CN111978508A - Organic silicon composite modified waterborne polyurethane and preparation method thereof - Google Patents
Organic silicon composite modified waterborne polyurethane and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
The invention discloses a preparation method of organic silicon composite modified waterborne polyurethane, which comprises the following raw materials in parts by mass: 21.5-23.9 parts of polyester polyol, 4.88-5.0 parts of polyisocyanate, 0.02-0.04 part of catalyst, 1.4-1.5 parts of hydrophilic chain extender, 0.6-0.9 part of hydroxyl silicone oil, 0.3-0.6 part of KH550, 10.0-11.0 parts of solvent, 1.0-1.1 parts of neutralizer, 0.02-0.04 part of post chain extender and 68.0-78.0 parts of deionized water. Firstly, preparing a prepolymer by using polyester polyol, polyisocyanate, hydroxyl silicone oil and a catalyst, and connecting KH550 to the prepolymer; and finally, adding deionized water for high-speed emulsification to prepare the organic silicon composite modified waterborne polyurethane with good emulsion stability and good emulsion film water resistance. The method has the advantages of simple process steps, easy operation and good repeatability.
Description
Technical Field
The invention relates to a preparation method of waterborne polyurethane, in particular to organic silicon composite modified waterborne polyurethane and a preparation method thereof.
Background
The chinlon has the advantages of excellent wear resistance, excellent mechanical property, high strength and the like; the silk fabric has soft hand feeling, good moisture absorption and heat resistance, ultraviolet resistance, sound absorption and health care, and the two fabrics are widely used in the fields of civil use, military use, industry and the like.
The color fixing agent and the finishing agent of the prior textile are not environment-friendly and contain formaldehyde. Such as urea-formaldehyde resin, low-formaldehyde resin, resin color fixing agent Y and the like which are generally adopted. The Waterborne Polyurethane (WPU) has excellent elasticity and film-forming property and does not contain formaldehyde. WPU is generally prepared through linear polymerization, the crosslinking density is limited, the water resistance and the solvent resistance of the WPU are poor, after the WPU is used for fabric color fixing finishing, the color fixing effect and various color fixing fastnesses of the fabric are not ideal, the color fading caused by various reasons can occur after the fabric is used, and the influence on the service life of the fabric is large.
Disclosure of Invention
The invention aims to provide organic silicon composite modified waterborne polyurethane and a preparation method thereof.
The invention is realized by the following technical scheme:
the organic silicon composite modified waterborne polyurethane comprises the following raw materials in parts by weight:
21.5-23.9 parts of polyester polyol, 4.88-5.0 parts of polyisocyanate, 0.02-0.04 part of catalyst, 1.4-1.5 parts of hydrophilic chain extender, 0.6-0.9 part of hydroxyl silicone oil, 0.3-0.6 part of silane coupling agent, 1.0-1.1 parts of neutralizing agent, 0.02-0.04 part of rear chain extender and 68.0-78.0 parts of deionized water.
Furthermore, the maximum water absorption rate of the organosilicon composite modified waterborne polyurethane reaches 9.6%, the maximum tensile strength is 35.36MPa, and the minimum breaking elongation is 432.49%.
The invention also discloses a preparation method of the organic silicon composite modified waterborne polyurethane, which comprises the following steps:
(2) mixing polyester polyol, hydroxyl silicone oil, polyisocyanate and a catalyst, and stirring and reacting for 1-2 hours at the temperature of 70-90 ℃ to obtain a prepolymer;
(2) uniformly mixing a hydrophilic chain extender and a silane coupling agent prepolymer, and reacting for 2-3h at the temperature of 70-85 ℃ to obtain a mixture after chain extension;
(3) cooling the mixture after chain extension, adding a neutralizing agent into the mixture, and reacting for 30-40min to obtain a neutralized salt solution mixed system;
adding the rear chain extender into deionized water, and uniformly mixing to obtain a rear chain extender solution;
(5) adding a rear chain extender solution into the neutralized salt solution mixed system, and emulsifying for 40-60min to obtain a composite modified waterborne polyurethane emulsion;
(5) drying and demoulding the composite modified waterborne polyurethane emulsion to obtain the organic silicon composite modified waterborne polyurethane.
Further, in the step (2), N-methyl pyrrolidone is simultaneously used for adjusting the viscosity of the mixture in the reaction process.
Further, before the step (1), the polyester polyol is subjected to dehydration treatment.
Further, the polyester polyol is PE3020 or PPG-2000.
Further, the polyisocyanate is hexamethylene diisocyanate or isophorone diisocyanate.
Further, the hydrophilic chain extender is 2, 2-dimethylolpropionic acid.
Further, the rear chain extender is anhydrous ethylenediamine.
Further, the catalyst is dibutyltin dilaurate; the neutralizing agent is triethylamine.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses organosilicon composite modified waterborne polyurethane which comprises multiple components, wherein polyester polyol, polyisocyanate, hydroxyl silicone oil and KH550 are key components, so that the waterborne polyurethane color fixing finishing agent has good stability, flexibility, water resistance and firm color. The hydroxyl silicone oil is used as a finishing agent of the fabric, the terminal hydroxyl has reactivity, can be subjected to condensation reaction with a hydroxyl or alkoxy compound under the catalytic action of a catalyst, can be subjected to reaction with-OH and the like on the surface of the fabric, and can increase the color fixing fastness. KH550 is an excellent adhesion promoter, and can improve the dispersibility of the pigment and improve its adhesion. By using-NH in KH5502And the reactivity of-OH in hydroxyl silicone oil and-NCO in polyisocyanate, KH550 is connected to the prepolymer, and water is added for emulsification to prepare the composite modified WPU copolymer emulsion with good emulsion stability and adhesive film flexibility. WPU through compound modification of hydroxyl silicone oil and KH550 carries out the fixation arrangement to washing fibre fabric, soft, smooth, full and have good stability when enabling fabric colour fastness to promote, has great using value as printing and dyeing auxiliary agent. The product development of the aqueous polyurethane textile printing and dyeing auxiliary agent is safe and environment-friendly, has the advantages of improving the color, luster, durability, softness and the like of the textile, and has great social benefit.
Furthermore, the maximum water absorption of the organosilicon composite modified waterborne polyurethane reaches 9.6%, the maximum tensile strength is 35.36MPa, and the minimum breaking elongation is 432.49%, which shows that the organosilicon composite modified waterborne polyurethane prepared by the invention has good hydrophobicity, tensile strength and softness, and after the organosilicon composite modified waterborne polyurethane is used for fabric finishing, the aspects of air permeability, durability, comfort and the like of the fabric can be greatly improved, and the service life of the fabric can be prolonged.
The invention discloses a preparation method of organosilicon composite modified waterborne polyurethane, which is a self-emulsifying direct polymerization method. The preparation method comprises the steps of firstly adding polyester polyol, polyisocyanate and hydroxyl silicone oil to react under the action of a catalyst to obtain a prepolymer, introducing a hydrophilic chain extender on the basis of the prepolymer, so that the system has a self-emulsifying function, and meanwhile, because the hydrophilic chain extender contains hydrophilic groups such as-COOH and the like, groups which are easy to ionize exist on a PU chain after the hydrophilic chain extender is introduced into a polyurethane molecular chain, so that mutual winding among molecular chain segments is weakened, the particle size of the WPU emulsion is reduced, and the stability of the WPU is finally improved. Adding KH550, and using-NH in KH5502KH550 is grafted to the prepolymer for reactivity with-NCO in the prepolymer. And finally, adding deionized water for high-speed emulsification to prepare the composite modified WPU copolymer emulsion with good emulsion stability and good emulsion film water resistance. The method has the advantages of simple process steps, easy operation and good repeatability.
Further, in the whole reaction process, when the viscosity of the reaction system is high, the viscosity of the reaction system is controlled by NMP, and the viscosity of the reaction system is high, so that the reaction can be broken down along with the reaction.
Furthermore, polyester polyol is dehydrated firstly to ensure that no water participates in a reaction system, so that planning is made on time during early preparation of an experiment, and the total time of the experiment can be reduced; the dehydration treatment avoids the introduction of water molecules and prevents the occurrence of implosion.
Drawings
FIG. 1 is an infrared image of organosilicon composite modified waterborne polyurethane prepared in examples 1-3 of the present invention;
FIG. 2 is a particle size distribution diagram of composite modified WPU emulsions according to examples 1 to 3 of the present invention;
figure 3 is the contact angle of the composite modified WPU of inventive example 1;
figure 4 is the contact angle of the composite modified WPU of inventive example 2;
figure 5 is the contact angle of composite modified WPU of inventive example 3;
FIG. 6 is a specific reaction circuit diagram of the preparation method of the organosilicon composite modified waterborne polyurethane of the invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The waterborne polyurethane for finishing the fabric comprises the following raw materials in parts by weight: 21.5-23.9 parts of polyester polyol, 4.88-5.0 parts of polyisocyanate, 0.02-0.04 part of catalyst, 1.4-1.5 parts of hydrophilic chain extender, 0.6-0.9 part of hydroxyl silicone oil, 0.3-0.6 part of silane coupling agent, 1.0-1.1 parts of neutralizing agent, 0.02-0.04 part of rear chain extender and 68.0-78.0 parts of deionized water. Hydroxy silicone oil HSO and silane coupling agent KH550 are used as modifiers in the invention.
Specifically, the polyester polyol is PE3020 or polypropylene glycol PPG-2000.
The polyisocyanate is hexamethylene diisocyanate HDI or isophorone diisocyanate IPDI.
The hydrophilic chain extender is 2, 2-dimethylolpropionic acid DMPA.
The catalyst is dibutyltin dilaurate DBTDL.
The solvent was N-methylpyrrolidone NMP.
The neutralizer is triethylamine TEA.
The rear chain extender is anhydrous Ethylenediamine (EDA).
Example 1
A preparation method of waterborne polyurethane for fabric finishing, wherein a specific reaction scheme is shown in figure 6, comprises the following steps:
(1) adding 21.5g of PE3020 or PPG-2000, 0.6g of hydroxy silicone oil, 4.88g of HDI or IPDI and 0.02g of DBTDL into a three-neck flask, mixing, and stirring at a low speed at 70 ℃ for reaction for 2h to obtain a prepolymer;
(2) adding 1.4g of DMPA into the prepared prepolymer, reacting for 1 hour, and carrying out chain extension; adding 0.6g of KH550 after chain extension is finished, carrying out graft modification, continuously reacting for 1h at 70 ℃, carrying out chain extension and introducing a modifier, and adjusting the viscosity of the system by using NMP in the whole process;
(3) stopping heating the mixed solution after chain extension modification, taking out the mixed solution, cooling the mixed solution for 30min, adding 1.0g of TEA into the mixed solution, and reacting the mixture for 30min to obtain a neutralized salt solution mixed system;
adding 0.02g of EDA into 68.0g of deionized water, and uniformly mixing to obtain a post-chain extender solution;
(4) and adding a rear chain extender solution into the neutralized salt solution mixed system, and emulsifying at a high speed for 40min to obtain the hydroxyl silicone oil and KH550 compound modified waterborne polyurethane emulsion.
(5) And weighing 20g of the obtained waterborne polyurethane emulsion, pouring the weighed waterborne polyurethane emulsion into a polytetrafluoroethylene template, naturally standing the polytetrafluoroethylene template for 24 hours at room temperature, then putting the polytetrafluoroethylene template into a 60 ℃ drying oven for drying for 24 hours, and taking out the waterborne polyurethane emulsion and putting the waterborne polyurethane emulsion into a self-sealing bag for storage.
Example 2
A preparation method of waterborne polyurethane for fabric finishing comprises the following steps:
(1) adding 22.8g of PE3020 or PPG-2000, 0.8g of hydroxy silicone oil, 4.90g of HDI or IPDI and 0.02g of DBTDL into a three-neck flask, mixing, and reacting at 80 ℃ under low-speed stirring for 1.5h to obtain a prepolymer;
(2) adding 1.45g of DMPA into the prepared prepolymer, reacting for 1 hour, and carrying out chain extension; adding 0.39g of KH550 after chain extension is finished, carrying out graft modification, continuously reacting for 1.5h at 80 ℃, carrying out chain extension and introducing a modifier, and adjusting the viscosity of the system by using NMP in the whole process;
(3) stopping heating the mixed solution after chain extension modification, taking out the mixed solution, cooling the mixed solution for 30min, adding 1.05g of TEA into the mixed solution, and reacting the mixture for 35min to obtain a neutralized salt solution mixed system;
adding 0.03g of EDA into 73.0g of deionized water, and uniformly mixing to obtain a post-chain extender solution;
(4) and adding a rear chain extender solution into the neutralized salt solution mixed system, and emulsifying at a high speed for 50min to obtain the hydroxyl silicone oil and KH550 compound modified waterborne polyurethane emulsion.
(5) And weighing 20g of the obtained waterborne polyurethane emulsion, pouring the weighed waterborne polyurethane emulsion into a polytetrafluoroethylene template, naturally standing the polytetrafluoroethylene template for 24 hours at room temperature, then putting the polytetrafluoroethylene template into a 60 ℃ drying oven for drying for 24 hours, and taking out the waterborne polyurethane emulsion and putting the waterborne polyurethane emulsion into a self-sealing bag for storage.
Example 3
A preparation method of waterborne polyurethane for fabric finishing comprises the following steps:
(1)23.9g of PE3020 or PPG-2000, 0.9g of hydroxy silicone oil, 5.0g of HDI or IPDI, and 0.04g of DBTDL, adding into a three-neck flask, mixing, and reacting at 90 ℃ under low-speed stirring for 1h to obtain a prepolymer;
(2) adding 1.5g of DMPA into the prepared prepolymer, reacting for 1 hour, and carrying out chain extension; adding 0.3g of KH550 after chain extension is finished, carrying out graft modification, continuously reacting for 2 hours at 85 ℃, carrying out chain extension and introducing silicon element, and regulating the viscosity of the system by using NMP in the whole process;
(3) stopping heating the mixed solution after chain extension modification, taking out the mixed solution, cooling the mixed solution for 30min, adding 1.1g of TEA into the mixed solution, and reacting the mixture for 40min to obtain a neutralized salt solution mixed system;
adding 0.04g of EDA into 78g of deionized water, and uniformly mixing to obtain a post-chain extender solution;
(4) and adding a rear chain extender solution into the neutralized salt solution mixed system, and emulsifying at a high speed for 60min to obtain the hydroxyl silicone oil and KH550 compound modified waterborne polyurethane emulsion.
(5) And weighing 20g of the obtained waterborne polyurethane emulsion, pouring the weighed waterborne polyurethane emulsion into a polytetrafluoroethylene template, naturally standing the polytetrafluoroethylene template for 24 hours at room temperature, then putting the polytetrafluoroethylene template into a 60 ℃ drying oven for drying for 24 hours, and taking out the waterborne polyurethane emulsion and putting the waterborne polyurethane emulsion into a self-sealing bag for storage.
Samples from examples 1-3 were taken and analyzed by Fourier Infrared Spectroscopy to obtain the curve shown in FIG. 1. As can be seen, the depth is 3354cm-1The absorption peak shows the stretching vibration peak of-OH and-NH in polyurethane, 2943cm-1The absorption peak corresponds to-CH in polyurethane3、—CH2-a moderately saturated C-H stretching vibration peak; 1716cm-1、1534cm-1、1156cm-1The positions of the C ═ O stretching vibration peak, the-NH bending vibration peak and the C-O stretching vibration peak in the polyurethane respectively correspond to the C ═ O stretching vibration peak, the-NH bending vibration peak and the C-O stretching vibration peak in the polyurethane; 1049cm-1Is an asymmetric stretching vibration absorption peak of Si-O; 1250cm-1Has a symmetric deformation vibration absorption peak of Si-C, and 952cm-1The peak at which the oscillation vibration is absorbed is Si-C, indicating that silicon has been incorporated into the molecular chain segment of the polyurethane. 2270cm in spectrum-1No absorption peak appears at the site, whichIt is described that-NCO in the aqueous polyurethane prepolymer and-OH in the hydroxyl silicone oil and-NH in KH5502The reaction is carried out, namely, the hydroxyl silicone oil and the KH550 are successfully grafted on the macromolecular chain of the polyurethane.
A distribution diagram shown in figure 2 is obtained by analyzing the particle size of the samples of the examples 1-3, the average particle size of the emulsion is 123.2nm, and the PDI index is 0.482, which shows that the emulsion is uniform in distribution and good in stability.
The contact angle of the samples of the examples 1 to 3 is measured to obtain contact angle graphs shown in figures 3 to 5, wherein the contact angle of the sample 1 is 64.9 degrees, the contact angle of the sample 2 is 78.4 degrees, the contact angle of the sample 3 is 98.3 degrees, and the contact angle of the adhesive film and the water is increased continuously to reach 98.3 degrees along with the change of the adding ratio of the hydroxyl silicone oil and the KH 550.
The invention also makes the following verification:
1. water absorption test
The test method comprises the following steps: the film of 20mm by 20mm is cut, dried in vacuum for 12h and weighed as W1Soaking in cloud ionized water for 48 hr, taking out, drying with dry filter paper, weighing, and recording as W2When the water absorption ratio is equal to (W)2-W1)/W1×100％。
2. Tensile test of film
And casting the prepared aqueous polyurethane emulsion on a polytetrafluoroethylene plate to form a film with the thickness of 1 mm. The mechanical properties of the adhesive film were tested by a GTS2000-S model multifunctional material testing machine of Taiwan high-speed rail science and technology Co., Ltd, and the tensile properties were tested by averaging 3 times for each sample measurement.
The results in table 1 show that the waterborne polyurethane prepared by the invention has good hydrophobicity, tensile strength and softness, and after the waterborne polyurethane is used for fabric color fixing finishing, various color fastness of the fabric subjected to color fixing treatment can be obviously improved, and the color and luster of clothes can be brighter and more attractive, and the service life, the comfort level and the like of the fabric can be greatly increased.
Claims (10)
1. The organic silicon composite modified waterborne polyurethane is characterized by comprising the following raw materials in parts by mass:
21.5-23.9 parts of polyester polyol, 4.88-5.0 parts of polyisocyanate, 0.02-0.04 part of catalyst, 1.4-1.5 parts of hydrophilic chain extender, 0.6-0.9 part of hydroxyl silicone oil, 0.3-0.6 part of silane coupling agent, 1.0-1.1 parts of neutralizing agent, 0.02-0.04 part of rear chain extender and 68.0-78.0 parts of deionized water.
2. The organosilicon composite modified waterborne polyurethane of claim 1, wherein the water absorption of the organosilicon composite modified waterborne polyurethane is up to 9.6% at most, the tensile strength is 35.36MPa at most, and the elongation at break is 432.49% at least.
3. The preparation method of the organosilicon composite modified waterborne polyurethane of any one of claims 1-2, characterized by comprising the following steps:
(1) mixing polyester polyol, hydroxyl silicone oil, polyisocyanate and a catalyst, and stirring and reacting for 1-2 hours at the temperature of 70-90 ℃ to obtain a prepolymer;
(2) uniformly mixing a hydrophilic chain extender and a silane coupling agent prepolymer, and reacting for 2-3h at the temperature of 70-85 ℃ to obtain a mixture after chain extension;
(3) cooling the mixture after chain extension, adding a neutralizing agent into the mixture, and reacting for 30-40min to obtain a neutralized salt solution mixed system;
adding the rear chain extender into deionized water, and uniformly mixing to obtain a rear chain extender solution;
(4) adding a rear chain extender solution into the neutralized salt solution mixed system, and emulsifying for 40-60min to obtain a composite modified waterborne polyurethane emulsion;
(5) drying and demoulding the composite modified waterborne polyurethane emulsion to obtain the organic silicon composite modified waterborne polyurethane.
4. The preparation method of the organosilicon composite modified waterborne polyurethane as claimed in claim 3, wherein in the step (2), N-methyl pyrrolidone is simultaneously used to adjust the viscosity of the mixture during the reaction.
5. The method for preparing the silicone composite modified aqueous polyurethane according to claim 3, wherein the polyester polyol is subjected to dehydration treatment before step (1).
6. The method for preparing the organosilicon composite modified waterborne polyurethane as claimed in claim 3, wherein the polyester polyol is PE3020 or PPG-2000.
7. The method for preparing the organosilicon composite modified waterborne polyurethane according to claim 3, wherein the polyisocyanate is hexamethylene diisocyanate or isophorone diisocyanate.
8. The preparation method of the organosilicon composite modified waterborne polyurethane as claimed in claim 3, wherein the hydrophilic chain extender is 2, 2-dimethylolpropionic acid.
9. The preparation method of the organosilicon composite modified waterborne polyurethane as claimed in claim 3, wherein the post-chain extender is anhydrous ethylenediamine.
10. The method for preparing the organosilicon composite modified waterborne polyurethane as claimed in claim 3, wherein the catalyst is dibutyltin dilaurate; the neutralizing agent is triethylamine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527614A (en) * | 2021-07-05 | 2021-10-22 | 重庆交通大学 | Water-based polymer emulsion with self-compensation hydrophobic surface function and preparation method thereof |
| CN114231155A (en) * | 2021-12-27 | 2022-03-25 | 安徽省金盾涂料有限责任公司 | Hydroxyalkyl aqueous organosilicon modified polyurethane aqueous dispersion composition and preparation method thereof |
| CN114381191A (en) * | 2022-01-17 | 2022-04-22 | 江苏第二师范学院 | Hydroxyl silicone oil modified waterborne polyurethane coating with high tensile strength and high water resistance coating film |
| CN114477917A (en) * | 2022-03-04 | 2022-05-13 | 南京亨瑞斯新材料科技有限公司 | Super-hydrophobic concrete and use method thereof |
| CN114583170A (en) * | 2021-12-06 | 2022-06-03 | 深圳市研一新材料有限责任公司 | Softening agent and preparation method and application thereof |
| CN115679704A (en) * | 2020-12-26 | 2023-02-03 | 江苏苏净集团有限公司 | Preparation method of adsorption dehumidification material for dehumidification rotating wheel |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838719A (en) * | 2012-09-21 | 2012-12-26 | 中国海洋石油总公司 | High hydrophobic organic silicon-polyurethane insulation compound material and preparation method thereof |
| CN103382245A (en) * | 2012-05-03 | 2013-11-06 | 高明志 | Preparation method for organosilicon-modified crosslinking polyurethane emulsion |
| CN105255348A (en) * | 2015-10-13 | 2016-01-20 | 厦门大学 | One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof |
| CN105566608A (en) * | 2016-03-17 | 2016-05-11 | 兰州科天水性高分子材料有限公司 | Anionic water-based polyurethane resin for sofa leather wet-process impregnated bases |
| CN105601872A (en) * | 2015-12-25 | 2016-05-25 | 杭州中一科技有限公司 | Hydroxyl silicone oil and silane coupling agent composite modified waterborne polyurethane and preparing method thereof |
| CN107141434A (en) * | 2017-06-08 | 2017-09-08 | 合肥科天水性科技有限责任公司 | It is a kind of for waterborne polyurethane resin of synthetic leather fabric and preparation method thereof |
-
2020
- 2020-08-28 CN CN202010888422.2A patent/CN111978508A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103382245A (en) * | 2012-05-03 | 2013-11-06 | 高明志 | Preparation method for organosilicon-modified crosslinking polyurethane emulsion |
| CN102838719A (en) * | 2012-09-21 | 2012-12-26 | 中国海洋石油总公司 | High hydrophobic organic silicon-polyurethane insulation compound material and preparation method thereof |
| CN105255348A (en) * | 2015-10-13 | 2016-01-20 | 厦门大学 | One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof |
| CN105601872A (en) * | 2015-12-25 | 2016-05-25 | 杭州中一科技有限公司 | Hydroxyl silicone oil and silane coupling agent composite modified waterborne polyurethane and preparing method thereof |
| CN105566608A (en) * | 2016-03-17 | 2016-05-11 | 兰州科天水性高分子材料有限公司 | Anionic water-based polyurethane resin for sofa leather wet-process impregnated bases |
| CN107141434A (en) * | 2017-06-08 | 2017-09-08 | 合肥科天水性科技有限责任公司 | It is a kind of for waterborne polyurethane resin of synthetic leather fabric and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 官慧等: "有机硅改性形状记忆水性聚氨酯的制备", 《合成树脂及塑料》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115679704A (en) * | 2020-12-26 | 2023-02-03 | 江苏苏净集团有限公司 | Preparation method of adsorption dehumidification material for dehumidification rotating wheel |
| CN113527614A (en) * | 2021-07-05 | 2021-10-22 | 重庆交通大学 | Water-based polymer emulsion with self-compensation hydrophobic surface function and preparation method thereof |
| CN113527614B (en) * | 2021-07-05 | 2022-09-23 | 重庆交通大学 | Water-based polymer emulsion with self-compensation hydrophobic surface function and preparation method thereof |
| CN114583170A (en) * | 2021-12-06 | 2022-06-03 | 深圳市研一新材料有限责任公司 | Softening agent and preparation method and application thereof |
| CN114583170B (en) * | 2021-12-06 | 2023-11-21 | 深圳市研一新材料有限责任公司 | Softening agent and preparation method and application thereof |
| CN114231155A (en) * | 2021-12-27 | 2022-03-25 | 安徽省金盾涂料有限责任公司 | Hydroxyalkyl aqueous organosilicon modified polyurethane aqueous dispersion composition and preparation method thereof |
| CN114381191A (en) * | 2022-01-17 | 2022-04-22 | 江苏第二师范学院 | Hydroxyl silicone oil modified waterborne polyurethane coating with high tensile strength and high water resistance coating film |
| CN114477917A (en) * | 2022-03-04 | 2022-05-13 | 南京亨瑞斯新材料科技有限公司 | Super-hydrophobic concrete and use method thereof |
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