CN105037734B - A kind of preparation method of response type carbon nanotube fire retardant - Google Patents
A kind of preparation method of response type carbon nanotube fire retardant Download PDFInfo
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- CN105037734B CN105037734B CN201510299859.1A CN201510299859A CN105037734B CN 105037734 B CN105037734 B CN 105037734B CN 201510299859 A CN201510299859 A CN 201510299859A CN 105037734 B CN105037734 B CN 105037734B
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Abstract
The present invention relates to a kind of preparation methods of response type carbon nanotube fire retardant, since polysiloxanes and carbon nanotube itself belong to fire retardant, polysiloxanes is grafted on the carbon nanotubes by chemical bond, flame retardant property of the synergistic effect both to make is generated between polysiloxanes and carbon nanotube and is not fully exerted；The vinyl of polysiloxanes institute band is also provided on carbon nano tube structure after polysiloxane-grafted, reactive flame retardant can be grafted in a variety of synthetic materials such as unsaturated polyester (UP), silicon rubber by the vinyl, phenyl in polysiloxanes can improve the carbon-forming performance and flame retardant property of polymer in combustion, the flame retardant property of matrix can not only be improved, and is conducive to improve the performances such as machinery, the electricity of material；Polysiloxanes, carbon nanotube belong to carbon-forming type flame-retardant agent, and the phenyl ring in polysiloxane structure can further be strengthened this acted at charcoal in combustion so that entire reaction-type flame-retarding system has outstanding flame retardant property.
Description
Technical field
The present invention relates to a kind of preparation methods of response type carbon nanotube fire retardant.
Background technology
In recent years, carbon nanotube relies on its excellent heat resistance and mechanical property, it is fire-retardant initially as synthetic material
Agent uses, but since carbon nanotube has larger draw ratio (being typically in the range of between 300~1000) and very strong electrostatic phase
Interaction, carbon pipe easily gather into bundles in a polymer matrix, cause its dispersibility to be deteriorated, cannot function well as fire-retardant work
With.Solution commonly used in the prior art is that organic matter is grafted to carbon nano tube surface, to improve it in the polymer
Dispersibility.Using composite material high stability, such as Chen et al. made from this method [Chen GX, Shimizu
H.Multiwalled carbon nanotubes grafted with polyhedral oligomeric
silsesquioxane and its dispersion in poly(L-lactide)matrix.Polymer,2008,49
(4):943-951.] POSS is grafted to carbon nano tube surface, then polylactic acid/carbon mano-tube composite is prepared, due to carbon nanometer
Strong interface binding power is produced between pipe and matrix, therefore fine dispersion can be kept under various processing conditions.
When using traditional organic compound as covalent modification agent, drawn due to Van der Waals force although carbon nanotube can be weakened
The aggregation tendency risen, improves its dispersibility in the base, still, since organic matter itself has inflammability, tends not to reach
To the purpose for improving Flame Retardancy.
Invention content
The technical problem to be solved by the invention for the present situation of prior art is to provide a kind of resistances of response type carbon nanotube
The preparation method of agent is fired, reactive flame retardant prepared by this method is efficient, cleans, is environmentally friendly harmless, and with preferable
Dispersibility can not only improve convenient for the reactive flame retardant to be grafted in a variety of synthetic materials such as unsaturated polyester (UP), silicon rubber
The flame retardant property of matrix, and be conducive to improve the performances such as machinery, the electricity of material.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of system of response type carbon nanotube fire retardant
Preparation Method, it is characterised in that include the following steps：
(1) preparation of polysiloxanes
Amino-silane monomer, vinyl silane monomer and phenyl silane monomer are mixed and are dissolved in solvent, to the reaction
Base catalyst is added in system, the pH value for controlling reaction solution is 7~10, and collection product is contained after reacting 2~6h at room temperature
There is the polysiloxanes of amino, vinyl, phenyl；
(2) preparation of response type carbon nanotube fire retardant
Functionalized multi-wall carbonnanotubes and thionyl chloride are dissolved in organic solvent, are ultrasonically treated and react 24~30h, instead
Solution is removed after answering and is dried to obtain acyl chlorides carbon nano tube；
Polysiloxanes prepared by the acyl chlorides carbon nano tube and step (1) is according to mass ratio 1:1~4 mixing is placed in
In organic solvent, 24~30h of back flow reaction is to get fire-retardant to response type carbon nanotube under the boiling temperature of the organic solvent
Agent.
As a further improvement on the present invention, the amino-silane monomer, the vinyl silane monomer being added in step (1)
Mass ratio with phenyl silane monomer is 1~5:1~5:2~20.Since the reaction mechanism of the present invention is the ammonia in polysiloxanes
Base is chemically reacted with the carbon nanotube after chloride, and the phenyl in polysiloxanes improves polymer in combustion
Carbon-forming performance and flame retardant property；Therefore, when the amino and vinyl content in structure is too low, the reactivity of product will be reduced,
And when the amino and vinyl too high levels in structure, then phenyl ring content will be less, finally influences carbon-forming performance；Using upper
Reaction mass ratio is stated, the ratio between amino, vinyl and phenyl ring can be made to be in optimal combination range, to make the present invention's
Response type carbon nanotube fire retardant has preferable flame retardant property.
Preferably, the amino-silane monomer is NH2C3H6SiX3Or NH2C3H6R1SiX2；Wherein, R1For-CH3Or-
C6H5, X is-Cl ,-OCH3Or-OC2H5。
Preferably, the vinyl silane monomer is CH=CH2SiX3Or CH=CH2R1SiX2；Wherein, R1For-CH3
Or-C6H5, X is-Cl ,-OCH3Or-OC2H5。
Preferably, the phenyl silane monomer is C6H5SiX3；Wherein, X is-Cl ,-OCH3Or-OC2H5。
Further preferably, the carboxyl-content of step (2) described functionalized multi-wall carbonnanotubes is 1~5wt%.
Preferably, the base catalyst be alkali metal hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide,
Tetrabutylammonium hydroxide or ammonia.
In the above embodiments, the organic solvent be methanol, ethyl alcohol, propyl alcohol, acetone, one kind in tetrahydrofuran or
It is several.
Compared with the prior art, the advantages of the present invention are as follows：
Since polysiloxanes and carbon nanotube itself belong to fire retardant, there is flame retardant property, in the preparation side of the present invention
In method, polysiloxanes is grafted on the carbon nanotubes by chemical bond, synergistic effect is generated between polysiloxanes and carbon nanotube
Flame retardant property both to make is not fully exerted；Meanwhile also being had on the carbon nano tube structure after polysiloxane-grafted
The vinyl of polysiloxanes institute band, can be grafted to unsaturated polyester (UP), silicon rubber by the vinyl by reactive flame retardant
Etc. in a variety of synthetic materials, the phenyl in polysiloxanes can improve the carbon-forming performance and anti-flammability of polymer in combustion
Can, the flame retardant property of matrix can not only be improved, and be conducive to improve the performances such as machinery, the electricity of material；
Polysiloxanes, carbon nanotube in the present invention belong to carbon-forming type flame-retardant agent, and the phenyl ring in polysiloxane structure
It can further strengthen in combustion and this be acted at charcoal so that entire reaction-type flame-retarding system has outstanding resistance
Fire performance；
Polysiloxanes in the present invention has good compatibility with polymeric matrix, can help carbon nanotube improve its
Dispersibility in polymeric matrix can be with simultaneously because vinyl in modified carbon nano-tube structure has preferable reactivity
It helps carbon nanotube to be connected with chemical bond with polymeric matrixs such as unsaturated polyester (UP), silicon rubber in application, further increases anti-
Answer the dispersion performance of type flame-retardant system；
Polysiloxanes, carbon nanotube in the present invention belong to green new flame retardant, not will produce in combustion
Poisonous and harmful substances, it is environmentally friendly harmless.
Description of the drawings
Fig. 1 is the TEM figures of functionalized multi-wall carbonnanotubes in the embodiment of the present invention 1；
Fig. 2 is the TEM figures for the response type carbon nanotube fire retardant being prepared in the embodiment of the present invention 1；
Fig. 3 is the x-ray photoelectron spectroscopy figure for the response type carbon nanotube fire retardant being prepared in inventive embodiments 1.
Specific implementation mode
Below in conjunction with attached drawing embodiment, present invention is further described in detail.
Embodiment 1：
The preparation method of response type carbon nanotube fire retardant includes the following steps in the present embodiment：
(1) preparation of polysiloxanes
15mL ethyl alcohol, 5mL deionized waters are measured, 0.2g aminopropyl triethoxysilanes, 0.2g vinyl trimethoxies is added
Base silane, 2g phenyltrimethoxysila,es, stir evenly；It is slowly added to tetramethylammonium hydroxide into the reaction system, controls
The pH value of reaction solution is 8, and reaction 4h is stirred at room temperature；Product is collected by rotary evaporator after the completion of reaction, finally in room
The lower vacuum drying of temperature obtains the polysiloxanes containing amino, vinyl, phenyl；
(2) preparation of response type carbon nanotube fire retardant
200mg functionalized multi-wall carbonnanotubes are mixed with 20mL thionyl chlorides, 1mLDMF and be ultrasonically treated makes carbon
Nanotube is fully dispersed in solution, reacts under magnetic stirring for 24 hours；Thionyl chloride is steamed after reaction, and resultant product is true
Sky is dried to obtain acyl chlorides carbon nano tube；
200mg acyl chlorides carbon nano tubes are added in 200mL tetrahydrofuran solutions, 400mg steps (1) preparation is added
Polysiloxanes, be added dropwise 5 drop pyridines, flow back at 65.4 DEG C of the boiling point of tetrahydrofuran for 24 hours to get to response type carbon nanotube hinder
Fire agent.
As shown in Figure 1, 2, carbon nanotube caliber after graft modification is obviously thicker.
As shown in figure 3, occurring at 100eV, 150eV by polysiloxane-modified response type carbon nanotube fire retardant
Apparent peak, they have respectively represented Si2p, Si2s.
Embodiment 2：
The preparation method of response type carbon nanotube fire retardant includes the following steps in the present embodiment：
(1) preparation of polysiloxanes
30mL ethyl alcohol, 10mL deionized waters are measured, 0.5g aminopropyl trimethoxysilanes, 0.2g vinyl methyls two is added
Methoxy silane, 1g phenyltrimethoxysila,es, stir evenly；It is slowly added to tetraethyl ammonium hydroxide into the reaction system,
The pH value for controlling reaction solution is 10, and reaction 6h is stirred at room temperature；Product is collected by rotary evaporator after the completion of reaction, finally
Vacuum drying obtains the polysiloxanes containing amino, vinyl, phenyl at room temperature；
(2) preparation of response type carbon nanotube fire retardant
200mg functionalized multi-wall carbonnanotubes are mixed with 20mL thionyl chlorides, 1mLDMF and be ultrasonically treated makes carbon
Nanotube is fully dispersed in solution, reacts 30h under magnetic stirring；Thionyl chloride is steamed after reaction, and resultant product is true
Sky is dried to obtain acyl chlorides carbon nano tube；
200mg acyl chlorides carbon nano tubes are added in 200mL tetrahydrofuran solutions, 200mg steps (1) preparation is added
Polysiloxanes, be added dropwise 5 drop pyridines, at 65.4 DEG C of the boiling point of tetrahydrofuran flow back 28h to get to response type carbon nanotube hinder
Fire agent.
Embodiment 3：
The preparation method of response type carbon nanotube fire retardant includes the following steps in the present embodiment：
(1) preparation of polysiloxanes
30mL ethyl alcohol, 10mL deionized waters are measured, 0.5g aminopropyl trimethoxysilanes, 0.2g vinyl methyls two is added
Methoxy silane, 1g phenyltrimethoxysila,es, stir evenly；It is slowly added to tetrabutylammonium hydroxide into the reaction system,
The pH value for controlling reaction solution is 10, and reaction 6h is stirred at room temperature；Product is collected by rotary evaporator after the completion of reaction, finally
Vacuum drying obtains the polysiloxanes containing amino, vinyl, phenyl at room temperature；
(2) preparation of response type carbon nanotube fire retardant
200mg functionalized multi-wall carbonnanotubes are mixed with 20mL thionyl chlorides, 1mLDMF and be ultrasonically treated makes carbon
Nanotube is fully dispersed in solution, reacts 30h under magnetic stirring；Thionyl chloride is steamed after reaction, and resultant product is true
Sky is dried to obtain acyl chlorides carbon nano tube；
200mg acyl chlorides carbon nano tubes are added in 200mL tetrahydrofuran solutions, 200mg steps (1) preparation is added
Polysiloxanes, be added dropwise 5 drop pyridines, at 65.4 DEG C of the boiling point of tetrahydrofuran flow back 28h to get to response type carbon nanotube hinder
Fire agent.
Embodiment 4：
The preparation method of response type carbon nanotube fire retardant includes the following steps in the present embodiment：
(1) preparation of polysiloxanes
30mL ethyl alcohol, 10mL deionized waters are measured, 0.1g aminopropyl trimethoxysilanes, 0.2g vinyl methyls two is added
Methoxy silane, 1g phenyltrimethoxysila,es, stir evenly；Tetrabutylammonium hydroxide ammonia is slowly added into the reaction system,
The pH value for controlling reaction solution is 7, and reaction 2h is stirred at room temperature；Product is collected by rotary evaporator after the completion of reaction, finally
Vacuum drying obtains the polysiloxanes containing amino, vinyl, phenyl at room temperature；
(2) preparation of response type carbon nanotube fire retardant
200mg functionalized multi-wall carbonnanotubes are mixed with 20mL thionyl chlorides, 1mLDMF and be ultrasonically treated makes carbon
Nanotube is fully dispersed in solution, reacts 26h under magnetic stirring；Thionyl chloride is steamed after reaction, and resultant product is true
Sky is dried to obtain acyl chlorides carbon nano tube；
200mg acyl chlorides carbon nano tubes are added in 200mL tetrahydrofuran solutions, 800mg steps (1) preparation is added
Polysiloxanes, be added dropwise 5 drop pyridines, at 65.4 DEG C of the boiling point of tetrahydrofuran flow back 30h to get to response type carbon nanotube hinder
Fire agent.
Embodiment 5：
The preparation method of response type carbon nanotube fire retardant includes the following steps in the present embodiment：
(1) preparation of polysiloxanes
30mL propyl alcohol, 10mL deionized waters are measured, 0.5g aminopropyl trimethoxysilanes, 0.2g vinyl methyls two is added
Methoxy silane, 2g phenyltrimethoxysila,es, stir evenly；It is slowly added to tetramethylammonium hydroxide into the reaction system,
The pH value for controlling reaction solution is 9, and reaction 6h is stirred at room temperature；Product is collected by rotary evaporator after the completion of reaction, finally
It is empty at room temperature to be dried to obtain the polysiloxanes containing amino, vinyl, phenyl；
(2) preparation of response type carbon nanotube fire retardant
200mg functionalized multi-wall carbonnanotubes are mixed with 20mL thionyl chlorides, 1mLDMF and be ultrasonically treated makes carbon
Nanotube is fully dispersed in solution, reacts 26h under magnetic stirring；Thionyl chloride is steamed after reaction, and resultant product is true
Sky is dried to obtain acyl chlorides carbon nano tube；
200mg acyl chlorides carbon nano tubes are added in 200mL tetrahydrofuran solutions, 800mg steps (1) preparation is added
Polysiloxanes, be added dropwise 5 drop pyridines, at 65.4 DEG C of the boiling point of tetrahydrofuran flow back 30h to get to response type carbon nanotube hinder
Fire agent.
Embodiment 6：
The preparation method of response type carbon nanotube fire retardant includes the following steps in the present embodiment：
(1) preparation of polysiloxanes
30mL acetone, 10mL deionized waters are measured, 0.1g aminopropyl trimethoxysilanes, 0.2g vinyl methyls two is added
Methoxy silane, 1g phenyltrimethoxysila,es, stir evenly；It is slowly added to tetramethylammonium hydroxide into the reaction system,
The pH value for controlling reaction solution is 7, and reaction 2h is stirred at room temperature；Product is collected by rotary evaporator after the completion of reaction, finally
Vacuum drying obtains the polysiloxanes containing amino, vinyl, phenyl at room temperature；
(2) preparation of response type carbon nanotube fire retardant
200mg functionalized multi-wall carbonnanotubes are mixed with 20mL thionyl chlorides, 1mLDMF and be ultrasonically treated makes carbon
Nanotube is fully dispersed in solution, reacts 26h under magnetic stirring；Thionyl chloride is steamed after reaction, and resultant product is true
Sky is dried to obtain acyl chlorides carbon nano tube；
200mg acyl chlorides carbon nano tubes are added in 200mL tetrahydrofuran solutions, 800mg steps (1) preparation is added
Polysiloxanes, be added dropwise 5 drop pyridines, at 65.4 DEG C of the boiling point of tetrahydrofuran flow back 30h to get to response type carbon nanotube hinder
Fire agent.
Functionalized multi-wall carbonnanotubes in the present invention come from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
Claims (4)
1. a kind of preparation method of response type carbon nanotube fire retardant, it is characterised in that include the following steps：
(1) preparation of polysiloxanes
Amino-silane monomer, vinyl silane monomer and phenyl silane monomer are mixed and are dissolved in solvent, to the reaction system
Middle addition base catalyst, the pH value for controlling reaction solution are 7~10, and collection product is obtained containing ammonia after reacting 2~6h at room temperature
The polysiloxanes of base, vinyl, phenyl；
The amino-silane monomer is NH2C3H6SiX3Or NH2C3H6R1SiX2；Wherein, R1For-CH3Or-C6H5, X be-Cl ,-
OCH3Or-OC2H5；
The vinyl silane monomer is CH=CH2SiX3Or CH=CH2R1SiX2；Wherein, R1For-CH3Or-C6H5, X be-
Cl、-OCH3Or-OC2H5；
The phenyl silane monomer is C6H5SiX3；Wherein, X is-Cl ,-OCH3Or-OC2H5；
(2) preparation of response type carbon nanotube fire retardant
Functionalized multi-wall carbonnanotubes and thionyl chloride are dissolved in organic solvent, is ultrasonically treated and reacts 24~30h, reacted
Solution is removed after finishing and is dried to obtain acyl chlorides carbon nano tube；
Polysiloxanes prepared by the acyl chlorides carbon nano tube and step (1) is according to mass ratio 1:1~4 mixing is placed in organic
In solvent, 24~30h of back flow reaction is to get to response type carbon nanotube fire retardant under the boiling temperature of the organic solvent.
2. the preparation method of response type carbon nanotube fire retardant according to claim 1, it is characterised in that：In step (1)
The mass ratio of the amino-silane monomer, vinyl silane monomer and the phenyl silane monomer that are added is 1~5:1~5:2~20.
3. the preparation method of response type carbon nanotube fire retardant according to claim 1, it is characterised in that：Step (2) institute
The carboxyl-content for stating functionalized multi-wall carbonnanotubes is 1~5wt%.
4. the preparation method of response type carbon nanotube fire retardant according to claim 1, it is characterised in that：The alkali is urged
Agent is alkali metal hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide or ammonia.
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| 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 |
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| CN110016139B (en) * | 2019-04-01 | 2021-06-18 | 东华大学 | Schiff base hyperbranched polysiloxane flame retardant and preparation method and application thereof |
| 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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