CN102108179A - Ceramic fiber-containing flame-retardant and reinforced bulk polymerization-prepared acrylonitrile-butadiene-styrene (ABS) complex and preparation method thereof - Google Patents
Ceramic fiber-containing flame-retardant and reinforced bulk polymerization-prepared acrylonitrile-butadiene-styrene (ABS) complex and preparation method thereof Download PDFInfo
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- CN102108179A CN102108179A CN2009102472345A CN200910247234A CN102108179A CN 102108179 A CN102108179 A CN 102108179A CN 2009102472345 A CN2009102472345 A CN 2009102472345A CN 200910247234 A CN200910247234 A CN 200910247234A CN 102108179 A CN102108179 A CN 102108179A
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Abstract
The invention relates to ceramic fiber-containing flame-retardant and reinforced bulk polymerization-prepared acrylonitrile-butadiene-styrene (ABS) and a complex obtained by modifying fire retardance and heat resistance of the bulk polymerization-prepared ABS. The complex comprises the following raw materials in part by weight: 60 to 80 parts of ABS resin, 5 to 25 parts of ceramic fibers, 5 to 10 parts of fire retardant, 1 to 5 parts of heat resistant modifier and 2 parts of processing aid. The complex has the advantage that: as a functional modifying component, the ceramic fibers have the characteristics of high flame retardant property, high heat resistance, high surface hardness, high rigidity and the like. The complex can be applied to products, such as shells of electric appliances, internal components of the electric appliances and the like, having relatively high requirements on fire retardance, heat resistance and performance, particular to external components having a special requirement on color.
Description
Technical field
The present invention relates to a kind of ceramic fiber reinforced flame retardant substance law ABS mixture and preparation method thereof.
Background technology
Ceramic fiber is a kind of fibrous light refractory materials that integrates conventional insulation material, refractory materials premium properties, has low heat conductivity, good thermostability, chemical stability, non-corrosiveness.The diameter of ceramic fiber is generally 2 μ m～5 μ m, and length mostly is 30mm～250mm, and it is slick cylindrical that fiber surface is, and cross section is normally circular.Its constructional feature is void content height (generally greater than 90%), and air vent aperture and specific surface area are big.Because the air in the pore has good heat-blocking action, thereby the size of air vent aperture and the character (ventilate or the hole of holding one's breath) of pore have decisive influence to its heat conductivility in the fiber.In fact, the internal organizational structure of ceramic fiber is a kind of mixed structure of being made up of solid-state fiber and air, its microstructure characteristics all are that form with external phase exists in solid phase and gas phase, therefore, in this structure, solid matter exists with filamentous form, and constitutes the external phase skeleton, gas phase then continued presence among the skeleton gap of filamentary material.Have this structure just because of ceramic fiber, make that its void content is higher, air vent aperture and specific surface area be bigger, thereby make ceramic fiber have good heat-proof quality and smaller volume density.Be used for industry insulation, sealing, protective material, electric heating device insulation, lagging material, the insulation of plant and instrument, electrical heating element and heat insulation material, automobile industry lagging material etc. more.
The liquid crystal polyester dipping ceramic fiber of printed circuit board (PCB) and the refinforced cement based composites that is used to build also appear being used in recent years.Do not see that ceramic fiber is used for the report of ABS plastic modification.
Styrene acrylonitrile copolymer, being ABS (acrylnitrile-butadiene-strene copolymer), is the multipolymer of acrylonitrile-butadiene-styrene (ABS), is a kind of thermoplastics of excellent property, has high impulse strength, thermotolerance and dimensional stability, chemical resistances etc. are because its various advantages that has, be widely used in industrial spare and accessory parts, shells of electronics and driving member, office equipment, and other field.
The production method of ABS resin is a lot, and what application was more on the present full scale plant in the world is that emulsion connects skill fusion method and continuous bulk.Continuous bulk ABS technology is further perfect in recent years, has progressively established it and has been the status of main ABS production technique.Because the continuous bulk ABS resin is because its particular performances, mass polymerization uses vinylbenzene as solvent, and it can be reclaimed fully and recycle in process of production, and little residual is at the finished product, do not need emulsifying agent, the resin of production has natural white.And the process of mass polymerization is a successive, so the quality of resin is very stable and consistent, under normal injecting condition, it is stable that its color also can keep, the high purity of product can also reduce the generation of crazing (radiation line), help improving product percent of pass, when keeping the ABS high-performance, it is significantly improved on using value.
ABS compares with emulsion method, substance law ABS has advantages such as high pure property, low smell are lowly organicly distributed, low gloss, has application prospect widely than emulsion method ABS, but itself flame retardant resistance of substance law ABS resin is extremely low, oxygen index only is about 18, and vertical combustion experiment can't reach the UL94V-2 standard, and uses the occasion of ABS matrix material often to need product to have flame retardant resistance, therefore use at present ABS resin flame-retardant modifiedly seem extremely important; Because the resistance toheat of general ABS resin itself is not high, the general about 82-84 of heat-drawn wire ℃ (ASTM D648,1.82MPa), can further descend through the ABS resin heat resisting temperature after flame-retardant modified, thereby must carry out flame-retardant modified to it, also need further to improve the thermotolerance of substance law ABS, just can widen its Application Areas.But in existing study on the modification such as heat-resisting, fire-retardant, do not appear in the newspapers and introduce suitable ceramic fiber, improve heat-resisting, the flame retardant properties and the balance physical and mechanical property of substance law ABS mixture as function modified component.The present invention is just from these angles, provide a kind of novel heat-proof combustion-resistant to strengthen substance law ABS resinoid, utilize composite modification technology on the basis that has kept original excellent flame retardancy energy of fire-retardant substance law ABS resin and processing characteristics, utilize ceramic fiber enhancing and heat resistance modified method to improve its heat-drawn wire again, thereby satisfy in the specific occasion the multiple requesting of substance law ABS resin flame retardant resistance and heat-resisting and higher mechanical property.
Summary of the invention
The present invention seeks to disclose a kind of fire-retardant enhancing substance law ABS mixture that contains ceramic fiber and preparation method thereof,, satisfy the needs of association area development to overcome the above-mentioned defective that prior art exists.
Fire-retardant enhancing substance law ABS mixture of the present invention, its typical weight umber consists of:
60～80 parts of substance law ABS resin;
5～30 parts of ceramic fibers;
5～10 parts of fire retardants;
Heat-proof modifier 1-5 part;
2 parts of processing aids.
The matrix resin that the present invention adopts is a substance law ABS resinoid, and the rubber phase weight content is 8-20%, as the ABS3453,3904 of DOW company.
The ceramic fiber that the present invention adopts preferably adopts the ceramic fiber of handling through composite coupler, preferred Luanping, Hebei Ao Tesiding Industrial Co., Ltd, and specification is the ceramic fiber of high temperature (HT) type, 2～4 microns of Fibre diameters.
The composite coupler parts by weight that ceramic fiber is handled consist of:
Phosphate coupling agent 20-40 part, silane coupling agent 35-55 part, Resins, epoxy 5-15 part, glycidyl ester 15-35 part.
Phosphate coupling agent is a chelating type tetra-sodium titanate coupling agent, and can adopt the U.S. Kenrich company trade mark is the product of KR-238S;
The chemical name of silane coupling agent is a vinyltriethoxysilane, and can adopt the domestic Qingdao big chemical industry company limited in the sea trade mark is the product of A-151;
It is the product of R-140 that Resins, epoxy can adopt the Mitsui chemistry trade mark;
Glycidyl ester is isocyanuric acid three-glycidyl ester (TGIC), and domestic a plurality of producers are all on sale.Said composite coupler consumption is for being 0.5～2% based on ceramic fiber weight.
Treatment process is as follows:
Earlier treatment agents such as phosphate coupling agent, silane coupling agent, Resins, epoxy, glycidyl ester are mixed and are positioned in the treatment trough by top proportioning, the ceramic fiber after wire drawing is handled is handled back (flooding 5～10 seconds) by the composite treating agent in the treatment trough and is promptly got the ceramic fiber that required modification is handled.
Ceramic fiber after the processing can play good enhancement to material, makes material have high-modulus and rigidity, gives good infiltration, the coating of ceramic fiber and resin, makes that the ceramic fiber height is heat-resisting, fire-resistance property is played a role in resin system.
Said fire retardant is selected from oxide compound or oxyhydroxide micron order magnesium, the oxide compound of aluminium and a kind of or mixture of oxyhydroxide of nano level magnesium, aluminium among the present invention, micron order mainly plays synergistic flame retardant, can effectively reach fire-retardant and press down the purpose of cigarette, because particle diameter is little, its flame retardant effect relatively can be more outstanding.
The heat-proof modifier that adopts in of the present invention is selected from alpha-methyl styrene (a kind of or its mixture in α-MS), syndiotactic polystyrene (SPS), N-phenylmaleimide (PMI), the bismaleimides (BMI), it mainly acts on is increase the polymer segment motion sterically hindered, improves resistance toheat.
The processing aid that adopts among the present invention comprises lubricant and coupling agent, and these processing aids can effectively improve each component dispersiveness, reduce harmful friction when processing and moulding, thereby improve processing characteristics.Lubricant comprises the mixture of some soap, fatty acid amide and/or these compounds, specifically comprise solid paraffin, whiteruss, low molecular weight polyethylene, calcium stearate, Zinic stearas, stearic amide, methylene bis stearic amide and N, N-ethylene bis stearic acid amide (EBS) etc.Coupling agent comprises titanic acid ester and aluminic acid ester cpds, as KH-550, KH-560, A-189,101 etc.
The preparation method of the fire-retardant reinforced ABS mixture that contains ceramic fiber of the present invention is as follows:
With the substance law ABS resin, thorough mixing under heat-proof modifier and the processing aid high-speed stirring, the pay-off of delicate metering is sent in the twin screw extruder then, in the high speed shear of screw rod, mixing following with conveying, material is able to sufficient fusing, and is compound, again through extruding, tie rod, cooling, pelletizing obtains a step material; And then with thorough mixing under step material and a fire retardant, the processing aid high-speed stirring, send in the twin screw extruder by the pay-off of delicate metering, by the side direction feeding ceramic fiber metering is evenly added forcing machine, in the high speed shear of screw rod, mixing following with conveying, material is able to sufficient fusing, and is compound, again through extruding, tie rod, cooling, pelletizing is packaged as finished product at last.
This method adopts the length-to-diameter ratio of twin screw extrusion equipment to be at least 32, more preferably greater than 36; And have precise dose control and a vacuum-pumping equipment.Each section of the first step extruder temperature should be controlled between 220～260 ℃, is preferably between 220～255 ℃, and each section extruder temperature in second step should be controlled between 180～220 ℃, is preferably between 190～210 ℃.Screw speed is preferably between 300～500 rev/mins between 100～600 rev/mins.
Product of the present invention had both had the good flame performance, had characteristics such as height is heat-resisting, high surface hardness, high rigidity simultaneously again.Flame retardant rating can reach UL94V-0, can satisfy the service requirements of electric appliance casing, inner structural members based article.The fire-retardant enhancing substance law ABS mixture that contains ceramic fiber of the present invention adopts the twin screw extrusion equipment, have flow process simple, continuously, the advantage of high, the constant product quality of production efficiency.
Embodiment
Embodiment 1～3
Preparation and the physicals that contains the fire-retardant enhancing substance law ABS mixture of ceramic fiber of the present invention sees attached list 1, and the testing method standard of employing sees attached list 2:
The substance law ABS resin that adopts in the present embodiment is the ABS3453 or 3904 of DOW company; Heat-proof modifier is the AS-MS-NA of Japanese electrochemical company,, be the multipolymer of N-phenylmaleimide and AS; Fire retardant is that fire retardant is super Hai Qi Science and Technology Ltd. produces in Beijing the particle diameter magnesium hydroxide less than 100 nanometers; Ceramic fiber is the ceramic fiber of high temperature (HT) type of Luanping, Hebei Ao Tesiding Industrial Co., Ltd production, 2～4 microns of Fibre diameters; The processing and lubrication auxiliary agent is homemade EBS, also has a small amount of white mineral oil.
The preparation process of material is as described below: with the substance law ABS resin, thorough mixing under heat-proof modifier and the processing aid high-speed stirring, the pay-off of delicate metering is sent in the twin screw extruder then, the extruder screw length-to-diameter ratio is 36: 1, has strong shearing screwing element distributed combination, each section extruder temperature is controlled between 240～250 ℃, and screw speed is 300～400 rev/mins, in the high speed shear of screw rod, mixing following with conveying, material is able to sufficient fusing, and is compound, again through extruding, tie rod, cooling, pelletizing obtains a step material; And then with thorough mixing under step material and a fire retardant, the processing aid high-speed stirring, send in the twin screw extruder by the pay-off of delicate metering, by the side direction feeding ceramic fiber metering is evenly added forcing machine, forcing machine has vacuum-pumping equipment, screw slenderness ratio is 40: 1, each section extruder temperature is controlled between 190～200 ℃, screw speed is 400～500 rev/mins of high speed shear at screw rod, and mixing following with conveying, material is able to sufficient fusing, compound, again through extruding tie rod, cooling, pelletizing is packaged as finished product at last.
Table 1
Table 2
| Physicals | Testing standard | Unit |
| Tensile strength | ISO527/2-93 | MPa |
| Flexural strength | ISO178-93 | MPa |
| Notched Izod impact strength | ISO180-93 | KJ/m2 |
| Heat-drawn wire | ISO75-1 | ℃ |
| Flame retardant properties | UL94 | Class |
Claims (8)
1. a fire-retardant enhancing substance law ABS mixture that contains ceramic fiber is characterized in that, is made up of following weight part raw material:
60 parts-80 parts of substance law ABS resin,
5 parts-25 parts of ceramic fibers,
5 parts-10 parts of fire retardants,
1 part-5 parts of heat-proof modifiers,
2 parts of processing aids.
2. according to the said a kind of fire-retardant enhancing substance law ABS mixture that contains ceramic fiber of claim 1, it is characterized in that described ceramic fiber is the ceramic fiber of handling through composite coupler, specification is the ceramic fiber of high temperature (HT) type, 2 ~ 4 microns of Fibre diameters.
3. according to the said a kind of fire-retardant enhancing substance law ABS mixture that contains ceramic fiber of claim 1, it is characterized in that described matrix resin is a substance law ABS resinoid, the rubber phase weight content is 8-20%.
4. according to the said a kind of fire-retardant enhancing substance law ABS mixture that contains ceramic fiber of claim 1, it is characterized in that described fire retardant is oxide compound or oxyhydroxide micron order magnesium, the oxide compound of aluminium and a kind of or mixture of oxyhydroxide of nano level magnesium, aluminium.
5. according to the said a kind of fire-retardant enhancing substance law ABS mixture that contains ceramic fiber of claim 1, it is characterized in that described heat-proof modifier is alpha-methyl styrene (a kind of or its mixture in α-MS), syndiotactic polystyrene (SPS), N-phenylmaleimide (PMI), the bismaleimides (BMI).
6. according to the said a kind of preparation method who contains the fire-retardant enhancing substance law ABS mixture of ceramic fiber of claim 1; it is characterized in that; the steps include: that ABS resin, heat-proof modifier and the processing aid that will measure mix; make a step material by twin screw extruder; again a step material and fire retardant, processing aid metering are mixed; in twin screw extruder ceramic fiber is added, extrude, granulation obtains product.
7. according to the said a kind of fire-retardant enhancing substance law ABS mixture that contains ceramic fiber of claim 1, it is characterized in that said processing aid comprises lubricant and coupling agent.Lubricant comprises the mixture of some soap, fatty acid amide and/or these compounds, specifically comprise solid paraffin, whiteruss, low molecular weight polyethylene, calcium stearate, Zinic stearas, stearic amide, methylene bis stearic amide and N, N-ethylene bis stearic acid amide (EBS) etc.Coupling agent comprises titanic acid ester and aluminic acid ester cpds, as KH-550, KH-560, A-189,101 etc.
8. according to the said ceramic fiber of handling through composite coupler of claim 2, it is characterized in that said composite coupler is phosphate coupling agent 20-40 part, silane coupling agent 35-55 part, Resins, epoxy 5-15 part, glycidyl ester 15-35 part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102472345A CN102108179A (en) | 2009-12-28 | 2009-12-28 | Ceramic fiber-containing flame-retardant and reinforced bulk polymerization-prepared acrylonitrile-butadiene-styrene (ABS) complex and preparation method thereof |
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| CN2009102472345A CN102108179A (en) | 2009-12-28 | 2009-12-28 | Ceramic fiber-containing flame-retardant and reinforced bulk polymerization-prepared acrylonitrile-butadiene-styrene (ABS) complex and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740042A (en) * | 2013-12-31 | 2014-04-23 | 宁波小康塑料有限公司 | Flame-retardant enhanced acrylonitrile-butadiene-styrene copolymer |
| CN104448685A (en) * | 2014-12-17 | 2015-03-25 | 天津金发新材料有限公司 | Ceramic fiber reinforced flame retardant ABS and preparation method thereof |
| CN109096684A (en) * | 2018-07-11 | 2018-12-28 | 合肥铭佑高温技术有限公司 | A kind of heat-resistant engineering plastic of high tenacity |
-
2009
- 2009-12-28 CN CN2009102472345A patent/CN102108179A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740042A (en) * | 2013-12-31 | 2014-04-23 | 宁波小康塑料有限公司 | Flame-retardant enhanced acrylonitrile-butadiene-styrene copolymer |
| CN104448685A (en) * | 2014-12-17 | 2015-03-25 | 天津金发新材料有限公司 | Ceramic fiber reinforced flame retardant ABS and preparation method thereof |
| CN109096684A (en) * | 2018-07-11 | 2018-12-28 | 合肥铭佑高温技术有限公司 | A kind of heat-resistant engineering plastic of high tenacity |
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Application publication date: 20110629 |