CN104109457A - Preparation method of flame-retardant and waterproof aqueous polyurethane coating and adhesive - Google Patents
Preparation method of flame-retardant and waterproof aqueous polyurethane coating and adhesive Download PDFInfo
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Abstract
The invention discloses a preparation method of a flame-retardant and waterproof aqueous polyurethane coating and adhesive. The method comprises the following steps: mixing 1,4-di(dimethyl hydroxysilyl) benzene with isophorone diisocyanate in the presence of modified fullerene A, adding a synergist and 2-butoxyl-N-(2-diethylaminoethyl)-4-quinoline formamide hydrochloride and reacting for 1 to 5 hours at 70 DEG C to 80 DEG C so as to obtain a polyurethane prepolymer A; adding a chain extender and a solvent into the prepolymer A, reacting for 3 to 4 hours at 60 DEG C to 80 DEG C, then adding triethylamine and carrying out a neutral reaction for 30 to 60 minutes; then adding a modified manganese hypophosphate solution, coconut oil monoethanolamide and sulfaquinoxaline and reacting for 1 hour at 70 DEG C; and adding water and sodium dodecyl sulfate and emulsifying for 60 minutes, thereby obtaining the flame-retardant and waterproof aqueous polyurethane coating and adhesive. The prepared flame-retardant and waterproof aqueous polyurethane coating and adhesive is environment-friendly and low in cost, and can be widely applied to walls, furniture and metalware surfaces as well as can serve as an adhesive for plastics, glass, papermaking and textiles.
Description
Technical field
The present invention relates to the preparation method of polyurethane coating, particularly the preparation method of fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent.
Background technology
Water-proof material main application fields comprises the roofing of building construction, underground, exterior wall and indoor; The public works such as urban road bridges and the underground space; The bridge of motorway and high-speed railway, tunnel; The traffic engineering such as sub.; The hydro projects such as flume, reservoir, dam body, natural flow station and water treatment, be applicable to roofing and lavatory bathe between, the waterproof of vault, water reservoir, metope, antiseepage, protection against the tide.According to application material, divide and can be used for the fields such as papermaking, weaving, leather.
Urethane synthesizes the normal dibutyl tin laurate that adopts and makees catalyzer, but because Heavy Metal, Sn is working the mischief to environment along with the degraded of urethane, the catalyzer of screening high effect nontoxic is a great problem during urethane synthesizes.
Soccerballene has good catalytic performance, and through modification, it is expected to improve the catalytic efficiency of urethane preparation process.
Aqueous polyurethane (claiming again waterbased urethane) is a kind of urethane resin that contains hydrophilic radical in the molecular chain of urethane, has very strong affinity with glassware for drinking water, adopts specific technique can make it in water, to disperse and form stable system.Aqueous polyurethane is mainly used in the aspects such as leather finish, textile printing and dyeing, paper-making industry, building coating, tackiness agent, steel moulder's paint, related is nearly all inflammable material, these materials as without fire-retardant finish, must become the potential safety hazard of initiation fire in use.Fire-retardantization of aqueous polyurethane is one of important directions of aqueous polyurethane functionalization.
summary of the invention
Technical problem to be solved by this invention is, the preparation method of a kind of fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent is provided, select modification soccerballene to make catalyzer, there is 1 of flame retardant resistance and water-repellancy, two (dimethyl hydroxyl the is silica-based) benzene of 4-reacts with isophorone diisocyanate, utilize synergistic agent and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate to carry out synergy to modification soccerballene, with fire-retardant, waterproof material is as chainextender, the material with flame retardant resistance is made solvent and is reacted, add the modification manganous hypophosphite that smoke-suppressing is strong to reduce the release amount of smoke of burning simultaneously, reach fire-retardant and double effects waterproof.
A preparation method for fire-retardant and water-repellancy aqueous polyurethane coating and tackiness agent, is characterized in that:
(1) preparation of catalyzer: add 10mg soccerballene and 30ml heavily to steam quadrol in there-necked flask, 70 ℃ of reaction 12h of oil bath under nitrogen protection, excessive quadrol is removed in decompression, gained brown dope dissolves with 2ml distilled water, then adds 40ml ethanol, has a large amount of beige Precipitations, centrifugal, solids is used vacuum-drying at twice, 80 ℃ of washing with alcohol again, obtains the pulverous soccerballene ethylene diamine derivative of beige; Above-mentioned soccerballene ethylene diamine derivative is dissolved in to 10 ml distilled water, pour in the aqueous solution that 30ml is dissolved with 200mg Tai-Ace S 150 and 100mg magnesium sulfate, be heated to 80 ℃, there is brown precipitation to produce, after insulation 30min, centrifugal while hot, solids distilled water wash 3 times, vacuum-drying, obtains the modification soccerballene A of brown solid;
(2) modification manganous hypophosphite preparation: manganous hypophosphite, rhubarb yellow, Tai-Ace S 150, water are mixed according to weight ratio 1:3:2.1:5, regulate pH to 4, be heated to 50 ℃, stirring reaction time 1h, obtains modification manganous hypophosphite solution;
(3) under the condition existing at the modification soccerballene A of step (1), by 1, two (dimethyl hydroxyl the is silica-based) benzene of 4-and isophorone diisocyanate be 1:1.4 ~ 1 by weight: 2.8 mix, add synergistic agent and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate, at 70 ~ 80 ℃, react 1 ~ 5h, obtain base polyurethane prepolymer for use as A, described catalyst levels is 1, 0.12 ~ 0.32% of two (dimethyl hydroxyl the is silica-based) benzene of 4-and isophorone diisocyanate gross weight, synergistic agent and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate consumption is respectively 1, two (dimethyl hydroxyl the is silica-based) benzene of 4-, isophorone diisocyanate, 0.12 ~ 0.20% and 0.3 ~ 0.8% of modification soccerballene A gross weight,
(4) to performed polymer A, add the chainextender of performed polymer A weight 0.8 ~ 3.6% and the solvent of performed polymer A weight 15 ~ 25%, under 60 ~ 80 ℃ of conditions, react 3 ~ 4h, the triethylamine that is 10 ~ 18% by performed polymer A weight carries out neutralization reaction 30 ~ 60min, add modification manganous hypophosphite solution, Coconut Fatty Acid Monoethanolamide, sulfaquinoxaline, in 70 ℃ of reaction 1h, add water and sodium laurylsulfonate and carry out emulsification 60min, obtain fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent, sodium laurylsulfonate is 0.2 ~ 0.5% of performed polymer A weight, modification manganous hypophosphite solution, Coconut Fatty Acid Monoethanolamide, sulfaquinoxaline is respectively 1% of performed polymer A weight, 2%, 1.2%.
Synergistic agent is that diethylin sulfur trifluoride, the tetrabutyl are fluoridized phosphine, two (2-methoxy ethyl) amino sulfur trifluoride, butyl triphenyl and fluoridized phosphine, 2,3,4, and 6-tetra--o-acetyl-α-D-fluoridizes any one in Glucopyranose; Chainextender is any one of compound of 3-aminopropyl ortho-siliformic acid, D-MANNOSE aldehydic acid list sodium salt and methyl ortho-siliformic acid (1:1); Solvent is a kind of of adenosine cyclic phosphate, tricresyl phosphate (2,3-, bis-chloropropyls) ester, the chloro-1-of 2-(2,4 dichloro benzene base) vinyl diethyl phosphate.
The present invention has following characteristics:
(1) synergistic agent and modification soccerballene carry out synergy to catalyzer, and synergistic agent also has certain flame retardant properties simultaneously;
(2) selecting waterproof, flame-retardant materials is chainextender, has improved waterproof and flame retardant properties;
(3) organosilicon of flame retardant resistance and waterproof is done prepolymerization reaction monomer, and performance is significantly improved;
(4) flame-retardant materials is made solvent, and the flame retardant properties of urethane is significantly improved.
(5) select quadrol, Tai-Ace S 150, magnesium sulfate to carry out modification to soccerballene, both can make catalyst efficiency strengthen, and this modification soccerballene also has flame retardant resistance;
(6) in aqueous medium link, manganous hypophosphite, rhubarb yellow, Tai-Ace S 150 react, and generate a complex compound, and this complex compound has good solubleness in water-based;
(7) manganous hypophosphite has good smoke-suppressing, reaches the desirable flame retardant effect of fire-proof smoke-proof.
embodimentbelow in conjunction with example, further illustrate the present invention.
example one
(1) preparation of catalyzer: add 10mg soccerballene and 30ml heavily to steam quadrol in the 250ml there-necked flask with agitator, thermometer, 70 ℃ of reaction 12h of oil bath under nitrogen protection, excessive quadrol is removed in decompression, gained brown dope dissolves with 2ml distilled water, then adds 40ml ethanol, has a large amount of beige Precipitations, centrifugal, solids is used vacuum-drying at twice, 80 ℃ of washing with alcohol again, obtains the pulverous soccerballene ethylene diamine derivative of beige; Above-mentioned soccerballene ethylene diamine derivative is dissolved in to 10 ml distilled water, pour in the aqueous solution that 30ml is dissolved with 200mg Tai-Ace S 150 and 100mg magnesium sulfate, be heated to 80 ℃, there is brown precipitation to produce, after insulation 30min, centrifugal while hot, solids distilled water wash 3 times, vacuum-drying, obtains the modification soccerballene A of brown solid;
(2) modification manganous hypophosphite preparation: manganous hypophosphite 1g, rhubarb yellow 3g, Tai-Ace S 150 2.1g, water 5g are joined in the there-necked flask of 25ml, regulate pH to 4, be heated to 50 ℃, stirring reaction time 1h, obtains modification manganous hypophosphite solution;
(3) in the 250ml there-necked flask with agitator, prolong, thermometer, add 1,4-two (dimethyl hydroxyl is silica-based) benzene 30g, isophorone diisocyanate 42g and modification soccerballene A0.09g, add diethylin sulfur trifluoride 0.09g and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate 0.21g, at 70 ℃, react 1h, obtaining base polyurethane prepolymer for use as A is 71g;
(4) in performed polymer A, add 3-aminopropyl ortho-siliformic acid 0.57g and adenosine cyclic phosphate 10.7g, under 60 ℃ of conditions, react 3h, add triethylamine 7.1g and carry out neutralization reaction 30min, add again modification manganous hypophosphite solution 0.71g, Coconut Fatty Acid Monoethanolamide 1.42g, sulfaquinoxaline 0.85g, in 70 ℃ of reaction 1h, add water 80g and sodium laurylsulfonate 0.14g carries out emulsification 60min, obtain fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent.
Example two
(1) preparation of catalyzer: add 10mg soccerballene and 30ml heavily to steam quadrol in the 250ml there-necked flask with agitator, thermometer, 70 ℃ of reaction 12h of oil bath under nitrogen protection, excessive quadrol is removed in decompression, gained brown dope dissolves with 2ml distilled water, then adds 40ml ethanol, has a large amount of beige Precipitations, centrifugal, solids is used vacuum-drying at twice, 80 ℃ of washing with alcohol again, obtains the pulverous soccerballene ethylene diamine derivative of beige; Above-mentioned soccerballene ethylene diamine derivative is dissolved in to 10 ml distilled water, pour in the aqueous solution that 30ml is dissolved with 200mg Tai-Ace S 150 and 100mg magnesium sulfate, be heated to 80 ℃, there is brown precipitation to produce, after insulation 30min, centrifugal while hot, solids distilled water wash 3 times, vacuum-drying, obtains the modification soccerballene A of brown solid;
(2) modification manganous hypophosphite preparation: manganous hypophosphite 1g, rhubarb yellow 3g, Tai-Ace S 150 2.1g, water 5g are joined in the there-necked flask of 25ml, regulate pH to 4, be heated to 50 ℃, stirring reaction time 1h, obtains modification manganous hypophosphite solution;
(3) in the 500ml there-necked flask with agitator, prolong, thermometer, add 1,4-two (dimethyl hydroxyl is silica-based) benzene 30g, isophorone diisocyanate 84g and modification soccerballene A0.36g, add again the tetrabutyl to fluoridize phosphine 0.23g and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate 0.91g, at 80 ℃, react 5h, obtain base polyurethane prepolymer for use as A115g;
(4) in performed polymer A, add D-MANNOSE aldehydic acid list sodium salt 2.07g, methyl ortho-siliformic acid 2.07g and tricresyl phosphate (2,3-bis-chloropropyls) ester 29g, under 80 ℃ of conditions, react 4h, add triethylamine 20.7g to carry out neutralization reaction 60min, add again modification manganous hypophosphite solution 1.15g, Coconut Fatty Acid Monoethanolamide 2.3g and sulfaquinoxaline 1.38g, in 70 ℃ of reaction 1h, add water 100g and sodium laurylsulfonate 0.58g carries out emulsification 60min, obtain fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent.
example three
(1) preparation of catalyzer: add 10mg soccerballene and 30ml heavily to steam quadrol in the 250ml there-necked flask with agitator, thermometer, 70 ℃ of reaction 12h of oil bath under nitrogen protection, excessive quadrol is removed in decompression, gained brown dope dissolves with 2ml distilled water, then adds 40ml ethanol, has a large amount of beige Precipitations, centrifugal, solids is used vacuum-drying at twice, 80 ℃ of washing with alcohol again, obtains the pulverous soccerballene ethylene diamine derivative of beige; Above-mentioned soccerballene ethylene diamine derivative is dissolved in to 10 ml distilled water, pour in the aqueous solution that 30ml is dissolved with 200mg Tai-Ace S 150 and 100mg magnesium sulfate, be heated to 80 ℃, there is brown precipitation to produce, after insulation 30min, centrifugal while hot, solids distilled water wash 3 times, vacuum-drying, obtains the modification soccerballene A of brown solid;
(2) modification manganous hypophosphite preparation: manganous hypophosphite 1g, rhubarb yellow 3g, Tai-Ace S 150 2.1g, water 5g are joined in the there-necked flask of 25ml, regulate pH to 4, join 50 ℃, stirring reaction time 1h, obtains modification manganous hypophosphite solution;
(3) in the 500ml there-necked flask with agitator, prolong, thermometer, add 1,4-two (dimethyl hydroxyl is silica-based) benzene 40g, isophorone diisocyanate 84g and modification soccerballene A0.27g, add two (2-methoxy ethyl) amino sulfur trifluoride 0.2g and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate 0.68g, at 75 ℃, react 3h, obtain base polyurethane prepolymer for use as A124g;
(4) in performed polymer A, add 3-aminopropyl ortho-siliformic acid 2.7g and the chloro-1-(2 of 2-, 4-dichlorophenyl) vinyl diethyl phosphate 25g, under 70 ℃ of conditions, react 3.5h, add triethylamine 17.4g to carry out neutralization reaction 45min, add modification manganous hypophosphite solution 1.24g, Coconut Fatty Acid Monoethanolamide 2.5g, sulfaquinoxaline 1.5g, in 70 ℃ of reaction 1h, add water 110g and sodium laurylsulfonate 0.43g carries out emulsification 60min, obtain fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent.
example four
(1) preparation of catalyzer: add 10mg soccerballene and 30ml heavily to steam quadrol in the 250ml there-necked flask with agitator, thermometer, 70 ℃ of reaction 12h of oil bath under nitrogen protection, excessive quadrol is removed in decompression, gained brown dope dissolves with 2ml distilled water, then adds 40ml ethanol, has a large amount of beige Precipitations, centrifugal, solids is used vacuum-drying at twice, 80 ℃ of washing with alcohol again, obtains the pulverous soccerballene ethylene diamine derivative of beige; Above-mentioned soccerballene ethylene diamine derivative is dissolved in to 10 ml distilled water, pour in the aqueous solution that 30ml is dissolved with 200mg Tai-Ace S 150 and 100mg magnesium sulfate, be heated to 80 ℃, there is brown precipitation to produce, after insulation 30min, centrifugal while hot, solids distilled water wash 3 times, vacuum-drying, obtains the modification soccerballene A of brown solid;
(2) modification manganous hypophosphite preparation: manganous hypophosphite 1g, rhubarb yellow 3g, Tai-Ace S 150 2.1g, water 5g and boric acid 1g are joined in the there-necked flask of 25ml, regulate pH to 4, be heated to 50 ℃, stirring reaction time 1h, obtains modification manganous hypophosphite solution;
(3) in the 250ml there-necked flask with agitator, prolong, temperature, add 1,4-two (dimethyl hydroxyl is silica-based) benzene 30g, isophorone diisocyanate 42g and modification soccerballene A0.09g, add butyl triphenyl to fluoridize phosphine 0.09g and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate 0.21g, at 70 ℃, react 1h, obtaining base polyurethane prepolymer for use as A is 71g;
(4) in performed polymer A, add 3-aminopropyl ortho-siliformic acid 0.57g and adenosine cyclic phosphate 10.7g, under 60 ℃ of conditions, react 3h, add triethylamine 7.1g to carry out neutralization reaction 30min, add again modification manganous hypophosphite solution 0.71g, Coconut Fatty Acid Monoethanolamide 1.42g, sulfaquinoxaline 0.85g, in 70 ℃ of reaction 1h, add water 80g and sodium laurylsulfonate 0.14g carries out emulsification 60min, obtain fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent.
example five
(1) preparation of catalyzer: add 10mg soccerballene and 30ml heavily to steam quadrol in the 250ml there-necked flask with agitator, thermometer, 70 ℃ of reaction 12h of oil bath under nitrogen protection, excessive quadrol is removed in decompression, gained brown dope dissolves with 2ml distilled water, then adds 40ml ethanol, has a large amount of beige Precipitations, centrifugal, solids is used vacuum-drying at twice, 80 ℃ of washing with alcohol again, obtains the pulverous soccerballene ethylene diamine derivative of beige; Above-mentioned soccerballene ethylene diamine derivative is dissolved in to 10 ml distilled water, pour in the aqueous solution that 30ml is dissolved with 200mg Tai-Ace S 150 and 100mg magnesium sulfate, be heated to 80 ℃, there is brown precipitation to produce, after insulation 30min, centrifugal while hot, solids distilled water wash 3 times, vacuum-drying, obtains the modification soccerballene A of brown solid;
(2) modification manganous hypophosphite preparation: manganous hypophosphite 1g, rhubarb yellow 3g, Tai-Ace S 150 2.1g, water 5g and Zulkovsky starch 2g are joined in the there-necked flask of 25ml, regulate pH to 4, be heated to 50 ℃, stirring reaction time 1h, obtains modification manganous hypophosphite solution;
(3) in the 500ml there-necked flask with agitator, prolong, temperature, add 1,4-two (dimethyl hydroxyl is silica-based) benzene 30g, isophorone diisocyanate 84g and modification soccerballene A0.36g, add again 2,3,4,6-tetra--o-acetyl-α-D-fluoridizes Glucopyranose 0.23g and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate 0.91g, at 80 ℃, reacts 5h, obtains base polyurethane prepolymer for use as A115g;
(4) in performed polymer A, add D-MANNOSE aldehydic acid list sodium salt 2.07g, methyl ortho-siliformic acid 2.07g and tricresyl phosphate (2, 3-bis-chloropropyls) ester 29g, under 80 ℃ of conditions, react 4h, add triethylamine 20.7g to carry out neutralization reaction 60min, add modification manganous hypophosphite solution 1.15g, Coconut Fatty Acid Monoethanolamide 2.3g and sulfaquinoxaline 1.38g, in 70 ℃ of reaction 1h, add water 100g and sodium laurylsulfonate 0.58g carries out emulsification 60min, add silicone grease 1.68g, 40 ℃ of temperature of reaction, reaction times 1h, obtain fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent.
Below by related experiment data, further illustrate beneficial effect of the present invention:
Water-repellancy employing is got appropriate emulsion and is evenly coated on sheet glass, after drying and forming-film, sheet glass is put into deionized water and soak under certain temperature, and observing films becomes blue, turn white, bubble, send out the situation of wrinkling, coming off.
Table one fire-retardant with waterproof polyurethane coating and sizing agent institute film forming properties
| Experimental group | Example one | Example two | Example three | Example four | Example five |
| Film outward appearance (water tolerance 48h) | Transparent | Transparent | Transparent | Transparent | Transparent |
| Hardness | B | B | B | B | B |
| Sticking power/level | 2 | 3 | 3 | 3 | 3 |
| Snappiness/mm | 2 | 2 | 2 | 2 | 3 |
From table two, can find, from film outward appearance, hardness, sticking power, flexibility better performances.
The fire-retardant mechanical property with waterproof polyurethane coating and sizing agent gained film of table two
| Experimental group | Example one | Example two | Example three | Example four | Example five |
| Elongation at break/% | 152 | 147 | 158 | 168 | 182 |
| Tensile strength/MPa | 5.7 | 5.6 | 5.7 | 6.9 | 6.8 |
| Abrasion resisting/level | 3.5 | 4 | 4 | 4.5 | 4.5 |
The reference of table two middle finger object detection method (Jiang Weiqi. leather finished product 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 better.
Flame retardant resistance is to weigh by smoke density method (maximum smoke density, reach the maximum smoke density time), oxygen index, vertical combustion index (flaming combustion time, flameless combustion time), and elongation at break characterizes its mechanical property.
The fire-retardant flame retardant resistance with waterproof polyurethane coating and sizing agent gained film of table three
| Example one | Example two | Example three | Example four | Example five | Market PU-1 | |
| Maximum smoke density | 23 | 26 | 28 | 12 | 7 | 43 |
| Reach maximum smoke density time/s | 160 | 160 | 185 | 210 | 210 | 120 |
| Oxygen index | 26.5 | 25.7 | 25.8 | 26.8 | 27.7 | 23 |
| Flaming combustion time/s | 22.4 | 22.4 | 13.3 | 10.8 | 10.1 | 24 |
| Flameless combustion time/s | 0 | 0 | 0 | 0 | 0 | 0 |
The detection of table three indices is respectively according to following standard: smoke density is measured according to GB8323-2008, and oxygen index adopts GB/T5454-1997 < < textile combustion performance test-oxygen index method > > to measure; Flaming combustion time and flameless combustion time are to be measured by test-normal beam technique > > by GB/T 5455-1997 < < textile combustion.
as shown in Table 3, the present invention fire-retardant with waterproof polyurethane coating gained film when burning, maximum smoke density significantly reduces, and reaches maximum smoke density time significant prolongation, oxygen index obviously improves, obviously shorten combustion time.
Claims (4)
1. a preparation method for fire-retardant and water-repellancy aqueous polyurethane coating and tackiness agent, is characterized in that:
(1) preparation of catalyzer: add 10mg soccerballene and 30ml heavily to steam quadrol in there-necked flask, 70 ℃ of reaction 12h of oil bath under nitrogen protection, excessive quadrol is removed in decompression, gained brown dope dissolves with 2ml distilled water, then adds 40ml ethanol, has a large amount of beige Precipitations, centrifugal, solids is used vacuum-drying at twice, 80 ℃ of washing with alcohol again, obtains the pulverous soccerballene ethylene diamine derivative of beige; Above-mentioned soccerballene ethylene diamine derivative is dissolved in to 10 ml distilled water, pour in the aqueous solution that 30ml is dissolved with 200mg Tai-Ace S 150 and 100mg magnesium sulfate, be heated to 80 ℃, there is brown precipitation to produce, after insulation 30min, centrifugal while hot, solids distilled water wash 3 times, vacuum-drying, obtains the modification soccerballene A of brown solid;
(2) modification manganous hypophosphite preparation: manganous hypophosphite, rhubarb yellow, Tai-Ace S 150, water are mixed by weight 1:3:2.1:5, regulate pH to 4, be heated to 50 ℃, stirring reaction time 1h, obtains modification manganous hypophosphite solution;
(3) under the condition existing at the modification soccerballene A of step (1), by 1, two (dimethyl hydroxyl the is silica-based) benzene of 4-and isophorone diisocyanate be 1:1.4 ~ 1 by weight: 2.8 mix, add synergistic agent and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate, at 70 ~ 80 ℃, react 1 ~ 5h, obtain base polyurethane prepolymer for use as A, described catalyst levels is 1, 0.12 ~ 0.32% of two (dimethyl hydroxyl the is silica-based) benzene of 4-and isophorone diisocyanate gross weight, synergistic agent and 2-butoxy-N-(2-diethyllaminoethyl)-4-quinoline formyl amine hydrochlorate consumption is respectively 1, two (dimethyl hydroxyl the is silica-based) benzene of 4-, isophorone diisocyanate, 0.12 ~ 0.20% and 0.3 ~ 0.8% of modification soccerballene A gross weight,
(4) to performed polymer A, add the chainextender of performed polymer A weight 0.8 ~ 3.6% and the solvent of performed polymer A weight 15 ~ 25%, under 60 ~ 80 ℃ of conditions, react 3 ~ 4h, add the triethylamine that performed polymer A weight is 10 ~ 18% and carry out neutralization reaction 30 ~ 60min, add modification manganous hypophosphite solution, Coconut Fatty Acid Monoethanolamide, sulfaquinoxaline, in 70 ℃ of reaction 1h, add water and sodium laurylsulfonate and carry out emulsification 60min, obtain fire-retardant and water-repellancy aqueous polyurethane coating and sizing agent, sodium laurylsulfonate is 0.2 ~ 0.5% of performed polymer A weight, modification manganous hypophosphite solution, Coconut Fatty Acid Monoethanolamide, sulfaquinoxaline is respectively 1% of performed polymer A weight, 2%, 1.2%.
2. the preparation method of a kind of fire-retardant and water-repellancy aqueous polyurethane coating as claimed in claim 1 and tackiness agent, it is characterized in that: synergistic agent is that diethylin sulfur trifluoride, the tetrabutyl are fluoridized phosphine, two (2-methoxy ethyl) amino sulfur trifluoride, butyl triphenyl and fluoridized phosphine, 2,3,4,6-, tetra--o-acetyl-α-D-fluoridizes any one in Glucopyranose.
3. the preparation method of a kind of fire-retardant and water-repellancy aqueous polyurethane coating as claimed in claim 1 and tackiness agent, is characterized in that: chainextender is 3-aminopropyl ortho-siliformic acid, D-MANNOSE aldehydic acid list sodium salt and methyl ortho-siliformic acid any one of compound of 1:1 by weight.
4. the preparation method of a kind of fire-retardant and water-repellancy aqueous polyurethane coating as claimed in claim 1 and tackiness agent, it is characterized in that: solvent is adenosine cyclic phosphate, tricresyl phosphate (2,3-bis-chloropropyls) ester, the chloro-1-of 2-(2,4 dichloro benzene base) vinyl diethyl phosphate is a kind of.
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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 |
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| CN113248795A (en) * | 2021-06-16 | 2021-08-13 | 山东泰星新材料股份有限公司 | Preparation method of halogen-free flame retardant special for water-based PU adhesive |
| CN113248795B (en) * | 2021-06-16 | 2022-06-21 | 山东泰星新材料股份有限公司 | Preparation method of halogen-free flame retardant special for water-based PU adhesive |
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