CN102558750A - Organosilicon fire retardant for ABS and preparation method thereof - Google Patents
Organosilicon fire retardant for ABS and preparation method thereof Download PDFInfo
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- CN102558750A CN102558750A CN201210020496XA CN201210020496A CN102558750A CN 102558750 A CN102558750 A CN 102558750A CN 201210020496X A CN201210020496X A CN 201210020496XA CN 201210020496 A CN201210020496 A CN 201210020496A CN 102558750 A CN102558750 A CN 102558750A
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Abstract
The invention relates to an organosilicon fire retardant for ABS and a preparation method thereof. The invention provides an organosilicon fire retardant for ABS with good consistency with ABS, small mechanical properties influence on ABS, less addition, excellent flame retardation performance and other characteristics and provides a preparation method of the organosilicon fire retardant for ABS. The organosilicon fire retardant of ABS is a polymer. Under a condition of nitrogen protection, dimethyl siloxane cycle, aminosilane, trialkoxy silane and catalyst undergo a reaction with hexamethyldisiloxane as an end-capping reagent at a temperature of 80 to 140 DEG C. After the reaction, a low-boiling-point substance is extracted by pressure reduction and the organosilicon fire retardant product for ABS can be obtained.
Description
Technical field
The present invention relates to a kind of fire retardant, especially relate to organic silicon fibre retardant of a kind of ABS of being used for and preparation method thereof.
Background technology
The terpolymer that ABS (Acrylonitrile Butadiene Styrene) is made up of vinyl cyanide, divinyl and vinylbenzene; As a kind of thermoplastic engineering plastic; With its excellent mechanical property, unreactiveness and workability, be widely used in fields such as automotive industry, electronics, electrical equipment, weaving, utensil and building materials.But the flame retardant resistance extreme difference of ABS itself; Its limiting oxygen index(LOI) (LOI) is merely about 18%, belongs to inflammable material, and testing vertical flammability also can't reach the UL94V-2 standard; And can produce a large amount of smog during burning and be harmful to other, therefore make its use range be restricted.
At present, to the flame-retardant modified aspect of ABS, halogenated flame retardant is still occupied an leading position, but because of its burning produces a large amount of poisonous and corrosive gasess, under given conditions, can also decomposite carcinogens, is used by European Union and majority state restriction.And aspect the halogen-free flameproof modification, mainly be to realize halogen-free flameproof through adding a large amount of hydroxide hydrates, organic phosphates fire retardant, the compound swelling agent of phosphorus nitrogen, silicon-series five-retardant.
Xiang Suyun, and Zang Kefeng etc. (Xiang Suyun, Zang Kefeng etc. the performance [J] of natural brucite and fire-retardant PP and ABS plastic. additives for plastics, 2004,4:21-24) with Mg (OH)
2ABS is carried out flame-retardant modified, as nanometer Mg (OH)
2Addition is 60% o'clock, and the ABS fire retardant material can reach difficult combustion level, but the mechanical property of ABS seriously descends.Zhang Weili (Chinese patent CN101469101A) adopts ammonium polyphosphate, tetramethylolmethane, metallic compound and little auxiliary to come flame-proof ABS resin, and the ABS fire retardant material UL94 combustion test after the modification reaches the V-0 level, and has the characteristics low, that toxicity is little of being fuming.Yet the tetramethylolmethane facile hydrolysis can make the matrix material that makes have stronger water absorbability, and simultaneously the consistency of itself and matrix resin is relatively poor, and this all can influence the mechanical property of material.
Organic silicon fibre retardant is a kind of BACN that development in recent years is got up.The fire retardant synergistic is fire-retardant studies to the synthetic of organic silicon fibre retardant and with other for many investigators.A kind of organic silicon fibre retardant that Zheng Yiquan (Chinese patent CN101440204A) provides is mainly used in and carries out flame-retardant modified to the fragrant polycarbonate; Zhao Jianqing etc. (Chinese patent CN1974648A) have synthesized the special-purpose siliceous fire retardant of a kind of polyolefine, and with its same respectively inorganic combustion inhibitor, the composite use of expanding fire retardant, have flame retardant effect preferably.Yet, domestic still blank at present with the research report of organic silicon fibre retardant about ABS.
Summary of the invention
It is good that the present invention aims to provide a kind of and ABS consistency, and on the basis that keeps ABS original excellent performance, what have characteristics such as little to the influence of ABS mechanical property, that addition is less, flame retardant properties is good is used for organic silicon fibre retardant of ABS and preparation method thereof.
The organic silicon fibre retardant of the said ABS of being used for is a polymkeric substance, and its molecular structure is:
R wherein
1, R
2Be alkyl, R
3Be aminoalkyl group, R
4Be alkyl or alkoxyl group; X, y and z form mark, x=0.8～0.9, y=0.05～0.15, z=0.005～0.05, x+y+z=1 for each structural unit; The organic silicon fibre retardant of the said ABS of being used for is water white transparency or is the white shape liquid of micro emulsion.
The preparing method's of the said organic silicon fibre retardant that is used for ABS concrete steps are following:
At N
2Under the condition of protection, dimethyl siloxane ring body, aminosilane, trialkoxy silane and catalyzer being reacted, is end-capping reagent with the SWS-F 221; 80～140 ℃ of reactions down; After reaction finished, low-boiling-point substance was extracted in decompression out, obtained being used for the organic silicon fibre retardant product of ABS.
The mass ratio of said dimethyl siloxane ring body, aminosilane, trialkoxy silane and catalyzer is the dimethyl siloxane ring body: aminosilane: trialkoxy silane: catalyzer=100: (8～33): (0.5～3.3): (0.2～0.5).
Said catalyzer can be selected from a kind of in Pottasium Hydroxide, sodium hydroxide, dibutyl tin laurate, dibutyltin diacetate or the stannous octoate etc.; Said dimethyl siloxane ring body can be selected from octamethylcyclotetrasiloxane (D4) or dimethyl siloxane mixed methylcyclosiloxane (DMC) etc.; Said aminosilane can be selected from a kind of in γ-aminopropyl methyldiethoxysilane (KH-902), N-(cyclohexyl)-γ-aminopropyl methyl dimethoxysilane, the N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane (KH-602) etc.; Said trialkoxy silane can be selected from a kind of in γ-methacryloxypropyl trimethoxy silane (KH-570), methyltrimethoxy silane, the vinyltriethoxysilane etc.
The time of said reaction can be 5～10h.
It is generally acknowledged that organic silicon fibre retardant is to realize its flame retardant efficiency through generating cracking charcoal layer with the oxidation-resistance that improves the charcoal layer.Organic silicon fibre retardant adds in the macromolecular material, most likely moves to material surface, forms the organic silicon fibre retardant enriched layer.This enriched layer can form the inorganic oxygen barrier heat-insulating protective layer that contains Si-O key and Si-C key when burning, reach fire-retardant effect.But, simple linear polysiloxane, the flame retardant effect of itself is unsatisfactory, and has the ZGK 5 of branched structure, and its branched structure helps in the solid phase residue, to form crosslinking structure, and therefore, its flame retardant effect is than the good flame retardation effect of linear polysiloxane.
The organic silicon fibre retardant that is used for ABS according to the invention contains side chain in its molecular structure, have flame retardant properties preferably.The present invention adopts the method for control feed ratio to regulate the degree of branching, makes organic silicon fibre retardant under the prerequisite of the good flowing transport property of maintenance, has certain crosslinked ability again.
The organic silicon fibre retardant that is used for ABS that the present invention obtains can be used as halogen-free flame retardants or the halogen-free flameproof synergist of ABS, has good fire-retardant and cooperative flame retardant effect.
The present invention has following beneficial effect:
1) consistency of organic silicon fibre retardant that is used for ABS provided by the present invention and ABS is better, changes lessly with the mechanical property of the anti-flaming ABS material that obtains after the ABS blend, and flame retardant effect is remarkable.
2) organic silicon fibre retardant of the ABS of being used for provided by the invention is used for the flame-retardant modified of ABS; It is little to have addition, and the characteristics that fire retarding effect is good are when addition is 8wt%; The oxygen index that can use ABS brings up to 29.6 from 18, and flame retardant properties reaches the UL94V-1 level.
3) the organic silicon fibre retardant preparation technology of the ABS of being used for provided by the invention is simple and easy to; And the equal price of fire retarding synergist Magnesium Stearate is lower; Simultaneously, because the organic silicon fibre retardant that is used for ABS of the present invention is less at the addition of ABS, so the present invention also has lower-cost advantage.
Description of drawings
Fig. 1 is the infrared spectrum that is used for the organic silicon fibre retardant of ABS.In Fig. 1, X-coordinate is wave number/cm
-1
Fig. 2 is the organic silicon fibre retardant that is used for ABS
1H NMR spectrogram.In Fig. 2, X-coordinate is chemical shift δ.
Fig. 3 is the organic silicon fibre retardant that is used for ABS
1H NMR composes enlarged view.In Fig. 3, X-coordinate is chemical shift δ.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is described further, listed embodiment only be used to the present invention is described and be not used in the restriction scope of the present invention.
Embodiment 1
500ml is dry, and four-hole boiling flask is loaded onto mechanical stirring, TM, reflux condensing tube and N
2Conduit; Add 96g dimethyl siloxane mixed methylcyclosiloxane (DMC), 13.75g γ-aminopropyl methyldiethoxysilane (KH-902), 0.60g γ-methacryloxypropyl trimethoxy silane (KH-570) and 0.50g SWS-F 221 and 0.055g Pottasium Hydroxide; At 110 ℃ of following balanced reaction 3h; Be warmed up to 135 ℃ then and keep 1h, residual monomer is extracted in decompression out, obtains being used for the organic silicon fibre retardant of ABS.
Embodiment 2
500ml is dry, and four-hole boiling flask is loaded onto mechanical stirring, TM, reflux condensing tube and N
2Conduit; Add 96g dimethyl siloxane mixed methylcyclosiloxane (DMC), 12.5gN-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane (KH-602), 0.60g γ-methacryloxypropyl trimethoxy silane (KH-570) and 0.50g SWS-F 221 and 0.055g Pottasium Hydroxide; At 110 ℃ of following balanced reaction 3h; Be warmed up to 135 ℃ then and keep 1h, residual monomer is extracted in decompression out, obtains being used for the organic silicon fibre retardant of ABS.
500ml is dry, and four-hole boiling flask is loaded onto mechanical stirring, TM, reflux condensing tube and N
2Conduit; Add 96g dimethyl siloxane mixed methylcyclosiloxane (DMC), 13.75g γ-aminopropyl methyldiethoxysilane (KH-902), 0.42g vinyltrimethoxy silane and 0.50g SWS-F 221 and 0.06g sodium hydroxide; At 110 ℃ of following balanced reaction 3h, be warmed up to 135 ℃ then and keep 1h, after reaction finishes; Residual monomer is extracted in decompression out, obtains the organic silicon fibre retardant that is used for ABS of micro emulsion white liquid shape.
500ml is dry, and four-hole boiling flask is loaded onto mechanical stirring, TM, reflux condensing tube and N
2Conduit; Add 96g dimethyl siloxane mixed methylcyclosiloxane (DMC), 12.5g N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane (KH-602), 0.33g methyltrimethoxy silane and 0.50g SWS-F 221 and 0.06g sodium hydroxide; At 110 ℃ of following balanced reaction 3h, be warmed up to 135 ℃ then and keep 1h, after reaction finishes; Residual monomer is extracted in decompression out, obtains the organic silicon fibre retardant that is used for ABS of micro emulsion white liquid shape.
The application implementation example
For the organic silicon fibre retardant that further specifies the ABS of the being used for of the present invention flame retardant effect to ABS, product and fire retarding synergist Magnesium Stearate that embodiment 1～4 is obtained add to respectively among the ABS, and compare with pure ABS.Preparation method of sample is: elder generation opens refining or melt extrudes through two rollers organic silicon fibre retardant that is used for ABS and ABS blend are made flame-proof ABS, carries out granulation then, after moulding press is processed the standard batten.Each component and the mass fraction of flame-proof ABS are seen table 1, and physicals is seen table 2, and its physicals is tested according to China's national standard and U.S.'s UL standard respectively, and is as shown in table 3.
The proportioning of table 1 organic silicon fibre retardant and ABS
The physicals of table 2 flame-proof ABS
Can find out from the test result of table 2, add the organic silicon fibre retardant that is used for ABS that the present invention obtained, the flame retardant properties of ABS is significantly improved.When the total addition of the organic silicon fibre retardant that is used for ABS was 8wt%, the limiting oxygen index(LOI) of flame-proof ABS can reach 29.6, has risen 11.6; Flame retardant properties reaches the UL94V-1 level; And the mechanical property of material changes less; Simultaneously, the situation of being fuming and drippage situation during the ABS burning have obtained obvious improvement, this shows; The organic silicon fibre retardant that is used for ABS that the present invention obtained is used for ABS when fire-retardant, has the advantage that consumption is few, little to the influence of ABS mechanical property and flame retardant properties is good.
Table 3 testing standard
For the further explanation organic silicon fibre retardant that is used for ABS of the present invention, with the product of embodiment 1 gained through FT-IR with
1H NMR characterizes.Fig. 1 provides the infrared spectrum of organic silicon fibre retardant, as can beappreciated from fig. 1, and at 2963cm
-1Be the stretching vibration of C-H, 1376,1442cm
-1Be-CH
3,-CH
2-flexural vibration, 802cm
-1Be Si-CH
3Flexural vibration, 1036 and 1063cm
-1Be the stretching vibration of Si-O-Si skeleton, 1261cm
-1Be CH
3-Si-CH
3Flexural vibration.Explaining in the molecule has-Si (CH
3)
2O-,-Si (CH
3) RO-, ,-CH
2-wait structural unit or group, can judge tentatively that the molecular backbone structure is a ZGK 5; At 3399cm
-1Be-NH
2Stretching vibration, 1766cm
-1, 1721cm
-1For-CO
2Stretching vibration, 1645cm
-1Be the stretching vibration of C=C, can find out in the side chain of molecule and also contain amino, ester group and alkylene.
Fig. 2 provides the organic silicon fibre retardant that is used for ABS
1HNMR spectrogram, Fig. 3 provide the organic silicon fibre retardant that is used for ABS
1H NMR composes enlarged view, can find out from Fig. 2 and 3, and chemical shift δ=7.25 are solvent C DCl
3The peak; δ=0.05 belongs to Si-CH
3In H; δ is that 0.5,1.5 and 2.65 places belong to-CH successively
2CH
2CH
2NH
2Middle CH
2Proton peak, and NH
2Proton peak appear at 3.47;-OCOC (CH
3)=CH
2In-CH
3And C=CH
2The chemical shift of H be respectively 1.71 and 5.29.
In conjunction with FT-IR with
1H NMR spectrum analysis can be inferred, and embodiment 1 product conforms to the organic silicon fibre retardant of the described ABS of being used for, and its concrete structure is as follows:
Claims (8)
1. an organic silicon fibre retardant that is used for ABS is characterized in that being polymkeric substance, and its molecular structure is:
R wherein
1, R
2Be alkyl, R
3Be aminoalkyl group, R
4Be alkyl or alkoxyl group; X, y and z form mark, x=0.8～0.9, y=0.05～0.15, z=0.005～0.05, x+y+z=1 for each structural unit.
2. a kind of preparation method who is used for the organic silicon fibre retardant of ABS as claimed in claim 1 is characterized in that its concrete steps are following:
At N
2Under the condition of protection, dimethyl siloxane ring body, aminosilane, trialkoxy silane and catalyzer being reacted, is end-capping reagent with the SWS-F 221; 80～140 ℃ of reactions down; After reaction finished, low-boiling-point substance was extracted in decompression out, obtained being used for the organic silicon fibre retardant product of ABS.
3. a kind of preparation method who is used for the organic silicon fibre retardant of ABS as claimed in claim 2, the mass ratio that it is characterized in that said dimethyl siloxane ring body, aminosilane, trialkoxy silane and catalyzer is the dimethyl siloxane ring body: aminosilane: trialkoxy silane: catalyzer=100: (8～33): (0.5～3.3): (0.2～0.5).
4. like claim 2 or 3 described a kind of preparing methods that are used for the organic silicon fibre retardant of ABS, it is characterized in that said catalyzer is selected from a kind of in Pottasium Hydroxide, sodium hydroxide, dibutyl tin laurate, dibutyltin diacetate or the stannous octoate.
5. like claim 2 or 3 described a kind of preparing methods that are used for the organic silicon fibre retardant of ABS, it is characterized in that said dimethyl siloxane ring body is selected from octamethylcyclotetrasiloxane or dimethyl siloxane mixed methylcyclosiloxane.
6. like claim 2 or 3 described a kind of preparing methods that are used for the organic silicon fibre retardant of ABS, it is characterized in that said aminosilane is selected from a kind of in γ-aminopropyl methyldiethoxysilane, N-(cyclohexyl)-γ-aminopropyl methyl dimethoxysilane, the N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane.
7. like claim 2 or 3 described a kind of preparing methods that are used for the organic silicon fibre retardant of ABS, it is characterized in that said trialkoxy silane is selected from a kind of in γ-methacryloxypropyl trimethoxy silane, methyltrimethoxy silane, the vinyltriethoxysilane.
8. a kind of preparation method who is used for the organic silicon fibre retardant of ABS as claimed in claim 2, the time that it is characterized in that said reaction is 5～10h.
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| CN103044919A (en) * | 2012-12-20 | 2013-04-17 | 涌奇材料技术（上海）有限公司 | Halogen-free phosphate-free environment-friendly synergistic flame retardant and use thereof |
| CN103342817A (en) * | 2013-06-21 | 2013-10-09 | 安徽硅宝翔飞有机硅新材料有限公司 | Method for recycling diamino silicane high boiling substance |
| GB2509128A (en) * | 2012-12-20 | 2014-06-25 | Dow Corning | Process for improving fire resistance of an organic polymer |
| CN106589381A (en) * | 2016-12-17 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of flame retardant for ABS resin |
| CN106633066A (en) * | 2016-12-20 | 2017-05-10 | 衢州普信新材料有限公司 | Preparation method of organosilicon fire retardant |
| CN106750314A (en) * | 2016-12-22 | 2017-05-31 | 衢州普信新材料有限公司 | A kind of preparation method of the organic silicon fibre retardant for ABS resin |
| CN109880104A (en) * | 2019-03-14 | 2019-06-14 | 普信氟硅新材料（衢州）有限公司 | A kind of preparation method of phosphorus system organic silicon type fire retardant |
| CN111534097A (en) * | 2020-05-13 | 2020-08-14 | 江苏百通塑业发展有限公司 | Formula and preparation method of high-temperature-resistant special engineering plastic |
| CN112387310A (en) * | 2020-09-21 | 2021-02-23 | 长春工业大学 | Preparation of siloxane block copolymer composite material based on phosphotungstic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2509128A (en) * | 2012-12-20 | 2014-06-25 | Dow Corning | Process for improving fire resistance of an organic polymer |
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| CN106633066B (en) * | 2016-12-20 | 2019-09-03 | 普信氟硅新材料（衢州）有限公司 | A kind of preparation method of organic silicon fibre retardant |
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| CN106750314A (en) * | 2016-12-22 | 2017-05-31 | 衢州普信新材料有限公司 | A kind of preparation method of the organic silicon fibre retardant for ABS resin |
| CN106750314B (en) * | 2016-12-22 | 2020-02-18 | 普信氟硅新材料（衢州）有限公司 | Preparation method of organic silicon flame retardant for ABS resin |
| CN109880104A (en) * | 2019-03-14 | 2019-06-14 | 普信氟硅新材料（衢州）有限公司 | A kind of preparation method of phosphorus system organic silicon type fire retardant |
| CN109880104B (en) * | 2019-03-14 | 2021-05-28 | 普信氟硅新材料（衢州）有限公司 | Preparation method of phosphorus-based organic silicon type flame retardant |
| CN111534097A (en) * | 2020-05-13 | 2020-08-14 | 江苏百通塑业发展有限公司 | Formula and preparation method of high-temperature-resistant special engineering plastic |
| CN112387310A (en) * | 2020-09-21 | 2021-02-23 | 长春工业大学 | Preparation of siloxane block copolymer composite material based on phosphotungstic acid |
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