CN105133347A - Preparation method of hydrostatic-pressure-resistant flame-retardant waterborne polyurethane and application - Google Patents
Preparation method of hydrostatic-pressure-resistant flame-retardant waterborne polyurethane and application Download PDFInfo
- Publication number
- CN105133347A CN105133347A CN201510586967.7A CN201510586967A CN105133347A CN 105133347 A CN105133347 A CN 105133347A CN 201510586967 A CN201510586967 A CN 201510586967A CN 105133347 A CN105133347 A CN 105133347A
- Authority
- CN
- China
- Prior art keywords
- reaction
- resistance
- hydrostatic pressure
- preparation
- add
- 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
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of hydrostatic-pressure-resistant flame-retardant waterborne polyurethane and application and belongs to the technical field of the textile chemical industry. The method comprises the following steps: mixing polyether diol, hydrophilic chain extender and trihydroxy polyether, then performing vacuum dehydration, adding solvent for dilution under the protection of nitrogen, and then adding aromatic isocyanate for reaction to obtain a prepolymer A; adding reactive phosphorus-containing flame retardant into the prepolymer A for reaction to obtain solution B; adding lipophilic chain extender into the solution B for reaction to obtain solution C; adding triethylamine into the solution C for neutralization, adding deionized water under agitation for emulsification, standing and then removing the solvent to obtain the waterborne polyurethane. The prepared waterborne polyurethane can be used as fabric coating agent and is applied to the field of textile coating. Especially when the waterborne polyurethane is applied to polyester low-stretch yarn coating, the hydrostatic-pressure-resistant performance is good and the value of the resisted hydrostatic pressure can reach 10 to 23KPa; the flame-retardant effect is good and the waterborne polyurethane can pass class B1 of GB/T5455-1997 textile combustion performance vertical tests.
Description
Technical field
The present invention relates to a kind of preparation method and application of resistance to hydrostatic pressure extinguishing waterborn polyurethane, belong to technical field of textile chemical engineering.
Background technology
Waterborne Polyurethane Fabric Coatings is a kind of macromolecule compound that can be spread evenly across fabric face, one or more layers film is formed at fabric face by adhesive effect, it can not only improve appearance of fabrics and style, and can fabric functional be made, make it have waterproof, moisture-inhibiting, the specific function such as fire-retardant.Aqueous polyurethane is dispersant with water, has environmental friendliness, the advantage such as nontoxic, safe.But there is a lot of shortcoming in functional single aqueous polyurethane, as resistance to hydrostatic pressure ability, inflammable, weatherability is poor, and the combination property of material cannot meet the demand of people in the covering with paint application of textiles.Therefore, the functional modification of research aqueous polyurethane, makes aqueous polyurethane possess resistance to hydrostatic pressure and the function such as fire-retardant simultaneously, had both met the development trend of textile coating agent, and also can meet the demand of people to material, and had huge economic and social benefit prospect.
The preparation method of the high hydrostatic pressure resistance anion aqueous polyurethane textile coating agent that patent CN102418274B announces, this polyurethane loomage coating agent is that the form of emulsion process in addition under the effect of emulsifying agent neopelex is prepared from, this kind of method is unstable because need additional emulsifying agent easily to make Waterborne Polyurethane Fabric Coatings store, affect application performance (as feel, mechanical property etc.), and because this polyurethane loomage coating agent is linear structure, also there is larger problem in the lasting maintenance of its resistance to hydrostatic pressure.(Li Haibei in one section of article that the people such as Li Haibei deliver, magnify human relations, Luo Yunjun etc. the development [J] of waterborne polyurethane coatings for fabrics. printing and dyeing assistant, 2004,21 (1): 45-47), although have employed interior crosslinking technological to have prepared the Waterborne Polyurethane Fabric Coatings with high hydrostatic pressure resistance, resistance to hydrostatic pressure value can reach 21600Pa, but adding of this crosslinking agent is easy to cause prepolymerization reaction viscosity excessive, reaction is made to be difficult to control.The Chen He of seminar of Luo Yun army etc. adopt a kind of phosphorous response type halogen-free flame retardants ExolitOP550 to synthesize a series of halogen-free flameproof aqueous polyurethane, flame retardant effect is relatively good, can by the B1 level in the test of GB/T5455-1997 textile combustion performance vertical method, but its resistance to hydrostatic pressure ability can not meet market instructions for use.
At present, the polyurethane simultaneously possessing resistance to hydrostatic pressure performance and fire resistance yet there are no people's report.
Summary of the invention
For defect of the prior art, the object of the present invention is to provide a kind of preparation method and application of resistance to hydrostatic pressure extinguishing waterborn polyurethane, aqueous polyurethane storage stability prepared by described method is good, asepsis environment-protecting, possess fire-retardant and resistance to hydrostatic pressure dual-use function, can be used as textile coating agent and be applied to textiles covering with paint field.
The object of the invention is to be achieved through the following technical solutions.
A preparation method for resistance to hydrostatic pressure extinguishing waterborn polyurethane textile coating agent, described method step is as follows:
Step one, polyether Glycols, hydrophilic chain extender are mixed with trihydroxy polyethers after, vacuum dehydration 0.5 ~ 1.5h at 100 ~ 120 DEG C;
Step 2, Temperature fall to 60 ~ 75 DEG C, under nitrogen protection, add solvent dilution, add aromatic isocyanates again, remove nitrogen and temperature of reaction system is risen to 75 ~ 90 DEG C and react, with di-n-butylamine method Ce Shi – NCO content, reaction close to theoretical value, obtains performed polymer A Zhi – NCO content;
Step 3, add response type phosphonium flame retardant react in performed polymer A, with di-n-butylamine method Ce Shi – NCO content, reaction close to theoretical value, obtains solution B Zhi – NCO content;
Step 4, add lipophile chain extender react in solution B, with di-n-butylamine method Ce Shi – NCO content, reaction close to theoretical value, obtains solution C Zhi – NCO content;
After step 5, solution C are down to room temperature, add triethylamine neutralization, after reaction 0.5 ~ 5min, the deionized water adding 0 ~ 10 DEG C under 2000 ~ 3000r/min stirs carries out emulsification, leaves standstill 8 ~ 12h, then except desolventizing, obtains described aqueous polyurethane.
The theoretical value of Suo Shu – NCO content is in corresponding reaction system, the content that hydroxyl complete reaction Hou ， – NCO is remaining.
In reaction raw materials gross mass for 100%, in reaction, required each constituent mass percentage is: polyether Glycols 27.8 ~ 43.3%, trihydroxy polyethers 5.4 ~ 11.5%, hydrophilic chain extender 5.54 ~ 6.76%, aromatic isocyanates 23.4 ~ 34.8%, response type phosphonium flame retardant 10.0 ~ 20.0%, lipophile chain extender 1.2 ~ 1.5% and triethylamine 4.2 ~ 5.2%.
Described deionized water and reaction raw materials total mass ratio are 1.86 ~ 2.33:1.
Described polyether Glycols is polytetrahydrofuran diol (PTMG) and/or polypropylene glycol (PPG).
Described hydrophilic chain extender is dihydromethyl propionic acid or dimethylolpropionic acid.
Described solvent is acetone, butanone or oxolane.
Described aromatic isocyanates is liquefaction methyl diphenylene diisocyanate (liquefied mdi), methyl diphenylene diisocyanate (MDI) or toluene di-isocyanate(TDI) (TDI).
The preferred German Clariant ExolitOP550 of described response type phosphonium flame retardant.
Described lipophile chain extender is BDO, diglycol, trimethylolpropane or pentaerythrite.
An application for resistance to hydrostatic pressure extinguishing waterborn polyurethane of the present invention, prepared aqueous polyurethane can be used as textile coating agent and is applied to textiles covering with paint field.
Beneficial effect
The aqueous polyurethane storage stability prepared according to the method for the invention is good, asepsis environment-protecting and possess fire-retardant and resistance to hydrostatic pressure dual-use function; After being applied to textile finishing, there is the advantages such as the good and safety of coating transparent, good hand touch, caking property.Especially, when it is applied to low elastic polyester filament coating, its resistance to hydrostatic pressure value can reach 10 ~ 23KPa, meets market instructions for use; Good flame retardation effect, by the B1 level in the test of GB/T5455-1997 textile combustion performance vertical method.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated.
In following examples:
Agents useful for same and instrument:
Reaction vessel used is the four-hole boiling flask with tetrafluoro paddle;
Di-n-butylamine method measures-NCO content: clean conical flask put into by the sample accurately taking about 3g, add 20mL dry toluene, make sample dissolution, pipette 10.00mL di-n-butylamine-toluene solution with pipette, rock and liquid in bottle is mixed, room temperature places 25min, add 45mL isopropyl alcohol, adding several bromocresol greens is indicator, with the titration of 0.5mol/LHCl standard liquid, when solution is terminal by blueness flavescence look, and do blank test.Its computing formula is:
W in formula
-NCOthe mass fraction of-NCO in-reaction system;
V
0-blank titration consumes the volume of hydrochloric acid standard solution, mL;
V
1the titration of-sample consumes the volume of hydrochloric acid standard solution, mL;
The concentration of c-hydrochloric acid standard solution, mol/L;
M-sample quality, g;
The molal weight of 42--NCO, g/mol.
Embodiment 1
Get the PTMG that 21g molecular weight is 2000, 4.05g trihydroxy polyethers N330 and 4.6g dihydromethyl propionic acid are in four-hole boiling flask, after 120 DEG C of dehydrated under vacuum 1h, Temperature fall to 60 DEG C, logical nitrogen, condensing reflux pipe is installed, add the butanone of 40g, after temperature stabilization, constant pressure funnel drips 26.25g liquefied mdi, control rate, about 0.5h adds, remove nitrogen, be warming up to 75 DEG C, react about 2h, in detection display solution ,-NCO content is close to theoretical value, add 15.1gExolitOP550 again, react about 3h, in detection display solution ,-NCO content is close to theoretical value, add 1g1 again, 4-butanediol, react about 1h, in detection display solution ,-NCO content is close to theoretical value, be down to room temperature, to add again in 3.5g triethylamine and after 30s, under 2000r/min stirs, add 140g temperature is that the deionized water of 0 DEG C carries out emulsification, leave standstill 12h.Remove butanone with Rotary Evaporators, obtain aqueous polyurethane.
The aqueous polyurethane 40g obtained, and then add 3 ammoniacal liquor, 1 defoamer K3 and 1g thickener 601H, after stirring, be coated on low elastic polyester filament, after coating, make low elastic polyester filament weightening finish 30g/m
2.Test the low elastic polyester filament after coating with digital seepage of water analyzer, its resistance to hydrostatic pressure mean value is 19886Pa.Low elastic polyester filament after coating is by the B1 level in the test of GB/T5455-1997 textile combustion performance vertical method.
Embodiment 2
Get the PTMG that 33g molecular weight is 2000, 6.35g trihydroxy polyethers N330 and 4.6g dimethylolpropionic acid are in four-hole boiling flask, after 100 DEG C of dehydrated under vacuum 1.5h, Temperature fall to 70 DEG C, logical nitrogen, condensing reflux pipe is installed, add the oxolane of 40g, after temperature stabilization, constant pressure funnel drips 26.25gMDI, control rate, about 0.5h adds, remove nitrogen, be warming up to 85 DEG C, react about 1.5h, in detection display solution ,-NCO content is close to theoretical value, add 8.3gExolitOP550 again, react about 3h, in detection display solution ,-NCO content is close to theoretical value, add 1g1 again, 4-butanediol, react about 0.5h, in detection display solution ,-NCO content is close to theoretical value, be down to room temperature, to add again in 3.5g triethylamine and after 5min, under 2500r/min stirs, add 154g temperature is that the deionized water of 0 DEG C carries out emulsification, leave standstill 8h.Remove oxolane with Rotary Evaporators, obtain aqueous polyurethane.
The aqueous polyurethane 40g obtained, and then add 3 ammoniacal liquor, 1 defoamer K3 and 1g thickener 601H, after stirring, be coated on low elastic polyester filament, after coating, make low elastic polyester filament weightening finish 30g/m
2.Test the low elastic polyester filament after coating with digital seepage of water analyzer, its resistance to hydrostatic pressure mean value is 22387Pa.Low elastic polyester filament after coating is by the B1 level in the test of GB/T5455-1997 textile combustion performance vertical method.
Embodiment 3
Get the PPG that 33.8g molecular weight is 2000, 9g trihydroxy polyethers N330 and 4.6g dihydromethyl propionic acid are in four-hole boiling flask, after 100 DEG C of dehydrated under vacuum 1.5h, Temperature fall to 75 DEG C, logical nitrogen, condensing reflux pipe is installed, add 50g oxolane, after temperature stabilization, constant pressure funnel drips 18.3gTDI, control rate, about 0.5h adds, remove nitrogen, be warming up to 80 DEG C, react about 2h, in detection display solution ,-NCO content is close to theoretical value, add 7.8gExolitOP550 again, react about 3.5h, in detection display solution ,-NCO content is close to theoretical value, add 1g diglycol again, react about 1h, in detection display solution ,-NCO content is close to theoretical value, be down to room temperature, to add again in 3.5g triethylamine and after 2min, under 3000r/min stirs, add 182g temperature is that the deionized water of 10 DEG C carries out emulsification, leave standstill 10h.Remove oxolane with Rotary Evaporators, obtain aqueous polyurethane.
The aqueous polyurethane 40g obtained, and then add 3 ammoniacal liquor, 1 defoamer K3 and 1g thickener 601H, after stirring, be coated on low elastic polyester filament, after coating, make low elastic polyester filament weightening finish 30g/m
2.Test the low elastic polyester filament after coating with digital seepage of water analyzer, its resistance to hydrostatic pressure mean value is 17935Pa.Low elastic polyester filament after coating is by the B1 level in the test of GB/T5455-1997 textile combustion performance vertical method.
Embodiment 4
Get the PTMG that 20g molecular weight is 2000, 12.35g molecular weight is the PPG of 2000, 5g trihydroxy polyethers N330 and 4.6g dimethylolpropionic acid are in four-hole boiling flask, after 120 DEG C of dehydrated under vacuum 0.5h, Temperature fall to 70 DEG C, logical nitrogen, condensing reflux pipe is installed, add 50g acetone, after temperature stabilization, constant pressure funnel drips 18.3gTDI, control rate, about 0.5h adds, remove nitrogen, be warming up to 90 DEG C, react about 1.5h, in detection display solution ,-NCO content is close to theoretical value, add 13.6gExolitOP550 again, react about 3h, in detection display solution ,-NCO content is close to theoretical value, add 1g trimethylolpropane again, react about 0.5h, in detection display solution ,-NCO content is close to theoretical value, be down to room temperature, to add again in 3.5g triethylamine and after 30s, under 3000r/min stirs, add 158g temperature is that the deionized water of 0 DEG C carries out emulsification, leave standstill 12h.Remove acetone with Rotary Evaporators, obtain aqueous polyurethane.
The aqueous polyurethane 40g obtained, and then add 3 ammoniacal liquor, 1 defoamer K3 and 1g thickener 601H, after stirring, be coated on low elastic polyester filament, after coating, make low elastic polyester filament weightening finish 30g/m
2.Test the low elastic polyester filament after coating with digital seepage of water analyzer, its resistance to hydrostatic pressure mean value is 10965Pa.Low elastic polyester filament after coating is by the B1 level in the test of GB/T5455-1997 textile combustion performance vertical method.
The present invention includes but be not limited to above embodiment, every any equivalent replacement of carrying out under the principle of spirit of the present invention or local improvement, all will be considered as within protection scope of the present invention.
Claims (8)
1. a preparation method for resistance to hydrostatic pressure extinguishing waterborn polyurethane, is characterized in that: described method step is as follows:
Step one, polyether Glycols, hydrophilic chain extender are mixed with trihydroxy polyethers after, vacuum dehydration 0.5 ~ 1.5h at 100 ~ 120 DEG C;
Step 2, Temperature fall to 60 ~ 75 DEG C, under nitrogen protection, add solvent dilution, add aromatic isocyanates again, remove nitrogen and temperature of reaction system is risen to 75 ~ 90 DEG C and react, with di-n-butylamine method Ce Shi – NCO content, reaction close to theoretical value, obtains performed polymer A Zhi – NCO content;
Step 3, add response type phosphonium flame retardant react in performed polymer A, with di-n-butylamine method Ce Shi – NCO content, reaction close to theoretical value, obtains solution B Zhi – NCO content;
Step 4, add lipophile chain extender react in solution B, with di-n-butylamine method Ce Shi – NCO content, reaction close to theoretical value, obtains solution C Zhi – NCO content;
After step 5, solution C are down to room temperature, add triethylamine neutralization, after reaction 0.5 ~ 5min, the deionized water adding 0 ~ 10 DEG C under 2000 ~ 3000r/min stirs carries out emulsification, leaves standstill 8 ~ 12h, then except desolventizing, obtains described aqueous polyurethane;
The theoretical value of Suo Shu – NCO content is in corresponding reaction system, the content that hydroxyl complete reaction Hou ， – NCO is remaining;
In reaction raw materials gross mass for 100%, in reaction, required each constituent mass percentage is: polyether Glycols 27.8 ~ 43.3%, trihydroxy polyethers 5.4 ~ 11.5%, hydrophilic chain extender 5.54 ~ 6.76%, aromatic isocyanates 23.4 ~ 34.8%, response type phosphonium flame retardant 10.0 ~ 20.0%, lipophile chain extender 1.2 ~ 1.5% and triethylamine 4.2 ~ 5.2%;
Described deionized water and reaction raw materials total mass ratio are 1.86 ~ 2.33:1.
2. the preparation method of a kind of resistance to hydrostatic pressure extinguishing waterborn polyurethane according to claim 1, is characterized in that: described polyether Glycols is polytetrahydrofuran diol and/or polypropylene glycol.
3. the preparation method of a kind of resistance to hydrostatic pressure extinguishing waterborn polyurethane according to claim 1, is characterized in that: described hydrophilic chain extender is dihydromethyl propionic acid or dimethylolpropionic acid.
4. the preparation method of a kind of resistance to hydrostatic pressure extinguishing waterborn polyurethane according to claim 1, is characterized in that: described solvent is acetone, butanone or oxolane.
5. the preparation method of a kind of resistance to hydrostatic pressure extinguishing waterborn polyurethane according to claim 1, is characterized in that: described aromatic isocyanates is liquefaction methyl diphenylene diisocyanate, methyl diphenylene diisocyanate or toluene di-isocyanate(TDI).
6. the preparation method of a kind of resistance to hydrostatic pressure extinguishing waterborn polyurethane according to claim 1, is characterized in that: described response type phosphonium flame retardant is German Clariant ExolitOP550.
7. the preparation method of a kind of resistance to hydrostatic pressure extinguishing waterborn polyurethane according to claim 1, is characterized in that: described lipophile chain extender is BDO, diglycol, trimethylolpropane or pentaerythrite.
8. an application for resistance to hydrostatic pressure extinguishing waterborn polyurethane as claimed in claim 1, is characterized in that: prepared aqueous polyurethane can be used as textile coating agent and is applied to textiles covering with paint field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510586967.7A CN105133347B (en) | 2015-09-15 | 2015-09-15 | A kind of preparation method and application of resistance to hydrostatic pressure extinguishing waterborn polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510586967.7A CN105133347B (en) | 2015-09-15 | 2015-09-15 | A kind of preparation method and application of resistance to hydrostatic pressure extinguishing waterborn polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105133347A true CN105133347A (en) | 2015-12-09 |
| CN105133347B CN105133347B (en) | 2017-04-05 |
Family
ID=54718898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510586967.7A Active CN105133347B (en) | 2015-09-15 | 2015-09-15 | A kind of preparation method and application of resistance to hydrostatic pressure extinguishing waterborn polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105133347B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105484042A (en) * | 2016-01-11 | 2016-04-13 | 北京理工大学 | After-chain-extension inflaming retarding waterborne polyurethane fabric coating with high resistance to static water pressure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845269A (en) * | 2010-05-31 | 2010-09-29 | 淄博永麒化工技术开发有限公司 | Waterborne polyurethane finishing agent for PVC (Polyvinyl Chloride) protective gloves and preparation method thereof |
| CN102226314A (en) * | 2011-04-29 | 2011-10-26 | 北京理工大学 | Environmentally-friendly halogen-free reaction type soft and hard segment co-modified flame retardant waterborne polyurethane fabric coating agent and preparation method thereof |
| US20140162516A1 (en) * | 2012-12-11 | 2014-06-12 | Hi-Tex, Inc. | Liquid Repelling Coating |
| CN104018354A (en) * | 2014-06-24 | 2014-09-03 | 北京理工大学 | Hyperbranched waterborne polyurethane/organic phosphorus hard segment flame-retardant modified waterborne polyurethane coating agent and preparation method thereof |
-
2015
- 2015-09-15 CN CN201510586967.7A patent/CN105133347B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845269A (en) * | 2010-05-31 | 2010-09-29 | 淄博永麒化工技术开发有限公司 | Waterborne polyurethane finishing agent for PVC (Polyvinyl Chloride) protective gloves and preparation method thereof |
| CN102226314A (en) * | 2011-04-29 | 2011-10-26 | 北京理工大学 | Environmentally-friendly halogen-free reaction type soft and hard segment co-modified flame retardant waterborne polyurethane fabric coating agent and preparation method thereof |
| US20140162516A1 (en) * | 2012-12-11 | 2014-06-12 | Hi-Tex, Inc. | Liquid Repelling Coating |
| CN104018354A (en) * | 2014-06-24 | 2014-09-03 | 北京理工大学 | Hyperbranched waterborne polyurethane/organic phosphorus hard segment flame-retardant modified waterborne polyurethane coating agent and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105484042A (en) * | 2016-01-11 | 2016-04-13 | 北京理工大学 | After-chain-extension inflaming retarding waterborne polyurethane fabric coating with high resistance to static water pressure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105133347B (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101581039B (en) | Durable antistatic finishing agent for fabrics and preparation method | |
| CN102634318B (en) | Low-temperature-resisting solvent type polyurethane bonding agent and preparation method thereof | |
| CN104611933B (en) | A kind of preparation method of high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings | |
| CN101970519B (en) | Aqueous dispersions of anionically modified polyurethane-ureas for coating textiles | |
| CN102618204A (en) | Hot-melt adhesive for bonding layer of artificial leather and preparation method as well as application thereof | |
| CN107057027B (en) | A kind of preparation method of high-solid-content and low-viscosity aqueous polyurethane | |
| CN103965430B (en) | A kind of selfreparing polyurethane, printing in textiles coating and preparation method thereof | |
| CN109970948A (en) | A kind of Gao Hangu anion aqueous polyurethane lotion and preparation method thereof | |
| CN101812167B (en) | Method for preparing waterborne polyurethane/organosilicon montmorillonite nano composite material | |
| CN101914857A (en) | Method for preparing reactive polyurethane film-forming color fixing agent | |
| CN102965064B (en) | Preparation method and applications of solvent-free polyurethane adhesive | |
| CN102964564B (en) | Low-foam and anti-ageing wet type polyurethane resin for synthetic leather and preparation method thereof | |
| CN105316949A (en) | Hard-segment modified chain-extension flame-retardant aqueous polyurethane coating agent and preparation method thereof | |
| CN101818458A (en) | Organosilicon modified polyurethane hyperchromic improver and preparation method thereof | |
| CN106883375A (en) | A kind of super branched polyurethane modified aqueous polyurethane, preparation method and application | |
| CN104018354A (en) | Hyperbranched waterborne polyurethane/organic phosphorus hard segment flame-retardant modified waterborne polyurethane coating agent and preparation method thereof | |
| CN103865023A (en) | Environment-friendly polyurethane grouting material and preparation method thereof | |
| CN115197395A (en) | Aqueous polyurethane for impregnation of microfiber leather and preparation method and application thereof | |
| CN105133347A (en) | Preparation method of hydrostatic-pressure-resistant flame-retardant waterborne polyurethane and application | |
| CN105418887A (en) | Anionic polyurethane color fixing agent for acid dyes as well as preparation method and application of color fixing agent | |
| CN113167023A (en) | Urethane resin composition, coating film, and synthetic leather | |
| CN105484042A (en) | After-chain-extension inflaming retarding waterborne polyurethane fabric coating with high resistance to static water pressure | |
| CN105019248A (en) | Preparation method of positive ion reaction type environment-friendly fabric stiffening agent | |
| CN104047180A (en) | Hyperbranched waterborne polyurethane/organophosphorus soft segment flame-retardant modified waterborne polyurethane coating agent and preparation method of coating agent | |
| CN107700214A (en) | High-efficient, no-freon waterproofing agent and preparation method comprising telechelic polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |