CN102295560A - Difluoroalkyl maleate and preparation method thereof - Google Patents
Difluoroalkyl maleate and preparation method thereof Download PDFInfo
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- CN102295560A CN102295560A CN2011101988950A CN201110198895A CN102295560A CN 102295560 A CN102295560 A CN 102295560A CN 2011101988950 A CN2011101988950 A CN 2011101988950A CN 201110198895 A CN201110198895 A CN 201110198895A CN 102295560 A CN102295560 A CN 102295560A
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- maleic acid
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- esters
- fluorine
- tetrahydrochysene
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Abstract
The invention relates to a fluorine containing monomer used for synthesis of an organic fluorine containing polymeric material, and discloses difluoroalkyl maleate and a preparation method thereof. According to the invention, maleic anhydride and 1,1,2,2-tetrahydro-tridecafluoro-octanol are subjected to an esterification reaction under the catalysis of protonic acid so as to prepare fluorine containing monomer maleic acid bis(1,1,2,2-tetrahydro-tridecafluoro-octanol) ester, in the molecular structure of which, two fluoroalkyl groups are connected with two ends of the double bond of carbon-carbon through ester groups and are in a state of dense accumulation, and repulsive interaction between the two fluoroalkyl groups enables the fluoroalkyl groups to be more easily perpendicular to the surface of a substrate, thereby providing a greater fluorine shielding effect; the fluoroalkyl groups are short carbon chain fluoroalkyl groups, which enables low cost to be achieved and are not in the banned range of perfluorooctane sulfonamide derivatives; fluorine containing alcohol and maleic anhydride are used as raw materials, and the raw materials are easily available; the esterification reaction is an routine esterification reaction; conditions for preparation of difluoroalkyl maleate are mild; requirements for equipment are low; high yield is achieved; industrial production of difluoroalkyl maleate is easy to realize.
Description
Technical field
The present invention relates to a kind of organo-fluorine polymer material synthetic fluorochemical monomer that is used for, two fluoroalkyl esters of particularly a kind of maleic acid and preparation method thereof belong to technical field of polymer materials.
Background technology
Organic fluorine material comes out year surplus in the of existing 60, wherein the organo-fluorine polymer material has low surface energy characteristic, high heat resistance energy, chemical-resistant reagent etc., being used for material surface and handling the unique low surface energy of availability energy, is the irreplaceable finish materials in this field.
At present, being widely used in fluoropolymer synthetic fluorochemical monomer mainly is fluorinated acrylate or fluorine-containing methacrylate, as acrylate or methyl acrylic ester, the perfluoroalkyl sulphonamide deutero-esters of acrylic acid of perfluoroalkyl alcohol, contain three kinds of the esters of acrylic acids of perfluoroalkyl tertiary amine.Wherein, the monomeric structure of the acrylate of perfluoroalkyl alcohol or methyl acrylic ester is CH
2=CR-COOR
f, R wherein
fBe perfluoroalkyl, 1, the 2 dihydro perfluoroalkyl or 1,1,2 that contains 6～10 carbon atoms, 2-tetrahydrochysene perfluoroalkyl, R be H or-CH
3When R is-CH
3The time, help the hydrophobicity of product, when being H, R then helps the product oleophobic property.It should be noted that perfluoroalkyl R
fCarbon chain lengths must just can provide good low surface energy greater than 6.This is because the fluoroalkyl that contains in the acrylate copolymer is difficult to have only the perfluoroalkyl carbon chain lengths just can provide good fluoroalkyl shielding effect greater than 6 fully perpendicular to substrate surface.
Summary of the invention
The present invention is directed to short fluoroalkyl monomer in the deficiency that can not effectively shield the treated material surface that is used for existing when material surface is handled, a kind of fluorine shielding effect that can effectively improve fluoroalkyl to substrate surface is provided, and processing condition gentleness, the yield height is very easily realized two fluoroalkyl esters of maleic acid of suitability for industrialized production and preparation method thereof.
The two fluoroalkyl esters of a kind of maleic acid provided by the invention, it is two (1,1,2, the 2-tetrahydrochysene ten trifluoro octyl groups) esters of maleic acid, has following structure:
The preparation method of the two fluoroalkyl esters of maleic acid provided by the present invention comprises the steps:
1, by weight, 1 part of MALEIC ANHYDRIDE, 5～10 parts of fluorine-containing alcohols and 0.05～0.5 part of hydroquinone of polymerization retarder are joined in 8～15 parts of organic solvents, be stirred to dissolving fully; Described fluorine-containing alcohol is 1,1,2,2-tetrahydrochysene ten trifluoro octanols;
2, above-mentioned solution is warming up to 50～145 ℃ after, add 0.05～0.4 part tosic acid, insulation reaction 3～24 hours;
3, the limpid filtrate water that obtains behind the reacting liquid filtering is washed till neutrality, adds anhydrous sodium sulphate and carry out drying treatment, the anhydrous sodium sulphate consumption is 5～20% of a fluorine-containing alcohol quality;
4, remove by filter anhydrous sodium sulphate, the filtrate that obtains is underpressure distillation under the condition of 0.133～1.33KPa at 40～100 ℃, vacuum tightness, removes to obtain two (1,1,2, the 2-tetrahydrochysene ten trifluoro octyl groups) esters of product maleic acid after desolvating.
Described organic solvent is a kind of in benzene,toluene,xylene and the hexanaphthene, or wherein any two kinds are the mixture of 1～5:5～1 by weight.
By the two fluoroalkyl esters of the maleic acid of technical solution of the present invention preparation, compare with long carbochain perfluoroalkyl acrylate or perfluoroalkyl methacrylic ester monomer, two fluoroalkyls in its molecular structure are connected in the carbon-carbon double bond two ends by ester group, two fluoroalkyls are in the dense accumulation state, fluoroalkyl repulsive interaction each other makes fluoroalkyl easier in substrate surface, thereby higher fluorine shielding effect can be provided.
Compare with long carbochain perfluoroalkyl acrylate or perfluoroalkyl methacrylic ester monomer commonly used, the two fluoroalkyl esters of maleic acid provided by the invention have the advantage of following several respects:
1, the two fluoroalkyls in the molecular structure are in the dense accumulation state, are prepared into the repulsive interaction each other of latter two fluoroalkyl of polymkeric substance and make fluoroalkyl easier in substrate surface, thereby higher fluorine shielding effect can be provided;
2, the fluoroalkyl of Cai Yonging is the short carbon chain fluoroalkyl, is not perfluorinated octyl sulfuryl amine derivative (PFOS) forbidding scope, has that cost is low, the advantage of environmental protection;
3, the two fluoroalkyls of maleic acid are that raw material reaction forms with fluorine-containing alcohol and MALEIC ANHYDRIDE directly, and raw material is easy to get;
4, when preparation synthesizes by conventional esterification, and the preparation process condition gentleness, equipment requirements is low, yield is high, very easily realizes suitability for industrialized production.
Description of drawings
Fig. 1 is infrared spectra (FT-IR) figure by two (1,1,2,2-tetrahydrochysene ten trifluoro octyl groups) esters of maleic acid of embodiment of the invention technical scheme preparation;
Fig. 2 is high resolution mass spectrum (HRMS) spectrogram by two (1,1,2,2-tetrahydrochysene ten trifluoro octyl groups) esters of maleic acid of embodiment of the invention technical scheme preparation.
Embodiment
Below in conjunction with drawings and Examples technical solution of the present invention is further described.
Embodiment one
In the reactor that induction stirring, reflux condensing tube, water trap and thermometer are housed, add MALEIC ANHYDRIDE 19.6 g, 1,1,2,2-tetrahydrochysene ten trifluoro octanol 145.6g, Resorcinol 1.9g, tosic acid 3.0g and toluene 220g.At N
2Be stirred to dissolving fully under the protection; Be heated to 111 ℃, react 8 hours, divide water outlet about 4.6mL, stopped reaction to no longer including the water generation.
After the reaction mixture cooling, to filter and obtain limpid light yellow filtrate, filtrate water is washed till neutrality, adds the 8g anhydrous Na
2SO
4After the drying treatment 6 hours, remove by filter siccative, filtrate underpressure distillation under 58 ℃, the condition of vacuum tightness 0.665KPa (5mmHg) desolventizes, obtain the light yellow transparent oily product maleic acid of 120g two (1,1,2,2-tetrahydrochysene ten trifluoro octyl groups) ester, productive rate 82%.
Referring to accompanying drawing 1, it is infrared spectra (FT-IR) figure by two (1,1,2,2-tetrahydrochysene ten trifluoro octyl groups) esters of maleic acid of present embodiment technical scheme preparation; The FT-IR(KBr compressing tablet, cm
-1): 3001.5,1742.0,1647.3,1467.7,1389.4,1334.0,1289.9,1226.3,1158.1,1110.7,1095.5,1047.8,963.6,943.4,826.8,735.4,704.2.
1H?NMR（CDCl
3）δ（ppm）：6.306（2H,m），4.478（4H，t，J=?10Hz），2.595（4H,t，J=10.4Hz）。
19F?NMR?（CDCl
3,300MHz）δ：?-64.822（m，12F）,?-81.161(t，J=14.4Hz?,6F)?,?-108.536(m，4F),?-124.090(m，J=11.7Hz,?4F)?ppm。MS（EI,70eV）m/z(%)?:99.0080(100),?195.0045(23.16),?445.0072(26.07)?。Show among the FT-IR figure of product, at 1746cm
-1The absorption peak at place is a C=O stretching vibration absorption peak, 1630 cm
-1Place's absorption peak ownership is the charateristic avsorption band of C=C, 1098 cm
-1Be C-O-C stretching vibration absorption peak, 1279 cm
-1Corresponding to-CF
3The stretching vibration absorption peak.
Referring to accompanying drawing 2, it is high resolution mass spectrum (HRMS) figure by two (1,1,2,2-tetrahydrochysene ten trifluoro octyl groups) esters of maleic acid of present embodiment technical scheme preparation; The molecular formula M of two (the ten trifluoro octyl groups) esters of maleic acid is C
20H
10O
4F
26, test result shows HRMS(m/z among the product HRMS figure): calculated value 808.0164, measured value 808.0146, the actual measurement examination coincide with calculated value.
Embodiment two
In the reactor that induction stirring, reflux condensing tube, water trap and thermometer are housed, add MALEIC ANHYDRIDE 26.6 g, 1,1,2,2-tetrahydrochysene ten trifluoro octanol 142.5g, Resorcinol 1.8g, tosic acid 3.0g and hexanaphthene 250g.At N
2Be heated with stirring to 80 ℃ under the protection, react 12 hours, divide water outlet about 5.2mL, stopped reaction to no longer including the water generation.
After the reaction mixture cooling, filter and obtain limpid light yellow filtrate, filtrate water is washed till neutrality, adds the 10g anhydrous Na
2SO
4After the drying treatment 8 hours, cross the filtering siccative, filtrate is at 50 ℃, vacuum tightness 0.796KPa(6mmHg) condition under underpressure distillation desolventize and obtain the light yellow transparent oily product maleic acid of 126g two (1,1,2,2-tetrahydrochysene ten trifluoro octyl groups) ester, productive rate 86%.
Two (1,1,2, the 2-tetrahydrochysene ten trifluoro octyl groups) esters of maleic acid and butyl acrylate, methyl methacrylate and acrylamide that present embodiment provides is quarternary copolymerized, prepare polymeric film, concrete steps are as follows:
According to weight ratio, 3.6g Si dish-60 and 4.8g sodium lauryl sulphate are joined in the 500g water, add the maleic acid two (1 that present embodiment provides, 1,2,2-tetrahydrochysene ten trifluoro octyl groups) ester 152g, butyl acrylate 15g, methyl methacrylate 10g and acrylamide 4g, mixed solution in the high speed shear mulser, under 8000 rev/mins of rotating speeds, stirred 15 minutes the mix monomer pre-emulsion.
In the reactor that thermometer and reflux condensing tube are housed, add the mix monomer pre-emulsion, N
2Protection is stirred down, be heated to 75oC after, add the 2.0g ammonium persulphate and be dissolved in the initiator solution that forms in the 15g water.After 6 hours, the cooling reaction solution gets two (1,1,2, the 2-tetrahydrochysene ten trifluoro octyl groups) ester copolymer emulsions of maleic acid in insulation reaction under 75 ~ 78oC.
Two (1,1,2, the 2-tetrahydrochysene ten trifluoro octyl groups) ester copolymer emulsions of the maleic acid that obtains of preparation are dried film forming under 120oC, the contact angle of test co-polymer membrane and water reaches 148.2o, proves thus, and this polymeric film has very excellent water repellency.
Claims (3)
1. two fluoroalkyl esters of a maleic acid, it is characterized in that: it is two (1,1,2, the 2-tetrahydrochysene ten trifluoro octyl groups) esters of maleic acid, has following structure:
2. the preparation method of the two fluoroalkyl esters of a kind of maleic acid as claimed in claim 1 is characterized in that comprising the steps:
2. after above-mentioned solution being warming up to 50～145 ℃, add 0.05～0.4 part tosic acid, insulation reaction 3～24 hours;
3. the limpid filtrate water that obtains behind the reacting liquid filtering is washed till neutrality, adds anhydrous sodium sulphate and carry out drying treatment, the anhydrous sodium sulphate consumption is 5～20% of a fluorine-containing alcohol quality;
3. the preparation method of the two fluoroalkyl esters of a kind of maleic acid according to claim 2, it is characterized in that: described organic solvent is a kind of in benzene,toluene,xylene and the hexanaphthene, or wherein any two kinds are the mixture of 1～5:5～1 by weight.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652987A (en) * | 2017-10-17 | 2018-02-02 | 太原理工大学 | The preparation method of maleic acid cholesterol monoesters base citric acid three ester liquid crystal |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4167639A (en) * | 1973-06-09 | 1979-09-11 | Hoechst Aktiengesellschaft | Fluorinated sulfosuccinates |
| US4473371A (en) * | 1981-09-04 | 1984-09-25 | Hoechst Aktiengesellschaft | Perfluoroalkyl esters, a process for their preparation and their use as a soil-repellant agent |
| WO2009067415A1 (en) * | 2007-11-19 | 2009-05-28 | E. I. Du Pont De Nemours And Company | Process for making a color filter |
| CN101698703A (en) * | 2009-10-22 | 2010-04-28 | 厦门大学 | Maleic acid isoalcohol diester and prepration method thereof |
| CN102083785A (en) * | 2008-07-01 | 2011-06-01 | 纳幕尔杜邦公司 | Fluorinated esters |
-
2011
- 2011-07-15 CN CN2011101988950A patent/CN102295560A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4167639A (en) * | 1973-06-09 | 1979-09-11 | Hoechst Aktiengesellschaft | Fluorinated sulfosuccinates |
| US4473371A (en) * | 1981-09-04 | 1984-09-25 | Hoechst Aktiengesellschaft | Perfluoroalkyl esters, a process for their preparation and their use as a soil-repellant agent |
| WO2009067415A1 (en) * | 2007-11-19 | 2009-05-28 | E. I. Du Pont De Nemours And Company | Process for making a color filter |
| CN102083785A (en) * | 2008-07-01 | 2011-06-01 | 纳幕尔杜邦公司 | Fluorinated esters |
| CN101698703A (en) * | 2009-10-22 | 2010-04-28 | 厦门大学 | Maleic acid isoalcohol diester and prepration method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Langmuir》 20001229 Zhao-Tie Liu and Can Erkey Water in Carbon Dioxide Microemulsions with Fluorinated Analogues of AOT 第275页图1，第275页左栏倒数第7行至右栏第6行 1 第17卷, * |
| ZHAO-TIE LIU AND CAN ERKEY,: "Water in Carbon Dioxide Microemulsions with Fluorinated Analogues of AOT", 《LANGMUIR》, vol. 17, 29 December 2000 (2000-12-29) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652987A (en) * | 2017-10-17 | 2018-02-02 | 太原理工大学 | The preparation method of maleic acid cholesterol monoesters base citric acid three ester liquid crystal |
| CN107652987B (en) * | 2017-10-17 | 2020-06-23 | 太原理工大学 | Preparation method of maleic acid cholesterol monoester group citric acid triester liquid crystal |
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Application publication date: 20111228 |