CN101250375A - POSS/polyurethane aqueous composite paint and preparation method thereof - Google Patents
POSS/polyurethane aqueous composite paint and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a POSS/polyurethane water compound paint and the process for preparation, the water compound paint is prepared by the following process, firstly, preparing POSS which is not capped with a hydrolysis method, secondly, adopting silane coupling agent KH-550 to cap and get a POSS which contains amido group, and finally, chemically compounding POSS and water polyurethane dispersion to prepare a POSS/polyurethane water compound paint. The water compound paint of the invention has the advantages of excellent indoor temperature storage property, degree of hardness and waterproof property, and fire-resisting property and anti-ultraviolet light property are excellent. The process for preparation of the invention has the advantages of convenient and simple technique, high film coating quality, low production cost and extend application prospect and the like, which has no pollution to environment, the water paint is a new generation environmental-friendly high-performance chemical product, which can be applied in the fields such as automobile coating, wood coating, construction, office furniture, leather, textile finishing, pigment printing and mechanical equipment.
Description
Technical field
The invention belongs to water-borne coatings fabricating technology field, be specifically related to a kind of POSS/ polyurethane aqueous composite paint and preparation method thereof.
Background technology
Aqueous polyurethane is because it is dispersion medium with water, some important performance characteristics that not only have solvent borne polyurethane, also have low VOC, advantage such as nontoxic, nonflammable, free from environmental pollution, energy-conservation, safe and reliable simultaneously, so development in recent years is rapid.But the aqueous polyurethane of preparation is filmed and is remained further to be developed at aspects such as water tolerance, solvent resistance and physical and mechanical propertiess at present.In order to improve the over-all properties of aqueous polyurethane coating, enlarge its range of application, need to carry out composite modified to aqueous polyurethane coating, modal method of modifying still is organic composite modified aqueous polyurethane coatings such as Resins, epoxy and acrylic resin, and inorganic compounding modified aqueous polyurethane coatings such as nano silicon, nano-calcium carbonate, clay and polynite, wherein again with the composite modified the easiest and economical and effective of organic and inorganic.
Chinese patent CN1536032A has reported a kind of nanometer titanium dioxide silicon emulsion and manufacture method thereof, and this emulsion can directly join in the water-borne coatings, is used for the composite modified of water-borne coatings.Its manufacture method is: add water-soluble alcohol in the aqueous colloid solution of silicon-dioxide, add silane coupling agent, tensio-active agent and water etc. again and make; Perhaps in the nano silicon gel, add the aqueous solution of water-soluble alcohol or described alcohol, add preparations such as silane coupling agent, tensio-active agent and water again.Used 5～15% tensio-active agent in this nanometer titanium dioxide silicon emulsion, this will inevitably have a strong impact on the performance of aqueous composite paint, and reactions steps is many, and the cost height is used and received restriction.Chinese patent CN101007911A has reported another water-borne coatings and manufacture method thereof, silicon-dioxide can reach the 10-18% of water-borne coatings gross weight in this emulsion, product has adopted very micro-dispersion agent (＜0.1%), avoided of the influence of auxiliary agent content height effectively, but the suspension stability of product and rheological etc. are relatively poor to product performance.Chinese patent CN101029198A has reported a kind of water polyacrylic acid organic and inorganic composite coating and manufacture method thereof recently, it is a raw material with polyacrylate dispersion, water dispersible polyisocyanates, silicon dioxide gel, the hybrid inorganic-organic composite coating that makes by sol-gel process at water, this coating has construction stability preferably, and its coating has higher hardness, the transparency and water tolerance etc.Silicon dioxide gel and water-base resin coating are carried out blending and stirring according to a conventional method make but this technology still rests on, the dispersing uniformity of high-load silica component in water-based system, and organic and inorganic component is in the congenital difference of aspects such as density and polarity, make this hybrid inorganic-organic composite aqueous paint performance still with ideal in coating property differ obvious.
Cage shape polysilsesquioxane (POSS) is the inorganic materials that a class contains the three-dimensional cluster structure of Si/O, its size has nano effect in nanoscale, so in many macromolecule matrixes, introducing is less than 1% POSS, and the mechanical property and the thermal characteristics of macromolecular material improve significantly.Simultaneously, not end capped POSS molecule can also connect various functional group by end capping, to participate in the various organic reactions, prepare the different organic/inorganic composite materials that contains POSS, to realize the Organic on the nanoscale.
The Organic system of reporting in recent years based on POSS has POSS/ Resins, epoxy, POSS/ urethane resin, POSS/ silicone resin or the like.The adding of POSS can significantly improve the performance of polymer materials, as high temperature resistant, anti-oxidant, withstand voltage, fire-retardant and mechanical strength is high, at aspects such as photo-cured coating, porous material, heat-proof combustion-resistant material and modified polymer materials, has broad application prospects.Characteristics such as POSS has that specific surface area is big, density is low, heat and mechanical stability height, if carry out it and aqueous polyurethane coating composite modified, must on problems such as dispersiveness, density and coating, bring new breakthrough, and also not report and patent application both at home and abroad at present about the open source literature of POSS/ aqueous polyurethane organic and inorganic composite aqueous paint and preparation method thereof.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of POSS/ polyurethane aqueous composite paint and preparation method thereof is provided, it has good suspension stability and rheological, and it can obviously improve water tolerance, solvent resistance, optical property, ageing resistance, mechanical strength and the mechanical property etc. that aqueous polyurethane is filmed simultaneously.
The POSS/ polyurethane aqueous composite paint that the present invention proposes, prepare by following method: adopt the not end capped POSS of a kind of hydrolysis method preparation earlier, by KH-550 it is carried out inserting behind the end-blocking POSS of amino-contained active group again, mode by chemical bonding and aqueous polyurethane dispersion carry out chemically compositedly then, make a kind of POSS/ polyurethane dispersions aqueous composite paint.Can improve the degree of crosslinking while of aqueous polyurethane molecular chain after POSS and aqueous polyurethane are chemically composited by covalent linkage, the inorganic nano material that also will have the excellent heat mechanical property combines with polymeric matrix better.Preparation method of the present invention has that technology is convenient and simple, environmentally safe, film quality is high and advantage such as with low cost, be new generation of green environment-friendly and high-performance Chemicals, can be applicable to fields such as painting dressing automobiles, wood lacquer, building, office furniture, leather, textile finishing, pigment printing and mechanical means.
The preparation method of the POSS/ polyurethane aqueous composite paint that the present invention proposes is as follows:
(1) under agitation condition, 5～35g distilled water progressively increased slowly that (in 5～25g) the acetone soln, solution is back flow reaction 12～96 hours again to containing the trichloromethyl siloxanes.With the mixture washing purifying of acetone, pyridine and isopyknic concentrated hydrochloric acid and ice, collecting precipitation is washed with water to neutrality to the white solid that after reaction finishes collection is obtained respectively, and vacuum-drying is spent the night.After thoroughly extracting with ether at last, the white powder that obtains is not end capped polysilsesquioxane POSS.
(2) be equipped with in the four-hole boiling flask of thermometer, condenser, agitator, logical nitrogen at 250mL, temperature is controlled at 45～60 ℃, with silane resin acceptor kh-550 (1～10g) and tetrahydrofuran (THF) (5～25mL) solution dropwise add not end-blocking POSS (1～10g) and triethylamine ((in 20～100mL) solution, reaction mixture stirs 12～96h to 3～10mL) tetrahydrofuran (THF).Pour product in 400～1000mL frozen water and concentrated hydrochloric acid mixture washing and filtering, more repeatedly, promptly get POSS with the amido active group with deionized water wash.
(3) with vulcabond, polyester polyol, 2,2 '-dimethylol propionic acid, catalyzer and organic solvent are even with the mixed of 100: 300～400: 20～50: 0.05～5: 300～500 (weight), 50～80 ℃ of elevated temperatures, reacted 2～8 hours, make reaction be tending towards finishing, promptly be able to isocyanate-terminated polyurethane prepolymer.
(4) with above-mentioned isocyanate-terminated polyurethane prepolymer, POSS, catalyzer and the organic solvent of amino-contained, mix in ratio with 100: 0.2～20: 0.5～2: 50～200 (weight), temperature is controlled at 45～90 ℃, reaction continues 4～12 hours, temperature is reduced to 45～65 ℃, add 0.5～5g triethylamine again, reacted 15～60 minutes.Measure 200～500ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 30～90 minutes, and temperature is 35～60 ℃.After dropwising, temperature is 30～45 ℃, continues reaction 15～90 minutes again, after vacuum filtration is removed organic solvent, obtains the polyurethane aqueous composite dispersion of POSS/.
(5) mixture with the polyurethane aqueous composite dispersion of above-mentioned POSS/, deionized water, solubility promoter, wetting agent and membrane-forming agent mixes in the ratio with 100: 1～10: 1～10: 1～5: 1～5 (weight), high-speed stirring is 30～60 minutes at ambient temperature, add thickening material then, continue high-speed stirring and made the POSS/ polyurethane aqueous composite paint in 15～60 minutes.
Among the present invention, described vulcabond, it can be aromatic diisocyanate, as Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 5-naphthalene diisocyanate, the ethylbenzene vulcabond, 4, the 6-Xylene Diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, perhaps aliphatic diisocyanate is as hexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or different Buddhist ketone vulcabond etc.Said polyester polyol can be adipate polyester polyvalent alcohol, benzoic anhydride polyester polyol, polycaprolactone polyol, high-molecular-weight poly ester polyol, the extraordinary polyester polyol of being with side group or PCDL etc.; Said catalyzer can be dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine; Said organic solvent can be acetone, butanone, toluene, dimethylbenzene, ethyl acetate, N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide etc.
Among the present invention, described solubility promoter can be N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide etc.
Among the present invention, described thickening material can be Polyacrylic Acid Thickener, cellulose thickener or polyurethane associative thickener etc.
Among the present invention, described wetting agent can be dialkyl group (octyl group, hexyl, butyl) sulfosuccinate, alkyl how sodium sulfonate, Viscotrol C hydrosulfate, sodium laurylsulfonate, sulfuric acid laurel tallow, oleic acid butyl ester hydrosulfate, alkylphenol polyvinyl ether, Voranol EP 2001, polyoxyethylene glycol alkyl ester, polyoxyethylene glycol alkyl aryl ether, acetylene ethylene glycol or polyether modified siloxane etc.
Among the present invention, described membrane-forming agent can be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether or propylene glycol monobutyl ether etc.
The POSS/ polyurethane aqueous composite paint of the present invention's preparation, the long-term back (for example 3 months) of placing, this water-borne coatings still keep stable and do not have generation such as sedimentation phenomenon, and shelf characteric is good, hardness and water resistance improve, and are demonstrating excellent performance aspect thermotolerance and the ultraviolet-resistent property.
Advantage of the present invention is: 1. the present invention is incorporated into POSS in the base polyurethane prepolymer for use as by the method for chemical bonding, prepare the polyurethane aqueous composite dispersion of POSS/ by self-emulsification again, make a kind of POSS/ polyurethane aqueous composite paint at last, the package stability of this coating is good, and POSS and aqueous polyurethane have good binding; 2. the POSS/ polyurethane aqueous composite paint product of the present invention preparation, its water resistance be improved significantly, thermotolerance has obtained certain raising, and films and have good mechanical and mechanical property, has improved the traditional water based polyurethane in aspect defectives such as water tolerance and poor mechanical property; 3. the POSS/ polyurethane aqueous composite paint of the present invention preparation, it is filmed and has shown excellent anti-uv-ray, and transmitance is lower than 1% in the UV-light zone of 250～350nm; 4. preparation method of the present invention has that simple process is convenient, pollution-free, environmental friendliness, film quality height, input-output ratio is high and advantage such as with low cost.
Description of drawings
Table 1 is the film performance of POSS/ polyurethane aqueous composite paint.
Fig. 1 is POSS/ polyurethane aqueous composite paint size distribution figure.
Fig. 2 is the field emission scanning electron microscope photo of POSS/ polyurethane aqueous composite paint.
Fig. 3 is the thermogravimetric curve of POSS/ polyurethane aqueous composite paint.
Fig. 4 is the ultraviolet-visible light transmission rate of POSS/ polyurethane aqueous composite paint.
Embodiment
Embodiment 1
Under agitation condition 17.7g distilled water progressively increased and contain in the 250mL round-bottomed flask of 10g trichloromethyl siloxanes and 100mL acetone, be warming up to 50 ℃, solution reaction refluxed 48 hours.The white solid washing with acetone that after reaction finishes collection is obtained, filter back vacuum-drying 8 hours under 45 ℃ of conditions, spend the night with the pyridine suspension and the stirring of 20 times of weight again, at last pyridine solution is poured in the mixture of isopyknic concentrated hydrochloric acid and ice, collecting precipitation is washed with water to neutrality then, spends the night 45 ℃ of following vacuum-dryings.After thoroughly extracting with ether at last, obtain not end capped POSS.
With the above-mentioned not end capped POSS of 4.0g, 2g silane resin acceptor kh-550 and 20mL tetrahydrofuran (THF) mix, temperature is controlled at 55 ℃, add 5mL triethylamine and 60mL tetrahydrofuran (THF) again, the reaction times continues to pour product in 800mL frozen water and concentrated hydrochloric acid mixture washing and filtering after 36 hours, the precipitate with deionized water continuous washing that obtains is several times till solution is neutrality, the solid that filtration obtains is dry under 60 ℃ of vacuum,, promptly get the POSS of surperficial band amido.
Again with different Buddhist ketone vulcabond, polyester polyol, 2,2 '-dimethylol propionic acid, dibutyltin dilaurate and acetone were with 100: 270: 30: the mixed of 2: 400 (weight) is even, be warmed up to 60 ℃ of reactions 6 hours, promptly be able to isocyanate-terminated polyurethane prepolymer; Again with above-mentioned POSS, dibutyltin dilaurate and acetone with isocyanate-terminated polyurethane prepolymer, band amine groups, with 100: 1: 1: the ratio of 100 (weight), stir, temperature is controlled at about 60 ℃, reaction continues 5 hours, add the 1.2g triethylamine again, temperature is reduced to 45 ℃, reacts 30 minutes.Measure the 150g deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 45 minutes.After dropwising, continue reaction 30 minutes again.After removing acetone under 35 ℃ of vacuum, obtain the polyurethane aqueous composite dispersion of POSS/.At last with the polyurethane aqueous composite dispersion of above-mentioned POSS/, deionized water, N-Methyl pyrrolidone, dioctyl sulfosuccinate and ethylene glycol monobutyl ether in 100: 6: 4: the ratio of 1: 1 (weight) mixes, at ambient temperature, high-speed stirring 45 minutes, add 1% thickening material then, continue high-speed stirring and make the POSS/ polyurethane aqueous composite paint after 30 minutes.
The size distribution figure of this POSS/ polyurethane aqueous composite paint as shown in Figure 1, Fig. 2 is its sem photograph, its thermal characteristics and ultraviolet-visible light transmission rate are seen Fig. 3 and Fig. 4 respectively, the film performance of this polyurethane aqueous composite paint sees Table 1.
Embodiment 2
Identical with embodiment 1, but with the ratio of isocyanate-terminated polyurethane prepolymer, POSS, dibutyltin dilaurate and acetone 100: 1: 1: 100 become 100: 2: 1: 100.
The film performance of this POSS/ polyurethane aqueous composite paint sees Table 1, and its size distribution is seen Fig. 2, and its thermal characteristics and ultraviolet-visible light transmission rate are seen Fig. 3 and Fig. 4 respectively
Embodiment 3
Identical with embodiment 1, identical with embodiment 1, but with the ratio of isocyanate-terminated polyurethane prepolymer, POSS, dibutyltin dilaurate and acetone 100: 1: 1: 100 become 100: 5: 1: 100.
The film performance of this POSS/ polyurethane aqueous composite paint sees Table 1.
Embodiment 4
Identical with embodiment 1, but with the ratio of isocyanate-terminated polyurethane prepolymer, POSS, dibutyltin dilaurate and acetone 100: 1: 1: 100 become 100: 10: 1: 100.
Embodiment 5
Identical with embodiment 1, but different Buddhist ketone vulcabond, polyester polyol, 2, the ratio of 2 '-dimethylol propionic acid, dibutyltin dilaurate and acetone 100: 270: 30: become 100: 270: 20 at 2: 400: 2: 400.
Embodiment 6
Identical with embodiment 1, but different Buddhist ketone vulcabond, polyester polyol, 2, the ratio of 2 '-dimethylol propionic acid, dibutyltin dilaurate and acetone 100: 270: 30: become 100: 270: 40 at 2: 400: 2: 400.
Embodiment 7
Identical with embodiment 1, but hexanediamine becomes 1, the 4-butyleneglycol.
Embodiment 8
Identical with embodiment 1, but different Buddhist ketone vulcabond becomes Toluene-2,4-diisocyanate, the 4-vulcabond.
Embodiment 9
Identical with embodiment 1, but the dioctyl sulfosuccinate becomes the polyoxyethylene glycol alkyl ester.
Identical with embodiment 1, but ethylene glycol monobutyl ether becomes ethylene glycol monomethyl ether.
POSS/ polyurethane aqueous composite paint that obtains among the embodiment 2-10 and the coating of embodiment 1 have similar performance.
Table 1
Wherein: the shock resistance test is undertaken by GB/T 1732-93.
Pencil hardness test is undertaken by GB/T 6739-1996.
The sticking power test is undertaken by GB 1720-79 (80).
Water resistance test is undertaken by GB/T 1733-93
Claims (7)
1. POSS/ polyurethane aqueous composite paint, it is characterized in that preparing: at first adopt the not end capped POSS of hydrolysis method preparation by following method, by silane resin acceptor kh-550 it is carried out obtaining behind the end-blocking POSS of amino-contained active group again, mode by chemical bonding and aqueous polyurethane dispersion carry out chemically compositedly then, make a kind of POSS/ polyurethane aqueous composite paint.
2. the preparation method of a POSS/ polyurethane aqueous composite paint as claimed in claim 1 is characterized in that concrete steps are:
(1) under agitation condition 5～35g distilled water is slowly progressively increased in the acetone soln that contains 5～25g trichloromethyl siloxanes, solution is back flow reaction 12～96 hours again; With the mixture washing purifying of acetone, pyridine and isopyknic concentrated hydrochloric acid and ice, collecting precipitation is washed with water to neutrality to the white solid that after reaction finishes collection is obtained, vacuum-drying respectively; After thoroughly extracting with ether at last, the white powder that obtains is not end capped polysilsesquioxane POSS;
(2) be equipped with in the four-hole boiling flask of thermometer, condenser, agitator, logical nitrogen at 250mL, temperature is controlled at 45～60 ℃, the solution of 1～10g silane resin acceptor kh-550 and 5～25mL tetrahydrofuran (THF) dropwise added contain 1～10g not in 20～100mL tetrahydrofuran solution of end-blocking POSS and 3～10mL triethylamine, reaction mixture stirs 12～96h; Pour product in 400～1000mL frozen water and concentrated hydrochloric acid mixture washing and filtering, more repeatedly, promptly get POSS with the amido active group with deionized water wash;
(3) with vulcabond, polyester polyol, 2,2 '-dimethylol propionic acid, catalyzer and organic solvent mix with 100: 300～400: 20～50: 0.05～5: 300～500 part by weight, 50～80 ℃ of elevated temperatures, reacted 2～8 hours, make reaction be tending towards finishing, promptly be able to isocyanate-terminated polyurethane prepolymer;
(4) with above-mentioned isocyanate-terminated polyurethane prepolymer, POSS, catalyzer and the organic solvent of amino-contained, part by weight by 100: 0.2～20: 0.5～2: 50～200 mixes, temperature is controlled at 45～80 ℃, reaction continues 4～12 hours, temperature is reduced to 45～55 ℃, add 0.5～5g triethylamine again, reacted 15～60 minutes; Measure 200～500ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 30～60 minutes, and temperature is 45～50 ℃; After dropwising, temperature is 25～45 ℃, continues reaction 15～60 minutes again, after vacuum filtration is removed organic solvent, obtains the polyurethane aqueous composite dispersion of POSS/;
(5) mixture with the polyurethane aqueous composite dispersion of above-mentioned POSS/, deionized water, solubility promoter, wetting agent and membrane-forming agent mixes by the part by weight with 100: 1～10: 1～10: 1～5: 1～5, high-speed stirring is 30～60 minutes at ambient temperature, add thickening material then, continue high-speed stirring and made the POSS/ polyurethane aqueous composite paint in 15～60 minutes.
3. preparation method according to claim 2, it is characterized in that described vulcabond is an aromatic diisocyanate, perhaps aliphatic diisocyanate, said polyester polyol are the extraordinary polyester polyol or the PCDL of adipate polyester polyvalent alcohol, benzoic anhydride polyester polyol, polycaprolactone polyol, high-molecular-weight poly ester polyol, band side group; Said catalyzer is dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine; Said organic solvent is acetone, butanone, toluene, dimethylbenzene, ethyl acetate, N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide.
4. preparation method according to claim 2 is characterized in that said solubility promoter is N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide.
5. preparation method according to claim 2 is characterized in that said thickening material is Polyacrylic Acid Thickener, cellulose thickener or polyurethane associative thickener.
6. preparation method according to claim 2 is characterized in that said wetting agent is dialkyl group (octyl group, hexyl, butyl) sulfosuccinate, alkyl how sodium sulfonate, Viscotrol C hydrosulfate, sodium laurylsulfonate, sulfuric acid laurel tallow, oleic acid butyl ester hydrosulfate, alkylphenol polyvinyl ether, Voranol EP 2001, polyoxyethylene glycol alkyl ester, polyoxyethylene glycol alkyl aryl ether, acetylene ethylene glycol or polyether modified siloxane.
7. preparation method according to claim 2 is characterized in that said membrane-forming agent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether or propylene glycol monobutyl ether.
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