CN104877099A - Preparation method of organic fluorine modified hyperbranched water-based polyurethane - Google Patents
Preparation method of organic fluorine modified hyperbranched water-based polyurethane Download PDFInfo
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Abstract
The invention provides a preparation method of organic fluorine modified hyperbranched water-based polyurethane. The method comprises the following steps: (1), synthesizing water-based terminal hydroxyl hyperbranched polyurethane core; (2), synthesizing a double bond end capped linear polyurethane prepolymer through diisocyanate, low polymer divalent alcohol, a chain extendor, an end-capping reagent and the like; (3), grafting linear polyurethane onto terminal hydroxyl hyperbranched polyurethane; (4), leading a fluorine element onto a polymer through an emulsion method, so as to obtain the organic fluorine modified hyperbranched water-based polyurethane. According to the organic fluorine modified hyperbranched water-based polyurethane provided by the invention, raw materials are cheap and readily available, and are wide in sources, the synthesis process is simple, and industrialized production is facilitated. The organic fluorine modified hyperbranched water-based polyurethane is appropriate to be used independently, can be matched with other water-based resins, can be applied to the fields of water-resistant paints, environment-friendly water-based adhesives, water-based paints and the like, and has a broad application prospect.
Description
Technical field
The present invention relates to field of waterborne polyurethane, is exactly a kind of preparation method of organic fluorine modified ultra-branching aqueous polyurethane.
Background technology
As far back as nineteen fifty-two, Flory just proposes AB theoretically
n(n>=2) monomer can pass through the polymkeric substance from polycondensation height of formation branching, but it is just in widespread attention in recent years.Highly branched polymkeric substance can be divided into two large classes: dendritic macromole and hyperbranched polymer.Dendritic macromole has regular structure, and whole macromole is regular spherical, and only have branched structure and end structure in molecule, do not have linear structure, relative molecular mass distribution is narrower.The structure irregularity of hyperbranched polymer, whole macromolecular structure is elliposoidal, comprises branched structure, end structure and linear structure in molecule, and relative molecular mass distribution is generally wider.The synthesis of branch-shape polymer need by complicated polystep reaction, and every single step reaction all needs to carry out abstraction and purification and could obtain, and therefore, the cost synthesizing branch-shape polymer is very high, is unfavorable for realizing industrialized production.Although structurally there are some defects in hyperbranched polymer, but because its Measures compare prepared is simple, directly synthesize by single stage method or quasi-one step method, do not need to carry out purifying or only need carry out simple purifying obtaining, and there is the structure of similar dendritic macromole and special performance, as good hydrodynamic performance, easily film forming and low-viscosity etc., so have broad application prospects, be subject to extensive concern in recent years.
Although people, having synthesized super branched polyurethane in a variety of ways in recent years, still come with some shortcomings.Chinese patent CN101440150 (2009) generates hydrophilic monomer, with hydrophilic monomer and bB with vulcabond and the diol reaction containing hydrophilic radical
2monomer synthesize hyperbranched aqueous polyurethane, but the snappiness of this urethane is poor.Chinese patent CN101445697 (2009) is with vulcabond, oligopolymer dibasic alcohol and the diol chain-extension agent synthesizing linear base polyurethane prepolymer for use as containing hydrophilic radical, linear polyester performed polymer is grafted on Hyperbranched Polymer with Terminal Hydroxyl and generates super branched polyurethane, owing to not containing hydrophilic radical in hyperbranched polymer, thus can not reach the requirement of water-dispersion, and this reacts easy gel.
The electronegativity of fluorine atom is extremely strong, atomic radius is slightly larger than hydrogen atom, therefore the fluorine atom constraint of checking electronics and bonding electrons cloud to it is very strong, C-F key makes the interaction force between high-polymer molecular reduce, therefore polyaminoester emulsion not only has aqueous polyurethane (WPU) original characteristic after fluoridizing, also there are excellent surface property, water tolerance etc., thus promote film quality, make up the performance defect in these areas of WPU material.Fluorochemical urethane had both remained mechanical property and the two-phase microstructure features of urethane excellence, give again the surface property of material excellence, become the emerging development side of urethane (PU) material at present, and be applied in multiple field, especially for the top coat of industry, building, automobile, steamer, aircraft etc.
Core-shell Emulsion Polymerization can be divided into according to the technique of organic fluorine modified aqueous polyurethane, fluorochemical polyether (ester) introduces fluoro-containing group, fluorine-containing small molecule chain extender introduces the method such as fluoro-containing group.The method wherein introduced by fluorinated acrylate has more practical value, and can prepare the aqueous fluorine-containing urethane of more environmental protection.This product super branched polyurethane is due to containing more hydrophilic radical, transparent solution, to fluorinated acrylate monomer, there is good emulsifying effect, therefore in building-up process, comparatively stable emulsion can be obtained without the need to continuing to add emulsifying agent, super branched polyurethane act as the effect of emulsifying agent, thus realize agalactosis polymerization, avoid the problem causing product performance to decline because small-molecular emulsifier shows to move.
Summary of the invention
The object of the invention is to prepare a kind of organic fluorine modified ultra-branching urethane that can disperse in water.To be grafted on hyperbranched polymer containing double bond linear polyester exactly specifically, hydrophilic radical will be incorporated in hyperbranched polymer and linear polyester simultaneously, then by copolyreaction synthesis organic fluorine modified ultra-branching aqueous polyurethane.
The concrete technological method of the present invention is as follows:
A preparation method for organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that comprising the following steps:
(1) according to vulcabond and hydrophilic chain extender molar ratio be 3-6:1 feed in raw material, be uniformly mixed mixing in there-necked flask after, in atmosphere of inert gases, in 70-90 DEG C of reaction 1-4 hour, cryosel bath is cooled to less than 0 DEG C, dropping and residue-NCO group molar ratio are the secondary amine containing two hydroxyls of 0.4-0.8:1, after within 1-3 hour, dripping, drip rear continuation and stir 0.5-2 hour, be warming up to 60-110 DEG C of reaction 1-5 hour, obtain super branched polyurethane HBPU, it is solid containing being 30%-70% that building-up process uses DMF to make as solvent;
(2) be that 3-7:1 adds vulcabond and oligopolymer dibasic alcohol according to molar ratio, be uniformly mixed mixing in there-necked flask after, pass into rare gas element, in 70-90 DEG C of reaction 1-4 hour, add hydrophilic chain extender and non-hydrophilic chainextender makes the molar weight of residue-NCO group be the 10-35% of add-on, in 70-90 DEG C of reaction 1-5 hour, be cooled to 30-60 DEG C, add the end-capping reagent of the molar weight 50-70% of residue-NCO group, in 50-90 DEG C of reaction 1-4 hour, synthesis double bond endcapped linear base polyurethane prepolymer for use as;
(3) HBPU and double bond endcapped linear base polyurethane prepolymer for use as are mixed by a certain percentage, to make in HBPU containing containing in amount of substance and the performed polymer of-OH-ratio of NCO group is 0.5-2.5, in 50-110 DEG C of reaction 1-5 hour, to product add degree of neutralization be in the neutralizing agent of 100% and after, under agitation add water and carry out emulsion dispersion, Gu containing being 30-60%, organic solvent being revolved and steam removing, obtaining hyperbranched aqueous polyurethane;
(4) hyperbranched aqueous polyurethane that step (3) obtains is added the organic fluorine reagent of the 5-20% accounting for urethane total mass, and add the initiator of reaction monomers quality 0.5-2%, in 50-90 DEG C of reaction 1-5 hour, obtain organic fluorine hyperbranched aqueous polyurethane.
The preparation method of described organic fluorine modified ultra-branching aqueous polyurethane, it is characterized in that: hydrophilic chain extender be dimethylol propionic acid, dimethylolpropionic acid, quadrol base esilate, second dihydroxyl esilate one or more, non-hydrophilic chainextender is 1, the mixture of one or more in 4-butyleneglycol, 1,3 butylene glycol, glycol ether, ethylene glycol.
The preparation method of described organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that: the secondary amine containing two hydroxyls be diisopropanolamine (DIPA), diethanolamine one or both.
The preparation method of described organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that: vulcabond is the mixture of one or more in tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.
The preparation method of described organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that: oligopolymer dibasic alcohol is polytetrahydrofuran, polyoxyethylene glycol, the mixture of one or more in PCL, polyethers N210, polyethers N220.
The preparation method of described organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that: end-capping reagent is mixed by A and B two kinds of components or is made up of separately B component;
Component A is the one in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, n-Octanol, decyl alcohol;
B component is the one in hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate.
The preparation method of described organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that: neutralizing agent is one or both the mixture in ammoniacal liquor, triethylamine, sodium hydroxide, potassium hydroxide.
The preparation method of described organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that: organic fluorine reagent is the mixture of one or more in Hexafluorobutyl mathacrylate, methacrylic acid octafluoro pentyl ester, dodecafluoroheptyl methacrylate.
The preparation method of described organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that: initiator is one or both the mixture in benzoyl peroxide, Potassium Persulphate.
The present invention has the following advantages:
(1) in hyperbranched polymer and linear polyester performed polymer all containing hydrophilic radical, the super branched polyurethane of synthesis can be dispersed in water preferably, and super branched polyurethane act as the effect of emulsifying agent, thus realize agalactosis polymerization, avoid the problem causing product performance to decline because small-molecular emulsifier shows to move, in addition, the cavity structure in hyperbranched polymer molecule is conducive to product and associated water molecules, too increases the water dispersible of product;
(2) this raw materials used source of method synthesis of super branched urethane is wide, is cheaply easy to get, and technique is simple, is easy to suitability for industrialized production;
(3) adopt part NCO in end-capping reagent and linear polyester performed polymer to react, make most performed polymer only have one end to contain NCO group, make the reaction not easily gel of itself and HBPU;
(4) introducing of fluorine element makes emulsion not only have the original characteristic of aqueous polyurethane, also has the advantages such as excellent surface property, water tolerance and hydrophobicity.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
Prepare hyperbranched polymer and comprise following raw materials according:
IPDI 65.2 parts
DMPA 6.6 parts
DEOA 28.2 parts
DMF 100 parts
Concrete preparation method is as follows:
Take IPDI and DMPA and be dissolved in DMF (DMF), after stirring, pass into nitrogen, the air in eliminating system, be warming up to 85 DEG C of reaction 1.5h; Be cooled to-5 ~ 0 DEG C, slowly drip the DMF solution of DEOA, drip rear continuation and stir 30min, be warming up to 60 DEG C, reaction 2.0h, obtains super branched polyurethane (HBPU).
Prepare hyperbranched aqueous polyurethane and comprise following raw materials according:
TDI 26.2 parts
N210 60.2 parts
DMPA 4.8 parts
BDO 1.6 parts
HEMA 6.2 parts
HBPU 11 parts
TEA 3.4 parts
Concrete preparation method is as follows:
Take TDI and N210 (relative molecular mass 1000), pass into nitrogen, the air in eliminating system, in 85 DEG C of reactions 1.5 hours; Add DMPA and BDO, in 85 DEG C of reactions 2.5 hours; Be cooled to 60 DEG C, add a small amount of acetone and reduce system viscosity, add HEMA and carry out partially end-blocked reaction 1.0 hours, obtained linear polyester performed polymer; Add HBPU, in 80 DEG C of reactions 2.0 hours, in system, add TEA neutralization, rapid stirring also added water-dispersion, is finally revolved by organic solvent and steams removing.
Preparation organic fluorine modified ultra-branching aqueous polyurethane comprises following raw materials according:
HFMA 11 parts
BPO 0.08 part
K
2s
2o
80.08 part
Concrete preparation method is as follows:
Add after HFMA stirs and add BPO and K
2s
2o
8, be warming up to 70 DEG C of reaction 4h, obtain organic fluorine modified ultra-branching aqueous polyurethane.
Embodiment 2
Prepare hyperbranched polymer and comprise following raw materials according:
(with embodiment 1)
Concrete preparation method is as follows:
(with embodiment 1)
Prepare hyperbranched aqueous polyurethane and comprise following raw materials according:
IPDI 33.4 parts
N210 60.2 parts
DMBA 5.2 parts
BDO 1.6 parts
EtOH 1.1 parts
HEMA 3.1 parts
HBPU 11 parts
TEA 3.4 parts
Concrete preparation method is as follows:
Take IPDI and N210 (relative molecular mass 1000), pass into nitrogen, the air in eliminating system, in 85 DEG C of reactions 1.5 hours; Add DMBA and BDO, in 85 DEG C of reactions 2.5 hours; Be cooled to 50 DEG C, add a small amount of acetone and reduce system viscosity, add EtOH and HEMA and carry out partially end-blocked reaction 1.5 hours, obtained linear polyester performed polymer; Add HBPU, in 80 DEG C of reactions 2.0 hours, in system, add TEA neutralization, rapid stirring also added water-dispersion, is finally revolved by organic solvent and steams removing.
Preparation organic fluorine modified ultra-branching aqueous polyurethane comprises following raw materials according:
HFMA 11 parts
K
2s
2o
80.14 part
Concrete preparation method is as follows:
Add after HFMA stirs and add K
2s
2o
8, be warming up to 70 DEG C of reaction 4h, obtain organic fluorine modified ultra-branching aqueous polyurethane.
Embodiment 3
Prepare hyperbranched polymer and comprise following raw materials according:
(with embodiment 1)
Concrete preparation method is as follows:
(with embodiment 1)
Prepare hyperbranched aqueous polyurethane and comprise following raw materials according:
TDI 26.2 parts
PTMEG 60.2 parts
DMPA 4.8 parts
BDO 1.6 parts
HPMA 6.8 parts
HBPU 13 parts
TEA 3.4 parts
Concrete preparation method is as follows:
Take IPDI and PTMEG (relative molecular mass 1000), pass into nitrogen, the air in eliminating system, in 85 DEG C of reactions 1.5 hours; Add DMPA and BDO, in 85 DEG C of reactions 2.5 hours; Be cooled to 50 DEG C, add a small amount of acetone and reduce system viscosity, add HPMA and carry out partially end-blocked reaction 1.5 hours, obtained linear polyester performed polymer; Add HBPU, in 80 DEG C of reactions 2.0 hours, in system, add TEA neutralization, rapid stirring also added water-dispersion, is finally revolved by organic solvent and steams removing.
Preparation organic fluorine modified ultra-branching aqueous polyurethane comprises following raw materials according:
FMA 13 parts
BPO 0.2 part
Concrete preparation method is as follows:
Add after FMA stirs and add BPO, be warming up to 70 DEG C of reaction 4h, obtain organic fluorine modified ultra-branching aqueous polyurethane.
Claims (9)
1. a preparation method for organic fluorine modified ultra-branching aqueous polyurethane, is characterized in that comprising the following steps:
(1) according to vulcabond and hydrophilic chain extender molar ratio be 3-6:1 feed in raw material, be uniformly mixed mixing in there-necked flask after, in atmosphere of inert gases, in 70-90 DEG C of reaction 1-4 hour, cryosel bath is cooled to less than 0 DEG C, dropping and residue-NCO group molar ratio are the secondary amine containing two hydroxyls of 0.4-0.8:1, after within 1-3 hour, dripping, drip rear continuation and stir 0.5-2 hour, be warming up to 60-110 DEG C of reaction 1-5 hour, obtain super branched polyurethane HBPU, it is solid containing being 30%-70% that building-up process uses DMF to make as solvent;
(2) be that 3-7:1 adds vulcabond and oligopolymer dibasic alcohol according to molar ratio, be uniformly mixed mixing in there-necked flask after, pass into rare gas element, in 70-90 DEG C of reaction 1-4 hour, add hydrophilic chain extender and non-hydrophilic chainextender makes the molar weight of residue-NCO group be the 10-35% of add-on, in 70-90 DEG C of reaction 1-5 hour, be cooled to 30-60 DEG C, add the end-capping reagent of the molar weight 50-70% of residue-NCO group, in 50-90 DEG C of reaction 1-4 hour, synthesis double bond endcapped linear base polyurethane prepolymer for use as;
(3) HBPU and double bond endcapped linear base polyurethane prepolymer for use as are mixed by a certain percentage, to make in HBPU containing containing in amount of substance and the performed polymer of-OH-ratio of NCO group is 0.5-2.5, in 50-110 DEG C of reaction 1-5 hour, to product add degree of neutralization be in the neutralizing agent of 100% and after, under agitation add water and carry out emulsion dispersion, Gu containing being 30-60%, organic solvent being revolved and steam removing, obtaining hyperbranched aqueous polyurethane;
(4) hyperbranched aqueous polyurethane that step (3) obtains is added the organic fluorine reagent of the 5-20% accounting for urethane total mass, and add the initiator of reaction monomers quality 0.5-2%, in 50-90 DEG C of reaction 1-5 hour, obtain organic fluorine hyperbranched aqueous polyurethane.
2. the preparation method of organic fluorine modified ultra-branching aqueous polyurethane as claimed in claim 1, it is characterized in that: hydrophilic chain extender be dimethylol propionic acid, dimethylolpropionic acid, quadrol base esilate, second dihydroxyl esilate one or more, non-hydrophilic chainextender is 1, the mixture of one or more in 4-butyleneglycol, 1,3 butylene glycol, glycol ether, ethylene glycol.
3. the preparation method of organic fluorine modified ultra-branching aqueous polyurethane as claimed in claim 1, is characterized in that: the secondary amine containing two hydroxyls be diisopropanolamine (DIPA), diethanolamine one or both.
4. the preparation method of organic fluorine modified ultra-branching aqueous polyurethane as claimed in claim 1, is characterized in that: vulcabond is the mixture of one or more in tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.
5. the preparation method of organic fluorine modified ultra-branching aqueous polyurethane as claimed in claim 1, is characterized in that: oligopolymer dibasic alcohol is polytetrahydrofuran, polyoxyethylene glycol, the mixture of one or more in PCL, polyethers N210, polyethers N220.
6. the preparation method of organic fluorine modified ultra-branching aqueous polyurethane as claimed in claim 1, is characterized in that: end-capping reagent is mixed by A and B two kinds of components or is made up of separately B component;
Component A is the one in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, n-Octanol, decyl alcohol;
B component is the one in hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate.
7. the preparation method of organic fluorine modified ultra-branching aqueous polyurethane as claimed in claim 1, is characterized in that: neutralizing agent is one or both the mixture in ammoniacal liquor, triethylamine, sodium hydroxide, potassium hydroxide.
8. the preparation method of organic fluorine modified ultra-branching aqueous polyurethane as claimed in claim 1, is characterized in that: organic fluorine reagent is the mixture of one or more in Hexafluorobutyl mathacrylate, methacrylic acid octafluoro pentyl ester, dodecafluoroheptyl methacrylate.
9. the preparation method of organic fluorine modified ultra-branching aqueous polyurethane as claimed in claim 1, is characterized in that: initiator is one or both the mixture in benzoyl peroxide, Potassium Persulphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510264885.0A CN104877099B (en) | 2015-05-22 | 2015-05-22 | A kind of preparation method of Organic fluoride modified ultra-branching aqueous polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510264885.0A CN104877099B (en) | 2015-05-22 | 2015-05-22 | A kind of preparation method of Organic fluoride modified ultra-branching aqueous polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104877099A true CN104877099A (en) | 2015-09-02 |
| CN104877099B CN104877099B (en) | 2018-07-06 |
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Cited By (13)
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| CN105482060A (en) * | 2015-12-25 | 2016-04-13 | 华南理工大学 | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof |
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| CN105908366A (en) * | 2016-06-21 | 2016-08-31 | 齐鲁工业大学 | Hydrophobic and oleophilic-hydrophilic underwater oleophobic thin oil film as well as adjustment and control method, preparation process and application thereof |
| CN108505394A (en) * | 2017-12-26 | 2018-09-07 | 刘超 | A kind of manufacturing process of hyperbranched fluoropolymer material |
| CN108658736A (en) * | 2017-04-01 | 2018-10-16 | 中国科学院成都有机化学有限公司 | One kind having the short fluorocarbon chain fluorochemical monomer and preparation method of " tree-like " structure |
| CN108752563A (en) * | 2018-05-24 | 2018-11-06 | 哈尔滨工业大学无锡新材料研究院 | Aqueous hyperbranched structurally-modified polyether polyols of one kind and preparation method thereof and selfreparing diffusing reflection coating composition |
| CN108823987A (en) * | 2018-06-07 | 2018-11-16 | 南通纺织丝绸产业技术研究院 | A kind of preparation method of the floride-free water-proof aagent of reactivity for textile |
| CN110330634A (en) * | 2019-06-18 | 2019-10-15 | 湖北大学 | A kind of preparation method of the hyperbranched fluorine-containing aqueous polyurethane of novel hydrolysis |
| CN110358018A (en) * | 2019-06-24 | 2019-10-22 | 湖北大学 | A kind of water-resistant type comb shape fluorine-containing aqueous polyurethane and its preparation method and application |
| CN113683748A (en) * | 2021-07-23 | 2021-11-23 | 江苏苏博特新材料股份有限公司 | Fluorine-modified hyperbranched waterborne polyurethane resin and waterborne nano anti-corrosion self-cleaning finish paint using same |
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| CN116731590A (en) * | 2023-08-14 | 2023-09-12 | 赣州海盛硬质合金有限公司 | Preparation process of corrosion-resistant heat-insulating hard alloy coating |
| CN117304444A (en) * | 2023-10-31 | 2023-12-29 | 北京中彩印制有限公司 | Water-based polyurethane and preparation method thereof, and water-based scratch-off ink and preparation method thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105482060A (en) * | 2015-12-25 | 2016-04-13 | 华南理工大学 | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof |
| CN105646811A (en) * | 2016-01-04 | 2016-06-08 | 陕西科技大学 | Preparation method of organic-fluorine-modified polyurethane emulsion |
| CN105646811B (en) * | 2016-01-04 | 2018-06-01 | 陕西科技大学 | A kind of preparation method of Organic fluoride modified polyurethane emulsion |
| CN105908366A (en) * | 2016-06-21 | 2016-08-31 | 齐鲁工业大学 | Hydrophobic and oleophilic-hydrophilic underwater oleophobic thin oil film as well as adjustment and control method, preparation process and application thereof |
| CN108658736A (en) * | 2017-04-01 | 2018-10-16 | 中国科学院成都有机化学有限公司 | One kind having the short fluorocarbon chain fluorochemical monomer and preparation method of " tree-like " structure |
| CN108505394A (en) * | 2017-12-26 | 2018-09-07 | 刘超 | A kind of manufacturing process of hyperbranched fluoropolymer material |
| CN108505394B (en) * | 2017-12-26 | 2021-02-19 | 刘超 | Manufacturing process of hyperbranched fluorine-containing polymer material |
| CN108752563B (en) * | 2018-05-24 | 2020-12-15 | 哈尔滨工业大学无锡新材料研究院 | Waterborne hyperbranched structure modified polyurethane polymer, preparation method thereof and self-repairing diffuse reflection coating composition |
| CN108752563A (en) * | 2018-05-24 | 2018-11-06 | 哈尔滨工业大学无锡新材料研究院 | Aqueous hyperbranched structurally-modified polyether polyols of one kind and preparation method thereof and selfreparing diffusing reflection coating composition |
| CN108823987A (en) * | 2018-06-07 | 2018-11-16 | 南通纺织丝绸产业技术研究院 | A kind of preparation method of the floride-free water-proof aagent of reactivity for textile |
| CN110330634A (en) * | 2019-06-18 | 2019-10-15 | 湖北大学 | A kind of preparation method of the hyperbranched fluorine-containing aqueous polyurethane of novel hydrolysis |
| CN110358018A (en) * | 2019-06-24 | 2019-10-22 | 湖北大学 | A kind of water-resistant type comb shape fluorine-containing aqueous polyurethane and its preparation method and application |
| CN113683748A (en) * | 2021-07-23 | 2021-11-23 | 江苏苏博特新材料股份有限公司 | Fluorine-modified hyperbranched waterborne polyurethane resin and waterborne nano anti-corrosion self-cleaning finish paint using same |
| CN115216218A (en) * | 2022-08-17 | 2022-10-21 | 温州瓯海展新建设有限公司 | Water-based heat-insulating coating for glass curtain wall and spraying process thereof |
| CN116731590A (en) * | 2023-08-14 | 2023-09-12 | 赣州海盛硬质合金有限公司 | Preparation process of corrosion-resistant heat-insulating hard alloy coating |
| CN116731590B (en) * | 2023-08-14 | 2023-10-24 | 赣州海盛硬质合金有限公司 | Preparation process of corrosion-resistant heat-insulating hard alloy coating |
| CN117304444A (en) * | 2023-10-31 | 2023-12-29 | 北京中彩印制有限公司 | Water-based polyurethane and preparation method thereof, and water-based scratch-off ink and preparation method thereof |
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