CN108017991A - Fire-retardant, waterproof and the polyurethane coating of low VOC - Google Patents

Fire-retardant, waterproof and the polyurethane coating of low VOC Download PDF

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CN108017991A
CN108017991A CN201711419973.9A CN201711419973A CN108017991A CN 108017991 A CN108017991 A CN 108017991A CN 201711419973 A CN201711419973 A CN 201711419973A CN 108017991 A CN108017991 A CN 108017991A
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retardant
fire
acid
waterproof
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段宝荣
翟智宇
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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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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
    • C09D5/18—Fireproof paints including high temperature resistant paints

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  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Paints Or Removers (AREA)
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Abstract

The invention discloses fire-retardant,Polyurethane coating of waterproof and low VOC and preparation method thereof,Trimethyl silanol 3.5g and methyl ethyl ketone 16.8g is added into performed polymer A,3.5h is reacted under the conditions of 75 DEG C,Add modification manganese hypophosphite 7.2g prepared by step (1),4 Carboxybenzeneboronic acid 3.6g and nitrilotriacetic acid 2.8g,85 DEG C of reaction temperature,Reaction time 1h,Add triethylamine 14.5g and carry out neutralization reaction 60min,Add 4,8 dihydroxy quinoline, 2 formic acid 2.8g,Water 110g is stirred emulsification 1h,Obtain fire-retardant,Waterproof and the polyurethane coating of low VOC,Prepared is fire-retardant,Waterproof and the polyurethane coating environmental protection of low VOC,It is cheap,It is widely used in wall,Furniture,Ironware surface,As plastics,Glass,Papermaking,The adhesive of weaving.

Description

Fire-retardant, waterproof and the polyurethane coating of low VOC
The application is the polyurethane of a kind of entitled fire-retardant, waterproof of Application No. 201610761163.0 and low VOC The divisional application of the patent application of preparation method for coating.
Technical field
The present invention relates to a kind of preparation method of polyurethane coating, more particularly to fire-retardant, waterproof and low VOC polyurethane coatings Preparation method.
Background technology
Polyurethane is mainly used in the fields such as leather finish, textile printing and dyeing, paper-making industry, building coating and adhesive.By In the coating and paint that are sprayed at external and internal wall, furniture or ironware surface, directly or indirectly contacted with the mankind, therefore have Poison, harmful coating moment threaten people's health.Further, since the field used often contacts sunlight, and in sunray Containing the ultraviolet light being largely harmful to colored objects, its wavelength about 290~460nm, these harmful ultraviolet lights pass through chemically Redox, make coating occur color change.
Polyurethane is polymerize makees catalyst frequently with dibutyl tin laurate, but since Heavy Metal, Sn is with polyurethane Degraded and damage to environment, how dibutyltindilaurate catalyzed remaining tin is fixed, reduce polyurethane Coating residues have become a technical barrier to the extent of injury of environment.
Aqueous polyurethane（Also known as water-based polyurethane）It is a kind of poly- containing hydrophilic radical in the strand of polyurethane Urethane resin, is had very strong compatibility with water, can be allowed to disperse and formed stable system in water using specific technique. Aqueous polyurethane is mainly used in leather finish, textile printing and dyeing, paper-making industry, building coating, adhesive and steel moulder's paint etc., Involved is nearly all combustible material, these materials necessarily become the peace for triggering fire when in use as not fire retardant treated Full hidden danger.Aqueous polyurethane it is flame-retarded, be one of important directions of functionalization of waterborne polyurethane.
Polyurethane coating, i.e. carbamate coating, it, which is applied in membrane molecule, contains a considerable amount of polyurethane ester bonds. Polyurethane coating, also containing urea bond, ehter bond, ester bond, allophanic acid ester bond, is a kind of function admirable, answers in addition to containing ammonia ester bond Refer to volatilizable in solvent based coating and human contact with extensive coating VOC (Volatile Organic Compounds) Or the solvent of disease can be caused after suction.Often contain VOC in polyurethane coating.Health hazards of the VOC to human body is very big, it Not only there is corrosion function to skin, and have stimulation and destruction to human central nervous system, blood forming organ, respiratory system Effect, can cause the symptom such as headache, nausea, uncomfortable in chest, weak, vomiting, can twitch when serious, even death of going into a coma.It is global annual Because using toxic chemical solvent based coating and caused by the economic loss brought of environmental disruption and human injury be up to tens billion of U.S.s Member.Therefore, main coating material production state has launched respectively the exhaust emission regulation of limitation VOC in the world.Such as in the world On, according to European Community's ecological mark product --- the regulation of related VOC limitations, the most commonly used a kind of painting of people's house decoration Material is 30 g/L, the coating state compulsory standard in China《Limits of harmful substances in indoor decorating and refurnishing materials interior wall coating》 Regulation VOC must not exceed 200 g/L.Therefore, the direction that low VOC polyurethane coatings are polyurethane coating development is developed.
The content of the invention
The technical problem to be solved by the invention is to provide the polyurethane coating preparation method of fire-retardant, waterproof and low VOC, And effectively fixed its toxicity of mitigation is carried out by selecting catalyst and improves polymerization yield rate, reduce VOC content.
Technical scheme is as follows：
1. fire-retardant, waterproof and the polyurethane coating preparation method of low VOC, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 11.2g, boric acid 25.6g, diethanol amine 28g, hexaphenoxycyclotriphosphazene 7.2g and phloridzin 2.8g and water 65g, adjust pH To 4,80 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.6g, 70 DEG C of stirring reaction 1h, obtain modified time Manganese phosphate；
（2）, with blender, condenser pipe, thermometer 250ml there-necked flasks in add azoformic acid dibenzyl ester 0.25g, poly- Tetrahydrofuran ether glycol 72g and hexamethylene diisocyanate 18g, reacts 1h at 70 DEG C, obtains base polyurethane prepolymer for use as A, institute The molecular weight for stating polytetrahydrofuran ether glycol is 500；
（3）, the equal three nitrogen borine of 0.68g hexahydros and 8.8g methyl ethyl ketone are added into performed polymer A, react 3.0h under the conditions of 70 DEG C, Add 1g steps（1）Modification manganese hypophosphite, 3.2g4- Carboxybenzeneboronic acids and the N- hydroxy thiosuccinimide 3.5g of preparation, instead Temperature 70 C is answered, reaction time 1h, adds 7.8g triethylamines and carry out neutralization reaction 70min, water 70g is stirred emulsification 1h, obtains To fire-retardant, waterproof and the polyurethane coating of low VOC.
2. fire-retardant, waterproof and the polyurethane coating preparation method of low VOC, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 5.2g, boric acid 8g, diethanol amine 18g, benzilic acid 14g and 4- hydroxyphenethylamine 2.9g and water 70g, adjust pH to 4, 60 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.6g, 70 DEG C of stirring reaction 2h, obtain modified hypophosphorous acid Manganese；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in add；Tetramethyl ammonium chloride 0.74g, poly- four Hydrogen furans ether glycol 70g and hexamethylene diisocyanate 30g, react 4h at 80 DEG C, obtain base polyurethane prepolymer for use as A, described The molecular weight of polytetrahydrofuran ether glycol is 1000；
（3）, into performed polymer A add trimethyl silanol 3.5g and methyl ethyl ketone 16.8g, 3.5h is reacted under the conditions of 75 DEG C, add Step（1）Modification manganese hypophosphite 7.2g, 4- Carboxybenzeneboronic acid 3.6g and nitrilotriacetic acid 2.8g of preparation, 85 DEG C of reaction temperature, instead 1h between seasonable, adds triethylamine 14.5g and carries out neutralization reaction 60min, add 4,8- dihydroxy quinoline -2- formic acid 2.8g, water 110g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
3. fire-retardant, light resistance and the polyurethane coating preparation method of low VOC, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 8.2g, boric acid 26.4g, diethanol amine 22.6g, hexamethylolmelamine 13g and benzilic acid 2.8g and water 55g, PH to 4 is adjusted, is heated to 80 DEG C, stirring reaction 1h, EDTAP dipotassium ethylene diamine tetraacetate 0.9g, 60 DEG C of stirring reaction 2h, are modified Manganese hypophosphite；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in, add stearyl trimethyl ammonium chloride 0.52g, polytetrahydrofuran ether glycol 80g and hexamethylene diisocyanate 36g, react 2h at 70 DEG C, it is pre- to obtain polyurethane Aggressiveness A, the molecular weight of the polytetrahydrofuran ether glycol is 1000；
（3）, nitrilotriacetic acid 2.6g and methyl ethyl ketone 21.4g is added into performed polymer A, react 2.5h under the conditions of 80 DEG C, add step Suddenly（1）Modification manganese hypophosphite 7.9g, 4- Carboxybenzeneboronic acid 4.8g and diphenyl methane dimaleimide 3.6g of preparation, reaction temperature 85 DEG C, reaction time 3.5h of degree, adds triethylamine 16.2g and carries out neutralization reaction 40min, add sodium salicylate 3.2g, water 160g Stirring carries out emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
4. fire-retardant, waterproof and the polyurethane coating preparation method of low VOC, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 6.4g, boric acid 14g, diethanol amine 23.2g, hexaphenoxycyclotriphosphazene 9.5g and phloridzin 5.5g and water 80g, adjust pH and arrive 4,80 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.5g, 50 DEG C of stirring reaction 3h, obtain modified phosphorus Sour manganese；
（2）, with blender, condenser pipe, thermometer 250ml there-necked flasks in add triethyl aluminum 0.35g, PolyTHF Ether glycol 60g and hexamethylene diisocyanate 20g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, the poly- tetrahydrochysene The molecular weight of furans ether glycol is 1000；
（3）, nitrilotriacetic acid 0.52g and methyl ethyl ketone 9.2g is added into performed polymer A, react 3.5h under the conditions of 70 DEG C, add 4g Step（1）Modification manganese hypophosphite, 3.6g4- Carboxybenzeneboronic acids and the semicarbazides 2.6g of preparation, 80 DEG C of reaction temperature, reaction time 1h, adds 7.5g triethylamines and carries out neutralization reaction 30min, adds water 70g and is stirred emulsification 1h, obtain fire-retardant, waterproof with it is low The polyurethane coating of VOC.
5. fire-retardant, waterproof and the polyurethane coating preparation method of low VOC, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 3.2g, boric acid 9g, diethanol amine 36g, melamine cyanurate 15g and benzilic acid 3.2g and water 80g, adjust pH To 4,70 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.8g, 70 DEG C of stirring reaction 2h, obtain modified time Manganese phosphate；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in add isopropylmagnesium chloride 0.94g, poly- tetrahydrochysene Furans ether glycol 100g and hexamethylene diisocyanate 50g, react 1h at 90 DEG C, obtain base polyurethane prepolymer for use as A, described poly- The molecular weight of tetrahydrofuran ether glycol is 2000；
（3）, into performed polymer A add trimethyl silanol 4.2g and methyl ethyl ketone 25.5g, 3.5h is reacted under the conditions of 75 DEG C, add Step（1）Modification manganese hypophosphite 9.9g, 4- Carboxybenzeneboronic acid 7.4g and tetraethylenepentamine 2.8g of preparation, 95 DEG C of reaction temperature, Reaction time 1h, adds triethylamine 15.5g and carries out neutralization reaction 60min, add 4,8- dihydroxy quinoline -2- formic acid 3.7g, water 75g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
Advantage of the invention is that：
（1）Azoformic acid dibenzyl ester, tetramethyl ammonium chloride, stearyl trimethyl ammonium chloride, triethyl aluminum and isopropyl chlorination Magnesium substitutes traditional advantage and is tin compound catalyst；
（2）N- hydroxy thiosuccinimides, nitrilotriacetic acid, diphenyl methane dimaleimide, semicarbazides, tetraethylenepentamine Polymer is crosslinked, improves the defects of traditional HDI polyurethane intensity is not high, while reactant is chelated, is increased Absorption small molecule, reduces the VOC of release；
（3）The equal three nitrogen borine of hexahydro, trimethyl silanol, nitrilotriacetic acid are not only with chain extender but also with light resistance；
（4）Hexaphenoxycyclotriphosphazene, melamine cyanurate, hexamethylolmelamine have fire retardation, root skin Glucoside, benzilic acid improve its anti-flammability to fire-retardant carry out synergy.
Embodiment
The present invention is further illustrated with reference to example.
Example one
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 11.2g, boric acid 25.6g, diethanol amine 28g, hexaphenoxycyclotriphosphazene 7.2g and phloridzin 2.8g and water 65g, adjust pH To 4,80 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.6g, 70 DEG C of stirring reaction 1h, obtain modified time Manganese phosphate；
（2）, with blender, condenser pipe, thermometer 250ml there-necked flasks in add azoformic acid dibenzyl ester 0.25g, poly- Tetrahydrofuran ether glycol 72g and hexamethylene diisocyanate 18g, reacts 1h at 70 DEG C, obtains base polyurethane prepolymer for use as A, institute The molecular weight for stating polytetrahydrofuran ether glycol is 500；
(3）, the equal three nitrogen borine of 0.68g hexahydros and 8.8g methyl ethyl ketone are added into performed polymer A, react 3.0h under the conditions of 70 DEG C, Add 1g steps（1）Modification manganese hypophosphite, 3.2g4- Carboxybenzeneboronic acids and the N- hydroxy thiosuccinimide 3.5g of preparation, instead Temperature 70 C is answered, reaction time 1h, adds 7.8g triethylamines and carry out neutralization reaction 70min, water 70g is stirred emulsification 1h, obtains To fire-retardant, waterproof and the polyurethane coating of low VOC.
Example two
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 5.2g, boric acid 8g, diethanol amine 18g, benzilic acid 14g and 4- hydroxyphenethylamine 2.9g and water 70g, adjust pH to 4, 60 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.6g, 70 DEG C of stirring reaction 2h, obtain modified hypophosphorous acid Manganese；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in add；Tetramethyl ammonium chloride 0.74g, poly- four Hydrogen furans ether glycol 70g and hexamethylene diisocyanate 30g, react 4h at 80 DEG C, obtain base polyurethane prepolymer for use as A, described The molecular weight of polytetrahydrofuran ether glycol is 1000；
（3）, into performed polymer A add trimethyl silanol 3.5g and methyl ethyl ketone 16.8g, 3.5h is reacted under the conditions of 75 DEG C, add Step（1）Modification manganese hypophosphite 7.2g, 4- Carboxybenzeneboronic acid 3.6g and nitrilotriacetic acid 2.8g of preparation, 85 DEG C of reaction temperature, instead 1h between seasonable, adds triethylamine 14.5g and carries out neutralization reaction 60min, add 4,8- dihydroxy quinoline -2- formic acid 2.8g, water 110g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
Example three
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 8.2g, boric acid 26.4g, diethanol amine 22.6g, hexamethylolmelamine 13g and benzilic acid 2.8g and water 55g, PH to 4 is adjusted, is heated to 80 DEG C, stirring reaction 1h, EDTAP dipotassium ethylene diamine tetraacetate 0.9g, 60 DEG C of stirring reaction 2h, are modified Manganese hypophosphite；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in, add stearyl trimethyl ammonium chloride 0.52g, polytetrahydrofuran ether glycol 80g and hexamethylene diisocyanate 36g, react 2h at 70 DEG C, it is pre- to obtain polyurethane Aggressiveness A, the molecular weight of the polytetrahydrofuran ether glycol is 1000；
（3）, nitrilotriacetic acid 2.6g and methyl ethyl ketone 21.4g is added into performed polymer A, react 2.5h under the conditions of 80 DEG C, add step Suddenly（1）Modification manganese hypophosphite 7.9g, 4- Carboxybenzeneboronic acid 4.8g and diphenyl methane dimaleimide 3.6g of preparation, reaction temperature 85 DEG C, reaction time 3.5h of degree, adds triethylamine 16.2g and carries out neutralization reaction 40min, add sodium salicylate 3.2g, water 160g Stirring carries out emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
Example four
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 6.4g, boric acid 14g, diethanol amine 23.2g, hexaphenoxycyclotriphosphazene 9.5g and phloridzin 5.5g and water 80g, adjust pH and arrive 4,80 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.5g, 50 DEG C of stirring reaction 3h, obtain modified phosphorus Sour manganese；
（2）, with blender, condenser pipe, thermometer 250ml there-necked flasks in add triethyl aluminum 0.35g, PolyTHF Ether glycol 60g and hexamethylene diisocyanate 20g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, the poly- tetrahydrochysene The molecular weight of furans ether glycol is 1000；
（3）, nitrilotriacetic acid 0.52g and methyl ethyl ketone 9.2g is added into performed polymer A, react 3.5h under the conditions of 70 DEG C, add 4g Step（1）Modification manganese hypophosphite, 3.6g4- Carboxybenzeneboronic acids and the semicarbazides 2.6g of preparation, 80 DEG C of reaction temperature, reaction time 1h, adds 7.5g triethylamines and carries out neutralization reaction 30min, adds water 70g and is stirred emulsification 1h, obtain fire-retardant, waterproof with it is low The polyurethane coating of VOC.
Example five
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 3.2g, boric acid 9g, diethanol amine 36g, melamine cyanurate 15g and benzilic acid 3.2g and water 80g, adjust pH To 4,70 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.8g, 70 DEG C of stirring reaction 2h, obtain modified time Manganese phosphate；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in add isopropylmagnesium chloride 0.94g, poly- tetrahydrochysene Furans ether glycol 100g and hexamethylene diisocyanate 50g, react 1h at 90 DEG C, obtain base polyurethane prepolymer for use as A, described poly- The molecular weight of tetrahydrofuran ether glycol is 2000；
（3）, into performed polymer A add trimethyl silanol 4.2g and methyl ethyl ketone 25.5g, 3.5h is reacted under the conditions of 75 DEG C, add Step（1）Modification manganese hypophosphite 9.9g, 4- Carboxybenzeneboronic acid 7.4g and tetraethylenepentamine 2.8g of preparation, 95 DEG C of reaction temperature, Reaction time 1h, adds triethylamine 15.5g and carries out neutralization reaction 60min, add 4,8- dihydroxy quinoline -2- formic acid 3.7g, water 75g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
Beneficial effects of the present invention are further illustrated below by relevant experimental data：PU-1 is to be selected from Wuxi City great waves The polyurethane antiseptic finishing paint of Chemical Co., Ltd..
Table one is fire-retardant, the polyurethane coating institute filming performance of waterproof and low VOC
Experimental group Example one Example two Example three Example four Example five PU-1
Hardness B B B B B B
Adhesive force/level 3 3 2 2 2 2
Pliability/mm 2 3 3 3 3 2
From table two it can be found that from film outward appearance, hardness, adhesive force, flexibility better performances.
Table two is fire-retardant, the mechanical property of film obtained by the polyurethane coating of water proofing property and low VOC
Experimental group Example one Example two Example three Example four Example five
Elongation at break/% 158 169 145 132 198
Tensile strength/MPa 6.3 5.9 5.6 7.8 6.5
Abrasion resisting/level 4.0 3.5 4.5 4.5 4.0
Two middle finger object detection method of table refers to（Auspicious leather finish physical and chemical inspection [M] the China Light Industry Press of Jiang Wei, 1999）, film elongation at break, tensile strength, wear-resistant performance are preferable obtained by coating of the present invention.
Anti-flammability is to pass through smoke density method（Maximum smoke density, reach the maximum smoke density time）, oxygen index (OI), vertical combustion refer to Mark（Flaming combustion time, glowing time）To weigh, elongation at break characterizes its mechanical property.
Table three is fire-retardant, the anti-flammability of film obtained by the polyurethane coating of light resistance and low VOC
Example one Example two Example three Example four Example five
Maximum smoke density 13 27 26 17 8
Reach maximum smoke density time/s 180 195 195 240 180
Oxygen index (OI) 28.6 26.9 25.9 27.8 27.6
Flaming combustion time/s 8.5 8.8 12.6 10.9 9.2
Glowing time/s 0.1 0.2 0.3 0.4 0
The detection of three indices of table is respectively according to following standard：Smoke density is measured according to GB8323-2008, and oxygen index (OI) uses GB/T5454-1997《Textile combustion performance test-oxygen index method》Measure；Flaming combustion time and glowing time be by GB/T 5455-1997《Textile combustion can test-normal beam technique》To measure.
As shown in Table 3, when the present invention is burnt with sunproof polyurethane coating with adhesive gained film, maximum smoke density is shown Writing reduces, and reaches the maximum smoke density time and significantly extends, oxygen index (OI) significantly improves, and burning time is obviously shortened.
Tested according to limits of harmful substances standard in GB24408-2009 exterior coatings:
Table four is fire-retardant, the polyurethane coating VOC of waterproof and low VOC
Example one Example two Example three Example four Example five
Volatile organic compounds（VOC）Content 116 122 145 156 117
Table five is fire-retardant, the wherein important performance of the polyurethane coating of waterproof and low VOC
Example one Example two Example three Example four Example five
Impermeability（0.3Mpa, 30min） It is non-leakage It is non-leakage It is non-leakage It is non-leakage It is non-leakage
Film surface drying time/h 1.5（It is tack-free） 2（It is tack-free） 3（It is tack-free） 1.5（It is tack-free） 2（It is tack-free）
Film does solid work the time/h 5（Inadhesion） 8（Inadhesion） 7（Inadhesion） 6（Inadhesion） 5（Inadhesion）

Claims (5)

1. fire-retardant, waterproof and the polyurethane coating of low VOC, are prepared using following step, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 11.2g, boric acid 25.6g, diethanol amine 28g, hexaphenoxycyclotriphosphazene 7.2g and phloridzin 2.8g and water 65g, adjust pH To 4,80 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.6g, 70 DEG C of stirring reaction 1h, obtain modified time Manganese phosphate；
（2）, with blender, condenser pipe, thermometer 250ml there-necked flasks in add azoformic acid dibenzyl ester 0.25g, poly- Tetrahydrofuran ether glycol 72g and hexamethylene diisocyanate 18g, reacts 1h at 70 DEG C, obtains base polyurethane prepolymer for use as A, institute The molecular weight for stating polytetrahydrofuran ether glycol is 500；
(3）, the equal three nitrogen borine of 0.68g hexahydros and 8.8g methyl ethyl ketone are added into performed polymer A, react 3.0h under the conditions of 70 DEG C, Add 1g steps（1）Modification manganese hypophosphite, 3.2g4- Carboxybenzeneboronic acids and the N- hydroxy thiosuccinimide 3.5g of preparation, instead Temperature 70 C is answered, reaction time 1h, adds 7.8g triethylamines and carry out neutralization reaction 70min, water 70g is stirred emulsification 1h, obtains To fire-retardant, waterproof and the polyurethane coating of low VOC.
2. fire-retardant, waterproof and the polyurethane coating of low VOC, are prepared using following methods, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 5.2g, boric acid 8g, diethanol amine 18g, benzilic acid 14g and 4- hydroxyphenethylamine 2.9g and water 70g, adjust pH to 4, 60 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.6g, 70 DEG C of stirring reaction 2h, obtain modified hypophosphorous acid Manganese；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in add；Tetramethyl ammonium chloride 0.74g, poly- four Hydrogen furans ether glycol 70g and hexamethylene diisocyanate 30g, react 4h at 80 DEG C, obtain base polyurethane prepolymer for use as A, described The molecular weight of polytetrahydrofuran ether glycol is 1000；
（3）, into performed polymer A add trimethyl silanol 3.5g and methyl ethyl ketone 16.8g, 3.5h is reacted under the conditions of 75 DEG C, add Step（1）Modification manganese hypophosphite 7.2g, 4- Carboxybenzeneboronic acid 3.6g and nitrilotriacetic acid 2.8g of preparation, 85 DEG C of reaction temperature, instead 1h between seasonable, adds triethylamine 14.5g and carries out neutralization reaction 60min, add 4,8- dihydroxy quinoline -2- formic acid 2.8g, water 110g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
3. fire-retardant, light resistance and the polyurethane coating of low VOC, are prepared using following methods, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 8.2g, boric acid 26.4g, diethanol amine 22.6g, hexamethylolmelamine 13g and benzilic acid 2.8g and water 55g, PH to 4 is adjusted, is heated to 80 DEG C, stirring reaction 1h, EDTAP dipotassium ethylene diamine tetraacetate 0.9g, 60 DEG C of stirring reaction 2h, are modified Manganese hypophosphite；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in, add stearyl trimethyl ammonium chloride 0.52g, polytetrahydrofuran ether glycol 80g and hexamethylene diisocyanate 36g, react 2h at 70 DEG C, it is pre- to obtain polyurethane Aggressiveness A, the molecular weight of the polytetrahydrofuran ether glycol is 1000；
（3）, nitrilotriacetic acid 2.6g and methyl ethyl ketone 21.4g is added into performed polymer A, react 2.5h under the conditions of 80 DEG C, add step Suddenly（1）Modification manganese hypophosphite 7.9g, 4- Carboxybenzeneboronic acid 4.8g and diphenyl methane dimaleimide 3.6g of preparation, reaction temperature 85 DEG C, reaction time 3.5h of degree, adds triethylamine 16.2g and carries out neutralization reaction 40min, add sodium salicylate 3.2g, water 160g Stirring carries out emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
4. fire-retardant, waterproof and the polyurethane coating of low VOC, are prepared using following methods, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 6.4g, boric acid 14g, diethanol amine 23.2g, hexaphenoxycyclotriphosphazene 9.5g and phloridzin 5.5g and water 80g, adjust pH and arrive 4,80 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.5g, 50 DEG C of stirring reaction 3h, obtain modified phosphorus Sour manganese；
（2）, with blender, condenser pipe, thermometer 250ml there-necked flasks in add triethyl aluminum 0.35g, PolyTHF Ether glycol 60g and hexamethylene diisocyanate 20g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, the poly- tetrahydrochysene The molecular weight of furans ether glycol is 1000；
（3）, nitrilotriacetic acid 0.52g and methyl ethyl ketone 9.2g is added into performed polymer A, react 3.5h under the conditions of 70 DEG C, add 4g Step（1）Modification manganese hypophosphite, 3.6g4- Carboxybenzeneboronic acids and the semicarbazides 2.6g of preparation, 80 DEG C of reaction temperature, reaction time 1h, adds 7.5g triethylamines and carries out neutralization reaction 30min, adds water 70g and is stirred emulsification 1h, obtain fire-retardant, waterproof with it is low The polyurethane coating of VOC.
5. fire-retardant, waterproof and the polyurethane coating of low VOC, are prepared using following methods, it is characterised in that：
（1）, modified manganese hypophosphite preparation：With blender, thermometer 250ml there-necked flasks in add manganese hypophosphite 3.2g, boric acid 9g, diethanol amine 36g, melamine cyanurate 15g and benzilic acid 3.2g and water 80g, adjust pH To 4,70 DEG C, stirring reaction 2h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 1.8g, 70 DEG C of stirring reaction 2h, obtain modified time Manganese phosphate；
（2）, with blender, condenser pipe, thermometer 500ml there-necked flasks in add isopropylmagnesium chloride 0.94g, poly- tetrahydrochysene Furans ether glycol 100g and hexamethylene diisocyanate 50g, react 1h at 90 DEG C, obtain base polyurethane prepolymer for use as A, described poly- The molecular weight of tetrahydrofuran ether glycol is 2000；
（3）, into performed polymer A add trimethyl silanol 4.2g and methyl ethyl ketone 25.5g, 3.5h is reacted under the conditions of 75 DEG C, add Step（1）Modification manganese hypophosphite 9.9g, 4- Carboxybenzeneboronic acid 7.4g and tetraethylenepentamine 2.8g of preparation, 95 DEG C of reaction temperature, Reaction time 1h, adds triethylamine 15.5g and carries out neutralization reaction 60min, add 4,8- dihydroxy quinoline -2- formic acid 3.7g, water 75g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
CN201711419973.9A 2016-08-30 2016-08-30 Fire-retardant, waterproof and the polyurethane coating of low VOC Pending CN108017991A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113881016A (en) * 2021-11-03 2022-01-04 万华化学集团股份有限公司 Aqueous polyurethane dispersion for improving washing fastness of heavy silicone oil treated cloth and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105176368A (en) * 2015-10-26 2015-12-23 烟台大学 Preparation method of polyurethane coating and adhesive with flame retardance and light resistance

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140151596A1 (en) * 2012-11-30 2014-06-05 Energyguard Atlantic, Llc Thermally conductive, corrosion resistant coatings
CN103073696B (en) * 2013-01-30 2014-08-13 段宝荣 Preparation method of light-resistant waterborne polyurethane
CN104109457B (en) * 2014-08-12 2016-03-23 段小宁 A kind of fire-retardant with water-repellancy aqueous polyurethane coating and the preparation method of tackiness agent
CN104356915B (en) * 2014-11-29 2016-08-17 烟台史密得机电设备制造有限公司 A kind of fire-retardant preparation method with water proofing property aqueous polyurethane coating
CN104861851A (en) * 2015-05-05 2015-08-26 段宝荣 Method for preparing flame retardant aqueous polyurethane coating and adhesive

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105176368A (en) * 2015-10-26 2015-12-23 烟台大学 Preparation method of polyurethane coating and adhesive with flame retardance and light resistance

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
W.P.WEBER等: "《相转移催化剂》", 30 March 1980, 安徽省化工研究所 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113881016A (en) * 2021-11-03 2022-01-04 万华化学集团股份有限公司 Aqueous polyurethane dispersion for improving washing fastness of heavy silicone oil treated cloth and preparation method and application thereof

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Application publication date: 20180511