summary of the inventionthe object of this invention is to provide a kind of synthetic method of dumb light type waterborne polyurethane resin composite emulsion, to solve prior art Problems existing.
In order to achieve the above object, the technical solution adopted in the present invention is:
A synthetic method for dumb light type waterborne polyurethane resin composite emulsion, is characterized in that: comprise the following steps:
(1) silane coupling agent of aerosil modification, is prepared:
The deionized water of the silane coupling agent of 4.5 ~ 6% weight, 1 ~ 2% weight and the dehydrated alcohol of 92 ~ 94.5% weight are added in there-necked flask, stir 1 ~ 2 hour at 45 DEG C, add the aerosil of 8 ~ 15% weight, ultrasonic disperse 2h, after continuing to stir 5 ~ 10h under 45 DEG C of conditions, by aforesaid liquid underpressure distillation removing ethanol under 90 ~ 100 DEG C of conditions, then residue composition is incorporated in the N-Methyl pyrrolidone of 50% weight, obtain the silane coupling agent of aerosil modification;
(2), Waterborne Polyurethane Prepolymer is prepared:
By the macromolecular polyol of 20 ~ 40% weight after 100 ~ 120 DEG C of dehydration 0.5 ~ 1.5h, add the polyisocyanates of 10 ~ 20% weight, at 85 ~ 100 DEG C of reaction 2 ~ 3h, then the hydrophilic compounds of 1 ~ 2% weight and the small molecule chain extender of 0 ~ 3% weight is added, at 75 ~ 85 DEG C of reaction 2 ~ 3h, add the catalyzer of 0.02 ~ 0.06% weight again, at 60 ~ 75 DEG C of reaction 2 ~ 3h, obtain the polyurethane prepolymer that end group is NCO group, the acetone diluted of 25 ~ 50% weight is added, i.e. obtained waterborne polyurethane prepolymer in reaction process;
(3), composite aqueous emulsion is prepared:
The waterborne polyurethane prepolymer that step (2) is obtained transfers to high speed shear dispersion machine, the modified silane coupling agent that step (1) is obtained is added under 800 ~ 4000 revs/min of high speed shear and 0 ~ 20 DEG C of condition, disperse after 15 ~ 40 minutes, the triethylamine adding 0.5 ~ 1.5% weight again reacts 1 ~ 3 minute, then the deionized water of 150 ~ 250% weight and the polyamine of 0.2 ~ 0.5% weight is added, stir after 1 ~ 10 minute, finally obtain dumb light type waterborne polyurethane resin composite emulsion.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, it is characterized in that: in described step (1), silane coupling agent is γ-aminopropyl triethoxysilane KH550, or γ-glycidyl ether oxygen propyl trimethoxy silicane KH560, or γ-(methacryloxypropyl) propyl trimethoxy silicane KH570.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, it is characterized in that: in described step (1), aerosil is the aerosil of particle diameter 1 ~ 5um rank.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, it is characterized in that: in described step (2), macromolecular polyol is one or more in polycaprolactone polyol PJ, polycarbonate polyol PCD, polytetrahydrofuran ethoxylated polyhydric alcohol PTMG, polyethylene oxide polyol PEG, polyoxypropylene polyol PPG, hydroxy-terminated polybutadienes HTTP.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, it is characterized in that: in described step (2), polyisocyanates is tolylene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethanediisocyanate MDI, 1, hexamethylene-diisocyanate HDI, xylylene diisocyanate XDI, naphthalene-1, 5-vulcabond NDI, polymethylene multi-phenenyl isocyanate PAPI, tetramethylxylylene diisocyanate TMXDI, Methylcyclohexyl diisocyanate HTDI, one or more in dicyclohexyl methane diisocyanate HMDI.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, is characterized in that: in described step (2), hydrophilic compounds be dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl sad in one or more.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, it is characterized in that: in described step (2), small molecule chain extender is ethylene glycol, glycol ether, 1,4-butyleneglycol, 2,3-butyleneglycol, 2-methyl isophthalic acid, one or more in 3 propylene glycol, 1,6-hexylene glycol, neopentyl glycol, glycol ether, glycerine, sorbyl alcohol, TriMethylolPropane(TMP), hydroxymethyl-cyclohexane, pentaerythritol diacrylate PEDA, dipentaerythrityl ether tetraacrylate DPETA, TriMethylolPropane(TMP) mono acrylic ester TMPMA.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, it is characterized in that: in described step (2), catalyzer is dibutyl tin laurate.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, it is characterized in that: in described step (3), polyamine is quadrol, propylene diamine, hexanediamine, 2-methyl isophthalic acid, one or more in 5-pentamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, your ketone of different fluorine diamines, 1,3 hexanaphthene dimethylamine.
The synthetic method of described a kind of dumb light type waterborne polyurethane resin composite emulsion, is characterized in that: in described step (3), silane coupling agent accounts for 5 ~ 15% of waterborne polyurethane prepolymer weight.
Advantage of the present invention is: the present invention accesses silane coupler modified aerosil by chemical bond in aqueous polyurethane, obtain stronger stability and excellent matte effect, after covering with paint, film forming has good penetrating degree, can not impact scytoblastema color while reaching matte effect, " turn white, the burnt hair " phenomenon avoiding that additional matting agent easily occurs.Dumb light type waterborne polyurethane resin prepared by application the present invention, safety and environmental protection, emulsion property is stablized, and polymer materials has excellent mechanical property and scrape resistant, water resistance, can be widely used in the process of synthetic leather surface layer.
Embodiment
A synthetic method for dumb light type waterborne polyurethane resin composite emulsion, comprises the following steps:
(1) silane coupling agent of aerosil modification, is prepared:
The deionized water of the silane coupling agent of 4.5 ~ 6% weight, 1 ~ 2% weight and the dehydrated alcohol of 92 ~ 94.5% weight are added in there-necked flask, stir 1 ~ 2 hour at 45 DEG C, add the aerosil of 8 ~ 15% weight, ultrasonic disperse 2h, after continuing to stir 5 ~ 10h under 45 DEG C of conditions, by aforesaid liquid underpressure distillation removing ethanol under 90 ~ 100 DEG C of conditions, then residue composition is incorporated in the N-Methyl pyrrolidone of 50% weight, obtain the silane coupling agent of aerosil modification;
(2), Waterborne Polyurethane Prepolymer is prepared:
By the macromolecular polyol of 20 ~ 40% weight after 100 ~ 120 DEG C of dehydration 0.5 ~ 1.5h, add the polyisocyanates of 10 ~ 20% weight, at 85 ~ 100 DEG C of reaction 2 ~ 3h, then the hydrophilic compounds of 1 ~ 2% weight and the small molecule chain extender of 0 ~ 3% weight is added, at 75 ~ 85 DEG C of reaction 2 ~ 3h, add the catalyzer of 0.02 ~ 0.06% weight again, at 60 ~ 75 DEG C of reaction 2 ~ 3h, obtain the polyurethane prepolymer that end group is NCO group, the acetone diluted of 25 ~ 50% weight is added, i.e. obtained waterborne polyurethane prepolymer in reaction process;
(3), composite aqueous emulsion is prepared:
The waterborne polyurethane prepolymer that step (2) is obtained transfers to high speed shear dispersion machine, the modified silane coupling agent that step (1) is obtained is added under 800 ~ 4000 revs/min of high speed shear and 0 ~ 20 DEG C of condition, disperse after 15 ~ 40 minutes, the triethylamine adding 0.5 ~ 1.5% weight again reacts 1 ~ 3 minute, then the deionized water of 150 ~ 250% weight and the polyamine of 0.2 ~ 0.5% weight is added, stir after 1 ~ 10 minute, finally obtain dumb light type waterborne polyurethane resin composite emulsion.
In step (1), silane coupling agent is γ-aminopropyl triethoxysilane KH550, or γ-glycidyl ether oxygen propyl trimethoxy silicane KH560, or γ-(methacryloxypropyl) propyl trimethoxy silicane KH570.
In step (1), aerosil is the aerosil of particle diameter 1 ~ 5um rank.
In step (2), macromolecular polyol is one or more in polycaprolactone polyol PJ, polycarbonate polyol PCD, polytetrahydrofuran ethoxylated polyhydric alcohol PTMG, polyethylene oxide polyol PEG, polyoxypropylene polyol PPG, hydroxy-terminated polybutadienes HTTP.
In step (2), polyisocyanates is tolylene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethanediisocyanate MDI, 1, one or more in hexamethylene-diisocyanate HDI, xylylene diisocyanate XDI, naphthalene-1,5-vulcabond NDI, polymethylene multi-phenenyl isocyanate PAPI, tetramethylxylylene diisocyanate TMXDI, Methylcyclohexyl diisocyanate HTDI, dicyclohexyl methane diisocyanate HMDI.
In step (2), hydrophilic compounds be dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl sad in one or more.
In step (2), small molecule chain extender is ethylene glycol, glycol ether, 1,4-butyleneglycol, 2,3-butyleneglycol, 2-methyl isophthalic acid, one or more in 3 propylene glycol, 1,6-hexylene glycol, neopentyl glycol, glycol ether, glycerine, sorbyl alcohol, TriMethylolPropane(TMP), hydroxymethyl-cyclohexane, pentaerythritol diacrylate PEDA, dipentaerythrityl ether tetraacrylate DPETA, TriMethylolPropane(TMP) mono acrylic ester TMPMA.
In step (2), catalyzer is dibutyl tin laurate.
In step (3), polyamine is quadrol, propylene diamine, hexanediamine, 2-methyl isophthalic acid, one or more in 5-pentamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, your ketone of different fluorine diamines, 1,3 hexanaphthene dimethylamine.
In step (3), silane coupling agent accounts for 5 ~ 15% of waterborne polyurethane prepolymer weight.
Specific embodiment 1:
The silane coupling agent preparation of aerosil modification:
A) in the 500ml four-hole boiling flask that agitator, condensing reflux pipe, thermopair are housed, the dehydrated alcohol adding 5g Silane coupling agent KH550 and 1.5g deionized water and 93.5g adds in there-necked flask, stirs 1 hour at 45 DEG C.
B) the aerosil 10g of 2 μm of ranks is added and ultrasonic disperse 2 hours.Then under 45 DEG C of conditions, 10 hours are then stirred.
C) by liquid pressure-reducing distillation removing ethanol, then remaining solid part is incorporated in 80gN-methyl-2-pyrrolidone, obtain the silane coupling agent of modification.
The preparation of Waterborne Polyurethane Prepolymer:
A) in the 500ml four-hole boiling flask that agitator, condensing reflux pipe, thermopair are housed, the PTMG (2000) of PHA and 93.6g of 31.2g and the hydroxy silicon oil (2000) of 1.56g is added, 100 DEG C of temperature dehydration 0.5h.
B) HMDI of 53.04g is added, at 90 DEG C of reaction 2h.
C) DMPA and the 5.07g2-methyl isophthalic acid of 4.48g is added, 3 propylene glycol, at 80 DEG C of reaction 2h.
D) add the dibutyl tin laurate of 0.2g, at 60 DEG C of reaction 3h, obtain the polyurethane prepolymer that end group is NCO group.
E) acetone diluted of 145g is added in reaction process, i.e. obtained waterborne polyurethane prepolymer.
The preparation of composite aqueous emulsion:
A) above-mentioned prepolymer is proceeded to high speed shear dispersion machine, under 1000 revs/min of high speed shear and 20 DEG C of conditions, add the silane coupling agent (the silane coupling agent total mass of modification: prepolymer quality is 1:2) of above-mentioned modification.
B) disperse 40 minutes, the triethylamine adding 3.39g reacts 1 minute.
C) add the deionized water of 265.2g and 1 of 1.56g, 3 hexanaphthene dimethylamine, stir 1 minute, finally obtain dumb light type waterborne polyurethane resin.
Specific embodiment 2:
The silane coupling agent preparation of aerosil modification:
A) in the 500ml four-hole boiling flask that agitator, condensing reflux pipe, thermopair are housed, the dehydrated alcohol adding 5g Silane coupling agent KH550 and 1.5g deionized water and 93.5g adds in there-necked flask, stirs 1 hour at 45 DEG C.
B) the aerosil 10g of 2 μm of ranks is added and ultrasonic disperse 2 hours.Then under 45 DEG C of conditions, 10 hours are then stirred.
C) by liquid pressure-reducing distillation removing ethanol, then remaining solid part is incorporated in 80gN-methyl-2-pyrrolidone, obtain the silane coupling agent of modification.
The preparation of Waterborne Polyurethane Prepolymer:
A) in the 500ml four-hole boiling flask that agitator, condensing reflux pipe, thermopair are housed, the PPG (2000) of PHA and 93.6g of 31.2g and the hydroxy silicon oil (2000) of 1.56g is added, 100 DEG C of temperature dehydration 0.5h.
B) MDI of 53.04g is added, at 90 DEG C of reaction 2h.
C) DMPA and the 5.07g glycol ether of 4.48g is added, at 80 DEG C of reaction 2h.
D) add the dibutyl tin laurate of 0.2g, at 60 DEG C of reaction 3h, obtain the polyurethane prepolymer that end group is NCO group.
E) acetone diluted of 145g is added in reaction process, i.e. obtained waterborne polyurethane prepolymer.
The preparation of composite aqueous emulsion:
A) above-mentioned prepolymer is proceeded to high speed shear dispersion machine, under 1000 revs/min of high speed shear and 20 DEG C of conditions, add the silane coupling agent (the silane coupling agent total mass of modification: prepolymer quality is 1:2) of above-mentioned modification.
B) disperse 40 minutes, the triethylamine adding 3.39g reacts 1 minute.
C) add the deionized water of 265.2g and the different fluorine that ketone diamines of 1.56g, stir 1 minute, finally obtain dumb light type waterborne polyurethane resin.