CN102796014A - Preparation method of perfluorohexyl-containing tribasic alcohol - Google Patents
Preparation method of perfluorohexyl-containing tribasic alcohol Download PDFInfo
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- CN102796014A CN102796014A CN2012103297326A CN201210329732A CN102796014A CN 102796014 A CN102796014 A CN 102796014A CN 2012103297326 A CN2012103297326 A CN 2012103297326A CN 201210329732 A CN201210329732 A CN 201210329732A CN 102796014 A CN102796014 A CN 102796014A
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- perfluorohexyl
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- hexyl
- trivalent alcohol
- tribasic alcohol
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Abstract
The invention discloses a preparation method of perfluorohexyl-containing tribasic alcohol, which comprises the following steps: mixing 3-perfluorohexyl-1,2-epoxypropane and ethanolamine in an organic solvent; and in a nitrogen protective atmosphere, sufficiently mixing at 80-130 DEG C to react for 6-16 hours, and removing the solvent under reduced pressure to obtain the perfluorohexyl-containing tribasic alcohol. The perfluorohexyl-containing tribasic alcohol monomer prepared by the method disclosed by the invention has the advantages of cheap and accessible raw materials, simple preparation technique and high yield (higher than 95%). The perfluorohexyl-containing tribasic alcohol can be used as a chain extender to prepare cross-linked organofluorine modified polyurethane, can effectively enhance the high temperature resistance, chemical stability and water/oil repellency of the polyurethane, and has broad market prospects and high economic value.
Description
Technical field
The monomer that the present invention relates to a kind of synthetic organic fluorine modified polyurethane contains the preparation method of perfluoro hexyl trivalent alcohol.
Background technology
Advantages such as urethane has wear-resisting, anti-solvent, good processability have in daily life widely and use.But also exist shortcomings such as weathering resistance, poor water resistance simultaneously, restricted its development in some fields.
Fluorine atom has higher electronegativity and less van der Waals radius, and the C-F key is extremely short and bond energy is very high, makes fluorochemicals that lower surface energy arranged.The urethane of using the organic fluoride modification has the advantage of organofluorine compound and urethane concurrently, shows well weather-proof, erosion resistance.The low surface energy of fluorine and low-friction coefficient have given fluoropolymer excellent oil resistant, water-fast and anti-adhesivity simultaneously.The thermostability that fluorine is good in addition can well be improved the heat resistance of urethane.
At present, in the preparation of organic fluoride modified polyurethane commonly used to fluorine material mainly contain: fluorine-containing alkyl alcohol, fluorine-containing isocyanic ester, fluorine-containing alkenyl alcohol and fluorine-containing methacrylic ester etc.Patent CN101435159A as end-capping reagent and polyurethane reaction, has obtained fluorinated alohol fluoroalkyl and has been present in the urethane among the main chain, and its fluorine content is lower and water, oil and soil repellent property is all undesirable.Patent CN1445254A adopts side chain to contain the divalent alcohol of perfluoroalkyl with the mixture of other low-molecular-weight diol or diamine comes modified polyurethane as chainextender, and carbochain is moved not limited, and gained material hydrolysis, scale resistance are good.Patent CN102115524A changes fluoroalkyl alcohol into fluoropolymer two functionality chainextenders earlier, prepares fluorochemical urethane through chain extending reaction then.More than two kinds of methods all improved polymer properties to a certain extent.Patent CN101130594A uses fluorinated acrylate graft copolymerization after adopting 20 tetrafluoros, 16 carbon glycol to obtain the PUA pre-emulsion as chainextender and monomer, base polyurethane prepolymer for use as reaction again, obtains a kind of aquosity polyurethane inarching fluorine contained fabric finish agent.Patent CN1670051A adopts the polyurethane macromolecular monomer and the fluorine-containing methacrylate class monomer of terminal band polymerizable double bond to carry out emulsion copolymerization, directly prepares the copolymer emulsion that fluoro-containing group is a side group.Patent CN101157750A through and the fluorochemical polyether aqueous polyurethane that carries out the synthetic fluorochemical polyether graft modification of the reaction of grafting between macromole.Patent CN101041709A utilizes fluorochemical polyether, polyether glycol, POLYMETHYLENE POLYPHENYLISOCYANATE, catalyzer to prepare ionic fluorinated water based polyurethane for main raw material.Patent CN101003946A is that the synthetic self-emulsifying type emulsion of raw material is used for Waterproof, grease proof treating compound with perfluoroolefine, hydroxy silicon oil, oxyethane, vulcabond.Patent CN101177476A will make fluorochemical urethane by A component and the polyurethane prepolymer hybrid reaction that Fluorine containing olefine and vinyl alkyl ethers/ester and vinyl alcohol monomer copolymerization form.Mostly have advantages such as good water-fast, oil-proofness, thermostability with the organic fluorine modified polyurethane of method for preparing.But wherein the compound method of most of fluorochemical monomer is comparatively complicated, and procurement cost is higher, and some monomer contains perfluorinated carbon atom number >=8.The refractory organics of resin is directly proportional with fluorocarbon chain length, and it is long more therefore to contain fluorocarbon chain, big more to environmental hazard.
Contain the perfluoro hexyl trivalent alcohol and can be used as the organic fluorine modified polyurethane that chainextender prepares cross-linking type, can effectively improve high thermal resistance, chemicalstability and the water and oil repellant ability of urethane.Yet comparatively complicated about the preparation method of fluorine-containing trivalent alcohol, procurement cost is higher, demands urgently improving.
Summary of the invention
To the deficiency of prior art, the problem that the present invention will solve provides a kind of preparation method who contains the perfluoro hexyl trivalent alcohol.
The preparation method who contains the perfluoro hexyl trivalent alcohol according to the invention is to be raw material with 3-perfluoroalkyl-1,2 epoxy prapane, makes with hydroxy-containing compounds ring-opening reaction in solvent.
Above-mentioned reaction equation is following:
Wherein: n is the integer of 1-4, and Rf is the perfluoro alkane that contains 4-8 carbon atom, and X is amido, hydroxyl or sulfydryl.
Further, the above-mentioned preparation method who contains the perfluoro hexyl trivalent alcohol is in the four-hole bottle that TM, reflux condensing tube and nitrogen conduit are housed, to add thanomin and 3-perfluor n-hexyl-1; The 2-propylene oxide under the nitrogen protection, is warming up to 80～130 ℃ after in organic solvent, fully stirring; Reaction 6～16h; Decompression removes solvent, obtains the reddish-brown transparent liquid, is to contain the perfluoro hexyl trivalent alcohol; Wherein: the molar feed ratio of thanomin and 3-perfluor n-hexyl-1,2 epoxy prapane is 1 : 1.5～2.5, and said organic solvent is benzene, YLENE, toluene, THF or DMF.
Among the above-mentioned preparation method who contains the perfluoro hexyl trivalent alcohol: the molar feed ratio of said thanomin and 3-perfluor n-hexyl-1,2 epoxy prapane is 1 : 2～2.2 preferably.
Among the above-mentioned preparation method who contains the perfluoro hexyl trivalent alcohol: said organic solvent is toluene or YLENE preferably.
Among the above-mentioned preparation method who contains the perfluoro hexyl trivalent alcohol: saidly preferably be warming up to 90～110 ℃, reaction times 8～12h after in organic solvent, fully stirring.
Above-mentioned reaction equation is following:
The present invention has obtained title product perfluoro hexyl trivalent alcohol (N very easily; N-two-(3-perfluoro hexyl-2-hydroxypropyl) thanomin), preparation contain perfluoro hexyl trivalent alcohol monomer synthesis material relatively cheap, be easy to get, preparation technology is simple; Yield is higher, all more than 95%.The said perfluoro hexyl trivalent alcohol that contains can be used as the organic fluorine modified polyurethane that chainextender prepares cross-linking type, can effectively improve high thermal resistance, chemicalstability and the water and oil repellant ability of urethane, has vast market prospect and economic worth.
Embodiment
Embodiment 1
In the four-hole bottle of the 100mL that TM, reflux condensing tube and nitrogen conduit are housed, add 3-perfluor n-hexyl-1,2 epoxy prapane (7.52g, 20.0mmol) and thanomin (0.611g; 10.0mmol), YLENE 25.0mL is under the nitrogen protection; Be warming up to 110 ℃ after fully stirring, reaction 8h, reclaim under reduced pressure YLENE; Obtain the reddish-brown transparent liquid, i.e. title product perfluoro hexyl trivalent alcohol 8.02g, productive rate 98.6%.
Embodiment 2
In the four-hole bottle of the 100mL that TM, reflux condensing tube and nitrogen conduit are housed, add 3-perfluor n-hexyl-1,2 epoxy prapane (6.77g, 18.0mmol) and thanomin (0.611g; 10.0mmol), YLENE 25.0mL is under the nitrogen protection; Be warming up to 110 ℃ after fully stirring, reaction 8h, reclaim under reduced pressure YLENE; Obtain the reddish-brown transparent liquid, i.e. title product perfluoro hexyl trivalent alcohol 7.02g, productive rate 95.9%.
Embodiment 3
In the 100mL four-hole bottle that TM, reflux condensing tube and nitrogen conduit are housed, add 3-perfluor n-hexyl-1,2 epoxy prapane (7.52g, 20.0mmol) and thanomin (0.611g; 10.mmol), toluene 25.0mL is under the nitrogen protection; Be warming up to 80 ℃ after fully stirring, reaction 16h, reclaim under reduced pressure toluene; Obtain the reddish-brown transparent liquid, i.e. title product perfluoro hexyl trivalent alcohol 7.88g, productive rate 96.9%.
Embodiment 4
In the four-hole bottle of the 100mL that TM, reflux condensing tube and nitrogen conduit are housed, add 3-perfluor n-hexyl-1,2 epoxy prapane (8.27g, 22.0mmol) and thanomin (0.611g; 10.mmol), YLENE 25.0mL is under the nitrogen protection; Be warming up to 110 ℃ after fully stirring, reaction 12h, reclaim under reduced pressure YLENE; Obtain the reddish-brown transparent liquid, i.e. title product perfluoro hexyl trivalent alcohol 8.04g, productive rate 98.8%.
Embodiment 5
In the 100mL four-hole bottle that TM, reflux condensing tube and nitrogen conduit are housed, add 3-perfluor n-hexyl-1,2 epoxy prapane (7.52g, 20.0mmol) and thanomin (0.611g; 10.0mmol), DMF 25.0mL is under the nitrogen protection; Be warming up to 130 ℃ after fully stirring, reaction 10h, reclaim under reduced pressure DMF; Obtain the reddish-brown transparent liquid, i.e. title product perfluoro hexyl trivalent alcohol 8.03g, productive rate 98.7%.
Claims (4)
1. a preparation method who contains the perfluoro hexyl trivalent alcohol is in the four-hole bottle that TM, reflux condensing tube and nitrogen conduit are housed, to add thanomin and 3-perfluor n-hexyl-1,2 epoxy prapane; Under the nitrogen protection; Be warming up to 80～130 ℃ after in organic solvent, fully stirring, reaction 6～16h, decompression removes solvent; Obtain the reddish-brown transparent liquid, be and contain the perfluoro hexyl trivalent alcohol; Wherein: the molar feed ratio of thanomin and 3-perfluor n-hexyl-1,2 epoxy prapane is 1 : 1.5～2.5, and said organic solvent is benzene, YLENE, toluene, THF or DMF.
2. according to the said preparation method who contains the perfluoro hexyl trivalent alcohol of claim 1, it is characterized in that: the molar feed ratio of said thanomin and 3-perfluor n-hexyl-1,2 epoxy prapane is 1 : 2～2.2.
3. according to the said preparation method who contains the perfluoro hexyl trivalent alcohol of claim 1, it is characterized in that: said organic solvent is toluene or YLENE.
4. according to the said preparation method who contains the perfluoro hexyl trivalent alcohol of claim 1, it is characterized in that: saidly be warming up to 90～110 ℃, reaction times 8～12h after in organic solvent, fully stirring.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012103297326A CN102796014A (en) | 2012-09-07 | 2012-09-07 | Preparation method of perfluorohexyl-containing tribasic alcohol |
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| CN2012103297326A CN102796014A (en) | 2012-09-07 | 2012-09-07 | Preparation method of perfluorohexyl-containing tribasic alcohol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865026A (en) * | 2014-03-18 | 2014-06-18 | 山东大学 | Preparation method of organic fluorosiloxane modified polyurethane emulsion containing short fluoroalkyl chain |
| CN110028412A (en) * | 2019-04-23 | 2019-07-19 | 南京信息工程大学 | A kind of perfluor replaces small molecule end group glycol and its preparation method and application |
| CN113913078A (en) * | 2021-10-15 | 2022-01-11 | 安徽信达家居有限公司 | Water-based paint for bamboo chairs and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1412477A (en) * | 1972-11-28 | 1975-11-05 | Ciba Geigy Ag | Perfluoroalkylamindalkanols process for their manufacture and their use |
-
2012
- 2012-09-07 CN CN2012103297326A patent/CN102796014A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1412477A (en) * | 1972-11-28 | 1975-11-05 | Ciba Geigy Ag | Perfluoroalkylamindalkanols process for their manufacture and their use |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865026A (en) * | 2014-03-18 | 2014-06-18 | 山东大学 | Preparation method of organic fluorosiloxane modified polyurethane emulsion containing short fluoroalkyl chain |
| CN103865026B (en) * | 2014-03-18 | 2015-10-28 | 山东大学 | A kind of preparation method of the organic fluorinated silicone modified polyaminoester emulsion containing short fluorocarbon chain |
| CN110028412A (en) * | 2019-04-23 | 2019-07-19 | 南京信息工程大学 | A kind of perfluor replaces small molecule end group glycol and its preparation method and application |
| CN110028412B (en) * | 2019-04-23 | 2021-11-30 | 南京信息工程大学 | Perfluoro-substituted micromolecule end group diol and preparation method and application thereof |
| CN113913078A (en) * | 2021-10-15 | 2022-01-11 | 安徽信达家居有限公司 | Water-based paint for bamboo chairs and preparation method thereof |
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Application publication date: 20121128 |