CN1410551A - Polyurethane/inorganic nano composite leather tannin material and its preparation method - Google Patents
Polyurethane/inorganic nano composite leather tannin material and its preparation method Download PDFInfo
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- CN1410551A CN1410551A CN 02134175 CN02134175A CN1410551A CN 1410551 A CN1410551 A CN 1410551A CN 02134175 CN02134175 CN 02134175 CN 02134175 A CN02134175 A CN 02134175A CN 1410551 A CN1410551 A CN 1410551A
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Abstract
A composite tanning agent for leather is prepared through reaction between isocyanate, polyether polyol, cross-linking agent and catalyst at 70-85 deg.C for 2-5 hr, cooling to 35-60 deg.C, adding chain spreading agent, reacting for 2-3 hr, cooling to 30-45 deg.C, adding diluent, salt-forming agent and presoma containing nano metre SiO2 or TiO2, reacting for 0.5-1.5 hr to obtain prepolymer of polyurethane, adding it to deionized water and emulsifying for 0.5-1.5 hr to obtain the polyurethane/inorganic nanometre composite tanning agent.
Description
One, technical field
The present invention relates to urethane/inorganic nano composite leather tannin material and preparation method thereof, belong to the synthetic field of functional high molecule material.
Two, background technology
China is process hides big country, along with the transfer at process hides center, the world, and 2000, about 1.6 ten thousand families of China leather enterprise, surplus the practitioner 200 ten thousand, national light leather output 3.2 hundred million square meters are produced 5,100,000,000 pairs of footwear, and outlet reaches 174.7 hundred million dollars through volume, ranks first in the world.Wherein employed leather chemicals consumption reaches 170,000 tons, and chrome tanning agent reach 40,000 surplus the ton.Chromium is because of its special electron structure, have characteristics such as good flexibility, extensibility, heat-resistant stability and permeability to water vapour through tanned leather, since 1893 set up a bath chromic tanning, be widely used in the production of leather always, developed into prevailing process for tanning.But, because the utilization ratio of present chromic tanning chromic salts only is 65～75%, the direct discharging of a large amount of unabsorbed useless chrome liquors, wherein contained Cr
+ 3And Cr
+ 6Have carcinogenic and the transgenation effect to human and biology, caused the serious environmental pollution; Whole world chromium resource poorness, and skewness, China is one of poor relatively country of chromium resource, the poorness of chromium resource and Cr
+ 3And Cr
+ 6The environmental pollution that brings forces national governments and scientific research institution's cost great amount of manpower and material resources to seek various approach of dealing with problems.Therefore, Chrome-free, few chromic tanning, high-absorption chrome tanning method have become the focus of leather tanning theory and processing method research.From existing research work, recognize that the pollution that reduces chromium mainly contains three kinds of methods: the recycle method of useless chrome liquor; Chrome-free, few chromic tanning and high-absorption chrome tanning method.In recent years, high pH value chromic tanning, interpolation macromole auxiliary tanning agent chromic tanning have been developed again.Above-mentioned research method has all improved chrome uptake from different degree, has reduced the discharging of chromium in the waste liquid, but the chrome uptake rate still has only about 85%, and production technique is relatively harsh, and the production cycle is long, maybe needs to add other chrome tanning adjuvant, and process hides producer is difficult to acceptance.No matter what method of employing, as long as the intervention of chrome tanning agent is arranged, just cause the permanent injury of chromium ion inevitably to environment, therefore essential method is the chromic tanning of thorough abandoning tradition, seek new leather retanning agent, inquiring into new tannage and process for tanning, is the only way of tanning industry sustainable development.
Three, summary of the invention
A kind of urethane/inorganic nano composite leather tannin material that provides at the deficiencies in the prior art and preparation method thereof is provided.Be characterized in preparing urethane/inorganic nano composite leather tannin material, with nanoparticle TiO by sol-gel processing
2, perhaps SiO
2Introduce in the protein fibre gap, the hybrid inorganic-organic effect by protein-inorganic nano-particle realizes the tanning to rawhide, has both eliminated the environmental pollution that chromium brought, and can increase substantially the over-all properties of leather goods again.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specifying.
The recipe ingredient of urethane/inorganic nano composite leather tannin material is:
30～150 parts of isocyanic ester,
50～150 parts of polyethers (ester) polyvalent alcohols,
1～15 part of linking agent,
0.1～1.0 part of catalyzer
5～20 parts of chainextenders
30～100 parts of thinners
5～30 parts of salt forming agents
Contain nanometer SiO
2Or TiO
25～25 parts of presomas
Wherein urethane is the reaction product of isocyanic ester and polyethers (ester) polyvalent alcohol etc., and inorganic nano-particle is for containing nanometer SiO
2Or TiO
2The hydrolysate of presoma, this composite leather tannin material is faint yellow to translucent viscous liquid, effective constituent 35-45%, the pH=4-6 of 10% aqueous solution, with the dilution of water arbitrary proportion, stable storing phase 〉=12 month.
Isocyanic ester is at least a in 2,4 tolylene diisocyanates, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate and/or the isoflurane chalcone diisocyanate.
At least a in poly-the third two (three) alcohol, polyoxyethylene glycol, PTMG, poly adipate succinic acid ester glycol and/or the polyneopentyl glycol adipate glycol of polyethers (ester) polyvalent alcohol.
Linking agent is at least a in trihydroxy-propane, Viscotrol C, diethanolamine and/or the trolamine.
Inferior tin of octoate catalyst or dibutyl tin laurate.
Chainextender is at least a in N methyldiethanol amine, dimethylol propionic acid and/or the tartrate.
Salt forming agent is triethylamine or anhydrous acetic acid.
Thinner is at least a in acetone, pimelinketone, dimethyl methyl (second) acid amides and/or the N-Methyl pyrrolidone.
Contain nanometer SiO
2Or TiO
2Presoma be at least a in tetraethoxy, butyl silicate, titanium ethanolate and/or the butyl (tetra) titanate.
The preparation method of urethane/inorganic nano composite leather tannin material
(1) preparation of base polyurethane prepolymer for use as
With 30～150 parts of isocyanic ester, 50～150 parts of polyethers (ester) polyvalent alcohols, 0.1～1.0 part of 1～15 part of linking agent and catalyzer, add and have in the reactor of agitator, thermometer and reflux exchanger, be warming up to 70～85 ℃, reacted 2～5 hours, be cooled to 35～60 ℃, add 5～20 parts of chainextenders, continue reaction 2～3 hours, be cooled to 30～45 ℃, add 25～100 parts of thinners, 5～30 parts of salt forming agents add and contain nanometer SiO
2Or TiO
25～25 parts of presomas, reacted 0.5～1.5 hour, obtain base polyurethane prepolymer for use as.
(2) preparation of urethane/inorganic nano composite leather tannin material
Get 50～250 parts of base polyurethane prepolymer for use as, under stirring action, base polyurethane prepolymer for use as was added in 0.5～1.0 hour in the emulsification still that contains 65～350 parts of deionized waters, continue emulsification 0.5～1.5 hour, obtain urethane/inorganic nano composite leather tannin material.
The performance index of urethane/inorganic nano composite leather tannin material are:
Outward appearance: faint yellow to translucent viscous liquid;
The effective content of tanning agent: 35-45%; The stable storing phase: 〉=12 months
PH value: 4-6 (10% aqueous solution) dilution stability: dilute with the water arbitrary proportion
The present invention has following advantage:
1. tanning agent of the present invention makes by sol-gel processing, the inorganic nano-particle SiO that silicon ester or the hydrolysis of titanate ester presoma produce
2Or TiO
2Be evenly dispersed in the polymkeric substance SiO
2Or TiO
2The average particle size of nanoparticle is 30～90nm, and polymkeric substance has control nano particle diameter and stable nanoparticles and prevents that it from the effect of reuniting taking place, therefore, and the having excellent storage stability of product.
2. all do not have " three wastes " discharging in preparation and use, the environmental pollution that chromium brought has been eliminated in the application of this tanning agent; Transform conventional industries with new technology, belonged to the new direction of Sustainable development chemical industry.
3. improved leather goods waterproof, grease proofing, antifouling, antiultraviolet and electromagenetic wave radiation performance, made leather goods have self-cleaning function; The fire prevention of leather goods, dustproof and wear resisting property and ageing-resistant performance have been improved; Improve the ventilative and sanitation performance of leather goods; Intensity, toughness and wet, the thermal stability of leather goods have been improved.
Four, embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified that can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment
1,68 kilograms of 2,4 toluene diisocyanates, 75 kilograms of polypropylene glycol N-210,12 kilograms of Viscotrol C, 0.45 kilogram of adding of stannous octoate are had in the reactor of agitator, thermometer and reflux exchanger, be warming up to 70 ℃, reacted 2.5 hours.Be cooled to 40 ℃, add acetone and reduce viscosity for 40 kilograms, in 9 kilograms of adding stills of N methyldiethanol amine, 55 ℃ of controlled temperature reacted 2 hours.Be cooled to 40-45 ℃, add 22 kilograms of tetraethoxys, 45 kilograms in acetone, 6 kilograms of reactions of anhydrous acetic acid 30-35 minute obtain base polyurethane prepolymer for use as.In another emulsification still, add 4.2 kilograms of 250 kilograms of deionized waters and anhydrous acetic acids, water temperature 25-30 ℃, under stirring action, in 40-60 minute, add base polyurethane prepolymer for use as in the emulsification still, continue emulsification 1.5 hours, obtain urethane/inorganic nano composite leather tannin material.
2,57 kilograms of hexamethylene diisocyanates, polypropylene glycol N-220 105 kg, 1.5 kilograms of TriMethylolPropane(TMP)s, 0.5 kilogram of adding of stannous octoate are had in the reactor of agitator, thermometer and reflux exchanger, be warming up to 80 ℃, reacted 2.5 hours.Be cooled to 45 ℃, add acetone and reduce viscosity for 40 kilograms, in 8.5 kilograms of adding stills of N methyldiethanol amine, 55 ℃ of controlled temperature reacted 2 hours.Lower the temperature 40-45 ℃, add 14 kilograms of positive titanium ethanolates, 40 kilograms in acetone, 5.5 kilograms of reactions of anhydrous acetic acid 35 minutes obtain base polyurethane prepolymer for use as.In another emulsification still, add 3.6 kilograms of 280 kilograms of deionized waters and anhydrous acetic acids, water temperature 25-30 ℃, under effect is cut in stirring, in 60 minutes, add base polyurethane prepolymer for use as in the emulsification still, continue emulsification 1.5 hours, obtain urethane/inorganic nano composite leather tannin material.
3, with 96 kilograms of isoflurane chalcone diisocyanates, 100 kilograms of PTMG (molecular weight 1500), 10 kilograms of polyoxyethylene glycol (molecular weight 1000), 4 kilograms of Viscotrol C, 0.4 kilogram of dibutyl tin laurate, add and have in the reactor of agitator, thermometer and reflux exchanger, be warming up to 85 ℃, reacted 3 hours.Be cooled to 45 ℃, add acetone and reduce viscosity for 45 kilograms, 13 kilograms of dimethylol propionic acids (with 20 kilograms of dissolvings of dimethyl formamide) are added in the still, 55 ℃ of controlled temperature reacted 2.5 hours.Be cooled to 40-45 ℃, add 20 kilograms of positive butyl (tetra) titanates, 20 kilograms of dimethyl formamides add 9.5 kilograms of reactions of triethylamine 30-40 minute, get base polyurethane prepolymer for use as.Add 4.0 kilograms of 320 kilograms of deionized waters and anhydrous acetic acids in another emulsification still, 30 ℃ of water temperatures under stirring action, added base polyurethane prepolymer for use as in the emulsification still in 1 hour, continued emulsification 1.5 hours, obtained urethane/inorganic nano composite leather tannin material.
4, with 2,60 kilograms of 4-tolylene diisocyanates, 135 kilograms of polypropylene glycol ether N-210,15 kilograms of polyoxyethylene glycol (molecular weight 600), 6 kilograms of trolamines, 0.4 kilogram of adding of stannous octoate have in the reactor of agitator, thermometer and reflux exchanger, be warming up to 75 ℃, reacted 2 hours.Be cooled to 40 ℃, add acetone and reduce viscosity for 35 kilograms, in 10 kilograms of adding stills of N methyldiethanol amine, 55 ℃ of controlled temperature reacted 2 hours.Be cooled to 45 ℃, add 23 kilograms of butyl silicates, 45 kilograms in acetone, 9.8 kilograms of reactions of anhydrous acetic acid 25-30 minute obtain base polyurethane prepolymer for use as.In another emulsification still, add 4.8 kilograms of 250 kilograms of deionized waters and anhydrous acetic acids, water temperature 25-30 ℃, under stirring action, in 50-60 minute, add base polyurethane prepolymer for use as in the emulsification still, continue emulsification 1 hour, obtain urethane/inorganic nano composite leather tannin material.
Claims (10)
1. urethane/inorganic nano composite leather tannin material is characterized in that the recipe ingredient (agent by weight) of this composite tanning agent is:
30～150 parts of isocyanic ester,
50～150 parts of polyethers (ester) polyvalent alcohols,
1～15 part of linking agent,
0.1～1.0 part of catalyzer
5～20 parts of chainextenders
30～100 parts of thinners
5～30 parts of salt forming agents
Contain nanometer SiO
2Or TiO
25～25 parts of presomas
Wherein urethane is the reaction product of isocyanic ester and polyethers (ester) polyvalent alcohol etc., and inorganic nano-particle is for containing nanometer SiO
2Or TiO
2The hydrolysate of presoma, median size is 30～90nm, this composite leather tannin material is faint yellow to translucent viscous liquid, effective constituent 35-45%, the pH=4-6 of 10% aqueous solution, with the dilution of water arbitrary proportion, stable storing phase 〉=12 month.
2. according to the described urethane/inorganic nano composite leather tannin material of claim 1, it is characterized in that isocyanic ester is 2, at least a in 4 tolylene diisocyanates, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate and/or the isoflurane chalcone diisocyanate.
3. according to the described urethane/inorganic nano composite leather tannin material of claim 1, it is characterized in that at least a in poly-the third two (three) alcohol, polyoxyethylene glycol, PTMG, poly adipate succinic acid ester glycol and/or the polyneopentyl glycol adipate glycol of polyethers (ester) polyvalent alcohol.
4. according to the described urethane/inorganic nano composite leather tannin material of claim 1, it is characterized in that linking agent is at least a in trihydroxy-propane, Viscotrol C, diethanolamine and/or the trolamine.
5. according to the described urethane/inorganic nano composite leather tannin material of claim 1, it is characterized in that catalyzer is stannous octoate or dibutyl tin laurate.
6. according to the described urethane/inorganic nano composite leather tannin material of claim 1, it is characterized in that chainextender is at least a in N methyldiethanol amine, dimethylol propionic acid and/or the tartrate.
7. according to the described urethane/inorganic nano composite leather tannin material of claim 1, it is characterized in that salt forming agent is triethylamine or anhydrous acetic acid.
8. according to the described urethane/inorganic nano composite leather tannin material of claim 1, it is characterized in that thinner is at least a in acetone, pimelinketone, dimethyl methyl (second) acid amides and/or the N-Methyl pyrrolidone.
9. tan according to the described urethane/inorganic nano composite leather of claim 1, it is characterized in that containing nanometer SiO
2Or TiO
2Presoma be at least a in tetraethoxy, butyl silicate, titanium ethanolate and/or the butyl (tetra) titanate.
10. according to the preparation method of the described urethane/inorganic nano composite leather tannin material of claim 1～9, it is characterized in that:
(1) preparation of base polyurethane prepolymer for use as
With 30～150 parts of isocyanic ester, 50～150 parts of polyethers (ester) polyvalent alcohols, 0.1～1.0 part of 1～15 part of linking agent and catalyzer, add and have in the reactor of agitator, thermometer and reflux exchanger, be warming up to 70～85 ℃, reacted 2～5 hours, be cooled to 35～60 ℃, add 5～20 parts of chainextenders, continue reaction 2～3 hours, lower the temperature 30～45 ℃, add 25～100 parts of thinners, 5～30 parts of salt forming agents add and contain nanometer SiO
2Or TiO
25～25 parts of presomas, reacted 0.5～1.5 hour, obtain base polyurethane prepolymer for use as,
(2) preparation of urethane/inorganic nano composite leather tannin material
Get 50～250 parts of base polyurethane prepolymer for use as, under stirring action, base polyurethane prepolymer for use as was added in 0.5～1.0 hour in the emulsification still that contains 65～350 parts of deionized waters, continue emulsification 0.5～1.5 hour, obtain urethane/inorganic nano composite leather tannin material.
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|---|---|---|---|
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|---|---|---|---|---|
| CN100392105C (en) * | 2006-05-24 | 2008-06-04 | 四川大学 | Nano SiO2,TiO2 leather tanning agent using modified fat as dispersible carrier, and its preparing method |
| CN101284941B (en) * | 2008-05-15 | 2010-08-04 | 苏州宝泽高分子材料有限公司 | High solid and high light resin composition for chemical leather |
| CN102504518A (en) * | 2011-11-09 | 2012-06-20 | 温州大学 | Method for preparing nano silicon dioxide/aqueous polyurethane hybrid material |
| CN101358252B (en) * | 2008-09-28 | 2012-07-04 | 四川大学 | Tanning method of nano SiO2 or TiO2 tanning agents |
| CN102643598A (en) * | 2012-04-09 | 2012-08-22 | 四川大学 | Antifouling seal-cleaning aqueous polyurethane leather finishing agent and preparation method thereof |
| CN103172817A (en) * | 2011-12-22 | 2013-06-26 | 财团法人纺织产业综合研究所 | Anionic aqueous polyurethane resin and method for producing same |
| CN104610869A (en) * | 2015-02-05 | 2015-05-13 | 林爱娜 | Waterproof anti-fouling waterborne polyurethane coating and preparation method thereof |
| CN104672740A (en) * | 2015-03-04 | 2015-06-03 | 建德市顺发化工助剂有限公司 | Special polyurethane resin for bright oily synthetic leather and preparation method of special polyurethane resin |
| CN105420425A (en) * | 2015-11-28 | 2016-03-23 | 成都德善能科技有限公司 | SiO2/alpha-bromo-amylene/coloring agent composite tanning agent |
| CN105795653A (en) * | 2016-03-12 | 2016-07-27 | 耿云花 | Cell phone case with leather hand feeling |
| CN106893467A (en) * | 2017-03-29 | 2017-06-27 | 安徽月娇家具有限公司 | A kind of preparation method of fibroin aqueous polyurethane nano composite water-proof leather finishing agent |
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| CN100392105C (en) * | 2006-05-24 | 2008-06-04 | 四川大学 | Nano SiO2,TiO2 leather tanning agent using modified fat as dispersible carrier, and its preparing method |
| CN101284941B (en) * | 2008-05-15 | 2010-08-04 | 苏州宝泽高分子材料有限公司 | High solid and high light resin composition for chemical leather |
| CN101358252B (en) * | 2008-09-28 | 2012-07-04 | 四川大学 | Tanning method of nano SiO2 or TiO2 tanning agents |
| CN102504518B (en) * | 2011-11-09 | 2013-07-24 | 温州大学 | Method for preparing nano silicon dioxide/aqueous polyurethane hybrid material |
| CN102504518A (en) * | 2011-11-09 | 2012-06-20 | 温州大学 | Method for preparing nano silicon dioxide/aqueous polyurethane hybrid material |
| CN103172817A (en) * | 2011-12-22 | 2013-06-26 | 财团法人纺织产业综合研究所 | Anionic aqueous polyurethane resin and method for producing same |
| CN103172817B (en) * | 2011-12-22 | 2015-02-18 | 财团法人纺织产业综合研究所 | Anionic aqueous polyurethane resin and method for producing same |
| CN102643598A (en) * | 2012-04-09 | 2012-08-22 | 四川大学 | Antifouling seal-cleaning aqueous polyurethane leather finishing agent and preparation method thereof |
| CN104610869A (en) * | 2015-02-05 | 2015-05-13 | 林爱娜 | Waterproof anti-fouling waterborne polyurethane coating and preparation method thereof |
| CN104672740A (en) * | 2015-03-04 | 2015-06-03 | 建德市顺发化工助剂有限公司 | Special polyurethane resin for bright oily synthetic leather and preparation method of special polyurethane resin |
| CN104672740B (en) * | 2015-03-04 | 2018-02-06 | 建德市顺发化工助剂有限公司 | Special polyurethane resin of bright stock leather synthetic leather and preparation method thereof |
| CN105420425A (en) * | 2015-11-28 | 2016-03-23 | 成都德善能科技有限公司 | SiO2/alpha-bromo-amylene/coloring agent composite tanning agent |
| CN105795653A (en) * | 2016-03-12 | 2016-07-27 | 耿云花 | Cell phone case with leather hand feeling |
| CN105795653B (en) * | 2016-03-12 | 2018-12-21 | 深圳市共进机械科技有限公司 | A kind of corium feel cell-phone cover |
| CN106893467A (en) * | 2017-03-29 | 2017-06-27 | 安徽月娇家具有限公司 | A kind of preparation method of fibroin aqueous polyurethane nano composite water-proof leather finishing agent |
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