CN106221550A - The polyurethane coating preparation method of fire-retardant, light resistance and low VOC - Google Patents

The polyurethane coating preparation method of fire-retardant, light resistance and low VOC Download PDF

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CN106221550A
CN106221550A CN201610761160.7A CN201610761160A CN106221550A CN 106221550 A CN106221550 A CN 106221550A CN 201610761160 A CN201610761160 A CN 201610761160A CN 106221550 A CN106221550 A CN 106221550A
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retardant
manganese hypophosphite
fire
light resistance
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CN106221550B (en
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段宝荣
翟智宇
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Zhongshan Hai Heng Packing Material 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
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
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    • 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
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    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

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Abstract

The invention discloses the polyurethane coating preparation method of fire-retardant, light resistance and low VOC, with agitator, condensing tube, thermometer 250ml there-necked flask in add triethylene tetramine 0.22g, PTMG 70g and hexamethylene diisocyanate 15g, at 80 DEG C, react 2h, obtain base polyurethane prepolymer for use as A；0.62g acetamide and 8.2g butanone is added in performed polymer A, 3.5h is reacted under the conditions of 75 DEG C, add modified manganese hypophosphite prepared by 2g step (1), 4g4 Carboxybenzeneboronic acid and diethylene triamine pentamethylene phosphonic 2.5g, reaction temperature 80 DEG C, response time 2h, add 7.1g triethylamine and be neutralized reaction 60min, add vitamin C 0.9g, water 70g is stirred emulsifying, obtain fire-retardant, light resistance and the polyurethane coating of low VOC, prepared is fire-retardant, light resistance and the polyurethane coating environmental protection of low VOC, cheap, it is widely used in body of wall, furniture, ironware surface, as plastics, glass, papermaking, the binding agent of weaving.

Description

The polyurethane coating preparation method of fire-retardant, light resistance and low VOC
Technical field
The present invention relates to the preparation method of a kind of polyurethane coating, be coated with low VOC polyurethane particularly to fire-retardant, light resistance Preparation method for material.
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 being sprayed at external and internal wall, furniture or the coating on ironware surface and paint, directly or indirectly contact with the mankind, therefore have Malicious, harmful coating moment threatens the health of people.Further, since the field used often contacts sunlight, and in sunray Containing ultraviolet light harmful to colored objects in a large number, its wavelength about 290～460nm, these harmful ultraviolet lights are by chemically Redox, make the change of coating generation color.
Polyurethane carries out being polymerized and makees catalyst frequently with dibutyl tin laurate, but owing to Heavy Metal, Sn is along with polyurethane Degraded and environment is worked the mischief, how the stannum of dibutyltindilaurate catalyzed remnants is fixed, reduces polyurethane The coating residues extent of injury to environment, has become as a technical barrier.
In order to improve the light resistance of polyurethane resin, frequently with adding UV absorbent and the mode of antioxidant, but It is bigger that traditional synthetized oxidation preventive agent has butylhydroxy anisole, t-butyl hydroperoxide and tert-butyl hydroquinone etc. to have Toxic and side effects and carcinogenecity, and add organosilicon material with traditional to improve the effect of water proofing property unsatisfactory, therefore Need to find the waterproof and fast light measure of more high-efficiency environment friendly.
Aqueous polyurethane (also known as water-based polyurethane) is a kind of poly-containing hydrophilic radical in the strand of polyurethane Urethane resin, has the strongest affinity with water, uses specific technique can be allowed to disperse and formed stable system in water. Aqueous polyurethane is mainly used in the aspects such as leather finish, textile printing and dyeing, paper-making industry, building coating, adhesive and steel moulder's paint, Involved is nearly all combustible material, and these materials as the most fire retardant treated, necessarily become the peace of initiation fire in use Full hidden danger.Aqueous polyurethane flame-retarded, is one of the important directions of aqueous polyurethane functionalization.
Polyurethane coating, i.e. carbamate coating, it is coated with in membrane molecule containing a considerable amount of polyurethane ester bonds. Polyurethane coating is in addition to containing ammonia ester bond, possibly together with urea bond, ehter bond, ester bond, allophanic acid ester bond, is a kind of function admirable, answers With coating widely
After VOC (Volatile Organic Compounds) refers to volatilizable in solvent based coating and human contact or sucks May result in the solvent of disease.Often containing VOC in polyurethane coating.VOC is very big to the health hazard of human body, and it is not only to skin There is corrosion function, and human central nervous system, hemopoietic organ, respiratory system are had stimulation and destruction, can cause The symptoms such as headache, nauseating, uncomfortable in chest, weak, vomiting, can twitch time serious, go into a coma even dead.The whole world is poisoned because use has every year The economic loss that the environmental disruption learning solvent based coating and cause and human injury bring is up to tens billion of dollar.Therefore, generation
Coating material production state main in boundary has launched respectively the exhaust emission regulation limiting VOC.The most in the world, according to Europe The regulation of coenosarc ecological mark product relevant VOC limitation, people's house decoration uses most class coating to be 30 g/ L, coating state compulsory standard " limits of harmful substances in indoor decorating and refurnishing materials interior wall coating " the regulation VOC of China is not Must be more than 200 g/L.Therefore, the direction that low VOC polyurethane coating is polyurethane coating development is developed.
Summary of the invention
The technical problem to be solved is to provide the polyurethane coating preparation side of fire-retardant, light resistance and low VOC Method, and carry out effectively fixing alleviating its toxicity and improving polymerization yield rate by selecting catalyst, reduce VOC content.
Technical scheme is as follows:
The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 9g, Boric acid 23g, diethanolamine 20g, hexaphenoxycyclotriphosphazene 6.2g and 3-aminopropyl ortho-siliformic acid 2.6g and water 60g, adjust Joint pH to 4, is heated to 70 DEG C, stirring reaction 1h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 60 DEG C of stirring reaction 2h, obtains modification Manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 250ml there-necked flask in add triethylene tetramine 0.22g, poly-tetrahydrochysene furan Mutter ether glycol 70g and hexamethylene diisocyanate 15g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, and described poly-four The molecular weight of hydrogen furan ether glycol is 1000；
(3), in performed polymer A, add 0.62g acetamide and 8.2g butanone, under the conditions of 75 DEG C, react 3.5h, add 2g step Suddenly modified manganese hypophosphite, 4g4-Carboxybenzeneboronic acid and the diethylene triamine pentamethylene phosphonic 2.5g that prepared by (1), reaction temperature 80 DEG C, response time 2h, add 7.1g triethylamine and be neutralized reaction 60min, add vitamin C 0.9g, water 70g and be stirred breast Change, obtain the polyurethane coating of fire-retardant, light resistance and low VOC.
The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 6g, Boric acid 10g, diethanolamine 15g, melamine cyanurate 12g and 4-hydroxyphenethylamine 2.8g and water 40g, regulate pH to 4, It is heated to 70 DEG C, stirring reaction 1h, add ethylenediamine tetraacetic acid,dipotassium salt 2g, 60 DEG C of stirring reaction 1h, obtain modified manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 500ml there-necked flask in add carbodiimides 0.64g, poly-tetrahydrochysene furan Mutter ether glycol 65g and hexamethylene diisocyanate 40g, reacts 2h, obtain base polyurethane prepolymer for use as A at 90 DEG C, and described poly-four The molecular weight of hydrogen furan ether glycol is 2000；
(3), in performed polymer A, add dithiothreitol, DTT 3.2g and butanone 16.5g, under the conditions of 75 DEG C, react 2.5h, add Modified manganese hypophosphite 6g, 4-Carboxybenzeneboronic acid 3.4g and ATMP 2.2g prepared by step (1), reaction temperature 95 DEG C, response time 2h, addition triethylamine 13.5g are neutralized and react 50min, addition 4,8-dihydroxy quinoline-2-formic acid 2.7g, Water 100g is stirred emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 4.2g, boric acid 26g, diethanolamine 22g, hexakis(hydroxymethyl)melamine 12g and 4,8-dihydroxy quinoline-2-formic acid 2.2g and water 45g, regulates pH to 4, is heated to 70 DEG C, stirring reaction 1h, ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 1h, is changed Property manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 500ml there-necked flask in, add sebacic dihydrazide 0.32g, poly-four Hydrogen furan ether glycol 85g and hexamethylene diisocyanate 32g, reacts 1h at 75 DEG C, obtains base polyurethane prepolymer for use as A, described The molecular weight of PTMG is 1000；
(3), in performed polymer A, add the equal three nitrogen borine 2.4g and butanone 20.4g of hexahydro, under the conditions of 70 DEG C, react 2.0h, Add modified manganese hypophosphite 8.9g, 4-Carboxybenzeneboronic acid 3.8g and triallyl cyanurate 2.6g prepared by step (1), reaction Temperature 75 DEG C, response time 2.5h, add triethylamine 15.2g and be neutralized reaction 30min, add sodium salicylate 2.2g, water 150g stirring carries out emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 6.2g, boric acid 13g, diethanolamine 22g, hexaphenoxycyclotriphosphazene 8.5g and 3-aminopropyl ortho-siliformic acid 3.5g and water 40g, regulates pH to 4, is heated to 70 DEG C, stirring reaction 3h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 2h, To modified manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 250ml there-necked flask in add tributyl 2-acetylcitrate 0.15g, poly- Oxolane ether glycol 60g and hexamethylene diisocyanate 20g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, institute The molecular weight stating PTMG is 1000；
(3), in performed polymer A, add acetamide 0.52g and butanone 9.2g, under the conditions of 60 DEG C, react 2.5h, add 4g step Suddenly modified manganese hypophosphite, 3.6g4-Carboxybenzeneboronic acid and the trimethylol-propane trimethacrylate 2.5g that prepared by (1), reaction Temperature 70 C, response time 2h, add 7.5g triethylamine and be neutralized reaction 40min, add vitamin C 1.6g, water 70g and carry out Stirring and emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 3g, Boric acid 10g, diethanolamine 35g, melamine cyanurate 12g and 4,8-dihydroxy quinoline-2-formic acid 2.8g and water 70g, Regulation pH to 4, is heated to 70 DEG C, stirring reaction 2h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 2h, is changed Property manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 500ml there-necked flask in add 5-Aminotetrazole 0.84g, poly-tetrahydrochysene furan Mutter ether glycol 80g and hexamethylene diisocyanate 40g, reacts 2h, obtain base polyurethane prepolymer for use as A at 90 DEG C, and described poly-four The molecular weight of hydrogen furan ether glycol is 2000；
(3), in performed polymer A, add dithiothreitol, DTT 3.9g and butanone 24.5g, under the conditions of 75 DEG C, react 2.5h, add Modified manganese hypophosphite 8.9g, 4-Carboxybenzeneboronic acid 6.4g and cyanuric acid 3.8g prepared by step (1), reaction temperature 85 DEG C, instead 2h between Ying Shi, adds triethylamine 14.5g and is neutralized reaction 60min, and 4,8-dihydroxy quinoline-2-formic acid 3.7g, water 75g are carried out Stirring and emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Present invention have an advantage that
(1) triethylene tetramine, carbodiimides, sebacic dihydrazide, tributyl 2-acetylcitrate and 5-Aminotetrazole substitute and pass The advantage of system is tin compound catalyst；
(2) diethylene triamine pentamethylene phosphonic, ATMP, triallyl cyanurate, trimethylolpropane tris first Polymer is cross-linked by base acrylate, cyanuric acid, improves the defect that tradition HDI polyurethane intensity is the highest, the most right Reactant chelates, and adds the little molecule of absorption, reduces the VOC of release；
(3) acetamide, dithiothreitol, DTT, the equal three nitrogen borines of hexahydro not only have chain extender but also have light resistance；
(4) hexaphenoxycyclotriphosphazene, melamine cyanurate, hexakis(hydroxymethyl)melamine have fire retardation, 3-ammonia Propyl group ortho-siliformic acid, 4-hydroxyphenethylamine, 4,8-dihydroxy quinoline-2-formic acid carries out potentiation to fire-retardant, improves its anti-flammability.
Detailed description of the invention
The present invention is further illustrated below in conjunction with example.
Example one
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 9g, Boric acid 23g, diethanolamine 20g, hexaphenoxycyclotriphosphazene 6.2g and 3-aminopropyl ortho-siliformic acid 2.6g and water 60g, adjust Joint pH to 4, is heated to 70 DEG C, stirring reaction 1h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 60 DEG C of stirring reaction 2h, obtains modification Manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 250ml there-necked flask in add triethylene tetramine 0.22g, poly-tetrahydrochysene furan Mutter ether glycol 70g and hexamethylene diisocyanate 15g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, and described poly-four The molecular weight of hydrogen furan ether glycol is 1000；
(3), in performed polymer A, add 0.62g acetamide and 8.2g butanone, under the conditions of 75 DEG C, react 3.5h, add 2g step Suddenly modified manganese hypophosphite, 4g4-Carboxybenzeneboronic acid and the diethylene triamine pentamethylene phosphonic 2.5g that prepared by (1), reaction temperature 80 DEG C, response time 2h, add 7.1g triethylamine and be neutralized reaction 60min, add vitamin C 0.9g, water 70g and be stirred breast Change, obtain the polyurethane coating of fire-retardant, light resistance and low VOC.
Example two
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 6g, Boric acid 10g, diethanolamine 15g, melamine cyanurate 12g and 4-hydroxyphenethylamine 2.8g and water 40g, regulate pH to 4, It is heated to 70 DEG C, stirring reaction 1h, add ethylenediamine tetraacetic acid,dipotassium salt 2g, 60 DEG C of stirring reaction 1h, obtain modified manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 500ml there-necked flask in add carbodiimides 0.64g, poly-tetrahydrochysene furan Mutter ether glycol 65g and hexamethylene diisocyanate 40g, reacts 2h, obtain base polyurethane prepolymer for use as A at 90 DEG C, and described poly-four The molecular weight of hydrogen furan ether glycol is 2000；
(3), in performed polymer A, add dithiothreitol, DTT 3.2g and butanone 16.5g, under the conditions of 75 DEG C, react 2.5h, add Modified manganese hypophosphite 6g, 4-Carboxybenzeneboronic acid 3.4g and ATMP 2.2g prepared by step (1), reaction temperature 95 DEG C, response time 2h, addition triethylamine 13.5g are neutralized and react 50min, addition 4,8-dihydroxy quinoline-2-formic acid 2.7g, Water 100g is stirred emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Example three
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 4.2g, boric acid 26g, diethanolamine 22g, hexakis(hydroxymethyl)melamine 12g and 4,8-dihydroxy quinoline-2-formic acid 2.2g and water 45g, regulates pH to 4, is heated to 70 DEG C, stirring reaction 1h, ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 1h, is changed Property manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 500ml there-necked flask in, add sebacic dihydrazide 0.32g, poly-four Hydrogen furan ether glycol 85g and hexamethylene diisocyanate 32g, reacts 1h at 75 DEG C, obtains base polyurethane prepolymer for use as A, described The molecular weight of PTMG is 1000；
(3), in performed polymer A, add the equal three nitrogen borine 2.4g and butanone 20.4g of hexahydro, under the conditions of 70 DEG C, react 2.0h, Add modified manganese hypophosphite 8.9g, 4-Carboxybenzeneboronic acid 3.8g and triallyl cyanurate 2.6g prepared by step (1), reaction Temperature 75 DEG C, response time 2.5h, add triethylamine 15.2g and be neutralized reaction 30min, add sodium salicylate 2.2g, water 150g stirring carries out emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Example four
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 6.2g, boric acid 13g, diethanolamine 22g, hexaphenoxycyclotriphosphazene 8.5g and 3-aminopropyl ortho-siliformic acid 3.5g and water 40g, regulates pH to 4, is heated to 70 DEG C, stirring reaction 3h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 2h, To modified manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 250ml there-necked flask in add tributyl 2-acetylcitrate 0.15g, poly- Oxolane ether glycol 60g and hexamethylene diisocyanate 20g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, institute The molecular weight stating PTMG is 1000；
(3), in performed polymer A, add acetamide 0.52g and butanone 9.2g, under the conditions of 60 DEG C, react 2.5h, add 4g step Suddenly modified manganese hypophosphite, 3.6g4-Carboxybenzeneboronic acid and the trimethylol-propane trimethacrylate 2.5g that prepared by (1), reaction Temperature 70 C, response time 2h, add 7.5g triethylamine and be neutralized reaction 40min, add vitamin C 1.6g, water 70g and carry out Stirring and emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Example five
(1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 3g, Boric acid 10g, diethanolamine 35g, melamine cyanurate 12g and 4,8-dihydroxy quinoline-2-formic acid 2.8g and water 70g, Regulation pH to 4, is heated to 70 DEG C, stirring reaction 2h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 2h, is changed Property manganese hypophosphite；
(2), with agitator, condensing tube, thermometer 500ml there-necked flask in add 5-Aminotetrazole 0.84g, poly-tetrahydrochysene furan Mutter ether glycol 80g and hexamethylene diisocyanate 40g, reacts 2h, obtain base polyurethane prepolymer for use as A at 90 DEG C, and described poly-four The molecular weight of hydrogen furan ether glycol is 2000；
(3), in performed polymer A, add dithiothreitol, DTT 3.9g and butanone 24.5g, under the conditions of 75 DEG C, react 2.5h, add Modified manganese hypophosphite 8.9g, 4-Carboxybenzeneboronic acid 6.4g and cyanuric acid 3.8g prepared by step (1), reaction temperature 85 DEG C, instead 2h between Ying Shi, adds triethylamine 14.5g and is neutralized reaction 60min, and 4,8-dihydroxy quinoline-2-formic acid 3.7g, water 75g are carried out Stirring and emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Further illustrate beneficial effects of the present invention: PU-1 below by relevant experimental data and 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 light resistance 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 2 3 3 2 2
Pliability/mm 3 3 3 2 3 2
From table two it is found that from film outward appearance, hardness, adhesive force, flexibility better performances.
Table two is fire-retardant, the mechanical property of the polyurethane coating gained film of light resistance and low VOC
Experimental group Example one Example two Example three Example four Example five PU-1
Elongation at break/% 162 158 161 167 172 157
Tensile strength/MPa 5.9 5.6 5.2 7.4 8.8 5.4
Abrasion resisting/level 3.0 4 4.0 3.5 4.5 3
The reference of table two middle finger object detection method (Jiang Weiqi. leather finish physical and chemical inspection [M]. China Light Industry Press, 1999), coating gained film elongation at break of the present invention, tensile strength, wear-resistant all performances are preferably.
Anti-flammability is to be referred to by smoke density method (maximum smoke density, reach the maximum smoke density time), oxygen index (OI), vertical combustion Mark (flaming combustion time, glowing time) is weighed, and elongation at break characterizes its mechanical property.
Table three is fire-retardant, the anti-flammability of the polyurethane coating gained film of light resistance and low VOC
Example one Example two Example three Example four Example five PU-1
Maximum smoke density 12 26 32 16 11 59
Reach maximum smoke density time/s 180 180 195 225 185 150
Oxygen index (OI) 27.6 26.8 24.9 26.8 27.2 24.1
Flaming combustion time/s 12.5 15.8 10.6 9.9 7.2 24
Glowing time/s 0.1 0.2 0 0 0 1
The detection of table three indices is respectively according to following standard: smoke density measures according to GB8323-2008, and oxygen index (OI) uses GB/T5454-1997 " textile combustion performance test-oxygen index method " measures；Flaming combustion time and glowing time be by GB/T 5455-1997 " textile combustion energy test-normal beam technique " measures.
As shown in Table 3, when the present invention is burnt with adhesive gained film with sunproof polyurethane coating, maximum smoke density shows Writing and reduce, reaching the maximum smoke density time significantly extends, and oxygen index (OI) significantly improves, and burning time substantially shortens.
For quantitative description resistance to light of coating energy, spectrophotometer is used to detect, to obtain inverse difference △ E, The light resistance of coating and finish paint is described.△ E represents color intensity of variation, and △ E is the biggest, and color change is the most obvious.General next Saying, △ E value is the 0～1.5 slight changes of genus；△ E value is that 1.5～3.0 genus can feel change；△ E value is that 3.0～6.0 genus substantially become Change (see Wang Fang, party's climax, Wang Liqin, the light degradation [J] of several organic historical relic's protection polymer coatings. Northwest University's journal, 2005,35(5): 56 ~ 58).
Table four is fire-retardant, the light resistance of the polyurethane coating gained film of light resistance and low VOC
Time/min Example one Example two Example three Example four Example five PU-1
90 0.1 0.2 0.3 0.2 0.1 0.2
150 0.3 0.3 0.4 0.5 0.2 0.3
270 0.5 0.4 0.4 0.5 0.4 0.6
330 0.7 0.8 0.5 0.5 0.4 0.9
390 0.8 0.8 0.7 0.7 0.5 1.0
450 0.9 0.8 0.7 0.7 0.6 1.2
510 1.0 1.1 0.9 0.9 0.6 1.9
540 1.1 1.2 1.1 0.9 0.8 2.2
600 1.3 1.2 1.2 1.2 0.8 2.8
From table four it is found that example one to the coating light resistance prepared by example five all in slight excursion, display very Good light resistance, and PU-1 already belongs to feel change at 510min.
Test according to limits of harmful substances standard in GB24408-2009 exterior coating:
Table five is fire-retardant, the polyurethane coating VOC of light resistance and low VOC
Example one Example two Example three Example four Example five PU-1
VOC (VOC) content 106 112 134 146 137 215

Claims (5)

  1. The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
    (1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 9g, Boric acid 23g, diethanolamine 20g, hexaphenoxycyclotriphosphazene 6.2g and 3-aminopropyl ortho-siliformic acid 2.6g and water 60g, adjust Joint pH to 4, is heated to 70 DEG C, stirring reaction 1h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 60 DEG C of stirring reaction 2h, obtains modification Manganese hypophosphite；
    (2), with agitator, condensing tube, thermometer 250ml there-necked flask in add triethylene tetramine 0.22g, poly-tetrahydrochysene furan Mutter ether glycol 70g and hexamethylene diisocyanate 15g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, and described poly-four The molecular weight of hydrogen furan ether glycol is 1000；
    (3), in performed polymer A, add 0.62g acetamide and 8.2g butanone, under the conditions of 75 DEG C, react 3.5h, add 2g step Suddenly modified manganese hypophosphite, 4g4-Carboxybenzeneboronic acid and the diethylene triamine pentamethylene phosphonic 2.5g that prepared by (1), reaction temperature 80 DEG C, response time 2h, add 7.1g triethylamine and be neutralized reaction 60min, add vitamin C 0.9g, water 70g and be stirred breast Change, obtain the polyurethane coating of fire-retardant, light resistance and low VOC.
  2. The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
    (1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 6g, Boric acid 10g, diethanolamine 15g, melamine cyanurate 12g and 4-hydroxyphenethylamine 2.8g and water 40g, regulate pH to 4, It is heated to 70 DEG C, stirring reaction 1h, add ethylenediamine tetraacetic acid,dipotassium salt 2g, 60 DEG C of stirring reaction 1h, obtain modified manganese hypophosphite；
    (2), with agitator, condensing tube, thermometer 500ml there-necked flask in add carbodiimides 0.64g, poly-tetrahydrochysene furan Mutter ether glycol 65g and hexamethylene diisocyanate 40g, reacts 2h, obtain base polyurethane prepolymer for use as A at 90 DEG C, and described poly-four The molecular weight of hydrogen furan ether glycol is 2000；
    (3), in performed polymer A, add dithiothreitol, DTT 3.2g and butanone 16.5g, under the conditions of 75 DEG C, react 2.5h, add Modified manganese hypophosphite 6g, 4-Carboxybenzeneboronic acid 3.4g and ATMP 2.2g prepared by step (1), reaction temperature 95 DEG C, response time 2h, addition triethylamine 13.5g are neutralized and react 50min, addition 4,8-dihydroxy quinoline-2-formic acid 2.7g, Water 100g is stirred emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
  3. The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
    (1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 4.2g, boric acid 26g, diethanolamine 22g, hexakis(hydroxymethyl)melamine 12g and 4,8-dihydroxy quinoline-2-formic acid 2.2g and water 45g, regulates pH to 4, is heated to 70 DEG C, stirring reaction 1h, ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 1h, is changed Property manganese hypophosphite；
    (2), with agitator, condensing tube, thermometer 500ml there-necked flask in, add sebacic dihydrazide 0.32g, poly-four Hydrogen furan ether glycol 85g and hexamethylene diisocyanate 32g, reacts 1h at 75 DEG C, obtains base polyurethane prepolymer for use as A, described The molecular weight of PTMG is 1000；
    (3), in performed polymer A, add the equal three nitrogen borine 2.4g and butanone 20.4g of hexahydro, under the conditions of 70 DEG C, react 2.0h, Add modified manganese hypophosphite 8.9g, 4-Carboxybenzeneboronic acid 3.8g and triallyl cyanurate 2.6g prepared by step (1), reaction Temperature 75 DEG C, response time 2.5h, add triethylamine 15.2g and be neutralized reaction 30min, add sodium salicylate 2.2g, water 150g stirring carries out emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
  4. The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
    (1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 6.2g, boric acid 13g, diethanolamine 22g, hexaphenoxycyclotriphosphazene 8.5g and 3-aminopropyl ortho-siliformic acid 3.5g and water 40g, regulates pH to 4, is heated to 70 DEG C, stirring reaction 3h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 2h, To modified manganese hypophosphite；
    (2), with agitator, condensing tube, thermometer 250ml there-necked flask in add tributyl 2-acetylcitrate 0.15g, poly- Oxolane ether glycol 60g and hexamethylene diisocyanate 20g, reacts 2h at 80 DEG C, obtains base polyurethane prepolymer for use as A, institute The molecular weight stating PTMG is 1000；
    (3), in performed polymer A, add acetamide 0.52g and butanone 9.2g, under the conditions of 60 DEG C, react 2.5h, add 4g step Suddenly modified manganese hypophosphite, 3.6g4-Carboxybenzeneboronic acid and the trimethylol-propane trimethacrylate 2.5g that prepared by (1), reaction Temperature 70 C, response time 2h, add 7.5g triethylamine and be neutralized reaction 40min, add vitamin C 1.6g, water 70g and carry out Stirring and emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
  5. The polyurethane coating preparation method of the most fire-retardant, light resistance and low VOC, it is characterised in that:
    (1), the preparation of modified manganese hypophosphite: with agitator, thermometer 250ml there-necked flask in add manganese hypophosphite 3g, Boric acid 10g, diethanolamine 35g, melamine cyanurate 12g and 4,8-dihydroxy quinoline-2-formic acid 2.8g and water 70g, Regulation pH to 4, is heated to 70 DEG C, stirring reaction 2h, adds ethylenediamine tetraacetic acid,dipotassium salt 2g, 50 DEG C of stirring reaction 2h, is changed Property manganese hypophosphite；
    (2), with agitator, condensing tube, thermometer 500ml there-necked flask in add 5-Aminotetrazole 0.84g, poly-tetrahydrochysene furan Mutter ether glycol 80g and hexamethylene diisocyanate 40g, reacts 2h, obtain base polyurethane prepolymer for use as A at 90 DEG C, and described poly-four The molecular weight of hydrogen furan ether glycol is 2000；
    (3), in performed polymer A, add dithiothreitol, DTT 3.9g and butanone 24.5g, under the conditions of 75 DEG C, react 2.5h, add Modified manganese hypophosphite 8.9g, 4-Carboxybenzeneboronic acid 6.4g and cyanuric acid 3.8g prepared by step (1), reaction temperature 85 DEG C, instead 2h between Ying Shi, adds triethylamine 14.5g and is neutralized reaction 60min, and 4,8-dihydroxy quinoline-2-formic acid 3.7g, water 75g are carried out Stirring and emulsifying, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
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CN109575227A (en) * 2018-12-27 2019-04-05 王世茸 The fire-retardant PU resin of environment-friendly type antibiotic
CN109706747A (en) * 2018-12-27 2019-05-03 王世茸 Flame-retardant leather brick and its embroidering method
CN111285989A (en) * 2020-02-07 2020-06-16 山东理工大学 Preparation of high-performance reaction type polyurethane flame retardant compounded by cyclic triphosphazenyl hexaphosphoric acid and derivative thereof

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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

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US20140151596A1 (en) * 2012-11-30 2014-06-05 Energyguard Atlantic, Llc Thermally conductive, corrosion resistant coatings
CN103073696A (en) * 2013-01-30 2013-05-01 段宝荣 Preparation method of light-resistant waterborne polyurethane
CN104109457A (en) * 2014-08-12 2014-10-22 段小宁 Preparation method of flame-retardant and waterproof aqueous polyurethane coating and adhesive
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

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* Cited by examiner, † Cited by third party
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CN109575227A (en) * 2018-12-27 2019-04-05 王世茸 The fire-retardant PU resin of environment-friendly type antibiotic
CN109706747A (en) * 2018-12-27 2019-05-03 王世茸 Flame-retardant leather brick and its embroidering method
CN111285989A (en) * 2020-02-07 2020-06-16 山东理工大学 Preparation of high-performance reaction type polyurethane flame retardant compounded by cyclic triphosphazenyl hexaphosphoric acid and derivative thereof

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