CN102558750B - 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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- CN102558750B CN102558750B CN 201210020496 CN201210020496A CN102558750B CN 102558750 B CN102558750 B CN 102558750B CN 201210020496 CN201210020496 CN 201210020496 CN 201210020496 A CN201210020496 A CN 201210020496A CN 102558750 B CN102558750 B CN 102558750B
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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 a kind of organic silicon fibre retardant for ABS and preparation method thereof.
Background technology
The terpolymer that ABS (Acrylonitrile Butadiene Styrene) is comprised 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 the 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 only 18% left and right, 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 making 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 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, be mainly to realize halogen-free flameproof by 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)
2When addition was 60%, the ABS fire retardant material can reach difficult combustion level, but the mechanical property degradation of ABS.Zhang Weili (Chinese patent CN101469101A) adopts ammonium polyphosphate, tetramethylolmethane, metallic compound and a small amount of auxiliary agent to come flame-proof ABS resin, ABS fire retardant material UL94 combustion test after 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 affect 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 is studied 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 carrying out flame-retardant modified to the fragrant polycarbonate; Zhao Jianqing etc. (Chinese patent CN1974648A) have synthesized a kind of Silicone-containing Flame Retardant of polyolefine special use, and with its same inorganic combustion inhibitor, composite use of expanding fire retardant respectively, 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, on the basis that keeps the original premium properties of ABS, has organic silicon fibre retardant that is used for ABS of the characteristics such as little to the ABS Effect on Mechanical Properties, that addition is less, flame retardant properties is good and preparation method thereof.
Described organic silicon fibre retardant for ABS is 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; Described organic silicon fibre retardant for ABS is water white transparency or is the white shape liquid of micro emulsion.
The preparation method's of described organic silicon fibre retardant for ABS concrete steps are as follows:
At N
2Under the condition of protection, dimethyl siloxane ring body, aminosilane, trialkoxy silane and catalyzer are reacted, take hexamethyldisiloxane as end-capping reagent; reaction under 80～140 ℃; react complete after, low-boiling-point substance is extracted in decompression out, obtains the organic silicon fibre retardant product for ABS.
The mass ratio of described 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).
Described catalyzer can be selected from a kind of in potassium hydroxide, sodium hydroxide, dibutyl tin laurate, dibutyltin diacetate or stannous octoate etc.; Described dimethyl siloxane ring body can be selected from octamethylcyclotetrasiloxane (D4) or dimethyl siloxane mixed methylcyclosiloxane (DMC) etc.; Described aminosilane can be selected from a kind of in γ-aminopropyl methyldiethoxysilane (KH-902), N-(cyclohexyl)-γ-aminopropyl methyl dimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane (KH-602) etc.; Described trialkoxy silane can be selected from a kind of in γ-methacryloxypropyl trimethoxy silane (KH-570), methyltrimethoxy silane, vinyltriethoxysilane etc.
The time of described reaction can be 5～10h.
It is generally acknowledged, organic silicon fibre retardant is to realize its flame retardant efficiency by the oxidation-resistance that generates cracking charcoal layer and raising charcoal layer.Organic silicon fibre retardant adds in 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 polysiloxane of branched structure, and its branched structure helps to form crosslinking structure in the solid phase residue, and therefore, its flame retardant effect is than the good flame retardation effect of linear polysiloxane.
Organic silicon fibre retardant for ABS of the present invention contains side chain in its molecular structure, have flame retardant properties preferably.The present invention adopts the method for controlling feed ratio to regulate the degree of branching, makes organic silicon fibre retardant under the prerequisite of the good flowing transport of maintenance, has again certain crosslinked ability.
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) organic silicon fibre retardant and the consistency of ABS for ABS provided by the present invention is better, changes littlely 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 for ABS provided by the invention is used for the flame-retardant modified of ABS, have addition little, 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 for ABS 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 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 for 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 for 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
The invention will be further described below in conjunction with the drawings and specific embodiments, and listed embodiment only is not used in for explanation the present invention and limits the scope of the invention.
Embodiment 1
500ml is dry, and four-hole boiling flask is loaded onto mechanical stirring, thermometer, 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 hexamethyldisiloxane and 0.055g potassium hydroxide, at 110 ℃ of lower balanced reaction 3h, then be warmed up to 135 ℃ and keep 1h, residual monomer is extracted in decompression out, obtains the organic silicon fibre retardant for ABS.
500ml is dry, and four-hole boiling flask is loaded onto mechanical stirring, thermometer, 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 hexamethyldisiloxane and 0.055g potassium hydroxide, at 110 ℃ of lower balanced reaction 3h, then be warmed up to 135 ℃ and keep 1h, residual monomer is extracted in decompression out, obtains the organic silicon fibre retardant for ABS.
Embodiment 3
500ml is dry, and four-hole boiling flask is loaded onto mechanical stirring, thermometer, 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 hexamethyldisiloxane and 0.06g sodium hydroxide, at 110 ℃ of lower balanced reaction 3h, then be warmed up to 135 ℃ 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, thermometer, 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 hexamethyldisiloxane and 0.06g sodium hydroxide, at 110 ℃ of lower balanced reaction 3h, then be warmed up to 135 ℃ 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.
Application Example
In order to further illustrate the organic silicon fibre retardant for ABS of the present invention to the flame retardant effect of ABS, product and fire retarding synergist Magnesium Stearate that embodiment 1～4 is obtained add in ABS respectively, and compare with pure ABS.Preparation method of sample is: first open refining by two rollers or melt extrude and will make flame-proof ABS for organic silicon fibre retardant and the ABS blend of ABS, then carrying out granulation, making the standard batten finally by moulding press.Each component and the mass fraction of flame-proof ABS see Table 1, and physicals sees 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 obtains, the flame retardant properties of ABS is significantly improved.When the total addition of 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 obtains is used for ABS when fire-retardant, has advantages of that consumption is few, little and flame retardant properties is good to the ABS Effect on Mechanical Properties.
Table 3 testing standard
For the further instruction organic silicon fibre retardant for ABS of the present invention, with the product of embodiment 1 gained by FT-IR and
1H NMR characterizes.Fig. 1 provides the infrared spectrum of organic silicon fibre retardant, as can be seen from Figure 1, and at 2963cm
-1The stretching vibration of C-H, 1376,1442cm
-1Be-CH
3,-CH
2-flexural vibration, 802cm
-1Si-CH
3Flexural vibration, 1036 and 1063cm
-1The stretching vibration of Si-O-Si skeleton, 1261cm
-1CH
3-Si-CH
3Flexural vibration.Illustrating in 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 polysiloxane; 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 for the organic silicon fibre retardant of ABS
1HNMR spectrogram, Fig. 3 provide for the organic silicon fibre retardant of 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 and
1H NMR spectrum analysis can be inferred, and embodiment 1 product conforms to described organic silicon fibre retardant for ABS, and its concrete structure is as follows:
Claims (5)
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;
The preparation method of described a kind of organic silicon fibre retardant for ABS, its concrete steps are as follows:
At N
2Under the condition of protection, dimethyl siloxane ring body, aminosilane, trialkoxy silane and catalyzer are reacted, take hexamethyldisiloxane as end-capping reagent, reaction under 80～140 ℃, react complete after, low-boiling-point substance is extracted in decompression out, obtains the organic silicon fibre retardant product for ABS;
Described aminosilane is selected from a kind of in γ-aminopropyl methyldiethoxysilane, N-(cyclohexyl)-γ-aminopropyl methyl dimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane;
Described trialkoxy silane is selected from a kind of in γ-methacryloxypropyl trimethoxy silane, methyltrimethoxy silane, vinyltriethoxysilane.
2. a kind of organic silicon fibre retardant for ABS as claimed in claim 1, the mass ratio that it is characterized in that described 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).
3. a kind of organic silicon fibre retardant for ABS as claimed in claim 1 is characterized in that described catalyzer is selected from a kind of in potassium hydroxide, sodium hydroxide, dibutyl tin laurate, dibutyltin diacetate or stannous octoate.
4. a kind of organic silicon fibre retardant for ABS as claimed in claim 1, is characterized in that described dimethyl siloxane ring body is selected from octamethylcyclotetrasiloxane or dimethyl siloxane mixed methylcyclosiloxane.
5. a kind of organic silicon fibre retardant for ABS as claimed in claim 1, the time that it is characterized in that described reaction is 5～10h.
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| CN103044919B (en) * | 2012-12-20 | 2014-09-17 | 涌奇材料技术（上海）有限公司 | Halogen-free phosphate-free environment-friendly synergistic flame retardant and use thereof |
| GB2509128A (en) * | 2012-12-20 | 2014-06-25 | Dow Corning | Process for improving fire resistance of an organic polymer |
| CN103342817B (en) * | 2013-06-21 | 2016-03-16 | 安徽硅宝翔飞有机硅新材料有限公司 | The method of the recycling of a kind of pair of aminosilane high boiling material |
| CN106589381B (en) * | 2016-12-17 | 2019-05-24 | 衢州普信新材料有限公司 | A kind of preparation method of ABS resin fire retardant |
| 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 |
| 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 |
| 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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