CN106366294A - Fluorine-containing hydrophobic epoxy curing agent and preparation method thereof - Google Patents
Fluorine-containing hydrophobic epoxy curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN106366294A CN106366294A CN201610863916.9A CN201610863916A CN106366294A CN 106366294 A CN106366294 A CN 106366294A CN 201610863916 A CN201610863916 A CN 201610863916A CN 106366294 A CN106366294 A CN 106366294A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- containing hydrophobic
- hydrophobic epoxy
- epoxy hardener
- fluoro
- 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
- 0 CC(CSCCCCCCS)C(OCCC(C(C(*C1(C(F)(F)F)F)(C1(F)F)F)(F)F)(F)F)=O Chemical compound CC(CSCCCCCCS)C(OCCC(C(C(*C1(C(F)(F)F)F)(C1(F)F)F)(F)F)(F)F)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
Abstract
Disclosed are a fluorine-containing hydrophobic epoxy curing agent and a preparation method thereof. The method performs an addition reaction on fluorine-containing acrylate monomer containing a C = C double bond and a polythiol compound under the condition of a catalyst, and includes steps of (1), dissolving the polythiol compound in ethanol in a mass ratio (1: 3 to 1: 1), adding the ethanol mixture to a three-necked flask equipped with a reflux condenser and a thermometer, and mechanically stirring; (2), adding the fluorine-containing acrylate monomer in the same molar weight as the polythiol compound, and catalyst of 0.67% of the total mass; (3), heating under stirring, and terminating the reaction when the mercapto content is reduced to half the amount of the addition; (4) depressurizing and distilling the reaction mixed solution at -0.09 MPa and 90 DEG C to remove the solvent to obtain the fluorine-containing hydrophobic epoxy curing agent. The hydrophobic property of the epoxy resin cured product is remarkably improved by using the product of the present invention as a curing component.
Description
Technical field
The invention belongs to chemical synthesis technical field, particularly to the fluorine-containing hydrophobic epoxy hardener of one kind and its preparation
Method.
Background technology
Epoxy resin because its shrinkage factor is little, caking property is good, intensity is high, good mechanical property the advantages of, be widely used in
High-performance coating, ink, binding agent and composite.But there is not high hydrophobic group in the chemical constitution of epoxy resin itself
Group, the water contact angle of its solidfied material is not typically high.So wanting to obtain hydrophobic epoxy curing compound to be accomplished by by chemical modification
Method hydrophobic group is incorporated in epoxy curing systems.
The c-f bond energy of fluoropolymer is big, polarizability is low, and organofluorine compound has excellent chemical stability, low table
The features such as face energy and self-lubricating.With fluoropolymer as curing agent component, can largely improve epoxy curing compound
Hydrophobicity.Existing fluorine-containing hydrophobic epoxy hardener species on the market is very rare, and the content of fluorine element is very low, in molecule
Position in structure can not show hydrophobic property well, so be directed to the fluorine-containing hydrophobic firming agent of epoxy resin special-purpose
Research and development do not have practical development.
Content of the invention
In order to overcome the defect of above-mentioned prior art, it is an object of the invention to provide a kind of fluorine-containing hydrophobic epoxy hardener
And preparation method thereof, this firming agent had both contained fluorin radical, contains again and can participate in asphalt mixtures modified by epoxy resin with the sulfydryl of epoxy reaction
The curing reaction of fat, is made its component move to cured product surface using the distinctive low surface free energy of fluorin radical, is reduced with this
Material surface tension, obtains good hydrophobic performance.
In order to achieve the above object, the purpose of the present invention is achieved through the following technical solutions:
A kind of fluorine-containing hydrophobic epoxy hardener, its structural formula is:
Wherein, r1For-(chx) n-, wherein n is 1～10 natural number, and x is 0～2 natural number, and m is 1～3 nature
Number；r2For h or-ch3,rfFor the fluoro-alkyl for c1～c10 for the carbon chain lengths, the hydrogen that fluoro-alkyl refers in alkyl chain is former
Son is by some or all of displacement of fluorine atom.
Based on a kind of above-mentioned preparation method of fluorine-containing hydrophobic epoxy hardener, comprise the following steps:
Step (1), by many sulfhydryl compounds 1:(1～3 in mass ratio) be dissolved in ethanol, be added to and reflux condensation mode be installed
In the there-necked flask of thermometer, mechanical agitation；
Step (2), add and the fluoro-acrylate monomer of many sulfhydryl compounds equal molar amount and account for gross mass 0.67%
Catalyst；
Reacting by heating under step (3), stirring condition, when sulfhydryl content is down to the half of addition, reaction terminates；
Step (4), by reaction mixture in -0.09mpa, 90 DEG C of vacuum distillations, remove solvent, obtain fluorine-containing hydrophobic epoxy
Firming agent；
Many sulfhydryl compounds described in step (1) are ethanthiol, dithioglycol and succinimide mercaptans, tri-thiol methyl-prop
At least one in alkane, Ji Wusi mercaptan.
Fluoro-acrylate monomer described in step (2) is preferably trifluoroethyl methacrylate, methacrylic acid hexafluoro
In isopropyl ester, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester, methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester at least
A kind of.
Catalyst described in step (2) is diethylamine, triethylamine, at least one in diethanolamine.
The present invention, with respect to prior art, has such advantages as and effect:
(1) present invention adopts the click-reaction of sulfydryl and double bond, has conveniently synthesized and has had fluorine-containing hydrophobic epoxy admittedly
Agent.
(2) the fluorine-containing sulfydryl epoxy hardener that the present invention is obtained, participates in Curing Process of Epoxy by the sulfydryl of end,
Make the grafting that fluoro-containing group and epoxy resin are realized on molecular level, play the hydrophobic effect of fluoro-containing group to greatest extent.
(3) the hydrophobic epoxy hardener obtaining is participated in cure test as one of the component of epoxy hardener by the present invention,
Obtain epoxy resin cured product；Water contact angle performance test is carried out to solidfied material, obtains a series of contact angular data, contact angle
Data is all higher than 90 °, illustrates that hydrophobicity is good.
Brief description
Fig. 1 is the nmr spectrum of embodiment monomethyl dodecafluorhe-ptylacrylate and the addition compound product of dithioglycol.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Test mode: contact angle instrument measures contact angle；Measure sulfhydryl content by gb/t1677-2008.
Embodiment one
The fluorine-containing hydrophobic epoxy hardener of one kind manufactured in the present embodiment, its general structure is expressed as:
The preparation method of the present embodiment, comprises the following steps:
Step (1), dithioglycol 9.42g is dissolved in 10g ethanol, is added to equipped with reflux condensation mode, thermometer, machinery stirs
In the there-necked flask mixed, mechanical agitation；
Step (2), stir after toward in system add 0.40g triethylamine as catalyst, by methacrylic acid 12
Fluorine heptyl ester 40g constant pressure funnel is to Deca in system；
Reacting by heating under step (3), stirring condition, when sulfhydryl content is down to the half of addition, reaction terminates；
Step (4), by reaction mixture in -0.09mpa, 90 DEG C of vacuum distillations, remove solvent, obtain fluorine-containing hydrophobic epoxy
Firming agent.
Involved chemical equation is as follows:
Structural analyses: the nuclear magnetic resoance spectrum being dodecafluoroheptyl methacrylate and the addition compound product of dithioglycol as Fig. 1
Figure it is shown that the proton signal (1.26-1.29ppm) of obvious sulfydryl, meanwhile, c=c double bond peak at 5.76-6.11ppm
It is wholly absent, illustrate target product has been synthesized.
Solidification effect: 27g tri-thiol firming agent (laboratory self-control), curing catalysts dmp-30,3g the present embodiment of 1g
The fluorine-containing hydrophobic epoxy hardener of preparation and the filler Colophonium mix homogeneously of 13g, then mix all with 25g epoxy resin e44
Even, with solidification 6h under room temperature, obtain epoxy resin cured product, its contact angle is 93 °.
Embodiment two
The fluorine-containing hydrophobic epoxy hardener of one kind manufactured in the present embodiment, its general structure is expressed as:
The preparation method of the present embodiment, comprises the following steps:
Step (1), ethanthiol 15g is dissolved in 30g ethanol, is added to equipped with reflux condensation mode, thermometer, mechanical agitation
There-necked flask in, mechanical agitation；
Step (2), stir after toward in system add 0.59g triethylamine as catalyst, by methacrylic acid 13
Fluorine monooctyl ester 43.2g, with constant pressure funnel to Deca in system；
Reacting by heating under step (3), stirring condition, when sulfhydryl content is down to the half of addition, reaction terminates；
Step (4), by reaction mixture in -0.09mpa, 90 DEG C of vacuum distillations, remove solvent, obtain fluorine-containing hydrophobic epoxy
Firming agent.
Involved chemical equation is as follows:
Solidification effect: 28g tri-thiol firming agent (laboratory self-control), curing catalysts dmp-30,3g the present embodiment of 1g
The fluorine-containing sulfydryl firming agent of preparation and the filler Colophonium mix homogeneously of 12g, then mix homogeneously with 25g epoxy resin e44, with
Solidify 6h under room temperature, obtain epoxy resin cured product, its contact angle is 95 °.
Embodiment three
The fluorine-containing hydrophobic epoxy hardener of one kind manufactured in the present embodiment, its general structure is expressed as:
The preparation method of the present embodiment, comprises the following steps:
Step (1), dithioglycol 9.42g is dissolved in 30g ethanol, is added to equipped with reflux condensation mode, thermometer, machinery stirs
In the there-necked flask mixed, mechanical agitation；
Step (2), stir after toward in system add 0.62g triethylamine as catalyst, by methacrylic acid 17
Fluorine certain herbaceous plants with big flowers ester 53.2g, with constant pressure funnel to Deca in system；
Reacting by heating under step (3), stirring condition, when sulfhydryl content is down to the half of addition, reaction terminates；
Step (4), by reaction mixture in -0.09mpa, 90 DEG C of vacuum distillations, remove solvent, obtain fluorine-containing hydrophobic epoxy
Firming agent.
Involved chemical equation is as follows:
Solidification effect: 30g tri-thiol firming agent (laboratory self-control), curing catalysts dmp-30,2g the present embodiment of 1g
The fluorine-containing sulfydryl firming agent of preparation and the filler Colophonium mix homogeneously of 17g, then mix homogeneously with 25g epoxy resin e44, with
Solidify 6h under room temperature, obtain epoxy resin cured product, its contact angle is 95 °.
Claims (5)
1. a kind of fluorine-containing hydrophobic epoxy hardener is it is characterised in that its structural formula is:
Wherein, r1For-(chx) n-, wherein n is 1～10 natural number, and x is 0～2 natural number, and m is 1～3 natural number；r2
For h or-ch3,rfFor the fluoro-alkyl for c1～c10 for the carbon chain lengths, fluoro-alkyl refers to hydrogen atom in alkyl chain by fluorine
Atomic component or whole displacement.
2. the synthetic method based on a kind of fluorine-containing hydrophobic epoxy hardener described in claim 1 is it is characterised in that include following
Step:
Step (1), many sulfhydryl compounds (1:3～1:1) in mass ratio are dissolved in ethanol, be added to be provided with reflux condensation mode and
In the there-necked flask of thermometer, mechanical agitation；
Step (2), add and the fluoro-acrylate monomer of many sulfhydryl compounds equal molar amount and account for gross mass 0.67% and be catalyzed
Agent；
Reacting by heating under step (3), stirring condition, when sulfhydryl content is down to the half of addition, reaction terminates；
Step (4), by reaction mixture in -0.09mpa, 90 DEG C of vacuum distillations, remove solvent, obtain fluorine-containing hydrophobic curable epoxide
Agent.
3. a kind of synthetic method of fluorine-containing hydrophobic epoxy hardener according to claim 2 is it is characterised in that step (1)
Described in many sulfhydryl compounds be ethanthiol, in dithioglycol and succinimide mercaptans, tri-thiol methylpropane, Ji Wusi mercaptan
At least one.
4. a kind of synthetic method of fluorine-containing hydrophobic epoxy hardener according to claim 2 is it is characterised in that step (2)
Described in fluoro-acrylate monomer be trifluoroethyl methacrylate, methacrylic acid hexafluoro isopropyl ester, methacrylic acid ten
At least one in difluoro heptyl ester, methacrylic acid ten trifluoro monooctyl ester, methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester.
5. a kind of synthetic method of fluorine-containing hydrophobic epoxy hardener according to claim 2 is it is characterised in that step (2)
Described in catalyst be diethylamine, triethylamine, at least one in diethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610863916.9A CN106366294B (en) | 2016-09-29 | 2016-09-29 | Fluorine-containing hydrophobic epoxy hardener of one kind and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610863916.9A CN106366294B (en) | 2016-09-29 | 2016-09-29 | Fluorine-containing hydrophobic epoxy hardener of one kind and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106366294A true CN106366294A (en) | 2017-02-01 |
| CN106366294B CN106366294B (en) | 2018-11-09 |
Family
ID=57898109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610863916.9A Active CN106366294B (en) | 2016-09-29 | 2016-09-29 | Fluorine-containing hydrophobic epoxy hardener of one kind and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106366294B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111356714A (en) * | 2017-09-27 | 2020-06-30 | 阿科玛股份有限公司 | Addition and condensation polymers prepared from halogenated reactants |
| CN112795012A (en) * | 2020-12-30 | 2021-05-14 | 江苏富琪森新材料有限公司 | Emulsion type waterborne epoxy curing agent and preparation method and application thereof |
| CN113122133A (en) * | 2021-04-15 | 2021-07-16 | 上海大学 | Dynamic hydrophobic and oleophobic coating, preparation method, use method and dynamic hydrophobic and oleophobic coating |
| CN114890927A (en) * | 2021-06-03 | 2022-08-12 | 深圳飞扬兴业科技有限公司 | Epoxy resin curing agent, preparation method thereof and epoxy adhesive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482529A (en) * | 2010-02-10 | 2012-05-30 | 乐金华奥斯有限公司 | Resin composite for forming hard coat layer |
| CN102516912A (en) * | 2011-11-30 | 2012-06-27 | 安徽中铁工程材料科技有限公司 | Method for preparing composite curing agent modified bisphenol F thermosetting adhesive repairing agent special for ballastless track gap and crack damage |
| CN102911344A (en) * | 2012-10-18 | 2013-02-06 | 铜陵市陵阳化工有限责任公司 | Preparation method of cationic acrylate epoxy resin |
-
2016
- 2016-09-29 CN CN201610863916.9A patent/CN106366294B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482529A (en) * | 2010-02-10 | 2012-05-30 | 乐金华奥斯有限公司 | Resin composite for forming hard coat layer |
| CN102516912A (en) * | 2011-11-30 | 2012-06-27 | 安徽中铁工程材料科技有限公司 | Method for preparing composite curing agent modified bisphenol F thermosetting adhesive repairing agent special for ballastless track gap and crack damage |
| CN102911344A (en) * | 2012-10-18 | 2013-02-06 | 铜陵市陵阳化工有限责任公司 | Preparation method of cationic acrylate epoxy resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111356714A (en) * | 2017-09-27 | 2020-06-30 | 阿科玛股份有限公司 | Addition and condensation polymers prepared from halogenated reactants |
| 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 |
| CN112795012A (en) * | 2020-12-30 | 2021-05-14 | 江苏富琪森新材料有限公司 | Emulsion type waterborne epoxy curing agent and preparation method and application thereof |
| CN113122133A (en) * | 2021-04-15 | 2021-07-16 | 上海大学 | Dynamic hydrophobic and oleophobic coating, preparation method, use method and dynamic hydrophobic and oleophobic coating |
| CN114890927A (en) * | 2021-06-03 | 2022-08-12 | 深圳飞扬兴业科技有限公司 | Epoxy resin curing agent, preparation method thereof and epoxy adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106366294B (en) | 2018-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106366294A (en) | Fluorine-containing hydrophobic epoxy curing agent and preparation method thereof | |
| CN103739827B (en) | Resin combination | |
| CN102898932A (en) | Composite ultraviolet-curing coating containing vinyl-terminated fluorinated alkyl ester polymer, its preparation and application | |
| CN103936996B (en) | Synthesis of photo-cured fluorosilicone polymer and preparation method of photo-cured fluorosilicone polymer coating | |
| CN104761994A (en) | Preparation method of photocuring organic silicon modified epoxy resin paint film | |
| CN102516326B (en) | Method for synthesizing tannin-based hyperbranched acrylic acid ester | |
| CN103274955B (en) | Containing the synthetic method of the betaine type amphoteric ionic compound of reactive group | |
| CN105001088B (en) | Method for preparing all-bio-based photocuring activated monomer and application of all-bio-based photocuring activated monomer | |
| CN110016311A (en) | A kind of fast-curing epoxy resin adhesive and preparation method thereof | |
| RU2012155687A (en) | CURING COMPOSITIONS | |
| CN107089914A (en) | A kind of cashew nut phenolic group acrylate reactive diluent and its preparation method and application | |
| CN109776419A (en) | Sulfosalt and its preparation method and application containing pyrazoline group | |
| CN107868243A (en) | The preparation method of the phosphorous acid water reducer of one derived from amino acid | |
| KR101733075B1 (en) | Method for producing compound containing bis(perfluoroalkylsulfonyl)methyl group and salt thereof, and solid electrolyte membrane produced using same | |
| CN109912544A (en) | A method of bis- ((3,4- epoxycyclohexyl) methyl) adipate esters are prepared with micro passage reaction | |
| CN102875777B (en) | Novel epoxy hardener and preparation method thereof | |
| CN104877111B (en) | A kind of normal temperature solidified fluorine-containing epoxy hardener and its preparation and application | |
| CN108530421A (en) | The novel polyaryl sulphur salt compounds and the preparation method and application thereof containing dibenzothiophenes | |
| CN104844783A (en) | Fluorine-containing normal-temperature epoxy curing agent of block structure as well as preparation method and application of curing agent | |
| CN105085335A (en) | Method for preparing 3-mercapto-propionate | |
| JP2014201534A (en) | Silicon compound | |
| CN103387238A (en) | Preparation technology of Ethyl-bridged functionalized ordered mesoporous PMO | |
| CN101759670B (en) | Perfluoroalkoxy epoxy compound, preparation method and purpose thereof | |
| CN104744253A (en) | Tung oil based alkyd resin with side chain containing fluorocarbon and preparation method thereof | |
| CN106699939B (en) | A kind of Amino End Group fluorinated acrylate prepolymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |