CN105462430B - Thick coated type polyether-ether-ketone composite coating and preparation method and application - Google Patents
Thick coated type polyether-ether-ketone composite coating and preparation method and application Download PDFInfo
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- CN105462430B CN105462430B CN201510834496.7A CN201510834496A CN105462430B CN 105462430 B CN105462430 B CN 105462430B CN 201510834496 A CN201510834496 A CN 201510834496A CN 105462430 B CN105462430 B CN 105462430B
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention discloses a kind of thick coated type polyether-ether-ketone composite coating and its production and use, belong to anticorrosive paint technology field.Heretofore described thick coated type polyether-ether-ketone composite coating is prepared by polyether-ether-ketone and polyether-ether-ketone containing alkynyl for raw material, by using electrostatic coating method to spray thick coated type polyether-ether-ketone composite coating on conductive base；The base material of coating is coated with after 380~400 DEG C of 3~30min of high-temperature process；Repeated multiple times spraying overcoating is carried out using heat spraying method and high-temperature process is until coating layer thickness reaches requirement.Thick coated type polyether-ether-ketone coating and coating production of the present invention are simple, easy to operate, can rationally control, economical and practical；The generation of sagging phenomenon is avoided during prepares coating；The antiseptic property of polyether-ether-ketone coating is excellent, can effectively reduce the corrosion of industrial equipment, improves industrial equipment service life, reduces the probability that accident occurs because of device damage, so as to reduce cost, economize on resources.
Description
Technical field
The invention belongs to anticorrosive paint technology field, and in particular to a kind of thick coated type polyether-ether-ketone composite coating and its preparation
Method and application.
Background technology
Corrosion of metal is typically in natural environment or under working condition, due to occurring with its local environment medium
Go bad caused by chemistry or electrochemical action and destroy.In general, the corrosion of steel and ferrous alloy is mainly to get rusty
Based on, its reason is that it forms the corrosion being mainly made up of hydrous ferric oxide in the presence of water, oxygen and electrolyte in the environment
Product iron rust.Painting anticorrosion coating is one of most basic method of anti-corrosion of metal.By anticorrosive paint even compact coated in gold
On metal surface, its shielding action can effectively prevent corrosive medium from being contacted with the direct of metal surface, and then slow down the hair of corrosion
It is raw.Although anticorrosive paint has certain shielding action, as time went on, a small amount of water, oxygen and electrolyte are still suffered from
Through coating, make steel corrosion, corrosion product volume gradually expands, and final coating foaming comes off, and loses antiseptic property.It is anti-
The anticorrosion ability of corrosion resistant coating has direct relation with thickness.The electrification of Mayne combination Fick diffusion laws and coated steel sheet
Research is learned, coating life predictor formula is proposed on the basis of " film polarization resistance cybernetics "：
In formula：L is the life-span of coating；L is the thickness of coating；D is the diffusion coefficient of coating ion；For constant；psTo apply
The adhesive force of layer；σnTo be applied to the pressure of steel surface under coating.It can be seen that the service life L and coating layer thickness l of coating
It is square directly proportional.Zhao Qingbo exists《Bridge steel structure erosion shield is supporting and coating service life》In have also been made similar report,
I.e. as the increase of coating layer thickness, service life extend.To same coating, in general, the coating number of plies is more, and thickness is bigger,
The screening ability of coating is stronger, and the medium such as water, oxygen and electrolyte transmits more difficult in the coating, the antiseptic property of coating and makes
It is also longer with the life-span.And varying environment is different to coating thickness requirement, general coating layer thickness is 20~100 μm and is
Can, coating layer thickness needs 200~250 μm under salt mist environment, and long-acting anti-corrosion environment coating layer thickness then will be more than 350 μm.
In general solvent based coating because solid content is low, the coating layer thickness that single spin obtains generally 10~30 μm it
Between, in order to reach preferable thickness, it usually needs repeatedly spraying, to ensure corrosion-resistant effect, but easily top layer elephant skin occur
And phenomena such as internal layer is not dry, solvent can not fully volatilize and remain on a small quantity, influence the decay resistance of coating.Some new coatings
Such as mastic, high solid coating, solventless coatings, individual layer film thickness are the 10 of general coating up to more than 100 μm
Yu Bei, by the application of a small amount of number, 250~2000 μm of erosion shield can be obtained, there is lifting antiseptic property, save
Man-hour, reduce the advantages that pollution.
Powdery paints is not to grow very much in China's popularization and application time as a kind of new coating, but as China is to ring
The volatile organic matter (VOC) that border causes seriously to pollute strengthens limitation, and powdery paints is developed rapidly.Relative to traditional
Solvent based coating, its outstanding advantage are solvent-free release, and utilization efficiency of coatings is high, film physical and mechanical properties and resistant to chemical media
Superior performance, application is convenient, and production, storage, transportation safety are without hidden danger.The thickness of powdery paints can be controlled to 100~2000
In micrometer range, this is that conventional solvent coating is unapproachable.Therefore powdery paints is obtained in corrosion-resistant field and extensively should
With especially in pipeline corrosion protection application.
Polyether-ether-ketone (PEEK) is a kind of special engineering plastics of excellent performance, its have high temperature resistant, mechanical performance it is excellent,
The advantages that self lubricity is good, chemicals-resistant burn into is fire-retardant, peel resistance is good, wear-resisting, radioresistance, superpower mechanical performance, can be wide
It is general very wide applied to field, exploitation prospects such as Aero-Space, automobile making, electric, medical and food processings.
Polyether-ether-ketone has excellent chemical proofing (corrosion resistance), in common chemicals, can dissolve or destroy it
The only concentrated sulfuric acid, its corrosion resistance is close with nickel steel.Polyether-ether-ketone resin is prepared into polyether-ether-ketone powdery paints, not only
The advantages of inheriting polyether-ether-ketone resin, and the advantage of powdery paints can be played.If the polyether-ether-ketone coating finally given
Thickness reaches more than 350 μm, and its Corrosion Protection can be very excellent.
The problem of presently, there are is that blocked up polyether-ether-ketone powdery paints can produce serious sagging when forming coating and show
As.Polyether-ether-ketone belongs to thermoplastic resin, on polyether-ether-ketone powder paint to base material, (generally exists by high-temperature fusion
Between 370~400 DEG C) certain time, levelling forms smooth fused coating, final polyether-ether-ketone coating obtained after cooling.
During high-temperature fusion, melting polyether-ether-ketone in vertical surface is because thickness is excessive, under the influence of gravity, to flowing down
Pendant, formation top is thinning, bottom is thickening, serious spherical, bellows-shaped the surface of formation, finally influences coating performance.
The content of the invention
Serious sagging phenomenon can be produced when forming coating in order to solve above-mentioned polyether-ether-ketone powdery paints, the present invention carries
A kind of thick coated type polyether-ether-ketone composite coating is supplied, main component is polyether-ether-ketone and common polyether ether ketone containing alkynyl, best
The mass ratio for being polyether-ether-ketone containing alkynyl and common polyether ether ketone is 1:100~200, the average grain of the common polyether ether ketone
Footpath is 30~150 μm, and melt index is 40~150g/10min, and the polyether-ether-ketone molecular formula containing alkynyl is：
0 ＜ x≤1,0≤y ＜ 1 in molecular formula, x+y=1 (being preferably x/y=2/8,3/7 or 4/6), molecular weight Mn=
30000~110000.
The preparation method of the thick coated type polyether-ether-ketone composite coating is：According to polyether-ether-ketone and the matter of solvent containing alkynyl
Polyether-ether-ketone containing alkynyl is dissolved into the solvent by amount than the ratio for 0.01~0.12 forms solution.By polyether-ether-ketone powder
Last coating (common polyether ether ketone), which is added to be well mixed in above-mentioned solution, obtains mixed solution, then filters mixed solution simultaneously
Drying, is dispersed to 20-150 microns, obtains thick coated type polyether-ether-ketone composite coating.Wherein, the polyether-ether-ketone powdery paints
Average grain diameter is 30~150 μm, and melt index is 40~150g/10min.Polyether-ether-ketone powdery paints and the polyethers ether containing alkynyl
The mass ratio of ketone solution is (1~20):1.
The solvent is the solvent that can dissolve the polyether-ether-ketone containing alkynyl, preferably DMF (DMF), N, N-
1~3 kind in dimethyl acetamide (DMAc) and 1-METHYLPYRROLIDONE (NMP).
Thick coated type polyether-ether-ketone composite coating is used to be sprayed at surfaces of conductive substrates to prepare polyether-ether-ketone thick coating, specifically
Step is as follows：
First, thick coated type polyether-ether-ketone composite coating is sprayed on surfaces of conductive substrates using electrostatic coating method；
2nd, 3~30min is handled under the conditions of 380~400 DEG C；
3rd, overcoating is carried out using hot spray process；
4th, 3~30min is handled under the conditions of 380~400 DEG C；
5th, repeat step three and step 4 to coating layer thickness reach more than 300 microns, wherein it is preferred that 300 microns to 2000
Micron.
Beneficial effect：
1st, phenylacetylene base can crosslink reaction under the high temperature conditions, and PEEK coating needs to be formed by high-temperature fusion processing
Final coating, when high-temperature process, pure PEEK powdery paints starts melting and levelling, and the PEEK containing alkynyl is also crosslinked instead
Should.Crosslinking phenomena increases pure PEEK melt viscosity, reduces the mobility of pure PEEK powdery paints, gravity is influenceed it
Reduce as far as possible, so as to avoid the sagging phenomenon of pure PEEK powdery paints, form with the compound paintings of certain thickness PEEK
Layer, meet the requirement of corrosion-inhibiting coating under severe etching condition.
2nd, the preparation method of thick coated type polyether-ether-ketone coating and spraying coating process are simple, easy to operate, can rationally control, warp
Ji is practical.
3rd, the generation of sagging phenomenon is avoided using the thick coating of thick coated type polyether-ether-ketone coating preparation.
4th, the antiseptic property of polyether-ether-ketone thick coating is more excellent, can effectively reduce the corrosion of industrial equipment, improves industry
Service life of equipment, the probability that accident occurs because of device damage is reduced, cost is reduced so as to reach, the final mesh to economize on resources
's.
Brief description of the drawings
Fig. 1 polyether-ether-ketones coating and thick coated type polyether-ether-ketone composite coating melt viscosity vary with temperature curve.
Embodiment
Technical solution of the present invention is further explained and illustrated in the form of embodiment below.The present invention is in following implementation
The polyether-ether-ketone degree of polymerization Xn=201 (molecular weight Mn=73174) containing alkynyl used in example, it can be used in practical application poly-
It is right be 88~300 the polyether-ether-ketone containing alkynyl (molecular weight Mn is about 30,000~110,000).
Embodiment 1
Polyether-ether-ketone containing alkynyl is synthesized by polymerisation, wherein x=0.1 in the polyether-ether-ketone containing alkynyl, y=0.9；
The above-mentioned polyether-ether-ketone containing alkynyl is dissolved into DMF (DMF) and forms solution, solution quality percentage concentration
For 1%；Then prepare and polyether-ether-ketone powdery paints is added to stirring or ultrasonic disperse, wherein polyether-ether-ketone powder in above-mentioned solution
The average grain diameter of last coating is 30 μm, melt index 40g/10min, polyether-ether-ketone powdery paints and the polyether-ether-ketone containing alkynyl
The mass ratio of solution is 1:1；Mixed solution is filtered and dried, is dispersed to the particle diameter of suitable electrostatic spraying, finally gives thick painting
Type polyether-ether-ketone composite coating.
Embodiment 2
Polyether-ether-ketone thick coating, its preparation side are prepared using the thick coated type polyether-ether-ketone composite coating prepared in embodiment 1
Method step is as follows：
1) the compound painting of thick coated type polyether-ether-ketone prepared on conductive base using electrostatic coating method spraying embodiment 1
Material；
2) base material that coating is coated with step 1) is subjected to high-temperature process, that is, is warming up to 380 DEG C and maintains 3min；
3) overcoating is carried out using heat spraying method, i.e., the direct thermal spraying thick coated type polyethers on the base material of step 2) heat treatment
Ether ketone composite coating；
4) the base material repeat step 2 that will be obtained in step 3)) high-temperature process operation；
If 5) coating layer thickness is not reaching to requirement, repeat step 3) and 4)；
6) coating layer thickness reaches requirement, and the base material cooling treatment for scribbling coating is obtained into the compound painting of final polyether-ether-ketone
Layer, the thickness control of coating is at 300 μm or so.
Embodiment 3
Polyether-ether-ketone containing alkynyl is synthesized by polymerisation, wherein x=0.5 in the polyether-ether-ketone containing alkynyl, y=0.5；
The above-mentioned polyether-ether-ketone containing alkynyl is dissolved into DMA (DMAC) and forms solution, solution quality percentage concentration
For 10%；Then prepare and polyether-ether-ketone powdery paints is added to stirring or ultrasonic disperse, wherein polyether-ether-ketone in above-mentioned solution
The average grain diameter of powdery paints is 150 μm, melt index 150g/10min, polyether-ether-ketone powdery paints and the polyethers containing alkynyl
The mass ratio of ether ketone solution is 20:1；Mixed solution is filtered and dried, the particle diameter of suitable electrostatic spraying is dispersed to, finally gives
Thick coated type polyether-ether-ketone composite coating.
Embodiment 4
The thick coated type polyether-ether-ketone composite coating prepared using embodiment 3 prepares polyether-ether-ketone thick coating, its preparation method
Step is as follows：
1) the compound painting of thick coated type polyether-ether-ketone prepared on conductive base using electrostatic coating method spraying embodiment 3
Material；
2) base material that coating is coated with step 1) is subjected to high-temperature process, that is, is warming up to 400 DEG C and maintains 30min；
3) overcoating is carried out using heat spraying method, i.e., the direct thermal spraying thick coated type polyethers on the base material of step 2) heat treatment
Ether ketone composite coating；
4) the base material repeat step 2 that will be obtained in step 3)) high-temperature process operation；
If 5) coating layer thickness is not reaching to requirement, repeat step 3) and 4)；
6) coating layer thickness reaches requirement, and the base material cooling treatment for scribbling coating is obtained into the compound painting of final polyether-ether-ketone
Layer, the thickness control of coating is at 2000 μm or so.
Embodiment 5
Polyether-ether-ketone containing alkynyl is synthesized by polymerisation, wherein x=0.2 in the polyether-ether-ketone containing alkynyl, y=0.8；
The above-mentioned polyether-ether-ketone containing alkynyl is dissolved into 1-METHYLPYRROLIDONE (NMP) and forms solution, solution quality percentage concentration is
5%；Then prepare and polyether-ether-ketone powdery paints is added to stirring or ultrasonic disperse, wherein polyether-ether-ketone powder in above-mentioned solution
The average grain diameter of coating is 50 μm, melt index 60g/10min, and polyether-ether-ketone powdery paints and polyether-ether-ketone containing alkynyl are molten
The mass ratio of liquid is 10:1；Mixed solution is filtered and dried, the particle diameter of suitable electrostatic spraying is dispersed to, finally gives thick coated type
Polyether-ether-ketone composite coating.
Embodiment 6
The thick coated type polyether-ether-ketone composite coating prepared using embodiment 5 prepares polyether-ether-ketone thick coating, its preparation method
Step is as follows：
1) the compound painting of thick coated type polyether-ether-ketone prepared on conductive base using electrostatic coating method spraying embodiment 5
Material；
2) base material that coating is coated with step 1) is subjected to high-temperature process, that is, is warming up to 385 DEG C and maintains 10min；
3) overcoating is carried out using heat spraying method, i.e., the direct thermal spraying thick coated type polyethers on the base material of step 2) heat treatment
Ether ketone composite coating；
4) the base material repeat step 2 that will be obtained in step 3)) high-temperature process operation；
If 5) coating layer thickness is not reaching to requirement, repeat step 3) and 4)；
6) coating layer thickness reaches requirement, and the base material cooling treatment for scribbling coating is obtained into the compound painting of final polyether-ether-ketone
Layer, the thickness control of coating is at 500 μm or so.
Embodiment 7
Polyether-ether-ketone containing alkynyl is synthesized by polymerisation, wherein x=0.3 in the polyether-ether-ketone containing alkynyl, y=0.7；
The above-mentioned polyether-ether-ketone containing alkynyl is dissolved into DMF (DMF) and forms solution, solution quality percentage concentration
For 3%；Then prepare and polyether-ether-ketone powdery paints is added to stirring or ultrasonic disperse, wherein polyether-ether-ketone powder in above-mentioned solution
The average grain diameter of last coating is 70 μm, melt index 80g/10min, polyether-ether-ketone powdery paints and the polyether-ether-ketone containing alkynyl
The mass ratio of solution is 5:1；Mixed solution is filtered and dried, is dispersed to the particle diameter of suitable electrostatic spraying, finally gives thick painting
Type polyether-ether-ketone composite coating.
Embodiment 8
The thick coated type polyether-ether-ketone composite coating prepared using embodiment 7 prepares polyether-ether-ketone thick coating, its preparation method
Step is as follows：
1) the compound painting of thick coated type polyether-ether-ketone prepared on conductive base using electrostatic coating method spraying embodiment 7
Material；
2) base material that coating is coated with step 1) is subjected to high-temperature process, that is, is warming up to 390 DEG C and maintains 8min；
3) overcoating is carried out using heat spraying method, i.e., the direct thermal spraying thick coated type polyethers on the base material of step 2) heat treatment
Ether ketone composite coating；
4) the base material repeat step 2 that will be obtained in step 3)) high-temperature process operation；
If 5) coating layer thickness is not reaching to requirement, repeat step 3) and 4)；
6) coating layer thickness reaches requirement, and the base material cooling treatment for scribbling coating is obtained into the compound painting of final polyether-ether-ketone
Layer, the thickness control of coating is at 1200 μm or so.
Embodiment 9
Polyether-ether-ketone containing alkynyl is synthesized by polymerisation, wherein x=0.4 in the polyether-ether-ketone containing alkynyl, y=0.6；
The above-mentioned polyether-ether-ketone containing alkynyl is dissolved into 1-METHYLPYRROLIDONE (NMP) and forms solution, solution quality percentage concentration is
8%；Then prepare and polyether-ether-ketone powdery paints is added to stirring or ultrasonic disperse, wherein polyether-ether-ketone powder in above-mentioned solution
The average grain diameter of coating is 120 μm, melt index 120g/10min, polyether-ether-ketone powdery paints and the polyether-ether-ketone containing alkynyl
The mass ratio of solution is 15:1；Mixed solution is filtered and dried, is dispersed to the particle diameter of suitable electrostatic spraying, finally gives thick painting
Type polyether-ether-ketone composite coating.
Embodiment 10
The thick coated type polyether-ether-ketone composite coating prepared using embodiment 9 prepares polyether-ether-ketone thick coating, its preparation method
Step is as follows：
1) the compound painting of thick coated type polyether-ether-ketone prepared on conductive base using electrostatic coating method spraying embodiment 9
Material；
2) base material that coating is coated with step 1) is subjected to high-temperature process, that is, is warming up to 395 DEG C and maintains 25min；
3) overcoating is carried out using heat spraying method, i.e., the direct thermal spraying thick coated type polyethers on the base material of step 2) heat treatment
Ether ketone composite coating；
4) the base material repeat step 2 that will be obtained in step 3)) high-temperature process operation；
If 5) coating layer thickness is not reaching to requirement, repeat step 3) and 4)；
6) coating layer thickness reaches requirement, and the base material cooling treatment for scribbling coating is obtained into the compound painting of final polyether-ether-ketone
Layer, the thickness control of coating is at 1500 μm or so.
Embodiment 11
The preparation method of the polyether-ether-ketone containing alkynyl have references in the present invention《Photochemistry and photo-biological magazine A：Chemistry》In
Ma et al. synthetic method, (Journal of Photochemistry and Photobiology A:Chemistry 188
(2007) 43-50), the synthetic route of the polyether-ether-ketone containing alkynyl is as follows in the present embodiment：
Specific steps：
Into 5000mL beaker, 4- bromanilines (152 grams, 1mol) and water (200mL) are added, with dropping funel again
35% hydrochloric acid (340 milliliters, 4 moles) is slowly added dropwise into solution, sodium nitrite solution (69 then is added dropwise to this mixture
Gram, 1 mole) aqueous solution (300 milliliters of water), control temperature that resulting solution is added dropwise to equipped with Isosorbide-5-Nitrae-benzoquinones at 0-5 DEG C
In the bucket of the mixture of (100 grams, 0.93 mole), sodium acid carbonate (252 grams, 3 moles) and water (1000 milliliters), temperature within the barrel control
System is at 8-12 DEG C.After completion of dropwise addition, by reactant mixture stir about 2 hours.Sediment is collected by filtration, is fully washed with water
Recrystallized several times to product in golden yellow, the product from n-butanol, obtain yellow crystal.And under 60 degree, in vacuum oven
Middle drying, obtain 4- bromophenyl benzoquinones.
By the product 4- bromophenyls benzoquinones obtained by upper step and Zn powder (195 grams, 3 moles), 300mL deionized waters are put into
In 3000mL three-neck flasks, 90 DEG C are heated the mixture under agitation, then by adding hydrochloric acid (255mL, 3 moles), are dripped
Add control in the speed in per minute 30 drops.After addition, reactant mixture is flowed back 3 hours, then by mixture while hot
Filtering.There is acicular crystal wash-off after cooling, be filtrated to get crude product with water recrystallization.Obtain white needle-like crystals 4- bromophenyl hydrogen
Quinone.
In a nitrogen environment, by acetic anhydride (22.44 grams, 220 mMs) solution be added drop-wise to dropwise pyridine (17.16 grams,
220 mMs) with the mixed solution of 4- bromophenyls quinhydrones (26.5 grams, 100 mMs), the solution of stirring is heated into 70 DEG C
Reaction 2 hours.After being cooled to room temperature, reactant mixture is poured into 200mL water.The solid of precipitation is filtered, tied again from methanol
Crystalline substance, and dry, it is dried to obtain yellow solid in 50 DEG C of vacuum drying oven.
In a nitrogen environment, by the product (25 grams, 70 mMs) and triphenylphosphine of above-mentioned gained (0.785 gram, 3 mmoles
You) it is dissolved in 5mL dimethyl acetamide, it is poured in 250mL three-neck flask.Phenylacetylene (9 is added into solution
Gram, 88 mMs), palladium chloride (0.3 gram, 0.43 mM) and triethylamine (60mL).Mixture is slowly heated to 60 DEG C,
Then cuprous iodide (0.2 gram, 1 mM) and 60mL triethylamines are added thereto.Reactant mixture is heated to 80 DEG C, and protected
Hold 12 hours.After-frame on water knockout drum, temperature is increased to 120~130 DEG C, triethylamine is steamed.Reactant is cooled to room
Filtered after temperature, to remove inorganic salts.Then the product of concentration is poured into acid water, there is white solid appearance, filtering precipitation immediately
Solid, the recrystallization purifying from ethanol, and white solid is dried in vacuo to obtain at 50 DEG C.
Afterwards in 500mL three-neck flask, equipped with mechanical agitator, condenser and dropping funel.By gained
Product is dissolved in the mixture (120mL) of tetrahydrofuran (120mL) and methanol.Sodium hydroxide (9.6 grams, 240 mMs) is molten
Solution is added dropwise in the reactant mixture in 80mL water by dropping funel.It is after flowing back 12 hours under agitation, reaction is mixed
Compound is cooled and poured into 200mL acid water.Organic layer is extracted with dichloromethane, and dehydrated with anhydrous sodium sulfate.Cross
After filter and distillation, decolourize to purify by residue activated carbon and from re crystallization from toluene, it is double containing alkynyl to obtain white solid i.e. target
Phenol monomer (PEP-PH).
Exemplified by synthesizing the polyether-ether-ketone (x=0.2, y=0.8) containing alkynyl, according to alkynyl monomers：4,4'- difluoro benzophenones：
Resorcinol：Anhydrous potassium carbonate=1：5：4：The ratio of the amount of 5.5 materials, by biphenol monomers of the 0.08mol containing alkynyl, 0.4mol
4,4'- difluoro benzophenones, 0.32mol resorcinols, 0.44mol Anhydrous potassium carbonate solids are placed in 1000ml three-necked flask, are led to
Enter nitrogen protection, add 414ml 1-METHYLPYRROLIDONEs (NMP) and be used as reaction dissolvent, add 140ml toluene and be used as band water to try
Agent, reacted under the stirring of mechanical pulp.First stage temperature adjustment refluxing toluene, carries out point water and operated to 130 DEG C, first
Benzene constantly takes water caused by reaction out of, and reaction is warming up to 160 DEG C after carrying out 2 hours, reacts 4 hours, is accorded with to system viscosity
Discharged when conjunction requires, reaction solution poured into acid water, obtain white solid product, filtered after being crushed using pulverizer,
Fully washed by water and ethanol, be dried to obtain subject copolymers in an oven.Resorcinol can also be used pair in the present embodiment
Benzenediol substitutes.
Validation test
Varied with temperature by testing thick coated type polyether-ether-ketone composite coating melt viscosity, as shown in figure 1, can be with from figure
Find out in coating melt temperature scope (380~400 DEG C), the viscosity of thick coated type polyether-ether-ketone composite coating is gathered apparently higher than pure
Ether ether ketone coating, the melt viscosity for making pure polyether-ether-ketone this demonstrate the crosslinking phenomena of the polyether-ether-ketone containing alkynyl increase, avoided
Sagging phenomenon, can form thick coating.
Claims (8)
- A kind of 1. thick coated type polyether-ether-ketone composite coating, it is characterised in that：Main component is for the polyether-ether-ketone containing alkynyl and commonly Polyether-ether-ketone, the average grain diameter of the common polyether ether ketone is 30 ~ 150 μm, and melt index is 40 ~ 150g/10min；It is described The polyether-ether-ketone molecular formula containing alkynyl be：,0 ＜ x≤1,0≤y ＜ 1, x+y=1 in molecular formula；Molecular weight Mn=30000 ~ 110000.
- 2. thick coated type polyether-ether-ketone composite coating according to claim 1, it is characterised in that：Polyether-ether-ketone containing alkynyl point X/y=2/8,3/7 or 4/6 in minor.
- 3. thick coated type polyether-ether-ketone composite coating according to claim 1 or 2, it is characterised in that：Polyethers ether containing alkynyl The mass ratio of ketone and common polyether ether ketone is 1:100~200.
- 4. a kind of preparation method of the thick coated type polyether-ether-ketone composite coating described in claim 1, is concretely comprised the following steps：Alkynyl will be contained Polyether-ether-ketone be added in solvent and form solution, common polyether ether ketone powder coating is added in above-mentioned solution and is well mixed Mixed solution is obtained, then mixed solution is filtered and dried, particle diameter is dispersed to as 20 ~ 150 microns, obtains the thick coated type and gather Ether ether ketone composite coating；Wherein, the polyether-ether-ketone containing alkynyl and solvent quality ratio are 0.01 ~ 0.12；The solvent is that can dissolve the polyethers containing alkynyl The solvent of ether ketone；The mass ratio of common polyether ether ketone powder coating and polyether-ether-ketone solution containing alkynyl is（1~20）:1.
- 5. the preparation method of thick coated type polyether-ether-ketone composite coating according to claim 4, it is characterised in that：It can dissolve and contain The solvent of the polyether-ether-ketone of alkynyl be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and 1-METHYLPYRROLIDONE in 1 ~ 3 kinds.
- 6. thick coated type polyether-ether-ketone composite coating according to claim 1 is used for the application of surfaces of conductive substrates spraying.
- 7. the method that thick coated type polyether-ether-ketone composite coating according to claim 1 sprays in surfaces of conductive substrates, specifically Step is：Thick coated type polyether-ether-ketone composite coating is sprayed on surfaces of conductive substrates using electrostatic coating method；3 ~ 30min is handled under the conditions of 380 ~ 400 DEG C；Overcoating is carried out using hot spray process；3 ~ 30min is handled under the conditions of 380 ~ 400 DEG C；Repeat step three and step 4 to coating layer thickness reach more than 300 microns.
- 8. the method that thick coated type polyether-ether-ketone composite coating according to claim 7 sprays in surfaces of conductive substrates, it is special It is：Coating layer thickness reaches 300 microns ~ 2000 microns.
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