CN109438964A - Have both the light polyurethane foam and preparation method thereof of enhancing and antistatic property - Google Patents
Have both the light polyurethane foam and preparation method thereof of enhancing and antistatic property Download PDFInfo
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- CN109438964A CN109438964A CN201811196069.0A CN201811196069A CN109438964A CN 109438964 A CN109438964 A CN 109438964A CN 201811196069 A CN201811196069 A CN 201811196069A CN 109438964 A CN109438964 A CN 109438964A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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Abstract
The invention belongs to light polyurethane hard bubble technical fields, disclose a kind of light polyurethane foam and preparation method thereof for having both enhancing and antistatic property, comprising: lotion synthetic method synthesizes conducting polymer, and oxidant stoichiometry is added；Polymer monomer dilution is added dropwise, and reacts 6-24 hours；Product carries out conventional wash, and the modes such as filtering, evaporation or freeze-drying handle collection product；Small organic agents post-process the conventional of synthesis conducting polymer, impregnate 30 minutes to 24 hours (small organic agents will participate in reacting, and realize the enhancing to hard polyurethane foam, while not generating increase heavy influence to the density of hard bubble)；Conducting polymer is mixed with commercial polyurethane foam with black material or the effective of white material；Black material is sufficiently mixed with white material, and for blowing temperature at 10 DEG C -50 DEG C, foaming forms lightweight, high intensity, antistatic polyurethane foam.Frothing percentage of the present invention is high, and materials conductive rate is 106‑108Ω/cm2, shore hardness 25-90HD, Rockwell hardness 15-60HRC.
Description
Technical field
The invention belongs to light polyurethane hard bubble technical field more particularly to a kind of enhancing and antistatic properties of having both
Light polyurethane foam and preparation method thereof.
Background technique
Polyurethane foam possess good moistureproof and waterproof, insulation, sound insulation, shockproof properties and it is light, chemical-resistant resistance is rotten
The features such as erosion, is widely used in building materials, mine, space filling and automobile and other industries.2012, polyurethane foam was in global city
The share that place accounts for has had reached 40,100,000,000 dollars, and increases year by year, it is contemplated that is likely to be breached 61,900,000,000 dollars when by 2018.
Polyurethane foam functionalization is mainly include the following types: antistatic, enhancing, flame retarding function are modified.Wherein with bearing structure polyurethane
Hard bubble is that the high-strength polyurethane rigid foam plastic of representative is one of the important directions of current polyurethane foam research.This polyurethane
Hard bubble has excellent mechanical property, especially compressive strength, tensile strength and impact strength and elasticity modulus and size steady
It is qualitative, in terms of being commonly used for the component that tubing, bridge profile and military project aerospace device etc. need to bear high load capacity.Structural material
Demand has certain intensity, rigidity and toughness, common rigid polyurethane foam due to absolute intensity still compared with structural material
Low, mechanical property is poor, and the requirement as structural material is not achieved under many special operating conditions.To solve these
Problem is it is necessary to enhancing rigid polyurethane foam.It is worth noting that, polyurethane foamed material has high surface
Resistance and volume resistance, such as volume resistivity are up to 1011-1013Ω .m is easy to produce electrostatic to there is greatly electrostatic
Security risk, for example, generation electrostatic potential up to 3-4 × 103V.Electrostatic phenomenon will will affect electronic equipment, in integrated circuit
Electronic component performance, therefore in recent years polyurethane foam it is antistatic also more and more attention has been paid to.For example, the poly- ammonia being packed for
Ester foamed material requires conductivity to be not higher than 1011Ω .m, mine and tunnel then accepted standard MT113-1995, it is desirable that surface electricity
Resistance is less than 3.0 × 108Ω.m.Up to the present, the enhancing of hard polyurethane foams mainly uses conventional particle, commonly uses such as
CaCO2、SiO2、BaSO4, glass microballoon, talcum powder, ceramic microbead etc., fiber, including glass fibre, carbon fiber, organic fiber,
Natural plant fibre and alumina silicate fibre, metallic fiber, boron fibre and SiC fiber and ceramic fibre etc. and nanoparticle conduct
Reinforcement.Dosage is larger when the former is as reinforcement, is mixed using mechanical stirring, and dispersion is convenient, and compression performance mentions significantly；The latter
Dosage is minimum, easy to reunite, it is difficult to and it is evenly dispersed, but enhance high-efficient.For example, high elastic modulus and high-intensitive chopped strand mention
High foam tensile intensity and impact strength, but there are still several significant disadvantages for this method.Firstly, because enhancing volume density
Height is unable to satisfy the lighting requirement of material；Secondly, having promotion to the tensile property of foam, but not to the promotion of compression performance
Significantly；In addition, high bubble polyurethane lower for density, the compression for hardly improving foam using fibre-reinforced method are strong
Degree；Further more, because polyether polyol viscosity is big, poor fluidity is difficult to solve polyurethane and fiber impregnation before urethane cures
Uniform problem causes the strength of materials of production low, and intensity is uneven, unstable quality.Particulate reinforcement can significantly change
Compressive strength, elasticity modulus, dimensional stability and the hardness of kind foamed plastics, but tensile strength and impact strength can be reduced,
Meanwhile additive amount is larger in use for conventional particle reinforcement, and it is limited to promote effect.But containing when particulate reinforcement body
When amount is higher than some critical value, dispersibility is significantly reduced, and reduces the performance of material instead.For example, when hollow glass micropearl with
When polyether polyol mass ratio about 30 ︰ 100, do not change substantially in density of material, the compressive strength of foam is improved simultaneously
Reach maximum value.But mass ratio, when being more than 50:100, raw material is difficult to mix, performance decline.Other particles, such as calcium carbonate, two
Its enhancing mechanism such as silica is similar to hollow glass micropearl.Enhanced jointly using fiber, particulate reinforcement body, it can be simultaneously
The stretching of foam, compression performance are improved, this kind of enhancement method is commonly referred to as hybrid buildup.When quality is added into foam
The SiO that score is 20%2And 7.8% glass fibre when, the multinomial mechanical property of polyurethane has obtained optimal enhancing
Effect.But between hybrid buildup effect often individually enhances between two kinds of reinforcements.Nano material reinforcement additive amount is relatively
It is few, smaller, the unobvious density for improving material is influenced on foam process.It is currently applied to the nanometer enhancing of hard polyurethane foams
Body mainly has carbon nanotube, graphene, nano silica, nano-titanium dioxide etc., by being added on a small quantity into polyurethane
The reinforcing effect being unable to reach using conventional particle reinforcement may be implemented in above-mentioned nanometer reinforcement.For example, using ultrasonic wave added
Dispersion may be implemented to add more carbon nanotubes to realize better reinforcing effect, using the method, work as carbon nanotube mass
When score is up to 2.0%, the compressive strength of rigid polyurethane foam relatively improves nearly 30%, and modulus of elasticity in comperssion also improves
31.9%.Other nano materials such as nanoclay, carbon nano-fiber also enhance the compression performance of foamed plastics, but promote effect
Fruit is not ideal enough.It should be pointed out that no matter which kind of reinforcement used, the chemistry for requiring to carry out its surface complexity changes
Property.Modification activities chemical group on the surface of the material, such as by hydroxyl, carboxyl and amino, with improve reinforcement Surface binding energy,
Reduce reunite, increase surface and the associativity of foam with it is bonding, facilitate the reinforcing effect for preferably improving enhancing particle.Example
Such as, graphene oxide is modified using isocyanate group, or is realized using silane coupling agent, triethylene tetramine etc. to graphite oxide
The surface of alkene is modified, and finally promotes foam tensile, bending property, but enhances compression performance smaller.It is total with other polymers
It polymerize or prepares inierpeneirating network structure composite foam material, humidification can also be played to material.For example, epoxy resin
The damping characteristics that material can be enhanced are added, obtained material can be applied to the inside filling of aluminum profile, bisphenol A-type
Epoxy resin modification foam possesses higher thermal stability, the cross-linked network structure of phenolic resin and the preparation of PU prepolymer reaction
Foamed material flexibility with higher, pitch and modified PU foams mix can be prepared with stronger mechanical property and solidification
Later can insulating water-proof foamed material etc..
In conclusion problem of the existing technology is: existing polyurethane foam cannot still take into account enhancing with it is antistatic
Performance enhancement is more difficult, and it is too big with density variation that there are dispersions.
Solve the difficulty of above-mentioned technical problem
Either it is used as load-bearing material and is also used as packing material, the great business valence of light-high-strength hard polyurethane foam itself
Value, but the reinforcing material added at present is mainly inorganic and the materials such as metal, this kind of material additional amount is few then to cannot achieve increasing
By force, additional amount is more, leads to the big drop of the mechanical property of rigid foam material.Such as using traditional reinforcing material, either using independent
The mode of enhancing or hybrid buildup requires that the particle or fiber that mass fraction is 20% or more are added into polyurethane foam
Material, although the multinomial mechanical property of polyurethane is enhanced, such as compression performance enhancing of some performances is smaller.It is worth note
Meaning, is added beyond 20% reinforcing material, the density of polyurethane can be greatly improved.Nano material reinforcing material adds
Dosage is relatively fewer, but there is also enhancing promotion effect is not ideal enough.More have, no matter which kind of nanometer reinforcement is used, required
Implement complicated chemical modifying process to its surface, it is with high costs.How can solve can enhance and not increase density, or even
The condition for not increasing more costs realizes this target, needs under enhancing mechanism, enhancing process and reinforcing material itself
In the time, huge at present most researchs focus on the latter and ignore the above two, and the present invention exactly has breakthrough in these two aspects.We
It is intervened using small molecule and participates in foamable reaction, directly obtain reinforcing effect, for another function of rigid foam material --- resist quiet
Electrically, in the present invention, the amount of the electric polypyrrole of filling polyurethane is only 3-5%, and after foaming, material can not only possess splendid
Enhancing performance, and filler material can also disperse well, while solving the problems, such as polyurethane material both and enhance to have can be antistatic.
Solve the meaning of above-mentioned technical problem
Using method of the invention, light-high-strength can be prepared using simpler material direct, that cost is more cheap
Polyurethane rigid foam material.For load-bearing polyurethane material, it is meant that more load can be carried.On the other hand,
For there is the antistatic property of demand, the present invention also gives splendid solution.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of lightweight for having both enhancing and antistatic property is poly-
Urethane foam and preparation method thereof.
The invention is realized in this way a kind of conductive composite polymer, emulsion system oil in the conductive composite polymer
Water ratio is 3:1-1:1.
Another object of the present invention is to provide a kind of preparation method of conductive composite polymer, the conduction is compound
The preparation method of polymer the following steps are included:
Step 1, lotion synthetic method synthesize conducting polymer；
Step 2 synthesizes the conventional post-processing of conducting polymer, collects product using filtering, evaporation or frozen dried；
Oxidant stoichiometry is added in step 3；Polymer monomer dilution is added dropwise, and reacts 6-24 hours；Product is washed
It washs.
Further, the synthesis of the step 1 conducting polymer uses lotion synthetic method, and the emulsifier used is anion
Surfactant: the cooperation of one or more of carboxylic acid type, sulfonate type and sulfate type；
Emulsifier injected volume be 1-3wt/vol%, lotion oil mutually include ethyl acetate, petroleum ether, DMF, methylene chloride,
Chloroform, DMSO, THF, ether, benzene, toluene and their mixture；
The step 2 oxidant include ferric iron compound, hydrogen peroxide, ferro-compound, acid iodide, persulfate with
And mixture；
The step 3 washing reagent includes water, methanol, ethyl alcohol, chloroform, carbon dichloride, tetrahydrofuran, benzene, toluene, two
Toluene and mixture；In the synthesis post-processing of conducting polymer, collection is handled using filtering, evaporation or freeze-drying mode and is produced
Object.
Further, the molar ratio of the oxidant and pyrrole is 2.3:1.
Further, the mass ratio of pyrrole monomer and polyurethane is 3%.
Another object of the present invention is to provide it is a kind of using the conductive composite polymer have both enhancing and resist quiet
The preparation method of the light polyurethane foam of electrical property, the light polyurethane foam for having both enhancing and antistatic property
Preparation method includes:
Step 1, lotion synthetic method synthesize conducting polymer；
Step 2 synthesizes the conventional post-processing of conducting polymer, collects product using filtering, evaporation or frozen dried；
Oxidant stoichiometry is added in step 3；Polymer monomer dilution is added dropwise, and reacts 6-24 hours；Product carries out normal
Rule washing；
Step 4, post-processing of the small organic agents to synthesis conducting polymer, impregnates 30 minutes to 24 hours；
Step 5, conducting polymer are mixed with commercial polyurethane foam with black material or the effective of white material；
Step 6, black material are sufficiently mixed with white material, and at 10 DEG C -50 DEG C, foaming forms lightweight, high intensity, resists blowing temperature
Electrostatic polyurethane foam.
Further, the small organic agents use aldehydes, ketone, nitrile, chloroform, dichloro to the post-processing of conducting polymer
Change carbon, tetrahydrofuran, benzene,toluene,xylene and mixture；
Small organic agents impregnate the post-processing of conducting polymer 30 minutes to 24 hours.
Further, the conducting polymer is mixed with commercial polyurethane foam with the effective of black material, using mechanical blending, is surpassed
The mode of sound wave shock mixes.
Further, after effectively mix of the black material and white material, mixed material using it is live be directly poured by the way of construct；
After effectively the mixing and be poured of black material and white material, select blowing temperature at 10 DEG C -50 DEG C.
Another object of the present invention is to provide a kind of by the light polyurethane for having both enhancing and antistatic property
The light polyurethane foam of the preparation method preparation of foam, the adjustable 0.05-0.3g/cm of light polyurethane foam density3；Material
Expect conductivity 106-108Ω/cm2, shore hardness 25-90HD, Rockwell hardness 15-60HRC.
In conclusion advantages of the present invention and good effect are as follows: the present invention provides conductive path using conductive nano polypyrrole
Diameter, while participating in foaming using small organic agents, small organic agents are easily dispersed, the Reinforcement structure of formation can admirably with it is poly-
Urethane matrix is combined closely；Operating procedure is simply reliable.Small molecule material and polypyrrole and polyurethane comixing foam, successfully
(density can be down to 0.05g/cm for the high-intensitive lightweight being prepared for3) antistatic foam, compared with control sample, novel composite wood
Expect conductivity between 106-108Between Ω, the 25HD that the control sample of small organic agents is never added in shore hardness is increased to 90HD,
Rockwell hardness is increased to 60HRC from 15HRC, and tensile strength has been increased to 0.923MPa from 0.485MPa；Young's modulus from
2.94MPa has been increased to 5.44MPa.The present invention directlys adopt existing commercial polyurethane ingredient (black and white material or AB material)；Frothing percentage
Height, density is adjustable (0.05-0.3g/cm3)；Materials conductive rate is 106-108Ω/cm2Within), shore hardness 25-90HD, Lip river
Family name's hardness is 15-60HRC.
The present invention, as the additive that foaming is blended, efficiently solves the dispersion using small organic agents；Again
Using reacting for small organic agents and polyurethane foam material, reaction condition is controlled, can both have been enhanced and is had antistatic
The polyurethane foamed material of property.Gained modified material can form nano particle or nanofibrous structures, be different from tradition and close
At the resulting reunion strawberry type polymer architecture of method, this nanostructure may be implemented preferably to disperse, and reduce conductive material
Dosage reduces the contact resistance between nano material, is more advantageous to nano material and forms conductive network.
Detailed description of the invention
Fig. 1 is the preparation side of the light polyurethane foam provided in an embodiment of the present invention for having both enhancing and antistatic property
Method flow chart.
Fig. 2 is the non-reinforced Young's modulus figure of light polyurethane foam provided in an embodiment of the present invention.
Fig. 3 is the Young's modulus figure of light polyurethane foam enhancing provided in an embodiment of the present invention.
Fig. 4 is the non-reinforced hardness measurements schematic diagram of light polyurethane foam provided in an embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Present invention seek to address that existing polyurethane foam cannot still take into account enhancing and antistatic property enhancing is more difficult,
There is a problem of that dispersion and density variation are too big.The present invention provides simplicity, efficiently prepares lightweight, high intensity, antistatic polyurethane
The method of foam.The anti-static function is formed conductive channel realization by conducting polymer in polyurethane body, enhances function
Reaction in-situ is blended with polyurethane foam system by the small molecule solvent acetonitrile added to obtain.
Application principle of the invention is explained in detail with reference to the accompanying drawing.
As shown in Figure 1, the light polyurethane foam provided in an embodiment of the present invention for having both enhancing and antistatic property
Preparation method the following steps are included:
S101: lotion synthetic method synthesizes conducting polymer；
S102: the conventional post-processing of conducting polymer is synthesized, product is collected using filtering, evaporation or frozen dried；
S103: oxidant stoichiometry is added；Polymer monomer dilution is added dropwise, and reacts 6-24 hours；Product carries out conventional
Washing；
S104: post-processing of the small organic agents to synthesis conducting polymer is impregnated 30 minutes to 24 hours；
S105: conducting polymer is mixed with commercial polyurethane foam with black material or the effective of white material；
S106: black material is sufficiently mixed with white material, blowing temperature at 10 DEG C -50 DEG C, foaming formed lightweight, high intensity, resist it is quiet
Electric polyurethane foam.
In a preferred embodiment of the invention, the synthesis of conducting polymer uses lotion synthetic method, and the emulsifier used can
To be conventional anionic surfactant: the cooperation of one or more of carboxylic acid type, sulfonate type and sulfate type, often
With such as: R13-18-SO3Na, neopelex, lignosulfonate, cellulose ammonium salt or their mixture.
In a preferred embodiment of the invention, emulsifier injected volume is 1-3wt/vol%, and the oil of lotion mutually includes acetic acid second
Ester, petroleum ether, DMF, methylene chloride, chloroform, DMSO, THF, ether, benzene, toluene and their mixture.
In a preferred embodiment of the invention, oxidant includes ferric iron compound, hydrogen peroxide, ferro-compound, iodine
Acid, persulfate and their mixture.
In a preferred embodiment of the invention, in the conventional wash for synthesizing conducting polymer, reagent includes water, methanol, second
Alcohol, chloroform, carbon dichloride, tetrahydrofuran, benzene,toluene,xylene and their mixture；After the synthesis of conducting polymer
In reason, collection product is handled using filtering, evaporation or freeze-drying mode.
In a preferred embodiment of the invention, small organic agents can use aldehydes, ketone to the post-processing of conducting polymer
Class, nitrile, chloroform, carbon dichloride, tetrahydrofuran, benzene,toluene,xylene and their mixture.
In a preferred embodiment of the invention, small organic agents can impregnate 30 minutes extremely to the post-processing of conducting polymer
24 hours not equal times.
In a preferred embodiment of the invention, conducting polymer is mixed with commercial polyurethane foam with the effective of black material, is adopted
It is mixed with the mode of mechanical blending, ultrasonic oscillation.
In a preferred embodiment of the invention, after effectively mix of black material and white material, mixed material is directly poured using live
The mode of note is constructed；
In a preferred embodiment of the invention, after effectively the mixing and be poured of black material and white material, select blowing temperature 10
℃-50℃。
The preparation method of the light polyurethane foam provided in an embodiment of the present invention for having both enhancing and antistatic property has
Body the following steps are included:
Conductive composite polymer synthesizes (1) and prepares emulsion system；(2) oxidant stoichiometry is added；(3) polymer monomer is dilute
Dropwise addition is released, is reacted 6-24 hours；(4) product is subjected to conventional wash；
(1) emulsion system oil-water ratio is 3:1-1:1 in.
(2) oxidant described in include ferric iron compound, hydrogen peroxide, ferro-compound, acid iodide, in persulfate
It is one or more of.
(3) solvent in for the diluted polymer monomer of dropwise addition is oily mutually identical as matched emulsion system.
(4) in, washing reagent can be water, methanol, ethyl alcohol, chloroform, carbon dichloride, tetrahydrofuran, benzene, toluene, diformazan
Benzene one kind or more or their iodine and salt compounded of iodine.
The molar ratio of the oxidant and pyrrole is 2.3:1 in an embodiment of the invention.
The molar ratio of the oxidant described in an embodiment of the invention Shen and pyrrole is 2:1.
The mass ratio of the pyrrole monomer to feed intake and polyurethane is 3% in an embodiment of the invention.
The mass ratio of the pyrrole monomer to feed intake and polyurethane is 2% in an embodiment of the invention.
In embodiments of the invention, the processing of synthetic product can first be lyophilized, grind and be ultrasonically treated again.It grinds
Larger-size Particle Breakage is uniformly dispersed in it in solution by mill.Then it is aided with ultrasonic treatment again, it is smaller for size
Particle there is good broken dispersion effect, promote dispersion of the conductive material in polyurethane matrix.
In embodiments of the invention, the small organic agents post-processing of conducting polymer:
Polymer treatment reagent includes aldehydes, ketone, nitrile, chloroform, carbon dichloride, tetrahydrofuran, benzene, toluene, two
One kind of toluene or more.
The time of polymer treatment is 30 minutes to 24 hours.
In one embodiment of the invention, the processing of synthetic product can directly be scattered in black material or white with wet process
Expect in matrix, appropriate ultrasonic disperse auxiliary promotes dispersion of the conductive material in polyurethane matrix.
In one embodiment of the invention, the polyurethane of dispersed electro-conductive polypyrrole compound is cast in open-top receptacle
In, after foaming at normal temp, foaming conductive polyurethane is made.
The present invention provides the preparation method that the light polyurethane foam of enhancing and antistatic property is had both described in one kind.
Advantages of the present invention and good effect are as follows: existing commercial polyurethane ingredient (black and white material or AB material) can be directlyed adopt；Frothing percentage is high,
Density is adjustable (0.05-0.3g/cm3)；Materials conductive rate is 106-108Ω/cm2Within), shore hardness 25-90HD, Rockwell
Hardness is 15-60HRC.
Application principle of the invention is further described combined with specific embodiments below.
Embodiment 1: 100 milliliters of 50:50=H are added in 1 gram of neopelex, 4..7 grams of ferric trichloride2O:
CHCl3Solution forms uniform solution after stirring 0.5 hour.The solution reaction is added 24 hours in 1ml pyrrole monomer, is formed
Uniform black product.Product washs, drying colourless to eluate through 150ml methanol.By the enhanced reagent of polypyrrole before foaming
It impregnates 24 hours and dry, then electrically conductive composite is blended with black material, foam, it is 10 that conductivity, which can be obtained,6-8The enhancing of Ω cm
Polyurethane foam, density 0.06g/cm3。
Embodiment 2: by 1 gram of neopelex, 4.66 grams of ferric trichlorides, 3ml 30%H2O2It is added 100 milliliters
30:70=H2O:CHCl3Solution forms uniform solution after stirring 0.5 hour.The solution reaction is added in 1ml pyrrole monomer
24 hours, form uniform black product.Product washs colourless to eluate through methanol, water and methyl alcohol mixed liquor.It will before foaming
The enhanced reagent of polypyrrole impregnates 24 hours and dry, then electrically conductive composite is blended with black material, foaming, then by compound with it is black
Material is blended, foaming, and it is 10 that conductivity, which can be obtained,6-8The polyurethane foam of Ω cm, density 0.05g/cm3。
Embodiment 3: by 1 gram of neopelex, 4.06 grams of ferric trichlorides, 3.4ml 30%H2O2It is added 100 milliliters
30:70=H2O:CHCl3Solution forms uniform solution after stirring 0.5 hour.The solution reaction is added in 1ml pyrrole monomer
24 hours, form uniform black product.Product washs colourless to eluate through methanol, water and methyl alcohol mixed liquor.It will before foaming
The enhanced reagent of polypyrrole impregnates 24 hours and dry, then electrically conductive composite is blended with black material, foaming, then by compound with it is black
Material is blended, foaming, and it is 10 that conductivity, which can be obtained,6-8The polyurethane foam of Ω cm, density 0.07g/cm3。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of conductive composite polymer, which is characterized in that emulsion system oil-water ratio is 3 in the conductive composite polymer:
1-1:1。
2. a kind of preparation method of conductive composite polymer as described in claim 1, which is characterized in that the conduction composite polymeric
The preparation method of object the following steps are included:
Step 1, lotion synthetic method synthesize conducting polymer；
Step 2 synthesizes the conventional post-processing of conducting polymer, collects product using filtering, evaporation or frozen dried；
Oxidant stoichiometry is added in step 3；Polymer monomer dilution is added dropwise, and reacts 6-24 hours；Product carries out conventional wash
It washs；
Step 4, post-processing of the small organic agents to synthesis conducting polymer, impregnates 30 minutes to 24 hours；
Step 5, conducting polymer are mixed with commercial polyurethane foam with black material or the effective of white material；
Step 6, black material are sufficiently mixed with white material, and for blowing temperature at 10 DEG C -50 DEG C, foaming forms lightweight, high intensity, antistatic
Polyurethane foam.
3. the preparation method of conductive composite polymer as claimed in claim 2, which is characterized in that the step 1 conducting polymer
The synthesis of object uses lotion synthetic method, and the emulsifier used is anionic surfactant: carboxylic acid type, sulfonate type and sulfuric acid
The cooperation of one or more of salt form；
Emulsifier injected volume is 1-3wt/vol%, and the oil of lotion mutually includes ethyl acetate, petroleum ether, DMF, methylene chloride, chlorine
Imitative, DMSO, THF, ether, benzene, toluene and their mixture；
The step 2 oxidant includes ferric iron compound, hydrogen peroxide, ferro-compound, acid iodide, persulfate and mixes
Close object；
The step 3 washing reagent includes water, methanol, ethyl alcohol, chloroform, carbon dichloride, tetrahydrofuran, benzene,toluene,xylene
And mixture；In the synthesis post-processing of conducting polymer, collection product is handled using modes such as filtering, evaporation or freeze-dryings.
4. the preparation method of conductive composite polymer as claimed in claim 2, which is characterized in that the oxidant and monomer pyrrole
The molar ratio coughed up is 2.3:1.
5. the preparation method of conductive composite polymer as claimed in claim 2, which is characterized in that pyrrole monomer and polyurethane
Mass ratio is 3-5%.
6. the preparation method of the light polyurethane foam of enhancing and antistatic property is had both as claimed in claim 2, it is special
Sign is that the small organic agents use aldehydes, ketone, nitrile, chloroform, carbon dichloride, four to the post-processing of conducting polymer
Hydrogen furans, benzene,toluene,xylene and mixture；
Small organic agents impregnate the post-processing of conducting polymer 30 minutes to 24 hours.
7. the preparation method of the light polyurethane foam of enhancing and antistatic property is had both as claimed in claim 2, it is special
Sign is that the conducting polymer is mixed with commercial polyurethane foam with the effective of black material, using mechanical blending, ultrasonic oscillation
Mode mix.
8. the preparation method of the light polyurethane foam of enhancing and antistatic property is had both as claimed in claim 2, it is special
Sign is, after effectively mix of the black material and white material, mixed material using it is live be directly poured by the way of construct；
After effectively the mixing and be poured of black material and white material, select blowing temperature at 10 DEG C -50 DEG C.
9. prepared by a kind of preparation method of light polyurethane foam for having both enhancing and antistatic property as described in claim 2
Light polyurethane foam, which is characterized in that the adjustable 0.05-0.3g/cm of light polyurethane foam density3；Materials conductive
Rate is 106-108Ω/cm2, shore hardness 25-90HD, Rockwell hardness 15-60HRC.
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| CN113462145A (en) * | 2021-07-12 | 2021-10-01 | 洛阳双瑞橡塑科技有限公司 | Fiber-reinforced polyurethane wood-like material and forming method thereof |
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| CN113462145A (en) * | 2021-07-12 | 2021-10-01 | 洛阳双瑞橡塑科技有限公司 | Fiber-reinforced polyurethane wood-like material and forming method thereof |
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