CN104231209A - Preparation method for high-hardness waterborne polyurethane dispersion - Google Patents
Preparation method for high-hardness waterborne polyurethane dispersion Download PDFInfo
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- CN104231209A CN104231209A CN201410498604.3A CN201410498604A CN104231209A CN 104231209 A CN104231209 A CN 104231209A CN 201410498604 A CN201410498604 A CN 201410498604A CN 104231209 A CN104231209 A CN 104231209A
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Abstract
The invention discloses a preparation method for high-hardness waterborne polyurethane dispersion. An inorganic nano material and waterborne polyurethane are grafted through an in-situ polymerization method, so that the hybridization reaction of inorganic materials and the organic materials is realized and complementary advantages are realized. The preparation method comprises the following operation steps: adding polyisocyanate, macromolecule polyol, a catalyst, a chain extender and a silane coupling agent according to certain weight ratio in a flask for reacting to obtain a polyurethane prepolymer; after the reaction is ended, sequentially adding a neutralizer, inorganic nano material dispersion liquid and deionized water under the condition of low-temperature and high-speed stirring; finally, heating under the vacuum condition for removing the solvent to obtain the high-hardness waterborne polyurethane dispersion. Compared with the traditional inorganic and organic blending process, the preparation method has the characteristics that products prepared through the preparation method have the advantages of good stability, excellent water resistance, long-time aging resistance, excellent and high adhesion, high drying speed, high hardness, good fullness, higher light transmittance and the like, and are wide in application range.
Description
Technical field
The invention belongs to water-based industrial paint emulsion technology field, relate to a kind of preparation method of high rigidity aqueous polyurethane dispersing liquid specifically.
Background technology
From early 1990s, World Developed Countries just starts " Green Revolution ", drives paint industry to stride forward to the large step of " green " line of production.Since entering 21 century, perfect further along with environmental regulation, to alleviate the research of the water-borne coatings of the low VOC discharge carried out for the purpose of earth load, becomes the emphasis of research and development just increasingly.The discharge organism that traditional oiliness industrial paint is a large amount of, directly affects the healthy of people on the one hand; On the other hand its can in atmosphere with other chemical substance generation chemical reaction, form PM2.5, cause topsoil, the PM2.5 of annual solvent based coating in use discharge organic volatile formation, is only second to the pollution that vehicle exhaust causes air.And by contrast, water-based industrial paint have asepsis environment-protecting, odorlessness, volatilizable thing few, do not fire the advantages such as not quick-fried, can effectively solve solvent based coating form the emission problem of PM2.5, therefore the Water-borne modification of industrial paint will be trend of the times.Aqueous polyurethane dispersion because of its paint film plentiful, beautiful, there is the advantages such as excellent rotproofness, chemical proofing, weathering resistance, water tolerance, sticking power are good, but its difference of hardness, easily scratch, the dry shortcoming such as slow, significantly limit the application of aqueous polyurethane dispersion in water-based industrial paint.Traditional inorganic materials and aqueous polyurethane blending method, although the problem that effectively can solve waterborne polyurethane paint film lower hardness, also have impact on the water resistance of waterborne polyurethane paint film to a great extent, cannot tackle the problem at its root.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of high rigidity aqueous polyurethane dispersion is provided, can not affect under the water-fast prerequisite of paint film, effectively solve the problem that low, the easy scuffing of aqueous polyurethane dispersion hardness of paint film, rate of drying are slow.
Another object of the present invention is to solve inorganic materials in coating production process and be difficult to the problem be distributed in water-base resin, improve the stability in storage of coating.
In order to achieve the above object, by the following technical solutions, its step of preparation process is as follows in the present invention:
1, join in flask by macromolecular polyol, at temperature 100-140 DEG C, vacuum tightness is dewatered 1-3 hour under the condition of 0.01-0.04MPa, cools to 30-90 DEG C;
2, by being 1:1.5-50 with macromolecular polyol weight ratio, polyisocyanates adds in flask, and logical nitrogen protection, reacts 1-2 hour, adopt Di-n-Butyl Amine volumetry to judge reaction end in reaction process at 60-100 DEG C;
3, add in flask at 40-70 DEG C with macromolecular polyol weight ratio be 1:0.1-0.8 hydrophilic chain extender, account for small molecule chain extender that dispersion quality mark is 0.1-2% and account for dispersion quality mark 0.01-0.1% catalyzer, then at 70-85 DEG C, react 2-4 hour;
4, be cooled to 40-70 DEG C, add and account for dispersion quality mark 20-80% solvent reduction system viscosity, continue reaction 1-2 hour;
5, be cooled to 10-40 DEG C, add the silane coupling agent of the 0.5-5% accounting for dispersion quality mark, reaction 10-100 minute, obtains base polyurethane prepolymer for use as;
6, low whipping speed is under the agitation condition of 300-1500rpm, and drip with the hydrophilic chain extender amount of substance described in step (3) than the neutralizing agent for 1:0.8-1.2 at base polyurethane prepolymer for use as, reaction 1-10 minute, obtains the base polyurethane prepolymer for use as neutralized;
7, low whipping speed is under the agitation condition of 300-1500rpm, in and base polyurethane prepolymer for use as in add account for dispersion quality mark 10-50%, the nano inorganic material aqueous solution that concentration is 10-60wt%, reaction 1-10 minute;
8, low whipping speed is under the agitation condition of 300-1500rpm, continue in above-mentioned base polyurethane prepolymer for use as, slow dropping accounts for the deionized water that dispersion quality mark is 60 ~ 70%, the last rear chainextender reaction 10-60 minute adding the 0.5-5% accounting for dispersion quality mark again, forms polyurethane dispersions;
9, under vacuum tightness is 0.01-0.04MPa condition, in 40-80 DEG C of reaction 20-80 minute, remove the solvent added in reaction process, just can obtain a kind of high rigidity aqueous polyurethane dispersion.
Macromolecular polyol described in step (1) is selected from one or more amounts in polyether glycol, polyester polyol, sulfonated polyether polyvalent alcohol, sulfonated polyester polyol and the reduced branching degree polyester polyol that molecular weight is 600-5000.
Polyisocyanates described in step (2) is selected from tolylene diisocyanate (TDI), 4, in 4 '-diphenylmethanediisocyanate (MDI), 4,4'-dicyclohexyl methane diisocyanates (HMDI), isophorone diisocyanate (IPDI), hexamethylene-diisocyanate (HDI), xylylene diisocyanate (XDI) and poly methylene poly phenyl poly isocyanate (PAPI) one or more.
Hydrophilic chain extender described in step (3) be selected from dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), quadrol base ethyl sulfonic acid sodium and Isosorbide-5-Nitrae-butyleneglycol-2-sodium sulfonate one or more.
Small molecule chain extender described in step (3) be selected from glycol ether, BDO, neopentyl glycol, hexylene glycol, TriMethylolPropane(TMP) one or more.
Catalyzer described in step (3) be selected from dibutyl tin laurate, stannous octoate, N, N mono-dimethyl cyclohexyl amine, triethylenediamine one or more.
One or more in solvent selected from acetone described in step (4), butanone or toluene.
Silane coupling agent described in step (5) is selected from the one in methacryloxypropyl trimethoxy silane (KH570), γ-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560), anilinomethyl trimethoxy silane, anilino triethoxyl silane.
Neutralizing agent described in step (6) is selected from the one in sodium hydroxide, ammoniacal liquor, triethylamine.
The nano inorganic material aqueous solution described in step (7) is selected from the one in silicon sol, the nano silicon aqueous solution, nanometer titanium dioxide aluminum water solution, the nano-calcium carbonate aqueous solution.
Rear chainextender described in step (8) is selected from the one in quadrol, diamines, diethylenetriamine and isophorone diamine.
Patent of the present invention, pass through situ aggregation method, nano inorganic material and aqueous polyurethane are carried out graft reaction, utilize the reactive behavior of the hydroxyl of nano inorganic material particle surface and the isocyano of base polyurethane prepolymer for use as in the nano inorganic material aqueous solution, be better than the reactive behavior of the isocyano of water and base polyurethane prepolymer for use as, thus nano inorganic material is grafted on aqueous polyurethane molecular chain, well achieve the hydridization reaction of inorganic-organic material, both water tolerance and the sticking power of paint film had been ensure that, efficiently solve again waterborne polyurethane paint film hardness low, easy scuffing and the problem such as rate of drying is slow.Because inorganic materials is different from the membrane formation mechanism of organic materials, inorganic materials is grafted on the molecular chain of organic resin, effectively can improve the rate of drying of water-based industrial paint.Inorganic materials has the advantages such as hardness is high, ageing-resistant, chemicals-resistant is good, and organic materials has, and water-tolerant, glossiness are high, the excellent advantage of sticking power, the two makes up for each other's deficiencies and learn from each other, and reaches effective performance complement, thus the water-based industrial paint of energy forming property excellence.The present invention adopts rationally perfect operation steps and processing parameter, inorganic materials is effectively distributed in water-base resin, improves the stability in storage of coating.
Embodiment
The invention is further illustrated by the following examples, but described embodiment is only for illustration of the present invention instead of restriction the present invention.
embodiment 1
By molecular weight be 2000 polyester polyol add in four neck flasks, be 120 DEG C in temperature, vacuum tightness is under the condition of 0.02MPa, dewaters 2 hours, cool to 60 DEG C for subsequent use.Tolylene diisocyanate (TDI) and polyester polyol are added in four neck flasks by weight 1:3 dehydration, logical nitrogen protection, react 2 hours at 70 DEG C, be cooled to add with polyester polyol mass ratio at 60 DEG C be 1:0.2 dimethylolpropionic acid, account for 1 of dispersion quality mark 4%, 4 butyleneglycols and the dibutyl tin laurate accounting for dispersion quality mark 0.05%, then react 4 hours at 80 DEG C; Cool to 60 DEG C, add the acetone accounting for dispersion quality mark 20% and reduce system viscosity, react 1 hour.Continue to be cooled to 30 DEG C, add the KH550 accounting for dispersion quality mark 1%, react 20 minutes, add rapidly under 500rpm stirs with the amount of substance of dimethylolpropionic acid than the triethylamine for 1:1, low whipping speed is 500rpm subsequently, add successively and account for dispersion quality mark 10%, concentration is the 30wt% nano silicon aqueous solution and accounts for the deionized water that dispersion quality mark is 70%, add again and account for the reacting ethylenediamine 10 minutes that dispersion quality mark is 0.5%, form polyurethane dispersions, be finally 0.02MPa by above-mentioned dispersion in vacuum tightness, temperature is react 60 minutes under the condition of 60 DEG C, remove acetone, obtain aqueous polyurethane dispersion.Be applied on sheet glass, film thickness is 20 microns, its hardness >=2H, water-fast 120 hours non-whitenings, resistance to boiling water 15 minutes non-whitenings, and alkaline-resisting, resistance to alcohol 1 hour is without exception, and coating transmittance is unchanged.
embodiment 2
By molecular weight be 2000 sulfonated polyester polyol add in four neck flasks, be 120 DEG C in temperature, vacuum tightness is under the condition of 0.02MPa, dewaters 2 hours, cool to 60 DEG C for subsequent use.By diphenylmethanediisocyanate (MDI) and molecular weight be 2000 polyester polyol by weight 1:4 dehydration add in four neck flasks, logical nitrogen protection, react 1 hour at 70 DEG C, be cooled to 60 DEG C to add with sulfonated polyester polyol mass ratio be 1:0.1 dimethylolpropionic acid, add that to account for dispersion quality mark be the glycol ether of 2% and account for the dibutyl tin laurate that dispersion quality mark is 0.02%, then react 4 hours at 80 DEG C, add account for dispersion quality mark be 45% acetone react 30 minutes, be cooled to 30 DEG C, add that to account for dispersion quality mark be 2.5% silane coupling agent KH560, react 30 minutes, low whipping speed is 1300rpm, add rapidly with dimethylolpropionic acid amount of substance than the triethylamine for 1:1, adding concentration subsequently is successively 20wt%, account for dispersion quality mark be 10% the nanometer titanium dioxide calcium aqueous solution and account for dispersion quality mark be 60% deionized water add again and account for the isophorone diamine that dispersion quality mark is 1.5%, react 20 minutes, form polyurethane dispersions, be 0.02MPa by above-mentioned dispersion in vacuum tightness, temperature is under 60 DEG C of conditions, react and remove butanone in 30 minutes, obtain aqueous polyurethane dispersion.Be applied on sheet glass, film thickness is 10 microns, and its hardness reaches >=2H, water-fast 120 hours non-whitenings, resistance to boiling water 15 minutes non-whitenings, and alkaline-resisting, resistance to alcohol 1 hour is without exception, and coating transmittance is unchanged.
Claims (9)
1. a preparation method for high rigidity aqueous polyurethane dispersion, is characterized in that operation steps is as follows:
(1) join in flask by macromolecular polyol, at temperature 100-140 DEG C, vacuum tightness is dewatered 1-3 hour under the condition of 0.01-0.04MPa, cools to 30-90 DEG C;
(2) by being 1:1.5-50 with macromolecular polyol weight ratio, polyisocyanates adds in flask, and logical nitrogen protection, reacts 1-2 hour, adopt Di-n-Butyl Amine volumetry to judge reaction end in reaction process at 60-100 DEG C;
(3) at 40-70 DEG C drip with macromolecular polyol weight ratio be 1:0.1-0.8 hydrophilic chain extender, account for the small molecule chain extender of the 0.1-2% of dispersion quality mark and account for the catalyzer of dispersion quality mark 0.01-0.1%, then at 70-85 DEG C, react 2-4 hour;
(4) be cooled to 40-70 DEG C, add the solvent accounting for dispersion quality mark 20-80% and reduce system viscosity, continue reaction 1-2 hour;
(5) be cooled to 30 DEG C, add the silane coupling agent of the 0.5-5% accounting for dispersion quality mark, reaction 10-100 minute, obtains base polyurethane prepolymer for use as;
(6) low whipping speed is under the agitation condition of 300-1500rpm, and drip with the hydrophilic chain extender amount of substance described in step (3) than the neutralizing agent for 1:0.8-1.2, reaction 1-10 minute, obtains the base polyurethane prepolymer for use as neutralized;
(7) low whipping speed is under the agitation condition of 300-1500rpm, in and base polyurethane prepolymer for use as in add account for dispersion quality mark 10-50%, the nano inorganic material aqueous solution that concentration is 10-60wt%, reaction 1-10 minute;
(8) low whipping speed is under the agitation condition of 300-1500rpm, continue in above-mentioned base polyurethane prepolymer for use as, slow dropping accounts for the deionized water that dispersion quality mark is 60 ~ 70%, the last rear chainextender adding the 0.5-5% accounting for dispersion quality mark again, forms polyurethane dispersions;
(9) under vacuum tightness is 0.01-0.04MPa condition, in 40-80 DEG C of reaction 20-80 minute, remove the solvent added in reaction process, just can obtain a kind of high rigidity aqueous polyurethane dispersion.
2. the preparation method of a kind of high rigidity aqueous polyurethane dispersion according to claim 1, it is characterized in that, the macromolecular polyol described in step (1) be selected from polyether glycol, polyester polyol, sulfonated polyether polyvalent alcohol, sulfonated polyester polyol and the reduced branching degree polyester polyol that molecular weight is 600-5000 one or more.
3. the preparation method of a kind of high rigidity aqueous polyurethane dispersion according to claim 1, it is characterized in that, polyisocyanates described in step (2) is selected from tolylene diisocyanate (TDI), 4, in 4 '-diphenylmethanediisocyanate (MDI), 4,4'-dicyclohexyl methane diisocyanates (HMDI), isophorone diisocyanate (IPDI), hexamethylene-diisocyanate (HDI), xylylene diisocyanate (XDI) and poly methylene poly phenyl poly isocyanate (PAPI) one or more.
4. the preparation method of a kind of high rigidity aqueous polyurethane dispersion according to claim 1, it is characterized in that, hydrophilic chain extender described in step (3) be selected from dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), quadrol base sodium sulfonate and BDO-2-sodium sulfonate one or more; Small molecule chain extender described in step (3) be selected from glycol ether, BDO, neopentyl glycol, hexylene glycol, TriMethylolPropane(TMP) one or more; Catalyzer described in step (3) be selected from dibutyl tin laurate, stannous octoate, N, N mono-dimethyl cyclohexyl amine, triethylenediamine one or more.
5. the preparation method of a kind of high rigidity aqueous polyurethane dispersion according to claim 1, is characterized in that, the one in the solvent selected from acetone described in step (4), butanone or toluene.
6. the preparation method of a kind of high rigidity aqueous polyurethane dispersion according to claim 1, it is characterized in that, the silane coupling agent described in step (5) is selected from the one in methacryloxypropyl trimethoxy silane (KH570), γ-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560), anilinomethyl trimethoxy silane, anilino triethoxyl silane.
7. the preparation method of a kind of high rigidity aqueous polyurethane dispersion according to claim 1, is characterized in that, the neutralizing agent described in step (6) is selected from the one in sodium hydroxide, ammoniacal liquor, triethylamine.
8. the preparation method of a kind of high rigidity aqueous polyurethane dispersion according to claim 1, it is characterized in that, the nano inorganic material aqueous solution described in step (7) is selected from the one in silicon sol, the nano silicon aqueous solution, nanometer titanium dioxide aluminum water solution, the nano-calcium carbonate aqueous solution.
9. the preparation method of a kind of high rigidity aqueous polyurethane dispersion according to claim 1, is characterized in that, the rear chainextender described in step (8) is selected from the one in quadrol, diamines, diethylenetriamine and isophorone diamine.
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