CN102653585A - Method for preparing sulfoacid/carboxylic acid waterborne polyurethane - Google Patents
Method for preparing sulfoacid/carboxylic acid waterborne polyurethane Download PDFInfo
- Publication number
- CN102653585A CN102653585A CN2012101507298A CN201210150729A CN102653585A CN 102653585 A CN102653585 A CN 102653585A CN 2012101507298 A CN2012101507298 A CN 2012101507298A CN 201210150729 A CN201210150729 A CN 201210150729A CN 102653585 A CN102653585 A CN 102653585A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- product
- waterborne polyurethane
- sulfonic acid
- acid type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *C(CC(N(CCO)CCO)=O)C(*)=O Chemical compound *C(CC(N(CCO)CCO)=O)C(*)=O 0.000 description 1
Abstract
The invention discloses a method for preparing sulfoacid/carboxylic acid waterborne polyurethane. The method comprises the following steps of: reacting polyisocyanates with polymer polyol at the temperature between 80 and 100 DEG C, thus obtaining a product A; reacting A with a sulfoacid/carboxylic acid hydrophilic chain extender and a small-molecule chain extender at the temperature between 70 and 100 DEG C, thus obtaining a product B, cooling the product B, adding the product B into water in a stirring state for dispersing, adding an antifoaming agent into the mixture, thus obtaining a product C; and finally performing reduced pressure distillation on the product C at the temperature being below 50 DEG C for removing a cosolvent, thus obtaining the sulfoacid/carboxylic acid waterborne polyurethane. According to the method, sulfo group and carboxylic acid group are introduced into a polyurethane molecular main chain for one time, so that the sulfoacid/carboxylic acid waterborne polyurethane has the characteristics of sulfoacid waterborne polyurethane and carboxylic acid waterborne polyurethane; a waterborne polyurethane prepolymer can be emulsified and dispersed in water, the high solid content of a product is realized easily; the regularness of a polyurethane resin chain is protected; and the sulfoacid/carboxylic acid waterborne polyurethane has the advantages of simpleness in process line and high product yield.
Description
Technical field
The invention belongs to the synthetic field of aqueous polyurethane, be specifically related to a kind of sulfonic acid/carboxylic acid type Synthesis of Waterborne Polyurethane method.
Background technology
Along with the progress and development of society, environmental protection consciousness also more and more receives people's attention.Traditional solvent type polyurethane resin since in the production process in a large number with an organic solvent, therefore environment and HUMAN HEALTH are all had very big harm.And waterborne polyurethane resin is compared great the using and the discharging in physical environment of organic solvent of having reduced with solvent type polyurethane resin; Reduced harm to environment, HUMAN HEALTH; Also cause simultaneously the waste of the resource and the energy, have good market and answer prospect.China's waterborne polyurethane resin research starts from 1972; Start late, obtained certain progress, but the quality level of product, kind system are also very limited through the development of decades; Application Areas also very will be concentrated leather industry, and is also very limited in aspect researchs such as coating-forming agent, sizing agents.This is mainly still because China is relevant to aqueous polyurethane compound method, synthesis material research deficiency.
Waterborne polyurethane resin can be divided into three types of anionic, cationic, non-ionic types according to the type of contained hydrophilic radical.At present; Research is the aqueous polyurethane of anionic comparatively widely for aqueous polyurethane; With carboxylic acid group or sulfonic group is hydrophilic radical synthetic waterborne polyurethane resin, and it is applied to manufacture field as water-borne coatings, tackiness agent, spinning coating, leather finish etc.Yet the hydrophilic radicals different as anion-type water-thinned polyurethane can produce tremendous influence to its structure properties.Hydrophilic chain extender synthetic waterborne polyurethane resin solid content with carboxylic acid type is low, film forming is soft, is suitable as spinning coating, hide finishes use; So the hydrophilic chain extender resin with sulfonic acid type is high owing to the strong synthetic waterborne polyurethane resin percent crystallinity of hydrophilic radical wetting ability, solid content relatively also than higher, is suitable as uses such as sizing agent.Two types aqueous polyurethane characteristics separately is more outstanding, and the scope of application is more single, therefore, has also caused certain application limitation, and the processing that can not adapt to multiple field is used.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art, the object of the present invention is to provide a kind of sulfonic acid/carboxylic acid type Synthesis of Waterborne Polyurethane method, solved single this problem of present anionic water type polyurethane resin kind and performance.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of sulfonic acid/carboxylic acid type Synthesis of Waterborne Polyurethane method comprises the steps:
Step 1, the ratio that is 4 ~ 2:1 in molar ratio join POLYMETHYLENE POLYPHENYLISOCYANATE and polymer polyatomic alcohol in the reactor drum and react 1 ~ 2h down at 80 ~ 100 ℃, obtain product A;
Step 2; By the sulfonic acid/carboxylic acid type hydrophilic chain extender of A product quality adding 1 ~ 5% and 0 ~ 4% small molecule chain extender; Add solubility promoter according to the viscosity situation, react 2 ~ 4h down, obtain product B at 70 ~ 100 ℃; Product B is the hydrophilic performed polymer of aqueous polyurethane, and the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
Step 3; Product B is cooled to below 50 ℃; The dispersion that under agitation is added to the water, the usage quantity of water makes final aqueous pu dispersions solid content maintain between 30% ~ 60%, according to the bubble situation that produces in the dispersion process; Adding obtains product C in the skimmer of quality mark 0.1 ~ 0.2%;
Step 4 carrying out underpressure distillation removal solubility promoter below 50 ℃, obtains sulfonic acid/carboxylic acid type aqueous polyurethane with product C.
Described POLYMETHYLENE POLYPHENYLISOCYANATE is meant tolylene diisocyanate, different Buddhist diketone vulcabond, 1, and 6-is group diisocyanate and 4, one or more mixtures in the 4-'-diphenylmethane diisocyanate.
Described polymer polyatomic alcohol is meant relative molecular mass 1000 ~ 3000, one or more mixtures in polyester type divalent alcohol, polyether-type divalent alcohol and the polycarbonate type divalent alcohol.
Also add organo-bismuth class catalyzer in the reactor drum of said step 1, bismuth metal content is 20% in this catalyzer, for example is the Bicat8108 (20%Bi) of the leading chemistry of the U.S., and the add-on of catalyzer is 0.05% of a step 1 reactant quality.
Described small molecule chain extender is meant: terepthaloyl moietie, 1, one or more in 4-butyleneglycol and the TriMethylolPropane(TMP).
Described solubility promoter is meant: acetone or butanone, the amount of adding makes viscosity controller be not more than 20000CPS.
Described skimmer is meant polyether-modified organosilicon type skimmer.
Compared with prior art, advantage of the present invention is:
1) this sulfonic acid that the present invention announced/carboxylic acid type Synthesis of Waterborne Polyurethane method; Adopting a kind of sulfonic acid/carboxylic acid type hydrophilic chain extender of patent (application number 201210045962.X) is raw material, disposable sulfonic group and hydroxy-acid group is incorporated on the polyurethane molecular main chain simultaneously.
2) this sulfonic acid that the present invention announced/carboxylic acid type Synthesis of Waterborne Polyurethane method; Also contained hydroxy-acid group owing to both contained sulfonic acid group on the aqueous polyurethane molecular chain; Therefore; This product had both had the characteristics of sulfonic acid fundamental mode waterborne polyurethane resin, also had the characteristics of carboxylic acid fundamental mode waterborne polyurethane resin simultaneously;
3) this sulfonic acid that the present invention announced/carboxylic acid type Synthesis of Waterborne Polyurethane method; Owing to contain two kinds of hydrophilic radicals on the urethane resin molecular chain; Therefore help emulsification and the dispersion of aqueous polyurethane performed polymer in water, compare the high solids content of realizing product more easily with existing waterborne polyurethane resin product;
4) this sulfonic acid that the present invention announced/carboxylic acid type Synthesis of Waterborne Polyurethane method; Owing to adopted the better sulfonic acid of wetting ability/carboxylic acid type hydrophilic chain extender; So more traditional waterborne polyurethane resin; The hydrophilic chain extender consumption still less can reduce the influence of the introducing of hydrophilic chain extender to polyurethane molecular chain structure generation mechanical properties decrease like this, protects the regularity of urethane resin chain to a greater extent;
5) adopt the disclosed this hydrophilic chain extender synthetic water-base polyurethane material of the present invention, it is simple to have an operational path, the advantage that product yield is high.
Embodiment
Below in conjunction with embodiment the present invention is explained further details.
Embodiment one
(1) with 2.5mol tolylene diisocyanate (435g), 1mol molecular weight is 2000 pla-pcl glycol (2000g); Join in the reactor drum that whisking appliance, reflux condensing tube, nitrogen protection, temperature indication are housed; The catalyst B icat8108 (20%Bi) that adds 1.2g; React 1.5h down at 80 ℃, obtain product A;
(2) sulfonic acid/carboxylic acid type hydrophilic chain extender and the 6.2g terepthaloyl moietie chainextender of adding 36.5g in reactor drum; Add an amount of acetone according to viscosity situation (viscosity controller is not more than 20000CPS) and add reactor drum; React 3h down at 70 ℃; Obtain product B (the hydrophilic performed polymer of aqueous polyurethane), the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
(3) product B (the hydrophilic performed polymer of aqueous polyurethane) is cooled to below 50 ℃, under high-speed stirring, joins in the 2500g water and disperse, add the skimmer of 2.5g in the whipping process, obtain product C;
(4) product C is removed solubility promoter carrying out underpressure distillation below 50 ℃, will obtain a kind of sulfonic acid of the present invention/carboxylic acid type aqueous polyurethane.
Embodiment two
(1) with 2mol4; 4-'-diphenylmethane diisocyanate (500g), 1mol molecular weight are 2000 polytetrahydrofuran diol (2000g); Join in the reactor drum that whisking appliance, reflux condensing tube, nitrogen protection, temperature indication are housed; The catalyzer that adds 1.25g reacts 1h down at 85 ℃, obtains product A;
(2) sulfonic acid/carboxylic acid type hydrophilic chain extender and 9g1 of adding 75g in reactor drum; 4 chain expansion of succinic acid agent; According to viscosity situation (viscosity controller is not more than 20000CPS) an amount of acetone is added reactor drum; React 2h down at 75 ℃, obtain product B (the hydrophilic performed polymer of aqueous polyurethane), the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
(3) product B (the hydrophilic performed polymer of aqueous polyurethane) is cooled to below 50 ℃, under high-speed stirring, joins in the 3800g water and disperse, add the skimmer of 3.8g in the whipping process, obtain product C;
(4) product C is removed solubility promoter carrying out underpressure distillation below 50 ℃, will obtain a kind of sulfonic acid of the present invention/carboxylic acid type aqueous polyurethane.
Embodiment three
(1) with 3mol1; 6-group diisocyanate (505g), 1mol molecular weight is 1000 polyoxypropyleneglycol (1000g); Join in the reactor drum that whisking appliance, reflux condensing tube, nitrogen protection, temperature indication are housed; The catalyzer that adds 0.75g reacts 2h down at 90 ℃, obtains product A;
(2) sulfonic acid/carboxylic acid type hydrophilic chain extender, 25g terepthaloyl moietie, the 36g1 of adding 60g in reactor drum; The 4-butyleneglycol; According to viscosity situation (viscosity controller is not more than 20000CPS) an amount of butanone is added reactor drum; React 4h down at 85 ℃, obtain product B (the hydrophilic performed polymer of aqueous polyurethane), the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
(3) product B (the hydrophilic performed polymer of aqueous polyurethane) is cooled to below 50 ℃, under high-speed stirring, joins in the 1100g water and disperse, add the skimmer of 2g in the whipping process, obtain product C;
(4) product C is removed solubility promoter carrying out underpressure distillation below 50 ℃, will obtain a kind of sulfonic acid of the present invention/carboxylic acid type aqueous polyurethane.
Embodiment four
(1) with the different Buddhist diketone of 4mol vulcabond (888g), 1mol molecular weight be 2000 gather carbonic acid-1; 6-pinakon esterdiol (2000g); Join in the reactor drum that whisking appliance, reflux condensing tube, nitrogen protection, temperature indication are housed; The catalyzer that adds 1.45g reacts 1.5h down at 95 ℃, obtains product A;
(2) sulfonic acid/carboxylic acid type hydrophilic chain extender, 27g TriMethylolPropane(TMP), the 25g terepthaloyl moietie of adding 144g in reactor drum; According to viscosity situation (viscosity controller is not more than 20000CPS) an amount of butanone is added reactor drum; React 4h down at 95 ℃; Obtain product B (the hydrophilic performed polymer of aqueous polyurethane), the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
(3) product B (the hydrophilic performed polymer of aqueous polyurethane) is cooled to below 50 ℃, under high-speed stirring, joins in the 3000g water and disperse, add the skimmer of 4.5g in the whipping process, obtain product C;
(4) product C is removed solubility promoter carrying out underpressure distillation below 50 ℃, will obtain a kind of sulfonic acid of the present invention/carboxylic acid type aqueous polyurethane.
Embodiment five
(1) be that 2000 polytetrahydrofuran diol (1000g), 0.5mol molecular weight are 1000 polyoxypropyleneglycol (500g) with the different Buddhist diketone of 2.5mol vulcabond (555g), 0.5mol molecular weight; Join in the reactor drum that whisking appliance, reflux condensing tube, nitrogen protection, temperature indication are housed; The catalyzer that adds 1g; React 2h down at 90 ℃, obtain product A;
(2) sulfonic acid/carboxylic acid type hydrophilic chain extender and the 6g terepthaloyl moietie of adding 51g in reactor drum; According to viscosity situation (viscosity controller is not more than 20000CPS) an amount of butanone is added reactor drum; React 3h down at 90 ℃; Obtain product B (the hydrophilic performed polymer of aqueous polyurethane), the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
(3) product B (the hydrophilic performed polymer of aqueous polyurethane) is cooled to below 50 ℃, under high-speed stirring, joins in the 2100g water and disperse, add the skimmer of 2.1g in the whipping process, obtain product C;
(4) product C is removed solubility promoter carrying out underpressure distillation below 50 ℃, will obtain a kind of sulfonic acid of the present invention/carboxylic acid type aqueous polyurethane.
Embodiment six
(1) with the different Buddhist diketone of 1.5mol vulcabond (333g), 1mol1; 6-group diisocyanate (168g), 1mol molecular weight is that 2000 polytetrahydrofuran diol (2000g) joins in the reactor drum that whisking appliance, reflux condensing tube, nitrogen protection, temperature indication are housed; The catalyzer that adds 1.25g; React 2h down at 90 ℃, obtain product A;
(2) sulfonic acid/carboxylic acid type hydrophilic chain extender and 18g1 of adding 82g in reactor drum; The 4-butyleneglycol; According to viscosity situation (viscosity controller is not more than 20000CPS) an amount of butanone is added reactor drum; React 3h down at 90 ℃, obtain product B (the hydrophilic performed polymer of aqueous polyurethane), the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
(3) product B (the hydrophilic performed polymer of aqueous polyurethane) is cooled to below 50 ℃, under high-speed stirring, joins in the 3200g water and disperse, add the skimmer of 3.2g in the whipping process, obtain product C;
(4) product C is removed solubility promoter carrying out underpressure distillation below 50 ℃, will obtain a kind of sulfonic acid of the present invention/carboxylic acid type aqueous polyurethane.
Embodiment seven
(1) with 0.5mol4; 4-'-diphenylmethane diisocyanate (125g), the different Buddhist diketone of 2mol vulcabond (444g), 0.5mol molecular weight are that 2000 polytetrahydrofuran diol (1000g), 0.5mol molecular weight are 1000 polyoxypropyleneglycol (500g); Join in the reactor drum that whisking appliance, reflux condensing tube, nitrogen protection, temperature indication are housed; The catalyzer that adds 1g reacts 2h down at 90 ℃, obtains product A;
(2) sulfonic acid/carboxylic acid type hydrophilic chain extender and the 18g terepthaloyl moietie of adding 62g in reactor drum; According to viscosity situation (viscosity controller is not more than 20000CPS) an amount of butanone is added reactor drum; React 3h down at 90 ℃; Obtain product B (the hydrophilic performed polymer of aqueous polyurethane), the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
(3) product B (the hydrophilic performed polymer of aqueous polyurethane) is cooled to below 50 ℃, under high-speed stirring, joins in the 5000g water and disperse, add the skimmer of 5g in the whipping process, obtain product C;
(4) product C is removed solubility promoter carrying out underpressure distillation below 50 ℃, will obtain a kind of sulfonic acid of the present invention/carboxylic acid type aqueous polyurethane.
It is following that sulfonic acid according to the invention/the carboxylic acid type hydrophilic chain extender prepares process:
1) amidate action:
Get in the solvent that 99 parts MALEIC ANHYDRIDE is dissolved in 45～190 parts by mass fraction and to be made into solvent orange 2 A; Get in the solvent that 107 parts diethylolamine or 134 parts of HSDB 338s be dissolved in 40～180 parts by mass fraction and to process solution B; Solution A is joined in the reactor drum, also can in reactor drum, add 0.5 part catalyzer accelerated reaction process simultaneously, under the nitrogen protection environment temperature of reaction is being controlled under 40～100 ℃; Slowly solution B is joined in the reactor drum; Fully solvent is removed in reaction back underpressure distillation under appropriateness stirs, and obtains white powder, carries out recrystallization with ethanol again; Then crystallisate filtration and drying are obtained white powder, this white powder is the amidation midbody of the reaction of sulfonic acid/carboxylic acid type hydrophilic chain extender;
2) sulfonation reaction: get the amidated reaction intermediate of 100 parts of white powder, 45～62 parts sulphonating agent is dissolved in the water; Join in the reactor drum; Fully stir, nitrogen protection heats up down and carries out sulfonation reaction, and temperature is controlled at 80～100 ℃; Treat fully reaction back cooling, obtain white powder behind the solution filtration drying and be sulfonic acid/carboxylic acid type hydrophilic chain extender.
Wherein said solvent can be a kind of in water, acetone, butanone, chloroform, hexanaphthene, benzene, toluene or the N; The described catalyzer that quickens the amidate action process is N, the N-lutidine; Described sulphonating agent is sodium sulfite anhy 96 or S-WAT.
Claims (8)
1. sulfonic acid/carboxylic acid type Synthesis of Waterborne Polyurethane method is characterized in that, comprises the steps:
Step 1, the ratio that is 4 ~ 2:1 in molar ratio join POLYMETHYLENE POLYPHENYLISOCYANATE and polymer polyatomic alcohol in the reactor drum and react 1 ~ 2h down at 80 ~ 100 ℃, obtain product A;
Step 2; By the sulfonic acid/carboxylic acid type hydrophilic chain extender of A product quality adding 1 ~ 5% and 0 ~ 4% small molecule chain extender; Add solubility promoter according to the viscosity situation, react 2 ~ 4h down, obtain product B at 70 ~ 100 ℃; Product B is the hydrophilic performed polymer of aqueous polyurethane, and the molecular structure of described sulfonic acid/carboxylic acid type hydrophilic chain extender is as follows:
Step 3; Product B is cooled to below 50 ℃; The dispersion that under agitation is added to the water, the usage quantity of water makes final aqueous pu dispersions solid content maintain between 30% ~ 60%, according to the bubble situation that produces in the dispersion process; Adding obtains product C in the skimmer of quality mark 0.1 ~ 0.2%;
Step 4 carrying out underpressure distillation removal solubility promoter below 50 ℃, obtains sulfonic acid/carboxylic acid type aqueous polyurethane with product C.
2. sulfonic acid as claimed in claim 1/carboxylic acid type Synthesis of Waterborne Polyurethane method; It is characterized in that; Described POLYMETHYLENE POLYPHENYLISOCYANATE is meant tolylene diisocyanate, different Buddhist diketone vulcabond, 1; 6-is group diisocyanate and 4, one or more mixtures in the 4-'-diphenylmethane diisocyanate.
3. sulfonic acid as claimed in claim 1/carboxylic acid type Synthesis of Waterborne Polyurethane method; It is characterized in that; Described polymer polyatomic alcohol is meant relative molecular mass 1000 ~ 3000, one or more mixtures in polyester type divalent alcohol, polyether-type divalent alcohol and the polycarbonate type divalent alcohol.
4. sulfonic acid as claimed in claim 1/carboxylic acid type Synthesis of Waterborne Polyurethane method; It is characterized in that; Also add organo-bismuth class catalyzer in the reactor drum of said step 1, bismuth metal content is 20% in this catalyzer, and the add-on of catalyzer is 0.05% of a step 1 reactant quality.
5. sulfonic acid as claimed in claim 1/carboxylic acid type Synthesis of Waterborne Polyurethane method is characterized in that, said organo-bismuth class catalyzer is the Bicat8108 (20%) of the leading chemistry of the U.S..
6. sulfonic acid as claimed in claim 1/carboxylic acid type Synthesis of Waterborne Polyurethane method is characterized in that described small molecule chain extender is meant: terepthaloyl moietie, 1, one or more in 4-butyleneglycol and the TriMethylolPropane(TMP).
7. sulfonic acid as claimed in claim 1/carboxylic acid type Synthesis of Waterborne Polyurethane method is characterized in that described solubility promoter is meant: acetone or butanone, the amount of adding makes viscosity controller be not more than 20000CPS.
8. a kind of sulfonic acid as claimed in claim 1/carboxylic acid type Synthesis of Waterborne Polyurethane method is characterized in that, described skimmer is meant polyether-modified organosilicon type skimmer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210150729 CN102653585B (en) | 2012-05-15 | 2012-05-15 | Method for preparing sulfoacid/carboxylic acid waterborne polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210150729 CN102653585B (en) | 2012-05-15 | 2012-05-15 | Method for preparing sulfoacid/carboxylic acid waterborne polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102653585A true CN102653585A (en) | 2012-09-05 |
| CN102653585B CN102653585B (en) | 2013-10-09 |
Family
ID=46729328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210150729 Expired - Fee Related CN102653585B (en) | 2012-05-15 | 2012-05-15 | Method for preparing sulfoacid/carboxylic acid waterborne polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102653585B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360563A (en) * | 2013-07-09 | 2013-10-23 | 华南理工大学 | High-solid content waterborne polyurethane emulsion with particle size polydispersity and preparation method thereof |
| CN103897135A (en) * | 2014-04-09 | 2014-07-02 | 杭州传化精细化工有限公司 | Method for preparing waterborne polyurethane emulsion with high solid content |
| CN104861148A (en) * | 2015-06-08 | 2015-08-26 | 中国科学技术大学 | Preparation method of aqueous polyurethane based on anionic azo hydrophilic chain extender |
| CN106046288A (en) * | 2016-04-01 | 2016-10-26 | 华南师范大学 | Hydrophilic chain extender, and preparation method and application thereof |
| CN104371085B (en) * | 2014-10-29 | 2017-03-29 | 泉州三欣新材料科技有限公司 | A kind of preparation method of amphion aqueous polyurethane |
| CN110330620A (en) * | 2019-08-02 | 2019-10-15 | 山西省应用化学研究所(有限公司) | Plastic film water-based polyurethane ink binder and preparation method thereof |
| CN111234154A (en) * | 2020-04-06 | 2020-06-05 | 刘云晖 | Preparation method of self-repairable waterborne polyurethane |
| CN112063013A (en) * | 2020-08-31 | 2020-12-11 | 浙江工业大学 | Method for preparing waterborne polyurethane through hydrophilic modification after polyurethane foam is degraded and recovered |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080166485A1 (en) * | 2005-03-17 | 2008-07-10 | Pablo Steenwinkel | Aqueous Polyurethane Compositions |
| CN101412887A (en) * | 2008-11-10 | 2009-04-22 | 嘉丰木业（苏州）有限公司 | Floor paint |
| CN101440154A (en) * | 2008-12-31 | 2009-05-27 | 陕西科技大学 | Aqueous polyurethane and preparation thereof |
-
2012
- 2012-05-15 CN CN 201210150729 patent/CN102653585B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080166485A1 (en) * | 2005-03-17 | 2008-07-10 | Pablo Steenwinkel | Aqueous Polyurethane Compositions |
| CN101412887A (en) * | 2008-11-10 | 2009-04-22 | 嘉丰木业（苏州）有限公司 | Floor paint |
| CN101440154A (en) * | 2008-12-31 | 2009-05-27 | 陕西科技大学 | Aqueous polyurethane and preparation thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360563B (en) * | 2013-07-09 | 2015-04-22 | 华南理工大学 | High-solid content waterborne polyurethane emulsion with particle size polydispersity and preparation method thereof |
| CN103360563A (en) * | 2013-07-09 | 2013-10-23 | 华南理工大学 | High-solid content waterborne polyurethane emulsion with particle size polydispersity and preparation method thereof |
| CN103897135A (en) * | 2014-04-09 | 2014-07-02 | 杭州传化精细化工有限公司 | Method for preparing waterborne polyurethane emulsion with high solid content |
| CN103897135B (en) * | 2014-04-09 | 2015-12-30 | 杭州传化精细化工有限公司 | A kind of preparation method of high solid content aqueous polyurethane emulsion |
| CN104371085B (en) * | 2014-10-29 | 2017-03-29 | 泉州三欣新材料科技有限公司 | A kind of preparation method of amphion aqueous polyurethane |
| CN104861148A (en) * | 2015-06-08 | 2015-08-26 | 中国科学技术大学 | Preparation method of aqueous polyurethane based on anionic azo hydrophilic chain extender |
| CN104861148B (en) * | 2015-06-08 | 2017-11-24 | 中国科学技术大学 | A kind of aqueous polyurethane preparation method based on anionic azo hydrophilic chain extender |
| CN106046288A (en) * | 2016-04-01 | 2016-10-26 | 华南师范大学 | Hydrophilic chain extender, and preparation method and application thereof |
| CN106046288B (en) * | 2016-04-01 | 2019-02-19 | 华南师范大学 | A kind of hydrophilic chain extender and the preparation method and application thereof |
| CN110330620A (en) * | 2019-08-02 | 2019-10-15 | 山西省应用化学研究所(有限公司) | Plastic film water-based polyurethane ink binder and preparation method thereof |
| CN110330620B (en) * | 2019-08-02 | 2021-08-24 | 山西省应用化学研究所(有限公司) | Waterborne polyurethane ink binder for plastic film and preparation method thereof |
| CN111234154A (en) * | 2020-04-06 | 2020-06-05 | 刘云晖 | Preparation method of self-repairable waterborne polyurethane |
| CN112063013A (en) * | 2020-08-31 | 2020-12-11 | 浙江工业大学 | Method for preparing waterborne polyurethane through hydrophilic modification after polyurethane foam is degraded and recovered |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102653585B (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102653585B (en) | Method for preparing sulfoacid/carboxylic acid waterborne polyurethane | |
| US10611879B2 (en) | Polyester polyols from thermoplastic polyesters and dimer fatty acids | |
| CN104628982B (en) | A kind of preparation method of alkali lignin base water polyurethane | |
| WO2019070981A1 (en) | Isocyanates, derivatives, and processes for producing the same | |
| CN105452332B (en) | The manufacture method and PCDL of PCDL and the manufacture method and polyurethane of polyurethane | |
| CN107556452A (en) | A kind of castor oil-base hydrophilic chain extender and its preparation method and application | |
| US20130035448A1 (en) | Biomass-resource -derived polyurethane, method for producing same, and biomass-resource-derived polyester polyol | |
| CN102942678B (en) | Glycine betaine group modified cationic waterborne polyurethane and preparation method thereof | |
| WO2008007712A1 (en) | Method for producing polyurethane and use of polyurethane produced by the same | |
| CN107151302A (en) | One vegetable oil base flexible polyurethane foam and preparation method thereof | |
| CN109851748B (en) | Sulfonic acid type waterborne polyurethane and preparation method and application thereof | |
| CN105778029A (en) | Preparation method of hyperbranched poly(isocyanurate-ester) type waterborne polyurethane | |
| CN101418119B (en) | Method for preparing oxidative crosslinked starch modified waterborne polyurethane hybridization material | |
| CN107151520A (en) | A kind of tung oil base water polyurethane coating and preparation method thereof | |
| CN106750149B (en) | A kind of preparation method and application method of expansion type aqueous polyurethane | |
| CN102352010A (en) | Preparation method for aqueous polyurethane-polyurea dispersion | |
| SU703027A3 (en) | Method of producing porous plastic materials | |
| CN107151303A (en) | A kind of tung oil base RPUF and preparation method thereof | |
| CN117384342A (en) | Plant polyol, preparation method and application | |
| CN105778039B (en) | Aqueous polyurethane dispersing liquid of chain extension and preparation method thereof after click chemistry | |
| CN103012720B (en) | Polyurethane resin for tetramethylguanidine ionic liquid-modified waterborne synthetic leather and manufacturing method thereof | |
| CN106380437B (en) | The preparation method of di-t-butyl peroxide | |
| CN105797643B (en) | A kind of preparation method of nonionic polyurethane Gemini surface active | |
| CN106750117B (en) | A kind of aqueous polyurethane continuous synthesis method based on impingement mix and continuous emulsification | |
| US20040236011A1 (en) | Polyurethane dispersions and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131009 Termination date: 20210515 |