CN105968368A - Perfluoropolyether modified epoxy resin and preparation method thereof - Google Patents
Perfluoropolyether modified epoxy resin and preparation method thereof Download PDFInfo
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- CN105968368A CN105968368A CN201610351501.3A CN201610351501A CN105968368A CN 105968368 A CN105968368 A CN 105968368A CN 201610351501 A CN201610351501 A CN 201610351501A CN 105968368 A CN105968368 A CN 105968368A
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- epoxy resin
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides perfluoropolyether modified epoxy resin, wherein a perfluoropolyether side chain is introduced to the main chain of epoxy resin, the hydrophobic and oleophobic properties and the pollution resistance of the epoxy resin can be remarkably improved, and the problem of fluorine compound pollution caused by fluoroalkyl modification is solved. The perfluoropolyether contains a large quantity of ether bonds and has good flexibility as well as certain compatibility with other components, and the problems such as flexibility reduction caused by fluoroalkyl modification are solved; n is 1-9; R is an aliphatic or aromatic bivalent group, namely an aliphatic or aromatic group containing at least six carbon atoms; and PFPE is a perfluoropolyether chain segment. The invention also provides a preparation method which comprises the following steps: under the protection of nitrogen or other inert gas, adding perfluoropolyether alcohol, a solvent and diisocyanate into a reaction kettle with a condensation reflux device; after reaction, adding a catalyst, and preserving heat for 1-2 hours; cooling to 35 DEG C and adding epoxy resin; heating; after reaction, reducing pressure and pumping out the solvent; and cooling to 35 DEG C and discharging.
Description
[technical field]
The present invention relates to Epoxy Resin Technology field, particularly relate to a kind of perfluoropolyether-modified epoxy resin and preparation thereof
Method.
[background technology]
Epoxy resin has corrosion resistance, solvent resistance, thermostability, dielectricity and the adhesive strength of excellence, and hardness is high,
Pliability is good, is therefore widely used in adhesive, coating, composite.Fluorine-containing groups is introduced epoxy resin, tree can be reduced
Fat surface energy, dielectric loss and water absorption rate, improve hydrophobic oleophobic, resistance to soiling, expands the application of epoxy resin.
Conventional fluorine richness epoxy resin is that main chain section adds a small amount of fluorine atom, because fluorinated volume is low, to the hydrophobicity of resin, resistance to
Dirt promotes inconspicuous.Also have on main chain or side chain, introduce perfluoroalkyl side base, though the hydrophobicity of resin, resistance to soiling can be promoted
Deng, but rigidity is difficult to degrade more than the long-chain perfluoroalkyl of 8 carbon atoms, and coating adhesion and pliability are poor.Such as Chinese patent
CN 101215367 B discloses a kind of epoxy resin preparation method containing perfluoroalkyl side chain, by diisocyanate by perfluor
Alkyl is incorporated on epoxy resin side chain, more cured dose of solidification, and coating hydrophobic angle is up to more than 100 degree, but owing to introducing
Whole-fluoroalkyl chain segment, is harmful to environment and organism.Chinese patent CN 102898567B first synthesizes by fluorine-containing alkyl monomer
Fluoropolymer containing end carboxyl, then react generation fluorine-containing epoxy resin through esterification and epoxy prapanol, obtain fluorinated volume high
Epoxy resin, but the hardness of coating is low, and actual application is by a definite limitation.
The present invention is introducing perfluoropolyether segment on the side chain of epoxy resin, and the dredging of epoxy resin can not only be substantially improved
Water oleophobic property, resistance to soiling, and solve the fluorine compounds pollution problem that fluoroalkyl brings.It addition, PFPE contains
Having substantial amounts of ehter bond, the flexibility of segment is better than fluoroalkyl, solves degradation problem under the flexibility that fluoroalkyl causes.
Therefore, it is necessary to provide a kind of new perfluoropolyether-modified epoxy resin and preparation method thereof to overcome in fact above-mentioned
Technical problem.
[summary of the invention]
The perfluor that the technical issues that need to address of the present invention are to provide a kind of hydro-oleophobicity, resistance to soiling, pliability are good gathers
Epoxy resin that ether is modified and preparation method thereof.
A kind of perfluoropolyether-modified epoxy resin of the present invention, structure is shown below:
Wherein, n=1-9；R is aliphatic or aromatic divalent group, comprise the aliphatic group no less than six carbon,
Aromatic group；PFPE is perfluoropolyether segment, containing CF in segment2CF2O—、—CF2CF(CF3)O—、—CF2O—、—
CF(CF3)O—、—CF2CF2CF2O—、—C(CF3) 2One or more repetitives in O, molecular weight is 300-8000.
Preferably, described perfluoropolyether-modified epoxy resin is to be existed with isocyanates, PFPE alcohol by epoxy resin
Under catalyst action, reaction generates；In isocyano in the described hydroxyl in epoxy resin, isocyanates, PFPE alcohol
The ratio of hydroxyl three meet 1:0.3-0.5:0.15-0.25.
Preferably, described epoxy resin is bisphenol A type epoxy resin, and epoxide number is 0.10-0.56, structure such as following formula institute
Show: n=1-9 in formula.
Preferably, one or more during described epoxy resin is 6101,616,604.
Preferably, the structure of described isocyanates is shown below:
In formula, R is aliphatic or aromatic divalent group, comprises the aliphatic group no less than six carbon, aromatic series
Group.
Preferably, described isocyanates be toluene di-isocyanate(TDI) TDI, methyl diphenylene diisocyanate MDI, six methylenes
One or more in group diisocyanate HDI.
Preferably, described catalyst is organic tin or tertiary amine catalyst, for dibutyl tin dilaurate, stannous octoate,
One or more in zinc naphthenate, triethylamine, triethylenediamine, consumption is the 0.1-3% of gross mass.
Present invention also offers the preparation method of above-mentioned perfluoropolyether-modified epoxy resin, preparation method is as follows: at nitrogen
Under gas or other inert gas shielding, in the reactor with condensation reflux unit, put into PFPE alcohol, solvent and two different
Cyanate, reacts 1-8 hour at 60-80 DEG C；It is subsequently adding catalyst, is incubated 1-2 hour；It is cooled at 35 DEG C add epoxy
Resin, then heats up, and reacts 1-8 hour at 60-80 DEG C；Solvent is taken out in decompression, is cooled to 35 DEG C of bottom discharges, i.e. completes perfluor
The preparation of polyether-modified epoxy resin.
Preferably, under nitrogen or other inert gas shielding, put into complete in the reactor with condensation reflux unit
Perfluoroalkyl polyether alcohol, solvent and diisocyanate, react 2-4 hour at 60-80 DEG C.It is subsequently adding catalyst, is incubated 1-2 hour.
It is cooled at 35 DEG C add epoxy resin, then heats up, react 2-4 hour at 60-80 DEG C.Solvent is taken out in decompression, is cooled to
35 DEG C of bottom discharges, are perfluoropolyether-modified epoxy resin.
Preferably, described solvent be methyl acetate, ethyl acetate, butyl acetate, acetone, butanone, a fluorine dichloroethanes,
Trifluorotrichloroethane, benzotrifluoride, two chlorobenzotrifluoride, tetrafluoro ethyl-methyl ether, tetrafluoro ethyl diethyldithiocarbamate ether, four fluoro ethyls third
One or more in base ether, tetrafluoro ethyl-butyl ether, tetrafluoro ethylo benzene methyl ether.
Perfluoropolyether-modified epoxy resin that the present invention provides and preparation method thereof, is to draw on the main chain of epoxy resin
Enter PFPE side chain, the hydro-oleophobicity of epoxy resin, resistance to soiling can not only be substantially improved, and solve fluoroalkyl
The fluorine compounds pollution problem brought.And containing substantial amounts of ehter bond in PFPE, there is good pliability, and with other components
There is certain compatibility, solve degradation problem under the flexibility that fluoroalkyl causes.
[detailed description of the invention]
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
By 200 parts of PFPE alcohol (molecular weight is 4000), 60 parts of tetrafluoro ethyl-butyl ethers and 20 parts of toluene diisocynates
After ester mix homogeneously, react 2 hours at 70 DEG C, be subsequently adding 0.5 part of dibutyl tin dilaurate, be incubated 1 hour.Cooling
At 35 DEG C, add 40 parts of epoxy resin 6101s, then heat up, react 2 hours at 80 DEG C.Solvent is taken out in decompression, is cooled to 35
DEG C bottom discharge, is perfluoropolyether-modified epoxy resin.
10 parts of prepared perfluoropolyether-modified epoxy resin, 3 parts of triethylene tetramines, 5 parts of ethyl acetates are turned at 1000rpm
The lower dispersion of speed 1 hour, filters after stirring, obtains hydrophobic coating.It is sprayed on tinplate, cold curing 24 hours.
Recording the water contact angle 103 degree of coating, hexadecane contact angle 67 degree, soaking at room temperature is water absorption rate 0.42% after 24 hours.
Embodiment 2
By 200 parts of PFPE alcohol (molecular weight is 4000), 90 parts of benzotrifluorides and 30 parts of diphenylmethane diisocyanates
After ester mix homogeneously, react 2 hours at 75 DEG C, be subsequently adding 1 part of dibutyl tin dilaurate, be incubated 1 hour.It is cooled to 35
Add 40 parts of epoxy resin 616 at DEG C, then heat up, react 2 hours at 75 DEG C.Solvent is taken out in decompression, is cooled at 35 DEG C
Discharging, is perfluoropolyether-modified epoxy resin.
By 10 parts of prepared perfluoropolyether-modified epoxy resin, 5 parts of m-diaminobenzene .s, 5 parts of Trifluoroacetic Acid Ethyl Esters at 1500rpm
Disperse 1 hour under rotating speed, filter after stirring, obtain hydrophobic coating.Being sprayed on tinplate, cold curing 24 is little
Time.Recording the water contact angle 107 degree of coating, hexadecane contact angle 68 degree, soaking at room temperature is water absorption rate 0.34% after 24 hours.
Embodiment 3
By 100 parts of PFPE alcohol (molecular weight is 2000), 60 parts of ethyl acetates and 30 parts of diphenylmethane diisocyanates
After ester mix homogeneously, react 2 hours at 60 DEG C, be subsequently adding 1 part of zinc naphthenate, be incubated 1 hour.It is cooled at 35 DEG C add
40 parts of epoxy resin 616, then heat up, and react 2 hours at 70 DEG C.Solvent is taken out in decompression, is cooled to 35 DEG C of bottom discharges, is
Perfluoropolyether-modified epoxy resin.
By 10 parts of prepared perfluoropolyether-modified epoxy resin, 6 parts of fluorine richness organic amines, 5 parts of Trifluoroacetic Acid Ethyl Ester ethyl esters
Disperse 1 hour under 1500rpm rotating speed, filter after stirring, obtain hydrophobic coating.It is sprayed on tinplate, room temperature
Solidify 24 hours.Recording the water contact angle 108 degree of coating, hexadecane contact angle 70 degree, soaking at room temperature is water absorption rate after 24 hours
0.31%.
Compared with correlation technique, the beneficial effects of the present invention is, the perfluoropolyether-modified asphalt mixtures modified by epoxy resin that the present invention provides
Fat and preparation method thereof, is introducing PFPE side chain on the main chain of epoxy resin, epoxy resin can not only be substantially improved
Hydro-oleophobicity, resistance to soiling, and solve the fluorine compounds pollution problem that fluoroalkyl brings.And PFPE contains
Substantial amounts of ehter bond, has good pliability, and has certain compatibility with other components, solve what fluoroalkyl caused
Flexible lower degradation problem.
Above-described is only embodiments of the present invention, it should be noted here that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, it is also possible to make improvement, but these belong to the protection model of the present invention
Enclose.
Claims (10)
1. a perfluoropolyether-modified epoxy resin, it is characterised in that structure is shown below:
Wherein, n=1-9；R is aliphatic or aromatic divalent group, comprises the aliphatic group no less than six carbon, fragrance
Race's group；PFPE is perfluoropolyether segment, containing CF in segment2CF2O—、—CF2CF(CF3)O—、—CF2O—、—CF
(CF3)O—、—CF2CF2CF2O—、—C(CF3)2One or more repetitives in O, molecular weight is 300-8000.
The most perfluoropolyether-modified epoxy resin, it is characterised in that described perfluoropolyether-modified ring
Epoxy resins is to be reacted generation under catalyst action by epoxy resin and isocyanates, PFPE alcohol；Described epoxy resin
In hydroxyl, the isocyano in isocyanates, the ratio of the hydroxyl three in PFPE alcohol meet 1:0.3-0.5:0.15-
0.25。
The most perfluoropolyether-modified epoxy resin, it is characterised in that described epoxy resin is bisphenol-A
Type epoxy resin, epoxide number is 0.10-0.56, and structure is shown below: n=1-9 in formula.
The most perfluoropolyether-modified epoxy resin, it is characterised in that described epoxy resin is 6101,
616, one or more in 604.
The most perfluoropolyether-modified epoxy resin, it is characterised in that the structure of described isocyanates is such as
Shown in following formula:
In formula, R is aliphatic or aromatic divalent group, comprises the aliphatic group no less than six carbon, aromatic series base
Group.
The most perfluoropolyether-modified epoxy resin, it is characterised in that described isocyanates is toluene two
One or more in isocyanates TDI, methyl diphenylene diisocyanate MDI, hexamethylene diisocyanate HDI.
The most perfluoropolyether-modified epoxy resin, it is characterised in that described catalyst is organic tin
Or tertiary amine catalyst, for the one in dibutyl tin dilaurate, stannous octoate, zinc naphthenate, triethylamine, triethylenediamine
Or several, consumption is the 0.1-3% of gross mass.
8. a preparation method for the perfluoropolyether-modified epoxy resin as described in any one of claim 1-7, its feature exists
In, preparation method is as follows: under nitrogen or other inert gas shielding, puts into complete in the reactor with condensation reflux unit
Perfluoroalkyl polyether alcohol, solvent and diisocyanate, react 1-8 hour at 60-80 DEG C；It is subsequently adding catalyst, is incubated 1-2 hour；
It is cooled at 35 DEG C add epoxy resin, then heats up, react 1-8 hour at 60-80 DEG C；Solvent is taken out in decompression, is cooled to
35 DEG C of bottom discharges, i.e. complete the preparation of perfluoropolyether-modified epoxy resin.
The preparation method of perfluoropolyether-modified epoxy resin the most according to claim 8, it is characterised in that at nitrogen or
Under other inert gas shielding, in the reactor with condensation reflux unit, put into PFPE alcohol, solvent and two Carbimide .s
Ester, reacts 2-4 hour at 60-80 DEG C.It is subsequently adding catalyst, is incubated 1-2 hour.It is cooled at 35 DEG C add asphalt mixtures modified by epoxy resin
Fat, then heats up, and reacts 2-4 hour at 60-80 DEG C.Solvent is taken out in decompression, is cooled to 35 DEG C of bottom discharges, is PFPE
Modified epoxy.
The preparation method of perfluoropolyether-modified epoxy resin the most according to claim 9, it is characterised in that described molten
Agent is methyl acetate, ethyl acetate, butyl acetate, acetone, butanone, a fluorine dichloroethanes, trifluorotrichloroethane, fluoroform
Benzene, two chlorobenzotrifluoride, tetrafluoro ethyl-methyl ether, tetrafluoro ethyl diethyldithiocarbamate ether, tetrafluoro ethyl propyl ether, tetrafluoro ethyl-butyl
One or more in ether, tetrafluoro ethylo benzene methyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610351501.3A CN105968368A (en) | 2016-05-25 | 2016-05-25 | Perfluoropolyether modified epoxy resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610351501.3A CN105968368A (en) | 2016-05-25 | 2016-05-25 | Perfluoropolyether modified epoxy resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108341621A (en) * | 2018-02-28 | 2018-07-31 | 无锡金久泓科技有限公司 | A kind of resin concrete and preparation method thereof that fluorine monomer is modified |
| CN114163648A (en) * | 2020-09-11 | 2022-03-11 | 海洋化工研究院有限公司 | Organic fluorine modified epoxy resin, preparation method and anticorrosive paint |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104186A (en) * | 1986-05-14 | 1988-04-06 | 奥西蒙特公司 | Resins, epoxy with crosslinked with multifunctional perfluoro-polyether |
| CN101215367A (en) * | 2007-12-29 | 2008-07-09 | 海洋化工研究院 | Epoxy resin containing perfluoroalkyl side chain and its preparing method and application |
-
2016
- 2016-05-25 CN CN201610351501.3A patent/CN105968368A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104186A (en) * | 1986-05-14 | 1988-04-06 | 奥西蒙特公司 | Resins, epoxy with crosslinked with multifunctional perfluoro-polyether |
| CN101215367A (en) * | 2007-12-29 | 2008-07-09 | 海洋化工研究院 | Epoxy resin containing perfluoroalkyl side chain and its preparing method and application |
Non-Patent Citations (1)
| Title |
|---|
| 韦军 主编: "《高分子合成工艺学》", 28 February 2011, 华东理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108341621A (en) * | 2018-02-28 | 2018-07-31 | 无锡金久泓科技有限公司 | A kind of resin concrete and preparation method thereof that fluorine monomer is modified |
| CN114163648A (en) * | 2020-09-11 | 2022-03-11 | 海洋化工研究院有限公司 | Organic fluorine modified epoxy resin, preparation method and anticorrosive paint |
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Effective date of registration: 20181228 Address after: 410200 Sheng Tong Industrial Park, 109 Jinxing Road, Wangcheng District, Changsha, Hunan. Applicant after: Suntown Technology Group Corporation Address before: No. 109, Wangcheng District, Wangcheng District, Changsha, Hunan Applicant before: The bright logical nanometer novel material company limited in Hunan |
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Application publication date: 20160928 |