CN109536111A - A kind of resistance to fire-retardant adhesive and preparation method thereof of carbon nano-tube modification - Google Patents
A kind of resistance to fire-retardant adhesive and preparation method thereof of carbon nano-tube modification Download PDFInfo
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- CN109536111A CN109536111A CN201811635062.4A CN201811635062A CN109536111A CN 109536111 A CN109536111 A CN 109536111A CN 201811635062 A CN201811635062 A CN 201811635062A CN 109536111 A CN109536111 A CN 109536111A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention provides a kind of resistance to fire-retardant adhesive and preparation method thereof of carbon nano-tube modification, is related to technical field of composite materials.This adhesive is reacted by polymerizable raw material to be made, in parts by weight, the raw material includes: 65~85 parts of aqueous polyurethane, 10~20 parts of vinyl-acrylate copolymer, 5-10 parts of nanotube dispersion, 3~8 parts of fire retardant, 1~3 part of initiator, 0.1~0.2 part of crosslinking agent.The adhesive is environmentally protective based on aqueous polyurethane.Nanotube dispersion and fire retardant are introduced, flame-retardant composition can be used as, effectively improve the flame retardant effect of adhesive.Processing is modified to aqueous polyurethane using vinyl-acrylate copolymer, the adhesive strength of adhesive can be further increased, and guarantee that product obtains stability.
Description
Technical field
The present invention relates to field of compound material, and in particular to a kind of carbon nano-tube modification resistance to fire-retardant adhesive and its system
Preparation Method.
Background technique
Aqueous polyurethane has high resiliency, good flexibility, higher springform as a kind of common adhesives
Amount and excellent wear-resisting property, are widely used in many industrial circles.But Aqueous Polyurethane Adhesives product strength is not high,
The performances such as heat-resisting, water-fast, antistatic, fire-retardant are poor, limit its further application.Carbon nanotube is that one kind is made of carbon atom
Individual layer laminated structure, have intensity height, large specific surface area, high IR emissivity, physical mechanical property good and gas barrier
The characteristics such as performance.It introduces carbon nanotubes in the adhesive material of aqueous polyurethane, the performance that carbon nanotube can be utilized excellent
To increase substantially the heat dissipation of adhesive material, the performances such as fire-retardant.
Inventor is the study found that carbon nanotube causes to be prone to reunite and highly conductive spy due to its high-specific surface area
Property, cause it to be easy to happen precipitating in resin matrix, influences the heat dissipation effect and intensity of product.
Summary of the invention
The purpose of the present invention is to provide a kind of resistance to fire-retardant adhesive of carbon nano-tube modification, this adhesive has good
Anti-flammability, and intensity is high.
Another object of the present invention is to provide a kind of resistance to fire-retardant adhesive and preparation method thereof of carbon nano-tube modification, this
Preparation method can be effectively disperseed carbon nanotube and fire retardant, and interface performance is good.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of resistance to fire-retardant adhesive of carbon nano-tube modification: it is reacted by polymerizable raw material is made, according to
Parts by weight meter, the raw material include: 65~85 parts of aqueous polyurethane, 10~20 parts of vinyl-acrylate copolymer, carbon nanometer
5-10 parts of pipe dispersion, 3~8 parts of fire retardant, 1~3 part of initiator, 0.1~0.2 part of crosslinking agent.
The present invention also provides the preparation methods of the resistance to fire-retardant adhesive of above-mentioned carbon nano-tube modification, comprising the following steps:
S1, by the carbon nanotube of the aqueous polyurethane of 1/20-1/10, whole fire retardants and 1/3-1/2
Dispersion mixing, is subsequently placed in plasma generator, with CF4、N2、CCl4In any one be reaction gas, reaction pressure is
10~30Pa, reaction power are 100~200W, and the reaction time, 3~15min obtained mixture；
S2, by the mixture, 1/10-1/5 the vinyl-acrylate copolymer and 1/20-1/10 described in draw
Agent stirring is sent out, 60 DEG C -70 DEG C is warming up to and is reacted to obtain reactant I；
The remaining nanotube dispersion is added under heat-retaining condition in S3 in the reactant I, and stirring 20~
50min obtains reactant II；
The remaining aqueous polyurethane, the vinyl-acrylate copolymer and described is added in S4 in reactant II
Initiator is warming up to 80-85 DEG C of reaction 2-3h, and the crosslinking agent is added and is continuously heating to 90-100 DEG C of reaction 0.5-1h, is down to
The adhesive is obtained by filtration after room temperature.
The beneficial effect of the resistance to fire-retardant adhesive of the carbon nano-tube modification of the embodiment of the present invention and preparation method thereof is: the glue
Glutinous agent is environmentally protective based on aqueous polyurethane.By introducing nanotube dispersion and fire retardant in aqueous polyurethane,
Can heat dissipation as adhesive and flame-retardant composition, effectively change the anti-flammability of adhesive, and carry out to the object of gluing effective
Heat dissipation.In addition, being modified processing to aqueous polyurethane using vinyl-acrylate copolymer, it can further increase and cohere
The adhesive strength of agent, and enable to adhesive that can receive relatively large number of filler, guarantee that product obtains stability.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Fire-retardant adhesive resistance to the carbon nano-tube modification of the embodiment of the present invention and preparation method thereof carries out specifically below
It is bright.
The resistance to fire-retardant adhesive of a kind of carbon nano-tube modification provided in an embodiment of the present invention is reacted by polymerizable raw material and is made
, in parts by weight, the raw material includes: 65~85 parts of aqueous polyurethane, vinyl-acrylate copolymer 10~20
Part, 5-10 parts of nanotube dispersion, 3~8 parts of fire retardant, 1~3 part of initiator, 0.1~0.2 part of crosslinking agent.
In the preferred embodiment, aqueous polyurethane is by 45-60 parts of polyalcohols, 12-15 parts of diisocyanate, 0.3-0.5
Part catalyst, 30-50 parts of organic solvents, 5-8 parts of chain extenders, 2-3 parts of neutralizers and 220-260 parts of water are prepared.
Aqueous polyurethane can be synthesized according to polymerization in the prior art, specifically, in this implementation, aqueous polyurethane
Preparation step are as follows: under nitrogen protection, polyalcohol, diisocyanate, catalyst are added in organic solvent, in 70-85
2-4h is reacted under the conditions of DEG C, and chain extender and organic solvent is then added, reacts 2-4h under the conditions of 90-95 DEG C, is cooled to room temperature
Neutralizer is added, reacts 0.5-1h, is eventually adding water, after being dispersed with stirring, vacuum distillation removal organic solvent is obtained described aqueous
Polyurethane.
In the preferred embodiment, polyalcohol is the polycarbonate glycol and dihydromethyl propionic acid that mass ratio is 4:1, is had
Solvent is butanone, and catalyst is dibutyl tin dilaurate, organo-bismuth or organo-bismuth zinc, and neutralizer is triethylamine.
In the preferred embodiment, chain extender is 1,2-PD carbonic ester and the dihydric alcohol that diamine polymerization reaction obtains
Chain extender.Specifically, 1,2-PD carbonic ester and diamine that mass ratio is 1:0.7 are put into flask, dichloromethane is added
Alkane is as solvent, and in 50 DEG C of heating stirring 20h, removed under reduced pressure methylene chloride is dried in vacuo with butyl ether, ethanol washing product
To chain extender.Chain extender is prepared by 1,2-PD carbonic ester and diamine open loop, aqueous poly- ammonia can be effectively improved
The content of ammonia ester bond in ester can effectively promote the adhesion strength of adhesive.
In the preferred embodiment, nanotube dispersion the preparation method comprises the following steps: dissolve the dispersant into solvent, be added
After ultrasonic 10-20min, surfactant is added in carbon nanotube and coupling agent, continues ultrasound 30-120min and obtain the carbon to receive
Nanotube dispersion.Carbon atom in carbon nanotube is with sp2Based on hydridization, be made of the carbon atom of hexagonal arrangement several layers to
Tens of layers of coaxial round tube.The distance being kept fixed between layers, about 0.34nm, diameter are generally 2~20nm.Carbon nanotube
With intensity height, large specific surface area, the characteristic of high IR emissivity.The thermal coefficient of single-walled carbon nanotube is up to 6600W/m
K, the thermal coefficient of multi-walled carbon nanotube are up to 3000W/mK, and heating conduction is splendid, can improve close-burning thermal stability,
Thermal conductivity and adhesive strength.In addition, the tensile strength highest of carbon nanotube is up to 80GPa, it is viscous that adhesive can be significantly improved
Intensity after knot.It obtains directly addition carbon nanotube in compared with the prior art to be modified, the present invention selects dispersion performance splendid
Nanotube dispersion is obtained, can guarantee that carbon nano-tube material obtains fine dispersion, and avoids occurring to be precipitated, precipitate etc. bad existing
As.
In the preferred embodiment, the mass ratio of the carbon nanotube, the coupling agent and the surfactant is 1:
2.0~2.5:0.1~0.2, coupling agent select silane coupling agent, and surfactant for example can be sodium lignin sulfonate, hard
Resin acid, sodium citrate etc..The dispersing agent be selected from one of polyvinyl alcohol or hydroxymethyl cellulose, the dispersing agent with it is described
The mass ratio of carbon nanotube is 0.4-0.6:1.In the preferred embodiment, the solvent is N-Methyl pyrrolidone, the carbon
Mass fraction of the nanotube in the carbon nano tube paste is 3-5%.Carbon nanotube is modified using silane coupling agent,
Coupling reaction can occur in carbon nanotube, generate a large amount of protrusion, significantly improve the interface performance of carbon nanotube.
In the preferred embodiment, the fire retardant is selected from organic phosphorus flame retardant, inorganic phosphorus flame retardant, LDHs, changes
One of property LDHs.Preferably, select modified LDHs as fire retardant, preparation method are as follows: the chlorine for being 2:1:3 by molar ratio
Change zinc, aluminium chloride and urea to be dispersed in water, phosphinic acids ammonium salt solution is added dropwise, 6~36h is reacted under the conditions of 80~100 DEG C, then
It is washed, be dried to obtain modified LDHs, wherein the molar ratio of the phosphinic acids ammonium in phosphinic acids ammonium salt solution and zinc chloride be 0.4:1.
Using phosphinic acids ammonium intercalation modifying LDHs as fire retardant, has the effect of cooperative flame retardant.
The embodiment of the present invention also provides the preparation method of the resistance to fire-retardant adhesive of above-mentioned carbon nano-tube modification, including following
Step:
S1, by the carbon nanotube of the aqueous polyurethane of 1/20-1/10, whole fire retardants and 1/3-1/2
Dispersion mixing, is subsequently placed in plasma generator, with CF4、N2、CCl4In any one be reaction gas, reaction pressure is
10~30Pa, reaction power are 100~200W, and the reaction time, 3~15min obtained mixture；
S2, by the mixture, 1/10-1/5 the vinyl-acrylate copolymer and 1/20-1/10 described in draw
Agent stirring is sent out, 60 DEG C -70 DEG C is warming up to and is reacted to obtain reactant I；
The remaining nanotube dispersion is added under heat-retaining condition in S3 in the reactant I, and stirring 20~
50min obtains reactant II；
The remaining aqueous polyurethane, the vinyl-acrylate copolymer and described is added in S4 in reactant II
Initiator is warming up to 80-85 DEG C of reaction 2-3h, and the crosslinking agent is added and is continuously heating to 90-100 DEG C of reaction 0.5-1h, is down to
The adhesive is obtained by filtration after room temperature.
During the preparation process, first fire retardant and part nanotube dispersion and part aqueous polyurethane are mixed, then
Plasma modification processing, can improve the interface performance of fire retardant, carbon nanotube and resin matrix.Pass through plasma surface
It is modified, it is collided by plasma and material surface, so that fire retardant, carbon nanotube and resin matrix is formed chemical activity high
Free radical, then form new chemical bond, the binding force in resin matrix both improved, for improving adhesive various aspects
Performance have great humidification, and can significantly promote the service life of adhesive.
In addition, carrying out segmentation reaction by S1 step and S4 step, guarantee that each component can sufficiently be reacted, is formed
The product of quality stable homogeneous forms fine and close network structure inside resin, further enhances intensity.Meanwhile in batches plus
Enter nanotube dispersion, the carbon nanotube dispersity more broken up can be formed in resin matrix, avoid carbon nanometer
Product caused by pipe dispersion is uneven is easily peelable to wait adverse reactions.Especially carbon nanotube, its dispersion can be significantly improved by being added portionwise
Performance.
In the preferred embodiment, crosslinking agent is praseodynium aluminium, and initiator is that benzoyl peroxide or azo two are different
Butyronitrile.When using praseodynium aluminium as crosslinking agent, the performance of product is greatly improved, such as mechanical performance, heat resistance, resistance to ring
Border stress cracking performance is improved, and enables to that chemical bond occurs between aqueous polyurethane and vinyl-acrylate copolymer
It closes, is cross-linked to form fine and close reticular structure, improves the intensity of product.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of aqueous polyurethanes, are prepared according to following steps:
To with agitating device, thermometer, N2Enter 56 parts of polycarbonate two in four mouthfuls of glass flasks of entrance and condenser pipe
First alcohol, 14 parts of dihydromethyl propionic acids, 0.4 part of dibutyl tin dilaurate and 25 parts of butanone, react 3h under the conditions of 80 DEG C, then
6 parts of glycol chain extenders and 20 parts of organic solvents are added, react 2h under the conditions of 95 DEG C, is cooled to room temperature and 2 parts of triethylamines is added,
1h is reacted, 240 parts of water are eventually adding, after being dispersed with stirring, vacuum distillation removal butanone obtains aqueous polyurethane.
Embodiment 2
The present embodiment provides a kind of nanotube dispersions, are prepared according to following steps:
3 parts of polyvinyl alcohol are dissolved in 100 parts of N-Methyl pyrrolidones, 5 parts of carbon nanotubes and 12 parts of silane idols are added
Join agent, after ultrasonic 10-20min, 1 part of sodium lignin sulfonate is added, continues ultrasound 120min and obtain the nanotube dispersion.
Embodiment 3
The resistance to fire-retardant adhesive of a kind of carbon nano-tube modification provided in this embodiment, is prepared according to following steps:
(1) it is on the waiting list raw material: 70 parts of aqueous polyurethane, 16 parts of vinyl-acrylate copolymer, nanotube dispersion 10
Part, 8 parts of modified LDHs, 2 parts of azodiisobutyronitrile, 0.1 part of praseodynium aluminium.Wherein, aqueous polyurethane and carbon nanotube point
Granular media is made according to the method for embodiment 1 and embodiment 2 respectively.
(2) to agitating device, thermometer, N210 parts of addition is aqueous poly- in four mouthfuls of glass flasks of entrance and condenser pipe
LDHs and 5 part of urethane, 8 parts of modifications nanotube dispersion mixing, are subsequently placed in plasma generator, with N2For reaction gas
Body, reaction pressure 20Pa, reaction power 180W, the reaction time, 12min obtained mixture；
(3) by mixture, 2 parts of vinyl-acrylate copolymers and 0.2 part of azodiisobutyronitrile stirring, 65 DEG C are warming up to
It is reacted to obtain reactant I；Under heat-retaining condition, 5 parts of nanotube dispersions are added in reactant I, stir 40min,
Obtain reactant II；
(4) 60 parts of aqueous polyurethanes, 14 parts of vinyl-acrylate copolymers and 1.8 parts of azos are added in reactant II
Bis-isobutyronitrile is warming up to 85 DEG C of reaction 2h, and 0.1 part of praseodynium aluminium is added and is continuously heating to 95 DEG C of reaction 1h, is down to room temperature
After the adhesive is obtained by filtration.
Embodiment 4
The present embodiment is substantially the same manner as Example 3, the difference is that being added 8 parts of nanotube dispersion, and divides two halves
It is separately added into.
Embodiment 5
The present embodiment is substantially the same manner as Example 3, the difference is that being added 5 parts of nanotube dispersion, and divides two halves
It is separately added into.
Comparative example 1
This comparative example 1 is substantially the same manner as Example 4, and difference is added 8 parts of pure nano-carbon tube, and two halves is divided to add respectively
Enter.
Comparative example 2
Comparative example 2 and implementation 3 are essentially identical, the difference is that being added 15 parts of nanotube dispersion.
Comparative example 3
Comparative example 2 and implementation 3 are essentially identical, the difference is that being added 3 parts of nanotube dispersion.Test example 1
Adhesive prepared by embodiment 3~5 and comparative example 1-3 dries on being coated with two aluminium blocks, then at being 120 DEG C in temperature
Roasting 9s, is detected, testing result is as shown in table 1 below.
1 performance test table of table
It can be seen that the adhesive of the embodiment of the present invention has good stripping performance and flame retardant effect.It is received using carbon
Nanotube dispersion enables to carbon nanotube effectively to disperse in resin matrix, carbon nanotube is added compared to simple, effect is more
It is excellent.The additional amount of carbon nanotube also has a significant impact its stripping performance and flame retardant effect.In addition, using modified LDHs
There can be more excellent flame retardant effect.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of resistance to fire-retardant adhesive of carbon nano-tube modification, which is characterized in that reacted and be made by polymerizable raw material, according to weight
Number meter, the raw material include: 65~85 parts of aqueous polyurethane, 10~20 parts of vinyl-acrylate copolymer, carbon nanotube point
5-10 parts of granular media, 3~8 parts of fire retardant, 1~3 part of initiator, 0.1~0.2 part of crosslinking agent.
2. the resistance to fire-retardant adhesive of carbon nano-tube modification according to claim 1, which is characterized in that according to parts by weight
Meter, the aqueous polyurethane are had by 45-60 parts of polyalcohols, 12-15 parts of diisocyanate, 0.3-0.5 parts of catalyst, 30-50 parts
Solvent, 5-8 part chain extender, 2-3 parts of neutralizers and 220-260 parts of water are prepared.
3. the resistance to fire-retardant adhesive of carbon nano-tube modification according to claim 2, which is characterized in that the chain extender is 1,
The glycol chain extender that 2- propylene carbonate and diamine polymerization reaction obtain.
4. the resistance to fire-retardant adhesive of carbon nano-tube modification according to claim 1, which is characterized in that the carbon nanotube point
Granular media the preparation method comprises the following steps: dissolve the dispersant into solvent, be added carbon nanotube and coupling agent, after ultrasonic 10-20min, add
Enter surfactant, continues ultrasound 30-120min and obtain the nanotube dispersion.
5. the resistance to fire-retardant adhesive of carbon nano-tube modification according to claim 4, which is characterized in that the carbon nanotube,
The mass ratio of the coupling agent and the surfactant is 1:2.0~2.5:0.1~0.2, and the dispersing agent is selected from polyethylene
One of alcohol or hydroxymethyl cellulose are a variety of, and the mass ratio of the dispersing agent and the carbon nanotube is 0.4-0.6:1.
6. the resistance to fire-retardant adhesive of carbon nano-tube modification according to claim 5, which is characterized in that the solvent is N- first
Base pyrrolidones, mass fraction of the carbon nanotube in the carbon nano tube paste are 3-5%.
7. the resistance to fire-retardant adhesive of carbon nano-tube modification according to claim 1, which is characterized in that the fire retardant is selected from
One of organic phosphorus flame retardant, inorganic phosphorus flame retardant, LDHs, modified LDHs.
8. the resistance to fire-retardant adhesive of carbon nano-tube modification according to claim 7, which is characterized in that the fire retardant is to change
Property LDHs's the preparation method comprises the following steps: by molar ratio be 2:1:3 zinc chloride, aluminium chloride and urea be dispersed in water, be added dropwise phosphinic acids
Ammonium salt solution reacts 6~36h under the conditions of 80~100 DEG C and obtains, wherein the phosphinic acids ammonium in phosphinic acids ammonium salt solution and zinc chloride
Molar ratio is 0.4:1.
9. a kind of preparation method of the resistance to fire-retardant adhesive of carbon nano-tube modification as described in claim 1-8 any one,
It is characterized in that, comprising the following steps:
S1 disperses the carbon nanotube of the aqueous polyurethane of 1/20-1/10, whole fire retardants and 1/3-1/2
Body mixing, is subsequently placed in plasma generator, with CF4、N2、CCl4In any one be reaction gas, reaction pressure be 10~
30Pa, reaction power are 100~200W, and the reaction time, 3~15min obtained mixture；
S2, by the mixture, the initiator of the vinyl-acrylate copolymer of 1/10-1/5 and 1/20-1/10
Stirring, is warming up to 60 DEG C -70 DEG C and is reacted to obtain reactant I；
The remaining nanotube dispersion is added under heat-retaining condition in S3 in the reactant I, and stirring 20~
50min obtains reactant II；
The remaining aqueous polyurethane, the vinyl-acrylate copolymer and the initiation is added in S4 in reactant II
Agent is warming up to 80-85 DEG C of reaction 2-3h, and the crosslinking agent is added and is continuously heating to 90-100 DEG C of reaction 0.5-1h, is down to room temperature
After the adhesive is obtained by filtration.
10. preparation method according to claim 9, which is characterized in that the aqueous polyurethane is made in accordance with the following steps:
Under nitrogen protection, polyalcohol, diisocyanate, catalyst are added in organic solvent, it is anti-under the conditions of 70-85 DEG C
2-4h is answered, chain extender and organic solvent is then added, reacts 2-4h under the conditions of 90-95 DEG C, is cooled to room temperature addition neutralizer,
0.5-1h is reacted, water is eventually adding, after being dispersed with stirring, vacuum distillation removal organic solvent obtains the aqueous polyurethane.
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