CN103087624B

CN103087624B - A kind of UV curing polyaniline/FeSO4Microwave absorbing coating and preparation method thereof

Info

Publication number: CN103087624B
Application number: CN201310038010.XA
Authority: CN
Inventors: 钟荣; 曹朝贵; 熊璠
Original assignee: Nanchang Hangkong University
Current assignee: Nanchang Hangkong University
Priority date: 2013-01-31
Filing date: 2013-01-31
Publication date: 2016-05-18
Anticipated expiration: 2033-01-31
Also published as: CN103087624A

Abstract

The invention discloses a kind of UV curing polyaniline absorbing material and preparation method thereof. Described UV curing polyaniline absorbing material is taking urethane acrylate as matrix material, polyaniline/FeSO₄Composite evenly spreads in matrix material and adds the auxiliary agent such as monomer diluent and light trigger composition. This material can not only have the coating thickness of the electromagnetic effect of good absorption and formation can be reduced to below 2mm at 2-18GHz, and the curing of coatings time is less than 2 minutes and has good coating performance.

Description

A kind of UV curing polyaniline/FeSO4Microwave absorbing coating and preparation method thereof

Technical field

The present invention relates to a kind of UV curing polyaniline/FeSO₄Absorbing material and preparation method thereof, using and can inhale and involve the purposes such as domestic electromagnetic shielding in order to airborne vehicle as coating.

Background technology

Along with social development, microwave absorption technology not only militarily has important using value, and in daily life, prevents disturbed the having great importance such as electromagnetic pollution and electronic instrument that the electrical equipment such as mobile phone produce.

Although inorganic microwave absorption is in the industrial development obtaining to a certain extent, its density is large, and re-workability is poor, and its application is restricted, and if Ferrite Material is as microwave absorbing material, its wave-absorbing mechanism is mainly domain wall resonance and natural resonance. Because it is cheap, relative permeability is large, absorbing property is good, even if still have good absorbing property in the situation that of low frequency, thin thickness, is therefore the first choice of wave absorbing agent at low frequency stage Ferrite Material. But its shortcoming is that density is large, temperature stability is poor. People hope the novel wave-absorbing material with searching with little, the high temperature resistant and steady chemical structure of high-absorbility, bandwidth, density, and conducting high polymers thing arises at the historic moment as absorbing material of new generation. In conducting polymer polyaniline because electrical conductivity is high, the environmental stability of light weight, doping state and the state of not adulterating is good, be easy to preparation and cost compared with the low extensive concern that causes. When polyaniline obtains further investigation, the research of the copolymer of its composite and derivative has also obtained corresponding progress. Being on the one hand therefrom to obtain phenomenon that pure polyaniline is difficult to obtain and the rule of summary, is that the polymer of substituted aniline also has its special nature on the other hand.

The application form of current absorbing material is generally coating structure, mainly be bonded together by adhesive, coating is to have the magnetic loss of material and electrical loss to determine to electromagnetic loss, thereby the general absorptivity that improves material from impedance matching and the electromagnetic parameter aspect that improves material in research, attenuate coating layer thickness. Overweight coating increases quality of materials, and can make the mechanical performance of coating decline, make it reach enough working bands to require to reach as far as possible impedance matching and increase the bandwidth of microwave absorbing coating, make the total reflectivity of air and material interface very little, adopting MULTILAYER COMPOSITE is one of effective way increasing coating bandwidth.

UV-curing technology has the characteristics such as curing rate is fast, environmental protection. Add the photocureable coating formula of monomer diluent and light trigger composition taking urethane acrylate as matrix. By regulating its formula can make high rigidity, high adhesion force coating. Introducing conducting high polymers thing at ultraviolet light polymerization formula, is matrix and adhesive in conjunction with the absorbing property of conducting high polymers thing and the feature of photocuring, can effectively reduce the thickness of coating.

Summary of the invention

The object of the present invention is to provide a kind of UV curing polyaniline/FeSO₄The preparation method of absorbing material and this material.

UV curing polyaniline/FeSO of the present invention₄Absorbing material, is characterized in that having following steps:

1. polyaniline/FeSO₄The preparation of powder

(1) under zinc powder exists, secondary decompression distillation obtains pure aniline.

（2）FeSO₄Through surface treatment.

(3) aniline monomer/FeSO₄Powder adds in the hydrochloric acid of 0.1mol/L according to certain mass ratio (4-1:1), then under stirring state, and (the NH of 0-5 DEG C of dropping and aniline mol ratio 1:1₄)₂S₂O₈Hydrochloric acid solution, reaction 3-5 hour, and then room temperature reaction 8-12 hour.

(4) to finish rear be colourless with 0.1mol/L hydrochloric acid solution and deionized water washed product to filtrate respectively in reaction, 60 DEG C of vacuum drying 24h.

2. polyaniline/FeSO₄The preparation of composite wave-suction material

Polyaniline/FeSO₄Powder joins in UV curing system after by mechanical lapping, polyaniline/FeSO in combined system₄1%-20%, urethane acrylate 50%-80%, monomer diluent 10%-50%, light trigger 1%-5%, other auxiliary agents 1%-2%, the mixing and stirring new coating that completes.

3. polyaniline/FeSO₄The preparation of composite wave-absorbing coating

Gained coating can spread upon on base material by dip-coating, spraying method, without N₂The lower ultra violet lamp 15-30S of protection makes coating, and gained signal layer coating thickness is at 500-1000 μ m.

According to above-mentioned 1,2, the method gained signal layer coating thickness described in 3 is below 1000 μ m, and gained coating has its hardness of excellent mechanical property and reaches 3-4H, and adhesive force reaches 1 grade. Recording its maximum reflectivity within the scope of 2-18GHz by vector analysis instrument is-10dB.

The invention has the beneficial effects as follows that preparation has the absorbing material of bandwidth, mechanical property that coating is thin, excellent.

Detailed description of the invention

[1] under zinc powder exists, secondary decompression distillation obtains pure aniline, FeSO₄Through surface treatment.

[2] above-mentioned [1] gained aniline and FeSO₄Add according to certain mass ratio in the hydrochloric acid of 0.1mol/L, then under stirring state, (the NH of 0-5 DEG C of dropping and aniline mol ratio 1:1₄)₂S₂O₈Hydrochloric acid solution, reaction 3-5 hour, and then room temperature reaction 8-12 hour. It is colourless with 0.1mol/L hydrochloric acid solution and deionized water washed product to filtrate respectively that reaction finishes rear, 60 DEG C of vacuum drying 24h.

[3] polyaniline/FeSO₄Powder joins in UV curing system after by mechanical lapping, urethane acrylate 50%-80% in combined system, monomer diluent 10%-50%, light trigger 1%-5%, polyaniline/FeSO₄1%-20%, other auxiliary agents 1%-2% mix and blend makes polyaniline/FeSO₄The dispersed coating of manufacturing of powder.

[4] gained coating can spread upon iron-based by modes such as dip-coating, spraying, blade coating, curtain paintings, on aluminium base sheet material, is having or not ultra violet lamp 120S under protective atmosphere just can completely solidify and obtain coating.

[5] gained signal layer coating thickness is less than 2mm, records its hardness and can reach 3-4H, and adhesive force reaches 1 grade.

[6] coating adopts vector analysis instrument method to record it to be greater than 10dB in 2-18GHz scope internal reflection decay.

Claims

1. a UV curing polyaniline/FeSO₄The preparation method of microwave absorbing coating, is characterized in that, prepared by the coating composition that microwave absorbing coating is made up of following weight ratio ingredient: urethane acrylate 50%-80%, monomer diluent 10%-50%, light trigger 1%-5%, polyaniline/FeSO₄1%-20%, other auxiliary agents 1-2%; The degree of functionality of described urethane acrylate is 2-6; Described monomer diluent is propenoic acid beta-hydroxy ethyl ester, iso-bornyl acrylate, tripropylene glycol diacrylate, 1, the one in 6-hexanediyl ester, two diacrylates of Poly-propylene glycols, trimethylolpropane triacrylate; Described light trigger is 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, 2,4, one or more in 6-trimethylbenzoyl-diphenyl phosphine oxide; Described other auxiliary agents are defoamer and levelling agent;

Described microwave absorbing coating is prepared by following steps:

Step 1, polyaniline/FeSO₄The preparation of powder: secondary decompression distillation obtains pure aniline under zinc powder exists, by FeSO₄Through surface treatment; By aniline monomer and FeSO₄Powder adds according to mass ratio 4-1:1 in the hydrochloric acid of 0.1mol/L, then under stirring state, drips (the NH with aniline monomer mol ratio 1:1 at 0-5 DEG C₄)₂S₂O₈Hydrochloric acid solution, reaction 3-5 hour, and then room temperature reaction 8-12 hour, it is colourless with 0.1mol/L hydrochloric acid solution and deionized water washed product to filtrate respectively that reaction finishes rear, 60 DEG C of vacuum drying 24h;

Step 2, polyaniline/FeSO₄The preparation of composite wave-absorbing coating: by polyaniline/FeSO in step 1₄Powder joins in UV curing system after by mechanical lapping, polyaniline/FeSO in combined system₄1%-20%, urethane acrylate 50%-80%, monomer diluent 10%-50%, light trigger 1%-5%, other auxiliary agents 1%-2%, the mixing and stirring coating that completes;

Step 3, polyaniline/FeSO₄The preparation of composite wave-absorbing coating: coating in step 2 is spread upon on base material by dip-coating or spraying method, without N₂The lower ultra violet lamp 15-30s of protection makes coating, and gained signal layer coating thickness is at 500-1000 μ m.

2. the preparation method of microwave absorbing coating as claimed in claim 1, is characterized in that: described polyaniline/FeSO₄Powder is by aniline/FeSO₄Under different quality ratio, obtain.

3. the preparation method of microwave absorbing coating as claimed in claim 1, is characterized in that: gained signal layer coating has its hardness of excellent mechanical property and reaches 3-4H, and adhesive force reaches 1 grade.

4. the preparation method of microwave absorbing coating as claimed in claim 1, is characterized in that: solidify gained signal layer coating has good assimilation effect and reach-10dB of signal layer coating reflectivity in 2-18GHz frequency range.