CN106117395A - The preparation method of unsaturated fluoropolymer - Google Patents
The preparation method of unsaturated fluoropolymer Download PDFInfo
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- CN106117395A CN106117395A CN201610462988.2A CN201610462988A CN106117395A CN 106117395 A CN106117395 A CN 106117395A CN 201610462988 A CN201610462988 A CN 201610462988A CN 106117395 A CN106117395 A CN 106117395A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
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Abstract
The invention discloses the preparation method of a kind of unsaturated fluoropolymer.With fluoropolymer as raw material, it is dissolved in organic solvent, " one pot " reaction carrying out Hofmann and Zaitsev can be placed in variable frequency microwave experimental machine, in the short time, just can get the fluoropolymer that unsaturated bond content is higher and content is controlled under the effect of alkali or alkali and a small amount of catalyst.The present invention has that technique is simple, it is quick, with low cost to react, reaction dissolvent recoverable, productivity be more than 95%, it is not necessary to the features such as harsh pollution control measures.Product is widely used, and can apply as the intermediate of functional fluorine-bearing polymer and processing compounding ingredient etc..
Description
Technical field
The present invention relates to the preparation method of unsaturated fluoropolymer.
Background technology
Fluoropolymer, because of the performance of its excellence, has been widely used in different fields and industry.Unsaturated fluorine-containing
Polymer prepares intermediate important in industry and processing compounding ingredient as fluorine material, has market prospect and important widely
Using value.
At present, the most mainly the 3M company of the U.S. and Dow Corning Corporation be engaged in unsaturated fluoropolymer research and
Exploitation, but due to unsaturated fluoropolymer, often to there is product crosslinking, unsaturated bond content in preparation process uncontrollable, secondary
The shortcomings such as reaction is many and last handling process is complicated, seriously polluted, and unrealized large-scale production.Wherein, Minnesota Mining and Manufacturing Company is sent out
Bright preparation method is directly to add in extruder by fluoropolymer, the solid base of excess and phase transfer catalyst, at 200 DEG C
Lower extrusion.Although, this technique does not uses organic solvent, but under the alkaline reagent and high temperature action of excess, causes side reaction
Generation: (1) fluoropolymer chain cracking reaction and degrade, (2) a large amount of alkali effect produces hydroxyl, and (3) peroxidating creates carboxylic
Base；The unsaturated bond content of modified product is difficult to be controlled, and reacts the alkali of residual and phase transfer catalyst cannot letter
Single removes from product.Even to this day, yet there are no the report of the preparation method of unsaturated fluoropolymer both at home and abroad.
Summary of the invention
In order to solve the problems referred to above, the invention provides the preparation method of a kind of unsaturated fluoropolymer.Realize first
Unsaturated bond content is higher, and the preparation of the controlled fluoropolymer of content, and in preparation process, side reaction has obtained effective control,
The most quickly, aftertreatment technology is simple and environmentally-friendly, and productivity is more than 95% in reaction.
The present invention is achieved through the following technical solutions:
It is specially with fluoropolymer as raw material, is dissolved in organic solvent, can be at the work of alkali or alkali with a small amount of catalyst
Under with, it is placed in variable frequency microwave experimental machine " one pot " reaction carrying out Hofmann and Zaitsev, just can get unsaturated bond and contain
Measure higher, and the fluoropolymer that content is controlled, specifically include following steps:
A fluoropolymer is dissolved in organic solvent by (), after being completely dissolved, be not added with or add a small amount of phase transfer catalysis
Agent；
B () adds the aqueous slkali that mass concentration is 2.5～45%；Microwave power controls under 6～560KW, reaction 5～
270 minutes；
C () reaction separates organic facies and inorganic phase after terminating, purify after washing organic facies.Rotation is steamed organic solvent and carries out
Recovery can utilize by secondary, and product is dried under vacuum to constant weight at 55～70 DEG C.
Further, in technique scheme, described fluoropolymer raw material is to contain on main chain or side chain carbon
Having the polymer of fluorine atom, described polymer is high polymer and/or oligomer, and its number-average molecular weight is 0.5 × 103～1 × 106
In the range of, preferably 1 × 103～1 × 106, and strand has following structure:
Wherein R, R ' are identical or different, and each stand alone as the elements such as H, F, Cl, Br, I, CN；Also can each stand alone as straight
Alkyl group ,-(CH2)nCH3The integer of 0～10 (n be), is preferably-CH3、-CH2CH3；Hydroxyl straight chained alkyl ,-(CH2)mOH(m
It is the integer of 1～10), it is preferably-CH2OH；Carboxylic straight chained alkyl ,-(CH2)pThe COOH integer of 0～10 (p be), preferably
For-COOH ,-CH2COOH；Aryl, such as-C6H5；Phenoxy group, such as-OC6H5；Fluoroalkyl ,-(CF2)qCF3The integer of 0～10 (q be),
It is preferably-CF3、-CF2CF3；Fluoroalkyloxy ,-O (CF2)xOCF3The integer of 0～10 (x be), is preferably-OCF3,-O (CF2)5OCF3。
Can be homopolymer, such as: Kynoar；Can also be fluoroolefins analog copolymer, such as: vinylidene-tetrafluoro second
Alkene copolymer, vinylidene-chlorotrifluoroethylcopolymer copolymer, vinylidene-perfluoro methyl vinyl ether copolymer, inclined fluorine second
Alkene-hexafluoropropylene copolymer, vinylidene-perfluoroethylvinyl ether copolymer, vinylidene-perfluoro propyl vinyl ether are common
Polymers, biasfluoroethylene-hexafluoropropylene-tetrafluoroethylene terpolymer, vinylidene-tetrafluoroethylene-perfluoro methyl vinyl ether
Terpolymer, vinylidene-tetrafluoroethylene-perfluoro ethyl vinyl ether terpolymer, vinylidene-tetrafluoroethene-complete
Methyl fluoride vinyl ethers-one chlorotrifluoroethylene quadripolymer；Can also be fluoroolefins class and non-fluoroolefin copolymer, such as: four
Fluorothene-propylene copolymer, tetrafluoroethylene-perfluoro methyl vinyl ether-ethylene copolymer, vinylidene-ethylene copolymer, partially
Fluorothene-propylene copolymer, vinylidene-ethylene-tetrafluoroethylene terpolymer, vinylidene fluoride-propylene-tetrafluoroethylene triple
Copolymer, hexafluoropropene-ethylene copolymer, hexafluoropropene-tetrafluoroethylene-propylene terpolymer, vinylidene-hexafluoro third
Alkene-ethylene-tetrafluoroethylene quadripolymer etc.；Copolymer can also be the fluoropolymer containing elements such as Cl, Br, I or CN, excellent
Elect vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-tetrafluoraoethylene-hexafluoropropylene copolymer as.
Further, in technique scheme, the organic solvent dissolving fluoropolymer is polar organic solvent, fluorine-containing
Polymer solution mass concentration can be 5～25%, preferably 10～15%.Optional ethyl acetate, butyl acetate, trifluoro trichlorine
One or more the complex solvent system such as ethane, oxolane, preferably ethyl acetate, butyl acetate, oxolane/acetic acid
Ethyl ester compound system；It is that dichloromethane, normal hexane, hexamethylene, methanol, ethanol etc. are insoluble fluorine-containing poly-for purification of products reagent
The compounding organic solvent of one or more of compound, preferably dichloromethane, normal hexane.
Further, in technique scheme, described phase transfer catalyst can be immobilized or non-supported
Quaternary ammonium salt, has a below formula:
(R1R2R3R4N)+Z–
Wherein R1、R2、R3、R4Identical or different, and it is each independently 1～25 carbon atom straight chain alkyl, aryl；Z-For
Anion, such as Cl-、Br-、I-、HSO4 -.Can be tetrabutyl ammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutyl sulphuric acid
Hydrogen ammonium, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, benzyl triethyl ammonium chlorine
Change ammonium, tetradecyl trimethyl ammonium chloride etc. one or more, preferably tri-n-octyl methyl ammonium chloride, tetrabutylammonium chloride.
Can also be immobilized or non-supported season phosphonium salt class, there is below formula:
(R1′R2′R3′R4′P)+Z′–
Wherein R1′、R2′、R3′、R4' identical or different, and it is each independently the straight chained alkyl of 1～32 carbon atom, alkane
Epoxide, aryl, alkyl substituting aromatic base；Z′-For anion, such as Cl-、Br-、R5COO-, wherein, R5Straight chain alkane for carbon number 1～10
Base, such as-CH3、-CH2CH3.Can be tetraphenylphosphonium chloride, benzyl triphenyl phosphonium chloride phosphine, benzyltriphenylphosphonium bromide phosphine, (methoxy methyl
Base) triphenyl phosphine dichloride, (ethoxy carbonyl methyl) triphenyl phosphine dichloride, ethyl triphenyl acetic acid phosphine, four octyl group bromide phosphines, ten
Six alkyl trimethyl phosphonium chlorides etc. one or more, preferably benzyltriphenylphosphonium bromide phosphine, (ethoxy carbonyl methyl) triphenyl
Phosphonium chloride.
Further, in technique scheme, described phase transfer catalyst addition can be 0 or its addition with contain
The mass ratio of fluoropolymer can be 1:40～1:5, is preferably, 1:40～1:20.
Further, in technique scheme, described alkali can be organic amine compound, alkali metal hydroxide,
Carbonate or alkali-metal organic acid salt etc., optional triethylamine, potassium hydroxide, sodium hydroxide, sodium carbonate etc. one or more,
Aqueous slkali mass concentration can be 2.5～45%, preferably 2.5～10%, its addition be fluoropolymer quality 50～
2000%, preferably 100～1500%.
Further, in technique scheme, the response time is preferably 30～180 minutes, and microwave power is preferably 240
～400KW；The productivity of prepared unsaturated fluoropolymer is more than 95%, and aftertreatment technology is simple, and used organic molten
The most recyclable recycling of agent.
Further, in technique scheme, can be prepared containing multiple double bond structure and double bond content by the method
It can be controlled in the unsaturated fluoropolymer of 0.06～1mmol/g.
Further, product is carried out infrared spectrum (FTIR), nuclear-magnetism (19F-NMR, CFCl3For standard) and chlorine iodine method pair
Linkage content carries out testing and quantitative analysis, described in detail below:
The infared spectrum of all products shows at 1655cm-1Place all occurs in that carbon-to-carbon double bond characteristic peak；19F-NMR characterizes
Show and occur in that-CF=C (CF at δ-56 and-62ppm place3) characteristic peak ,-74ppm place occurs in that-CH=C (CF3) feature
Peak ,-81 occur in that the characteristic peak of-CH=CF-with-82ppm place, can be calculated carbon-to-carbon double bond by integration characteristic peak area
Content；Classical chlorine iodine method (standard GB/T/T 601-2002 and GB 1676-81) is used carbon-to-carbon double bond to be carried out quantitatively,
Double bond is titrated with the sodium thiosulfate of 0.1mol/L for standard solution, until indicator color fade is through calculating
Double bond content.
The beneficial effect of the invention
" one pot " that can be realized Hofmann and Zaitsev by the present invention is reacted, thus preparation is tied containing multiple double bond
Structure, and the unsaturated fluoropolymer that content is controlled.Involved preparation method has that technique is simple, reaction quickly, low cost
Honest and clean, after reacting especially with microwave-assisted, hence it is evident that shorten the response time.
Detailed description of the invention
Following nonlimiting examples can make those of ordinary skill in the art that the present invention be more fully understood, but not with
Any mode limits the present invention.
Embodiment 1
10g fluoropolymer (vinylidene fluoride-hexafluoropropylene copolymer) is used 100mL acetic acid ethyl dissolution, is placed in 500ml
In single port flask.It is sequentially added into phase transfer catalyst tri-n-octyl methyl ammonium chloride (0.25g), adds the potassium hydroxide water of 5wt%
Solution 150g, reacts 120 minutes under 400KW microwave.After reaction terminates, stand 10 minutes system layerings, extract upper strata organic
Phase, and add normal hexane and purify, solvent is steamed in rotation, and product is vacuum dried 24 hours at 55～70 DEG C.Product is carried out red
External spectrum (FTIR), nuclear-magnetism (19F-NMR, CFCl3For standard) and chlorine iodine method double bond content carry out testing and quantitative analysis:19F-
NMR unsaturated double-bond characteristic peak result of calculation is 1.94mol%, and double bond titration result of calculation is 0.19mmol/g.
Embodiment 2-4
Be prepared according to embodiment 1, test, computational methods, difference is phase transfer catalyst tri-n-octyl methyl ammonium chloride
The difference of consumption, concrete outcome is as shown in table 1.
Table 1
Embodiment 5-7
Be prepared according to embodiment 1, test, computational methods, difference be consumption of organic solvent be 100～120ml, specifically
Result is as shown in table 2.
Table 2
Embodiment 8-10
Be prepared according to embodiment 1, test, computational methods, difference is that organic solvent kind is different, concrete outcome such as table
Shown in 3.
Table 3
Embodiment 11-13
Be prepared according to embodiment 1, test, computational methods, difference is different for phase transfer catalyst kind, specifically ties
Fruit is as shown in table 4.
Table 4
Embodiment 14-18
Be prepared according to embodiment 1, test, computational methods, difference is microwave power different 160～480KW, specifically ties
Fruit is as shown in table 5.
Table 5
Embodiment 19-23
Be prepared according to embodiment 1, test, computational methods, difference is microwave power different 160～480KW, hydroxide
Potassium concn is 10wt%, and concrete outcome is as shown in table 6.
Table 6
Embodiment 24-26
Be prepared according to embodiment 1, test, computational methods, difference is that the kind of alkali is different, concrete outcome such as table 7 institute
Show.
Table 7
Embodiment 27-31
Be prepared according to embodiment 1, test, computational methods, difference is that the response time is different, concrete outcome such as table 8 institute
Show.
Table 8
Embodiment 32-36
Be prepared according to embodiment 1, test, computational methods, difference be microwave power be not all 160～480KW, reaction
Time is not all 180 minutes, and fluoropolymer species is different, for biasfluoroethylene-hexafluoropropylene-tetrafluoroethylene terpolymer,
Concrete outcome is as shown in table 9.
Table 9
Embodiment 37-41
Be prepared according to embodiment 1, test, computational methods, difference is that alkali consumption is different, concrete outcome such as table 10 institute
Show.
Table 10
From the above results, in described unsaturated fluoropolymer, double bond content is high, and its content is controlled；System
Preparation Method technique is simple, react quick, with low cost.
Embodiments of the present invention described in detail above, but, the present invention is not limited to the tool in above-mentioned embodiment
Body details, in the technology concept of the present invention, can carry out multiple simple variant to technical scheme, these letters
Monotropic type belongs to protection scope of the present invention.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. the preparation method of unsaturated fluoropolymer, it is characterised in that specifically include following steps:
A fluoropolymer is dissolved in polar organic solvent by (), be configured to mass concentration be 5～25% fluoropolymer have
Machine solution；
B () adds the aqueous slkali that mass concentration is 2.5～45%；Microwave power controls under 6～560KW, reacts 5～270 points
Clock；
C () reaction separates organic facies and inorganic phase after terminating, purify target product；
Or in step (a), after being completely dissolved, add the phase transfer that mass ratio is 1:40～1:5 with fluoropolymer and urge
Agent, carries out described step b, step c the most again.
2., according to the preparation method described in claim 1, it is characterised in that in described step (c), carry after organic facies is washed
Pure, revolve and steam organic solvent and carry out recovery and can utilize by secondary, product is dried under vacuum to constant weight at 55～70 DEG C.
3. according to the preparation method described in claim 1, it is characterised in that described fluoropolymer raw material is main chain or side
High polymer containing fluorine atom and/or oligomer on chain carbon atom, its number-average molecular weight is 0.5 × 103～1 × 106In the range of,
And strand has structure as shown below:
Wherein, R, R ' are identical or different, and are each independently selected from H, F, Cl, Br, I, CN, straight chained alkyl, hydroxyl or carboxyl
Straight chained alkyl, aryl, phenoxy group, fluoroalkyl, Fluoroalkyloxy；
Described straight chained alkyl chemistry formula is-(CH2)nCH3, n is the integer of 0～10；Described hydroxyl straight chained alkyl chemistry formula is-
(CH2)mOH, m are the integer of 1～10；Described carboxylic straight chained alkyl chemistry formula is-(CH2)pCOOH, p be 0～10 whole
Number；Described fluoroalkyl chemical formula is-(CF2)qCF3, q is the integer of 0～10；Described Fluoroalkyloxy chemical formula is-O (CF2)xOCF3, x is the integer of 0～10.
Preparation method the most according to claim 1, it is characterised in that described fluoropolymer is homopolymer, or be fluorine alkene
Hydrocarbon type copolymer, or be fluoroolefins class and non-fluoroolefin copolymer, or be the fluoropolymer containing Cl, Br, I, CN element.
Preparation method the most according to claim 1, it is characterised in that described fluoropolymer is homopolymer, selected from poly-inclined
Fluorothene；
Or be fluoroolefins analog copolymer, selected from skewed segregation, vinylidene-chlorotrifluoroethylene copolymerization
Thing, vinylidene-perfluoro methyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-perfluoro-ethyl
Vinyl ether co-polymer, vinylidene-perfluoro propyl vinyl ether copolymer, biasfluoroethylene-hexafluoropropylene-tetrafluoroethylene triple
Copolymer, vinylidene-tetrafluoroethylene-perfluoro methyl vinyl ether terpolymer, vinylidene-tetrafluoroethylene-perfluoro second
Base vinyl ethers terpolymer, vinylidene-tetrafluoroethylene-perfluoro methyl vinyl ether-chlorotrifluoroethylene is quarternary copolymerized
Thing；
Or be fluoroolefins class and non-fluoroolefin copolymer, selected from tetrafluoroethylene propylene copolymer, tetrafluoroethylene-perfluoro methyl second
Alkene ether-ethylene copolymer, vinylidene-ethylene copolymer, vinylidene fluoride-propylene copolymer, vinylidene-ethylene-tetrafluoro
Ethylene-dien terpolymer, vinylidene fluoride-propylene-tetrafluoroethylene terpolymer, hexafluoropropene-ethylene copolymer, hexafluoropropene-
Tetrafluoroethylene-propylene terpolymer, biasfluoroethylene-hexafluoropropylene-ethylene-tetrafluoroethylene quadripolymer；
Or be the fluoropolymer containing Cl, Br, I or CN element.
Preparation method the most according to claim 1 and 2, it is characterised in that for purification of products reagent for insoluble fluorine-containing
The organic solvent of polymer.
Preparation method the most according to claim 1 and 2, it is characterised in that the organic solvent of described dissolving fluoropolymer,
The complex solvent system of one or more in ethyl acetate, butyl acetate, trifluorotrichloroethane, oxolane；
For the organic solvent that purification of products reagent is insoluble fluoropolymer, selected from dichloromethane, normal hexane, hexamethylene,
One in methanol, ethanol, or multiple compounding organic solvent.
8. according to the preparation method described in claim 1, it is characterised in that described phase transfer catalyst is immobilized or non-solid
The quaternary ammonium salt of loadization, has a below formula:
(R1R2R3R4N)+Z–
Wherein R1、R2、R3、R4Identical or different, and it is each independently selected from the straight chained alkyl of 1～25 carbon atom, aryl；
Z-For anion, selected from Cl-、Br-、I-、HSO4 -。
Or be immobilized or non-supported season phosphonium salt class, there is below formula:
(R1′R2′R3′R4′P)+Z′–
Wherein R1′、R2′、R3′、R4' identical or different, and be each independently the straight chained alkyl of 1～32 carbon atom, alkoxyl,
Aryl, alkyl substituting aromatic base；
Z′-For anion, selected from Cl-、Br-、R5COO-, wherein, R5Straight chained alkyl for carbon number 1～10.
9. according to the preparation method described in claim 1, it is characterised in that:
Described phase transfer catalyst is selected from tetrabutyl ammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutyl hydrogen sulfate
Ammonium, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, benzyl triethyl ammonium chlorination
One or more in ammonium, tetradecyl trimethyl ammonium chloride.
Or selected from tetraphenylphosphonium chloride, benzyl triphenyl phosphonium chloride phosphine, benzyltriphenylphosphonium bromide phosphine, (methoxy) triphenyl chlorine
Change phosphine, (ethoxy carbonyl methyl) triphenyl phosphine dichloride, ethyl triphenyl acetic acid phosphine, four octyl group bromide phosphines, cetyl front three
Base phosphonium chloride one or more.
10. according to the preparation method described in claim 1, it is characterised in that described alkali is selected from organic amine compound, alkali gold
Belonging to hydroxide, carbonate or alkali-metal organic acid salt, addition is the 50～2000% of fluoropolymer quality.
11. according to the preparation method described in claim 1, it is characterised in that can be prepared containing multiple double bond by the method
Structure and double bond content can be controlled in the unsaturated fluoropolymer of 0.06～1mmol/g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417844A (en) * | 2017-06-02 | 2017-12-01 | 大连海事大学 | A kind of preparation method of terminal aldehyde group low molecule amount fluoropolymer |
| CN107674133A (en) * | 2017-10-26 | 2018-02-09 | 大连海事大学 | The method that boron hydride/rare earth element chloride reduction system prepares terminal hydroxy group low molecule amount fluoropolymer |
| CN115124637A (en) * | 2022-06-13 | 2022-09-30 | 沈阳化工大学 | Preparation method of high-performance low-molecular-weight amino-terminated fluorine-containing polymer |
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| WO2006090728A1 (en) * | 2005-02-23 | 2006-08-31 | Daikin Industries, Ltd. | Fluoroelastomer and process for producing fluoroelastomer |
| CN103435724A (en) * | 2013-09-09 | 2013-12-11 | 湖北工业大学 | Alkali treatment modification method of microwave reinforced halogenated olefin polymers |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006090728A1 (en) * | 2005-02-23 | 2006-08-31 | Daikin Industries, Ltd. | Fluoroelastomer and process for producing fluoroelastomer |
| CN103435724A (en) * | 2013-09-09 | 2013-12-11 | 湖北工业大学 | Alkali treatment modification method of microwave reinforced halogenated olefin polymers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417844A (en) * | 2017-06-02 | 2017-12-01 | 大连海事大学 | A kind of preparation method of terminal aldehyde group low molecule amount fluoropolymer |
| CN107674133A (en) * | 2017-10-26 | 2018-02-09 | 大连海事大学 | The method that boron hydride/rare earth element chloride reduction system prepares terminal hydroxy group low molecule amount fluoropolymer |
| CN107674133B (en) * | 2017-10-26 | 2019-08-20 | 大连海事大学 | Boron hydride/rare earth element chloride reduction system prepares the fluoropolymer-containing method of terminal hydroxy group low molecular weight |
| CN115124637A (en) * | 2022-06-13 | 2022-09-30 | 沈阳化工大学 | Preparation method of high-performance low-molecular-weight amino-terminated fluorine-containing polymer |
| CN115124637B (en) * | 2022-06-13 | 2023-11-28 | 沈阳化工大学 | Preparation method of high-performance low-molecular-weight amino-terminated fluorine-containing polymer |
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