CN105602411A - Fluorine-containing hydrophobic coating material and preparation method thereof - Google Patents
Fluorine-containing hydrophobic coating material and preparation method thereof Download PDFInfo
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- CN105602411A CN105602411A CN201610201837.1A CN201610201837A CN105602411A CN 105602411 A CN105602411 A CN 105602411A CN 201610201837 A CN201610201837 A CN 201610201837A CN 105602411 A CN105602411 A CN 105602411A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a fluorine-containing hydrophobic coating material and a preparation method thereof and relates to a hydrophobic coating material. The fluorine-containing hydrophobic coating material consists of the following components in parts by mass: 60-80 parts of epoxy resin, 5-15 parts of dendritic fluorine-containing curing agent, 5-15 parts of other curing agents, 10-30 parts of solvent and 1-5 parts of silane coupling agent. The preparation method comprises the following steps: sequentially dissolving the dendritic fluorine-containing curing agent, other curing agents and silane coupling agent in the solvent, and stirring for 0.5-1h; adding the epoxy resin by 4-6 times, and stirring for 1-2h to obtain a uniform sizing material; drying and applying pressure and heating to 140-170 DEG C; and preserving heat for 2-3h to obtain the fluorine-containing hydrophobic coating material. The method is simple, the fluorine content is high, and the surface energy of the coating can be effectively reduced. Amino can react with an epoxy group; and after curing, the fluorine element is introduced into the epoxy resin matrix at an atom level, and the crosslinking density is high. The prepared coating material has the advantages of low curing temperature and short curing time as well as good adhesive property.
Description
Technical field
The present invention relates to hydrophobic coating material, especially relate to a kind of fluorine-containing hydrophobic coating material and preparation method thereof.
Background technology
Rise the nineties in 20th century, and lotus leaf surface structure and performance are imitated in the fast development of Surface Science technology, prepare hydrophobic coating byGradually attract much attention, the lifting of study of surfaces technological means makes hydrophobic material realize suitability for industrialized production becomes possibility. It is current,The suitability for industrialized production that exploration realizes hydrophobic coating remains focus and the difficult point that coating industry faces. In hydrophobic coating field, fluorine unitThe electronegativity maximum of element, the carbon-fluorine bond bond distance that atomic radius is very little, form compared with short, bond energy is large, and fluorine element is introduced to coating materialIn, because fluorine element can move to coating surface, make coating surface there is very low surface energy, have hydrophobic and automatically cleaning merit concurrentlyCan, hydrophobic coating material has become the focus of people's research at present.
Aspect fluorine-containing coat research, (a kind of ultra-amphosphobic polymer and the ultra-amphosphobic surface of constructing thereof, the China such as Hu JiwenPatent, patent publication No.: CN102432742A) containing work after utilizing fluorine-containing siliceous copolymer and silicon dioxide microsphere blendProperty group surface-assembled film forming, give material surface good hydrophobic performance, the method needs blend assembling reaction, technique is multipleAssorted, also require substrate surface to contain active group, therefore do not there is universality. (a kind of preparation of super hydrophobic coating such as Chen EryuMethod and products thereof and application, Chinese patent, patent publication No.: CN104017440A) fluoropolymer breast that reaction is obtainedAfter liquid and polymer emulsion mix, add organic micro-and nano-particles, after diluent dilution, obtain a kind of hydrophobic coating, thoughThe preparation method that so this patent provides is simple, and cost is low, but the physical property of this coating is poor, and solidification temperature is higher.
In dendrimer curing agent field, Su Jiangxun etc. (Su Jiangxun etc. the preparation of epoxy radicals POSS/PAMAM hybrid material andPerformance, fine chemistry industry, 2011,28 (8)) taking 3-glycidyl oxygen propyl trimethoxy silicane (EPTMS) as raw material,The synthetic eight functional group's glycidol ether-polyhedral oligomeric silsesquioxanes (POSS-EP) that obtained, adopted for 4 amino gathering of tree type end in generationAcid amides-amine (PAMAM), as the curing agent of POSS-EP and epoxy resin blend, prepares epoxy radicals POSS/PAMAM hydridizationMaterial, this material has good hot property and mechanical property, but the solidification temperature of this material more than 200 DEG C, hardening timeLong, production cost is higher, is unfavorable for industrial production, and this material does not have hydrophobic performance.
The research that adopts the fluorine-containing curing agent of dendroid to prepare hydrophobic coating material at present there is not yet report.
Summary of the invention
The object of the invention is to provide a kind of fluorine-containing hydrophobic coating material and preparation method thereof.
Described fluorine-containing hydrophobic coating material consisting of in mass ratio: epoxy resin 60～80, the fluorine-containing curing agent 5～15 of dendroid,Other curing agent 5～15, solvent 10～30, silane coupler 1～5.
Described epoxy resin can adopt the compound that contains at least two epoxide groups in molecule, and described epoxy resin can be selected from shrinkOne in glycerin ether, glycidyl amine, ethylene oxidic ester etc.; Described glycidol ether can be selected from bisphenol A-type glycidol ether,One in Bisphenol F type glycidol ether, bisphenol S type glycidol ether etc.; Described glycidyl amine can be selected from aniline glycidolOne in amine, MDA four glycidyl amines etc.; Described ethylene oxidic ester can be selected from 2-glycidyl to (neighbour)One in phthalic acid ester etc.
The structural formula of the fluorine-containing curing agent of described dendroid is as follows:
The fluorine-containing curing agent of described dendroid can adopt following methods preparation:
(1) get acrylic ester monomer to there-necked flask, then ethylenediamine is dissolved in in methyl alcohol, to obtain the methyl alcohol of ethylenediamine moltenLiquid; In ice-water bath, drip the methanol solution of ethylenediamine to there-necked flask, under blanket of nitrogen, stir 0.5～1h; Then heat upTo 30～60 DEG C, in blanket of nitrogen, after stirring reaction 20～50h, decompression distillation, removes methyl alcohol and unreacted methyl acrylate obtainsThe PAMAM of 0.5G; The molar ratio of ethylenediamine, acrylic ester monomer is 1: (4～10);
(2) get the PAMAM of 0.5G and methyl alcohol in there-necked flask, logical nitrogen stir 0.5～1h under ice-water bath, then drips secondDiamines, to there-necked flask, is warming up to after 30～60 DEG C of stirring reaction 20～50h after stirring 0.5～1h, and decompression distillation, removes methyl alcoholObtain the PAMAM of 1.0G with unreacted ethylenediamine; The molar ratio of PAMAM, ethylenediamine is 1: (8～25);
(3) repeating step (1) and (2), obtain the PAMAM of the different algebraically such as 1.5～5.0G;
(4) get the different algebraically such as 1.0～5.0G PAMAM to there-necked flask, drip the methyl alcohol of acrylate containing fluorine monomerSolution (mol ratio, PAMAM: acrylate containing fluorine monomer=1: (1～64)), controls temperature at 30～60 DEG C, and nitrogen is protectedProtect lower stirring reaction 20～25h, then decompression distillation is removed methyl alcohol and is obtained the fluorine-containing curing agent of dendroid.
In step (4), the general structure of described acrylate containing fluorine monomer is CH2＝CRCOO(CH2)mCnF2n(R is H or CH to H3，M >=1, n >=1), described acrylate containing fluorine monomer can be selected from acrylic acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate etc.In one.
Described other curing agent can be selected from aminated compounds or anhydrides compound etc., described aminated compounds can be selected from ethylenediamine,One in diethylenetriamine, m-phenylene diamine (MPD) etc.; Described anhydrides compound can be selected from phthalic anhydride, pyromellitic dianhydride,One in methylcyclohexene tetracarboxylic anhydride etc.
Described solvent can adopt low boiling point solvent, and described solvent can be selected from least one in ethyl acetate, ethanol, acetone etc.
It is Y (CH that described silane coupler can adopt general formula2)nSiX3Silane coupler, wherein, n=0～3; X is chloro, acetylOxygen bases etc., Y is amino or epoxy radicals.
The preparation method of described fluorine-containing hydrophobic coating material is as follows:
Successively fluorine-containing the dendroid of amount of calculation curing agent, other curing agent, silane coupler are dissolved in solvent, stir 0.5～1h,Divide and add epoxy resin 4～6 times, stir 1～2h, obtain uniform sizing material; Dry after-applied pressure and be warming up to 140～170 DEG CInsulation 2～3h, makes fluorine-containing hydrophobic coating material.
The temperature of described oven dry can be 60～70 DEG C, and the time of oven dry can be 1～2h; Described pressure can be 0.5～1MPa.
First the present invention utilizes Michael addition reaction and amidation process to hocket and obtains PAMAM; Secondly by PAMAM with containFluorine monomer carries out Michael addition and obtains the fluorine-containing curing agent of dendroid that required fluorinated volume is high; Finally by curing agent curing cross-linkedEffect, is incorporated into fluorine element in resin base material with atomic level, gives the hydrophobic performance that coating material is good.
Compared with prior art, the present invention has the following advantages:
1) utilize PAMAM dendrimer and acrylate containing fluorine monomer carry out Michael addition obtain dendroid fluorine-containing solidifyAgent, method is simple, and fluorinated volume is high, can effectively reduce the surface energy of coating.
2) amino on the fluorine-containing curing agent of synthetic dendroid can with epoxy reaction, solidify after fluorine element is drawn with atomic levelEnter in epoxy resin-base, and crosslink density is high, improves the mechanical property of coating material.
3) to have solidification temperature low for the fluorine-containing curing agent of dendroid, the advantage that hardening time is short, and the coating material of preparation has goodAdhesive property.
Brief description of the drawings
Fig. 1 is the fluorine-containing curing agent of dendroid1HNMR nuclear magnetic spectrogram.
Fig. 2 is the static contact angle test result figure of the coating material of embodiment 1.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment 1:
(1) preparation of the fluorine-containing curing agent of dendroid
1. get 80 parts of acrylic ester monomers in there-necked flask, get 8 parts of ethylenediamines and be dissolved in the methyl alcohol that obtains ethylenediamine in 80 parts of methyl alcoholSolution; In ice-water bath, drip the methanol solution of ethylenediamine to there-necked flask, under blanket of nitrogen, stir 0.5h; Then heat upTo 35 DEG C, in blanket of nitrogen, after stirring reaction 24h, decompression distillation, removes methyl alcohol and unreacted methyl acrylate obtains 0.5G'sPAMAM；
2. get the PAMAM of 10 parts of 0.5G and 40 parts of methyl alcohol in there-necked flask, logical nitrogen stir 0.5h under ice-water bath, then drips35 parts of ethylenediamines, to there-necked flask, are warming up to after 35 DEG C of stirring reactions 24 after stirring 0.5h, and decompression distillation, removes methyl alcohol and not anti-The ethylenediamine of answering obtains the PAMAM of 1.0G;
3. get the PAMAM of 10 parts of 1.0G to there-necked flask, drip the methanol solution of 35 parts of dodecafluoroheptyl methacrylates, controlTemperature, at 35 DEG C, stops after stirring reaction 24h under nitrogen protection, and decompression distillation removes methyl alcohol and obtains the fluorine-containing curing agent of dendroid, hydrogen spectrum1HNMR characterizes as shown in Figure 1.
(2) preparation of fluorine-containing hydrophobic coating material
Successively by 7 parts of fluorine-containing curing agent of dendroid, 13 part 4,4-MDA, 1 part of aminopropyl triethoxysilane couplingAgent is dissolved in 10 parts of acetone, stirs 0.5h and obtains homogeneous phase solution afterwards, divides and in solution, adds 60 parts of epoxy resin 5 times, stirs fastMix 1h, obtain uniform sizing material. While solidifying, first at 60 DEG C, dry 1h by convection oven, then apply the pressure of 0.5MPa and riseTemperature, to 160 DEG C of insulation 2h, makes fluorine-containing hydrophobic coating material. Utilize contact angle tester to test fluorine-containing hydrophobic coating material and waterContact angle, the results are shown in Figure 2, and contact angle is 108 °.
Embodiment 2:
(1) preparation of the fluorine-containing curing agent of dendroid, with embodiment 1.
(2) preparation of fluorine-containing hydrophobic coating material
Successively by 6 parts of fluorine-containing curing agent of dendroid, 14 part 4,4-MDA, 1 part of aminopropyl triethoxysilane couplingAgent is dissolved in 10 parts of acetone, stirs 0.5h and obtains homogeneous phase solution afterwards, divides and in solution, adds 60 parts of epoxy resin 5 times, stirs 1h,Obtain uniform coating sizing material. While solidifying, first at 60 DEG C, dry 1.5h by convection oven, then apply the pressure of 0.5MPa and riseTemperature, to 160 DEG C of insulation 2h, makes fluorine-containing hydrophobic coating material. Utilize contact angle tester to test fluorine-containing hydrophobic coating material and waterContact angle is 107 °.
Embodiment 3:
(1) the fluorine-containing curing agent of dendroid, with embodiment 1.
(2) preparation of fluorine-containing hydrophobic coating material
Successively by 9 parts of fluorine-containing curing agent of dendroid, 11 part 4,4-MDA, 1 part of aminopropyl triethoxysilane couplingAgent is dissolved in 10 parts of acetone, stirs 0.5h and obtains homogeneous phase solution afterwards, divides and in solution, adds 70 parts of epoxy resin 5 times, stirs 1h,Obtain uniform coating sizing material. While solidifying, first at 60 DEG C, dry 1.5h by convection oven, then apply the pressure of 0.5MPa and riseTemperature, to 150 DEG C of insulation 2h, makes fluorine-containing hydrophobic coating material. Utilize contact angle tester to test fluorine-containing hydrophobic coating material and waterContact angle is 110 °.
Embodiment 4:
(1) preparation of the fluorine-containing curing agent of dendroid, with embodiment 1
(2) preparation of fluorine-containing hydrophobic coating material
Successively by 5 parts of fluorine-containing curing agent of dendroid, 15 part 4,4-MDA, 2 parts of aminopropyl triethoxysilane couplingsAgent is dissolved in 10 parts of acetone, stirs 0.5h and obtains homogeneous phase solution afterwards, divides and in solution, adds 70 parts of epoxy resin 5 times, stirs 1h,Obtain uniform coating sizing material. While solidifying, first at 65 DEG C, dry 2h by convection oven, then apply the pressure of 1.0MPa and heat upTo 170 DEG C of insulation 2h, make fluorine-containing hydrophobic coating material. Utilize contact angle tester to test connecing of fluorine-containing hydrophobic coating material and waterFeeler is 102 °.
The present invention is by changing the fluorine-containing curing agent of dendroid and other curing agent and the mass fraction proportioning of epoxy resin, preparation oneThe different hydrophobic coating material of series fluorine content. The fluorine-containing curing agent of dendroid has that preparation method is simple, reaction condition is gentle fluorine-containingMeasure high advantage; And by the effect of curing agent curing cross-linked, fluorine element is incorporated in resin base material with atomic level, makes to be coated withLayer material has low surface energy, reaches hydrophobic effect, thereby has a wide range of applications in hydrophobic material field.
Claims (10)
1. a fluorine-containing hydrophobic coating material, is characterized in that its consisting of in mass ratio: epoxy resin 60～80, dendroidFluorine-containing curing agent 5～15, other curing agent 5～15, solvent 10～30, silane coupler 1～5.
2. a kind of fluorine-containing hydrophobic coating material as claimed in claim 1, it is characterized in that described epoxy resin adopts in molecule containsThe compound of at least two epoxide groups, described epoxy resin can be selected from glycidol ether, glycidyl amine, ethylene oxidic esterOne; Described glycidol ether can be selected from bisphenol A-type glycidol ether, Bisphenol F type glycidol ether, bisphenol S type and shrink sweetOne in oil ether; Described glycidyl amine can be selected from aniline glycidyl amine, MDA four glycidyl aminesA kind of; Described ethylene oxidic ester can be selected from 2-glycidyl to the one in (neighbour) phthalic acid ester.
3. a kind of fluorine-containing hydrophobic coating material as claimed in claim 1, is characterized in that the structure of the fluorine-containing curing agent of described dendroidFormula is as follows:
4. a kind of fluorine-containing hydrophobic coating material as claimed in claim 1, it is characterized in that the fluorine-containing curing agent of described dendroid adopt withBelow legal system is standby:
(1) get acrylic ester monomer to there-necked flask, then ethylenediamine is dissolved in in methyl alcohol, to obtain the methyl alcohol of ethylenediamine moltenLiquid; In ice-water bath, drip the methanol solution of ethylenediamine to there-necked flask, under blanket of nitrogen, stir 0.5～1h; Then heat upTo 30～60 DEG C, in blanket of nitrogen, after stirring reaction 20～50h, decompression distillation, removes methyl alcohol and unreacted methyl acrylate obtainsThe PAMAM of 0.5G; The molar ratio of ethylenediamine, acrylic ester monomer is 1: (4～10);
(2) get the PAMAM of 0.5G and methyl alcohol in there-necked flask, logical nitrogen stir 0.5～1h under ice-water bath, then drips secondDiamines, to there-necked flask, is warming up to after 30～60 DEG C of stirring reaction 20～50h after stirring 0.5～1h, and decompression distillation, removes methyl alcoholObtain the PAMAM of 1.0G with unreacted ethylenediamine; The molar ratio of PAMAM, ethylenediamine is 1: (8～25);
(3) repeating step (1) and (2), obtain the PAMAM of the different algebraically of 1.5～5.0G;
(4) get the different algebraically of 1.0～5.0G PAMAM to there-necked flask, the methyl alcohol that drips acrylate containing fluorine monomer is moltenLiquid (mol ratio, PAMAM: acrylate containing fluorine monomer=1: (1～64)), controls temperature at 30～60 DEG C, nitrogen protectionLower stirring reaction 20～25h, then decompression distillation is removed methyl alcohol and is obtained the fluorine-containing curing agent of dendroid.
5. a kind of fluorine-containing hydrophobic coating material as claimed in claim 4, is characterized in that in step (4) described fluorine-containing propeneThe general structure of esters of gallic acid monomer is CH2＝CRCOO(CH2)mCnF2nH, wherein R is H or CH3, m >=1, n >=1, described fluorine-containing propeneEsters of gallic acid monomer can be selected from the one in acrylic acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate.
6. a kind of fluorine-containing hydrophobic coating material as claimed in claim 1, is characterized in that described other curing agent are selected from amine chemical combinationThing or anhydrides compound, described aminated compounds can be selected from the one in ethylenediamine, diethylenetriamine, m-phenylene diamine (MPD); DescribedAnhydrides compound can be selected from the one in phthalic anhydride, pyromellitic dianhydride, methylcyclohexene tetracarboxylic anhydride.
7. a kind of fluorine-containing hydrophobic coating material as claimed in claim 1, is characterized in that described solvent can adopt low boiling point solvent,Described solvent is selected from least one in ethyl acetate, ethanol, acetone.
8. a kind of fluorine-containing hydrophobic coating material as claimed in claim 1, is characterized in that described silane coupler adopts general formula to beY(CH2)nSiX3Silane coupler, wherein, n=0～3; X is chloro, acetoxyl group, and Y is amino or epoxy radicals.
9. the preparation method of fluorine-containing hydrophobic coating material as claimed in claim 1, is characterized in that its concrete steps are as follows:
Successively fluorine-containing the dendroid of amount of calculation curing agent, other curing agent, silane coupler are dissolved in solvent, stir 0.5～1h,Divide and add epoxy resin 4～6 times, stir 1～2h, obtain uniform sizing material; Dry after-applied pressure and be warming up to 140～170 DEG CInsulation 2～3h, makes fluorine-containing hydrophobic coating material.
10. the preparation method of fluorine-containing hydrophobic coating material as claimed in claim 9, the temperature that it is characterized in that described oven dry is 60～70 DEG C, the time of oven dry is 1～2h; Described pressure can be 0.5～1MPa.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106592333A (en) * | 2016-11-28 | 2017-04-26 | 浙江大胜达包装有限公司 | Preparation method of hydrophobic and oleophobic paper packaging material |
| CN106592332A (en) * | 2016-11-28 | 2017-04-26 | 浙江大胜达包装有限公司 | Preparing method of fluorine-containing waterproof paper packaging material |
| CN106758527A (en) * | 2016-11-28 | 2017-05-31 | 浙江大胜达包装有限公司 | The preparation method of super-hydrophobic paper wrapper |
| WO2019080287A1 (en) * | 2017-10-24 | 2019-05-02 | 南方科技大学 | Transparent hydrophobic wear-resistant coating and preparation method therefor |
| CN110098352A (en) * | 2019-05-17 | 2019-08-06 | 合肥京东方卓印科技有限公司 | Define solution, display base plate, display device and preparation pixel defining layer method |
| CN110922862A (en) * | 2019-12-18 | 2020-03-27 | 湖南科技大学 | Nano SiO2Preparation method of modified epoxy resin super-hydrophobic coating material |
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| CN106592333A (en) * | 2016-11-28 | 2017-04-26 | 浙江大胜达包装有限公司 | Preparation method of hydrophobic and oleophobic paper packaging material |
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| CN110922862A (en) * | 2019-12-18 | 2020-03-27 | 湖南科技大学 | Nano SiO2Preparation method of modified epoxy resin super-hydrophobic coating material |
| CN113072854A (en) * | 2021-03-30 | 2021-07-06 | 天津日津科技股份有限公司 | Fluorine modified epoxy resin composite coating and preparation method thereof |
| CN115197636A (en) * | 2022-07-07 | 2022-10-18 | 西安文理学院 | Hydrophobic and oleophobic coating material and preparation method thereof |
| CN115121046A (en) * | 2022-08-25 | 2022-09-30 | 中国船舶重工集团公司第七0七研究所 | Gas-water separation filter material and preparation method thereof |
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