CN105462141A - Antibacterial reinforced AS composite material and preparation method thereof - Google Patents
Antibacterial reinforced AS composite material and preparation method thereof Download PDFInfo
- Publication number
- CN105462141A CN105462141A CN201510932262.6A CN201510932262A CN105462141A CN 105462141 A CN105462141 A CN 105462141A CN 201510932262 A CN201510932262 A CN 201510932262A CN 105462141 A CN105462141 A CN 105462141A
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- district temperature
- coupling agent
- resin
- compatilizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an antibacterial reinforced AS composite material and a preparation method thereof. The composite material comprises, by weight parts, 59-79 parts of AS resin, 10-30 parts of glass fiber, 1-5 parts of compatilizer, 0.1-1 part of coupling agent, 0.5-2 parts of antibacterial agent and 0.1-3 parts of adjuvant. The compatilizer is an acrylics polymer or copolymer, and the polymeric monomer is one or more of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate and acrylic acid-2-ethylhexyl acrylate. According to the antibacterial AS composite material and the method for preparing the antibacterial AS composite material, the acrylics polymer or copolymer is utilized as compatilizer, and the acrylics polymer or copolymer has the advantages of being high in polarity, so that the interface state between the glass fiber and the resin can be effectively changed, the adhesive force of the interface is improved, and the performance of the composite material is improved.
Description
Technical field
The invention belongs to modified plastics field, especially relate to a kind of antibacterial enhancing AS matrix material and preparation method thereof.
Background technology
AS resin (acrylonitrile styrene resin (AS)) refers to that by vinylbenzene (St), vinyl cyanide (AN) two kinds of monomers be that raw material is polymerized obtained a kind of thermoplastics jointly.And 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 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/m
2.
General glass fiber reinforcement AS composition is by AS resin, glass fibre, coupling agent, compatilizer and a certain amount of auxiliary agent blended obtained, but the performance of current glass fiber reinforcement AS composition is on the market lower, simultaneously due to the raising of people's living standard, product hommization, one of the focus that health will be competition, therefore certain requirement be it is also proposed to the anti-microbial property of glass fiber reinforcement AS composition, the Anti-Bacterial Industrial standard of current plastics is: antibacterium rate meets the antibiotic plastic of I >=99% can as strong antibiotic plastic, antibacterium rate meets the antibiotic plastic of I >=90% can as there being anti-microbial effect plastics (see QB/T2591-2003 " antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect ").
Therefore, develop a kind of 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 present invention is intended to propose a kind of antibacterial enhancing AS matrix material and preparation method thereof, has the advantages such as excellent in mechanical performance, antibacterial effect be obvious, with low cost.
For achieving the above object, technical scheme of the present invention is achieved in that
A kind of antibacterial enhancing AS matrix material and preparation method thereof, comprises the component of following parts by weight:
Described compatilizer is acrylic polymer or multipolymer, and its polymerization single polymerization monomer is one or more in vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate.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, acrylic polymer or multipolymer is utilized to have the feature of high polarity, add acrylic polymer or multipolymer 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, and general formula is R
4nX, wherein R is four identical or different alkyl, and X is halogen anion or acid group.Bacterial cell surface is generally electronegative, and 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 the death because content oozes out, thus reaches antibacterial effect.
Further, described AS resin is vinyl cyanide, cinnamic multipolymer; Described glass fibre is long glass fibres and/or short glass fiber.
Preferably, 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 two amino-type silane coupling agents.Use two amino-type 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.
Matrix material of the present invention also comprises the auxiliary agent that parts by weight are 0.1-3 part, and described auxiliary agent is one or more the mixing in thermo-stabilizer, photostabilizer, processing aid, toner or pigment.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 one or more in low molecule ester class stearic acid, metallic soap (Cast, Znst), stearic acid complex ester or amides (erucicamide).
Another object of the present invention is to the preparation method proposing a kind of antibacterial enhancing AS matrix material, comprise the steps:
(1) take AS resin, compatilizer, antiseptic-germicide, coupling agent and auxiliary agent by weight 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, obtain antibacterial enhancing AS matrix material;
The condition wherein melt extruded described in step (2) 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;
Described in step (2), the length-to-diameter ratio of twin screw extruder is 40:1.
Relative to prior art, one of the present invention antibacterial enhancing AS matrix material 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) 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 employed, 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), after the present invention adds antiseptic-germicide, the antibacterial enhancing 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 preparation method of embodiments of the invention 1-3 and comparative example 1-3 comprises the steps:
(1) take AS resin, compatilizer, antiseptic-germicide, coupling agent and auxiliary agent by weight 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, obtain antibacterial enhancing AS matrix material.
In preparation method in embodiment 1-3 and comparative example 1-3, the processing conditions that forcing machine melt extrudes is as follows: district's temperature 190 DEG C, two district's temperature 220 DEG C, three district's temperature 230 DEG C, four district's temperature 220 DEG C, five district's temperature 230 DEG C, six district's temperature 230 DEG C, seven district's temperature 240 DEG C, eight district's temperature 200 DEG C, nine district's temperature 230 DEG C, engine speed 400 revs/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.Described antiseptic-germicide is various quaternary antiseptic-germicides commercially available at present.Silane coupling agent specification is KH-602, and chemical name is N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (two amino-type silane coupling agent).
The antibacterial AS composition that embodiment 1-3 and comparative example 1-3 obtains adopts relevant criterion in Chinese light industry standard QB/T2591-2003 " antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect " (experimental strain is intestinal bacteria and streptococcus aureus) to test its correlated performance.
The composition of raw materials (by ratio of weight and the number of copies) of the fiberglass reinforced AS composition of table 1 embodiment and comparative example
The performance data of the fiberglass reinforced AS composition of table 2 embodiment and comparative example
By embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, 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.
Contrasted as can be seen from embodiment 2 and comparative example 2, after adding silane coupling agent, the mechanical property of matrix material significantly improves, this is because by using silane coupling agent, can improve the bond properties of glass fibre and resin, thus improves 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.
It can also be seen that by upper table: after adding antiseptic-germicide, the antibacterial ability of material obviously increases.
In addition, can see from embodiment 3 and comparative example 3 contrast, when coupling agent usage ratio 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 short glass fiber AS matrix material (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.
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 2, 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 (6)
1. antibacterial enhancing AS matrix material and preparation method thereof, is characterized in that: the component comprising following parts by weight:
Described compatilizer is acrylic polymer or multipolymer, and its polymerization single polymerization monomer is one or more in vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate;
Described antiseptic-germicide is quarternary ammonium salt, and general formula is R
4nX, wherein R is four identical or different alkyl, and X is halogen anion or acid group.
2. antibacterial AS composition according to claim 1, is characterized in that: described AS resin is vinyl cyanide and cinnamic multipolymer; Described glass fibre is long glass fibres and/or short glass fiber.
3. antibacterial AS composition according to claim 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. antibacterial AS composition according to claim 1 and 2, is characterized in that: described coupling agent is two amino-type silane coupling agent.
5. antibacterial AS composition according to claim 1, is characterized in that: described auxiliary agent is one or more the mixing in thermo-stabilizer, photostabilizer, processing aid, toner or pigment.
6. the preparation method of the antibacterial AS composition described in claim 1-5, is characterized in that:
(1) component takes AS resin, compatilizer, antiseptic-germicide, coupling agent and auxiliary agent mix 1-3min in high mixer by weight; 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, obtain antibacterial enhancing AS matrix material;
Wherein: the condition melt extruded described in step (2) 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; Described in step (2), the length-to-diameter ratio of twin screw extruder is 40:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510932262.6A CN105462141A (en) | 2015-12-11 | 2015-12-11 | Antibacterial reinforced AS composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510932262.6A CN105462141A (en) | 2015-12-11 | 2015-12-11 | Antibacterial reinforced AS composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105462141A true CN105462141A (en) | 2016-04-06 |
Family
ID=55600330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510932262.6A Pending CN105462141A (en) | 2015-12-11 | 2015-12-11 | Antibacterial reinforced AS composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105462141A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106800739A (en) * | 2017-01-20 | 2017-06-06 | 南京南优新材料有限公司 | Acrylonitrile styrene copolymer composition and profiled spacer therefrom for preparing profiled spacer |
-
2015
- 2015-12-11 CN CN201510932262.6A patent/CN105462141A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106800739A (en) * | 2017-01-20 | 2017-06-06 | 南京南优新材料有限公司 | Acrylonitrile styrene copolymer composition and profiled spacer therefrom for preparing profiled spacer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104403222A (en) | High-performance, anti-static and anti-bacterial glass fiber reinforced AS (acrylonitrile-styrene) composite material and preparation method thereof | |
| JP6388889B2 (en) | A composition comprising polyamide 66 and polyamide 610, polyamide 1010, and polyamide selected from the group consisting of polyamide 1012 | |
| CN103589121B (en) | Glass fiber reinforcement PCT resin and preparation method thereof | |
| US20100160529A1 (en) | Glass Fiber-Reinforced Polyester Resin Composition and Molded Product Using the Same | |
| CN105440559A (en) | High-performance glass fiber-reinforced ABS composition and preparation method thereof | |
| CN102532849B (en) | PC/ASA/PBT (poly carbonate/ acrylonitrile-styrene-acrylate/polybutylene terephthalate) alloy material and preparation method thereof | |
| CN107245234A (en) | Fiber glass reinforced halogen-free flame retardant polycarbonate composite material and preparation method thereof | |
| CN105524367A (en) | Low-odor antistatic high-performance glass fiber reinforced AS composition and preparation method thereof | |
| CN105462139A (en) | Anti-static glass fiber reinforced AS composition and preparation method thereof | |
| CN105462095A (en) | Glass fiber reinforced AS composition and preparation method thereof | |
| CN104072923A (en) | High-heat-resistant transparent reinforcing material as well as preparation method and application thereof | |
| CN105462092A (en) | High performance, anti-static and antibacterial glass fiber reinforced AS composite material and preparation method thereof | |
| CN105462141A (en) | Antibacterial reinforced AS composite material and preparation method thereof | |
| CN105462093A (en) | High performance, anti-static and antibacterial glass fiber reinforced AS composition and preparation method thereof | |
| CN108084623A (en) | A kind of low floating fine fiberglass reinforced AS compositions and its preparation method and application | |
| CN104448599A (en) | Antibacterial glass fiber reinforced AS (acrylonitrile-styrene copolymer) composite material and preparation method thereof | |
| CN105086162A (en) | Fibrilia-reinforced polypropylene engineering composite as well as preparation method and application of fibrilia-reinforced polypropylene engineering composite | |
| CN104387690A (en) | Low-smell antibacterial glass fiber reinforced AS composition and preparation method thereof | |
| WO2004003075A1 (en) | Glass fiber filled thermoplastic compositions with good surface appearance | |
| CN109181292B (en) | Glass fiber reinforced PA66 high-speed rail substrate material and preparation method thereof | |
| CN105462094A (en) | Antibacterial AS composition and preparation method thereof | |
| CN104448600A (en) | Antibacterial glass fiber reinforced AS (acrylonitrile-styrene copolymer) composite material and preparation method thereof | |
| CN104387688A (en) | High-performance anti-static antibacterial glass-fiber reinforced AS composite material and preparation method thereof | |
| CN104387687A (en) | Glass-fiber-enhanced AS composition with good mechanical property and preparation method of Glass-fiber-enhanced AS composition | |
| CN103396643A (en) | Modifier-containing polyacrylate grafted vinyl chloride composite resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160406 |
|
| WD01 | Invention patent application deemed withdrawn after publication |