CN1861653A - Cross-linked water soluble fluorine resin, preparation process and application thereof - Google Patents
Cross-linked water soluble fluorine resin, preparation process and application thereof Download PDFInfo
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- CN1861653A CN1861653A CN 200610046822 CN200610046822A CN1861653A CN 1861653 A CN1861653 A CN 1861653A CN 200610046822 CN200610046822 CN 200610046822 CN 200610046822 A CN200610046822 A CN 200610046822A CN 1861653 A CN1861653 A CN 1861653A
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Abstract
An aqueous fluoric resin able to be cross-linked and used for building, industry, woodware, paper, textile, leather, etc is prepared proportionally from water, the fluoric copolymer of vinyl trifluorochloride, biacetone acrylamide, unsaturated carboxylic acid and non-fluoric monomers, and the compound with at least two hydrazino radicals in its molecule through emulsion polymerization and mixing with others.
Description
Technical field:
The present invention relates to macromolecular compound, particularly water-based fluororesin also relates to its method for making and application in addition.
Background technology:
Fluorinated copolymer has good weathering resistance, chemical-resistant, contamination resistance etc. because of it, and is widely used in fields such as building, industry, chemical industry.Answer requirement on environmental protection in recent years, water-based fluororesin has caused domestic and international company, scholar's extensive concern.Chinese patent CN1322775A adopts the back emulsion process, and emulsification made a kind of water-based fluororesin after soon the solvent-borne type fluoro-resin boiled off solvent.U.S. Pat 5856394 has been reported a kind of water-based fluororesin, and this water-based fluororesin is to adopt emulsion polymerization to make.Above-mentioned two kinds of water-based fluororesin complicated process of preparation, and all need to use solidifying agent such as self-emulsifying polymeric polyisocyanate, promptly made coating in use be two-pack, storage period, working life are shorter, make troubles to use.In addition at the construction field (site), it also is the comparison difficulty that solidifying agent is evenly dispersed in the water, degradation such as that this will cause filming is water-fast, weather-proof, anti-contamination.Chinese patent CN1362422A adopts the semi-continuous emulsion polymerizing method to prepare a kind of water-based fluororesin, can make the watersoluble fluorine paint of single component by this water-based fluororesin, this coating is easy to use, and have performances such as ageing-resistant preferably, water-fast, alkaline-resisting, but because crosslinking reaction does not take place in film process for it, so its solvent resistance is very poor.
Summary of the invention:
The objective of the invention is provides a kind of cross-linked water soluble fluorine resin for addressing the above problem, and has good storage stability and film performance, easy to use; Its method for making also is provided in addition, and method for making is simple, easy to operate; Its application aspect coating also is provided at last.
The technical scheme that the present invention is adopted for achieving the above object is: water as dispersion medium, fluorinated copolymer as the compound that contains two diazanyls groups in disperse phase and the molecule at least as solidifying agent;
Wherein fluorinated copolymer is to be polymerized by comonomer trifluorochloroethylene, diacetone-acryloamide(DAA), unsaturated carboxylic acid and other the non-fluorine monomers weight part ratio according to 15-50: 1-20: 0.1-10: 20-80.
Described solidifying agent is selected the compound that contains two diazanyl groups in the molecule at least for use.The example of the solidifying agent that is suitable for has the dicarboxyl acid dihydrazide, as ethylene acid hydrazide, propanedioic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide etc.The add-on of solidifying agent is the fluoropolymer of per 100 weight parts, and the suitable amounts of solidifying agent is 0.2-15 part, and is crosslinked insufficient if less than 0.2 part, if greater than 15 parts, and the degradation of filming.
Described fluorinated copolymer is the trifluorochloroethylene by the 15-50 weight part, the diacetone-acryloamide(DAA) of 1-20 weight part, and other non-fluorine monomers of the unsaturated carboxylic acid of 0.1-10 weight part and 20-80 weight part form through letex polymerization.
Described fluorinated copolymer comonomer trifluorochloroethylene consumption is 15-50, and the trifluorochloroethylene consumption is lower than at 15 o'clock, and the weathering resistance of filming is difficult to guarantee; If greater than 50, the bad dispersibility in water then, the stability of emulsion reduces, and Shi Yi scope is 20-40% especially;
The purpose of described comonomer diacetone-acryloamide(DAA) and other monomer copolymerizations is that active carbonyl is incorporated in the fluorinated copolymer, and it mainly acts on is to make crosslinking copolymers.The consumption of diacetone-acryloamide(DAA) is 1-15, and if 2-10 preferably is less than 1, the crosslinking degree of filming does not have due effect with deficiency, if greater than 15, can cause the weathering resistance variation of fluorinated copolymer, it can improve the stability of emulsion in addition, thereby reduces the consumption of emulsifying agent;
Described comonomer unsaturated carboxylic acid is CH
2=C (R
1)-R
2-COOH (1)
R wherein
1=CH
3, H, R
2=(CH
2)
n, n=0-6
Polymerizable unsaturated carboxylic acid by molecular formula (1) expression, it can be considered a kind of reactive emulsifying agent, in letex polymerization, can reduce the consumption of emulsifying agent, when having improved stability of emulsion, also improved the water tolerance of filming, for n=0-6 in the molecular formula (1), this point is very important, if greater than 6, the stability of polymerization rate, productive rate and emulsion is all undesirable; The consumption of unsaturated carboxylic acid is 0.1-10, is more preferably 1-8, if less than 0.1, just can not effectively play the effect of reactive emulsifier, if greater than 10, the water tolerance variation of filming, the example of suitable unsaturated carboxylic acid has vinylformic acid, methacrylic acid, butenoic acid etc.;
Other non-fluorine monomers of described comonomer are selected from least a in vinyl ester or vinyl ether or the acrylate monomer.The monomeric example of vinyl ester compound class that is suitable for has vinyl acetate, propionate, vinyl butyrate, vinyl caproate, sad vinyl acetate, capric acid vinyl acetate, isopropylformic acid vinyl acetate, new vinyl acetate acid, 2 ethyl hexanoic acid vinyl acetate, the tertiary ethylene carbonate with 9 or 10 carbonatomss, M-nitro benzoic acid vinyl acetate etc.; The example of vinyl ethers monomer has methylvinylether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, methylol vinyl ether, hydroxyethyl vinyl ether, hydroxy butyl vinyl ether etc.; The example of acrylic ester monomer has methyl acrylate, ethyl propenoate, butyl acrylate, octadecyl acrylate, ethyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate etc.Their consumption is 10-80,30-60 preferably, if less than 10, rate of polymerization is too low, and effect is relatively poor, if greater than 80, makes that the fluorine content of multipolymer is too low, and the weathering resistance of filming is poor.
Described copolymerization emulsifying agent is anionic or nonionic emulsifier, and they both can use separately, the use of also two class emulsifying agents can being arranged in pairs or groups.Anionic emulsifier has: the derivative of alkyl-sulphate, alkylbenzene sulfonate, alkylsulfonate, aerosol-OT salt, Brij30 vitriol and these salt.Nonionic emulsifier can be selected Voranol EP 2001, polyxyethylated alkylphenol, polyoxyethylene high-grade aliphatic ester and phenylol Soxylat A 25-7 etc. for use.The emulsifying agent consumption is the 0.5-6% of comonomer gross weight, if less than 0.5%, and the poor stability of emulsion; If greater than 6%, water-resistance property of coating and weathering resistance can variation.
Described copolymerization buffer reagent, be for stable p H value polymerization system is provided, helping polymeric carries out, the pH value buffer reagent that is suitable for has bicarbonate of ammonia, sodium bicarbonate, yellow soda ash, salt of wormwood, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic etc., its consumption and fluorinated copolymer weight part ratio are 0.1-5: 100, preferably phosphoric acid disodium hydrogen, optimum amount are and fluorinated copolymer weight part ratio 0.2-2.5: 100.
Described polymerization initiator is the general initiator of ordinary emulsion polymerization, comprises inorganic peroxide, for example hydrogen peroxide; Organo-peroxide, for example benzoyl peroxide, tert-butyl peroxide; Persulphate, for example Potassium Persulphate, Sodium Persulfate, ammonium persulphate; And azo initiator, for example Diisopropyl azodicarboxylate.Also has redox initiator in addition, as hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, Potassium Persulphate-sodium bisulfite and isopropyl benzene hydroperoxide-iron protochloride etc.Initiator system of ammonium persulfate of the present invention is as the polymeric initiator.
The described water yield and fluorinated copolymer weight part ratio are 50-400: 100, more be suitable for 70-150: 100, if the water yield is less than 50 parts, emulsion dispersion is mutually too much, particle diameter is excessive, cause in polymerization process or in the storage process emulsion stable inadequately, if the water yield is greater than 400 parts, then the solid content of emulsion is too low, is unfavorable for using.
Among the present invention, the temperature of copolyreaction is decided along with the type of the initiator that uses, usually in 0-150 ℃ scope.
The method for making of cross-linked water soluble fluorine resin of the present invention: respectively emulsifying agent, initiator, pH value buffer reagent and deionized water are mixed at first by a certain percentage, standby; Then starting monomer and most of emulsifier aqueous solution are carried out pre-emulsification under mixing is stirred, get pre-emulsified monomer, standby.In withstand voltage reactor, add remaining emulsifier aqueous solution and pH value aqueous solution of buffer agent, outgas, fill N
2After three times, the emulsified monomer that takes a morsel adds in the withstand voltage reactor repeatedly for gas, the degassing, stirs to heat up.Add the part initiator solution when temperature of reaction kettle reaches 50-70 ℃, polymerization begins, and exothermic heat of reaction heats up.After question response is mild, drip residue emulsified monomer and initiator solution simultaneously, in 2-4h, drip.Temperature is controlled in 72～90 ℃ of scopes, after continuing to react 6h, reaction system is cooled to 30～40 ℃ gets the fluorinated copolymer emulsion, adds aqueous solution of curing agent at last, and discharging behind the continuation stirring 20min obtains cross-linked water soluble fluorine resin.
The present invention can be widely used in the binding material of numerous areas such as building, industry, woodenware, paper, weaving, leather; The present invention is applied to onepot coating.
Cross-linked water soluble fluorine resin of the present invention, used solidifying agent crosslinking reaction in water can not be carried out, therefore after solidifying agent joins in the water-based fluororesin, chemically remaining stable, during use, along with evaporation of water, between active carbonyl and the diazanyl dehydration reaction takes place, take place crosslinked, thereby filming of having obtained solidifying, thereby can make the coating of single component, easy to use.And after applying, along with the volatilization of moisture in the coating, at room temperature crosslinking reaction can take place with its coatings formulated, filming except having good contamination resistance, ageing resistance, water tolerance, alkali resistance of formation also has anti-preferably solvent properties.
Embodiment:
Below in conjunction with specific embodiment, the present invention is further specified, but the present invention is not only limited to these embodiment.
Embodiment 1
Add 130.0g deionized water and 1.0g sodium lauryl sulphate (SDS) in mixing tank, 5.0g polyoxyethylene nonylphenol ether (OP-10) and 3.5g polyoxyethylene nonylphenol ether (OP-30) make emulsifier aqueous solution after stirring, and be standby; The 1.0g ammonium persulphate is dissolved in the 60.0g water, stand-by; The 1.0g Sodium phosphate dibasic is dissolved in the 20.0g water, standby; In pre-emulsification still, add 60.0g trifluorochloroethylene, 95.0g vinyl acetate, 10.0g diacetone-acryloamide(DAA), 35.0g ethyl propenoate, 10.0g vinylformic acid and 2/3 emulsifier aqueous solution, mix to stir and carry out pre-emulsification, get emulsified monomer, standby; In the 1L autoclave that has stirring and heating unit, add the remaining emulsifier aqueous solution and the Sodium phosphate dibasic aqueous solution, outgas, fill N
2Gas, the degassing after three times, are got 1/3 emulsified monomer and are added in the reactor repeatedly, begin to stir and heat up; When temperature reaches 65 ℃, add initiator solution 21.0g, polyreaction begins, and heat release is warmed up to 72～80 ℃, after reaction is mild, drips residual emulsifier monomer and initiator solution simultaneously, dropwises in the 3h.72～90 ℃ of holding temperatures after continuing to react 6h, are cooled to 30～40 ℃ with reaction system, add the aqueous solution (10%) of 11g adipic dihydrazide then, and discharging behind the continuation stirring 20min obtains cross-linked water soluble fluorine resin.
Embodiment 2
Add 130.0g deionized water and 1.0g sodium lauryl sulphate (SDS) in mixing tank, 4.0g polyoxyethylene nonylphenol ether (OP-20) and 3.5g polyoxyethylene nonylphenol ether (OP-30) make emulsifier aqueous solution after stirring, and be standby; The 1.0g ammonium persulphate is dissolved in the 60.0g water, stand-by; The 1.0g Sodium phosphate dibasic is dissolved in the 20.0g water, standby; In pre-emulsification still, add 60.0g trifluorochloroethylene, 55.0g vinyl acetate, 15.0g diacetone-acryloamide(DAA), 30.0g butyl acrylate, the new n-nonanoic acid vinyl acetate of 40.0g, 10.0g vinylformic acid and 2/3 emulsifier aqueous solution, mix to stir and carry out pre-emulsification, get emulsified monomer, standby; In the 1L autoclave that has stirring and heating unit, add the remaining emulsifier aqueous solution and the Sodium phosphate dibasic aqueous solution, outgas, fill N
2Gas, the degassing after three times, are got 1/2 emulsified monomer and are added in the reactor repeatedly, begin to stir and heat up; When temperature reaches 60 ℃, add initiator solution 31.0g, polyreaction begins, and heat release is warmed up to 72～80 ℃, keeps reaction 1h, drips residual emulsifier monomer and initiator solution then, dropwises in the 2h.72～90 ℃ of holding temperatures after continuing to react 6h, are cooled to 30～40 ℃ with reaction system, add the aqueous solution (10%) of 17g adipic dihydrazide then, and discharging behind the continuation stirring 20min obtains cross-linked water soluble fluorine resin.
Embodiment 3-4 formula table sees Table 1, and preparation method and technology are identical with example 1.
Comparative example 1
Add 140.0g deionized water and 0.8g sodium lauryl sulphate (SDS) in mixing tank, 4.7g polyoxyethylene nonylphenol ether (OP-10) and 3.0g polyoxyethylene nonylphenol ether (OP-30) make emulsifier aqueous solution after stirring, and be standby; The 1.0g ammonium persulphate is dissolved in the 60.0g water, stand-by; The 1.0g Sodium phosphate dibasic is dissolved in the 20.0g water, standby; In pre-emulsification still, add 54.0g trifluorochloroethylene, 90.0g vinyl acetate, 35.0g ethyl propenoate, 10.0g vinylformic acid and 2/3 emulsifier aqueous solution, mix to stir and carry out pre-emulsification, get emulsified monomer, standby; In the 1L autoclave that has stirring and heating unit, add the remaining emulsifier aqueous solution and the Sodium phosphate dibasic aqueous solution, outgas, fill N
2Gas, the degassing after three times, are got 1/3 emulsified monomer and are added in the reactor repeatedly, begin to stir and heat up; When temperature reaches 60 ℃, add initiator solution 21.0g, polyreaction begins, and heat release is warmed up to 72～80 ℃, after reaction is mild, drips residual emulsifier monomer and initiator solution simultaneously, dropwises in the 3h.72～90 ℃ of holding temperatures continue reaction 6h.Then reaction system is cooled to 20～40 ℃ of dischargings, obtains water-based fluororesin.
Comparative example 2,4 formula tables see Table 1, and preparation method and technology are identical with comparative example 1.
In comparative example 1, do not contain the cross-linking monomer diacetone-acryloamide(DAA) in the preparation of fluorinated copolymer.In comparative example 2, the add-on of solidifying agent is very few.In comparative example 3, not according to the present invention, but with undecylenic acid as the polymerizable unsaturated carboxylic acid.
Table 1 example 3,4 and comparative example 2,3 formula tables
| Monomer | Example 3 | Example 4 | Comparative example 2 | Comparative example 3 |
| Trifluorochloroethylene | 70.0g | 75.0g | 70.0g | 60.0g |
| Diacetone-acryloamide(DAA) | 10.0g | 8.0g | 10.0g | 15.0g |
| Vinyl acetate | 60.0g | -- | 60.0g | 55.0g |
| New n-nonanoic acid vinyl acetate | -- | 40.0g | -- | 40.0g |
| Butyl acrylate | -- | 30.0g | -- | 30.0g |
| Ethyl propenoate | 20.0g | -- | 20.0g | -- |
| Ethyl vinyl ether | 30.0g | 20.0g | 30.0g | -- |
| Vinylformic acid | -- | 10.0g | -- | -- |
| Undecylenic acid | -- | -- | -- | 10.0g |
| Methacrylic acid | 15.0g | -- | 15.0g | -- |
| Sodium lauryl sulphate | -- | -- | -- | 1.0g |
| Sodium dodecylbenzene sulfonate | 2.0g | 2.0g | 2.0g | -- |
| OP-10 | 2.0g | 3.0g | 2.0g | 5.0g |
| OP-30 | 4.5g | 5.0g | 4.5g | 3.5g |
| Ammonium persulphate | 1.1g | 1.1g | 1.1g | 1.0g |
| Sodium phosphate dibasic | 1.0g | 1.0g | 1.0g | 1.0g |
| Deionized water | 210g | 210g | 210g | 210g |
| Adipic dihydrazide (10% aqueous solution) | 12g | 10g | 4.0 | 17g |
The water-based fluororesin that makes is detected, the results are shown in Table 2.
Table 2 water-based fluororesin performance
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Solid content (%) | 46.1 | 45.4 | 44.2 | 45.6 | 45.5 | 44.9 | 41.3 |
| Median size (nm) | 165 | 171 | 183 | 190 | 157 | 179 | 230 |
| Viscosity (mPas) | 82 | 75 | 52 | 58 | 60 | 61 | 193 |
| Fluorine content (%) | 13.1 | 13.6 | 16.8 | 19.5 | 13.4 | 16.9 | 10.4 |
| Package stability | By | By | By | By | By | By | Gu shape |
| Calcium ion stability | By | By | By | By | By | By | By |
| Mechanical stability | By | By | By | By | By | By | By |
| Freeze-thaw stability | By | By | By | By | By | By | Breakdown of emulsion |
| Dilution stability | By | By | By | By | By | By | By |
Use:
Get 30 parts rutile TiO
2Slurry (solid content 70%) joins in the water-based fluororesin that 100 parts example 1 makes, and adds an amount of thickening material, defoamer, film coalescence aid then, mixes, and makes white mono-component aqueous fluorine coating I.Use the same method, get the water-based fluororesin of example 2, example 3, example 4, comparative example 1 and comparative example 2 preparations respectively and make white mono-component aqueous fluorine coating II, III, IV, V, VI.What the gained coating property detected the results are shown in Table 3, and therefrom the coating of water-based fluororesin manufacturing of the present invention as can be seen also has anti-preferably xylol except having excellent in water resistance, alkali resistance, abrasion resistance, artificial ageing resistance.
Table 3 watersoluble fluorine paint performance measurement result
| The mensuration project | I | II | III | IV | V | VI |
| Anti-xylol | 200 times | 200 times | 200 times | 300 times | ＜20 times | ＜80 times |
| Water tolerance | 30 days | 60 days | 60 days | 120 days | 15 days | 50 days |
| Alkali resistance | 30 days | 60 days | 60 days | 120 days | 15 days | 50 days |
| Abrasion resistance | 50000 times | 50000 times | 50000 times | 50000 times | 25000 times | 50000 times |
| Artificial ageing resistance | Equal 0 grade of 3500h efflorescence, variable color. | Equal 0 grade of 4000h efflorescence, variable color. | Equal 0 grade of 4000h efflorescence, variable color. | Equal 0 grade of 5000h efflorescence, variable color. | 0 grade of 3000h efflorescence, 1 grade of variable color. | Equal 1 grade of 4000h efflorescence, variable color. |
Detect test
1, Ca
2+Stability: 0.5%CaCl
2, 48h is not stratified, breakdown of emulsion not.
2, mechanical stability: 2500r/min, 0.5h, no abnormal.
3, freeze-thaw stability: (18 ± 2) ℃, 18h; (23 ± 2) ℃, 6h.3 circulations, no abnormal.
4, dilution stability: water dilution (3 ± 0.5) %, 72h, not stratified, breakdown of emulsion not.
5, package stability: (50 ± 2) ℃, 3 months, (23 ± 2) ℃, 3h, no layering, lump and flocculation.
6, the model preparation method is with reference to test preparation of specimen method among the GB/T 9755-2001.
7, water tolerance is undertaken by GB/T 1733-1993 first law regulation.
8, alkali resistance is undertaken by GB/T 9265 regulations.
9, abrasion resistance is undertaken by GB/T 9266 regulations.
10, the artificial ageing resistance property testing is undertaken by GB/T 1865; Result evaluation is undertaken by GB/T 1766.
11, anti-xylol: film with the wiping of dimethylbenzene wetted cotton yarn, until the obvious shedding of paint film.
Claims (10)
1. cross-linked water soluble fluorine resin is characterized in that: water as dispersion medium, fluorinated copolymer as the compound that contains two diazanyls groups in disperse phase and the molecule at least as solidifying agent;
Wherein fluorinated copolymer is to be polymerized by comonomer trifluorochloroethylene, diacetone-acryloamide(DAA), unsaturated carboxylic acid and other the non-fluorine monomers weight part ratio according to 15-50: 1-20: 0.1-10: 20-80.
2, cross-linked water soluble fluorine resin according to claim 1 is characterized in that: solidifying agent is the dicarboxyl acid dihydrazide, as ethylene acid hydrazide, propanedioic acid two hydrazides, succinic acid hydrazide ii or adipic dihydrazide etc.
3, cross-linked water soluble fluorine resin according to claim 1 is characterized in that: the consumption of solidifying agent is the 0.2-15% of fluorinated copolymer weight.
4, cross-linked water soluble fluorine resin according to claim 1 is characterized in that: the comonomer unsaturated carboxylic acid of fluorinated copolymer is:
CH
2＝C(R
1)-R
2-COOH (1)
R wherein
1=CH
3, H, R
2=(CH
2)
n, n=O-6.
5, cross-linked water soluble fluorine resin according to claim 1 is characterized in that: other non-fluorine monomers of fluorinated copolymer comonomer are selected from least a in vinyl ester or vinyl ether or the acrylate monomer.
6, cross-linked water soluble fluorine resin according to claim 1, it is characterized in that: fluorinated copolymer adopts emulsion polymerization to make, and wherein water, comonomer, emulsifying agent, buffer reagent, each ingredients weight parts of initiator are than being water: comonomer: emulsifying agent: buffer reagent: initiator=50-400: 100: 0.5-6: 0.1-5: 0.05-5.
7, cross-linked water soluble fluorine resin according to claim 6 is characterized in that: the copolymerization emulsifying agent is that anionic is or/and nonionic emulsifier; The copolymerization buffer reagent is bicarbonate of ammonia, sodium bicarbonate, yellow soda ash, salt of wormwood, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic; Polymerization initiator is inorganic peroxide, organo-peroxide, persulphate, azo initiator or redox initiator.
8, according to the method for making of the arbitrary described cross-linked water soluble fluorine resin of claim 1-7, it is characterized in that: respectively emulsifying agent, initiator, pH value buffer reagent and deionized water are mixed at first by a certain percentage, standby; Then starting monomer and most of emulsifier aqueous solution are carried out pre-emulsification under mixing is stirred, get pre-emulsified monomer, standby; In withstand voltage reactor, add remaining emulsifier aqueous solution and pH value aqueous solution of buffer agent, outgas, fill N
2After three times, the emulsified monomer that takes a morsel adds in the withstand voltage reactor repeatedly for gas, the degassing, stirs to heat up; Add the part initiator solution when temperature of reaction kettle reaches 50-70 ℃, polymerization begins, and exothermic heat of reaction heats up; After question response is mild, drip residue emulsified monomer and initiator solution simultaneously, in 2-4h, drip, in 72～90 ℃ of scopes of temperature control, after continuing reaction 6h, reaction system is cooled to 30～40 ℃ gets the fluorinated copolymer emulsion, in the fluorinated copolymer emulsion, add aqueous solution of curing agent at last, discharging behind the continuation stirring 15-30min obtains cross-linked water soluble fluorine resin.
9, according to the arbitrary described cross-linked water soluble fluorine resin of claim 1-7, be applied to numerous areas tackiness agents such as building, industry, woodenware, paper, weaving, leather.
10, be applied to onepot coating according to the arbitrary described cross-linked water soluble fluorine resin of claim 1-7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087523A (en) * | 2019-12-31 | 2020-05-01 | 山东华夏神舟新材料有限公司 | Normal-temperature curing fluorocarbon resin emulsion for back plate film and preparation method and application thereof |
| CN112759699A (en) * | 2020-12-25 | 2021-05-07 | 山东华夏神舟新材料有限公司 | Preparation method of high-solid-content water-based crosslinking copolymer emulsion |
| CN114836088A (en) * | 2022-05-18 | 2022-08-02 | 龙牌涂料(北京)有限公司 | Coating composition and preparation method thereof |
-
2006
- 2006-06-02 CN CN 200610046822 patent/CN1861653A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087523A (en) * | 2019-12-31 | 2020-05-01 | 山东华夏神舟新材料有限公司 | Normal-temperature curing fluorocarbon resin emulsion for back plate film and preparation method and application thereof |
| CN111087523B (en) * | 2019-12-31 | 2021-12-07 | 山东华夏神舟新材料有限公司 | Normal-temperature curing fluorocarbon resin emulsion for back plate film and preparation method and application thereof |
| CN112759699A (en) * | 2020-12-25 | 2021-05-07 | 山东华夏神舟新材料有限公司 | Preparation method of high-solid-content water-based crosslinking copolymer emulsion |
| CN114836088A (en) * | 2022-05-18 | 2022-08-02 | 龙牌涂料(北京)有限公司 | Coating composition and preparation method thereof |
| CN114836088B (en) * | 2022-05-18 | 2023-09-19 | 龙牌涂料(北京)有限公司 | Coating composition and preparation method thereof |
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