CN106366294B - Fluorine-containing hydrophobic epoxy hardener of one kind and preparation method thereof - Google Patents
Fluorine-containing hydrophobic epoxy hardener of one kind and preparation method thereof Download PDFInfo
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- CN106366294B CN106366294B CN201610863916.9A CN201610863916A CN106366294B CN 106366294 B CN106366294 B CN 106366294B CN 201610863916 A CN201610863916 A CN 201610863916A CN 106366294 B CN106366294 B CN 106366294B
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- fluorine
- containing hydrophobic
- epoxy hardener
- sulfhydryl
- hydrophobic epoxy
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Classifications
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- 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
Fluorine-containing hydrophobic epoxy hardener of one kind and preparation method thereof, it is with more sulfhydryl compounds under catalysts conditions by the fluorinated acrylate monomer of the double bond containing C=C, and progress addition reaction forms, and preparation method is：Step (1), by more sulfhydryl compounds in mass ratio (1:3~1:1) it is dissolved in ethyl alcohol, is added in the three-necked flask for being equipped with reflux condensation mode and thermometer, mechanical agitation；Step (2) is added the fluoro-acrylate monomer with more sulfhydryl compound equal molar amounts and accounts for 0.67% catalyst of gross mass；Reaction is heated under step (3), stirring condition, when sulfhydryl content is down to the half of additive amount, reaction terminates；Step (4), by reaction mixture in -0.09MPa, 90 DEG C of vacuum distillations remove solvent, obtain fluorine-containing hydrophobic epoxy hardener；Using products therefrom of the present invention as curing component, the hydrophobic performance of epoxy resin-cured product significantly improves.
Description
Technical field
The invention belongs to chemical synthesis technical field, more particularly to a kind of fluorine-containing hydrophobic epoxy hardener and its preparation
Method.
Background technology
Epoxy resin is widely used in because of the advantages that its shrinking percentage is small, caking property is good, intensity is high, good mechanical property
High-performance coating, ink, adhesive and composite material.But in the chemical constitution of epoxy resin itself and high hydrophobic group is not present
Group, the water contact angle of solidfied material be not generally high.It just needs to pass through chemical modification so wanting to obtain hydrophobic epoxy curing compound
Method hydrophobic grouping is introduced into epoxy curing systems.
Fluoropolymer-containing C-F bond energys are big, polarizability is low, and organofluorine compound possesses excellent chemical stability, low table
The features such as face energy and self-lubricating.It uses fluoropolymer as curing agent component, can largely improve epoxy curing compound
Hydrophobicity.Existing fluorine-containing hydrophobic epoxy hardener type on the market is very rare, and the content of fluorine element is very low, in molecule
Position in structure cannot show hydrophobic property well, so be directed to the fluorine-containing hydrophobic curing agent of epoxy resin special-purpose
There is no practical developments for research and development.
Invention content
In order to overcome the defect of the above-mentioned prior art, the purpose of the present invention is to provide a kind of fluorine-containing hydrophobic epoxy hardeners
And preparation method thereof, which not only contains fluorin radical, but also contains 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, is reduced with this using the distinctive low surface free energy of fluorin radical
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, structural formula are:
Wherein, R1For-(CHx) n-, the natural number that wherein n is 1~10, the natural number that x is 0~2, the nature that m is 1~3
Number；R2For H or-CH3,RfThe fluoro-alkyl for being C1~C10 for carbon chain lengths, fluoro-alkyl refer to the original of the hydrogen in alkyl chain
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, include the following steps：
Step (1), by more sulfhydryl compounds in mass ratio 1:(1~3) is dissolved in ethyl alcohol, is added to and is equipped with reflux condensation mode
In the three-necked flask of thermometer, mechanical agitation；
Step (2) is added the fluoro-acrylate monomer with more sulfhydryl compound equal molar amounts and accounts for gross mass 0.67%
Catalyst；
Reaction is heated under step (3), stirring condition, when sulfhydryl content is down to the half of additive amount, reaction terminates；
Step (4), by reaction mixture in -0.09MPa, 90 DEG C of vacuum distillations remove solvent, obtain fluorine-containing hydrophobic epoxy
Curing agent；
More sulfhydryl compounds described in step (1) are ethanthiol, dithioglycol and succinimide mercaptans, tri-thiol methyl-prop
At least one of alkane, Ji Wusi mercaptan.
Fluoro-acrylate monomer described in step (2) is preferably trifluoroethyl methacrylate, methacrylic acid hexafluoro
In isopropyl ester, dodecafluoroheptyl methacrylate, ten trifluoro monooctyl ester of methacrylic acid, 17 fluorine certain herbaceous plants with big flowers ester of methacrylic acid at least
It is a kind of.
Catalyst described in step (2) is diethylamine, triethylamine, at least one of diethanol amine.
The present invention compared with the existing technology, has the following advantages and effect：
(1) present invention uses the click-reaction of sulfydryl and double bond, has conveniently synthesized solid with fluorine-containing hydrophobic epoxy
Agent.
(2) fluorine-containing sulfydryl epoxy hardener produced by the present invention participates in Curing Process of Epoxy by the sulfydryl of end,
So that fluoro-containing group is realized the grafting on molecular level with epoxy resin, plays the hydrophobic effect of fluoro-containing group to greatest extent.
(3) obtained hydrophobic epoxy hardener is participated in cure test 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 are all higher than 90 °, illustrate that hydrophobicity is good.
Description of the drawings
Fig. 1 is the nmr spectrum of the addition compound product of embodiment monomethyl dodecafluorhe-ptylacrylate and dithioglycol.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Test mode：Contact angle instrument measures contact angle；Sulfhydryl content is measured by GB/T1677-2008.
Embodiment one
The fluorine-containing hydrophobic epoxy hardener of one kind manufactured in the present embodiment, general structure are expressed as：
The preparation method of the present embodiment, includes the following steps:
Dithioglycol 9.42g is dissolved in 10g ethyl alcohol by step (1), is added to equipped with reflux condensation mode, thermometer, machinery stirs
In the three-necked flask mixed, mechanical agitation；
0.40g triethylamines are added into system after stirring evenly as catalyst, by methacrylic acid 12 for step (2)
Fluorine heptyl ester 40g is added dropwise with constant pressure funnel into system；
Reaction is heated under step (3), stirring condition, when sulfhydryl content is down to the half of additive amount, reaction terminates；
Step (4), by reaction mixture in -0.09MPa, 90 DEG C of vacuum distillations remove solvent, obtain fluorine-containing hydrophobic epoxy
Curing agent.
Involved chemical equation is as follows：
Structural analysis：Such as the nuclear magnetic resoance spectrum for the addition compound product that Fig. 1 is dodecafluoroheptyl methacrylate and dithioglycol
Figure, it is shown that the proton signal (1.26-1.29ppm) of apparent sulfydryl, meanwhile, the C=C double bonds peak at 5.76-6.11ppm
It completely disappears, illustrates that reaction has synthesized target product.
Solidification effect：Curing catalysts DMP-30,3g the present embodiment of 27g tri-thiols curing agent (laboratory self-control), 1g
The filler pitch of the fluorine-containing hydrophobic epoxy hardener and 13g that prepare is uniformly mixed, then is mixed with 25g epoxy resin E44
It is even, and cure 6h at room temperature, obtain epoxy resin cured product, contact angle is 93 °.
Embodiment two
The fluorine-containing hydrophobic epoxy hardener of one kind manufactured in the present embodiment, general structure are expressed as：
The preparation method of the present embodiment, includes the following steps:
Ethanthiol 15g is dissolved in 30g ethyl alcohol by step (1), is added to equipped with reflux condensation mode, thermometer, mechanical agitation
Three-necked flask in, mechanical agitation；
0.59g triethylamines are added into system after stirring evenly as catalyst, by methacrylic acid 13 for step (2)
Fluorine monooctyl ester 43.2g is added dropwise with constant pressure funnel into system；
Reaction is heated under step (3), stirring condition, when sulfhydryl content is down to the half of additive amount, reaction terminates；
Step (4), by reaction mixture in -0.09MPa, 90 DEG C of vacuum distillations remove solvent, obtain fluorine-containing hydrophobic epoxy
Curing agent.
Involved chemical equation is as follows：
Solidification effect：Curing catalysts DMP-30,3g the present embodiment of 28g tri-thiols curing agent (laboratory self-control), 1g
The filler pitch of the fluorine-containing sulfydryl curing agent and 12g that prepare is uniformly mixed, then is uniformly mixed with 25g epoxy resin E44, with
Cure 6h at room temperature, obtain epoxy resin cured product, contact angle is 95 °.
Embodiment three
The fluorine-containing hydrophobic epoxy hardener of one kind manufactured in the present embodiment, general structure are expressed as：
The preparation method of the present embodiment, includes the following steps:
Dithioglycol 9.42g is dissolved in 30g ethyl alcohol by step (1), is added to equipped with reflux condensation mode, thermometer, machinery stirs
In the three-necked flask mixed, mechanical agitation；
0.62g triethylamines are added into system after stirring evenly as catalyst, by methacrylic acid 17 for step (2)
Fluorine certain herbaceous plants with big flowers ester 53.2g, is added dropwise with constant pressure funnel into system；
Reaction is heated under step (3), stirring condition, when sulfhydryl content is down to the half of additive amount, reaction terminates；
Step (4), by reaction mixture in -0.09MPa, 90 DEG C of vacuum distillations remove solvent, obtain fluorine-containing hydrophobic epoxy
Curing agent.
Involved chemical equation is as follows：
Solidification effect：Curing catalysts DMP-30,2g the present embodiment of 30g tri-thiols curing agent (laboratory self-control), 1g
The filler pitch of the fluorine-containing sulfydryl curing agent and 17g that prepare is uniformly mixed, then is uniformly mixed with 25g epoxy resin E44, with
Cure 6h at room temperature, obtain epoxy resin cured product, contact angle is 95 °.
Claims (5)
1. a kind of fluorine-containing hydrophobic epoxy hardener, which is characterized in that its structural formula is:
Wherein, R1For-(CHx) n-, the natural number that wherein n is 1~10, the natural number that x is 0~2, the natural number that m is 1~3；R2
For H or-CH3,RfThe fluoro-alkyl for being C1~C10 for carbon chain lengths, fluoro-alkyl refer to the hydrogen atom in alkyl chain by fluorine
Atomic component or all displacement.
2. based on a kind of synthetic method of fluorine-containing hydrophobic epoxy hardener described in claim 1, which is characterized in that including following
Step：
Step (1), by more sulfhydryl compounds in mass ratio 1:3~1:1 is dissolved in ethyl alcohol, is added to and is equipped with reflux condensation mode and temperature
It spends in the three-necked flask of meter, mechanical agitation；
Step (2) is added the fluoro-acrylate monomer with more sulfhydryl compound equal molar amounts and accounts for the catalysis of gross mass 0.67%
Agent；
Reaction is heated under step (3), stirring condition, when sulfhydryl content is down to the half of additive amount, 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, which is characterized in that step (1)
Described in more sulfhydryl compounds be ethanthiol, dithioglycol and succinimide mercaptans at least one.
4. a kind of synthetic method of fluorine-containing hydrophobic epoxy hardener according to claim 2, which is characterized in that step (2)
Described in fluoro-acrylate monomer be trifluoroethyl methacrylate, methacrylic acid hexafluoro isopropyl ester, methacrylic acid ten
At least one of difluoro heptyl ester, ten trifluoro monooctyl ester of methacrylic acid, 17 fluorine last of the ten Heavenly stems ester of methacrylic acid.
5. a kind of synthetic method of fluorine-containing hydrophobic epoxy hardener according to claim 2, which is characterized in that step (2)
Described in catalyst be diethylamine, triethylamine, at least one of diethanol amine.
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| MX2020003244A (en) * | 2017-09-27 | 2020-09-18 | Arkema Inc | 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 |
| CN112795012B (en) * | 2020-12-30 | 2022-02-18 | 江苏富琪森新材料有限公司 | Emulsion type waterborne epoxy curing agent and preparation method and application thereof |
| CN113122133B (en) * | 2021-04-15 | 2022-12-13 | 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 |
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| CN102516912B (en) * | 2011-11-30 | 2013-09-04 | 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 |
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