CN105037734A - Preparation method of reactive carbon nanotube flame retardant - Google Patents
Preparation method of reactive carbon nanotube flame retardant Download PDFInfo
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- CN105037734A CN105037734A CN201510299859.1A CN201510299859A CN105037734A CN 105037734 A CN105037734 A CN 105037734A CN 201510299859 A CN201510299859 A CN 201510299859A CN 105037734 A CN105037734 A CN 105037734A
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Abstract
The invention relates to a preparation method of a reactive carbon nanotube flame retardant. Since both the polysiloxane and carbon nanotube belong to flame retardants, after the polysiloxane is grafted onto the carbon nanotube through chemical bonds, a synergistic action is generated between the polysiloxane and carbon nanotube, thereby fully displaying the flame retardancy of the polysiloxane and carbon nanotube. The polysiloxane-grafted carbon nanotube structure has vinyl carried by the polysiloxane, the reactive flame retardant can be grafted to unsaturated polyester, silicone rubber and many other synthetic materials through the vinyl, and the phenyl in the polysiloxane can enhance the carbonization property and flame retardancy of the polymer in the combustion process, thereby enhancing the flame retardancy of the matrix and being beneficial to improving the mechanical, electric and other properties of the material. Both the polysiloxane and carbon nanotube belong to carbonization flame retardants, and the benzene ring in the polysiloxane structure can further enhance the carbonization effect in the combustion process, so that the whole reactive flame-retardant system has higher flame retardancy.
Description
Technical field
The present invention relates to a kind of preparation method of response type carbon nanotube fire retardant.
Background technology
In the last few years, carbon nanotube relies on resistance toheat and the mechanical property of its excellence, start to use as synthetic materials fire retardant, but because carbon nanotube has larger length-to-diameter ratio (generally between 300 ~ 1000) and very strong electrostatic interaction, carbon pipe very easily assembles bunchy in polymeric matrix, cause its dispersed variation, fire retardation can not be played well.Solution conventional in prior art is that organism is grafted to carbon nano tube surface, thus improves its dispersiveness in the polymer.The matrix material stability adopting the method obtained is higher, people [the ChenGX such as such as Chen, ShimizuH.Multiwalledcarbonnanotubesgraftedwithpolyhedral oligomericsilsesquioxaneanditsdispersioninpoly (L-lactide) matrix.Polymer, 2008, 49 (4): 943-951.] POSS is grafted to carbon nano tube surface, prepare poly(lactic acid)/carbon mano-tube composite again, owing to creating strong interface binding power between carbon nanotube and matrix, therefore good distribution can be kept under various processing conditions.
When adopting traditional organic compound as covalent modification agent, although the gathering tendency that carbon nanotube causes due to Van der Waals force can be weakened, improve its dispersiveness in the base, because organism itself has inflammableness, the object improving Flame Retardancy often can not be reached.
Summary of the invention
Technical problem to be solved by this invention is the present situation for prior art, a kind of preparation method of response type carbon nanotube fire retardant is provided, reactive flame retardant prepared by the method is efficient, clean, environmentally friendly harmless, and there is good dispersiveness, be convenient to this reactive flame retardant to be grafted in the multiple synthetic materials such as unsaturated polyester, silicon rubber, the flame retardant properties of matrix can not only be improved, and be conducive to the performance such as machinery, electricity improving material.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of response type carbon nanotube fire retardant, is characterized in that comprising the following steps:
(1) preparation of polysiloxane
Amino-silane monomer, vinyl silane monomer and phenyl silane monomer are mixed and is dissolved in solvent, alkaline catalysts is added in this reaction system, the pH value controlling reaction solution is 7 ~ 10, collects the polysiloxane that namely product obtains containing amino, vinyl, phenyl under room temperature after reacting 2 ~ 6h;
(2) preparation of response type carbon nanotube fire retardant
Be dissolved in organic solvent by functionalized multi-wall carbonnanotubes and thionyl chloride, supersound process also reacts 24 ~ 30h, removes solution drying obtains chloride carbon nanotube after completion of the reaction;
The polysiloxane described chloride carbon nanotube and step (1) prepared mixes according to mass ratio 1:1 ~ 4 and is placed in organic solvent, back flow reaction 24 ~ 30h under the boiling temperature of this organic solvent, namely obtains response type carbon nanotube fire retardant.
As a further improvement on the present invention, the mass ratio of the described amino-silane monomer, vinyl silane monomer and the phenyl silane monomer that add in step (1) is 1 ~ 5:1 ~ 5:2 ~ 20.Because reaction mechanism of the present invention is the amino in polysiloxane and the carbon nanotube generation chemical reaction after chloride, and the phenyl in polysiloxane improves carbon-forming performance and the flame retardant properties of polymkeric substance in combustion; Therefore, when the amino in structure and contents of ethylene too low time, will the reactivity of product be reduced, and when the amino in structure and contents of ethylene too high time, then phenyl ring content will be less, finally affects carbon-forming performance; Adopt above-mentioned reaction mass ratio, amino can be made, ratio between vinyl and phenyl ring is in best of breed scope, thus makes response type carbon nanotube fire retardant of the present invention have good flame retardant properties.
As preferably, described amino-silane monomer is NH
2c
3h
6siX
3or NH
2c
3h
6r
1siX
2; Wherein, R
1for-CH
3or-C
6h
5, X is-Cl ,-OCH
3or-OC
2h
5.
Preferably, described vinyl silane monomer is CH=CH
2siX
3or CH=CH
2r
1siX
2; Wherein, R
1for-CH
3or-C
6h
5, X is-Cl ,-OCH
3or-OC
2h
5.
Preferably, described phenyl silane monomer is C
6h
5siX
3; Wherein, X is-Cl ,-OCH
3or-OC
2h
5.
Further preferably, the carboxyl-content of step (2) described functionalized multi-wall carbonnanotubes is 1 ~ 5wt%.
Preferably, described alkaline catalysts is alkali metal hydroxide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH or ammonia.
In above-mentioned each scheme, described organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, acetone, tetrahydrofuran (THF).
Compared with prior art, the invention has the advantages that:
Because polysiloxane and carbon nanotube itself all belong to fire retardant, there is flame retardant properties, in the preparation process in accordance with the present invention, by polysiloxane by chemical bond grafting on the carbon nanotubes, produce synergy between polysiloxane and carbon nanotube thus the flame retardant properties of the two is not fully exerted; Simultaneously, by the carbon nanotube structure after polysiloxane-grafted is also provided with polysiloxane with vinyl, reactive flame retardant can be grafted in the multiple synthetic materials such as unsaturated polyester, silicon rubber by this vinyl, phenyl in polysiloxane can improve carbon-forming performance and the flame retardant properties of polymkeric substance in combustion, the flame retardant properties of matrix can not only be improved, and be conducive to the performance such as machinery, electricity improving material;
Polysiloxane in the present invention, carbon nanotube all belong to carbon-forming type flame-retardant agent, and the phenyl ring in polysiloxane structure can strengthen the effect of this one-tenth charcoal in combustion further, make whole reaction-type flame-retarding system have outstanding flame retardant properties;
Polysiloxane in the present invention and polymeric matrix have good consistency, carbon nanotube can be helped to improve its dispersiveness in polymeric matrix, simultaneously because the vinyl in modified carbon nano tube tubular construction has good reactivity, carbon nanotube can being helped to be connected with chemical bond with the polymeric matrix such as unsaturated polyester, silicon rubber when applying, to improve the dispersing property of reaction-type flame-retarding system further;
Polysiloxane in the present invention, carbon nanotube all belong to green BACN, can not produce poisonous and harmful substances in combustion, environmentally friendly harmless.
Accompanying drawing explanation
Fig. 1 is the TEM figure of functionalized multi-wall carbonnanotubes in the embodiment of the present invention 1;
Fig. 2 is the TEM figure of the response type carbon nanotube fire retardant prepared in the embodiment of the present invention 1;
Fig. 3 is the x-ray photoelectron energy spectrogram of the response type carbon nanotube fire retardant prepared in inventive embodiments 1.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1:
In the present embodiment, the preparation method of response type carbon nanotube fire retardant comprises the following steps:
(1) preparation of polysiloxane
Measure 15mL ethanol, 5mL deionized water, add 0.2g aminopropyl triethoxysilane, 0.2g vinyltrimethoxy silane, 2g phenyltrimethoxysila,e, stir; In this reaction system, slowly add Tetramethylammonium hydroxide, the pH value controlling reaction solution is 8, at room temperature stirring reaction 4h; Collect product by rotatory evaporator after having reacted, finally obtain the polysiloxane containing amino, vinyl, phenyl in ambient temperature in vacuum drying;
(2) preparation of response type carbon nanotube fire retardant
Being mixed with 20mL thionyl chloride, 1mLDMF by 200mg functionalized multi-wall carbonnanotubes and carrying out supersound process makes carbon nanotube fully be distributed in solution, reacts 24h under magnetic stirring; Steam thionyl chloride after reaction terminates, resultant product vacuum-drying obtains chloride carbon nanotube;
200mg chloride carbon nanotube is joined in 200mL tetrahydrofuran solution, add polysiloxane prepared by 400mg step (1) again, drip 5 pyridines, reflux 24h at the boiling point 65.4 DEG C of tetrahydrofuran (THF), namely obtains response type carbon nanotube fire retardant.
As shown in Figure 1, 2, carbon nanotube caliber after graft modification is obviously thicker.
As shown in Figure 3, occurred obvious peak through polysiloxane-modified response type carbon nanotube fire retardant at 100eV, 150eV place, they represent Si2p, Si2s respectively.
Embodiment 2:
In the present embodiment, the preparation method of response type carbon nanotube fire retardant comprises the following steps:
(1) preparation of polysiloxane
Measure 30mL ethanol, 10mL deionized water, add 0.5g aminopropyl trimethoxysilane, 0.2g vinyl methyl dimethoxysilane, 1g phenyltrimethoxysila,e, stir; In this reaction system, slowly add tetraethyl ammonium hydroxide, the pH value controlling reaction solution is 10, at room temperature stirring reaction 6h; Collect product by rotatory evaporator after having reacted, finally obtain the polysiloxane containing amino, vinyl, phenyl in ambient temperature in vacuum drying;
(2) preparation of response type carbon nanotube fire retardant
Being mixed with 20mL thionyl chloride, 1mLDMF by 200mg functionalized multi-wall carbonnanotubes and carrying out supersound process makes carbon nanotube fully be distributed in solution, reacts 30h under magnetic stirring; Steam thionyl chloride after reaction terminates, resultant product vacuum-drying obtains chloride carbon nanotube;
200mg chloride carbon nanotube is joined in 200mL tetrahydrofuran solution, add polysiloxane prepared by 200mg step (1) again, drip 5 pyridines, reflux 28h at the boiling point 65.4 DEG C of tetrahydrofuran (THF), namely obtains response type carbon nanotube fire retardant.
Embodiment 3:
In the present embodiment, the preparation method of response type carbon nanotube fire retardant comprises the following steps:
(1) preparation of polysiloxane
Measure 30mL ethanol, 10mL deionized water, add 0.5g aminopropyl trimethoxysilane, 0.2g vinyl methyl dimethoxysilane, 1g phenyltrimethoxysila,e, stir; In this reaction system, slowly add TBAH, the pH value controlling reaction solution is 10, at room temperature stirring reaction 6h; Collect product by rotatory evaporator after having reacted, finally obtain the polysiloxane containing amino, vinyl, phenyl in ambient temperature in vacuum drying;
(2) preparation of response type carbon nanotube fire retardant
Being mixed with 20mL thionyl chloride, 1mLDMF by 200mg functionalized multi-wall carbonnanotubes and carrying out supersound process makes carbon nanotube fully be distributed in solution, reacts 30h under magnetic stirring; Steam thionyl chloride after reaction terminates, resultant product vacuum-drying obtains chloride carbon nanotube;
200mg chloride carbon nanotube is joined in 200mL tetrahydrofuran solution, add polysiloxane prepared by 200mg step (1) again, drip 5 pyridines, reflux 28h at the boiling point 65.4 DEG C of tetrahydrofuran (THF), namely obtains response type carbon nanotube fire retardant.
Embodiment 4:
In the present embodiment, the preparation method of response type carbon nanotube fire retardant comprises the following steps:
(1) preparation of polysiloxane
Measure 30mL ethanol, 10mL deionized water, add 0.1g aminopropyl trimethoxysilane, 0.2g vinyl methyl dimethoxysilane, 1g phenyltrimethoxysila,e, stir; In this reaction system, slowly add tetrabutylammonium hydroxide ammonia, the pH value controlling reaction solution is 7, at room temperature stirring reaction 2h; Collect product by rotatory evaporator after having reacted, finally obtain the polysiloxane containing amino, vinyl, phenyl in ambient temperature in vacuum drying;
(2) preparation of response type carbon nanotube fire retardant
Being mixed with 20mL thionyl chloride, 1mLDMF by 200mg functionalized multi-wall carbonnanotubes and carrying out supersound process makes carbon nanotube fully be distributed in solution, reacts 26h under magnetic stirring; Steam thionyl chloride after reaction terminates, resultant product vacuum-drying obtains chloride carbon nanotube;
200mg chloride carbon nanotube is joined in 200mL tetrahydrofuran solution, add polysiloxane prepared by 800mg step (1) again, drip 5 pyridines, reflux 30h at the boiling point 65.4 DEG C of tetrahydrofuran (THF), namely obtains response type carbon nanotube fire retardant.
Embodiment 5:
In the present embodiment, the preparation method of response type carbon nanotube fire retardant comprises the following steps:
(1) preparation of polysiloxane
Measure 30mL propyl alcohol, 10mL deionized water, add 0.5g aminopropyl trimethoxysilane, 0.2g vinyl methyl dimethoxysilane, 2g phenyltrimethoxysila,e, stir; In this reaction system, slowly add Tetramethylammonium hydroxide, the pH value controlling reaction solution is 9, at room temperature stirring reaction 6h; Collect product by rotatory evaporator after having reacted, finally under room temperature, empty drying obtains the polysiloxane containing amino, vinyl, phenyl;
(2) preparation of response type carbon nanotube fire retardant
Being mixed with 20mL thionyl chloride, 1mLDMF by 200mg functionalized multi-wall carbonnanotubes and carrying out supersound process makes carbon nanotube fully be distributed in solution, reacts 26h under magnetic stirring; Steam thionyl chloride after reaction terminates, resultant product vacuum-drying obtains chloride carbon nanotube;
200mg chloride carbon nanotube is joined in 200mL tetrahydrofuran solution, add polysiloxane prepared by 800mg step (1) again, drip 5 pyridines, reflux 30h at the boiling point 65.4 DEG C of tetrahydrofuran (THF), namely obtains response type carbon nanotube fire retardant.
Embodiment 6:
In the present embodiment, the preparation method of response type carbon nanotube fire retardant comprises the following steps:
(1) preparation of polysiloxane
Measure 30mL acetone, 10mL deionized water, add 0.1g aminopropyl trimethoxysilane, 0.2g vinyl methyl dimethoxysilane, 1g phenyltrimethoxysila,e, stir; In this reaction system, slowly add Tetramethylammonium hydroxide, the pH value controlling reaction solution is 7, at room temperature stirring reaction 2h; Collect product by rotatory evaporator after having reacted, finally obtain the polysiloxane containing amino, vinyl, phenyl in ambient temperature in vacuum drying;
(2) preparation of response type carbon nanotube fire retardant
Being mixed with 20mL thionyl chloride, 1mLDMF by 200mg functionalized multi-wall carbonnanotubes and carrying out supersound process makes carbon nanotube fully be distributed in solution, reacts 26h under magnetic stirring; Steam thionyl chloride after reaction terminates, resultant product vacuum-drying obtains chloride carbon nanotube;
200mg chloride carbon nanotube is joined in 200mL tetrahydrofuran solution, add polysiloxane prepared by 800mg step (1) again, drip 5 pyridines, reflux 30h at the boiling point 65.4 DEG C of tetrahydrofuran (THF), namely obtains response type carbon nanotube fire retardant.
Functionalized multi-wall carbonnanotubes in the present invention is from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
Claims (8)
1. a preparation method for response type carbon nanotube fire retardant, is characterized in that comprising the following steps:
(1) preparation of polysiloxane
Amino-silane monomer, vinyl silane monomer and phenyl silane monomer are mixed and is dissolved in solvent, alkaline catalysts is added in this reaction system, the pH value controlling reaction solution is 7 ~ 10, collects the polysiloxane that namely product obtains containing amino, vinyl, phenyl under room temperature after reacting 2 ~ 6h;
(2) preparation of response type carbon nanotube fire retardant
Be dissolved in organic solvent by functionalized multi-wall carbonnanotubes and thionyl chloride, supersound process also reacts 24 ~ 30h, removes solution drying obtains chloride carbon nanotube after completion of the reaction;
The polysiloxane described chloride carbon nanotube and step (1) prepared mixes according to mass ratio 1:1 ~ 4 and is placed in organic solvent, back flow reaction 24 ~ 30h under the boiling temperature of this organic solvent, namely obtains response type carbon nanotube fire retardant.
2. the preparation method of response type carbon nanotube fire retardant according to claim 1, is characterized in that: the mass ratio of the described amino-silane monomer added in step (1), vinyl silane monomer and phenyl silane monomer is 1 ~ 5:1 ~ 5:2 ~ 20.
3. the preparation method of response type carbon nanotube fire retardant according to claim 2, is characterized in that: described amino-silane monomer is NH
2c
3h
6siX
3or NH
2c
3h
6r
1siX
2; Wherein, R
1for-CH
3or-C
6h
5, X is-Cl ,-OCH
3or-OC
2h
5.
4. the preparation method of response type carbon nanotube fire retardant according to claim 2, is characterized in that: described vinyl silane monomer is CH=CH
2siX
3or CH=CH
2r
1siX
2; Wherein, R
1for-CH
3or-C
6h
5, X is-Cl ,-OCH
3or-OC
2h
5.
5. the preparation method of response type carbon nanotube fire retardant according to claim 2, is characterized in that: described phenyl silane monomer is C
6h
5siX
3; Wherein, X is-Cl ,-OCH
3or-OC
2h
5.
6. the preparation method of response type carbon nanotube fire retardant according to claim 1, is characterized in that: the carboxyl-content of step (2) described functionalized multi-wall carbonnanotubes is 1 ~ 5wt%.
7. the preparation method of response type carbon nanotube fire retardant according to claim 1, is characterized in that: described alkaline catalysts is alkali metal hydroxide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH or ammonia.
8. the preparation method of response type carbon nanotube fire retardant according to claim 1, it is characterized in that: the preparation method of response type carbon nanotube fire retardant according to claim 1, is characterized in that: described organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, acetone, tetrahydrofuran (THF).
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| CN107894640A (en) * | 2017-12-28 | 2018-04-10 | 江苏亨通光电股份有限公司 | One kind limits Fracture Force and makes somebody a mere figurehead leading in cable |
| CN107892739A (en) * | 2017-12-13 | 2018-04-10 | 上海东大聚氨酯有限公司 | A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof |
| CN107964082A (en) * | 2017-12-13 | 2018-04-27 | 上海东大聚氨酯有限公司 | A kind of polyisocyanates, polyurethane foam plastics and preparation method thereof, application |
| CN110016139A (en) * | 2019-04-01 | 2019-07-16 | 东华大学 | A kind of Containing Schiff-bases hyperbranched polyorganosiloxane fire retardant and the preparation method and application thereof |
| CN111171322A (en) * | 2020-03-12 | 2020-05-19 | 衢州学院 | Preparation method of carbon nano tube amidated grafted polysilsesquioxane flame retardant |
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| CN107964082A (en) * | 2017-12-13 | 2018-04-27 | 上海东大聚氨酯有限公司 | A kind of polyisocyanates, polyurethane foam plastics and preparation method thereof, application |
| CN107964082B (en) * | 2017-12-13 | 2019-07-09 | 上海东大聚氨酯有限公司 | A kind of polyisocyanates, polyurethane foam plastics and preparation method thereof, application |
| CN107892739B (en) * | 2017-12-13 | 2019-07-09 | 上海东大聚氨酯有限公司 | A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof |
| CN107894640A (en) * | 2017-12-28 | 2018-04-10 | 江苏亨通光电股份有限公司 | One kind limits Fracture Force and makes somebody a mere figurehead leading in cable |
| CN110016139A (en) * | 2019-04-01 | 2019-07-16 | 东华大学 | A kind of Containing Schiff-bases hyperbranched polyorganosiloxane fire retardant and the preparation method and application thereof |
| CN110016139B (en) * | 2019-04-01 | 2021-06-18 | 东华大学 | Schiff base hyperbranched polysiloxane flame retardant and preparation method and application thereof |
| CN111171322A (en) * | 2020-03-12 | 2020-05-19 | 衢州学院 | Preparation method of carbon nano tube amidated grafted polysilsesquioxane flame retardant |
| CN111171322B (en) * | 2020-03-12 | 2022-01-25 | 衢州学院 | Preparation method of carbon nano tube amidated grafted polysilsesquioxane flame retardant |
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