CN101508879B - Method of preparing watersoluble polyurethane adhesive - Google Patents
Method of preparing watersoluble polyurethane adhesive Download PDFInfo
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- CN101508879B CN101508879B CN2009100215708A CN200910021570A CN101508879B CN 101508879 B CN101508879 B CN 101508879B CN 2009100215708 A CN2009100215708 A CN 2009100215708A CN 200910021570 A CN200910021570 A CN 200910021570A CN 101508879 B CN101508879 B CN 101508879B
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Abstract
The invention discloses a preparation method of a waterborne polyurethane adhesive, comprising the following steps: evenly mixing vulcabond and polyglycols, adding in proper amount of catalyst, and reacting so as to obtain polyurethane prepolymer; reacting by adding in hydrophilic chain extender and crosslinking agent, adding 2-hydroxyethyl acrylate into the reaction system so as to obtain polyurethane, terminal group of which is double bond; reducing temperature, neutralizing and emusifying by adding in water under high-speed cutting so as to obtain polyurethane emulsion; and heating up, adding vinyl monomer into the emulsion, and polymerizing initiated by water-soluble initiator so as to obtain the modified waterborne polyurethane emulsion. The invention can completely eliminate the harmful effect to the application and the environment protection of the polyurethane emulsion product caused by small molecular emulsifier and organic solvent. The invention can make full use of combination property through the copolymerization modification between the polyurethane and polyacrylic ester.
Description
Technical field
The invention belongs to chemical field, particularly a kind of preparation method of waterborne polyurethane adhesive.
Background technology
China has become maximum in the world shoemaking state, at present main solvent-borne type neoprene tamanori and the bonding footwear material of polyurethane adhesives of adopting in China's shoemaking industry.Consumption is less, but the good cold bonding of tack, low price etc. are its advantages; But these traditional tamanoris contain volatile organic matter (VOCs) and benzene class noxious solvent; Exist problems such as environmental pollution, potential safety hazard; And having damaged health of operators, this is fatal shortcoming, the requirement of incompatibility shoemaking industry development.Along with progress of science and technology, and the requirement of environmental protection relevant laws and regulations becomes sternly, and the research and development of environmentally friendly tamanori are paid attention to day by day.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of preparation method who does not contain the waterborne polyurethane adhesive of conventional emulsifier and harmful organic solvent is provided.
For achieving the above object, the technical scheme that the present invention adopts is:
1) at first, with vulcabond and polyglycol by 1: the mass ratio of 1.3-1.7 mixes, and adds the dibutyl tin laurate of mixture quality 0.005%～0.05% then, under 75-90 ℃, react base polyurethane prepolymer for use as A;
2) with hydrophilic chain extender, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A by 1: the mass ratio of 0.05-0.5: 13-25 stirs; Under 65-75 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 0.5-2h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 1-2;
3) be cooled to 15～35 ℃, in urethane C, add water and alkali, wherein the mass ratio of urethane C, water and alkali is 1: 1.1-1.5: 0.005-0.08, and emulsification obtains polyaminoester emulsion D under shearing;
4) with vinyl monomer and polyaminoester emulsion D by 1: after the mass ratio of 8-20 mixes; At the mixed solution and dripping water soluble starter; Water soluble starter and vinyl monomer mass ratio are 0.2-3: 100, continue promptly to get waterborne polyurethane adhesive behind the polymerization 2-6h at 70-90 ℃ then.
Vulcabond of the present invention is isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate or diphenylmethanediisocyanate; Polyglycol is polyether Glycols or polyester diol, and polyether Glycols and polyester diol number average relative molecular mass be respectively 1000 or 2000, and polyether Glycols is polyoxypropyleneglycol or polytetrahydrofuran diol; Polyester diol is polycaprolactone divalent alcohol, PCDL, polyethylene glycol adipate divalent alcohol or gathers hexanodioic acid-1,4-butanediol ester glycol; Hydrophilic chain extender has sulfonate type or carboxylic acid type, and the sulfonate type chainextender is quadrol base ethyl sulfonic acid sodium or 1, and 4-butyleneglycol-2-sodium sulfonate, carboxylic acid type chainextender are dimethylol propionic acid or dimethylolpropionic acid; Alkali is ammonia, sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate, Trimethylamine 99, triethylamine or trolamine; Vinyl monomer is methyl acrylate, TEB 3K, ethyl propenoate, Jia Jibingxisuanyizhi, Bing Xisuandingzhi, NSC 20956, NSC 11786, N-Hexyl methacrylate, octadecyl acrylate, stearyl methacrylate, vinylbenzene or vinyl toluene; Water soluble starter is ammonium persulphate, Potassium Persulphate, ammonium persulphate-sulfurous acid (hydrogen) sodium, Potassium Persulphate-sulfurous acid (hydrogen) sodium, ammonium persulphate-Sulfothiorine, Potassium Persulphate-Sulfothiorine or water-soluble azo initiator.
The present invention adopts aqueous polyurethane as tamanori, and it is good to have snappiness, and smell is little, and is easy to operate, the cull easy to clean, and characteristics such as bonding strength is good have good development prospect.The present invention has eliminated the use of small-molecular emulsifier and poisonous organic solvent fully, has both eliminated the disadvantageous effect to environment, has also eliminated the infringement healthy to operator; And it is very extensive to be suitable for raw material type of the present invention.
Embodiment
Embodiment 1:1) at first, isophorone diisocyanate and the polyoxypropyleneglycol mass ratio by 1: 1.5 is mixed, adds the dibutyl tin laurate of mixture quality 0.02% then, under 80 ℃, react base polyurethane prepolymer for use as A;
2) quadrol base ethyl sulfonic acid sodium, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A are stirred by 1: 0.05: 25 mass ratio; Under 65 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 0.5h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 1.15;
3) be cooled to 30 ℃, in urethane C, add water and ammonia, wherein the mass ratio of urethane C, water and ammonia is 1: 1.3: 0.005, and emulsification obtains polyaminoester emulsion D under shearing;
4) methyl acrylate and polyaminoester emulsion D are mixed by 1: 15 mass ratio after; At mixed solution and dripping water soluble starter ammonium persulphate; Water soluble starter and vinyl monomer mass ratio are 1.5: 100, continue promptly to get waterborne polyurethane adhesive behind the polymerization 4h at 80 ℃ then.
Embodiment 2:1) at first, tolylene diisocyanate and the polytetrahydrofuran diol mass ratio by 1: 1.3 is mixed, adds the dibutyl tin laurate of mixture quality 0.04% then, under 75 ℃, react base polyurethane prepolymer for use as A;
2) with 1; 4-butyleneglycol-2-sodium sulfonate, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A stir by 1: 0.08: 15 mass ratio; Under 75 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 2h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 1.8;
3) be cooled to 15 ℃, in urethane C, add water and sodium hydroxide, wherein the mass ratio of urethane C, water and sodium hydroxide is 1: 1.5: 0.015, and emulsification obtains polyaminoester emulsion D under shearing;
4) TEB 3K and polyaminoester emulsion D are mixed by 1: 10 mass ratio after; At mixed solution and dripping water soluble starter Potassium Persulphate; Water soluble starter and vinyl monomer mass ratio are 3: 100, continue promptly to get waterborne polyurethane adhesive behind the polymerization 6h at 70 ℃ then.
Embodiment 3:1) at first, hexamethylene diisocyanate and the polycaprolactone divalent alcohol mass ratio by 1: 1.6 is mixed, adds the dibutyl tin laurate of mixture quality 0.008% then, under 78 ℃, react base polyurethane prepolymer for use as A;
2) dimethylol propionic acid, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A are stirred by 1: 0.1: 18 mass ratio; Under 68 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 1h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 1;
3) be cooled to 35 ℃, in urethane C, add water and yellow soda ash, wherein the mass ratio of urethane C, water and yellow soda ash is 1: 1.2: 0.03, and emulsification obtains polyaminoester emulsion D under shearing;
4) ethyl propenoate and polyaminoester emulsion D are mixed by 1: 20 mass ratio after; At mixed solution and dripping water soluble starter ammonium persulphate-S-WAT; Water soluble starter and vinyl monomer mass ratio are 0.8: 100, continue promptly to get waterborne polyurethane adhesive behind the polymerization 2h at 90 ℃ then.
Embodiment 4:1) at first, diphenylmethanediisocyanate and the PCDL mass ratio by 1: 1.4 is mixed, adds the dibutyl tin laurate of mixture quality 0.03% then, under 85 ℃, react base polyurethane prepolymer for use as A;
2) dimethylolpropionic acid, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A are stirred by 1: 0.3: 20 mass ratio; Under 72 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 1.5h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 1.5;
3) be cooled to 20 ℃, in urethane C, add water and sodium hydrogencarbonate, wherein the mass ratio of urethane C, water and sodium hydrogencarbonate is 1: 1.4: 0.06, and emulsification obtains polyaminoester emulsion D under shearing;
4) Jia Jibingxisuanyizhi and polyaminoester emulsion D are mixed by 1: 8 mass ratio after; At mixed solution and dripping water soluble starter Potassium Persulphate-sodium sulfite anhy 96; Water soluble starter and vinyl monomer mass ratio are 1: 100, continue promptly to get waterborne polyurethane adhesive behind the polymerization 5h at 73 ℃ then.
Embodiment 5:1) at first, isophorone diisocyanate and the polyethylene glycol adipate divalent alcohol mass ratio by 1: 1.7 is mixed, adds the dibutyl tin laurate of mixture quality 0.005% then, under 90 ℃, react base polyurethane prepolymer for use as A;
2) quadrol base ethyl sulfonic acid sodium, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A are stirred by 1: 0.5: 13 mass ratio; Under 70 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 0.5h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 1.3;
3) be cooled to 25 ℃, in urethane C, add water and Trimethylamine 99, wherein the mass ratio of urethane C, water and Trimethylamine 99 is 1: 1.1: 0.02, and emulsification obtains polyaminoester emulsion D under shearing;
4) Bing Xisuandingzhi and polyaminoester emulsion D are mixed by 1: 13 mass ratio after; At mixed solution and dripping water soluble starter ammonium persulphate-Sulfothiorine; Water soluble starter and vinyl monomer mass ratio are 2: 100, continue promptly to get waterborne polyurethane adhesive behind the polyase 13 h at 86 ℃ then.
Embodiment 6:1) at first; With hexamethylene diisocyanate with gather hexanodioic acid-1; 4-butanediol ester glycol mixes by 1: 1.3 mass ratio, adds the dibutyl tin laurate of mixture quality 0.05% then, under 83 ℃, react base polyurethane prepolymer for use as A;
2) dimethylol propionic acid, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A are stirred by 1: 0.2: 22 mass ratio; Under 66 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 1.5h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 2;
3) be cooled to 22 ℃, in urethane C, add water and triethylamine, wherein the mass ratio of urethane C, water and triethylamine is 1: 1.25: 0.03, and emulsification obtains polyaminoester emulsion D under shearing;
4) stearyl methacrylate and polyaminoester emulsion D are mixed by 1: 18 mass ratio after; At mixed solution and dripping water soluble starter Potassium Persulphate-Sulfothiorine; Water soluble starter and vinyl monomer mass ratio are 2.5: 100, continue promptly to get waterborne polyurethane adhesive behind the polymerization 4.5h at 77 ℃ then.
Embodiment 7:1) at first, diphenylmethanediisocyanate and the PCDL mass ratio by 1: 1.5 is mixed, adds the dibutyl tin laurate of mixture quality 0.025% then, under 88 ℃, react base polyurethane prepolymer for use as A;
2) with 1; 4-butyleneglycol-2-sodium sulfonate, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A stir by 1: 0.4: 16 mass ratio; Under 74 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 2h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 1.6;
3) be cooled to 33 ℃, in urethane C, add water and trolamine, wherein the mass ratio of urethane C, water and trolamine is 1: 1.36: 0.08, and emulsification obtains polyaminoester emulsion D under shearing;
4) vinyl toluene and polyaminoester emulsion D are mixed by 1: 11 mass ratio after; At the mixed solution and dripping water-soluble azo initiator; Water soluble starter and vinyl monomer mass ratio are 1.8: 100, continue promptly to get waterborne polyurethane adhesive behind the polyase 13 .5h at 82 ℃ then.
Claims (7)
1. the preparation method of waterborne polyurethane adhesive is characterized in that:
1) at first, with vulcabond and polyglycol by 1: the mass ratio of 1.3-1.7 mixes, and adds the dibutyl tin laurate of mixture quality 0.005%～0.05% then, under 75-90 ℃, react base polyurethane prepolymer for use as A;
2) with hydrophilic chain extender, linking agent TriMethylolPropane(TMP) and base polyurethane prepolymer for use as A by 1: the mass ratio of 0.05-0.5: 13-25 stirs; Under 65-75 ℃, react polymer B; And then obtain urethane C after Hydroxyethyl acrylate added in the polymer B reaction 0.5-2h, wherein the mass ratio of polymer B and Hydroxyethyl acrylate is 100: 1-2;
3) be cooled to 15～35 ℃, in urethane C, add water and alkali, wherein the mass ratio of urethane C, water and alkali is 1: 1.1-1.5: 0.005-0.08, and emulsification obtains polyaminoester emulsion D under shearing;
4) with vinyl monomer and polyaminoester emulsion D by 1: after the mass ratio of 8-20 mixes; At the mixed solution and dripping water soluble starter; Water soluble starter and vinyl monomer mass ratio are 0.2-3: 100, continue promptly to get waterborne polyurethane adhesive behind the polymerization 2-6h at 70-90 ℃ then.
2. the preparation method of waterborne polyurethane adhesive according to claim 1, it is characterized in that: described vulcabond is isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate or diphenylmethanediisocyanate.
3. the preparation method of waterborne polyurethane adhesive according to claim 1; It is characterized in that: described polyglycol is polyether Glycols or polyester diol; And polyether Glycols and polyester diol number average relative molecular mass are respectively 1000 or 2000, and polyether Glycols is polyoxypropyleneglycol or polytetrahydrofuran diol; Polyester diol is polycaprolactone divalent alcohol, polyethylene glycol adipate divalent alcohol or gathers hexanodioic acid-1,4-butanediol ester glycol.
4. the preparation method of waterborne polyurethane adhesive according to claim 1; It is characterized in that: described hydrophilic chain extender has sulfonate type or carboxylic acid type; The sulfonate type chainextender is quadrol base ethyl sulfonic acid sodium or 1; 4-butyleneglycol-2-sodium sulfonate, carboxylic acid type chainextender are dimethylol propionic acid or dimethylolpropionic acid.
5. the preparation method of waterborne polyurethane adhesive according to claim 1, it is characterized in that: said alkali is ammonia, sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate, Trimethylamine 99, triethylamine or trolamine.
6. the preparation method of waterborne polyurethane adhesive according to claim 1, it is characterized in that: said vinyl monomer is methyl acrylate, TEB 3K, ethyl propenoate, Jia Jibingxisuanyizhi, Bing Xisuandingzhi, NSC 20956, NSC 11786, N-Hexyl methacrylate, octadecyl acrylate, stearyl methacrylate, vinylbenzene or vinyl toluene.
7. the preparation method of waterborne polyurethane adhesive according to claim 1, it is characterized in that: said water soluble starter is ammonium persulphate, Potassium Persulphate, ammonium persulphate-S-WAT, ammonium persulfate-sodium bisulfite, Potassium Persulphate-S-WAT, Potassium Persulphate-sodium sulfite anhy 96, ammonium persulphate-Sulfothiorine, Potassium Persulphate-Sulfothiorine or water-soluble azo initiator.
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| CN2009100215708A CN101508879B (en) | 2009-03-17 | 2009-03-17 | Method of preparing watersoluble polyurethane adhesive |
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| CN2009100215708A CN101508879B (en) | 2009-03-17 | 2009-03-17 | Method of preparing watersoluble polyurethane adhesive |
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| CN101508879B true CN101508879B (en) | 2012-05-09 |
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