CN101307181B - Anion polyurethane and amino silicon oil composite water dispersion, preparation and applications - Google Patents
Anion polyurethane and amino silicon oil composite water dispersion, preparation and applications Download PDFInfo
- Publication number
- CN101307181B CN101307181B CN2008100537266A CN200810053726A CN101307181B CN 101307181 B CN101307181 B CN 101307181B CN 2008100537266 A CN2008100537266 A CN 2008100537266A CN 200810053726 A CN200810053726 A CN 200810053726A CN 101307181 B CN101307181 B CN 101307181B
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- silicone oil
- silicon oil
- molecular weight
- preparation
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses an anionic polyurethane and amino silicone oil composite aqueous dispersion and a preparation method and an application thereof. High molecular weight polyether glycol and anionic diol chain extender react with diisocyanate to form anionic polyurethane after end capping. The anionic polyurethane and low molecular weight amino terminated silicone oil are blended and added with a salt forming agent for tertiary amine and biacrylic ester to conduct self-emulsification at the room temperature to form amino silicone oil/polyurethane blended anionic aqueous dispersion microemulsion. The anionic aqueous dispersion microemulsion is heated to complete a chain extension of amino silicone oil on opposite terminals of the biacrylic ester, and thus the preparation of high molecular weight amino silicone oil/polyurethane composite aqueous dispersion is realized. The high molecular weight amino silicone oil/polyurethane composite aqueous dispersion has characteristics of small grain size and good stability, and can be coated on the surfaces of fabrics to improve the hand feeling of the fabrics and the hydrophilcity and hydrophobicity of the surfaces of the fabrics.
Description
Technical field
The invention belongs to polymer composite water dispersion and preparation thereof, particularly a kind of ionic polyurethanes/amino silicone oil composite aqueous dispersions and preparation thereof, this type of composite water dispersion can be used for the fabric sofetening arrangement.
Background technology
Water dispersible polyurethane and water-dispersion organic silicone oil are important fabric post-treatment auxiliary agents, can give the good flexibility of fabric and certain wrinkle resistance, and hydrophilic, the oleophylic, the water permeability that change fabric face.Urethane (PU) is the chain segment type block superpolymer (segmented blockpolymer) that is polymerized by polyisocyanates (mainly being vulcabond) and polyvalent alcohol.Owing to combine the strong polarity of the hard section of carbamate and the kindliness of polyethers or soft polyester section, polyurethane material has good physical and mechanical propertiess such as high strength, anti-solvent, good tack and snappiness, wear-resisting, anti tear, anti-subduing property, and reactive.Utilize the self-emulsifying ability of charged urethane, can prepare nano level aqueous dispersions easily.The waterbased urethane dispersion liquid has been used in the fabric post-treatment technologies such as wash and wear finisher, fabric coating finish agent and Wool fabric anti-felting agent of fabric.
Amino-modified silicone is leading-in end hydrocarbon amino or a side hydrocarbon amino on the polysiloxane macromolecular chain.Use it for fabric finishing agent,, give the good film-forming properties of fabric, durable wrinkle resistance, rebound resilience, flexibility, hydrophobicity, the smooth comfortableness of feel, become the principal item of fabric sofetening arrangement because of directed keying action amino and fabric fibre.Amino silicon oil emulsion commonly used can be produced by letex polymerization or machinery emulsification method.Emulsifying agent can be selected cationic non-ionic type usually.The existence of a large amount of emulsifying agents can influence amido silicon oil to the adhering to of fabric, and reduces soft effect.On the other hand, though adopt the machinery emulsification method conveniently amido silicon oil to be emulsified into microemulsion, make the dispersion liquid of particle diameter less than 150nm, the molecular weight of amido silicon oil can not be too high, otherwise be difficult for emulsification because of viscosity is high.Adopt emulsion polymerization can make the high-molecular weight amido silicon oil, but because the balance of epoxy silane ring-opening polymerization, still have the low molecular weight fraction of big content in the system, it is certain unfavorable that the use of amido silicon oil aqueous dispersions is caused.Therefore be necessary to prepare the high molecular amido silicon oil nanometer aqueous dispersions that does not contain low molecule emulsifying agent.
The performance of comprehensive urethane and amido silicon oil, preparation polyurethane/organosilicon composite water dispersion is expected to obtain special performances.Especially utilize characteristics such as the self-emulsifying of charged urethane and high reaction activity, can remove low molecule emulsifying agent, reduce dispersed particle size, improve the stability of dispersion, and with the consistency of other auxiliary agents, realize the multifunction of fabric finishing agent.Therefore the polyurethane/organosilicon composite water dispersion has very big application potential.
Realize that urethane and organosilicon composite methods can be divided into copolymerization method and blending method two big classes.Though the organic silicon modified polyurethane PSU aqueous dispersions that copolymerization method obtains is stable, chemistry connects the uncompatibility that more easily overcomes both, has obtained comparatively extensive studies and application.But copolymerization method can reduce the flexibility of organosilicon molecular chain, damages organosilyl Practical Performance, and perhaps the silicone ingredients of Yin Ruing can not fully play the advantage of two kinds of polymkeric substance very little.Therefore, blending method realizes that organosilicon has great significance to the modification of aqueous polyurethane.But the research of at present relevant polyurethane/organosilicon compound system blend all concentrates on two kinds of polymkeric substance are made dispersion system respectively, carry out emulsion blending again.This method has been avoided the big and problem of the blend difference that causes of urethane and organosilyl polarity difference.But it is two alternate evenly compound that emulsion dispersion is difficult to reach, simultaneously owing to there is a large amount of emulsifying agents to be present in the system, reduced organosilicon to the bonding force between fiber and urethane, make the use properties of compound system be subjected to influence, be difficult to make the polyurethane/organosilicon compound system of satisfied application performance.
Another kind of organosilicon and the urethane composite methods of making is to realize in same dispersed particle mixing of organosilicon and urethane, prepares the hud typed aqueous dispersions of polyurethane/organosilicon.Utilize the self-emulsifying ability of charged urethane, realize that the nano level composite water is diffusing, increases urethane and organosilyl mixing uniformity effectively.
But because urethane and organosilyl consistency are poor, dissolubility difference is very big, is in serious phase-separated state in co-mixing system, is difficult to make nano level composite dispersion liquid, especially for the high-molecular weight amido silicon oil.And adopt low-molecular-weight amido silicon oil will reduce the tack and the weather resistance of silicone oil.
Summary of the invention
The present invention aims to provide a kind of anion polyurethane and amino silicone oil composite aqueous dispersion and preparation and application.After adopting low-molecular-weight end amido silicon oil and urethane in specific solvent, to mix to finish composite emulsifying, realize the chain extending reaction of amido silicon oil again by the Micheal addition reaction with double methacrylate, thereby prepared the composite nano aqueous dispersion of urethane/high molecular amido silicon oil, this composite dispersion liquid has good storage stability.This composite polyurethane/high molecular amino silicone oil composite nanometer aqueous dispersions can be used for the back arrangement of fabric, provides soft, crease-resistant etc. multi-functional.
A kind of anion polyurethane provided by the invention and amino silicone oil composite aqueous dispersion comprise that anionic polyurethane and amino silicone oil composite constitute, the particle diameter of the dispersed particle of this dispersion liquid is below 150nm, and it is 10～50% that the quality of amido silicon oil in dispersed particle formed.
The molecular weight of described amido silicon oil is more than 20,000, and it is by molecular weight 2,000～10, and 000 end amido silicon oil makes through the Micheal of double methacrylate addition reaction chain extension.
Described anion polyurethane is made by polyether glycol, negatively charged ion diol chain-extension agent, isophorone diisocyanate reaction.
The preparation method of anion polyurethane provided by the invention and amino silicone oil composite aqueous dispersion is characterized in that comprising following steps:
1) polyether glycol, negatively charged ion diol chain-extension agent and vulcabond were reacted between 60～90 ℃ 4～10 hours, behind end-blocking, make anion polyurethane.Specifically:
(a) usually with polyether glycol logical nitrogen processed 2 hours under 100～120 ℃, vacuum.After being as cold as 60～90 ℃, add vulcabond, keep 60～90 ℃ of reactions 4～6 hours;
(b) add with N-tetramethyleneimine (NMK) dissolved anionic diol chain-extension agent,, add end-capping reagent again, reacted 2～3 hours down, make anionic polyurethane in 60～90 ℃ 60～90 ℃ of reactions 2～3 hours.
2) blend under solvent action with this anion polyurethane and low-molecular-weight end amido silicon oil at room temperature adds the neutralization of tertiary amines salt forming agent, and after adding the chainextender double methacrylate, adds the water self-emulsifying and form the water-dispersion microemulsion;
3) between elevated temperature to 60～80 ℃, reacted 1～6 hour, finish the chain extending reaction of double methacrylate opposite end amido silicon oil, make product.
4) under 40～60 ℃, 0.01～0.05MPa or vacuum, remove organic solvent.
The mol ratio of described negatively charged ion chainextender and polyether glycol is 1～3: 1, and the mol ratio of NCO/OH is 1.1～1.5: 1, NCO represents isocyanate group, OH represents hydroxyl.
Described polyether glycol is the poly(propylene oxide) ether (EO content is less than 50%) of poly(propylene oxide) ether or ethylene oxide segment (EO) modification, and molecular weight is 1,000～6,000.
Adopt polyether(poly)urethane that good hydrolytic resistance can be provided.Introduce the wetting ability that partial oxidation ethene (EO) chain link can improve urethane, help being emulsified into littler particle.It is that the polymerization process of catalyzer is synthetic with KOH that described polyethers can adopt conventional, also can adopt bimetallic catalyst to prepare the low-unsaturation-degree polyether of higher molecular weight.The polyethers of higher molecular weight helps improving the consistency with amido silicon oil, also helps providing more soft and urethane favorable elasticity.
Described double methacrylate has following structure:
Wherein the R group is that carbon number is not more than 6 alkyl or contains oxygen ether alkyl;
Double methacrylate: amido silicon oil=1.1～1.5: 1, mol ratio.The consumption of double methacrylate is easy to take place crosslinked after a little while.
The end amido silicon oil is the modified dimethyl polysiloxane that contains primary amine or secondary amine, and its molecular weight 000, has following molecular structure 2,000～10:
R is alkyl or H
(integers of m＜4)
During R=H, described end amido silicon oil has following structure:
Described solvent is methylene dichloride or tetrahydrofuran (THF), preferred methylene dichloride.The consumption of solvent is 30～50%.
Described anion polyurethane and amino silicone oil composite aqueous dispersion are as fabric finishing agent.
Used vulcabond can be aromatic isocyanate or aliphatic isocyanates, preferably adopts the aliphatics cyanate, has yellowing resistance preferably, as isophorone diisocyanate IPDI, and hexamethylene-diisocyanate HDI.
Described negatively charged ion chainextender can be dimethylol propionic acid or dimethylolpropionic acid.
Used end-capping reagent can be the compound that can form the stable ammonia carbamate, as Virahol, also can be the compound that can form masked isocyanate with the NCO group, as Diisopropylamine, ketoxime, imidazoles etc.The dispersion liquid of employing masked isocyanate in use, can under suitable processing temperature (140～180 ℃), generate isocyanate group by deblocking, and then with object being treated in active group, as reactions such as hydroxyl, amido, carboxyls, improve bonding force and weather resistance.
The mol ratio of NCO/OH is controlled at 1.1～1.5 in the preparation: 1 (NCO represents isocyanate group, and OH represents hydroxyl).Higher NCO/OH ratio can obtain more high-molecular weight urethane.When needs prepare end of the chain dead front type PU, can adopt higher NCO/OH ratio.In the polyethers and the chainextender part of hydroxyl, the mol ratio of chainextender/polyether glycol is controlled at 1～5: 1.Higher chainextender consumption can reduce the particle diameter of dispersed particle, improves the perviousness of dispersion liquid in treating processes.
In the mixture of urethane and amido silicon oil, amido silicon oil is the end amido silicone oil that contains primary amine or secondary amine, and its molecular weight is 2,000～10,000, and promptly the ammonia value is at 0.20～1.0mmol/g.Branching or crosslinked when hope obtains high molecular weight, easily takes place in the wayward chain extension degree of more low-molecular-weight amido silicon oil.More the high-molecular weight amido silicon oil is difficult for forming uniform mixture with urethane.The add-on of amido silicon oil accounts for 10～50% of the solid shape amount of system.Because the polarity of amido silicon oil and urethane differs greatly, add appropriate solvent to the formation homogeneous phase solution, and follow-up common emulsification is most important.
Anionic polyurethane/amino silicone oil composite the aqueous dispersions of the present invention's preparation can be used for the crease-resistant and softening of fabric.Through the high molecular silicone oil behind the chain extension fabric is had better sticking power and weather resistance, increased washing fastness and finishing effect.Simultaneously, the certain degree of crosslinking that produces in the chain extension process can increase the elasticity (fullness ratio) of fabric.
Embodiment
Provide specific embodiments of the invention below, so that embody content of the present invention and specific operation process in more detail.Used raw material all is industrialization raw materials among the embodiment, and used code name only shows its primary structure feature, and does not reflect commercial code or the trade mark that it is concrete.Main raw material and the code name that uses is as follows:
IPDI: isophorone diisocyanate
DMPA: dimethylol propionic acid
SDA-1: the ammonia value is the amino polydimethylsiloxane of the end of 1.04mmol/g
SDA-2: the ammonia value is the amino polydimethylsiloxane of the end of 0.22mmol/g
DAR: chainextender ethylene glycol diacrylate (170)
N-210: hydroxyl value is the poly(propylene oxide) ether glycol of 112mgKOH/g
N-220: hydroxyl value is the poly(propylene oxide) ether glycol of 55mgKOH/g
N-240: hydroxyl value is the poly(propylene oxide) ether glycol of 27mgKOH/g
N-260: hydroxyl value is the poly(propylene oxide) ether glycol of 18mgKOH/g
The NMK:N-tetramethyleneimine
DCM: methylene dichloride
THF: tetrahydrofuran (THF)
The raw material that uses need carry out processed in case of necessity according to the synthetic requirement of urethane.Described raw material umber all refers to mass fraction when not having special instruction.
Embodiment 1
In the four-hole bottle that prolong and whipping appts are housed, add polyethers N-210 and 8.0g (36mmol) IPDI that 20g (20mmol) has dewatered, under 60 ℃ of water-baths, react 4.5h.Add DMPA, continue to react 2h down, add 1.0g Virahol end-blocking, reaction 2h at 80 ℃ with 4g NMK dissolved 1.34g (10mmol).Cool to 40 ℃, add 20.0g dichloromethane solvent and 6.0g (3mmol) end amido silicon oil SDA-1 and 0.6g (3.6mmol) ethylene glycol diacrylate chainextender, mix.Add in 1.2g (12mmol) triethylamine and 15min.Drip 150g water under stirring and finish emulsification, with emulsion heat release to 60 ℃ chain extension 2h.Deviate from solvent under the vacuum, get product anionic polyurethane/amino silicone oil composite aqueous dispersions, the dispersion particle diameter is 110nm, and solid content is 20%.
Embodiment 2
In the four-hole bottle that prolong and whipping appts are housed, add polyethers N-210 and 8.0g (36mmol) IPDI that 20g (20mmol) has dewatered, under 90 ℃ of water-baths, react 4.5h.Add DMPA, continue to react 2h down, add 1.0g Virahol end-blocking, reaction 2h at 80 ℃ with 4g NMK dissolved 1.34g (10mmol).Cool to 40 ℃, add 30.0g dichloromethane solvent and 20.0g (2.0mmol) end amido silicon oil SDA-2 and 0.4g (2.4mmol) ethylene glycol diacrylate chainextender, mix.Add in 1.2g (12mmol) triethylamine and 15min.Drip 200g water under stirring and finish emulsification, with emulsion heat release to 80 ℃ chain extension 6h.Deviate from solvent under the vacuum, get product anionic polyurethane/amino silicone oil composite aqueous dispersions, the dispersion particle diameter is 150nm, and solid content is 25%.
Other similar prescriptions are listed in table 1 (embodiment 3-8).Reactions steps and condition are with example two.
Table 1 urethane/polymer amino silicone oil composite aqueous dispersions preparation
| Sequence number | Polyethers specification and consumption, g | The IPDI amount, g | The DMPA amount, g | End-capping reagent kind and consumption, g | End amido silicon oil and amount, g | The DAR amount, g | Solvent and consumption, g | The triethylamine amount, g | Water yield G |
| 3 | N220，20 | 6.7 | 1.34 | Virahol, 1.0 | SDA-1，10 | 1.0 | DCM，20 | 1.2 | 150 |
| 4 | N240，20 | 4.0 | 1.34 | Diisopropylamine, 1.5 | SDA-2，5 | 0.13 | THF，15 | 1.2 | 150 |
| 5 | N260，20 | 4.0 | 1.34 | Virahol, 1.0 | SDA-1，15 | 1.5 | THF，30 | 1.2 | 150 |
| 6 | N240，20 | 5.8 | 2.0 | Virahol, 1.0 | SDA-1，20 | 1.9 | DCM，30 | 1.8 | 200 |
| 7 | N220，20 | 6.7 | 2.0 | Virahol, 1.0 | SDA-2，10 | 0.25 | THF，30 | 1.8 | 150 |
| 8 | N210，20 | 9.3 | 2.0 | Virahol, 1.0 | SDA-2，10 | 0.25 | THF，30 | 1.8 | 150 |
Embodiment 9
In the four-hole bottle that prolong and whipping appts are housed, add polyethers N-240 and 5.8g (26mmol) IPDI that 20g (5mmol) has dewatered, under 80 ℃ of water-baths, react 6h.Add DMPA, continue to react 2h down, add 1.0g Virahol end-blocking, reaction 3h at 80 ℃ with 5g NMK dissolved 2.0g (15mmol).Cool to 40 ℃, add 30.0g dichloromethane solvent and 10.0g (1.0mmol) end amido silicon oil SDA-2 and 0.2g (1.2mmol) ethylene glycol diacrylate chainextender, mix.Add in 1.2g (12mmol) triethylamine and 15min.Drip 150g water under stirring and finish emulsification, with emulsion heat release to 80 ℃ chain extension 4h.Deviate from solvent under the vacuum, get product anionic polyurethane/amino silicone oil composite aqueous dispersions, the dispersion particle diameter is 120nm, and solid content is 20%.
Claims (8)
1. anion polyurethane and amino silicone oil composite aqueous dispersion, comprise that anionic polyurethane and amino silicone oil composite constitute, the particle diameter of the dispersed particle of this dispersion liquid is below 150nm, it is 10～50% that the quality of amido silicon oil in dispersed particle formed, the molecular weight that it is characterized in that described amido silicon oil is more than 20,000, and it is by molecular weight 2,000～10,000 end amido silicon oil makes through the Micheal of double methacrylate addition reaction chain extension.
2. anion polyurethane according to claim 1 and amino silicone oil composite aqueous dispersion is characterized in that described anion polyurethane is made by polyether glycol, negatively charged ion diol chain-extension agent, isophorone diisocyanate reaction.
3. the preparation method of described anion polyurethane of claim 1 and amino silicone oil composite aqueous dispersion is characterized in that comprising following steps:
1) polyether glycol, negatively charged ion diol chain-extension agent and vulcabond were reacted between 60～90 ℃ 4～10 hours, behind end-blocking, make anion polyurethane;
2) blend under solvent action with this anion polyurethane and low-molecular-weight end amido silicon oil at room temperature adds the neutralization of tertiary amines salt forming agent, and after adding double methacrylate, adds the water self-emulsifying and form the water-dispersion microemulsion;
3) between elevated temperature to 60～80 ℃, reacted 1～6 hour, finish the chain extending reaction of double methacrylate opposite end amido silicon oil, make product;
4) under 40～60 ℃, 0.01～0.05MPa or vacuum, remove organic solvent.
4. preparation method according to claim 3, the mol ratio that it is characterized in that described negatively charged ion chainextender and polyether glycol is 1～3: 1, isocyanate group: the mol ratio of hydroxyl is 1.1～1.5: 1.
5. preparation method according to claim 3 is characterized in that described polyether glycol is the poly(propylene oxide) ether of poly(propylene oxide) ether or ethylene oxide segment modification, and the mass content of EO is less than 50%, and molecular weight is 1,000～6,000.
6. preparation method according to claim 3 is characterized in that described double methacrylate has following structure:
Wherein the R group is that carbon number is not more than 6 alkyl or contains oxygen ether alkyl;
Double methacrylate: amido silicon oil=1.1～1.5: 1, mol ratio.
7. preparation method according to claim 3 is characterized in that described end amido silicon oil has following structure:
(integers of m＜4)
Its molecular weight is 2,000～10,000.
8. the application of anion polyurethane according to claim 1 and amino silicone oil composite aqueous dispersion is characterized in that it is as fabric finishing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100537266A CN101307181B (en) | 2008-07-02 | 2008-07-02 | Anion polyurethane and amino silicon oil composite water dispersion, preparation and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100537266A CN101307181B (en) | 2008-07-02 | 2008-07-02 | Anion polyurethane and amino silicon oil composite water dispersion, preparation and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101307181A CN101307181A (en) | 2008-11-19 |
| CN101307181B true CN101307181B (en) | 2010-06-02 |
Family
ID=40123876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100537266A Expired - Fee Related CN101307181B (en) | 2008-07-02 | 2008-07-02 | Anion polyurethane and amino silicon oil composite water dispersion, preparation and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101307181B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167795A (en) * | 2010-12-31 | 2011-08-31 | 王奇 | Amino silicone modified waterborne polyurethane and preparation method thereof |
| ES2743816T3 (en) * | 2015-02-28 | 2020-02-20 | Evonik Operations Gmbh | OEM textile finishing compositions |
| US20200299462A1 (en) * | 2018-04-27 | 2020-09-24 | Changzhou University | Method for preparing ultraviolet (uv) curing polymethyl siloxane containing acrylate structure |
| CN109736093A (en) * | 2018-11-22 | 2019-05-10 | 江阴兴吴呢绒科技有限公司 | A kind of felt-proofing finishing method of machine washable wool fabric |
| CN109897538B (en) * | 2019-03-18 | 2020-12-08 | 陕西师范大学 | Anti-icing isolating agent for roads |
| CN110467842A (en) * | 2019-07-30 | 2019-11-19 | 清远市美佳乐环保新材股份有限公司 | There is one kind wetting to thicken multifunctional aqueous auxiliary agent and preparation method thereof |
| CN110818878B (en) * | 2019-10-31 | 2021-11-12 | 上海交通大学 | Preparation method of waterproof high-strength transparent waterborne polyurethane |
| CN112981963B (en) * | 2021-02-07 | 2022-09-30 | 武汉纺织大学 | Net-shaped association type polyurethane composite modified organic silicon softener emulsion and preparation method thereof |
| CN114539531A (en) * | 2022-02-08 | 2022-05-27 | 西北工业大学 | Controllable thermosetting organic silicon polyurea resin and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0458742A1 (en) * | 1990-05-16 | 1991-11-27 | Ciba-Geigy Ag | Fluorinated silicone polymers |
| CN1422305A (en) * | 2000-04-04 | 2003-06-04 | 西巴特殊化学品普法希股份有限公司 | Silicone compositions for treating wool materials |
| CN1621606A (en) * | 2004-10-19 | 2005-06-01 | 东华大学 | Polyurethane wool anti-felting finish agent and preparation method thereof |
| CN1854165A (en) * | 2005-04-20 | 2006-11-01 | 广州宏昌胶粘带厂 | Organic silicon modified aqueous polyurethane |
| CN1878807A (en) * | 2003-11-04 | 2006-12-13 | 巴斯福股份公司 | Polyurethane dispersion comprising siloxane groups |
-
2008
- 2008-07-02 CN CN2008100537266A patent/CN101307181B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0458742A1 (en) * | 1990-05-16 | 1991-11-27 | Ciba-Geigy Ag | Fluorinated silicone polymers |
| CN1422305A (en) * | 2000-04-04 | 2003-06-04 | 西巴特殊化学品普法希股份有限公司 | Silicone compositions for treating wool materials |
| CN1878807A (en) * | 2003-11-04 | 2006-12-13 | 巴斯福股份公司 | Polyurethane dispersion comprising siloxane groups |
| CN1621606A (en) * | 2004-10-19 | 2005-06-01 | 东华大学 | Polyurethane wool anti-felting finish agent and preparation method thereof |
| CN1854165A (en) * | 2005-04-20 | 2006-11-01 | 广州宏昌胶粘带厂 | Organic silicon modified aqueous polyurethane |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-261644A 2003.09.19 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101307181A (en) | 2008-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101307181B (en) | Anion polyurethane and amino silicon oil composite water dispersion, preparation and applications | |
| CN101307180B (en) | Cationoid polyurethane and modified silicon oil composite water dispersion, preparation and applications | |
| CN101235130B (en) | Cation water polyurethane emulsion and preparation method thereof | |
| CN101225226B (en) | Method for preparing water-dispersion montmorillonite/organic block polyurethane nano composite material and uses thereof | |
| KR20070100889A (en) | Aqueous polyurethane resin, method for producing aqueous polyurethane resin and film | |
| CN111808238B (en) | Preparation method of aqueous polyurethane dispersion liquid | |
| CN1084756C (en) | Aqueous polyurethane dispersions based on polyether polyols of low monol content | |
| CN105131239A (en) | Water resistance solvent-free polyurethane emulsion and preparation method thereof | |
| CN102093530A (en) | Preparation method of organosilicon-modified aqueous polyurethane | |
| CN103649146A (en) | Process for the production of polyurethane polyureas containing side chains and of aqueous dispersions of these | |
| CN105968304A (en) | High-performance waterborne polyurethane curing agent and preparing method and application thereof | |
| CN105170019A (en) | Preparation method for cationic polyurethane macro-molecule surfactant | |
| CN109705792A (en) | Shoes Aqueous Polyurethane Adhesives and preparation method thereof | |
| KR101860708B1 (en) | Water-dispersive polyurethane resin composition for dip coating of suede and its manufacturing process | |
| CN109734875A (en) | A kind of aminosilane coupling agent modifying aqueous polyurethane and preparation method thereof | |
| CN109897160B (en) | Blocked polyurethane curing agent emulsion and preparation method and application thereof | |
| CN107973894A (en) | A kind of preparation method of comprehensive performance high-environmental type modified aqueous polyurethane | |
| KR101313713B1 (en) | compositions of polyurethane resin has anti-hydrolysis property, Manufacturing method of polyurethane resin using the same and polyurethane adhesive with polyurethane resin | |
| KR20060132777A (en) | Dispersion polycarbonate polyurethane resin | |
| CN104371085A (en) | Preparation method of zwitterionic waterborne polyurethane | |
| KR101593753B1 (en) | Method for manufacturing coating material containing water-dispersible polyurethane | |
| CN108178822A (en) | A kind of preparation method of environment-friendly modified aqueous polyurethane | |
| CN100344663C (en) | Aqueous poly (urea/urethanes) dispersions using polyester glycol | |
| CN100471889C (en) | Extender for treatment of fiber materials | |
| KR20170111865A (en) | Hydrophilic water-dispersive polyurethane resin for textile coating and manufacturing process 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 |
Granted publication date: 20100602 Termination date: 20210702 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |