CN116375922A - Fluorine-containing organic polymer and preparation method thereof - Google Patents
Fluorine-containing organic polymer and preparation method thereof Download PDFInfo
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 61
- 239000011737 fluorine Substances 0.000 title claims abstract description 61
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000002978 peroxides Chemical class 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- NOPJRYAFUXTDLX-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane Chemical compound COC(F)(F)C(F)(F)C(F)(F)F NOPJRYAFUXTDLX-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- -1 R113 Chemical compound 0.000 claims 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 9
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 13
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 3
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical group FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of fluorine-containing polymer synthesis, in particular to a fluorine-containing organic polymer and a preparation method thereof. The invention provides a fluorine-containing organic polymer, which has a structure shown in a formula I; in the formula I, 20< n <1000. The invention takes peroxide as an initiator to initiate the free radical polymerization reaction of fluorine-containing monomers containing unsaturated bonds and cyclic monomers to prepare the vinylidene fluoride copolymer with a cyclic structure on the main chain. The copolymer has lower crystallinity, better transparency and higher Tg. Meanwhile, the method is simple and practical in reaction operation and mild in reaction condition.
Description
Technical Field
The invention relates to the technical field of fluorine-containing polymer synthesis, in particular to a fluorine-containing organic polymer and a preparation method thereof.
Background
Polyvinylidene fluoride is a special engineering plastic, and has excellent chemical corrosion resistance, high temperature resistance, weather resistance, ultraviolet resistance, high hardness, wear resistance, high heat distortion temperature, good electrical insulation performance and the like. Accordingly, research on polyvinylidene fluoride has been attracting attention. To widen the application of the material in the cable field, the flexibility of polyvinylidene fluoride needs to be further improved. Among them, copolymerization of vinylidene fluoride (VDF) with a second monomer is an important research direction. For example, copolymers containing vinylidene fluoride (VDF), hexafluoropropylene (HFP) or Chlorotrifluoroethylene (CTFE) have been proposed (WO 1999/034372).
The copolymerization results described above do improve some of the properties of PVDF, but the Tg of these copolymers is lower and the films produced have a degree of haze. In the field of optical applications, however, polymeric materials are required to have chemical resistance, optical transparency, and a relatively high Tg. Patent CN105669891a mentions that after replacing trifluoromethyl ethylene in vinylidene fluoride, trifluoromethyl ethylene copolymers with 2, 3-tetrafluoropropene, these copolymers formed have excellent optical properties, erosion resistance, electrical properties and low haze, however, the Tg of these copolymers is lower, which affects the range of applications. In CN1189489C, the crystallinity of the copolymer is reduced by copolymerizing hexafluoropropylene with vinylidene fluoride, and when the hexafluoropropylene content in the copolymer reaches 36% or more, the crystallinity of the copolymer is 0, and it can be seen that the disadvantage of this technique is that the crystallinity can be greatly reduced when the hexafluoropropylene content in the copolymer is high.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a fluorine-containing organic polymer and a preparation method thereof, wherein the fluorine-containing organic polymer has a lower crystallinity and a higher Tg.
The invention provides a fluorine-containing organic polymer, which has a structure shown in a formula I:
in the formula I, 20< n <1000.
The invention also provides a preparation method of the fluorine-containing organic polymer, which comprises the following steps:
the fluorine-containing monomer with the structure shown in the formula II and the cyclic monomer with the structure shown in the formula III are subjected to polymerization reaction under the action of an initiator to obtain the fluorine-containing organic polymer with the structure shown in the formula I;
in the formula I, 20< n <1000.
Preferably, the molar ratio of the fluorine-containing monomer having the structure shown in formula II to the cyclic monomer having the structure shown in formula III is 0.2 to 1:0.1 to 1.
Preferably, the initiator is a peroxide;
the molar ratio of the initiator to the fluorine-containing monomer with the structure shown in the formula II is 0.001-0.020: 0.1 to 1.
Preferably, the peroxide comprises at least one of ammonium persulfate, potassium persulfate, tert-butyl peroxypivalate, and diisopropyl peroxydicarbonate.
Preferably, the temperature of the polymerization reaction is-30-120 ℃ and the time is 24-48 h.
Preferably, the polymerization reaction temperature is 60 to 100 ℃.
Preferably, the method comprises the following steps:
mixing an organic solvent, a fluorine-containing monomer with a structure shown in a formula II, a cyclic monomer with a structure shown in a formula III and an initiator solution under the condition that the oxygen content is less than 20ppm, and performing polymerization reaction to obtain the fluorine-containing organic polymer with the structure shown in the formula I.
Preferably, the organic solvent comprises at least one of ethyl acetate, butyl acetate, acetone, tetrahydrofuran, R113 and HFE-347;
the solvent in the initiator solution comprises at least one of ethyl acetate, butyl acetate, acetone, tetrahydrofuran, R113 and HFE-347;
the mass concentration of the initiator solution is 4-6%.
Preferably, the ratio of the fluorine-containing monomer with the structure shown in the formula II to the organic solvent is 0.1-5.0 mmol:1mL.
The invention provides a fluorine-containing organic polymer (vinylidene fluoride and cyclopentadiene copolymer) which has a structure shown in a formula I:
in the formula I, 20< n <1000.
The invention takes peroxide as an initiator to initiate the free radical polymerization reaction of fluorine-containing monomers containing unsaturated bonds and cyclic monomers to prepare the vinylidene fluoride copolymer with a cyclic structure on the main chain. The copolymer has lower crystallinity, better transparency and higher Tg. Meanwhile, the method is simple and practical in reaction operation and mild in reaction condition.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a white powder obtained in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a fluorine-containing organic polymer (vinylidene fluoride and cyclopentadiene copolymer) which has a structure shown in a formula I:
in the formula I, 20< n <1000.
In the present invention, when the mass content of dicyclopentadiene in the fluorine-containing organic polymer reaches 27% or more, the Tg of the fluorine-containing organic polymer is not lower than 98 ℃, the crystallinity is 0%, and the transparency is excellent.
In the fluorine-containing organic polymer provided by the invention, when the mass content of dicyclopentadiene is 10% -27%, the Tg of the fluorine-containing organic polymer is 51-98 ℃, and the crystallinity is 0% -13%. Specifically, when the mass content of dicyclopentadiene in the fluorine-containing organic polymer is 10%, the Tg of the fluorine-containing organic polymer is 51℃and the crystallinity thereof is 13%. Or when the mass content of dicyclopentadiene in the fluorine-containing organic polymer is 15%, the Tg of the fluorine-containing organic polymer is 71 ℃ and the crystallinity is 7%. Or when the mass content of dicyclopentadiene in the fluorine-containing organic polymer is 19%, the Tg of the fluorine-containing organic polymer is 76 ℃ and the crystallinity is 5%. Or when the mass content of dicyclopentadiene in the fluorine-containing organic polymer is 27%, the Tg of the fluorine-containing organic polymer is 98 ℃ and the crystallinity is 0%.
The invention also provides a preparation method of the fluorine-containing organic polymer, which comprises the following steps:
the fluorine-containing monomer with the structure shown in the formula II and the cyclic monomer with the structure shown in the formula III are subjected to polymerization reaction under the action of an initiator to obtain the fluorine-containing organic polymer with the structure shown in the formula I;
in the formula I, 20< n <1000.
In certain embodiments of the present invention, the molar ratio of the fluoromonomer having the structure of formula II to the cyclic monomer having the structure of formula III is from 0.2 to 1:0.1 to 1; preferably 1:1, a step of; the method specifically comprises the following steps of 1:1. 1:0.3 or 1:0.15.
in certain embodiments of the invention, the initiator is a peroxide. Specifically, the peroxide comprises at least one of ammonium persulfate, potassium persulfate, tert-butyl peroxypivalate and diisopropyl peroxydicarbonate; diisopropyl peroxydicarbonate is preferred.
The molar ratio of the initiator to the fluorine-containing monomer with the structure shown in the formula II is 0.001-0.020: 0.1 to 1; specifically, 0.001:0.4 or 0.001:0.2.
in certain embodiments of the invention, the polymerization is carried out at an oxygen content of less than 20ppm. The invention may be carried out by purging the reaction vessel with nitrogen, sealing the reaction vessel, and vacuum/nitrogen displacing the reaction vessel until the oxygen content in the reaction vessel is less than 20ppm.
In certain embodiments of the invention, the polymerization reaction is carried out in an organic solvent. The organic solvent comprises at least one of ethyl acetate, butyl acetate, acetone, tetrahydrofuran, R113 and HFE-347; r113 is preferred. The dosage ratio of the fluorine-containing monomer with the structure shown in the formula II to the organic solvent is 0.1-5.0 mmol:1mL; preferably 0.1 to 3.0mmol:1mL.
In certain embodiments of the invention, the polymerization reaction is carried out at a temperature of-30 to 120 ℃ for a period of 24 to 48 hours; specifically 24 hours. Preferably, the temperature of the polymerization reaction is 60-100 ℃; specifically 40℃or 60 ℃. The polymerization reaction is carried out under stirring, and the polymerization reaction is carried out in a high-pressure reaction kettle.
In certain embodiments of the present invention, the method of preparing the fluorine-containing organic polymer comprises the steps of:
mixing an organic solvent, a fluorine-containing monomer with a structure shown in a formula II, a cyclic monomer with a structure shown in a formula III and an initiator solution under the condition that the oxygen content is less than 20ppm, and performing polymerization reaction to obtain the fluorine-containing organic polymer with the structure shown in the formula I.
In certain embodiments, the mixing is stirring mixing.
The solvent in the initiator solution comprises at least one of ethyl acetate, butyl acetate, acetone, tetrahydrofuran, R113 and HFE-347; preferably R113;
the mass concentration of the initiator solution is 4% -6%; specifically 5%.
In certain embodiments of the present invention, after the polymerization reaction, further comprising:
and pouring the product solution after the polymerization reaction into excessive n-hexane to separate out the product, removing the upper organic solvent, and drying to obtain the polymerized product, namely the fluorine-containing organic polymer with the structure shown in the formula I.
The mass ratio of the normal hexane to the product solution is greater than 10:1, a step of; the specific method is 11:1.
the temperature of the n-hexane is less than or equal to 25 ℃; specifically 23 ℃.
The drying temperature is 70-90 ℃, and is specifically 80 ℃; the time is 10-14 h, specifically 12h.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The beneficial effects are that:
1) The invention takes peroxide as an initiator to initiate the free radical polymerization reaction of fluorine-containing monomers containing unsaturated bonds and cyclic monomers to prepare the vinylidene fluoride copolymer with a cyclic structure on the main chain. The copolymer has lower crystallinity, better transparency and higher Tg.
2) The method is simple and practical in reaction operation and mild in reaction condition;
3) The double bonds remaining in the side chains of the copolymers synthesized according to the invention can be used for crosslinking.
In order to further illustrate the present invention, the following examples are provided to describe in detail a fluorine-containing organic polymer and a method for preparing the same, but are not to be construed as limiting the scope of the present invention.
In the examples, tg and crystallinity are measured according to standard D3418, and the Tg values shown in the examples are midpoint Tg.
Example 1
Purging the 1L high-pressure reaction kettle with nitrogen, sealing the reaction kettle, replacing the reaction kettle with vacuum/nitrogen until the oxygen content in the kettle is less than 20ppm, adding 0.4L R113, 88g (667 mmol) of a cyclic monomer with a structure shown in a formula III, 128g (2000 mmol) of a fluorine-containing monomer with a structure shown in a formula II and 10mL of an R113 solution of diisopropyl peroxydicarbonate (1.03 g,5 mmol), reacting at 40 ℃ for 24h, stopping stirring, emptying to normal pressure, collecting a product solution, pouring excessive 23 ℃ n-hexane (the mass ratio of the n-hexane to the product solution is 11:1), precipitating a copolymer, removing an upper organic solvent, and drying the copolymer in a vacuum oven at 80 ℃ for 12h to obtain 65g of white powder.
The obtained white powder was subjected to nuclear magnetic resonance hydrogen spectrum analysis, and the results are shown in fig. 1. FIG. 1 is a nuclear magnetic resonance spectrum of a white powder obtained in example 1 of the present invention, 20 in the polymer of FIG. 1<n<1000. As can be seen from FIG. 1, in the nuclear magnetic resonance hydrogen spectrum, 5.5 to 6.5ppm of C-H whose peak is the unsaturated double bond of the polymer I; 1.5 to 2.0ppm of CF with polymer I 2 Adjacent C-H. Thus, the resulting white powder had the structure shown in formula I.
From the nuclear magnetic data calculation, the mass content of dicyclopentadiene in the polymer was 15%, and the mass content of 1, 1-vinylidene fluoride was 85%. The Tg of the fluorine-containing organic polymer with the structure shown in the formula I is 71 ℃ and the crystallinity is 7 percent. See in particular table 1.
Example 2
Purging the 1L autoclave with nitrogen, sealing the autoclave, replacing the autoclave with vacuum/nitrogen until the oxygen content in the autoclave is less than 20ppm, adding 88g (667 mmol) of 0.4L R113 cyclic monomer having the structure shown in formula III, 128g (2000 mmol) of fluorine-containing monomer having the structure shown in formula II and 10mL of R113 solution of tert-butyl peroxypivalate (0.87 g,5 mmol), reacting at 60 ℃ for 24h, stopping stirring, emptying to normal pressure, collecting the product solution, pouring excessive 23 ℃ n-hexane (the mass ratio of the n-hexane to the product solution is 11:1), precipitating the copolymer, removing the upper organic solvent, and drying the copolymer in a vacuum oven at 80 ℃ for 12h to obtain 73g of white powder.
From the nuclear magnetic data, the mass content of dicyclopentadiene in the polymer was 19% and the mass content of 1, 1-vinylidene fluoride was 81%. The Tg of the fluorine-containing organic polymer with the structure shown in the formula I is 76 ℃ and the crystallinity is 5 percent. See in particular table 1.
Example 3
Purging the 1L autoclave with nitrogen, sealing the autoclave, replacing the autoclave with vacuum/nitrogen until the oxygen content in the autoclave is less than 20ppm, adding 0.4L R113, 44g (333 mmol) of cyclic monomer with the structure shown in formula III, 128g (2000 mmol) of fluoromonomer with the structure shown in formula II and 10mL of R113 solution of tert-butyl peroxypivalate (0.87 g,5 mmol), reacting at 60 ℃ for 24h, stopping stirring, evacuating to normal pressure, collecting the product solution, pouring excessive 23 ℃ n-hexane (the mass ratio of the n-hexane to the product solution is 11:1), precipitating the copolymer, removing the upper organic solvent, and drying the copolymer in a vacuum oven at 80 ℃ for 12h to obtain 81g of white powder.
From the nuclear magnetic data, the mass content of dicyclopentadiene in the polymer was 10% and the mass content of 1, 1-vinylidene fluoride was 90%. The detection shows that the Tg of the fluorine-containing organic polymer with the structure shown in the formula I is 51 ℃ and the crystallinity is 13%. See in particular table 1.
Example 4
Purging the 1L high-pressure reaction kettle with nitrogen, sealing the reaction kettle, replacing the reaction kettle with vacuum/nitrogen until the oxygen content in the kettle is less than 20ppm, adding 0.4L R113, 132g (1000 mmol) of cyclic monomer with a structure shown in a formula III, 64g (1000 mmol) of fluorine-containing monomer with a structure shown in a formula II and 10mL of R113 solution of tert-butyl peroxypivalate (0.87 g,5 mmol), reacting at 60 ℃ for 24 hours, stopping stirring, emptying to normal pressure, collecting a product solution, pouring excessive 23 ℃ n-hexane (the mass ratio of the n-hexane to the product solution is 11:1), precipitating a copolymer, removing an upper organic solvent, and drying the copolymer in a vacuum oven at 80 ℃ for 12 hours to obtain 26g of white powder.
From the nuclear magnetic data, the mass content of dicyclopentadiene in the polymer was 27%, and the mass content of 1, 1-vinylidene fluoride was 73%. The detection shows that the Tg of the fluorine-containing organic polymer with the structure shown in the formula I is 98 ℃ and the crystallinity is 0%. See in particular table 1.
TABLE 1 monomer mass content and crystallinity in the copolymers obtained in examples 1 to 4
| Examples | 1, 1-vinylidene fluoride content | Dicyclopentadiene content | Crystallinity degree |
| 1 | 85％ | 15％ | 7％ |
| 2 | 81％ | 19％ | 5％ |
| 3 | 90％ | 10％ | 13％ |
| 4 | 73％ | 27％ | 0％ |
Comparative examples 1 to 3
Patent CN1189489C, entitled "low crystallinity copolymer of 1, 1-vinylidene fluoride and hexafluoropropylene", mentions that the crystallinity of the copolymer is 0 only when the hexafluoropropylene content in the copolymer reaches 36% and above. When the hexafluoropropylene content was 31%, the crystallinity of the copolymer was 7%. When the hexafluoropropylene content was 29%, the crystallinity of the copolymer was 10%. See in particular table 1.
TABLE 1 monomer mass content and crystallinity in the copolymers obtained in comparative examples 1 to 3
| Comparative example | 1, 1-vinylidene fluoride content | Hexafluoropropylene content | Crystallinity degree |
| 1 | 64％ | 36％ | 0％ |
| 2 | 69％ | 31％ | 7％ |
| 3 | 71％ | 29％ | 10％ |
Comparing examples 1 to 4 of the present invention with comparative examples 1 to 3, it is understood that the crystallinity of the copolymer can be reduced to 0% when the mass content of dicyclopentadiene in the copolymer is 27%; when hexafluoropropylene and vinylidene fluoride are copolymerized, the crystallinity of the copolymer can be reduced to 0% only when the mass content of hexafluoropropylene reaches 36%. Thus, dicyclopentadiene can lower the crystallinity of the vinylidene fluoride copolymer more effectively than hexafluoropropylene.
Experimental results show that the fluorine-containing organic polymer provided by the invention has lower crystallinity (better transparency) and higher Tg.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A fluorine-containing organic polymer having a structure represented by formula i:
in the formula I, 20< n <1000.
2. A method for preparing a fluorine-containing organic polymer, comprising the steps of:
the fluorine-containing monomer with the structure shown in the formula II and the cyclic monomer with the structure shown in the formula III are subjected to polymerization reaction under the action of an initiator to obtain the fluorine-containing organic polymer with the structure shown in the formula I;
in the formula I, 20< n <1000.
3. The preparation method according to claim 2, wherein the molar ratio of the fluorine-containing monomer having the structure represented by formula ii to the cyclic monomer having the structure represented by formula iii is 0.2 to 1:0.1 to 1.
4. The method of claim 2, wherein the initiator is a peroxide;
the molar ratio of the initiator to the fluorine-containing monomer with the structure shown in the formula II is 0.001-0.020: 0.1 to 1.
5. The method according to claim 4, wherein the peroxide comprises at least one of ammonium persulfate, potassium persulfate, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate.
6. The method according to claim 2, wherein the polymerization reaction is carried out at a temperature of-30 to 120 ℃ for a time of 24 to 48 hours.
7. The process according to claim 2, wherein the polymerization reaction temperature is 60 to 100 ℃.
8. The preparation method according to claim 2, characterized by comprising the steps of:
mixing an organic solvent, a fluorine-containing monomer with a structure shown in a formula II, a cyclic monomer with a structure shown in a formula III and an initiator solution under the condition that the oxygen content is less than 20ppm, and performing polymerization reaction to obtain the fluorine-containing organic polymer with the structure shown in the formula I.
9. The method of preparing according to claim 8, wherein the organic solvent comprises at least one of ethyl acetate, butyl acetate, acetone, tetrahydrofuran, R113, and HFE-347;
the solvent in the initiator solution comprises at least one of ethyl acetate, butyl acetate, acetone, tetrahydrofuran, R113 and HFE-347;
the mass concentration of the initiator solution is 4-6%.
10. The process according to claim 8, wherein the ratio of the fluoromonomer having the structure represented by formula II to the organic solvent is 0.1 to 5.0mmol:1mL.
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