CN109796568B - High-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane - Google Patents
High-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane Download PDFInfo
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Abstract
The invention discloses high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane which comprises the following components in parts by weight: polyol: 20-70 parts of diisocyanate: 10-25 parts of a sulfonate chain extender: 2-5 parts of a hydroxy acid salt type chain extender: 2-5 parts of mesoporous molecular sieve: 2-5 parts of poly N-isopropyl acrylamide: 1-2 parts of a cross-linking agent: 1-3 parts of catalyst: 0.05 part. In the invention, the common use of the sulfonate chain extender and the carboxylate chain extender is mainly adopted, and the chain segments between polyurethanes are increased as the chain extenders in the whole reaction system of the polyurethanes, so that the chain segments between polyurethane molecules are changed, active groups are increased, the water solubility is higher, the integral solid content is improved, and the integral viscosity is greatly improved.
Description
Technical Field
The invention relates to a polyurethane material, in particular to high-solid low-viscosity sulfonic acid/hydroxyl acid aqueous polyurethane.
Background
With the enhancement of environmental awareness of people and the increasing attention of various countries on the problem of environmental pollution, waterborne polyurethane is gradually replacing solvent-based polyurethane and is widely applied to the fields of coatings, adhesives, leather, textiles and the like. The waterborne polyurethane takes water as a dispersion medium, no VOCs is discharged, and the waterborne polyurethane is low in cost and safe to use. However, the solid content of the existing waterborne polyurethane is about 30 percent, and the defects of long drying time and high energy consumption exist because the latent heat of evaporation of water is higher than that of the organic solvent, so that the popularization and the application of the waterborne polyurethane are greatly restricted. The solid content of the waterborne polyurethane is improved, so that the drying time can be greatly shortened, and the energy consumption can be reduced.
In the prior art, more waterborne polyurethane with high solid content has appeared, but the waterborne polyurethane with high solid content has higher viscosity due to higher solid content, less internal solvent and increased viscous components, thereby influencing the downstream use.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane,
comprises the following components in parts by weight:
polyol: 20 to 70 portions of
Diisocyanate: 10 to 25 portions of
Sulfonate type chain extender: 2 to 5 portions of
Hydroxyl acid type chain extender: 2 to 5 portions of
Mesoporous molecular sieve: 2 to 5 portions of
poly-N-isopropylacrylamide: 1 to 2 portions of
A crosslinking agent: 1 to 3 portions of
Catalyst: 0.05 part.
As a further improvement of the invention:
the diisocyanate is at least one of 4,4' -methylene bis (phenyl isocyanate), hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate and hydrogenated toluene diisocyanate.
As a further improvement of the invention:
the polyalcohol is at least one of ethylene glycol, glycerol, diethylene glycol, triacetyl propyl silanetriol and 1,2, 10-decanetriol.
As a further improvement of the invention:
the sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt.
As a further improvement of the invention:
the sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt in a mass ratio of 6: 1.
As a further improvement of the invention:
the hydroxyl acid type chain extender is at least one of dimethylolbutyric acid, tartaric acid and hydroxyl-containing half-ester dihydric alcohol.
As a further improvement of the invention:
the cross-linking agent is 3-glycidoxypropyl (dimethoxy) methylsilane.
As a further improvement of the invention:
the mesoporous molecular sieve is obtained by oxidizing an MCM-41 molecular sieve for 1-6 hours by hydrogen peroxide.
As a further improvement of the invention:
the poly-N-isopropylacrylamide is prepared by the following method:
dissolving N-isopropyl acrylamide and N, N-methylene bisacrylamide in hydrochloric acid solution with pH of 1.5,
mixing, adding ammonium persulfate, tetramethylethylenediamine and 2-ethyl cyanoacrylate, and introducing nitrogen
Sealing the reaction container for 1min, heating to 65 ℃, reacting for 4 hours at constant temperature, and stopping heating and stirring to obtain poly N-isopropyl acrylamide;
wherein the mass ratio of the 2-cyanoacrylate to the N-isopropylacrylamide to the ammonium persulfate to the N, N-methylenebisacrylamide to the tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
as a further improvement of the invention:
the preparation method of the waterborne polyurethane comprises the following steps:
step one, mixing a mesoporous molecular sieve and poly N-isopropylacrylamide, keeping the temperature in an ice bath at 5-10 ℃ for 24 hours, then heating to 40 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the mesoporous molecular sieve loaded with the poly N-isopropylacrylamide;
adding polyol, diisocyanate and a catalyst into a reaction container, and reacting at 60-90 ℃ for 2-4 hours to obtain a diisocyanate-based prepolymer;
step three: adding a hydroxyl acid type chain extender and a sulfonate type chain extender, and reacting for 2-4 hours at the temperature of 60-90 ℃;
step four: cooling to below 60 ℃ to obtain an ionomer;
step five: adding mesoporous molecular sieve loaded with poly N-isopropyl acrylamide and 20 parts of deionized water into the ionomer, keeping the temperature at 30-40 ℃, and reacting for 2-4 hours to obtain a product.
In the invention, the common use of the sulfonate chain extender and the hydroxy acid chain extender is mainly adopted, in the whole reaction system of the polyurethane, the chain segments between the polyurethanes are increased as the chain extenders, so that the chain segments between the polyurethane molecules are changed, and active groups are increased, so that the water solubility is higher, and the whole solid content is improved.
Detailed Description
The first embodiment is as follows:
a high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane,
comprises the following components in parts by weight:
polyol: 45 portions of
Diisocyanate: 25 portions of
Sulfonate type chain extender: 2 portions of
Hydroxyl acid type chain extender: 3 portions of
Mesoporous molecular sieve: 3 portions of
poly-N-isopropylacrylamide: 2 portions of
A crosslinking agent: 1 part of
Catalyst: 0.05 part
The catalyst is an organic silver catalyst.
The diisocyanate is 4,4' -methylenebis (phenyl isocyanate).
The polyalcohol is ethylene glycol;
the sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt.
The sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt in a mass ratio of 6: 1.
The hydroxyl acid type chain extender is at least one of dimethylolbutyric acid, tartaric acid and hydroxyl-containing half-ester dihydric alcohol.
The cross-linking agent is 3-glycidoxypropyl (dimethoxy) methylsilane.
The mesoporous molecular sieve is obtained by oxidizing an MCM-41 molecular sieve for 3 hours by hydrogen peroxide.
The poly-N-isopropylacrylamide is prepared by the following method:
dissolving N-isopropyl acrylamide and N, N-methylene bisacrylamide in hydrochloric acid solution with pH of 1.5,
uniformly mixing, adding ammonium persulfate, tetramethylethylenediamine and 2-ethyl cyanoacrylate, introducing nitrogen for 1min, sealing the reaction container, heating to 65 ℃, reacting at constant temperature for 4 hours, and stopping heating and stirring to obtain poly-N-isopropylacrylamide;
wherein the mass ratio of the 2-cyanoacrylate to the N-isopropylacrylamide to the ammonium persulfate to the N, N-methylenebisacrylamide to the tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
the preparation method of the waterborne polyurethane comprises the following steps:
step one, mixing a mesoporous molecular sieve and poly N-isopropylacrylamide, keeping the temperature in an ice bath at 5-10 ℃ for 24 hours, then heating to 40 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the mesoporous molecular sieve loaded with the poly N-isopropylacrylamide;
adding polyol, diisocyanate and a catalyst into a reaction container, and reacting at 60-90 ℃ for 2-4 hours to obtain a diisocyanate-based prepolymer;
step three: adding a hydroxyl acid type chain extender and a sulfonate type chain extender, and reacting for 2-4 hours at 75 ℃;
step four: cooling to below 60 ℃ to obtain an ionomer;
step five: adding mesoporous molecular sieve loaded with poly N-isopropyl acrylamide and 20 parts of deionized water into the ionomer, keeping the temperature at 30-40 ℃, and reacting for 2-4 hours to obtain a product.
Example two:
a high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane,
comprises the following components in parts by weight:
polyol: 20 portions of
Diisocyanate: 15 portions of
Sulfonate type chain extender: 5 portions of
Hydroxyl acid type chain extender: 2 portions of
Mesoporous molecular sieve: 3 portions of
poly-N-isopropylacrylamide: 2 portions of
A crosslinking agent: 1 part of
Catalyst: 0.05 part
The catalyst is an organic silver catalyst.
The diisocyanate is hexamethylene diisocyanate.
The polyol is glycerol;
the sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt.
The sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt in a mass ratio of 6: 1.
The hydroxyl acid type chain extender is at least one of dimethylolbutyric acid, tartaric acid and hydroxyl-containing half-ester dihydric alcohol.
The cross-linking agent is 3-glycidoxypropyl (dimethoxy) methylsilane.
The mesoporous molecular sieve is obtained by oxidizing an MCM-41 molecular sieve for 3 hours by hydrogen peroxide.
The poly-N-isopropylacrylamide is prepared by the following method:
dissolving N-isopropyl acrylamide and N, N-methylene bisacrylamide in hydrochloric acid solution with pH of 1.5,
uniformly mixing, adding ammonium persulfate, tetramethylethylenediamine and 2-ethyl cyanoacrylate, introducing nitrogen for 1min, sealing the reaction container, heating to 65 ℃, reacting at constant temperature for 4 hours, and stopping heating and stirring to obtain poly-N-isopropylacrylamide;
wherein the mass ratio of the 2-cyanoacrylate to the N-isopropylacrylamide to the ammonium persulfate to the N, N-methylenebisacrylamide to the tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
the preparation method of the waterborne polyurethane comprises the following steps:
step one, mixing a mesoporous molecular sieve and poly N-isopropylacrylamide, keeping the temperature in an ice bath at 5-10 ℃ for 24 hours, then heating to 40 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the mesoporous molecular sieve loaded with the poly N-isopropylacrylamide;
adding polyol, diisocyanate and a catalyst into a reaction container, and reacting at 60-90 ℃ for 2-4 hours to obtain a diisocyanate-based prepolymer;
step three: adding a hydroxyl acid type chain extender and a sulfonate type chain extender, and reacting for 2-4 hours at 75 ℃;
step four: cooling to below 60 ℃ to obtain an ionomer;
step five: adding mesoporous molecular sieve loaded with poly N-isopropyl acrylamide and 20 parts of deionized water into the ionomer, keeping the temperature at 30-40 ℃, and reacting for 2-4 hours to obtain a product.
Example three:
a high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane,
comprises the following components in parts by weight:
polyol: 70 portions of
Diisocyanate: 10 portions of
Sulfonate type chain extender: 3 portions of
Hydroxyl acid type chain extender: 5 portions of
Mesoporous molecular sieve: 3 portions of
poly-N-isopropylacrylamide: 2 portions of
A crosslinking agent: 1 part of
Catalyst: 0.05 part
The catalyst is an organic silver catalyst.
The diisocyanate is 4,4' -methylenebis (phenyl isocyanate).
The polyol is a mixture of ethylene glycol and triacetyl propyl silanetriol in a mass ratio of 5: 1.
The sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt.
The sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt in a mass ratio of 6: 1.
The hydroxyl acid type chain extender is dimethylolbutyric acid.
The cross-linking agent is 3-glycidoxypropyl (dimethoxy) methylsilane.
The mesoporous molecular sieve is obtained by oxidizing an MCM-41 molecular sieve for 3 hours by hydrogen peroxide.
The poly-N-isopropylacrylamide is prepared by the following method:
dissolving N-isopropyl acrylamide and N, N-methylene bisacrylamide in hydrochloric acid solution with pH of 1.5,
uniformly mixing, adding ammonium persulfate, tetramethylethylenediamine and 2-ethyl cyanoacrylate, introducing nitrogen for 1min, sealing the reaction container, heating to 65 ℃, reacting at constant temperature for 4 hours, and stopping heating and stirring to obtain poly-N-isopropylacrylamide;
wherein the mass ratio of the 2-cyanoacrylate to the N-isopropylacrylamide to the ammonium persulfate to the N, N-methylenebisacrylamide to the tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
the preparation method of the waterborne polyurethane comprises the following steps:
step one, mixing a mesoporous molecular sieve and poly N-isopropylacrylamide, keeping the temperature in an ice bath at 5-10 ℃ for 24 hours, then heating to 40 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the mesoporous molecular sieve loaded with the poly N-isopropylacrylamide;
adding polyol, diisocyanate and a catalyst into a reaction container, and reacting at 60-90 ℃ for 2-4 hours to obtain a diisocyanate-based prepolymer;
step three: adding a hydroxyl acid type chain extender and a sulfonate type chain extender, and reacting for 2-4 hours at 75 ℃;
step four: cooling to below 60 ℃ to obtain an ionomer;
step five: adding mesoporous molecular sieve loaded with poly N-isopropyl acrylamide and 20 parts of deionized water into the ionomer, keeping the temperature at 30-40 ℃, and reacting for 2-4 hours to obtain a product.
Example four
A high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane,
comprises the following components in parts by weight:
polyol: 45 portions of
Diisocyanate: 25 portions of
Sulfonate type chain extender: 2 portions of
Hydroxyl acid type chain extender: 3 portions of
Mesoporous molecular sieve: 3 portions of
poly-N-isopropylacrylamide: 2 portions of
A crosslinking agent: 1 part of
Catalyst: 0.05 part
The catalyst is an organic silver catalyst.
The diisocyanate is 4,4' -methylenebis (phenyl isocyanate).
The polyalcohol is ethylene glycol;
the sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt.
The sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt in a mass ratio of 6: 1.
The hydroxyl acid type chain extender is dimethylolbutyric acid.
The cross-linking agent is 3-glycidoxypropyl (dimethoxy) methylsilane.
The mesoporous molecular sieve is obtained by oxidizing an MCM-41 molecular sieve for 3 hours by hydrogen peroxide.
The poly-N-isopropylacrylamide is prepared by the following method:
dissolving N-isopropyl acrylamide and N, N-methylene bisacrylamide in hydrochloric acid solution with pH of 1.5,
uniformly mixing, adding ammonium persulfate, tetramethylethylenediamine and 2-ethyl cyanoacrylate, introducing nitrogen for 1min, sealing the reaction container, heating to 65 ℃, reacting at constant temperature for 4 hours, and stopping heating and stirring to obtain poly-N-isopropylacrylamide;
wherein the mass ratio of the 2-cyanoacrylate to the N-isopropylacrylamide to the ammonium persulfate to the N, N-methylenebisacrylamide to the tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
the preparation method of the waterborne polyurethane comprises the following steps:
adding polyol, diisocyanate and a catalyst into a reaction container, and reacting at 60-90 ℃ for 2-4 hours to obtain a diisocyanate-based prepolymer;
step two: adding a hydroxyl acid type chain extender and a sulfonate type chain extender, and reacting for 2-4 hours at 75 ℃;
step three: cooling to below 60 ℃ to obtain an ionomer;
step four: adding poly-N-isopropylacrylamide, a mesoporous molecular sieve and 20 parts of deionized water into the ionomer, keeping the temperature at 30-40 ℃, and reacting for 2-4 hours to obtain a product.
Comparative example 1
A high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane,
comprises the following components in parts by weight:
polyol: 45 portions of
Diisocyanate: 25 portions of
Hydroxyl acid type chain extender: 3 portions of
poly-N-isopropylacrylamide: 2 portions of
A crosslinking agent: 1 part of
Catalyst: 0.05 part
The catalyst is an organic silver catalyst.
The diisocyanate is 4,4' -methylenebis (phenyl isocyanate).
The polyalcohol is ethylene glycol;
the hydroxyl acid type chain extender is at least one of dimethylolbutyric acid, tartaric acid and hydroxyl-containing half-ester dihydric alcohol.
The cross-linking agent is 3-glycidoxypropyl (dimethoxy) methylsilane.
The poly-N-isopropylacrylamide is prepared by the following method:
dissolving N-isopropyl acrylamide and N, N-methylene bisacrylamide in hydrochloric acid solution with pH of 1.5,
uniformly mixing, adding ammonium persulfate, tetramethylethylenediamine and 2-ethyl cyanoacrylate, introducing nitrogen for 1min, sealing the reaction container, heating to 65 ℃, reacting at constant temperature for 4 hours, and stopping heating and stirring to obtain poly-N-isopropylacrylamide;
wherein the mass ratio of the 2-cyanoacrylate to the N-isopropylacrylamide to the ammonium persulfate to the N, N-methylenebisacrylamide to the tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
the preparation method of the waterborne polyurethane comprises the following steps:
step one, keeping the temperature of poly N-isopropyl acrylamide in an ice bath at 5-10 ℃ for 24 hours, then heating to 40 ℃, reacting for 2 hours, and cooling to room temperature;
adding polyol, diisocyanate and a catalyst into a reaction container, and reacting at 60-90 ℃ for 2-4 hours to obtain a diisocyanate-based prepolymer;
step three: adding hydroxy acid type chain extender, and reacting for 2-4 hours at 75 ℃;
step four: cooling to below 60 ℃ to obtain an ionomer;
step five: adding poly-N-isopropylacrylamide loaded with poly-N-isopropylacrylamide and 20 parts of deionized water into the ionomer, keeping the temperature at 30-40 ℃, and reacting for 2-4 hours to obtain a product.
Comparative example No. two
A high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane,
comprises the following components in parts by weight:
polyol: 45 portions of
Diisocyanate: 25 portions of
Sulfonate type chain extender: 2 portions of
Mesoporous molecular sieve: 3 portions of
A crosslinking agent: 1 part of
Catalyst: 0.05 part
The catalyst is an organic silver catalyst.
The diisocyanate is 4,4' -methylenebis (phenyl isocyanate).
The polyalcohol is ethylene glycol;
the sulfonate chain extender is N, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt.
The cross-linking agent is 3-glycidoxypropyl (dimethoxy) methylsilane.
The mesoporous molecular sieve is obtained by oxidizing an MCM-41 molecular sieve for 3 hours by hydrogen peroxide.
The poly-N-isopropylacrylamide is prepared by the following method:
dissolving N-isopropyl acrylamide and N, N-methylene bisacrylamide in hydrochloric acid solution with pH of 1.5,
uniformly mixing, adding ammonium persulfate, tetramethylethylenediamine and 2-ethyl cyanoacrylate, introducing nitrogen for 1min, sealing the reaction container, heating to 65 ℃, reacting at constant temperature for 4 hours, and stopping heating and stirring to obtain poly-N-isopropylacrylamide;
wherein the mass ratio of the 2-cyanoacrylate to the N-isopropylacrylamide to the ammonium persulfate to the N, N-methylenebisacrylamide to the tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
the preparation method of the waterborne polyurethane comprises the following steps:
step one, keeping the temperature of the mesoporous molecular sieve in an ice bath at 5-10 ℃ for 24 hours, then heating to 40 ℃, reacting for 2 hours, and cooling to room temperature;
adding polyol, diisocyanate and a catalyst into a reaction container, and reacting at 60-90 ℃ for 2-4 hours to obtain a diisocyanate-based prepolymer;
step three: adding a sulfonate chain extender, and reacting for 2-4 hours at 75 ℃;
step four: cooling to below 60 ℃ to obtain an ionomer;
step five: adding the mesoporous molecular sieve and 20 parts of deionized water into the ionomer, keeping the temperature at 30-40 ℃, and reacting for 2-4 hours to obtain a product.
And (3) testing: the technical schemes of the examples and the comparative examples were tested for solid content, viscosity, and whether delamination and air permeability occurred after 30, 60, 90, and 180 days of standing.
Table one: solid content and viscosity test
Table two: delamination test (at 25 ℃ C.)
Table three: air permeability test (unit g/m)2·24h）
In the invention, the common use of the sulfonate chain extender and the hydroxy acid chain extender is mainly adopted, in the whole reaction system of the polyurethane, the chain segments between the polyurethanes are increased as the chain extenders, so that the chain segments between the polyurethane molecules are changed, and active groups are increased, so that the water solubility is higher, and the whole solid content is improved. Particularly, a mixture of sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate and sodium 2-acrylamide-2-methylpropanesulfonate in a mass ratio of 6:1 is preferred for selecting the sulfonate type chain extender, so that the solid content can be better increased and the viscosity can be better reduced.
Meanwhile, the inventor finds that the viscosity can be effectively reduced by properly adding a part of the triacetyl propyl silanetriol in the selection of the polyol, so that the most preferable example is given in example three, and the polyol selects the mixture of the ethylene glycol and the triacetyl propyl silanetriol with the mass ratio of 5: 1.
In the prior art, the porosity of the polyurethane surface is constant, and even if the polyurethane expands with heat and contracts with cold with the temperature change, the porosity does not change too much, so the air permeability of the polyurethane is constant, although in Chinese patent with the application number of CN200910153507.X, a polyurethane resin for coating the synthetic leather surface with an intelligent moisture permeable function is disclosed, wherein an organic polyol polymer is a mixture of polyester diol and polyether diol, and the mass ratio of the polyester diol and the polyether diol is 1: 0.2-4. The diisocyanate is 4,4' -diphenylmethane diisocyanate, toluene diisocyanate or isophorone diisocyanate; the chain extender is 1, 4-butanediol, glycol or diethylene glycol. The invention has the advantages that: (1) combines the advantages of polyurethane taking polyester diol as a soft segment and polyurethane taking polyethylene glycol as a soft segment, makes up for deficiencies, and obtains the polyurethane which has good moisture permeability and good mechanical properties. (2) The intelligent moisture-permeable transition temperature of the polyurethane resin is within the range of 20-50 ℃, and the transition temperature can be controlled by adjusting the molecular weight and the proportion of the polyester diol and the polyethylene glycol.
But the molecular weight and proportion of polyethylene glycol are difficult to control, and the rejection rate is high.
The applicant has therefore made further studies to improve the air permeability of the monolithic material by adding a mesoporous molecular sieve and to add poly-N-isopropylacrylamide to provide environmental compatibility, wherein poly-N-isopropylacrylamide has better new temperature-sensitive properties, and poly-N-isopropylacrylamide has a minimum critical solution temperature (LCST) due to its molecular structure, i.e., below the LCST temperature, the poly-N-isopropylacrylamide molecules have certain pores, and the material remains as it is, and when the temperature is gradually increased, and above the LCST, poly-N-isopropylacrylamide shrinks and the pores decrease, which generally occurs in the prior art and thus the air permeability decreases, but in this application, in a preferred embodiment, poly-N-isopropylacrylamide is filled into the mesoporous molecular sieve, the mesoporous molecular sieve is preferably an oxidized mesoporous molecular sieve, the loading efficiency is higher, at low temperature, the poly-N-isopropylacrylamide per se has certain pores, so that certain air permeability can be realized, although the poly-N-isopropylacrylamide shrinks along with the rise of temperature, the pores on the poly-N-isopropylacrylamide are reduced, but the gap between the poly-N-isopropylacrylamide and the mesoporous molecular sieve is enlarged, in the selection of the poly-N-isopropylacrylamide, 2-ethyl cyanoacrylate is added in the preparation process for grafting, so that the pore change of the poly-N-isopropylacrylamide is smaller than the pore change between the poly-N-isopropylacrylamide and the mesoporous molecular sieve, the temperature is increased, and the air permeability of the whole material is improved, and the fault-tolerant rate of this scheme is high, and is lower to the control of condition, reaches corresponding technological effect comparatively easily. Then, the mesoporous molecular sieve loading the poly N-isopropylacrylamide can be crosslinked in the whole polyurethane molecule by adding the crosslinking agent, so that a complete molecular structure system is formed. 3-glycidoxypropyl (dimethoxy) methylsilane is preferred in the selection of the cross-linking agent, and on one hand, the cross-linking effect of the cross-linking agent is better, and on the other hand, the water-solubility of the cross-linking agent is stronger, so that the cross-linking agent is more suitable for a system of waterborne polyurethane.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (7)
1. A high-solid low-viscosity sulfonic acid/hydroxyl acid waterborne polyurethane is characterized in that:
comprises the following components in parts by weight:
polyol: 20 to 70 portions of
Diisocyanate: 10 to 25 portions of
Sulfonate type chain extender: 2 to 5 portions of
Hydroxyl acid type chain extender: 2 to 5 portions of
Mesoporous molecular sieve: 2 to 5 portions of
poly-N-isopropylacrylamide: 1 to 2 portions of
A crosslinking agent: 1 to 3 portions of
Catalyst: 0.05 part;
the preparation method of the waterborne polyurethane comprises the following steps:
step one, mixing a mesoporous molecular sieve and poly N-isopropylacrylamide, keeping the temperature in an ice bath at 5-10 ℃ for 24 hours, then heating to 40 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the mesoporous molecular sieve loaded with the poly N-isopropylacrylamide;
adding polyol, diisocyanate and a catalyst into a reaction container, and reacting at 60-90 ℃ for 2-4 hours to obtain a diisocyanate-based prepolymer;
step three: adding a hydroxyl acid type chain extender and a sulfonate type chain extender, and reacting for 2-4 hours at the temperature of 60-90 ℃;
step four: cooling to below 60 ℃ to obtain an ionomer;
step five: adding a mesoporous molecular sieve loaded with poly N-isopropylacrylamide and 20 parts of deionized water into an ionomer, keeping the temperature at 30-40 ℃, and reacting for 2-4 hours to obtain a product;
the mesoporous molecular sieve is obtained by oxidizing an MCM-41 molecular sieve for 1-6 hours by hydrogen peroxide;
the poly-N-isopropylacrylamide is prepared by the following method:
dissolving N-isopropyl acrylamide and N, N-methylene bisacrylamide in hydrochloric acid solution with pH of 1.5,
mixing, adding ammonium persulfate, tetramethylethylenediamine and 2-ethyl cyanoacrylate, and introducing nitrogen
Sealing the reaction container for 1min, heating to 65 ℃, reacting for 4 hours at constant temperature, and stopping heating and stirring to obtain poly N-isopropyl acrylamide;
wherein the mass ratio of the 2-cyanoacrylate to the N-isopropylacrylamide to the ammonium persulfate to the N, N-methylenebisacrylamide to the tetramethylethylenediamine is 1: 5: 0.3: 1: 1.
2. the high-solid low-viscosity sulfonic/hydroxyacid waterborne polyurethane according to claim 1, wherein:
the diisocyanate is at least one of 4,4' -methylene bis (phenyl isocyanate), hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate and hydrogenated toluene diisocyanate.
3. The high-solid low-viscosity sulfonic/hydroxyacid waterborne polyurethane according to claim 1, wherein:
the polyalcohol is at least one of ethylene glycol, glycerol, diethylene glycol and 1,2, 10-decanetriol.
4. The high-solid low-viscosity sulfonic/hydroxyacid waterborne polyurethane according to claim 1, wherein:
the sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt.
5. The high-solid low-viscosity sulfonic/hydroxyacid waterborne polyurethane according to claim 4, wherein:
the sulfonate chain extender is a mixture of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2-acrylamide-2-methylpropanesulfonic acid sodium salt in a mass ratio of 6: 1.
6. The high-solid low-viscosity sulfonic/hydroxyacid waterborne polyurethane according to claim 1, wherein:
the hydroxyl acid type chain extender is at least one of dimethylolbutyric acid, tartaric acid and hydroxyl-containing half-ester dihydric alcohol.
7. The high-solid low-viscosity sulfonic/hydroxyacid waterborne polyurethane according to claim 1, wherein:
the cross-linking agent is 3-glycidoxypropyl (dimethoxy) methylsilane.
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