CN102702665B - Flame-retardant ABS (acrylonitrile butadiene styrene) nano hybrid resin material and preparation method thereof - Google Patents
Flame-retardant ABS (acrylonitrile butadiene styrene) nano hybrid resin material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel flame-retardant ABS (acrylonitrile butadiene styrene) nano hybrid resin material and a preparation method thereof. The novel flame-retardant ABS nano hybrid resin material includes the following components: by weight, 65-75 parts of ABS, 1-2 parts of ATO (arsenic trioxide), 10-20 parts of brominated flame retardant, 5-10 parts of antimonic flame retardant, 0.1-0.3 part of antioxidant and 0.2-0.3 part of lubricant. The material with nanoscale ATO controllably uniformly dispersed in the substrate ABS has stable flame retardant, excellent mechanical property and anti-static and uvioresistant functions. All the components are non-toxic and free of side effects, operation is safe, and process is simple and easy. The novel flame-retardant ABS nano hybrid resin material obtained has fine overall performances and excellent application prospect.
Description
Technical field
The present invention relates to a kind of nano hybridization resin material and preparation method thereof, relate in particular to a kind of antistatic, fire-retardant acrylonitrile-butadiene-phenylethylene terpolymer (ABS) nano hybridization resin material that uvioresistant performance is superior and preparation method thereof.
Background technology
The character of the characteristic of nano material and its Component units (1-100nm) is closely related, and the nanoparticle system of these yardsticks between both macro and micro atom, the molecule material level new as a class, the character of many uniquenesses and new rule have appearred, for example metal Cu just becomes electric poor conductor, SiO to nano level
2there is good insulativity, and start conduction while reaching 20nm.Due to the structure uniqueness of nanoparticle, thereby the nano material especially formed has traditional material and the unexistent new performance of device and function.The unique texture of nanoparticle, it is produced some special effects, as small-size effect, surface effects, quantum size effect, macro quanta tunnel effect.Thereby give nano-hybrid material with properties such as light, electricity, magnetic, absorption, catalysis and biological activitys.
Acrylonitrile-butadiene-phenylethylene terpolymer (ABS) resin is important engineering plastics, have good thermotolerance, high impact properties, dimensional stability, electroconductibility better, stable chemical nature, be easy to the plurality of advantages such as machine-shaping and recovery, its use temperature can change between-40 ℃～100 ℃, and therefore ABS resin is widely used in the device housings materials such as building, household electrical appliances, automobile, computer, daily living article in recent years.General ABS is used as sheating material, there is fire-retardant requirement in capital, generally now that fire retardant by adding halogen-containing system is to provide its flame retardant resistance, but the light fugitive of halogenated flame retardant own, and the performance such as the ABS uvioresistant that can deteriorate significantly, and contain two keys due to the butadiene molecule chain in the ABS self structure, two keys position very easily forms active centre, cause polystyrene segment degraded in ABS, and then cause xanthochromia, uvioresistant performance is very poor.In addition, when ABS material and other materials Surface Contact or friction, easily produce buildup of static electricity, cause dust suction, electric shock or spark, make troubles and potential safety hazard to the use of material.Therefore improve static resistance and the uvioresistant performance of flame-proof ABS, make ABS more widely as the application of exterior trimming parts material, be popular problem always.
At present, the raising flame-proof ABS resin is antistatic, the method for uvioresistant performance, normally adding a kind of is to add some static inhibitor, metal or carbon series conductive material to improve the static resistance of material, and more mentions the performances such as ultraviolet-resistent property that add photostabilizer, light absorber etc. to improve material for the raising of uvioresistant performance.But this type of method of adding the auxiliary agent class more or less all material as mechanical property, processing characteristics, the persistence aspect of modification existing problems especially.
Summary of the invention
The object of the present invention is to provide the nano hybridization resin material of the good flame-proof ABS of the over-all propertieies such as a kind of static resistance with lasting excellence, uvioresistant performance.
Another object of the present invention is to provide a kind of preparation method of novel flame-retardant ABS nano hybridization resin material.Present method can make ABS have lasting static resistance and uvioresistant and flame retardant properties, can effectively reduce the surface resistivity of ABS resin and improve its mechanics and processing characteristics, has a good application prospect.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation of novel flame-retardant ABS nano hybridization resin material comprises following component by weight:
Above-mentioned novel flame-retardant ABS nano hybridization resin material, it is described ATO (stibium doping stannic oxide), is through ionogenic surfactant Sodium hexametaphosphate 99 (NaPO
3)
6inorganic nano material after modification.
Above-mentioned novel flame-retardant ABS nano hybridization resin material, it is that described bromide fire retardant selects any one in decabromodiphynly oxide, TDE, brominated epoxy.
Above-mentioned novel flame-retardant ABS nano hybridization resin material, it is that described Sb system fire retardant selects antimonous oxide.
Above-mentioned novel flame-retardant ABS nano hybridization resin material, it is that described oxidation inhibitor is any one or more than one the mixture in antioxidant 1076, irgasfos 168 and antioxidant 1010.
Above-mentioned novel flame-retardant ABS nano hybridization resin material, it is that described lubricant is the EBS(ethylene bis stearic amide).
Above-mentioned novel flame-retardant ABS nano hybridization resin material, it is to adopt following preparation method to obtain:
(1) stopping composition pre-treatment: by ionogenic surfactant Sodium hexametaphosphate 99 (NaPO for stibium doping stannic oxide (ATO)
3)
6carry out surface treatment and obtain modification ATO nanoparticle; This surface treatment can be strengthened the electrostatic repulsion between particle, makes its active group with easy reaction, and resulting modification ATO nano particle diameter is about 20～50nm, and dispersed; By raw material A BS resin dry 2～4h under 80～90 ℃ of conditions;
(2) after dry raw material A BS, modification ATO nanoparticle, bromide fire retardant, Sb system fire retardant, antioxidant and mix lubricant is even, through twin-screw extrusion owner feed system, send into the Screw Extrusion granulation.Expressing technique: head is to the charging opening temperature, and Yi Dao 2nd district are 210～220 ℃, and San Dao 7th district are 220～235 ℃, and screw speed is 15-30r/min, and the material of extruding is standby through water-cooled, pelletizing, collection.
The preparation method of above-mentioned novel flame-retardant ABS nano hybridization resin material, it is to comprise the following steps:
(1) stopping composition pre-treatment: by ionogenic surfactant Sodium hexametaphosphate 99 (NaPO for stibium doping stannic oxide (ATO)
3)
6carry out surface treatment and obtain modification ATO nanoparticle; This surface treatment can be strengthened the electrostatic repulsion between particle, makes its active group with easy reaction, and resulting modification ATO nano particle diameter is about 20～50nm, and dispersed; By raw material A BS resin dry 2～4h under 80～90 ℃ of conditions;
(2) after dry raw material A BS, modification ATO nanoparticle, bromide fire retardant, Sb system fire retardant, antioxidant and mix lubricant is even, through twin-screw extrusion owner feed system, send into the Screw Extrusion granulation.Expressing technique: head is to the charging opening temperature, and Yi Dao 2nd district are 210～220 ℃, and San Dao 7th district are 220～235 ℃, and screw speed is 15-30r/min, and the material of extruding is standby through water-cooled, pelletizing, collection.
As preferred technical scheme:
The blend of ABS as above preparation is with after ATO nanoparticle after modification mixes by dry raw material A BS, first through homogenizer, mix 2～4min, realize the reaction that a blending technology is front, then bromide fire retardant, Sb system fire retardant, antioxidant, EBS and mixed ABS and modification ATO nanoparticle are joined in high mixer and stir 2～7min, send into screw rod through twin-screw extrusion owner feed system, its technological process is: screw speed 30r/min; Head is to the charging opening temperature, 235 ℃, 210 220 235 235 235 235 ℃， 7th district, ℃， 6th district, ℃， 5th district, ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district, 160 ℃ of charging openings.
Technical scheme of the present invention is: control and disperse uniformly in the ABS resin material by modification ATO (stibium doping stannic oxide) nanoparticle by after finishing, be prepared into out and have static resistance and uvioresistant and the flame retardant properties organic and inorganic resin material of nano hybridization preferably.
Form by the organic-inorganic nano material hybridization, inorganic nano-particle is incorporated in common flame-proof ABS resin matrix, by controlling the uniformly dispersed of inorganic nano-particle, adopt surface modification technology, a kind of ABS nano hybridization resin material of excellent combination property is provided, and this material has over-all properties and the good flame retardant propertiess such as the static resistance, uvioresistant performance of lasting excellence.
Novel flame-retardant ABS nano hybridization resin material of the present invention, squeeze blending extrusion by ABS, ATO, bromide fire retardant, Sb system fire retardant, antioxidant and lubricant through twin screw and form.Because ATO is a kind of N-N-type semiconductorN material, there are very excellent photoelectric properties, through ionogenic surfactant Sodium hexametaphosphate 99 (NaPO
3)
6after processing, there is very strong electrostatic repulsion between particle, and because surface is easily dispersed in matrix with active group, be conducive to the transmission of electric charge, can improve the electroconductibility of ABS self material, and break through the thinking that original filling by carbon black realizes the static resistance material, the inorganic-organic nanocomposite hydridization of application ATO inorganic nano-particle and ABS organic matrix, when making the static resistance of flame-proof ABS compound system lasting, have more uvioresistant and the flame retardant properties of market practicality, yellowing resistance and can do light color, expanded greatly the marketing dynamics.
Beneficial effect of the present invention:
A kind of novel flame-retardant ABS nano hybridization resin material of the present invention and preparation method thereof, this resin material static resistance is permanent and effective, can make the surface resistivity of ABS resin be down to 10
5Ω cm is even lower, the antistatic material of manufacturing lastingly, can improve the uvioresistant performance of flame-proof ABS, effectively suppress aging in processing and use procedure of ABS, increase the service life, and material do not affect the toning of follow-up product, and there is good mechanical performance, the advantages such as processibility is good, application prospect is good.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiments of the invention adopt following material:
ABS, U.S. Dow chemical company, trade mark Calibre201-10, melting index is 10g/10min;
The ATO(stibium doping stannic oxide), Shanghai Huzheng Nano-Tech Co., Ltd.;
Brominated epoxy, the sincere Rong Huagong of Dongguan City company limited, model is CR2025K, molecular weight is 25000.
Superfine antimony trioxide, above tolerate it Feng Huagong company limited.
Antioxidant 1076, irgasfos 168, antioxidant 1010, vapour bar (CIBA) company that refines.
The EBS(ethylene bis stearic amide), Shanghai Lang Yu Industrial Co., Ltd..
Embodiment 1～3
Take ABS as matrix, and this ABS resin tensile strength is 40～60MPa, and the simply supported beam notched Izod impact strength is 25～35kJ/m
2, by this ABS resin dry 3h under 85 ℃ of conditions; To use ionogenic surfactant Sodium hexametaphosphate 99 (NaPO
3)
6carry out ATO after finishing as functional inorganic nano-particle stopping composition, particle diameter is about 20～50nm.With ionogenic surfactant Sodium hexametaphosphate 99 (NaPO
3)
6finishing ATO prepares the method for modification ATO nanoparticle, and can adopt the patent No. is 200610124202.2 disclosed methods, also can adopt disclosed other ordinary methods in this area.Each component concentration is as shown in table 1.By dry raw material A BS with after ATO nanoparticle after modification mixes, first through homogenizer, mix 2～4min, realize the reaction that a blending technology is front, then brominated epoxy, superfine antimony trioxide, antioxidant 1076 or/and joining in high mixer, antioxidant 1010, EBS and mixed ABS and modification ATO nanoparticle are stirred to 5min, send into screw rod through twin-screw extrusion owner feed system, its technological process is: screw speed 30r/min; Head is to the charging opening temperature, 235 ℃, 210 220 235 235 235 235 ℃， 7th district, ℃， 6th district, ℃， 5th district, ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district, 160 ℃ of charging openings.The injection moulding batten, its test result is in Table 2.
The component concentration of table 1 embodiment 1～3 novel flame-retardant ABS nano hybridization resin material
Table 2 embodiment 1～3 novel flame-retardant ABS nano hybridization resin material test result
Embodiment 4～6
Take ABS as matrix, and this ABS resin tensile strength is 40～60MPa, and the simply supported beam notched Izod impact strength is 25～35kJ/m
2, by this ABS resin dry 2h under 90 ℃ of conditions; To use ionogenic surfactant Sodium hexametaphosphate 99 (NaPO
3)
6carry out ATO after finishing as functional inorganic nano-particle stopping composition, particle diameter is about 20～50nm.With ionogenic surfactant Sodium hexametaphosphate 99 (NaPO
3)
6finishing ATO prepares the method for modification ATO nanoparticle, and can adopt the patent No. is 200610124202.2 disclosed methods, also can adopt disclosed other ordinary methods in this area.Each component concentration is as shown in table 3, by dry raw material A BS with after ATO nanoparticle after modification mixes, first through homogenizer, mix 2～4min, realize the reaction that a blending technology is front, then brominated epoxy, superfine antimony trioxide, irgasfos 168 or/and joining in high mixer, antioxidant 1010, EBS and mixed ABS and modification ATO nanoparticle are stirred to 5min, send into screw rod through twin-screw extrusion owner feed system, its technological process is: screw speed 30r/min; Head is to the charging opening temperature, 235 ℃, 210 220 235 235 235 235 ℃， 7th district, ℃， 6th district, ℃， 5th district, ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district, 160 ℃ of charging openings.The injection moulding batten, its test result is in Table 4.
The component concentration of table 3 embodiment 4～6 novel flame-retardant ABS nano hybridization resin materials
Table 4 embodiment 4～6 novel flame-retardant ABS nano hybridization resin material test results
In sum, introduce the ATO nanoparticle in the formula system of flame-proof ABS, with the peculiar photovoltaic effect of nanoparticle, the little effect of small size and surface effects, with the preparation method of organic-inorganic materials, making bromine is that the ABS material of flame-retardant system has extraordinary uvioresistant performance.The introducing of ATO, greatly reduce surface resistivity on the one hand, makes it have static resistance, even, not adding in other anlistatig situations, still have reasonable antistatic property, surface resistivity is 10
5～10
7the Ω left and right, and when the ATO component concentration is constant, basically surface resistivity values and flame-retardant system are relatively stable, reached the lasting requirement of material static resistance, and the simultaneously introducing of ATO is given flame-proof ABS system with uvioresistant performance and mechanical property preferably, formula system is simple, and over-all properties is stable excellent, the effect that this invention has had.
Claims (6)
1. a flame-proof ABS nano hybridization resin material comprises following component by weight:
The preparation of employing following methods:
(1) stopping composition pre-treatment: by ionogenic surfactant Sodium hexametaphosphate 99 (NaPO for stibium doping stannic oxide (ATO)
3)
6carry out surface treatment and obtain modification ATO nanoparticle; By raw material A BS resin dry 2～4h under 80～90 ℃ of conditions;
(2) after dry raw material A BS, modification ATO nanoparticle, bromide fire retardant, Sb system fire retardant, antioxidant and mix lubricant is even, through twin-screw extrusion owner feed system, send into the Screw Extrusion granulation.
2. flame-proof ABS nano hybridization resin material according to claim 1, is characterized in that described bromide fire retardant selects any one in decabromodiphynly oxide, TDE, brominated epoxy.
3. flame-proof ABS nano hybridization resin material according to claim 1, is characterized in that described Sb system fire retardant selects antimonous oxide.
4. flame-proof ABS nano hybridization resin material according to claim 1, is characterized in that described antioxidant is any one or more than one the mixture in antioxidant 1076, irgasfos 168 and antioxidant 1010.
5. flame-proof ABS nano hybridization resin material according to claim 1, is characterized in that described lubricant is EBS.
6. the preparation method of flame-proof ABS nano hybridization resin material claimed in claim 1 is characterized in that comprising the following steps:
(1) stopping composition pre-treatment: by ionogenic surfactant Sodium hexametaphosphate 99 (NaPO for stibium doping stannic oxide (ATO)
3)
6carry out surface treatment and obtain modification ATO nanoparticle; By raw material A BS resin dry 2～4h under 80～90 ℃ of conditions;
(2) after dry raw material A BS, modification ATO nanoparticle, bromide fire retardant, Sb system fire retardant, antioxidant and mix lubricant is even, through twin-screw extrusion owner feed system, send into the Screw Extrusion granulation.
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| CN114921051B (en) * | 2022-06-21 | 2024-02-02 | 江苏华信高新材料有限公司 | Antistatic ABS (Acrylonitrile butadiene styrene) substrate and preparation method thereof |
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|---|---|---|---|---|
| CN101638503A (en) * | 2008-07-30 | 2010-02-03 | 中山赛特工程塑料有限公司 | Environment-friendly composite flame retardant weatherproof ABS |
| CN101948604A (en) * | 2010-08-30 | 2011-01-19 | 浙江工业大学 | Preparation method of acrylonitrile-styrene-acrylate resin-based transparent heat insulation material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638503A (en) * | 2008-07-30 | 2010-02-03 | 中山赛特工程塑料有限公司 | Environment-friendly composite flame retardant weatherproof ABS |
| CN101948604A (en) * | 2010-08-30 | 2011-01-19 | 浙江工业大学 | Preparation method of acrylonitrile-styrene-acrylate resin-based transparent heat insulation material |
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Address after: 225500, Ma 986 Road, Jiangyan Economic Development Zone, Jiangsu, Taizhou, China Patentee after: 5ELEM HI-TECH CORPORATION Address before: 225500, Ma 986 Road, Jiangyan Economic Development Zone, Jiangsu, Taizhou, China Patentee before: Five lines material science and Technology (Jiangsu) Co., Ltd. |