CN105524367A - Low-odor antistatic high-performance glass fiber reinforced AS composition and preparation method thereof - Google Patents
Low-odor antistatic high-performance glass fiber reinforced AS composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-odor antistatic high-performance glass fiber reinforced AS composition, which contains, by weight, 30-80% of AS resin, 10-30% of glass fiber, 1-10% of a compatilizer, 1-5% of jellyfish granules, 0.1-1% of a coupling agent, 10-15% of an antistatic agent and 0.1-3% of an auxiliary agent. The total percentage of the above components is 100%. The antistatic agent is a permanent antistatic agent and contains molecular distilled glycerin monostearate component, which is specifically hardened palm glyceride. The jellyfish granules used in the invention are easily available, has advantages of simple preparation technology and low cost, can effectively remove odor and will not influence mechanical property of the composition. By adding the antistatic agent, surface resistivity of the AS composition can be reduced from 1016 Omega to 109 Omega, and the antistatic effect is good.
Description
Technical field
The present invention relates to modified plastics field, be specifically related to a kind of low smell, anlistatig high-performance fiberglass reinforced AS composition and method of making the same.
Background technology
Bing Xi Jing ?vinylbenzene (AS) resin be 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.
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; Therefore, develop a kind of low smell fiberglass reinforced AS matrix material, there is great market.
The reason that fiberglass reinforced AS matrix material smell is large is many-sided, and first, in the fabrication process, there is more small molecular weight impurity, smell is more unpleasant for AS resin, and total carbon emitting is also higher; And in the preparation process of glass fiber reinforcement AS matrix material, often add and variously add compatilizer, these compatilizers often give off an unpleasant smell to some extent.Therefore, in order to glass fiber reinforcement AS matrix material can be made to be more widely used, the method preparing low smell glass fiber reinforcement AS matrix material just must be found.
The basic skills reducing smell comprises chemical reaction and physical adsorption two kinds.Chemical reaction method refers to some additives that can react with scent of small-molecule substance, these additives and small molecules reaction, produce the another kind of compound that molecular chain is large, can not evaporate in general environment, thus elimination smell, such as zinc ricinate reduces smell by chelating aldehyde ketone molecule.And for physical adsorption, theoretically, a large amount of cavities can be adsorbed the small molecules of any generation smell or other fugitive constituents, therefore may be all effective to all respects producing odor problem.Physical absorbent conventional at present comprises gac, silica gel, Attapulgite, clay mineral system, molecular sieve, zeolite, wollastonite, wilkinite etc.
Patent 200510026760.0 mention smell be resin raw material, stablizer, mineral filler and processing cracking produce, smell solution: nano zine oxide and nano titanium oxide.Eichenauer etc. describe the ABS molding that a kind of smell improves in USP6297307, by adding the mixture of a kind of zinc oxide, magnesium oxide and at least one epoxy compounds, this approach improves smell.But these additives especially impact the mechanical property of AS matrix material and have a great impact
The performance requriements of household appliance technical field to fiberglass reinforced AS matrix material is generally: tensile strength >100MPa, modulus in flexure >6500MPa, heat-drawn wire >100 DEG C, glass weight content 19 ?22%, notched Izod impact strength >6.0kJ/m2.
The mechanical property of glass fiber reinforcement AS depends on the cohesive strength of AS and glass fibre to a great extent, because the bonding interface of resin and glass is poor, the enhancement of glass can not be given full play to, the composite material strength of formation, toughness, the poor-performings such as thermotolerance.
In addition, 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.
Therefore, develop a kind of low smell, excellent in mechanical performance and the fiberglass reinforced AS matrix material with antistatic effect seems particularly important, there is the huge market space.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, primary and foremost purpose of the present invention is to provide one to have low smell, anlistatig high-performance fiberglass reinforced AS composition.
Another object of the present invention is to the preparation method that a kind of above-mentioned low smell, anlistatig high-performance fiberglass reinforced AS composition are provided.
The present invention is achieved through the following technical solutions:
A kind of low smell, anlistatig high-performance fiberglass reinforced AS composition, by weight percentage, comprise following component:
Above-mentioned each component sum is 100%;
Described static inhibitor is permanent antistatic agent, comprises molecular distillation glyceryl monostearate composition, is specially the palm oil glycerides of sclerosis;
Wherein, described jellyfish grain by weight percentage, comprises following component:
Polypropylene 1% ?49%;
Water 50% ?98%;
Mineral filler 0.1 ?5%;
Above-mentioned each component sum is 100%.
Jellyfish grain of the present invention is by polypropylene, mineral filler and water composition mixture, this complex aqueous amount>=50%, preferably 60 ?90%; Described polypropylene is high melt strength, propylene, its melt strength>=5cN; Wherein, melt strength test condition is: under the experimental temperature of 190 DEG C, and use the capillary die that length-to-diameter ratio is 10:1, mouth mould is 24cm to the distance of roller, and plunger lowering speed is 0.10mm/s, and the acceleration of traction rollers is 5mm/s
2.
The preparation method of described jellyfish grain, comprises the steps:
(1) polypropylene is mixed by proportioning fully with mineral filler, 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) by the expanded polypropylene of high fondant-strength and water in super mixer mixed 5 ?10min, prepare the jellyfish grain of different moisture content, release stand-by.
Jellyfish grain add-on of the present invention preferably 1 ?5%, add too much jellyfish grain, jellyfish grain can seethe with excitement in screw rod, thus be unfavorable for produce.
Described AS resin is vinyl cyanide, cinnamic multipolymer.
Described glass fibre is the mixing of one or more of long glass fibres or short glass fiber.
Preferably, described long glass fibres is alkali free glass fibre, diameter be 10 ?16 μm; The length of described short glass fiber be 0.2 ?10mm, diameter be 8 ?20 μm.
Described compatilizer is acrylic polymer or multipolymer; Its polymerization single polymerization monomer is vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, Bing Xi Suan ?2 ?one or more in ethylhexyl.
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 coupling agent is titanate coupling agent.
Matrix material of the present invention also comprise 0.1 ?the auxiliary agent of 3% (weight percent), described auxiliary agent is the mixing of one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment.Because the present invention is automotive trim AS matrix material, can be used alone above-mentioned auxiliary agent according to the structure of different automotive trim, technical requirements etc., or compound use.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 (Cast, Znst), stearic acid complex ester or amides (erucicamide).
The preparation method of low smell of the present invention, anlistatig high-performance fiberglass reinforced AS composition, comprises the following steps:
(1) take by weight percentage AS resin, compatilizer, jellyfish grain, coupling agent, static inhibitor and auxiliary agent mix in high mixer 1 ?3min; Mix, obtain Preblend;
(2) Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying, to obtain final product.
The described condition melt extruded is: district's temperature 180 ?210 DEG C, two district's temperature 190 ?220 DEG C, three district's temperature 190 ?230 DEG C, four district's temperature 190 ?240 DEG C, five district's temperature 190 ?240 DEG C, six district's temperature 190 ?240 DEG C, seven district's temperature 190 ?240 DEG C, eight district's temperature 190 ?240 DEG C, nine district's temperature 190 ?240 DEG C, engine speed 250 ?600 revs/min; The length-to-diameter ratio of twin screw extruder is 40:1.
The present invention compared with prior art, has following beneficial effect:
1) 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 composition;
2) 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
9Ω, antistatic effect is good.
3) 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 titanate 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.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
In following examples and comparative example, the processing conditions that forcing machine melt extrudes is as follows: district's temperature 180 ?210 DEG C, two district's temperature 190 ?220 DEG C, three district's temperature 190 ?230 DEG C, four district's temperature 190 ?240 DEG C, five district's temperature 190 ?240 DEG C, six district's temperature 190 ?240 DEG C, seven district's temperature 190 ?240 DEG C, eight district's temperature 190 ?240 DEG C, nine district's temperature 190 ?240 DEG C, engine speed 250 ?600 revs/min; The length-to-diameter ratio of twin screw extruder is 40:1.
AS resin is selected from the NF2200 of Taiwan, roving glass fiber be selected from megalith group ER13 ?2000 ?988A, its Fibre diameter is 13 μm, and linear density is 2000tex; Short glass fiber be selected from ShenzhenYataida company ECS ?13 ?4.5 series, the length of its glass fibre is 4.5mm, and diameter is 13 μm.
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; By the expanded polypropylene of high fondant-strength and water in super mixer mixed 5 ?10min, prepare the jellyfish grain of water content as shown in table 1, release stand-by.
Each component concentration (weight percent) of table 1 jellyfish grain
Embodiment 1 ?6, comparative example 6
A fiberglass reinforced AS composition 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 by weight percentage AS resin, compatilizer, jellyfish grain, titanate coupling agent, static inhibitor and auxiliary agent mix in high mixer 1 ?3min; 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 composition 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 by weight percentage AS resin, compatilizer and auxiliary agent mix in high mixer 1 ?3min; 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 composition 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 by weight percentage AS resin, titanate coupling agent and auxiliary agent mix in high mixer 1 ?3min; 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 composition 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, static inhibitor and auxiliary agent mix in high mixer 1 ?3min; 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 composition 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, simulates 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.
The composition of raw materials (by weight percentage) of the fiberglass reinforced AS composition of table 3 embodiment and comparative example
Titanate coupling agent specification used in table 4 embodiment and comparative example
The performance data of the fiberglass reinforced AS composition 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 titanate coupling agent, the mechanical property of matrix material significantly improves, this is because by using titanate 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: titanate 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 titanate 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 titanate coupling agent, its coupling effect wants excellent in the coupling effect of medium-sized titanate coupling agent, specifically, use two amino-type titanate 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 titanate 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.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, 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
2risen to 8 ?9KJ/m
2etc..
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to invention, although the present invention discloses as above with preferred embodiment, but be not intended to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be do not depart from technical solution of the present invention content, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (8)
1. low smell, an anlistatig high-performance fiberglass reinforced AS composition, is characterized in that, by weight percentage, comprise following component:
Above-mentioned each component sum is 100%;
Described static inhibitor is permanent antistatic agent, comprises molecular distillation glyceryl monostearate composition, is specially the palm oil glycerides of sclerosis;
Wherein, described jellyfish grain by weight percentage, comprises following component:
Polypropylene 1% ?49%;
Water 50% ?98%;
Mineral filler 0.1 ?5%;
Above-mentioned each component sum is 100%.
2. a kind of low smell as claimed in claim 1, anlistatig high-performance fiberglass reinforced AS composition, it is characterized in that, the preparation method of described jellyfish grain, comprises the steps:
(1) polypropylene is mixed by proportioning fully with mineral filler, 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) by the expanded polypropylene of high fondant-strength and water in super mixer mixed 5 ?10min, prepare the jellyfish grain of different moisture content, release stand-by.
3. a kind of low smell as claimed in claim 1, anlistatig high-performance fiberglass reinforced AS composition, it is characterized in that, described AS resin is vinyl cyanide and cinnamic multipolymer.
4. a kind of low smell as claimed in claim 1, anlistatig high-performance fiberglass reinforced AS composition, it is characterized in that, described glass fibre is the mixing of one or more of long glass fibres or short glass fiber;
Described long glass fibres is alkali free glass fibre, diameter be 10 ?16 μm; The length of described short glass fiber be 0.2 ?10mm, diameter be 8 ?20 μm.
5. a kind of low smell as claimed in claim 1, anlistatig high-performance fiberglass reinforced AS composition, 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, Bing Xi Suan ?2 ?one or more in ethylhexyl.
6. a kind of low smell as claimed in claim 1, anlistatig high-performance fiberglass reinforced AS composition, it is characterized in that, described coupling agent is titanate coupling agent.
7. the preparation method of low smell as claimed in claim 1, anlistatig high-performance fiberglass reinforced AS composition, comprises the following steps:
(1) take by weight percentage AS resin, compatilizer, jellyfish grain, coupling agent and auxiliary agent mix in high mixer 1 ?3min; 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.
8. the preparation method of low smell as claimed in claim 1, anlistatig high-performance fiberglass reinforced AS composition, it is characterized in that, described in the condition that melt extrudes be: district's temperature 180 ?210 DEG C, two district's temperature 190 ?220 DEG C, three district's temperature 190 ?230 DEG C, four district's temperature 190 ?240 DEG C, five district's temperature 190 ?240 DEG C, six district's temperature 190 ?240 DEG C, seven district's temperature 190 ?240 DEG C, eight district's temperature 190 ?240 DEG C, nine district's temperature 190 ?240 DEG C, engine speed 250 ?600 revs/min; The length-to-diameter ratio of twin screw extruder is 40:1.
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| CN109749267A (en) * | 2017-11-02 | 2019-05-14 | 丹阳博亚新材料技术服务有限公司 | A kind of flame retardant type plastic formula |
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| CN110885502A (en) * | 2019-12-13 | 2020-03-17 | 天津金发新材料有限公司 | Low-emission precipitation-resistant antistatic talcum powder filled polypropylene material and preparation method thereof |
| CN112961444A (en) * | 2021-02-05 | 2021-06-15 | 浙江科普特新材料有限公司 | Primer-free reinforced SAN material for soft PVC wrapping edges and preparation method and application thereof |
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