CN106634434A - Fire-retardant paint and preparation method thereof - Google Patents

Fire-retardant paint and preparation method thereof Download PDF

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CN106634434A
CN106634434A CN201611189368.2A CN201611189368A CN106634434A CN 106634434 A CN106634434 A CN 106634434A CN 201611189368 A CN201611189368 A CN 201611189368A CN 106634434 A CN106634434 A CN 106634434A
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parts
anhydride
solution
epoxy resin
fire
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CN106634434B (en
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蓝豆
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Yecai Environmental Protection Technology Jiangsu Co ltd
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Liuzhou Chang Quan Trading Co Ltd
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • 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
    • 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
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses fire-retardant paint and a preparation method thereof, and belongs to the technical field of chemical engineering paint processing. The fire-retardant paint is prepared by dissolving the following ingredients in parts by weight into a solvent: 100 to 120 parts of epoxy resin, 20 to 30 parts of modified polyamide acid solution, 15 to 20 parts of filling materials, 10 to 15 parts of fire-retardant filling materials, 5 to 15 parts of pigments, a coupling agent solution, 0.5 to 1 part of dibenzoyl peroxide, 0.5 to 1 part of N,N-dimethylaniline, 0.05 to 0.1 part of imidazole promoters and amine curing agents, wherein the equivalent ratio of active hydrogen in the amine curing agents to epoxy groups in the epoxy resin in the paint is 0.45 to 0.55. The modified polyamide acid solution prepared from castor oil, isocyanate, tripolycyanamide and anhydride is used for modifying the epoxy resin; the prepared paint has good coating performance and can be fast cured at low temperature; after the curing, the bonding performance of the coating is good; the toughness is good; the fire-retardant effect is good.

Description

A kind of anti-flaming dope and preparation method thereof
【Technical field】
The present invention relates to chemistry painting industry processing technique field, and in particular to a kind of anti-flaming dope and preparation method thereof.
【Background technology】
Humidity, acid-base value and oxygen in air can penetrate into material internal and with material reaction, cause material aging or Deformation, for protection materials, often in material surface spraying protective layer coating.Coating is usually first by matrix resin, filling material Material and firming agent etc. are prepared into coating, by coatings or are sprayed on material surface, and one layer is formed after solidifying under certain condition Glued membrane is attached on material surface, by material and atmospheric isolation, prevents material water suction, oxidation or aging by acid and alkali corrosion.
Using the coating cementability that epoxy resin is prepared as matrix resin it is good, shrinkage factor is low, dimensionally stable, electrical property are excellent Good, resistant to chemical media, configuration easily, process is simple, using temperature it is broad, adaptability relatively strong, toxicity is very low, it is also little to endanger, no Pollution environment etc., all has good stickiness, also sealing, insulation, leakproof, fixation, anti-corrosion, decoration etc. to multiple material Various functions, are referred to as all-purpose adhesive, but toughness is not enough after epoxy resin cure, limits its use range.Polyimides are comprehensive Close one of optimal high-molecular organic material of performance, high temperature resistant up to more than 400 DEG C, -200～300 DEG C of life-time service temperature range, Without sharp melting point, with high insulating properties, good flexible and extremely low dielectric constant, but polyimides adhesive property Difference, and it is insoluble do not melt, not easy processing.
Because the matrix resin in coating is mainly organic resin, easily burn, the fire spreads quickly is difficult to control after catching fire , there is potential threat in system, immeasurable loss, therefore the flame retardant effect after paint solidification are caused to property to the life of people It is one of 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 use for having halogen organic material is unfavorable for the health of environment and human body, is used by restriction, and halogen-free flameproof Filler flame retardant effect is also undesirable.
【The content of the invention】
It is an object of the invention to：For above-mentioned problem, there is provided a kind of anti-flaming dope and preparation method thereof, this Bright coating can under less hardener dose completion of cure, the coated adhesive performance after solidification is good, and toughness is good, also with good Good flame retardant effect.
To achieve these goals, the technical solution used in the present invention is as follows：
A kind of anti-flaming dope, is made up in a solvent of the component dissolving of following parts by weight：Epoxy resin 100-120 parts, Modified polyamide acid solution 20-30 parts, filler 15-20, fire-retardant filler 10-15 parts, pigment 5-15 parts, dibenzoyl peroxide 0.5-1 parts, DMA 0.5-1 parts, Imidizole accelerator 0.05-0.1 parts, amine curing agent and coupling agent solution, institute The equivalent proportion for stating the epoxy radicals in reactive hydrogen in coating in amine curing agent and epoxy resin is 0.45-0.55, the coating Solid be 45-50%, the consumption of the coupling agent solution is the 0.5- of the powder being made up of filler, fire-retardant filler and pigment 1%, the coupling agent solution mass concentration is 20-30%；
The modified polyamide acid solution is obtained by the following method：Oleum Ricini and diisocyanate are pressed into hydroxyl and isocyanide Perester radical mol ratio is 1:The ratio mixed dissolution of 2-2.2 reacts in N-Methyl pyrrolidone, obtains terminal isocyanate group and gathers Urethane performed polymer, then terminal isocyanate group base polyurethane prepolymer for use as is added into the melamine solution Jing after dimethyl sulfoxide dilution In, amido in the remaining isocyanate base of the terminal isocyanate group base polyurethane prepolymer for use as being added and melamine solution rubs You are than being 1:3-3.01, reaction obtains the excessive modified cyanurotriamide of amido, finally anhydride is added in modified cyanurotriamide, institute Carboxyl in the anhydride of addition is 1 with the mol ratio of amido remaining in modified cyanurotriamide:0.9-0.99, must be modified after reaction Polyamic acid solution.
The epoxy resin is in bisphenol A type epoxy resin, diglycidyl ether type epoxy resin and cycloaliphatic epoxy resin One or more compositionss；The diisocyanate is toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, right XDI, own diisocyanate resin or isophorone diisocyanate.
Described filler is titanium dioxide and/or aluminium hydroxide；The fire-retardant filler is halogen-free flameproof filler；The pigment is Titanium dioxide, white carbon black, phthalocyanine blue or ferrum oxide.
The coupling agent solution is that silane coupler or titanate coupling agent dissolving are prepared from ethanol, the coupling Agent solution mass concentration is 20-30%, and the consumption of the coupling agent solution is the powder being made up of filler, fire-retardant filler and pigment 0.5-1%.
The solvent is one or more the compositionss in Ketohexamethylene, butanone and N-Methyl pyrrolidone.
The anhydride is methyl tetrahydro phthalic anhydride, maleic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydro O-phthalic Anhydride and 3,3 ', one or more the compositionss in 4,4 '-benzophenone tetracarboxylic dianhydride.
Present invention also offers a kind of preparation method of described anti-flaming dope, comprises the steps：
(1) it is its 3-4 times of N-Methyl pyrrolidone dilution by Oleum Ricini weight；Diisocyanate is dissolved in into 2-3 In the N-Methyl pyrrolidone of times of weight, Jing N-Methyl pyrrolidone is slowly added dropwise while stirring in 60-80 DEG C of oil bath dilute The mol ratio of the NCO in the castor oil solution after releasing, the hydroxyl in the Oleum Ricini of institute's Deca and diisocyanate is 1: 2-2.2, continues stirring reaction 40-60 minute after being added dropwise to complete, and is cooled to after room temperature and discharges, and obtains isocyanate terminated based polyurethanes pre- Aggressiveness；
(2) it is that its 3-4 times of dimethyl sulfoxide dilution is placed in 60-80 DEG C of oil bath by tripolycyanamide weight, side Stirring side is slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as obtained in step (1), the poly- ammonia of terminal isocyanate group of institute's Deca The mol ratio of the amido in ester performed polymer in remaining NCO and tripolycyanamide is 1:3-3.01, continue after being added dropwise to complete Stirring 40-60 minutes, modified cyanurotriamide is reacted to obtain, after being cooled to 40-60 DEG C, anhydride was added every 4 hours under stirring, added altogether Three times, the anhydride mass ratio of three additions is 3:2:1, add the carboxyl and amido remaining in modified cyanurotriamide in anhydride Mol ratio is 1:0.9-0.99, continues stirring reaction 12-24 hour, obtains modified polyamide acid solution, stand-by after sealing cooling；
(3) powder mixed by 15-20 part fillers, 10-15 parts fire-retardant filler and 5-15 part pigment is put at a high speed In batch mixer, after the coupling agent solution and mix homogeneously of the 0.5-1% that weight is above-mentioned powder is sprayed in high speed mixer, will Powder is transferred to baking 1-2 hours in 60-90 DEG C of baking oven, obtains the powder of drying；By 100-120 part epoxy resin, above-mentioned baking In dry mixed powder and appropriate solvent input dispersion machine, after stirring 30-40 minutes under the rotating speed of 800-1000r/min, turn Enter sand milling 40-60 minutes in sand mill, obtain the solution of homogenizing, then by obtained modified polyamide acid in 20-30 part steps (2) Solution is put in dispersion machine with above-mentioned homogeneous solution, is disperseed 30-40 minutes under the rotating speed of 800-1000r/min, finally by work Property hydrogen and the equivalent proportion of epoxy radicals add amine curing agent for the ratio of 0.45-0.55, and add 0.5-1 part diphenyl peroxide first Acyl, 0.5-1 parts DMA and 0.05-0.1 parts Imidizole accelerator are simultaneously stirred 20-30 minutes, and acquisition solid is 45- 50% mixed liquor, as described anti-flaming dope.
Oleum Ricini is the triglyceride of fatty acid, and hydroxyl average functionality is 2.7, and unsaturated double-bond is also contained in molecule, Oleum Ricini can pass through had hydroxyl, double bond and ester bond carries out various chemical reactions, with good pliability and instead Ying Xing.
Tripolycyanamide is made up of carbamide, and its performance is more biased towards and inorganic material, and three amidos are contained in molecule, is to prepare One of raw material of amide, tripolycyanamide is non-combustible, stable in properties at normal temperatures, and resin matrix is changed using tripolycyanamide Property, improve the flame retardant effect of resin.
Polyamic acid is the presoma of polyimides, with solubility and reactivity, abundant raw material source, and synthesis technique Simply, the resin of excellent can be modified to resin matrix.
In sum, as a result of above-mentioned technical proposal, the invention has the beneficial effects as follows：
(1) present invention is connected to the good castor oil molecule of toughness fire-retardant using the high reaction activity of NCO In the good melamine molecule of effect, the tripolycyanamide after toughening modifying is recycled to prepare the excessive polyamides of anhydride with anhydride reaction Amino acid, polyamic acid is modified to epoxy resin, and the carboxyl and amido in polyamic acid can react with epoxy resin, by castor Oleum Sesami molecule and melamine molecule are grafted on epoxy molecule, meanwhile, in heat curing process, in polyamic acid Carboxyl and amido can also occur cyclodehydration reaction, 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 for adding in modified polyamide acid molecule Changing two formyls can both cause double-bond polymerization also to reduce the temperature of curable epoxide, reduce the consumption of firming agent, reduce reaction temperature Degree, improves reaction rate；
The present invention prepare coating can under less hardener dose completion of cure, the coated adhesive performance after solidification Good, toughness is good, also with good flame retardant effect.
【Specific embodiment】
With reference to the explanation that specific embodiment is made further to carry out to technical scheme.
Embodiment 1
(1) it is its 3 times of N-Methyl pyrrolidone dilution by Oleum Ricini weight；XDI is dissolved in In the N-Methyl pyrrolidone of 3 times of weight, the dilution of Jing N-Methyl pyrrolidone is slowly added dropwise while stirring in 60 DEG C of oil bath Castor oil solution afterwards, the hydroxyl in the Oleum Ricini of institute's Deca is 1 with the mol ratio of NCO in toluene di-isocyanate(TDI): 2, continue stirring reaction 60 minutes after being added dropwise to complete, it is cooled to after room temperature and discharges, obtain terminal isocyanate group base polyurethane prepolymer for use as；
(2) it is that its 4 times of dimethyl sulfoxide dilution is placed in 60 DEG C of oil bath, while stirring by tripolycyanamide weight It is slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as obtained in step (1), the terminal isocyanate group polyurethane prepolymer of institute's Deca The mol ratio of the amido in body in remaining NCO and tripolycyanamide is 1:3, continue to stir 60 minutes after being added dropwise to complete, Modified cyanurotriamide is reacted to obtain, after being cooled to 40 DEG C, methyl tetrahydro phthalic anhydride was added every 4 hours under stirring, added three times, three times altogether The mass ratio of the methyl tetrahydro phthalic anhydride of addition is 3:2:1, the carboxyl and modified cyanurotriamide in the methyl tetrahydro phthalic anhydride for being added Middle remaining amido mol ratio is 1:0.9, continue stirring reaction 24 hours, modified polyamide acid solution is obtained, it is stand-by after sealing cooling；
(3) powder mixed by 15 parts of aluminium hydroxide, 15 parts of halogen-free flameproof fillers and 5 parts of white carbon blacks is put into mixed at a high speed In material machine, after weight is above-mentioned powder 0.5% silane coupler solution and mix homogeneously is sprayed in high speed mixer, will 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 Ketohexamethylene input dispersion machine in, under the rotating speed of 800r/min stir 40 minutes after, proceed to sand in sand mill Mill 60 minutes, obtains the solution of homogenizing, then by obtained modified polyamide acid solution and above-mentioned homogeneous solution in 20 parts of steps (2) In input dispersion machine, disperse under the rotating speed of 800r/min 40 minutes, be finally 0.55 by the equivalent proportion of reactive hydrogen and epoxy radicals Ratio add amine curing agent, and add 1 part of dibenzoyl peroxide, 1 part of DMA and 0.1 part of imidazoles to promote Agent is simultaneously stirred 30 minutes, obtains the mixed liquor that solid is 50%, the as anti-flaming dope described in the embodiment of the present invention 1.
Comparative example 1
The powder mixed by 15 parts of aluminium hydroxide, 15 parts of halogen-free flameproof fillers and 5 parts of white carbon blacks is put into into high speed batch mixing In machine, after weight is above-mentioned powder 0.5% silane coupler solution and mix homogeneously is sprayed in high speed mixer, by powder Material is transferred in 60 DEG C of baking oven and toasts 2 hours, obtains the powder of drying；By 120 parts of bisphenol A type epoxy resins, above-mentioned drying In powder and appropriate Ketohexamethylene input dispersion machine, after stirring 40 minutes under the rotating speed of 800r/min, sand milling in sand mill is proceeded to 60 minutes, the solution of homogenizing is obtained, finally add amine curing agent in the ratio that the equivalent proportion of reactive hydrogen and epoxy radicals is 0.70, and Add 1 part of dibenzoyl peroxide, 1 part of DMA and 0.1 part of Imidizole accelerator and stir 30 minutes, obtain solid Part for 50% mixed liquor, the anti-flaming dope described in comparative example 1 as of the present invention.
Embodiment 2
(1) it is its 4 times of N-Methyl pyrrolidone dilution by Oleum Ricini weight；'-diphenylmethane diisocyanate is dissolved In the N-Methyl pyrrolidone of 2 times of weight, Jing N-Methyl pyrrolidone is slowly added dropwise while stirring in 80 DEG C of oil bath dilute In castor oil solution after releasing, the hydroxyl in the Oleum Ricini of institute's Deca and '-diphenylmethane diisocyanate NCO mole Than for 1:2.2, continue stirring reaction 40 minutes after being added dropwise to complete, it is cooled to after room temperature and discharges, obtain isocyanate terminated based polyurethanes Performed polymer；
(2) it is that its 3 times of dimethyl sulfoxide dilution is placed in 80 DEG C of oil bath, while stirring by tripolycyanamide weight It is slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as obtained in step (1), the terminal isocyanate group polyurethane prepolymer of institute's Deca The mol ratio of the amido in body in remaining NCO and tripolycyanamide is 1:3.01, continue to stir 40 points after being added dropwise to complete Clock, obtains modified cyanurotriamide, after being cooled to 60 DEG C, adds by methyl tetrahydrophthalic anhydride and first every 4 hours under stirring Base hexahydrophthalic anhydride is 1 by weight:1 mixed acid anhydride, adds altogether three times, the mass ratio of the mixed acid anhydride of three additions For 3:2:1, the carboxyl in the mixed acid anhydride for being added is 1 with the mol ratio of remaining amido in modified cyanurotriamide:0.99, continue Stirring reaction 12 hours, obtains modified polyamide acid solution, stand-by after sealing cooling；
(3) by weight it is 2 by perlite and aluminium hydroxide:1 ratio mixing obtains mixed fillers, will be by 20 parts of mixing The powder that filler, 10 parts of halogen-free flameproof fillers and 15 parts of titanium dioxide are mixed is put in high speed mixer, to high speed batch mixing After weight is above-mentioned powder 1% coupling agent solution and mix homogeneously 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 are than being 2:1 ratio mixing epoxy resin, it is above-mentioned dry powder and appropriate butanone input dispersion machine in, in 1000r/ After stirring 30 minutes under the rotating speed of min, sand milling 40 minutes in sand mill are proceeded to, the solution of homogenizing is obtained, then by 30 parts of steps (2) In in obtained modified polyamide acid solution and above-mentioned homogeneous solution input dispersion machine, disperse 30 under the rotating speed of 1000r/min Minute, finally amine curing agent is added in the ratio that the equivalent proportion of reactive hydrogen and epoxy radicals is 0.45, and add 0.5 part of peroxidating Dibenzoyl, 0.5 part of DMA and 0.05 part of Imidizole accelerator are simultaneously stirred 20 minutes, and it is 45% to obtain solid Mixed liquor, the as anti-flaming dope described in the embodiment of the present invention 2.
Comparative example 2
(1) it is that its 3 times of dimethyl sulfoxide dilution is placed in 60 DEG C of oil bath by m-diaminobenzene. weight, stirring is lower every It is 1 to add every 4 hours by methyl tetrahydrophthalic anhydride and methylhexahydrophthalic anhydride by weight:1 mixed acid Acid anhydride, adds altogether three times, and the mass ratio of the mixed acid anhydride of three additions is 3:2:1, the carboxyl and isophthalic in the mixed acid anhydride for being added Amido mol ratio in diamidogen is 1:0.99, continue stirring reaction 12 hours, polyamic acid solution is obtained, it is stand-by after sealing cooling；
(2) by weight it is 2 by perlite and aluminium hydroxide:1 ratio mixing obtains mixed fillers, will be by 20 parts of mixing The powder that filler, 10 parts of halogen-free flameproof fillers and 15 parts of titanium dioxide are mixed is put in high speed mixer, to high speed batch mixing After weight is above-mentioned powder 1% coupling agent solution and mix homogeneously 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 are than being 2:1 ratio mixing epoxy resin, it is above-mentioned dry powder and appropriate butanone input dispersion machine in, in 1000r/ After stirring 30 minutes under the rotating speed of min, sand milling 40 minutes in sand mill are proceeded to, the solution of homogenizing is obtained, then by 30 parts of steps (1) In in obtained polyamic acid solution and above-mentioned homogeneous solution input dispersion machine, disperse 30 minutes under the rotating speed of 1000r/min, Finally amine curing agent is added in the ratio that the equivalent proportion of reactive hydrogen and epoxy radicals is 0.45, and add 0.5 part of diphenyl peroxide Formyl, 0.5 part of DMA and 0.05 part of Imidizole accelerator are simultaneously stirred 20 minutes, obtain the mixing that solid is 45% Liquid, the anti-flaming dope described in comparative example 2 as of the present invention.
Embodiment 3
(1) it is its 3.5 times of N-Methyl pyrrolidone dilution by Oleum Ricini weight；Isophorone diisocyanate is molten Solution is slowly added dropwise while stirring Jing N- crassitudes in the N-Methyl pyrrolidone of 2.5 times of weight, in 70 DEG C of oil bath Castor oil solution after ketone dilution, the hydroxyl in the Oleum Ricini of institute's Deca and the NCO in isophorone diisocyanate Mol ratio be 1:2.1, continue stirring reaction 50 minutes after being added dropwise to complete, it is cooled to after room temperature and discharges, obtain terminal isocyanate group Base polyurethane prepolymer for use as；
(2) it is that its 3.5 times of dimethyl sulfoxide dilution is placed in 70 DEG C of oil bath by tripolycyanamide weight, side stirring While terminal isocyanate group base polyurethane prepolymer for use as obtained in being slowly dropped into step (1), the isocyanate terminated based polyurethanes for being added are pre- Amido in remaining isocyanate base in aggressiveness and tripolycyanamide and mol ratio be 1:3, continue to stir 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 ' is added every 4 hours under stirring, 4,4 '-benzophenone tetracarboxylic dianhydride, altogether plus three times, and the 3,3 ', 4 of three additions, 4 '-benzophenone tetracarboxylic dianhydride mass ratio is 3:2:1, 3,3 ' for being added, the carboxyl in 4,4 '-benzophenone tetracarboxylic dianhydride is 1 with remaining amido mol ratio in modified cyanurotriamide: 0.95 continues stirring reaction 20 hours, obtains modified polyamide acid solution, stand-by after sealing cooling；
(3) powder mixed by 17 parts of perlites, 13 parts of halogen-free flameproof fillers and 10 parts of phthalocyanine blues is put at a high speed In batch mixer, after weight is above-mentioned powder 0.6% coupling agent solution and mix homogeneously is sprayed in high speed mixer, by powder Material is transferred in 80 DEG C of baking oven and toasts 1.5 hours, obtains the powder of drying；By 110 parts of cycloaliphatic epoxy resins, above-mentioned drying In powder and appropriate N-Methyl pyrrolidone input dispersion machine, after stirring 35 minutes under the rotating speed of 900r/min, sand milling is proceeded to Sand milling 50 minutes in machine, obtain the solution of homogenizing, then that obtained modified polyamide acid solution in 25 parts of steps (2) is equal with above-mentioned In matter solution input dispersion machine, disperse under the rotating speed of 900r/min 35 minutes, finally by reactive hydrogen and the equivalent proportion of epoxy radicals For 0.50 ratio add amine curing agent, and add 0.7 part of dibenzoyl peroxide, 0.6 part of DMA and 0.07 part of Imidizole accelerator is simultaneously stirred 25 minutes, obtains the mixed liquor that solid is 48%, the fire-retardant painting of as described embodiment 3 Material.
Comparative example 3
As different from Example 3, comparative example 3 does not add dibenzoyl peroxide.
Test respectively coating prepared by various embodiments of the present invention and comparative example solidification temperature when being optimal performance and Hardening time carries out contrast test, while its performance of preparation sample test after coating is solidified under optimum condition of cure, test As a result it is as shown in table 1.
Performance test includes adhesive property test, fire resistance test, pliability test,
Method of testing is as follows respectively：
(1) adhesive property test is that coating is coated on base material after completion of cure, 50 × 100 millimeters of the model in coating The interior grid for drawing 15 × 15 millimeters is enclosed, then by adhesive tape in the coating for drawing grid, to adhesive plaster forcing tightly for 500g is applied, On the direction of vertical coating surface, adhesive tape is quickly torn, check that grid is completely qualified, various disbondings are unqualified；
(2) fire resistance method of testing is to be tested according to UL94 standards；
(3) pliability method of testing is, into thin film, its elongation at break to be tested after completion of cure by coating preparation.
Table 1：Anti-flaming dope the performance test results prepared by the embodiment of the present invention and comparative example
Show through above-mentioned contrast test result, utilize by Oleum Ricini, isocyanates, melamine in various embodiments of the present invention Modified polyamide acid solution prepared by amine and anhydride is modified to epoxy resin, and the coating of preparation has good coating Can, coating can express delivery solidification at low temperature, 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 levels, identical Temperature is issued to and also increases the hardening time of optimum performance；Toughening modifying is not carried out to polyamic acid in comparative example 2, and with fragrance Diamidogen replacement tripolycyanamide prepares polyamic acid and epoxy resin is modified, and the coating toughness of preparation is not good, 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 levels.
Described above is the detailed description for the present invention preferably possible embodiments, but embodiment is not limited to this Bright patent claim, the equal change completed under the technical spirit suggested by all present invention or modification change, all should belong to Cover the scope of the claims in the present invention.

Claims (7)

1. a kind of anti-flaming dope, it is characterised in that be made up in a solvent of the component dissolving of following parts by weight：Epoxy resin 100-120 parts, modified polyamide acid solution 20-30 parts, filler 15-20, fire-retardant filler 10-15 parts, pigment 5-15 parts, peroxidating Dibenzoyl 0.5-1 parts, N, accelerine 0.5-1 parts, Imidizole accelerator 0.05-0.1 parts, amine curing agent and coupling agent The equivalent proportion of the epoxy radicals in solution, the reactive hydrogen in the coating in amine curing agent and epoxy resin is 0.45-0.55, institute The solid for stating coating is 45-50%, and the consumption of the coupling agent solution is the powder being made up of filler, fire-retardant filler and pigment 0.5-1%, the coupling agent solution mass concentration be 20-30%；
The modified polyamide acid solution is obtained by the following method：Oleum Ricini and diisocyanate are pressed into hydroxyl and isocyanates Base mol ratio is 1:The ratio mixed dissolution of 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 Jing after dimethyl sulfoxide dilution, institute The mol ratio of the amido in the remaining isocyanate base and melamine solution of the terminal isocyanate group base polyurethane prepolymer for use as of addition For 1:3-3.01, reaction obtains the excessive modified cyanurotriamide of amido, finally anhydride is added in modified cyanurotriamide, is added Anhydride in carboxyl and modified cyanurotriamide in the mol ratio of remaining amido be 1:0.9-0.99, must be modified polyamides after reaction Amino acid solution.
2. anti-flaming dope according to claim 1, it is characterised in that the epoxy resin is bisphenol A type epoxy resin, contracting One or more compositionss in water ethoxylated glycerol type epoxy resin and cycloaliphatic epoxy resin；The diisocyanate is Toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, terephthalylidene diisocyanate, own diisocyanate resin or different Fo Er Ketone diisocyanate.
3. anti-flaming dope according to claim 1, it is characterised in that described filler is titanium dioxide and/or aluminium hydroxide； The fire-retardant filler is halogen-free flameproof filler；The pigment is titanium dioxide, white carbon black, phthalocyanine blue or ferrum oxide.
4. anti-flaming dope according to claim 1, it is characterised in that the coupling agent solution is silane coupler or metatitanic acid The dissolving of ester coupling agent is prepared from ethanol.
5. anti-flaming dope according to claim 1, it is characterised in that the solvent is Ketohexamethylene, butanone and N- methyl pyrroles One or more compositionss in pyrrolidone.
6. anti-flaming dope according to claim 1, it is characterised in that the anhydride be methyl tetrahydro phthalic anhydride, maleic anhydride, Methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and 3,3 ', one kind in 4,4 '-benzophenone tetracarboxylic dianhydride or Two or more compositionss.
7. the preparation method of the anti-flaming dope described in a kind of any one of claim 1 to 6, it is characterised in that comprise the steps：
(1) it is its 3-4 times of N-Methyl pyrrolidone dilution by Oleum Ricini weight；Diisocyanate is dissolved in into 2-3 weight In N-Methyl pyrrolidone again, it is slowly added dropwise while stirring in 60-80 DEG C of oil bath Jing after N-Methyl pyrrolidone dilution Castor oil solution, the mol ratio of the NCO in the hydroxyl in the Oleum Ricini of institute's Deca and diisocyanate is 1:2- 2.2, continue stirring reaction 40-60 minute after being added dropwise to complete, it is cooled to after room temperature and discharges, obtain terminal isocyanate group polyurethane prepolymer Body；
(2) it is that its 3-4 times of dimethyl sulfoxide dilution is placed in 60-80 DEG C of oil bath by tripolycyanamide weight, side stirring While being slowly dropped into terminal isocyanate group base polyurethane prepolymer for use as obtained in step (1), the isocyanate terminated based polyurethanes of institute's Deca are pre- The mol ratio of the amido in aggressiveness in remaining NCO and tripolycyanamide is 1:3-3.01, continues to stir after being added dropwise to complete 40-60 minutes, modified cyanurotriamide is reacted to obtain, after being cooled to 40-60 DEG C, anhydride was added every 4 hours under stirring, Jia three altogether Secondary, the anhydride mass ratio of three additions is 3:2:1, add the carboxyl in anhydride to rub with amido remaining in modified cyanurotriamide You are than being 1:0.9-0.99, continues stirring reaction 12-24 hour, obtains modified polyamide acid solution, stand-by after sealing cooling；
(3) powder mixed by 15-20 part fillers, 10-15 parts fire-retardant filler and 5-15 part pigment is put into into high speed batch mixing In machine, after the coupling agent solution and mix homogeneously of the 0.5-1% that weight is above-mentioned powder is sprayed in high speed mixer, by powder Baking 1-2 hours in 60-90 DEG C of baking oven are transferred to, the powder of drying is obtained；By 100-120 part epoxy resin, above-mentioned drying In mixed powder and appropriate solvent input dispersion machine, after stirring 30-40 minutes under the rotating speed of 800-1000r/min, sand is proceeded to Sand milling 40-60 minutes in grinding machine, the solution of homogenizing is obtained, then by obtained modified polyamide acid solution in 20-30 part steps (2) In above-mentioned homogeneous solution input dispersion machine, disperse 30-40 minutes under the rotating speed of 800-1000r/min, finally by reactive hydrogen Add amine curing agent for the ratio of 0.45-0.55 with the equivalent proportion of epoxy radicals, and add 0.5-1 part dibenzoyl peroxides, 0.5-1 parts DMA and 0.05-0.1 parts Imidizole accelerator are simultaneously stirred 20-30 minutes, and acquisition solid is 45- 50% mixed liquor, as described anti-flaming dope.
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