A kind of high-solid lower-viscosity sulfonic acid/hydroxy acid aqueous polyurethaneTechnical field
The present invention relates to a kind of polyurethane material, more particularly to a kind of high-solid lower-viscosity sulfonic acid/hydroxy acid is aqueous poly-Urethane.
Background technique
With the enhancing of people's environmental consciousness, the pay attention to day by day of various countries' environmental pollution, aqueous polyurethane is just graduallyReplace solvent borne polyurethane, is widely used in the numerous areas such as coating, adhesive, leather, weaving.Aqueous polyurethane is point with waterDispersion media, VOC free s discharge, and water price it is honest and clean, using safe.However at present the solid content of aqueous polyurethane mostly 30% or so,Since the evaporation latent heat of water is higher than the evaporation latent heat of organic solvent, have the shortcomings that drying time is long, energy consumption is high, greatly makesThe about popularization and application of aqueous polyurethane.The solid content for improving aqueous polyurethane is substantially shorter drying time and reduces energy consumption.
The aqueous polyurethane of more high solids content has been had already appeared in the prior art, but since solid content is higher,Internal solvent is less, and viscosity component increases, and the aqueous polyurethane viscosity for resulting in high solids content is larger, has influenced downstreamIt uses.
Summary of the invention
It is aqueous in view of the deficiencies of the prior art, the present invention intends to provide a kind of high-solid lower-viscosity sulfonic acid/hydroxy acidPolyurethane.
To achieve the above object, the present invention provides the following technical scheme that
A kind of high-solid lower-viscosity sulfonic acid/hydroxy acid aqueous polyurethane,
It is formed including following weight parts:
Polyalcohol: 20~70 parts
Diisocyanate: 10~25 parts
Sulfonate type chain extender: 2~5 parts
Hydroxy acid salt form chain extender: 2~5 parts
Mesopore molecular sieve: 2~5 parts
Poly-N-isopropyl acrylamide: 1~2 part
Crosslinking agent: 1~3 part
Catalyst: 0.05 part.
As a further improvement of the present invention:
The diisocyanate is 4,4 '-di-2-ethylhexylphosphine oxides (phenyl isocyanate), hexamethylene diisocyanate, hydrogenation hexicholAt least one of dicyclohexylmethane diisocyanate, hydrogenated toluene diisocyanate.
As a further improvement of the present invention:
The polyalcohol is ethylene glycol, in glycerine, diethylene glycol (DEG), triacetate propyl silane triol, 1,2,10- last of the ten Heavenly stems triolsIt is at least one.
As a further improvement of the present invention:
The sulfonate type chain extender is N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- acrylamide -2- methylThe mixture of propane sulfonic acid sodium.
As a further improvement of the present invention:
The sulfonate type chain extender is that mass ratio is 6: 1, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- thirdThe mixture of acrylamide -2- methyl propane sulfonic acid sodium.
As a further improvement of the present invention:
The hydroxy acid type chain extender is at least one of dimethylolpropionic acid, tartaric acid, hydroxyl half ester dihydric alcohol.
As a further improvement of the present invention:
The crosslinking agent is 3- glycidylpropyl (dimethoxy) methyl-monosilane.
As a further improvement of the present invention:
The mesopore molecular sieve is that MCM-41 molecular sieve obtains after hydrogen peroxide oxidation 1~6 hour.
As a further improvement of the present invention:
Poly-N-isopropyl acrylamide is prepared by the following method:
By n-isopropyl acrylamide and N, N- methylene-bisacrylamide is dissolved in the hydrochloric acid solution of pH 1.5,
It is uniformly mixed, ammonium persulfate, tetramethylethylenediamine, 2- cyanacrylate is added later, lead to nitrogen 1min, it is closeReaction vessel is sealed, 65 DEG C is warming up to, isothermal reaction 4 hours, stops heating and stirring, obtain poly-N-isopropyl acrylamide；
Wherein 2- cyanacrylate, n-isopropyl acrylamide, ammonium persulfate, N, N- methylene-bisacrylamide,The mass ratio of tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
As a further improvement of the present invention:
The preparation method of aqueous polyurethane:
Step 1: mesopore molecular sieve and poly-N-isopropyl acrylamide are mixed, and maintain the temperature at 5~10 DEG C of ice bathIn 24 hours, be warming up to 40 degrees Celsius later and react 2 hours, be cooled to room temperature, obtain load poly-N-isopropyl acrylamideMesopore molecular sieve；
Step 2: polyalcohol, diisocyanate and catalyst are added in reaction vessel, 2 are reacted at 60~90 DEG C~4 hours, obtain the performed polymer of diisocyanate ester group；
Step 3: hydroxy acid salt form chain extender and sulfonate type chain extender is added, is reacted 2~4 hours at 60~90 DEG C；StepRapid four: being cooled to 60 DEG C hereinafter, obtaining from aggressiveness；
Step 5: the mesopore molecular sieve for loading poly-N-isopropyl acrylamide, 20 parts of deionized waters are added to from poly-Body keeps dimension at 30~40 DEG C, and reaction obtains product in 2~4 hours.
In the present invention, main being used in conjunction with using sulfonate type chain extender and hydroxy acid salt form chain extender, entireIn the reaction system of polyurethane, the segment between polyurethane is increased as chain extender, thus between the polyurethane molecular changedSegment, increase active group so that it is water-soluble more, improve whole solid content, and in comparative example one and comparisonIt can must find out in data in example two, increase in the effect of solid content, be not simple addition sulfonate type chain extender or hydroxylThe technical effect that hydrochlorate type chain extender can be obtained by, although solid content can be improved by reducing solvent, its entiretyViscosity can significantly be promoted.
Specific embodiment
Embodiment one:
A kind of high-solid lower-viscosity sulfonic acid/hydroxy acid aqueous polyurethane,
It is formed including following weight parts:
Polyalcohol: 45 parts
Diisocyanate: 25 parts
Sulfonate type chain extender: 2 parts
Hydroxy acid salt form chain extender: 3 parts
Mesopore molecular sieve: 3 parts
Poly-N-isopropyl acrylamide: 2 parts
Crosslinking agent: 1 part
Catalyst: 0.05 part
Catalyst is organic silver catalyst.
The diisocyanate is 4,4 '-di-2-ethylhexylphosphine oxides (phenyl isocyanate).
The polyalcohol is ethylene glycol；
The sulfonate type chain extender is N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- acrylamide -2- methylThe mixture of propane sulfonic acid sodium.
The sulfonate type chain extender is that mass ratio is 6: 1, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- thirdThe mixture of acrylamide -2- methyl propane sulfonic acid sodium.
The hydroxy acid type chain extender is at least one of dimethylolpropionic acid, tartaric acid, hydroxyl half ester dihydric alcohol.
The crosslinking agent is 3- glycidylpropyl (dimethoxy) methyl-monosilane.
The mesopore molecular sieve is that MCM-41 molecular sieve obtains after hydrogen peroxide oxidation 3 hours.
Poly-N-isopropyl acrylamide is prepared by the following method:
By n-isopropyl acrylamide and N, N- methylene-bisacrylamide is dissolved in the hydrochloric acid solution of pH 1.5,
It is uniformly mixed, ammonium persulfate, tetramethylethylenediamine, 2- cyanacrylate is added later, lead to nitrogen 1min, it is closeReaction vessel is sealed, 65 DEG C is warming up to, isothermal reaction 4 hours, stops heating and stirring, obtain poly-N-isopropyl acrylamide；
Wherein 2- cyanacrylate, n-isopropyl acrylamide, ammonium persulfate, N, N- methylene-bisacrylamide,The mass ratio of tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
The preparation method of aqueous polyurethane:
Step 1: mesopore molecular sieve and poly-N-isopropyl acrylamide are mixed, and maintain the temperature at 5~10 DEG C of ice bathIn 24 hours, be warming up to 40 degrees Celsius later and react 2 hours, be cooled to room temperature, obtain load poly-N-isopropyl acrylamideMesopore molecular sieve；
Step 2: polyalcohol, diisocyanate and catalyst are added in reaction vessel, 2 are reacted at 60~90 DEG C~4 hours, obtain the performed polymer of diisocyanate ester group；
Step 3: hydroxy acid salt form chain extender and sulfonate type chain extender is added, is reacted 2~4 hours at 75 DEG C；
Step 4: 60 DEG C are cooled to hereinafter, obtaining from aggressiveness；
Step 5: the mesopore molecular sieve for loading poly-N-isopropyl acrylamide, 20 parts of deionized waters are added to from poly-Body keeps dimension at 30~40 DEG C, and reaction obtains product in 2~4 hours.
Embodiment two:
A kind of high-solid lower-viscosity sulfonic acid/hydroxy acid aqueous polyurethane,
It is formed including following weight parts:
Polyalcohol: 20 parts
Diisocyanate: 15 parts
Sulfonate type chain extender: 5 parts
Hydroxy acid salt form chain extender: 2 parts
Mesopore molecular sieve: 3 parts
Poly-N-isopropyl acrylamide: 2 parts
Crosslinking agent: 1 part
Catalyst: 0.05 part
Catalyst is organic silver catalyst.
The diisocyanate is hexamethylene diisocyanate.
The polyalcohol is glycerine；
The sulfonate type chain extender is N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- acrylamide -2- methylThe mixture of propane sulfonic acid sodium.
The sulfonate type chain extender is that mass ratio is 6: 1, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- thirdThe mixture of acrylamide -2- methyl propane sulfonic acid sodium.
The hydroxy acid type chain extender is at least one of dimethylolpropionic acid, tartaric acid, hydroxyl half ester dihydric alcohol.
The crosslinking agent is 3- glycidylpropyl (dimethoxy) methyl-monosilane.
The mesopore molecular sieve is that MCM-41 molecular sieve obtains after hydrogen peroxide oxidation 3 hours.
Poly-N-isopropyl acrylamide is prepared by the following method:
By n-isopropyl acrylamide and N, N- methylene-bisacrylamide is dissolved in the hydrochloric acid solution of pH 1.5,
It is uniformly mixed, ammonium persulfate, tetramethylethylenediamine, 2- cyanacrylate is added later, lead to nitrogen 1min, it is closeReaction vessel is sealed, 65 DEG C is warming up to, isothermal reaction 4 hours, stops heating and stirring, obtain poly-N-isopropyl acrylamide；
Wherein 2- cyanacrylate, n-isopropyl acrylamide, ammonium persulfate, N, N- methylene-bisacrylamide,The mass ratio of tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
The preparation method of aqueous polyurethane:
Step 1: mesopore molecular sieve and poly-N-isopropyl acrylamide are mixed, and maintain the temperature at 5~10 DEG C of ice bathIn 24 hours, be warming up to 40 degrees Celsius later and react 2 hours, be cooled to room temperature, obtain load poly-N-isopropyl acrylamideMesopore molecular sieve；
Step 2: polyalcohol, diisocyanate and catalyst are added in reaction vessel, 2 are reacted at 60~90 DEG C~4 hours, obtain the performed polymer of diisocyanate ester group；
Step 3: hydroxy acid salt form chain extender and sulfonate type chain extender is added, is reacted 2~4 hours at 75 DEG C；
Step 4: 60 DEG C are cooled to hereinafter, obtaining from aggressiveness；
Step 5: the mesopore molecular sieve for loading poly-N-isopropyl acrylamide, 20 parts of deionized waters are added to from poly-Body keeps dimension at 30~40 DEG C, and reaction obtains product in 2~4 hours.
Embodiment three:
A kind of high-solid lower-viscosity sulfonic acid/hydroxy acid aqueous polyurethane,
It is formed including following weight parts:
Polyalcohol: 70 parts
Diisocyanate: 10 parts
Sulfonate type chain extender: 3 parts
Hydroxy acid salt form chain extender: 5 parts
Mesopore molecular sieve: 3 parts
Poly-N-isopropyl acrylamide: 2 parts
Crosslinking agent: 1 part
Catalyst: 0.05 part
Catalyst is organic silver catalyst.
The diisocyanate is 4,4 '-di-2-ethylhexylphosphine oxide (phenyl isocyanates.
The polyalcohol is the mixture of the ethylene glycol that mass ratio is 5: 1 and triacetate propyl silane triol.
The sulfonate type chain extender is N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- acrylamide -2- methylThe mixture of propane sulfonic acid sodium.
The sulfonate type chain extender is that mass ratio is 6: 1, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- thirdThe mixture of acrylamide -2- methyl propane sulfonic acid sodium.
The hydroxy acid type chain extender is dimethylolpropionic acid.
The crosslinking agent is 3- glycidylpropyl (dimethoxy) methyl-monosilane.
The mesopore molecular sieve is that MCM-41 molecular sieve obtains after hydrogen peroxide oxidation 3 hours.
Poly-N-isopropyl acrylamide is prepared by the following method:
By n-isopropyl acrylamide and N, N- methylene-bisacrylamide is dissolved in the hydrochloric acid solution of pH 1.5,
It is uniformly mixed, ammonium persulfate, tetramethylethylenediamine, 2- cyanacrylate is added later, lead to nitrogen 1min, it is closeReaction vessel is sealed, 65 DEG C is warming up to, isothermal reaction 4 hours, stops heating and stirring, obtain poly-N-isopropyl acrylamide；
Wherein 2- cyanacrylate, n-isopropyl acrylamide, ammonium persulfate, N, N- methylene-bisacrylamide,The mass ratio of tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
The preparation method of aqueous polyurethane:
Step 1: mesopore molecular sieve and poly-N-isopropyl acrylamide are mixed, and maintain the temperature at 5~10 DEG C of ice bathIn 24 hours, be warming up to 40 degrees Celsius later and react 2 hours, be cooled to room temperature, obtain load poly-N-isopropyl acrylamideMesopore molecular sieve；
Step 2: polyalcohol, diisocyanate and catalyst are added in reaction vessel, 2 are reacted at 60~90 DEG C~4 hours, obtain the performed polymer of diisocyanate ester group；
Step 3: hydroxy acid salt form chain extender and sulfonate type chain extender is added, is reacted 2~4 hours at 75 DEG C；
Step 4: 60 DEG C are cooled to hereinafter, obtaining from aggressiveness；
Step 5: the mesopore molecular sieve for loading poly-N-isopropyl acrylamide, 20 parts of deionized waters are added to from poly-Body keeps dimension at 30~40 DEG C, and reaction obtains product in 2~4 hours.
Example IV
A kind of high-solid lower-viscosity sulfonic acid/hydroxy acid aqueous polyurethane,
It is formed including following weight parts:
Polyalcohol: 45 parts
Diisocyanate: 25 parts
Sulfonate type chain extender: 2 parts
Hydroxy acid salt form chain extender: 3 parts
Mesopore molecular sieve: 3 parts
Poly-N-isopropyl acrylamide: 2 parts
Crosslinking agent: 1 part
Catalyst: 0.05 part
Catalyst is organic silver catalyst.
The diisocyanate is 4,4 '-di-2-ethylhexylphosphine oxides (phenyl isocyanate).
The polyalcohol is ethylene glycol；
The sulfonate type chain extender is N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- acrylamide -2- methylThe mixture of propane sulfonic acid sodium.
The sulfonate type chain extender is that mass ratio is 6: 1, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium, 2- thirdThe mixture of acrylamide -2- methyl propane sulfonic acid sodium.
The hydroxy acid type chain extender is dimethylolpropionic acid.
The crosslinking agent is 3- glycidylpropyl (dimethoxy) methyl-monosilane.
The mesopore molecular sieve is that MCM-41 molecular sieve obtains after hydrogen peroxide oxidation 3 hours.
Poly-N-isopropyl acrylamide is prepared by the following method:
By n-isopropyl acrylamide and N, N- methylene-bisacrylamide is dissolved in the hydrochloric acid solution of pH 1.5,
It is uniformly mixed, ammonium persulfate, tetramethylethylenediamine, 2- cyanacrylate is added later, lead to nitrogen 1min, it is closeReaction vessel is sealed, 65 DEG C is warming up to, isothermal reaction 4 hours, stops heating and stirring, obtain poly-N-isopropyl acrylamide；
Wherein 2- cyanacrylate, n-isopropyl acrylamide, ammonium persulfate, N, N- methylene-bisacrylamide,The mass ratio of tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
The preparation method of aqueous polyurethane:
Step 1: polyalcohol, diisocyanate and catalyst are added in reaction vessel, 2 are reacted at 60~90 DEG C~4 hours, obtain the performed polymer of diisocyanate ester group；
Step 2: hydroxy acid salt form chain extender and sulfonate type chain extender is added, is reacted 2~4 hours at 75 DEG C；
Step 3: 60 DEG C are cooled to hereinafter, obtaining from aggressiveness；
Step 4: poly-N-isopropyl acrylamide and mesopore molecular sieve, 20 parts of deionized waters are added to from aggressiveness, protectedDimension is held at 30~40 DEG C, reaction obtains product in 2~4 hours.
Comparative example one
A kind of high-solid lower-viscosity sulfonic acid/hydroxy acid aqueous polyurethane,
It is formed including following weight parts:
Polyalcohol: 45 parts
Diisocyanate: 25 parts
Hydroxy acid salt form chain extender: 3 parts
Poly-N-isopropyl acrylamide: 2 parts
Crosslinking agent: 1 part
Catalyst: 0.05 part
Catalyst is organic silver catalyst.
The diisocyanate is 4,4 '-di-2-ethylhexylphosphine oxides (phenyl isocyanate).
The polyalcohol is ethylene glycol；
The hydroxy acid type chain extender is at least one of dimethylolpropionic acid, tartaric acid, hydroxyl half ester dihydric alcohol.
The crosslinking agent is 3- glycidylpropyl (dimethoxy) methyl-monosilane.
Poly-N-isopropyl acrylamide is prepared by the following method:
By n-isopropyl acrylamide and N, N- methylene-bisacrylamide is dissolved in the hydrochloric acid solution of pH 1.5,
It is uniformly mixed, ammonium persulfate, tetramethylethylenediamine, 2- cyanacrylate is added later, lead to nitrogen 1min, it is closeReaction vessel is sealed, 65 DEG C is warming up to, isothermal reaction 4 hours, stops heating and stirring, obtain poly-N-isopropyl acrylamide；
Wherein 2- cyanacrylate, n-isopropyl acrylamide, ammonium persulfate, N, N- methylene-bisacrylamide,The mass ratio of tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
The preparation method of aqueous polyurethane:
Step 1: by poly-N-isopropyl acrylamide and maintaining the temperature in 5~10 DEG C of ice bath 24 hours, heat up laterIt reacts 2 hours, is cooled to room temperature to 40 degrees Celsius；
Step 2: polyalcohol, diisocyanate and catalyst are added in reaction vessel, 2 are reacted at 60~90 DEG C~4 hours, obtain the performed polymer of diisocyanate ester group；
Step 3: hydroxy acid salt form chain extender is added, is reacted 2~4 hours at 75 DEG C；
Step 4: 60 DEG C are cooled to hereinafter, obtaining from aggressiveness；
Step 5: the poly-N-isopropyl acrylamide for loading poly-N-isopropyl acrylamide, 20 parts of deionized waters are addedTo from aggressiveness, keep dimension at 30~40 DEG C, reaction obtains product in 2~4 hours.
Comparative example two
A kind of high-solid lower-viscosity sulfonic acid/hydroxy acid aqueous polyurethane,
It is formed including following weight parts:
Polyalcohol: 45 parts
Diisocyanate: 25 parts
Sulfonate type chain extender: 2 parts
Mesopore molecular sieve: 3 parts
Crosslinking agent: 1 part
Catalyst: 0.05 part
Catalyst is organic silver catalyst.
The diisocyanate is 4,4 '-di-2-ethylhexylphosphine oxides (phenyl isocyanate).
The polyalcohol is ethylene glycol；
The sulfonate type chain extender is N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium.
The crosslinking agent is 3- glycidylpropyl (dimethoxy) methyl-monosilane.
The mesopore molecular sieve is that MCM-41 molecular sieve obtains after hydrogen peroxide oxidation 3 hours.
Poly-N-isopropyl acrylamide is prepared by the following method:
By n-isopropyl acrylamide and N, N- methylene-bisacrylamide is dissolved in the hydrochloric acid solution of pH 1.5,
It is uniformly mixed, ammonium persulfate, tetramethylethylenediamine, 2- cyanacrylate is added later, lead to nitrogen 1min, it is closeReaction vessel is sealed, 65 DEG C is warming up to, isothermal reaction 4 hours, stops heating and stirring, obtain poly-N-isopropyl acrylamide；
Wherein 2- cyanacrylate, n-isopropyl acrylamide, ammonium persulfate, N, N- methylene-bisacrylamide,The mass ratio of tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
The preparation method of aqueous polyurethane:
Step 1: mesopore molecular sieve is maintained the temperature in 5~10 DEG C of ice bath 24 hours, it is warming up to 40 degrees Celsius laterReaction 2 hours, is cooled to room temperature；
Step 2: polyalcohol, diisocyanate and catalyst are added in reaction vessel, 2 are reacted at 60~90 DEG C~4 hours, obtain the performed polymer of diisocyanate ester group；
Step 3: sulfonate type chain extender is added, is reacted 2~4 hours at 75 DEG C；
Step 4: 60 DEG C are cooled to hereinafter, obtaining from aggressiveness；
Step 5: mesopore molecular sieve, 20 parts of deionized waters are added to from aggressiveness, keep dimension at 30~40 DEG C, insteadIt answers 2~4 hours and obtains product.
Test: the technical solution of embodiment and comparative example is subjected to solid content, viscosity and is placed 30,60,90,180 daysWhether it is layered afterwards, gas permeability is tested.
Table one: solid content, viscosity test
| Solid content | Viscosity |
| Embodiment one | 63% | 750cps/25℃ |
| Embodiment two | 65% | 780cps/25℃ |
| Embodiment three | 62% | 620cps/25℃ |
| Example IV | 60% | 720cps/25℃ |
| Comparative example one | 35% | 2100cps/25℃ |
| Comparative example two | 40% | 1850cps/25℃ |
Table two: zonal testing (at 25 DEG C)
| 30 days | 60 days | 90 days | 180 days |
| Embodiment one | It is not stratified | It is not stratified | It is not stratified | It is not stratified |
| Embodiment two | It is not stratified | It is not stratified | It is not stratified | It is not stratified |
| Embodiment three | It is not stratified | It is not stratified | It is not stratified | It is not stratified |
| Example IV | It is not stratified | It is not stratified | It is not stratified | It is not stratified |
| Comparative example one | It is not stratified | Layering | Layering | Layering |
| Comparative example two | It is not stratified | It is not stratified | Layering | Layering |
Table three: permeability test (unit g/m2·24h)
| 20℃ | 25℃ | 35℃ | 45℃ | 55℃ |
| Embodiment one | 1200 | 1350 | 2110 | 5030 | 8120 |
| Embodiment two | 1130 | 1280 | 2010 | 5000 | 8030 |
| Embodiment three | 1280 | 1410 | 2510 | 5320 | 8410 |
| Example IV | 3850 | 5210 | 7500 | 7480 | 7510 |
| Comparative example one | 1250 | 1100 | 930 | 850 | 820 |
| Comparative example two | 6320 | 6050 | 5800 | 5750 | 5700 |
In the present invention, main being used in conjunction with using sulfonate type chain extender and hydroxy acid salt form chain extender, entireIn the reaction system of polyurethane, the segment between polyurethane is increased as chain extender, thus between the polyurethane molecular changedSegment, increase active group so that it is water-soluble more, improve whole solid content, and in comparative example one and comparisonIt can must find out in data in example two, increase in the effect of solid content, be not simple addition sulfonate type chain extender or hydroxylThe technical effect that hydrochlorate type chain extender can be obtained by, although solid content can be improved by reducing solvent, its entiretyViscosity can significantly be promoted.Especially sulfonate type chain extender selects the preferred mass ratio for (the 2- hydroxyl second of 6: 1, N- bis-Base) -2-aminoethanesulfonic acid sodium, 2- acrylamide -2- methyl propane sulfonic acid sodium mixture, can preferably improve solid content andReduce viscosity.
Inventor has found in test of many times simultaneously, in the selection of polyalcohol, is properly added a part of triacetate thirdViscosity can be effectively reduced in base silane triol, therefore provides most preferred embodiment in the third embodiment, and polyalcohol selects mass ratioFor 5: 1 ethylene glycol and the mixture of triacetate propyl silane triol.
In the prior art, the porosity of polyurethane surface is certain, even if as temperature change is expanded with heat and contract with cold, holeRate there will not be too big variation, therefore the gas permeability of polyurethane is certain, although application No. isIn the Chinese patent of CN200910153507.X, a kind of poly- ammonia of synthetic leather top finishing with intelligent moisture-permeable function is disclosedEster resin, wherein organic multicomponent alkoxide polymer is the mixture of the pure and mild polyether Glycols of polyester binary, the pure and mild polyethers of polyester binaryThe ratio of the amount of the substance of dihydric alcohol is 1: 0.2~4.Diisocyanate is that 4,4 '-methyl diphenylene diisocyanates, toluene two are differentCyanate or isophorone diisocyanate；The chain extender is 1,4-butanediol, ethylene glycol or diglycol.The hairBright advantage is: (1) combining using polyester diol as the polyurethane of soft segment and using polyethylene glycol as the polyurethane of soft segmentAdvantage is learnt from other's strong points to offset one's weaknesses, the existing preferable water vapour permeability of obtained polyurethane, and has good mechanical performance.(2) of the present inventionPolyurethane resin intelligent moisture-permeable transition temperature within the scope of 20~50 DEG C, transition temperature can be by adjusting polyester diolIt is controlled with the molecular weight of polyethylene glycol and ratio.
But it is more difficult to control by the molecular weight and ratio of polyethylene glycol, rejection rate is higher.
Therefore the applicant, makes further research, is used to improve the saturating of integral material by the addition of mesopore molecular sieveThe addition of gas performance and poly-N-isopropyl acrylamide, to provide environmental suitability, poly-N-isopropyl acrylamide have compared withGood temperature sensitive new energy, poly-N-isopropyl acrylamide is because its molecular structure has a minimum overlooking solution temperature (LCST), i.e.,In LCST temperature hereinafter, poly-N-isopropyl acrylamide molecule has certain hole, material is kept intact, is gradually risen in temperatureHeight, and be higher than LCST when, poly-N-isopropyl acrylamide can be shunk, hole reduce, generally will lead to hole in the prior art and subtractIt is few, so that permeability declines, but in this application, in a preferred embodiment, by poly-N-isopropyl acrylamideFilling is into mesopore molecular sieve, and for mesopore molecular sieve preferably through the mesopore molecular sieve of oxidation, load efficiency is higher, in low temperatureWhen, there is poly-N-isopropyl acrylamide itself certain hole to increase so as to there is certain gas permeability with temperatureExtremely, although the contraction that poly-N-isopropyl acrylamide occurs, the hole on poly-N-isopropyl acrylamide is reduced, and poly- N- is differentGap between propylacrylamide and mesopore molecular sieve becomes larger, and the present invention is in the selection of poly-N-isopropyl acrylamide,It joined 2- cyanacrylate during the preparation process, be grafted, so that the hole of poly-N-isopropyl acrylamide changesLess than the hole variation between poly-N-isopropyl acrylamide and mesopore molecular sieve, so that temperature increases, integral materialPermeability is promoted, and the serious forgiveness of the program is high, lower to the control of condition, is relatively easy to reach corresponding technologyEffect.Later by the addition of crosslinking agent, the mesopore molecular sieve of load poly-N-isopropyl acrylamide is crosslinked wholeIn a polyurethane molecular, so as to form a complete molecular structure system.Preferred 3- shrinks sweet in the selection of crosslinking agentOily propyl (dimethoxy) methyl-monosilane, on the one hand the cross-linking effect of the crosslinking agent is preferable, and on the other hand its water-soluble ability is strong, moreMeet the system of aqueous polyurethane.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementationExample, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the artThose of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modificationsIt should be regarded as protection scope of the present invention.