CN109053512A - A kind of fluorine-containing sulfhydryl compound and its preparation method and application - Google Patents
A kind of fluorine-containing sulfhydryl compound and its preparation method and application Download PDFInfo
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- CN109053512A CN109053512A CN201810812720.6A CN201810812720A CN109053512A CN 109053512 A CN109053512 A CN 109053512A CN 201810812720 A CN201810812720 A CN 201810812720A CN 109053512 A CN109053512 A CN 109053512A
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- fluorine
- compound
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- sulfhydryl compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to coating additive fields, and in particular to a kind of fluorine-containing sulfhydryl compound and its preparation method and application, structural formula is as follows: Rf‑R1‑COO‑R2-SH；Wherein RfFor C2‑C20Linear chain or branched chain perfluoroalkyl or end contain hydrogen atom containing fluoroalkyl, R1For C1‑C6Linear or branched alkyl group, R2For C1‑C4Linear or branched alkyl group.The fluorine-containing sulfhydryl compound prepared through the invention, with very high reactivity, almost click-reaction can be carried out with all double bond containing compounds, be added in coating when by the minimal amount of compound, the surface free energy that coating can be significantly reduced obtains super-hydrophobic surface.
Description
Technical field
The invention belongs to coating additive fields, and in particular to a kind of fluorine-containing sulfhydryl compound and preparation method thereof and answer
With can be used for coating additive, prepare low-surface-energy material.
Background technique
Fluoropolymer has extremely low surface free energy, higher thermal stability, and resistance to acid and alkali etc. is often used to prepare
Antifouling paint, anti-fingerprint paint, anticorrosive paint etc..(per) fluoropolymer is poor in organic solvent solubility, and higher cost, at
Type processing difficulties carry out fluorochemical surface functionalization gradually to non-fluorine material so that fluoropolymer-containing application is restricted
A kind of material preparation technology as economical and efficient.
In recent years, mercaptan-alkene clicking reaction quickly, efficiently, without metal catalytic, quantitative reaction, no coupling product is generated because of it
Wide adaptability etc. is widely used in the constructing, is protein-modified of labyrinth material, biological medicine material and microelectronics system
Make equal fields.It is inspired by this, sulfhydryl compound provides new thinking for modifying surface of polymer material, by perfluoroalkylation
Conjunction object progress is mercapto-functionalized to prepare sulfydryl fluorochemical, carries out function of surface to material using mercaptan-alkene clicking reaction
Change, is the effective ways for preparing low-surface-energy material.
The preparation of sulfydryl fluorochemical is rarely reported, and US3886201 is using hydrogen sulfide or multi-functional thiol and containing complete
The fumaric acid of fluoroalkyl, maleic acid, itaconic acid etc. carry out radical reaction and are prepared for the fluorochemical blocked containing sulfydryl simultaneously
Applied to synthesis antifouling polymeric.US3544663, which is reacted using perfluoroalkyl salt compounded of iodine with thiocarbamide, is prepared for sulfydryl perfluoroalkylation
Object is closed, and is applied to textile finishing.
Hoyle etc. has done a large amount of research work to mercaptan-ene reaction system, and alkyl hydrosulfide is compared, α, β mercaptan carboxylic acid
The sulfydryl of ester can form hydrogen bond with ester carbonyl group, weaken sulphur hydrogen bond, have faster reaction rate
(J.Poly.Sci.Poly.Chem,2004,22,5301-5338).Directly utilize mercaptan carboxylic acid or sulfhydryl alkyl alcohol and perfluor
Alkylol or perfluoro carboxylic acid carry out the method that simple branching directly prepares the ester of perfluoro carboxylic acid containing sulfydryl not to be had yet so far
Report.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of completely new fluorine-containing sulfhydryl compound, and provides one kind
The preparation method of fluorine-containing sulfhydryl compound.
To achieve the above object, the present invention is using following technical solution: a kind of fluorine-containing sulfhydryl compound, feature exist
In structural formula is as follows:
Rf-R1-COO-R2-SH；
Wherein RfFor C2-C20Linear chain or branched chain perfluoroalkyl or end contain hydrogen atom containing fluoroalkyl, R1For C1-C6Directly
Chain or branched alkyl, R2For C1-C4Linear or branched alkyl group.
Wherein RfPreferably C6-C12Linear chain or branched chain perfluoroalkyl, most preferably C6-C10Linear perfluoroalkyl.
Preferably, R1For C2-C4Straight chained alkyl.Preferably, R2For C2-C4Straight chained alkyl.
A kind of preparation method of fluorine-containing sulfhydryl compound, is reacted with compound B by compound A and prepares fluorine-containing sulfydryl chemical combination
Object, reaction equation are as follows:
(A)Rf-R1-CO-X+Y-R2-SH(B)→Rf-R1-COO-R2-SH
Wherein RfFor C2-C20Linear chain or branched chain perfluoroalkyl or end contain hydrogen atom containing fluoroalkyl, R1For C1-C6Directly
Chain or branched alkyl, R2For C1-C4Linear or branched alkyl group, X are-H ,-OH ,-Cl ,-Br ,-OCH3,-OCH2CH3One kind, Y
For-OH, one kind of-COOH.
Used Compound A structure formula are as follows:
Rf-R1-CO-X
Preferably, RfFor C6-C10Linear perfluoroalkyl；R1For C1-C4Linear or branched alkyl group, most preferably C2-C4Straight chain alkane
Base；X is-H, one kind of-OH ,-Cl.
Used compound B structure formula are as follows:
Y-R2-SH
Wherein R2For C2-C4Straight chained alkyl；Y is-OH or-COOH.
A kind of application of fluorine-containing sulfhydryl compound, as coating additive, material modification, antifouling and antifog, release neck
Domain prepares low-surface-energy material.
A kind of fluorine-containing sulfhydryl compound, preparation process is reacted by compound A and compound B to be made, specifically mainly by changing
Conjunction object A and compound B carries out esterification under strong acid catalyst and obtains, and organic solvent toluene, hexamethylene are used in reaction process
Or both mixture as water entrainer, catalyst is done using strong acid, strong acid can be the concentrated sulfuric acid, concentrated nitric acid, to methylbenzene sulphur
Acid, methane sulfonic acid etc., preferably methane sulfonic acid.
It finding during the experiment, the dissolubility of fluorochemical is poor, when doing water entrainer using pure hexamethylene, dissolution
Property it is poor, be unfavorable for the progress of reaction, band water mainly done using the mixture of toluene or toluene and hexamethylene in the present invention
Agent.Esterification is balanced reaction, by constantly going out moisture to reaction system outlet, makes to balance the direction to product is generated
It is mobile, extent of reaction is tracked by the quality of measurement draining.Since sulfydryl is oxidized easily, this reaction is preferably in nitrogen item
Part reaction.
The fluorine-containing sulfhydryl compound prepared through the invention has very high reactivity, almost can be with all containing double
The compound of key carries out click-reaction, is added in coating when by the minimal amount of compound, can significantly reduce the table of coating
Face free energy obtains super-hydrophobic surface.
Specific embodiment
In order to explain the structural features and functions of the invention more clearly, come combined with specific embodiments below to the present invention into
Row is described in detail.
A kind of sulfydryl fluorochemical, structural formula are as follows:
Rf-R1-COO-R2-SH
Wherein RfFor C2-C20Linear chain or branched chain perfluoroalkyl or end contain hydrogen atom containing fluoroalkyl, R1For C1-C4Directly
Chain or branched alkyl, R2For C1-C4Linear or branched alkyl group.
It is preferred that RfFor C6-C12Linear chain or branched chain perfluoroalkyl, most preferably C6-C10Straight chained alkyl；It is preferred that R1For C2-C4Straight chain
Alkyl, preferably R2For C2-C4Straight chained alkyl.
A kind of sulfydryl fluorochemical is reacted to obtain, the structure of compound A and compound B by compound A with compound B
The reaction equation of formula and its preparation process is as follows:
Compound A:Rf-R1-CO-X
Compound B:Y-R2-SH
Reaction equation:
Wherein RfFor C2-C20Linear chain or branched chain perfluoroalkyl or end contain hydrogen atom containing fluoroalkyl, R1For C1-C4Directly
Chain or branched alkyl, R2For C1-C4Linear or branched alkyl group.
It is preferred that RfFor C6-C12Linear chain or branched chain perfluoroalkyl, most preferably C6-C10Straight chained alkyl；It is preferred that R1For C2-C4Straight chain
Alkyl, preferably R2For C2-C4Straight chained alkyl.
X is-H ,-OH ,-Cl ,-Br ,-OCH3,-OCH2CH3, preferably-H ,-OH ,-Cl；Y is-OH ,-COOH.
Embodiment 1: a kind of fluorine-containing sulfhydryl compound, structural formula are as follows:
The preparation process of above-mentioned sulfydryl fluorochemical is as follows:
In the four-hole bottle that 100ml has condenser, protractor, blender, 20g (55mmol) perfluorooctanol is added,
6.4g (60mmol) mercaptopropionic acid, 0.39g (4mmol) methane sulfonic acid, toluene 30ml maintain reaction under the conditions of nitrogen protection
Temperature in the kettle reacts 6-8 hours under the conditions of 105 DEG C -115 DEG C, by reaction product saturated sodium bicarbonate and distillation washing 2-3
It is secondary, after organic phase is neutral, organic phase anhydrous magnesium sulfate drying is collected, vacuum decompression obtains target product, yield
85%.
Nuclear-magnetism is carried out after above-mentioned products therefrom is dissolved with deuterated chloroform1H NMR characterization, data are as follows:
1H NMR(CDCl3): δ=1.65ppm (t, 1H), δ=2.59-2.62ppm (m, 2H), δ=2.68-2.74 ppm
(m, 2H), δ=2.38-2.47ppm (m, 2H), δ=4.34-4.37ppm (t, 2H)
Embodiment 2: a kind of sulfydryl fluorochemical, structural formula are as follows:
The preparation process of above-mentioned sulfydryl fluorochemical is as follows:
In the four-hole bottle that 100ml has condenser, protractor, blender, 20g (52mmol) perfluoro caprylic acid is added,
5.4g (57mmol) mercaptopropionic acid, 0.39g (4mmol) methane sulfonic acid, toluene 30ml maintain reaction under the conditions of nitrogen protection
Temperature in the kettle reacts 6-8 hours under the conditions of 105 DEG C -115 DEG C, by reaction product saturated sodium bicarbonate and distillation washing 2-3
It is secondary, after organic phase is neutral, organic phase anhydrous magnesium sulfate drying is collected, vacuum decompression obtains target product, yield
82%.
Nuclear-magnetism is carried out after above-mentioned products therefrom is dissolved with deuterated chloroform1H NMR characterization, data are as follows:
1H NMR(CDCl3): δ=1.65ppm (t, 1H), δ=2.59-2.62ppm (m, 2H), δ=2.68-2.74 ppm
(m, 2H), δ=2.38-2.47ppm (m, 2H), δ=4.34-4.37ppm (t, 2H)
Embodiment 3: a kind of sulfydryl fluorochemical, structural formula are as follows:
The preparation process of above-mentioned sulfydryl fluorochemical is as follows:
In the four-hole bottle that 100ml has condenser, protractor, blender, 20g (55mmol) perfluorooctanol is added,
5.5g (60mmol) thioacetic acid, 0.39g (4mmol) methane sulfonic acid, toluene 30ml maintain reaction under the conditions of nitrogen protection
Temperature in the kettle reacts 6-8 hours under the conditions of 105 DEG C -115 DEG C, by reaction product saturated sodium bicarbonate and distillation washing 2-3
It is secondary, after organic phase is neutral, organic phase anhydrous magnesium sulfate drying is collected, vacuum decompression obtains target product, yield
87%.
Nuclear-magnetism is carried out after above-mentioned products therefrom is dissolved with deuterated chloroform1H NMR characterization, data are as follows:
1H NMR(CDCl3): δ=1.65ppm (t, 1H), δ=2.60-2.63ppm (m, 2H), δ=2.38-2.47 ppm
(m, 2H), δ=4.34-4.37ppm (t, 2H)
Embodiment 4:
A kind of sulfydryl fluorochemical, structural formula are as follows:
The preparation process of above-mentioned sulfydryl fluorochemical is as follows:
In the four-hole bottle that 100ml has condenser, protractor, blender, 20g (52mmol) perfluoro caprylic acid is added,
4.5g (57mmol) mercaptoethanol, 0.39g (4mmol) methane sulfonic acid, toluene 30ml maintain reaction under the conditions of nitrogen protection
Temperature in the kettle reacts 6-8 hours under the conditions of 105 DEG C -115 DEG C, by reaction product saturated sodium bicarbonate and distillation washing 2-3
It is secondary, after organic phase is neutral, organic phase anhydrous magnesium sulfate drying is collected, vacuum decompression obtains target product, yield
86%.
Nuclear-magnetism is carried out after above-mentioned products therefrom is dissolved with deuterated chloroform1H NMR characterization, data are as follows:
1H NMR(CDCl3): δ=1.65ppm (t, 1H), δ=2.60-2.63ppm (m, 2H), δ=2.38-2.47 ppm
(m, 2H), δ=4.34-4.37ppm (t, 2H)
Application Example 1:
The coating fluid formula of 1 embodiment 1 of table (unit is weight percentage)
| Coating fluid 1 | Coating fluid 2 | |
| Acrylic resin | 60 | 60 |
| Reactive diluent | 34 | 35 |
| Photoinitiator | 3 | 3 |
| Other auxiliary agents | 2 | 2 |
| Sulfydryl fluorochemical (embodiment 1) | 1 | 0 |
The coating fluid of above-mentioned formula is coated on the slide of 150mm*20mm, 365nm light source solidification 2mim is then used
(energy 20mw/cm2), test result is as follows for obtained coating surface property:
The coating surface property test result of 2 embodiment 1 of table
| Coating 1 | Coating 2 | |
| Surface contact angle (water) | 110° | 80° |
| The test of oil resistivity pen | It can wipe easily | It stains |
Application Example 2:
The coating fluid formula of 3 embodiment 2 of table (unit is weight percentage)
| Coating fluid 1 | Coating fluid 2 | |
| Acrylic resin | 60 | 60 |
| Reactive diluent | 34 | 35 |
| Photoinitiator | 3 | 3 |
| Other auxiliary agents | 2 | 2 |
| Sulfydryl fluorochemical (embodiment 3) | 1 | 0 |
The coating fluid of above-mentioned formula is coated on the slide of 150mm*20mm, 365nm light source solidification 2mim is then used
(energy 20mw/cm2), test result is as follows for obtained coating surface property:
The coating surface property test result of 4 embodiment 2 of table
| Coating 1 | Coating 2 | |
| Surface contact angle (water) | 112° | 80° |
| The test of oil resistivity pen | It can wipe easily | It stains |
The present invention is not limited solely to the details of above-mentioned exemplary embodiment, and without departing substantially from spirit of the invention or
In the case where essential characteristic, the present invention can be realized in other specific forms.Therefore, in all respects, should all incite somebody to action
Embodiment regards exemplary, unrestricted as, and the scope of the present invention is by appended claims rather than above description limits
It is fixed.It is intended that including all changes that fall within the meaning and scope of the equivalent elements of the claims in the present invention.
In addition, although this specification is described in terms of embodiments, but not each embodiment only includes one only
Vertical technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should be by specification
As a whole, the technical solutions in the various embodiments may also be suitably combined, formed it will be appreciated by those skilled in the art that
Other embodiments.
Claims (8)
1. a kind of fluorine-containing sulfhydryl compound, which is characterized in that its structural formula is as follows:
Rf-R1-COO-R2-SH；
Wherein RfFor C2-C20Linear chain or branched chain perfluoroalkyl or end contain hydrogen atom containing fluoroalkyl, R1For C1-C6Straight chain or branch
Alkyl group, R2For C1-C4Linear or branched alkyl group.
2. fluorine-containing sulfhydryl compound as described in claim 1, it is characterised in that: wherein RfPreferably C6-C12Linear chain or branched chain is complete
Fluoroalkyl, most preferably C6-C10Linear perfluoroalkyl.
3. fluorine-containing sulfhydryl compound as described in claim 1, it is characterised in that: R1For C2-C4Straight chained alkyl.
4. fluorine-containing sulfhydryl compound as described in claim 1, it is characterised in that: R2For C2-C4Straight chained alkyl.
5. the preparation method of the fluorine-containing sulfhydryl compound as described in claim 1-4 any one, it is characterised in that: by compound
A is reacted with compound B prepares fluorine-containing sulfhydryl compound, and reaction equation is as follows:
(A)Rf-R1-CO-X+ Y-R2-SH(B)→Rf-R1-COO-R2-SH
Wherein RfFor C2-C20Linear chain or branched chain perfluoroalkyl or end contain hydrogen atom containing fluoroalkyl, R1For C1-C6Straight chain or
Branched alkyl, R2For C1-C4Linear or branched alkyl group, X are-H ,-OH ,-Cl ,-Br ,-OCH3,-OCH2CH3One kind, Y be-
One kind of OH ,-COOH.
6. the preparation method of fluorine-containing sulfhydryl compound as claimed in claim 5, it is characterised in that: used compound A knot
Structure formula are as follows:
Rf-R1-CO-X
Wherein RfFor C6-C10Linear perfluoroalkyl；R1For C1-C4Linear or branched alkyl group, most preferably C2-C4Straight chained alkyl；X be-
H ,-OH, one kind of-Cl.
7. the preparation method of fluorine-containing sulfhydryl compound as claimed in claim 5, it is characterised in that: used compound B knot
Structure formula are as follows:
Y-R2-SH
Wherein R2For C2-C4Straight chained alkyl；Y is-OH or-COOH.
8. the application of the fluorine-containing sulfhydryl compound as described in claim 1-4 any one, changes as coating additive, material
Property, antifouling and antifog, release field, prepare low-surface-energy material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116693958A (en) * | 2023-08-07 | 2023-09-05 | 中石油(上海)新材料研究院有限公司 | High-wear-resistance organic fluorine modified solution polymerized styrene-butadiene rubber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101111476A (en) * | 2004-11-05 | 2008-01-23 | 富士胶片株式会社 | Compound, polymerizable composition, optical device, and method for producing refractive index profile optical device |
| JP2009132773A (en) * | 2007-11-29 | 2009-06-18 | Agc Seimi Chemical Co Ltd | Resin composition, resin molding using the same, coating and article |
-
2018
- 2018-07-23 CN CN201810812720.6A patent/CN109053512A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101111476A (en) * | 2004-11-05 | 2008-01-23 | 富士胶片株式会社 | Compound, polymerizable composition, optical device, and method for producing refractive index profile optical device |
| JP2009132773A (en) * | 2007-11-29 | 2009-06-18 | Agc Seimi Chemical Co Ltd | Resin composition, resin molding using the same, coating and article |
Non-Patent Citations (2)
| Title |
|---|
| 原燃料化学工业部涂料技术训练班组织编写: "《涂料工艺 第2分册》", 31 December 1981 * |
| 朱淬砺 主编: "《药物合成反应》", 31 December 1982 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116693958A (en) * | 2023-08-07 | 2023-09-05 | 中石油(上海)新材料研究院有限公司 | High-wear-resistance organic fluorine modified solution polymerized styrene-butadiene rubber and preparation method thereof |
| CN116693958B (en) * | 2023-08-07 | 2023-11-03 | 中石油(上海)新材料研究院有限公司 | High-wear-resistance organic fluorine modified solution polymerized styrene-butadiene rubber and preparation method thereof |
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