CN105462140A - Environment-friendly glass fiber reinforced AS composite material and preparation method thereof - Google Patents
Environment-friendly glass fiber reinforced AS composite material and preparation method thereof Download PDFInfo
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- CN105462140A CN105462140A CN201510932211.3A CN201510932211A CN105462140A CN 105462140 A CN105462140 A CN 105462140A CN 201510932211 A CN201510932211 A CN 201510932211A CN 105462140 A CN105462140 A CN 105462140A
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Abstract
The invention provides an environment-friendly glass fiber reinforced AS composite material. The environment-friendly glass fiber reinforced AS composite material comprises, by weight percentage, AS resin, glass fiber, compatilizer, jellyfish grain, coupling agent, antibacterial agent and adjuvant, wherein the jellyfish grain comprises, by weight percentage, polypropylene, mineral filler and water. Compared with the prior art, the environment-friendly glass fiber reinforced AS composite material and the preparation method have the advantages that (1) a silane coupling agent is added, so that the adhesive strength between the glass fiber and the resin is enhanced; (2) the flavor can be removed effectively, and the mechanical property of the composite material is not affected by the utilization of the jellyfish grain; and (3) the prepared glass fiber reinforced AS composite material has excellent antibacterial effect through the addition of the antibacterial agent and can be utilized as antibacterial materials to be used in car, refrigerator and television industries.
Description
Technical field
The invention belongs to modifying plastics field, especially relates to a kind of environment-friendly type 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.But because fiberglass reinforced AS matrix material smell is very large, limit it at automobile, the application in the fields such as household electrical appliances; 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 low smell, excellent in mechanical performance and the fiberglass reinforced AS matrix material with antibacterial effect seems particularly important, there is the huge market space.
Summary of the invention
In view of this, the invention is intended to propose a kind of environment-friendly type fiberglass reinforced AS matrix material, to solve prior art Problems existing.
For achieving the above object, the technical scheme of the invention is achieved in that
A kind of environment-friendly type fiberglass reinforced AS matrix material, by weight percentage, comprises following component:
AS resin: 60-80%; Glass fibre: 15-20%; Compatilizer: 3-10%; Jellyfish grain: 2.5-5%; Coupling agent: 0.3-1%; Antiseptic-germicide: 0.5-2%; Auxiliary agent 0.1-3%;
Wherein, described AS resin is acrylonitritrile-styrene resin; Described jellyfish grain by weight percentage, comprises following component:
Polypropylene: 20%-36%; Water 50%-78%; Mineral filler 1-4%.
Further, described glass fibre is the mixing of one or more of 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 compatilizer is acrylic polymer or multipolymer, and its polymerization single polymerization monomer is vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, one or more in ethyl acrylate.
Further, described coupling agent is silane coupling agent.
Further, described antiseptic-germicide is four quaternary ammonium salts, general formula R
4nX, wherein four alkyl R are identical or different, and X is halogen anion or acid radical anion.
Further, described auxiliary agent is the mixing of one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment.
The preparation method also proposing a kind of jellyfish grain of the invention, comprises the steps: that polypropylene mixes by proportioning with mineral filler by (1) fully, extrudes strip polypropylene in an extruder, then be chopped into polypropylene pre-expanded particles;
(2) take water as whipping agent, polypropylene pre-expanded particles is foamed, prepares the expanded polypropylene of high fondant-strength;
(3) the mixed 5-10min in super mixer by the expanded polypropylene of high fondant-strength and water, prepares the jellyfish grain of different moisture content, releases stand-by.
Another object of the invention is the preparation method proposing a kind of environment-friendly type fiberglass reinforced AS matrix material, and to solve prior art Problems existing, the technical scheme of the invention comprises the following steps:
(1) take AS resin, compatilizer, jellyfish grain, 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.
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; The length-to-diameter ratio of twin screw extruder is 40:1.
Relative to prior art, environment-friendly type fiberglass reinforced AS matrix material described in the invention and preparation method thereof has following advantage:
1) the present invention uses acrylic polymer or multipolymer as compatilizer, acrylic polymer or multipolymer is utilized 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 improve 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) the jellyfish grain of the present invention's use is simple and easy to get, and preparation technology is simple, and cost is low, while effectively removing smell, and don't affects the mechanical property of matrix material;
3) 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.
Use in the specification and in the claims, odd number type " " and " this " comprise plural reference, clearly state unless context separately has.Such as, term " (one) cell " comprises the cell of plural number, comprises its mixture.
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 invention is described in detail below in conjunction with 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.
Raw material sources are as follows: AS resin is selected from the NF2200 of Taiwan; 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; Described antiseptic-germicide is various quaternary antiseptic-germicides commercially available at present.
The preparation of jellyfish grain:
The high melt strength, propylene of different melt intensity is mixed by proportioning shown in table 1 fully with mineral filler, extrudes strip polypropylene in an extruder, then be chopped into polypropylene pre-expanded particles; Take water as whipping agent, polypropylene pre-expanded particles is foamed, prepare the expanded polypropylene of high fondant-strength; The mixed 5-10min in super mixer by the expanded polypropylene of high fondant-strength and water, prepares the jellyfish grain of water content as shown in table 1, releases stand-by.
Each component concentration (weight percent) of table 1 jellyfish grain
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, jellyfish grain, silane coupling agent, 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 5.
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 5.
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 5.
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 by weight percentage, jellyfish grain, 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 5.
The fiberglass reinforced AS matrix material that embodiment and comparative example obtain adopts following methods to test its correlated performance:
(1) measurement of odor standard:
The sensory test of people and strict instrument test are comprised to the test of volatile gases in car and smell.This patent is by Volkswagen VW ' sPV3900E standard, and adopt 1 ~ 6 grade of evaluation, rank is higher, and smell is larger.Table 2 controls the evaluation content of the standard P V3900 of smell in Automobile for Volkswagen, be divided into 6 ranks.Its method is under certain experiment condition, part is placed in the vessel of a sealing, by the smell of professional with Olfactometry part.Subjective smell test experiments condition is as follows: a, normal temperature 23 DEG C, simulates normal riving condition; B, high temperature 40 DEG C, simulates the riving condition in summer; C, in 2h, under the condition that high temperature is 80 DEG C, simulation extreme temperature and the condition after being exposed to the sun summer in cab.
Table 2 Volkswagen interior material Odor Evaluations standard
(2) mechanical property: test by iso standard.
(3) 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 3 embodiment and comparative example
Silane coupling agent specification used in table 4 embodiment and comparative example
The performance data of the fiberglass reinforced AS matrix material of table 5 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.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.
Can see from embodiment and comparative example, after adding jellyfish grain, significantly can improve the smell of matrix material, its smell is the highest can reach 3 grades, and in addition, jellyfish grain water content is many, and addition is many, and its effect removing smell is more obvious.
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, and its shock strength has risen to 8-9KJ/m2 etc. than the material on market from 5.5-6.5KJ/m2.
The foregoing is only the preferred embodiment of the invention; not in order to limit the invention; within all spirit in the invention and principle, any amendment done, equivalent replacement, improvement etc., within the protection domain that all should be included in the invention.
Claims (10)
1. an environment-friendly type fiberglass reinforced AS matrix material, is characterized in that, by weight percentage, comprises following component:
AS resin: 60-80%; Glass fibre: 15-20%; Compatilizer: 3-10%; Jellyfish grain: 2.5-5%; Coupling agent: 0.3-1%; Antiseptic-germicide: 0.5-2%; Auxiliary agent 0.1-3%;
Wherein, described AS resin is acrylonitritrile-styrene resin; Described jellyfish grain by weight percentage, comprises following component:
Polypropylene: 20%-36%; Water 50%-78%; Mineral filler 1-4%.
2. environment-friendly type fiberglass reinforced AS matrix material according to claim 1, is characterized in that: described glass fibre is the mixing of one or more of long glass fibres or short glass fiber.
3. environment-friendly type fiberglass reinforced AS matrix material according to claim 1 and 2, 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.
4. environment-friendly type fiberglass reinforced AS matrix material according to claim 1, it is characterized in that: described compatilizer is acrylic polymer or multipolymer, its polymerization single polymerization monomer is vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, one or more in ethyl acrylate.
5. environment-friendly type fiberglass reinforced AS matrix material according to claim 1, is characterized in that: described coupling agent is silane coupling agent.
6. environment-friendly type fiberglass reinforced AS matrix material according to claim 1, is characterized in that: described antiseptic-germicide is four quaternary ammonium salts, general formula R
4nX, wherein four alkyl R are identical or different, and X is halogen anion or acid radical anion.
7. environment-friendly type fiberglass reinforced AS matrix material according to claim 1, is characterized in that: described auxiliary agent is the mixing of one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment.
8. the preparation method of jellyfish grain according to claim 1, it is characterized in that, comprise the steps: that polypropylene mixes by proportioning with mineral filler by (1) fully, extrude strip polypropylene in an extruder, then be chopped into polypropylene pre-expanded particles;
(2) take water as whipping agent, polypropylene pre-expanded particles is foamed, prepares the expanded polypropylene of high fondant-strength;
(3) the mixed 5-10min in super mixer by the expanded polypropylene of high fondant-strength and water, prepares the jellyfish grain of different moisture content, releases stand-by.
9. the preparation method of environment-friendly type fiberglass reinforced AS matrix material according to claim 1, is characterized in that, comprise the following steps:
(1) take AS resin, compatilizer, jellyfish grain, 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.
10. the preparation method of environment-friendly type fiberglass reinforced AS matrix material according to claim 9, 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; The length-to-diameter ratio of twin screw extruder is 40:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106918183A (en) * | 2017-02-14 | 2017-07-04 | 合肥华凌股份有限公司 | Ducting assembly and refrigerator |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106918183A (en) * | 2017-02-14 | 2017-07-04 | 合肥华凌股份有限公司 | Ducting assembly and refrigerator |
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