CN106634434B - A kind of anti-flaming dope and preparation method thereof - Google Patents
A kind of anti-flaming dope and preparation method thereof Download PDFInfo
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- CN106634434B CN106634434B CN201611189368.2A CN201611189368A CN106634434B CN 106634434 B CN106634434 B CN 106634434B CN 201611189368 A CN201611189368 A CN 201611189368A CN 106634434 B CN106634434 B CN 106634434B
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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
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
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- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08K3/00—Use of inorganic substances as compounding ingredients
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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
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
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Abstract
The invention discloses a kind of anti-flaming dopes and preparation method thereof, belong to chemistry painting industry processing technique field.The anti-flaming dope is made in a solvent of the component dissolution of following parts by weight: 100-120 parts of epoxy resin, 20-30 parts of modified polyamide acid solution, filler 15-20,10-15 parts of fire-retardant filler, 5-15 parts of pigment, coupling agent solution, 0.5-1 parts of dibenzoyl peroxide, N, 0.5-1 parts of accelerine, 0.05-0.1 parts of Imidizole accelerator and amine curing agent, the equivalent proportion of the epoxy group in reactive hydrogen and epoxy resin in the coating in amine curing agent are 0.45-0.55；The present invention is utilized and is modified by modified polyamide acid solution prepared by castor oil, isocyanates, melamine and acid anhydrides to epoxy resin, the coating of preparation has good paintability, can rapid curing, the coated adhesive performance after solidification are good at low temperature, toughness is good, good flame retardation effect.
Description
[technical field]
The present invention relates to chemistry painting industry processing technique fields, and in particular to a kind of anti-flaming dope and preparation method thereof.
[background technique]
Humidity, pH value and oxygen in air can penetrate into material internal and react with material, cause material aging or
Deformation, for protection materials, often spraying protective layer coating on the surface of the material.Coating is usually first by matrix resin, filling material
Material and curing agent etc. are prepared into coating, and coating is coated with or is sprayed on material surface, form one layer after solidifying under certain condition
Glue film sticks on the surface of the material, by material and atmospheric isolation, prevents material water suction, oxidation or the aging by acid and alkali corrosion.
The coating cementability prepared using epoxy resin as matrix resin is good, shrinking percentage is low, dimensionally stable, electrical property are excellent
Good, resistant to chemical media, configuration are easy, simple process, using temperature, broad, adaptability is relatively strong, toxicity is very low, harm is also small, no
Environment etc. is polluted, all there is good stickiness to multiple material, there are also sealing, insulation, leakproof, fixation, anti-corrosion, decorations etc.
A variety of functions, referred to as all-purpose adhesive, but toughness is insufficient after epoxy resin cure, limits its use scope.Polyimides is comprehensive
Close one of optimal high-molecular organic material of performance, high temperature resistant up to 400 DEG C or more, -200~300 DEG C of long-term use temperature range,
Without sharp melting point, there is high insulation performance, good flexible and extremely low dielectric constant, but polyimides adhesive property
Difference, and it is insoluble do not melt, it is not easy to be processed.
It since the matrix resin in coating is mainly organic resin, easily burns, the fire spreads quickly is difficult to control after kindling
System, to the life of people, there are potential threats, cause immeasurable loss to property, therefore the flame retardant effect after paint solidification
It is one of the important indicator of coating.
In existing coating, in order to obtain good flame retardation effect, fire-retardant filler is often added in coating, there is halogen fire-retardant filler
Good flame retardation effect, but the health for having the use of halogen organic material to be unfavorable for environment and human body are used by limitation, and halogen-free flameproof
Filler flame retardant effect is also undesirable.
[summary of the invention]
It is an object of the invention to: in view of the above problems, provide a kind of anti-flaming dope and preparation method thereof, this hair
Bright coating can under less hardener dose completion of cure, the coated adhesive performance after solidification is good, and toughness is good, also have it is good
Good flame retardant effect.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of anti-flaming dope is made in a solvent of the component dissolution of following parts by weight: 100-120 parts of epoxy resin,
20-30 parts of modified polyamide acid solution, filler 15-20,10-15 parts of fire-retardant filler, 5-15 parts of pigment, dibenzoyl peroxide
0.5-1 parts, 0.5-1 parts of n,N-Dimethylaniline, 0.05-0.1 parts of Imidizole accelerator, amine curing agent and coupling agent solution, institute
The equivalent proportion for stating the epoxy group in the reactive hydrogen and epoxy resin in coating in amine curing agent is 0.45-0.55, the coating
Solid be 45-50%, the dosage of the coupling agent solution is the 0.5- for the powder being made of filler, fire-retardant filler and pigment
1%, the coupling agent solution mass concentration is 20-30%；
The modified polyamide acid solution obtains by the following method: by castor oil and diisocyanate by hydroxyl and isocyanide
Perester radical molar ratio is that the ratio mixed dissolution of 1:2-2.2 reacts in N-Methyl pyrrolidone, and it is poly- to obtain terminal isocyanate group
Urethane performed polymer, then the melamine solution after dimethyl sulfoxide dilutes is added in terminal isocyanate group base polyurethane prepolymer for use as
In, the remaining isocyanate base of terminal isocyanate group base polyurethane prepolymer for use as and the rubbing for the amido in melamine solution that are added
You react than being 1:3-3.01 and obtain the excessive modified cyanurotriamide of amido, finally acid anhydrides is added in modified cyanurotriamide, institute
The molar ratio of remaining amido is 1:0.9-0.99 in carboxyl and modified cyanurotriamide in the acid anhydrides of addition, is obtained after reaction modified
Polyamic acid solution.
The epoxy resin is in bisphenol A type epoxy resin, diglycidyl ether type epoxy resin and cycloaliphatic epoxy resin
A combination of one or more object；The diisocyanate is toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, right
Benzene dimethylene diisocyanate, own diisocyanate resin or isophorone diisocyanate.
The filler is titanium dioxide and/or aluminium hydroxide；The fire-retardant filler is halogen-free flameproof filler；The pigment is
Titanium dioxide, carbon black, phthalocyanine blue or iron oxide.
The coupling agent solution is that silane coupling agent or titanate coupling agent dissolution are prepared in ethanol, the coupling
Agent solution mass concentration is 20-30%, and the dosage of the coupling agent solution is the powder being made of filler, fire-retardant filler and pigment
0.5-1%.
The solvent is the composition of one or more of cyclohexanone, butanone and N-Methyl pyrrolidone.
The acid anhydrides is methyl tetrahydro phthalic anhydride, maleic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydro O-phthalic
Acid anhydrides and 3,3 ', the composition of one or more of 4,4 '-benzophenone tetracid dianhydrides.
The present invention also provides the preparation methods of the anti-flaming dope described in one kind, include the following steps:
It (1) is the dilution of its 3-4 times N-Methyl pyrrolidone by castor oil weight；Diisocyanate is dissolved in 2-3
In the N-Methyl pyrrolidone of times of weight, it is slowly added dropwise while stirring in 60-80 DEG C of oil bath dilute through N-Methyl pyrrolidone
The molar ratio of castor oil solution after releasing, the isocyanate group in the hydroxyl and diisocyanate in castor oil being added dropwise is 1:
2-2.2 continues to be stirred to react 40-60 minutes after being added dropwise to complete, discharges after being cooled to room temperature, it is pre- to obtain isocyanate terminated based polyurethanes
Aggressiveness；
It (2) is that the dilution of its 3-4 times dimethyl sulfoxide is placed in 60-80 DEG C of oil bath by melamine weight, side
Stirring side is slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as made from step (1), the poly- ammonia of the terminal isocyanate group being added dropwise
The molar ratio of amido in ester performed polymer in remaining isocyanate group and melamine is 1:3-3.01, is continued after being added dropwise to complete
Stirring 40-60 minutes, reacts to obtain modified cyanurotriamide, after being cooled to 40-60 DEG C, every 4 hours addition acid anhydrides under stirring, adds altogether
Three times, the acid anhydrides mass ratio being added three times is 3:2:1, remaining amido in the carboxyl and modified cyanurotriamide in acid anhydrides be added
Molar ratio is 1:0.9-0.99, continues to be stirred to react 12-24 hours, obtains modified polyamide acid solution, stand-by after sealing is cooling；
(3) powder mixed by 15-20 parts of fillers, 10-15 parts of fire-retardant fillers and 5-15 parts of pigment is put into high speed
In batch mixer, the coupling agent solution and after mixing for the 0.5-1% that weight is above-mentioned powder, general are sprayed into high speed mixer
Powder is transferred in 60-90 DEG C of baking oven and toasts 1-2 hours, obtains the powder of drying；By 100-120 parts of epoxy resin, above-mentioned baking
In dry mixed powder and appropriate solvent investment dispersion machine, after being stirred 30-40 minutes under the revolving speed of 800-1000r/min, turn
Enter in sand mill and be sanded 40-60 minutes, obtain the solution of homogeneous, then by modified polyamide acid obtained in 20-30 parts of steps (2)
In solution and above-mentioned homogeneous solution investment dispersion machine, disperse under the revolving speed of 800-1000r/min 30-40 minutes, finally by work
Property hydrogen and epoxy group equivalent proportion be 0.45-0.55 ratio amine curing agent is added, and 0.5-1 parts of diphenyl peroxide first are added
Acyl, 0.5-1 part n,N-Dimethylaniline and 0.05-0.1 parts of Imidizole accelerators simultaneously stir 20-30 minutes, and acquisition solid is 45-
50% mixed liquor, the as described anti-flaming dope.
Castor oil is the glyceryl ester of fatty acid, and hydroxyl average functionality is 2.7, also contains unsaturated double-bond in molecule,
Castor oil can carry out a variety of chemical reactions by possessed hydroxyl, double bond and ester bond, with good flexibility and instead
Ying Xing.
Melamine is made of urea, and performance is more biased towards and inorganic material, is to prepare containing there are three amido in molecule
One of raw material of amide, melamine is non-combustible, and property is stablized at normal temperature, changes using melamine to resin matrix
Property, improve the flame retardant effect of resin.
Polyamic acid is the presoma of polyimides, has soluble and reactivity, raw material sources are abundant, and synthesis technology
Simply, the resin for obtaining function admirable can be modified to resin matrix.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
(1) present invention utilizes the high reaction activity of isocyanate group, the good castor oil molecule of toughness is connected to fire-retardant
In the good melamine molecule of effect, melamine and anhydride reaction after recycling toughening modifying prepare the excessive polyamides of acid anhydrides
Polyamic acid is modified epoxy resin by amino acid, and the carboxyl and amido in polyamic acid can be reacted with epoxy resin, by castor
Sesame oil molecule and melamine molecule are grafted on epoxy molecule, meanwhile, in heat curing process, in polyamic acid
Cyclodehydration reaction can also occur for carboxyl and amido, and the stable imide ring of forming properties is effectively improved the tough of epoxy resin
Property and flame retardant effect；
(2) due to containing excessive carboxyl, curable epoxy, while the peroxide being added in modified polyamide acid molecule
The temperature of curable epoxide can be reduced by changing two formyls both and can causing double-bond polymerization also, reduce the dosage of curing agent, reduce reaction temperature
Degree improves reaction rate；
Coating prepared by the present invention can under less hardener dose completion of cure, the coated adhesive performance after solidification
Good, toughness is good, also has good flame retardant effect.
[specific embodiment]
Make the explanation of further progress to technical solution of the present invention combined with specific embodiments below.
Embodiment 1
It (1) is the dilution of its 3 times N-Methyl pyrrolidone by castor oil weight；Xylene diisocyanate is dissolved in
In the N-Methyl pyrrolidone of 3 times of weight, it is slowly added dropwise in 60 DEG C of oil bath and is diluted through N-Methyl pyrrolidone while stirring
Castor oil solution afterwards, the molar ratio of isocyanate group is 1 in the hydroxyl and toluene di-isocyanate(TDI) in castor oil being added dropwise:
2, continue to be stirred to react 60 minutes after being added dropwise to complete, discharges after being cooled to room temperature, obtain terminal isocyanate group base polyurethane prepolymer for use as；
It (2) is that the dilution of its 4 times dimethyl sulfoxide is placed in 60 DEG C of oil bath by melamine weight, while stirring
It is slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as made from step (1), the terminal isocyanate group polyurethane prepolymer being added dropwise
The molar ratio of amido in body in remaining isocyanate group and melamine is 1:3, continues stirring 60 minutes after being added dropwise to complete,
Modified cyanurotriamide is reacted to obtain, after being cooled to 40 DEG C, every 4 hours addition methyl tetrahydro phthalic anhydrides under stirring, altogether plus three times, three times
The mass ratio of the methyl tetrahydro phthalic anhydride of addition is 3:2:1, the carboxyl and modified cyanurotriamide in methyl tetrahydro phthalic anhydride being added
Middle remnants amido molar ratio is 1:0.9, continues to be stirred to react 24 hours, obtains modified polyamide acid solution, stand-by after sealing is cooling；
(3) powder mixed by 15 parts of aluminium hydroxides, 15 parts of halogen-free flameproof fillers and 5 parts of carbon blacks high speed is put into mix
In material machine, 0.5% silane coupler solution and after mixing that weight is above-mentioned powder, general are sprayed into high speed mixer
Powder is transferred in 60 DEG C of baking oven and toasts 2 hours, obtains the powder of drying；By 100 parts of bisphenol A type epoxy resins, above-mentioned drying
Powder and appropriate cyclohexanone investment dispersion machine in, stirred under the revolving speed of 800r/min after forty minutes, be transferred to sand in sand mill
Mill 60 minutes, obtains the solution of homogeneous, then by modified polyamide acid solution obtained in 20 parts of steps (2) and above-mentioned homogeneous solution
It puts into dispersion machine, disperses under the revolving speed of 800r/min 40 minutes, be finally 0.55 by the equivalent proportion of reactive hydrogen and epoxy group
Ratio amine curing agent is added, and 1 part of dibenzoyl peroxide, 1 part of n,N-Dimethylaniline and 0.1 part of imidazoles is added and promotes
Agent is simultaneously stirred 30 minutes, and the mixed liquor that solid is 50%, as anti-flaming dope described in the embodiment of the present invention 1 are obtained.
Comparative example 1
The powder mixed by 15 parts of aluminium hydroxides, 15 parts of halogen-free flameproof fillers and 5 parts of carbon blacks is put into high speed mixing
In machine, 0.5% silane coupler solution and after mixing that weight is above-mentioned powder is sprayed into high speed mixer, by powder
Material, which is transferred in 60 DEG C of baking oven, to be toasted 2 hours, and the powder of drying is obtained；By 120 parts of bisphenol A type epoxy resins, above-mentioned drying
In powder and appropriate cyclohexanone investment dispersion machine, is stirred under the revolving speed of 800r/min after forty minutes, be transferred in sand mill and be sanded
60 minutes, the solution of homogeneous is obtained, amine curing agent finally is added in the ratio that the equivalent proportion of reactive hydrogen and epoxy group is 0.70, and
1 part of dibenzoyl peroxide, 1 part of n,N-Dimethylaniline and 0.1 part of Imidizole accelerator is added and stirs 30 minutes, obtains solid
Portion mixed liquor for being 50%, anti-flaming dope described in comparative example 1 as of the present invention.
Embodiment 2
It (1) is the dilution of its 4 times N-Methyl pyrrolidone by castor oil weight；'-diphenylmethane diisocyanate is dissolved
In the N-Methyl pyrrolidone of 2 times of weight, it is slowly added dropwise while stirring in 80 DEG C of oil bath dilute through N-Methyl pyrrolidone
Castor oil solution after releasing, mole of isocyanate group in the hydroxyl and '-diphenylmethane diisocyanate in castor oil being added dropwise
Than continuing to be stirred to react 40 minutes after being added dropwise to complete, discharging after being cooled to room temperature, obtain isocyanate terminated based polyurethanes for 1:2.2
Performed polymer；
It (2) is that the dilution of its 3 times dimethyl sulfoxide is placed in 80 DEG C of oil bath by melamine weight, while stirring
It is slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as made from step (1), the terminal isocyanate group polyurethane prepolymer being added dropwise
The molar ratio of amido in body in remaining isocyanate group and melamine is 1:3.01, continues 40 points of stirring after being added dropwise to complete
Clock obtains modified cyanurotriamide, after being cooled to 60 DEG C, is added every 4 hours by methyl tetrahydrophthalic anhydride and first under stirring
Base hexahydrophthalic anhydride is the mixed acid anhydride of 1:1 by weight, altogether plus three times, the mass ratio for the mixed acid anhydride being added three times
For 3:2:1, the molar ratio of remaining amido is 1:0.99 in the carboxyl and modified cyanurotriamide in mixed acid anhydride being added, and is continued
It is stirred to react 12 hours, obtains modified polyamide acid solution, it is stand-by after sealing is cooling；
(3) ratio that perlite and aluminium hydroxide are 2:1 by weight is mixed and obtains mixed fillers, will mixed by 20 parts
The powder that filler, 10 parts of halogen-free flameproof fillers and 15 parts of titanium dioxide mix is put into high speed mixer, to high speed mixing
1% coupling agent solution and after mixing that weight is above-mentioned powder is sprayed in machine, powder is transferred in 90 DEG C of baking oven
Baking 1 hour, obtains the powder of drying；120 parts are rubbed by weight by diglycidyl ether type epoxy resin and bisphenol A type epoxy resin
You than be 2:1 ratio mix epoxy resin, it is above-mentioned dry powder and appropriate butanone investment dispersion machine in, in 1000r/
It after being stirred 30 minutes under the revolving speed of min, is transferred in sand mill and is sanded 40 minutes, obtain the solution of homogeneous, then by 30 parts of steps (2)
In in modified polyamide acid solution obtained and above-mentioned homogeneous solution investment dispersion machine, disperse 30 under the revolving speed of 1000r/min
Minute, amine curing agent finally is added in the ratio that the equivalent proportion of reactive hydrogen and epoxy group is 0.45, and 0.5 part of peroxidating is added
Dibenzoyl, 0.5 part of n,N-Dimethylaniline and 0.05 part of Imidizole accelerator simultaneously stir 20 minutes, and obtaining solid is 45%
Mixed liquor, as anti-flaming dope described in the embodiment of the present invention 2.
Comparative example 2
It (1) is that the dilution of its 3 times dimethyl sulfoxide is placed in 60 DEG C of oil bath by m-phenylene diamine (MPD) weight, it is every under stirring
Be added every 4 hours by methyl tetrahydrophthalic anhydride and methylhexahydrophthalic anhydride be by weight 1:1 mixed acid
Acid anhydride, altogether plus three times, the mass ratio for the mixed acid anhydride being added three times are 3:2:1, the carboxyl and isophthalic in mixed acid anhydride being added
Amido molar ratio in diamines is 1:0.99, continues to be stirred to react 12 hours, obtains polyamic acid solution, stand-by after sealing is cooling；
(2) ratio that perlite and aluminium hydroxide are 2:1 by weight is mixed and obtains mixed fillers, will mixed by 20 parts
The powder that filler, 10 parts of halogen-free flameproof fillers and 15 parts of titanium dioxide mix is put into high speed mixer, to high speed mixing
1% coupling agent solution and after mixing that weight is above-mentioned powder is sprayed in machine, powder is transferred in 90 DEG C of baking oven
Baking 1 hour, obtains the powder of drying；120 parts are rubbed by weight by diglycidyl ether type epoxy resin and bisphenol A type epoxy resin
You than be 2:1 ratio mix epoxy resin, it is above-mentioned dry powder and appropriate butanone investment dispersion machine in, in 1000r/
It after being stirred 30 minutes under the revolving speed of min, is transferred in sand mill and is sanded 40 minutes, obtain the solution of homogeneous, then by 30 parts of steps (1)
In in polyamic acid solution obtained and above-mentioned homogeneous solution investment dispersion machine, disperse 30 minutes under the revolving speed of 1000r/min,
Amine curing agent finally is added in the ratio that the equivalent proportion of reactive hydrogen and epoxy group is 0.45, and 0.5 part of diphenyl peroxide is added
Formyl, 0.5 part of n,N-Dimethylaniline and 0.05 part of Imidizole accelerator simultaneously stir 20 minutes, obtain the mixing that solid is 45%
Liquid, anti-flaming dope described in comparative example 2 as of the present invention.
Embodiment 3
It (1) is the dilution of its 3.5 times N-Methyl pyrrolidone by castor oil weight；Isophorone diisocyanate is molten
Solution is slowly added dropwise while stirring in 70 DEG C of oil bath through N- crassitude in the N-Methyl pyrrolidone of 2.5 times of weight
Castor oil solution after ketone dilution, the isocyanate group in the hydroxyl and isophorone diisocyanate in castor oil being added dropwise
Molar ratio be 1:2.1, continue to be stirred to react 50 minutes after being added dropwise to complete, discharge after being cooled to room temperature, obtain terminal isocyanate group
Base polyurethane prepolymer for use as；
It (2) is that the dilution of its 3.5 times dimethyl sulfoxide is placed in 70 DEG C of oil bath by melamine weight, side stirring
While being slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as made from step (1), the isocyanate terminated based polyurethanes being added are pre-
Remaining isocyanate base in aggressiveness and the amido in melamine and molar ratio be 1:3, continue stirring 50 after being added dropwise to complete
Minute, reaction obtains the excessive modified cyanurotriamide solution of amido, after being cooled to 50 DEG C, 3,3 ' were added every 4 hours under stirring,
4,4 '-benzophenone tetracid dianhydrides, altogether plus three times, 3 be added three times, 3 ', 4,4 '-benzophenone tetracid dianhydride mass ratioes are 3:2:1,
3,3 ' be added, remaining amido molar ratio is 1 in the carboxyl and modified cyanurotriamide in 4,4 '-benzophenone tetracid dianhydrides:
0.95 continues to be stirred to react 20 hours, obtains modified polyamide acid solution, stand-by after sealing is cooling；
(3) powder mixed by 17 parts of perlites, 13 parts of halogen-free flameproof fillers and 10 parts of phthalocyanine blues is put into high speed
In batch mixer, 0.6% coupling agent solution and after mixing that weight is above-mentioned powder is sprayed into high speed mixer, by powder
Material, which is transferred in 80 DEG C of baking oven, to be toasted 1.5 hours, and the powder of drying is obtained；By 110 parts of cycloaliphatic epoxy resins, above-mentioned drying
In powder and appropriate N-Methyl pyrrolidone investment dispersion machine, after stirring 35 minutes under the revolving speed of 900r/min, it is transferred to sand milling
Be sanded 50 minutes in machine, obtain the solution of homogeneous, then by modified polyamide acid solution obtained in 25 parts of steps (2) and it is above-mentioned
Matter solution is put into dispersion machine, is dispersed 35 minutes under the revolving speed of 900r/min, is finally pressed the equivalent proportion of reactive hydrogen and epoxy group
For 0.50 ratio be added amine curing agent, and be added 0.7 part of dibenzoyl peroxide, 0.6 part of n,N-Dimethylaniline and
0.07 part of Imidizole accelerator simultaneously stirs 25 minutes, obtains the mixed liquor that solid is 48%, the fire-retardant painting of the as described embodiment 3
Material.
Comparative example 3
As different from Example 3, dibenzoyl peroxide is not added in comparative example 3.
Test respectively the coating of various embodiments of the present invention and comparative example preparation solidification temperature when being optimal performance and
Curing time compares test, while its performance of sample test, test are prepared after coating is solidified under optimal condition of cure
The results are shown in Table 1.
Performance test includes adhesive property test, flame retardant property is tested, flexibility is tested,
Test method difference is as follows:
(1) adhesive property test is that coating is coated in after curing completely on substrate, 50 × 100 millimeters of the model on coating
The interior grid for drawing 15 × 15 millimeters is enclosed, then by adhesive tape on the coating for drawing grid, applies forcing tightly for 500g to adhesive plaster,
On the direction of vertical coating surface, adhesive tape is quickly torn, checking grid completely is qualified, various disbondings, that is, unqualified；
(2) flame retardant property test method is to be tested according to UL94 standard；
(3) flexibility test method is by coating preparation into film, and after curing completely tests its elongation at break.
Table 1: the anti-flaming dope the performance test results of the embodiment of the present invention and comparative example preparation
The result shows that, utilized in various embodiments of the present invention by castor oil, isocyanates, melamine by above-mentioned contrast test
Amine and the modified polyamide acid solution of acid anhydrides preparation are modified epoxy resin, and the coating of preparation has good coating
Can, coating can solidify in express delivery at low temperature, and not only adhesive property is good for the coating after solidification, and toughness is good, also with splendid fire-retardant
Effect；Epoxy resin is not modified in comparative example 1, the coating poor toughness of preparation, flame retardant effect only reaches HB grades, identical
At a temperature of reach curing time of optimum performance and also increase；Toughening modifying is not carried out to polyamic acid in comparative example 2, and with fragrance
Diamines prepares polyamic acid instead of melamine and is modified to epoxy resin, and the coating toughness of preparation is bad, and flame retardant effect is not
It is good；Dibenzoyl peroxide is not added in comparative example 3, needs to solidify at relatively high temperatures, flame retardant effect is also down to V-1 grades.
Above description is the detailed description for the present invention preferably possible embodiments, but embodiment is not limited to this hair
Bright patent claim, it is all the present invention suggested by technical spirit under completed same changes or modifications change, should all belong to
In the covered the scope of the patents of the present invention.
Claims (7)
1. a kind of anti-flaming dope, which is characterized in that be made in a solvent of the component dissolution of following parts by weight: epoxy resin
100-120 parts, 20-30 parts of modified polyamide acid solution, filler 15-20,10-15 parts of fire-retardant filler, 5-15 parts of pigment, peroxidating
0.5-1 parts of dibenzoyl, N, 0.5-1 parts of accelerine, 0.05-0.1 parts of Imidizole accelerator, amine curing agent and coupling agent
Solution, the equivalent proportion of the epoxy group in reactive hydrogen and epoxy resin in the coating in amine curing agent are 0.45-0.55, institute
The solid for stating coating is 45-50%, and the dosage of the coupling agent solution is the powder being made of filler, fire-retardant filler and pigment
0.5-1%, the coupling agent solution mass concentration be 20-30%；
The modified polyamide acid solution obtains by the following method: by castor oil and diisocyanate by hydroxyl and isocyanates
Base molar ratio is that the ratio mixed dissolution of 1:2-2.2 reacts in N-Methyl pyrrolidone, obtains isocyanate terminated based polyurethanes
Performed polymer, then terminal isocyanate group base polyurethane prepolymer for use as is added in the melamine solution after dimethyl sulfoxide dilutes, institute
The remaining isocyanate base of the terminal isocyanate group base polyurethane prepolymer for use as of addition and the molar ratio of the amido in melamine solution
For 1:3-3.01, reaction obtains the excessive modified cyanurotriamide of amido, and finally acid anhydrides is added in modified cyanurotriamide, is added
Acid anhydrides in carboxyl and modified cyanurotriamide in the molar ratio of remaining amido be 1:0.9-0.99, polyamides must be modified after reaction
Amino acid solution.
2. anti-flaming dope according to claim 1, which is characterized in that the epoxy resin be bisphenol A type epoxy resin and
The composition of one or more of cycloaliphatic epoxy resin；The diisocyanate is toluene di-isocyanate(TDI), hexichol
Methane diisocyanate, terephthalylidene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
3. anti-flaming dope according to claim 1, which is characterized in that the filler is titanium dioxide and/or aluminium hydroxide；
The fire-retardant filler is halogen-free flameproof filler；The pigment is titanium dioxide, carbon black, phthalocyanine blue or iron oxide.
4. anti-flaming dope according to claim 1, which is characterized in that the coupling agent solution is silane coupling agent or metatitanic acid
The dissolution of ester coupling agent is prepared in ethanol.
5. anti-flaming dope according to claim 1, which is characterized in that the solvent is cyclohexanone, butanone and N- methyl pyrrole
The composition of one or more of pyrrolidone.
6. anti-flaming dope according to claim 1, which is characterized in that the acid anhydrides be methyl tetrahydro phthalic anhydride, maleic anhydride,
Methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and 3,3 ', one of 4,4 '-benzophenone tetracid dianhydrides or
Two or more compositions.
7. a kind of preparation method of anti-flaming dope as claimed in any one of claims 1 to 6, which comprises the steps of:
It (1) is the dilution of its 3-4 times N-Methyl pyrrolidone by castor oil weight；Diisocyanate is dissolved in 2-3 weight
In N-Methyl pyrrolidone again, it is slowly added dropwise after N-Methyl pyrrolidone dilutes while stirring in 60-80 DEG C of oil bath
Castor oil solution, the molar ratio of the isocyanate group in the hydroxyl and diisocyanate in castor oil being added dropwise is 1:2-
2.2, continue to be stirred to react 40-60 minutes after being added dropwise to complete, discharges after being cooled to room temperature, obtain terminal isocyanate group polyurethane prepolymer
Body；
It (2) is that the dilution of its 3-4 times dimethyl sulfoxide is placed in 60-80 DEG C of oil bath by melamine weight, side stirring
While being slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as made from step (1), the isocyanate terminated based polyurethanes being added dropwise are pre-
The molar ratio of amido in aggressiveness in remaining isocyanate group and melamine solution is 1:3-3.01, is continued after being added dropwise to complete
Stirring 40-60 minutes, reacts to obtain modified cyanurotriamide, after being cooled to 40-60 DEG C, every 4 hours addition acid anhydrides under stirring, adds altogether
Three times, the acid anhydrides mass ratio being added three times is 3:2:1, remaining amido in the carboxyl and modified cyanurotriamide in acid anhydrides be added
Molar ratio is 1:0.9-0.99, continues to be stirred to react 12-24 hours, obtains modified polyamide acid solution, stand-by after sealing is cooling；
(3) powder mixed by 15-20 parts of fillers, 10-15 parts of fire-retardant fillers and 5-15 parts of pigment is put into high speed mixing
In machine, the coupling agent solution and after mixing for the 0.5-1% that weight is above-mentioned powder is sprayed into high speed mixer, by powder
It is transferred in 60-90 DEG C of baking oven and toasts 1-2 hours, obtain the powder of drying；By 100-120 parts of epoxy resin, above-mentioned drying
In mixed powder and appropriate solvent investment dispersion machine, after stirring 30-40 minutes under the revolving speed of 800-1000r/min, it is transferred to sand
It is sanded 40-60 minutes in grinding machine, obtains the solution of homogeneous, then by modified polyamide acid solution obtained in 20-30 parts of steps (2)
In above-mentioned homogeneous solution investment dispersion machine, disperses under the revolving speed of 800-1000r/min 30-40 minutes, finally press reactive hydrogen
Amine curing agent is added with ratio that the equivalent proportion of epoxy group is 0.45-0.55, and be added 0.5-1 parts of dibenzoyl peroxides,
0.5-1 parts of n,N-Dimethylaniline and 0.05-0.1 parts of Imidizole accelerators simultaneously stir 20-30 minutes, and acquisition solid is 45-
50% mixed liquor, the as described anti-flaming dope.
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| CN102504494A (en) * | 2011-09-22 | 2012-06-20 | 长春工业大学 | Single-component epoxy resin potting compound and preparation method thereof |
| CN103450773A (en) * | 2012-05-30 | 2013-12-18 | 湖南博弈飞装备新材料研究所 | Epoxy acrylate modified high anticorrosion heat insulation paint containing porous ceramic addictive and production method thereof |
| CN105255418A (en) * | 2015-11-04 | 2016-01-20 | 无锡嘉联电子材料有限公司 | Preparation method of high-transparency flexible epoxy resin adhesive |
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| CN102504494A (en) * | 2011-09-22 | 2012-06-20 | 长春工业大学 | Single-component epoxy resin potting compound and preparation method thereof |
| CN103450773A (en) * | 2012-05-30 | 2013-12-18 | 湖南博弈飞装备新材料研究所 | Epoxy acrylate modified high anticorrosion heat insulation paint containing porous ceramic addictive and production method thereof |
| CN105255418A (en) * | 2015-11-04 | 2016-01-20 | 无锡嘉联电子材料有限公司 | Preparation method of high-transparency flexible epoxy resin adhesive |
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