CN104497432A - Anti-static glass fiber reinforced AS composition and preparation method thereof - Google Patents
Anti-static glass fiber reinforced AS composition and preparation method thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 30
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 14
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 14
- 239000002216 antistatic agent Substances 0.000 claims abstract description 3
- 239000011152 fibreglass Substances 0.000 claims description 38
- 230000003068 static effect Effects 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
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- 238000001035 drying Methods 0.000 claims description 3
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- 239000000049 pigment Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 19
- 230000008901 benefit Effects 0.000 abstract description 5
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- 230000002708 enhancing effect Effects 0.000 abstract 1
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001075561 Fioria Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
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- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 description 1
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- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides an anti-static glass fiber reinforced AS composition and a preparation method thereof. The composition is prepared from the following components in percentage by weight: 59-88% of AS resin, 10-30% of glass fibers, 0.8-10% of a compatilizer, 0.1-1% of a coupling agent, 10-15% of an anti-static agent and 0.1-3% of auxiliaries, wherein the compatilizer is polymethylmethacrylate and the coupling agent is a silane coupling agent. As the matrix is the AS resin, the composition has the advantages of excellent performance, low cost, simple preparation process and the like. By using PMMA as the compatilizer, not only is the binding force between the glass fibers and the AS resin enhanced, but also the composition is suitable for enhancing a fiber and resin composite material system with similar properties.
Description
Technical field
The invention belongs to modified plastics field, especially relate to a kind of anlistatig fiberglass reinforced AS composition and method of making the same.
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.
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 provide 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.
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.
To sum up, because glass-fibre reinforced resin matrix material has broad application prospects, therefore urgently develop a kind of excellent in mechanical performance, antistatic, preparation technology is simple, lower-cost antistatic fiberglass reinforced AS matrix material.
Summary of the invention
The invention provides a kind of anlistatig fiberglass reinforced AS composition and method of making the same, 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 anlistatig fiberglass reinforced AS composition, 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 antistatic 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 antistatic 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;
Silane coupling agent (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 static inhibitor is permanent antistatic agent, comprises metal-salt and polyoxyethylene in its composition.
Further, described auxiliary agent comprises any one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment;
Antistatic 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.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, and metallic soap is Cast or Znst; Described amides processing aid is erucicamide.
A preparation method for anlistatig fiberglass reinforced AS composition, comprises the steps:
S1, AS resin, compatilizer, coupling agent, static inhibitor and auxiliary agent will be taken by weight percentage be placed in high-speed mixer and mixing 1-3min, obtain the Preblend mixed;
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 antistatic fiberglass reinforced AS composition.
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.
Described fiberglass reinforced AS composition is otherwise known as fiberglass reinforced AS matrix material.
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 antistatic 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) the present invention is by adding static inhibitor, and the surface resistivity of AS composition can be made from 10
16Ω is reduced to 10
8Ω, antistatic effect is good.
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, AS resin, compatilizer, coupling agent, static inhibitor and the auxiliary agent weight percent listed in following table 1 taken respectively in each embodiment or each comparative example, said components in each embodiment or each comparative example is placed in high-speed mixer and mixing 1-3min, obtains the Preblend mixed;
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 1 from side spout and take each embodiment or glass fibre corresponding to each comparative example, carry out melt extruding, granulating and drying, obtain antistatic fiberglass reinforced AS composition;
S3, the antistatic fiberglass reinforced AS composition obtained by step S2 respectively make the Test strips meeting experiment condition according to iso standard, 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; Static inhibitor is selected from the PELESTAT6500 that Sanyo changes into.
The antistatic fiberglass reinforced AS matrix material that embodiment and comparative example obtain adopts iso standard to test its correlated performance: static resistance tests its surface resistivity according to GB/T1410-2006.
Table 1 embodiment 1-6 and comparative example 1-6 each amounts of components by weight percentage
Silane coupling agent specification used in table 2 embodiment 1-6 and comparative example 1-6
The performance data of table 3 embodiment 1-6 and comparative example 1-6
As can be seen from embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, contrast between embodiment 3 and comparative example 3, 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.
Can be seen by the contrast between embodiment 3,4,5, 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 glass fiber reinforcement AS (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 from 10
16Ω is reduced to 10
8Ω, antistatic effect is good.
As can be seen from embodiment 1-6, use the anlistatig fiberglass reinforced AS matrix material that the present invention produces, its mechanical property and thermal characteristics are very excellent.As 20% fiberglass reinforced AS matrix material 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 (10)
1. an anlistatig fiberglass reinforced AS composition, is characterized in that, comprises following component by weight percentage:
Described compatilizer is polymethylmethacrylate;
Described coupling agent is silane coupling agent.
2. one according to claim 1 anlistatig fiberglass reinforced AS composition, 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 anlistatig fiberglass reinforced AS composition, 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 anlistatig fiberglass reinforced AS composition, is characterized in that: described silane coupling agent is amino-type silane coupling agent.
5. one according to claim 4 anlistatig fiberglass reinforced AS composition, is characterized in that: described amino-type silane coupling agent contains two or three above amino.
6. one according to claim 1 anlistatig fiberglass reinforced AS composition, is characterized in that: described static inhibitor is permanent antistatic agent, comprises metal-salt and polyoxyethylene in its composition.
7. one according to claim 1 anlistatig fiberglass reinforced AS composition, is characterized in that: described auxiliary agent comprises any one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment.
8., as a preparation method for the antistatic fiberglass reinforced AS composition in claim 1-7 as described in any one, it is characterized in that comprising the steps:
S1, AS resin, compatilizer, coupling agent, static inhibitor and auxiliary agent will be taken by weight percentage be placed in high-speed mixer and mixing 1-3min, obtain the Preblend mixed;
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 antistatic fiberglass reinforced AS composition.
9. the preparation method of a kind of anlistatig fiberglass reinforced AS composition 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.
10. the preparation method of a kind of anlistatig fiberglass reinforced AS composition according to claim 8 or claim 9, is characterized in that: the length-to-diameter ratio of described twin screw extruder is 40:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106800743A (en) * | 2017-01-18 | 2017-06-06 | 安徽朗迪叶轮机械有限公司 | A kind of axial-flow leaf and preparation method thereof |
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