyl free radical.They can be oxidized or make the protein in bacterial cell, unsaturated fatty acids, glucosides etc. to react, and destroy its normal configuration, thus make bacterial death or lose multiplication capacity.
Fiberglass reinforced AS matrix material of the present invention, mainly for the manufacture of automotive trim, can be used alone above-mentioned auxiliary agent according to the structure of different automotive trim, technical requirements etc., or compound use.Also can be used for refrigerator, televisor industry.Thermo-stabilizer can improve the heat aging property of material in processing and use procedure, usually can be selected from more than one in phenols, phosphorous acid esters, monothioester class; Photostabilizer can improve material light aging resisting property in use, can be hindered amines or UV light absorber.Processing aid is more than one in low molecule ester class stearic acid, metallic soap, stearic acid complex ester or amides.
A preparation method for antibacterial fiberglass reinforced AS matrix material, is characterized in that comprising the steps:
S1, take AS resin, compatilizer, antiseptic-germicide, coupling agent and auxiliary agent by weight percentage mix 1-3min in high mixer; Mix, obtain Preblend; ;
S2, the main spout of Preblend from twin screw extruder to be dropped into, and adds the glass fibre taken by weight percentage from side spout, carry out melt extruding, granulating and drying, obtain described high performance antistatic antibacterial fiberglass reinforced AS matrix material.
Further, 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.
Further, the length-to-diameter ratio of described twin screw extruder is 40:1.
The advantage that the present invention has and positively effect are:
1) use polymethylmethacrylate as compatilizer, polymethylmethacrylate is utilized to have the feature of high polarity, interfacial state between effective change glass fibre and AS resin, the cohesive force between both raisings interface, thus the performance improving matrix material;
2) silane coupling agent have can with some radical reaction of fiberglass surfacing, again can with the feature of AS resin reaction, an interfacial layer is formed between glass fibre and AS resin matrix, coupling agent defines stable interface structure between glass fibre and AS resin, make disperse phase and external phase evenly, the compatibilized both namely realizing; This interface structure has the ability transmitting stress, enhances bond strength between glass fibre and AS resin, also improves the mechanical property of fiberglass reinforced AS matrix material; The silane coupling agent used is amino-type silane coupling agent, especially the amino-type silane coupling agent containing two amino or more than three amino is used, there is higher activity, more effectively enhance the bond strength between glass fibre and AS resin, thus the mechanical property of matrix material is significantly improved;
3) use of PMMA or coupling agent is not limited only to the bonding force between reinforcing glass fiber and AS resin, and is applicable to strengthen the fiber and resin composite materials system with similar quality.
4) matrix of the present invention is AS resin, has the advantages such as excellent performance, with low cost, preparation technology is simple.
5) 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
The invention provides embodiment 1-6 and comparative example 1-6, embodiment is identical with the preparation method of comparative example, and concrete steps are as follows:
S1, by the weight percent listed in following table 1, AS resin, compatilizer, coupling agent, antiseptic-germicide and the auxiliary agent taken respectively in each embodiment or each comparative example mixes 1-3min in high mixer; Mix, obtain Preblend; Wherein, embodiment and comparative example choose the coupling agent of dimension with reference to table 2
S2, the main spout of Preblend from twin screw extruder to be dropped into, and add the weight percent shown according to the form below 2 from side spout and take each embodiment or glass fibre corresponding to each comparative example, carry out melt extruding, granulating and drying, obtain described fiberglass reinforced AS matrix material.
S3, the fiberglass reinforced AS matrix material obtained by step S2 are respectively prepared into the Test strips meeting ISO, QB/T2591-2003 " antibiotic plastic---anti-microbial property evaluation and testing method thereof " examination criteria size, namely obtain embodiment 1-6 and comparative example 1-6.
The condition that melt extrudes in above-mentioned preparation process 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.
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 Shenzhen Yataida company, and the length of its glass fibre is 4.5mm, and diameter is 13 μm; Compatilizer is selected from the strange beautiful PMMA CM-207 in Taiwan; Silane coupling agent is selected from the KH-550 of the Chinese Academy of Sciences, KH-560 and KH-602; Described antiseptic-germicide is various quaternary antiseptic-germicides commercially available at present.。
The high-performance fiberglass reinforced AS matrix material that embodiment and comparative example obtain adopts ISO, QB/T2591-2003 " antibiotic plastic---anti-microbial property evaluation and testing method thereof " (experimental strain is intestinal bacteria, streptococcus aureus) its correlated performance of standard testing:
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, the X group of its one end and inorganic materials, the silanol groups reaction as surfaces such as glass fibre, silicate, metal oxides generates covalent linkage; The Y group of the other end 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.
It can also be seen that by upper table: after adding antiseptic-germicide, the antibacterial ability of material obviously increases.
As can be seen from embodiment, use the fiberglass reinforced AS matrix material that the present invention produces, its mechanical property and thermal characteristics 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..
Above one embodiment of the present of invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (9)
1. an antibacterial fiberglass reinforced AS matrix material, is characterized in that, comprises following component by weight percentage:
Described compatilizer is polymethylmethacrylate;
Described coupling agent is silane coupling agent;
Described antiseptic-germicide is by photocatalitic germicide and silver-based inorganic antibacterial agent is composite forms.
2. one according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: described glass fibre is at least one in long glass fibres or short glass fiber.
3. one according to claim 2 antibacterial fiberglass reinforced AS matrix material, is characterized in that: 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.
4. one according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: described silane coupling agent is amino-type silane coupling agent.
5. one according to claim 4 antibacterial fiberglass reinforced AS matrix material, is characterized in that: described amino-type silane coupling agent contains two or three above amino.
6. one according to claim 1 antibacterial fiberglass reinforced AS matrix material, is characterized in that: described auxiliary agent comprises any one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment.
7. a preparation method for the antibacterial fiberglass reinforced AS matrix material according to any one of claim 1-6, is characterized in that comprising the steps:
S1, take AS resin, compatilizer, antiseptic-germicide, coupling agent and auxiliary agent by weight percentage mix 1-3min in high mixer; Mix, obtain Preblend; ;
S2, the main spout of Preblend from twin screw extruder to be dropped into, and adds the glass fibre taken by weight percentage from side spout, carry out melt extruding, granulating and drying, obtain described high-performance fiberglass reinforced AS matrix material.
8. the preparation method of a kind of antibacterial fiberglass reinforced AS matrix material according to claim 7, it is characterized in that, described in the condition that melt extrudes be: 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.
9. the preparation method of a kind of antibacterial fiberglass reinforced AS matrix material according to claim 7 or 8, is characterized in that: the length-to-diameter ratio of described twin screw extruder is 40:1.
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Application publication date: 20150325 |