Summary of the invention
A kind of flame-retardant aqueous polyurethane coating adopts poly-hydroxy organosilicon to replace traditional polyester polyol and polyether glycol and isocyanate reaction; select thiophos and trifluoromethanesulfonic acid two fourth boron concerted catalysiss to replace traditional dibutyl tin laurate; with Organo-silicon on Polyurethane performed polymer, carry out chain extension; add aluminium salt suppress the amount of being fuming of urethane and improve flame retardant resistance simultaneously; the burning of gained urethane produces fine and close protective layer, and the smog discharging is little.
The present invention has adopted following technical scheme.
A preparation method for flame-retardant aqueous polyurethane coating, is characterized in that:
(1) under the condition, existing at trifluoromethanesulfonic acid two fourth B catalysts, by 1, two (dimethyl hydroxyl the is silica-based) benzene of 4-mixes according to weight ratio 2:1 with hexamethylene diisocyanate, at 80 ~ 110 ℃, react 2 ~ 4h, add again thiophos in reaction system, 80 ~ 110 ℃ of temperature of reaction, reaction times 40 ~ 60min, obtains base polyurethane prepolymer for use as; Described catalyst levels is 1,0.3 ~ 0.7% of two (dimethyl hydroxyl the is silica-based) benzene of 4-and hexamethylene diisocyanate gross weight, thiophos is 1.0 ~ 1.4% of Isosorbide-5-Nitrae-bis-(dimethyl hydroxyl is silica-based) benzene and hexamethylene diisocyanate gross weight;
(2), in base polyurethane prepolymer for use as, add the chainextender of base polyurethane prepolymer for use as gross weight 1.4 ~ 2.8% and the butanone of base polyurethane prepolymer for use as weight 16 ~ 24%, stirring reaction 3 ~ 5h under 65 ~ 85 ℃ of conditions, add triethylamine to carry out neutralization reaction 10 ~ 40min, add water and carry out emulsification, form a kind of aqueous polyurethane standby; Described triethylamine is 10 ~ 30% of base polyurethane prepolymer for use as weight;
(3), add the dispersion agent of aluminium salt compound solution weight 1.5 ~ 1.8% in the aluminium salt compound solution that is 10% to mass concentration, in temperature, be that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), N-aminoethyl-3-aminopropyl triethoxysilane of the volution phosphinylidyne Pyrrolidine ester of the aluminium salt dispersion liquid of aqueous polyurethane solid content 10 ~ 20%, the L-Glutimic acid of aqueous polyurethane solid content 1 ~ 2%, the urethane solid content 10 ~ 20% of water-based and aqueous polyurethane solid content 1 ~ 2% is joined in aqueous polyurethane, the condition down cut that is 7 at pH stirs 40 ~ 80min, obtains aqueous flame retardant polyurethane coating.
Chainextender is Diphenylsilanediol, 4, any one in two (dimethyl hydroxyl the is silica-based) phenyl ether of 4'-, silicon phthalocyanine dihydroxide; Aluminium salt compound is any one in diphenyl phosphonic acid aluminium, dipropyl phospho acid aluminium and diethyl phospho acid aluminium;
Dispersion agent is N, any one of N-dimethylamino propylamine, Sodium dodecylbenzene sulfonate, sodium polyacrylate, polyvinyl alcohol, cationic polyacrylamide, water glass, Sodium hexametaphosphate 99; Shear agitation speed 700 ~ 1200rpm.
The present invention has following characteristics:
(1) smog of comparing traditional flame retardant polyurethane release when prepared flame-retardant aqueous polyurethane coating burns significantly reduces, and fire-retardant cost performance is high;
(2) performed polymer synthetic in selected catalyst replaced the defect of the traditional obtained polyurethane film surface difference of dibutyl tin laurate, make product surface smooth smooth, good toughness.
(3) select organosilicon to make chainextender, performance nitrogen, phosphorus, silicon compound can form good tight zone, and aluminium salt compound has good smoke-suppressing, flame retardant resistance, accomplishes the optimum resistance combustion effect of fire-proof smoke-proof.
embodimentbelow in conjunction with example, further illustrate the present invention.
example one
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.3g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 80 ℃, react 2h, add again thiophos 0.99g in four-hole boiling flask, 80 ℃ of temperature of reaction, reaction times 40min, obtains base polyurethane prepolymer for use as 99.8g;
(2), in base polyurethane prepolymer for use as, add Diphenylsilanediol 1.4g and butanone 16g, stirring reaction 3h under 65 ℃ of conditions, add triethylamine 9.98g to carry out neutralization reaction 10min, add water 160g and carry out emulsification, form a kind of solid content and be 35.4% aqueous polyurethane 282g, be transferred in 500ml beaker standby;
(3), in 50ml beaker, add 3g diphenyl phosphonic acid aluminium, 27g water and N, N-dimethylamino propylamine 0.45g, is that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby in temperature;
(4), aluminium salt dispersion liquid 10.1g, L-Glutimic acid 1g, volution phosphinylidyne Pyrrolidine ester 10.1g and N-aminoethyl-3-aminopropyl triethoxysilane 1g are joined in above-mentioned (2), under the condition that is 7 at pH, 700rpm down cut stirs 40min, obtains flame-retardant polyurethane coating.
example two
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.7g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 110 ℃, react 4h, add again thiophos 1.39g in four-hole boiling flask, 110 ℃ of temperature of reaction, reaction times 60min, obtains base polyurethane prepolymer for use as 100.5g;
(2), in base polyurethane prepolymer for use as, add 4, two (dimethyl hydroxyl is silica-based) the phenyl ether 2.8g of 4'-and butanone 24.1g, stirring reaction 5h under 85 ℃ of conditions, add triethylamine 20.1g to carry out neutralization reaction 40min, add water 150g and carry out emulsification, form a kind of solid content and be 35% aqueous polyurethane 295g, be transferred in 500ml beaker standby;
(3) in temperature, be, in 50ml beaker, add 3g dipropyl phospho acid aluminium, 27g water and Sodium dodecylbenzene sulfonate 0.54g, that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), aluminium salt dispersion liquid 20.7g, L-Glutimic acid 2.1g, volution phosphinylidyne Pyrrolidine ester 20.7g and N-aminoethyl-3-aminopropyl triethoxysilane 2.1g are joined in above-mentioned (2), under the condition that is 7 at pH, 1200rpm down cut stirs 80min, obtains flame-retardant polyurethane coating.
example three
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.5g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 95 ℃, react 3h, add again thiophos 1.19g in four-hole boiling flask, 95 ℃ of temperature of reaction, reaction times 50min, obtains base polyurethane prepolymer for use as 100g;
(2), in base polyurethane prepolymer for use as, add silicon phthalocyanine dihydroxide 2.1g and butanone 20g, stirring reaction 4h under 75 ℃ of conditions, add triethylamine 15g to carry out neutralization reaction 25min, add water 150g and carry out emulsification, form a kind of solid content and be 35.8% aqueous polyurethane 285g, be transferred in 500ml beaker standby;
(3) in temperature, be, in 50ml beaker, add 3g diethyl phospho acid aluminium, 27g water and sodium polyacrylate 0.45g, that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), aluminium salt dispersion liquid 15.3g, L-Glutimic acid 1.5g, volution phosphinylidyne Pyrrolidine ester 15.3g and N-aminoethyl-3-aminopropyl triethoxysilane 1.5g are joined in above-mentioned (2), under the condition that is 7 at pH, 950rpm down cut stirs 60min, obtains flame-retardant polyurethane coating.
example four
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.7g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 110 ℃, react 4h, add again thiophos 1.39g in four-hole boiling flask, 110 ℃ of temperature of reaction, reaction times 60min, obtains base polyurethane prepolymer for use as 100.5g;
(2), in base polyurethane prepolymer for use as, add 4, two (dimethyl hydroxyl is silica-based) the phenyl ether 2.8g of 4'-and butanone 24.1g, stirring reaction 5h under 85 ℃ of conditions, add triethylamine 20.1g to carry out neutralization reaction 40min, add water 150g and carry out emulsification, form a kind of solid content and be 35% aqueous polyurethane 295g, be transferred in 500ml beaker standby;
(3) in temperature, be, in 50ml beaker, add 3g dipropyl phospho acid aluminium, 27g water and Sodium dodecylbenzene sulfonate 0.54g, that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), aluminium salt dispersion liquid 20.7g, L-Glutimic acid 2.1g, volution phosphinylidyne Pyrrolidine ester 20.7g, N-aminoethyl-3-aminopropyl triethoxysilane 2.1g and tartaric acid epinephrine 0.2g are joined in above-mentioned (2), under the condition that is 7 at pH, 1200rpm down cut stirs 80min, obtains flame-retardant polyurethane coating.
example five
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.5g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 95 ℃, react 3h, add again thiophos 1.19g in four-hole boiling flask, 95 ℃ of temperature of reaction, reaction times 50min, obtains base polyurethane prepolymer for use as 100g;
(2), in base polyurethane prepolymer for use as, add silicon phthalocyanine dihydroxide 2.1g and butanone solvent 20g, stirring reaction 4h under 75 ℃ of conditions, add triethylamine 15g to carry out neutralization reaction 25min, add water 150g and carry out emulsification, form a kind of solid content and be 35.8% aqueous polyurethane 285g, be transferred in 500ml beaker standby;
(3) in temperature, be, in 50ml beaker, add 3g diethyl phospho acid aluminium, 27g water and sodium polyacrylate 0.45g, that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), by 3 of aluminium salt dispersion liquid 15.3g, L-Glutimic acid 1.5g, volution phosphinylidyne Pyrrolidine ester 15.3g, N-aminoethyl-3-aminopropyl triethoxysilane 1.5g and 0.5g, 3'-diamino bisphenol S joins in above-mentioned (2), under the condition that is 7 at pH, 950rpm down cut stirs 60min, obtains flame-retardant polyurethane coating.
Table one is films that example one of the present invention becomes to the prepared a kind of flame-retardant aqueous polyurethane of example five with table two.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 flame retardant resistance of table one flame-retardant aqueous polyurethane film
|
Example one |
Example two |
Example three |
Example four |
Example five |
Market PU-1 |
Maximum smoke density |
22 |
25 |
27 |
11 |
6 |
43 |
Reach maximum smoke density time/s |
160 |
160 |
185 |
180 |
180 |
120 |
Oxygen index |
25.4 |
24.7 |
25.8 |
26.8 |
26.6 |
23 |
Flaming combustion time/s |
21.3 |
21.4 |
13.2 |
10.7 |
10.1 |
24 |
Flameless combustion time/s |
0 |
0 |
0 |
0 |
0 |
0 |
The detection of table one 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 1, during flame-retardant aqueous polyurethane burning of the present invention, maximum smoke density significantly reduces, and reaches maximum smoke density time significant prolongation, and oxygen index obviously improves, and obviously shorten combustion time.
The elongation at break of table two flame-retardant aqueous polyurethane film
|
Example one |
Example two |
Example three |
Example four |
Example five |
Market PU-1 |
Elongation at break/% |
185.06 |
192.07 |
177.38 |
?192.69 |
193.54 |
164.1 |
Table two middle finger object detection method is with reference to [2] Jiang Weiqi. leather finished product physical and chemical inspection [M]. China Light Industry Press, 1999,82-96, the elongation at break of flame-retardant polyurethane of the present invention be improved significantly.