CN110240671A - A kind of fluororesin and preparation method thereof - Google Patents
A kind of fluororesin and preparation method thereof Download PDFInfo
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- CN110240671A CN110240671A CN201810195474.4A CN201810195474A CN110240671A CN 110240671 A CN110240671 A CN 110240671A CN 201810195474 A CN201810195474 A CN 201810195474A CN 110240671 A CN110240671 A CN 110240671A
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- 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
- C08F214/24—Trifluorochloroethene
- C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
- C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
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- 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
- C09D127/00—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/165—Carbocyclic compounds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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Abstract
It include structural unit A in structural unit, the structural unit A is detailed in specification the invention discloses a kind of trifluorochlorethylene resin.Trifluorochlorethylene resin provided by the invention has many advantages, such as that storage stability is good, lower production costs.
Description
Technical field
The invention belongs to fluoro-containing macromolecule material fields, are related to a kind of fluororesin, more particularly, to a kind of room temperature curing fluorine
The novel fluororesin of coating.
Background technique
Cross-linking fluorocarbon resin coating is greatly expanded it and answers due to having the characteristics that solvent is solvable and room-temperature-curable
It is all existing wide in the fields such as external wall, steel construction and concrete-bridge, offshore steel structure equipment and new energy at present with field
General application.
The main component for constituting cross-linking fluorocarbon coating is fluorocarbon resin, is easy to happen gelation during storage,
Research at present is commonly considered as because chlorotrifluoroethylene decomposition produces inorganic acid substance during polymerization and storage, in the later period
Storage during cause resin portion crosslinking generate gelation, so as to cause resin molecular weight increase, molecular weight distribution broaden,
Influence the service performance of coating.
To solve fluorocarbon resin gelation problems, improve the stability of cross-linking fluorocarbon resin, the prior art made as
Lower effort:
(1) Chinese patent CN102325802B obtains one kind by adding potassium carbonate and hydrotalcite in the course of the polymerization process
Storage stability is good and is not easy the copolymer solution coloured.The polymer solution is stored 7 days at 70 DEG C, is not coagulated
Gelatinization has good stability.The method needs to be filtered to remove insoluble matter with diatomite after completion of polymerization, can just obtain stable fluorine
Carbon copolymer solution, so that process is tedious, the production cost increases；
(2) Chinese patent CN104704013A provides that a kind of storage stability is good and that the drying property of film is made is good
Fluorinated copolymer solution manufacturing method, realized by the way that compound with piperidyl is added in the course of the polymerization process, preparation
For copolymer solution after 70 DEG C store 14 days, less than 150%, 70 DEG C storage stability of weight average molecular weight increment rate is good.This side
The piperidinyl compounds price that method uses costly, will increase production cost.
The prior art generally by the course of the polymerization process or polymerization after add alkali carbonate, metal hydroxides or
Person's organic stabilizer improves the post storage stability of resin, all has the problems such as process is tedious, the production cost increases.Cause
This, it is necessary to further technological improvement is done to the stability of cross-linking fluorocarbon resin.
Summary of the invention
The purpose of the present invention is to provide a kind of novel fluororesin of room temperature curing fluoro coatings, good with storage stability,
The advantages that lower production costs.
The present invention in trifluorochlorethylene resin by introducing a kind of copolymerisable monomer containing tertiary amine groups, with trifluoro chloroethene
Alkene forms copolymer resins, and the technical solution provided is as follows:
A kind of trifluorochlorethylene resin, the trifluorochlorethylene resin include chlorotrifluoroethylene structural unit and A structure list
Member, wherein structural unit A is selected from following structural formula (A1) and/or (A2):
Wherein: R1Selected from hydrogen, C1~C4 alkyl, R2Selected from hydrogen, C1~C4 alkyl, n1And n2Independently selected from 1~6 it is whole
Number.
Structural unit shown in the structural formula (A1) that the present invention uses, substituent R in structure1Selected from hydrogen, C1~C4 alkane
Base.
Preferably, the substituent R1Selected from hydrogen, methyl, ethyl, tert-butyl.
Still further preferably, the substituent R1Selected from hydrogen, methyl.
Invent structural unit shown in the structural formula (A1) used, n in structure1Independently selected from 1~6 integer.
Preferably, the n1Independently selected from 2~4 integer.
Still further preferably, the n1Independently selected from 2~3 integer.
Structural unit shown in the structural formula (A2) that the present invention uses, substituent R in structure2Selected from hydrogen, C1~C4 alkane
Base.
Preferably, the substituent R2Selected from hydrogen, methyl, ethyl, isopropyl.
Still further preferably, the substituent R2Selected from hydrogen, methyl.
Structural unit shown in the structural formula (A2) that the present invention uses, n in structure2Independently selected from 1~6 integer.
Preferably, the n2Independently selected from 2~4 integer.
Still further preferably, the n2Independently selected from 2~3 integer.
Trifluorochlorethylene resin provided by the invention, the structural unit A and chlorotrifluoroethylene structural unit mole are matched
Trifluorochlorethylene resin is set to be not easy acidification during storage than meeting.
Preferably, the structural unit A and the mol ratio of chlorotrifluoroethylene structural unit are 1:25~1:500.
It may further be preferable that the structural unit A and the mol ratio of chlorotrifluoroethylene structural unit are 1:50~1:
150。
Trifluorochlorethylene resin provided by the invention removes structural unit A and chlorotrifluoroethylene structural unit, can also be into one
Step includes vinyl esters or alkyl vinyl ether structural unit, hydroxyalkyl vinylether structural unit and undecenoic acid structure list
Member etc..
When the trifluorochlorethylene resin further includes other structures unit, as a preferred mode, institute
Stating trifluorochlorethylene resin includes following structural unit:
(1) chlorotrifluoroethylene structural unit, and chlorotrifluoroethylene structural unit mole containing in trifluorochlorethylene resin
Amount is 45~55%；
(2) vinyl esters or alkyl vinyl ether structural unit, and vinyl esters or alkyl vinyl ether structural unit exist
Molar content in trifluorochlorethylene resin is 34~42%；
(3) hydroxyalkyl vinylether structural unit, and hydroxyalkyl vinylether structural unit is in trifluorochlorethylene resin
Molar content be 6~12%；
(4) undecenoic acid structural unit, and molar content of the undecenoic acid structural unit in trifluorochlorethylene resin is 0
~2%；
(5) structural unit A, and molar content of the structural unit A in trifluorochlorethylene resin is 0.1~3%.
Above-mentioned vinyl esters, it is preferred that the vinyl esters is selected from vinyl acetate, vinyl propionate, butyric acid ethylene
At least one of ester, vinyl caproate and tertiary ethylene carbonate.
It may further be preferable that the vinyl esters is selected from least one of vinyl acetate and tertiary ethylene carbonate.
Abovementioned alkyl vinyl ethers, it is preferred that the alkyl vinyl ether is selected from ethyl vinyl ether, cyclohexyl. vinyl
At least one of base ether, isopropyl-ethylene base ether and butyl vinyl ether.
It may further be preferable that the alkyl vinyl ether in ethyl vinyl ether and cyclohexyl vinyl ether extremely
Few one kind.
Above-mentioned hydroxyalkyl vinylether, it is preferred that the hydroxyalkyl vinylether is selected from hydroxyethyl vinylethers and 4-
One of hydroxy butyl vinyl ether.
When the trifluorochlorethylene resin includes chlorotrifluoroethylene structural unit, structural unit A, vinyl esters or alkyl second
When alkene ether structural unit, hydroxyalkyl vinylether structural unit and undecenoic acid structural unit, as a preferred mode,
In the trifluorochlorethylene resin:
Molar content of the chlorotrifluoroethylene structural unit in trifluorochlorethylene resin is 48-52%；
The molar content of vinyl esters or alkyl vinyl ether structural unit in trifluorochlorethylene resin is 36~40%；
Molar content of the hydroxyalkyl vinylether structural unit in trifluorochlorethylene resin is 8~10%；
Molar content of the undecenoic acid structural unit in trifluorochlorethylene resin is 0~1.5%；
Molar content of the structural unit A in trifluorochlorethylene resin is 0.3-2%.
The present invention also provides a kind of preparation methods of trifluorochlorethylene resin.As an example, the preparation side
Method may include:
(1) jacket of polymerization leads to chilled brine cooling, is down to 0 DEG C hereinafter, being vacuumized to reaction kettle, nitrogen to temperature
Displacement, until spare after oxygen content is qualified less than 30ppm displacement；
(2) by comonomer ethylene base ester or alkyl vinyl ether, hydroxyalkyl vinylether, undecenoic acid, structural unit
A, solvent, initiator proportionally sequentially add in polymeric kettle；
(3) chlorotrifluoroethylene monomer is added to polymeric kettle；
(4) reaction kettle heats up, and controls 48~60 DEG C of reaction temperature, 6~12h of reaction time；
(5) after polymerizeing, polymeric kettle cooling recycles unreacted chlorotrifluoroethylene monomer, releases polymer material；
(6) unreacted liquid monomer, concentration adjustment fluororesin solution viscosity to requirement are distilled to recover to get trifluoro is arrived
Vinyl chloride resin.
Initiator used in preparation method of the present invention can be initiator commonly used in the art.Preferably, institute
Stating initiator is oil soluble peroxides class initiator.As an example, the oil soluble peroxides class initiator can be
Aoxidize two diisopropyl carbonates.
The dosage of the initiator can be dosage commonly used in the art.Preferably, the dosage of the initiator is three
The 0.5%~1% of fluorine vinyl chloride monomer inventory.
Solvent used in preparation method of the present invention can be solvent commonly used in the art.As an example, described molten
Agent can be dimethylbenzene or butyl acetate, and the two can be used in mixed way with arbitrary proportion.
Trifluorochlorethylene resin provided by the invention, fluorine element content is greater than 24% in structure, trifluorochlorethylene resin
Glass transition temperature be 30~40 DEG C.
The present invention in trifluorochlorethylene resin by introducing a kind of copolymerisable monomer containing tertiary amine groups, with trifluoro chloroethene
Alkene forms copolymer resins, avoids the problem of trifluorochlorethylene resin solution system is easily acidified during storage, improves three
The stability of fluorine vinyl chloride resin storage.And the copolymerisable monomer relative low price containing tertiary amine groups introduced, is produced into
This is low, and polymerization technique will not be caused complicated, need not filter after polymerization, simple process.
Specific embodiment
Next combined with specific embodiments below invention is further explained, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
In following embodiment, fluororesin storage stability test method are as follows: by the fluororesin sample being prepared at 50 DEG C
The viscosity change situation of measurement sample storage front and back after storage at a constant temperature 30 days, is good if viscosity change ratio is less than 1.2
It is good.
Embodiment 1
By ethyl vinyl ether 258.2g, cyclohexyl vinyl ether 243.3g, hydroxy butyl vinyl ether 144.0g, N- (3-
Dimethylamino-propyl) Methacrylamide 23.4g, butyl acetate 500g, dimethylbenzene 1500g, di-isopropyl peroxydicarbonate
8g is sequentially added in autoclave, is vacuumized to reaction kettle, nitrogen displacement 3 times, spare after displacement is qualified, to polymeric kettle
Collet leads to chilled brine cooling, is down to 0 DEG C hereinafter, 900g chlorotrifluoroethylene monomer is added into polymeric kettle, to reaction to temperature
Kettle stirs and heats, and controls 48 DEG C, reaction time 10h of temperature in reaction kettle, after polymerization, stops stirring and being cooled to often
Temperature recycles remaining chlorotrifluoroethylene monomer, releases polymer material to concentration kettle, is concentrated, is concentrated into solid to resin solution
Content 50% or so obtains finished product, i.e. trifluorochlorethylene resin.
Embodiment 2
By ethyl vinyl ether 258.2g, cyclohexyl vinyl ether 238.1g, hydroxyethyl vinylethers 121.4g, acrylic acid
Dimethylaminoethyl 3.4g, dimethylbenzene 2000g, di-isopropyl peroxydicarbonate 8g is sequentially added in autoclave, to anti-
Kettle is answered to be vacuumized, nitrogen displacement 3 times, it is spare after displacement is qualified, chilled brine cooling is led to jacket of polymerization, is dropped to temperature
To 0 DEG C hereinafter, 900g chlorotrifluoroethylene monomer is added into polymeric kettle, reaction kettle is stirred and heated, controls reaction kettle
60 DEG C, reaction time 6h of interior temperature, after polymerization, stops stirring and is cooled to room temperature, recycle remaining chlorotrifluoroethylene monomer,
Polymer material is released to concentration kettle, resin solution is concentrated, solid content 50% or so is concentrated into and obtains finished product, i.e. trifluoro chlorine
Vinyl.
Embodiment 3
By vinyl acetate 467.4g, hydroxy butyl vinyl ether 128.0g, N- (3- dimethylamino-propyl) acrylamide
46.4g, undecenoic acid 15.2g, butyl acetate 2000g, di-isopropyl peroxydicarbonate 8g are sequentially added in autoclave,
Reaction kettle is vacuumized, nitrogen displacement 3 times, it is spare after displacement is qualified, chilled brine cooling is led to jacket of polymerization, to temperature
Degree is down to 0 DEG C hereinafter, 900g chlorotrifluoroethylene monomer is added into polymeric kettle, stirs and heats to reaction kettle, control is anti-
55 DEG C, reaction time 12h of temperature in kettle is answered, after polymerization, stops stirring and is cooled to room temperature, recycle remaining chlorotrifluoroethylene
Monomer releases polymer material to concentration kettle, is concentrated to resin solution, is concentrated into solid content 50% or so and obtains finished product, i.e.,
Trifluorochlorethylene resin.
Embodiment 4
By vinyl acetate 353.5g, tertiary ethylene carbonate (vv9) 101.5g, tertiary ethylene carbonate (vv10) 163.9g,
Hydroxy butyl vinyl ether 128.0g, dimethylaminoethyl methacrylate 19.7g, undecenoic acid 30.4g, dimethylbenzene 800g, vinegar
Acid butyl ester 1200g, di-isopropyl peroxydicarbonate 9g are sequentially added in autoclave, are vacuumized to reaction kettle, nitrogen
Gas is replaced 3 times, spare after displacement is qualified, is led to chilled brine cooling to jacket of polymerization, is down to 0 DEG C hereinafter, to polymerization to temperature
900g chlorotrifluoroethylene monomer is added in kettle, reaction kettle is stirred and heated, controls 55 DEG C of temperature, reaction time in reaction kettle
6h after polymerization, stops stirring and is simultaneously cooled to room temperature, recycles remaining chlorotrifluoroethylene monomer, releases polymer material to dense
Contracting kettle, is concentrated resin solution, is concentrated into solid content 50% or so and obtains finished product, i.e. trifluorochlorethylene resin.
Embodiment 5
By ethyl vinyl ether 278.1g, cyclohexyl vinyl ether 243.3g, hydroxy butyl vinyl ether 192.0g, N- (3-
Dimethylamino-propyl) ethyl acrylamide 50.4g, dimethylbenzene 600g, butyl acetate 1400g, di-isopropyl peroxydicarbonate
5g is sequentially added in autoclave, is vacuumized to reaction kettle, nitrogen displacement 3 times, spare after displacement is qualified, to polymeric kettle
Collet leads to chilled brine cooling, is down to 0 DEG C hereinafter, 810g chlorotrifluoroethylene monomer is added into polymeric kettle, to reaction to temperature
Kettle stirs and heats, and controls 50 DEG C, reaction time 8h of temperature in reaction kettle, after polymerization, stops stirring and being cooled to often
Temperature recycles remaining chlorotrifluoroethylene monomer, releases polymer material to concentration kettle, is concentrated, is concentrated into solid to resin solution
Content 50% or so obtains finished product, i.e. trifluorochlorethylene resin.
Embodiment 6
By ethyl vinyl ether 238.3g, cyclohexyl vinyl ether 208.5g, hydroxy butyl vinyl ether 128.0g, N- (3-
Dimethylamino-propyl) N-tert-butyl acrylamide 3.2g, dimethylbenzene 800g, butyl acetate 1200g, di-isopropyl peroxydicarbonate
5g is sequentially added in autoclave, is vacuumized to reaction kettle, nitrogen displacement 3 times, spare after displacement is qualified, to polymeric kettle
Collet leads to chilled brine cooling, is down to 0 DEG C hereinafter, 990g chlorotrifluoroethylene monomer is added into polymeric kettle, to reaction to temperature
Kettle stirs and heats, and controls 58 DEG C, reaction time 10h of temperature in reaction kettle, after polymerization, stops stirring and being cooled to often
Temperature recycles remaining chlorotrifluoroethylene monomer, releases polymer material to concentration kettle, is concentrated, is concentrated into solid to resin solution
Content 50% or so obtains finished product, i.e. trifluorochlorethylene resin.
Embodiment 7
By ethyl vinyl ether 258.2g, cyclohexyl vinyl ether 278.1g, hydroxy butyl vinyl ether 144.0g, N- (3-
Dimethylaminoethyl) Methacrylamide 30.8g, dimethylbenzene 1200g, butyl acetate 800g, di-isopropyl peroxydicarbonate
7g is sequentially added in autoclave, is vacuumized to reaction kettle, nitrogen displacement 3 times, spare after displacement is qualified, to polymeric kettle
Collet leads to chilled brine cooling, is down to 0 DEG C hereinafter, 846g chlorotrifluoroethylene monomer is added into polymeric kettle, to reaction to temperature
Kettle stirs and heats, and controls 60 DEG C, reaction time 7h of temperature in reaction kettle, after polymerization, stops stirring and being cooled to often
Temperature recycles remaining chlorotrifluoroethylene monomer, releases polymer material to concentration kettle, is concentrated, is concentrated into solid to resin solution
Content 50% or so obtains finished product, i.e. trifluorochlorethylene resin.
Embodiment 8
By ethyl vinyl ether 238.3g, cyclohexyl vinyl ether 243.3g, hydroxyethyl vinylethers 109.3g, ethyl third
Olefin(e) acid dimethylaminoethyl 41.9g, dimethylbenzene 2000g, di-isopropyl peroxydicarbonate 8g are sequentially added in autoclave,
Reaction kettle is vacuumized, nitrogen displacement 3 times, it is spare after displacement is qualified, chilled brine cooling is led to jacket of polymerization, to temperature
Degree is down to 0 DEG C hereinafter, 936g chlorotrifluoroethylene monomer is added into polymeric kettle, stirs and heats to reaction kettle, control is anti-
60 DEG C, reaction time 11h of temperature in kettle is answered, after polymerization, stops stirring and is cooled to room temperature, recycle remaining chlorotrifluoroethylene
Monomer releases polymer material to concentration kettle, is concentrated to resin solution, is concentrated into solid content 50% or so and obtains finished product, i.e.,
Trifluorochlorethylene resin.
Embodiment 9
By ethyl vinyl ether 238.3g, cyclohexyl vinyl ether 208.5g, hydroxyethyl vinylethers 72.8g, N- (3- bis-
Methylaminoethyl) acrylamide 43.8g, dimethylbenzene 1500g, butyl acetate 500g, di-isopropyl peroxydicarbonate 8g is successively
It is added in autoclave, reaction kettle is vacuumized, nitrogen displacement 3 times, it is spare after displacement is qualified, it is logical to jacket of polymerization
Chilled brine cooling is down to 0 DEG C hereinafter, 990g chlorotrifluoroethylene monomer is added into polymeric kettle, to reaction kettle progress to temperature
Stirring and heating control 55 DEG C, reaction time 12h of temperature in reaction kettle, after polymerization, stop stirring and are cooled to room temperature, return
Remaining chlorotrifluoroethylene monomer is received, polymer material is released to concentration kettle, resin solution is concentrated, solid content is concentrated into
50% or so obtains finished product, i.e. trifluorochlorethylene resin.
Embodiment 10
By vinyl acetate 376.2g, tertiary ethylene carbonate (vv9) 101.5g, tertiary ethylene carbonate (vv10) 163.9g,
Hydroxy butyl vinyl ether 128.0g, isopropylacrylic acid dimethylaminoethyl 39.7g, undecenoic acid 40.7g, butyl acetate
2000g, di-isopropyl peroxydicarbonate 8g are sequentially added in autoclave, are vacuumized to reaction kettle, nitrogen displacement 3
It is secondary, it is spare after displacement is qualified, chilled brine cooling is led to jacket of polymerization, is down to 0 DEG C hereinafter, being added into polymeric kettle to temperature
900g chlorotrifluoroethylene monomer, stirs and heats reaction kettle, controls 60 DEG C, reaction time 6h of temperature in reaction kettle, polymerization
After, stop stirring and be cooled to room temperature, recycle remaining chlorotrifluoroethylene monomer, releasing polymer material is right to concentration kettle
Resin solution is concentrated, and is concentrated into solid content 50% or so and is obtained finished product, i.e. trifluorochlorethylene resin.
Embodiment 11
By vinyl acetate 308.4g, tertiary ethylene carbonate (vv9) 101.5g, tertiary ethylene carbonate (vv10) 218.5g,
Hydroxy butyl vinyl ether 160.0g, dimethylaminoethyl methacrylate 19.7g, undecenoic acid 36.2g, dimethylbenzene 800g, acetic acid fourth
Ester 1200g, di-isopropyl peroxydicarbonate 8g are sequentially added in autoclave, are vacuumized to reaction kettle, nitrogen is set
It changes 3 times, it is spare after displacement is qualified, chilled brine cooling is led to jacket of polymerization, is down to 0 DEG C hereinafter, into polymeric kettle to temperature
900g chlorotrifluoroethylene monomer is added, reaction kettle is stirred and heated, controls 50 DEG C, reaction time 10h of temperature in reaction kettle,
After polymerization, stop stirring and be cooled to room temperature, recycle remaining chlorotrifluoroethylene monomer, releases polymer material and be extremely concentrated
Resin solution is concentrated in kettle, is concentrated into solid content 50% or so and obtains finished product, i.e. trifluorochlorethylene resin.
Embodiment 12
By vinyl acetate 308.4g, tertiary ethylene carbonate (vv9) 203.0g, tertiary ethylene carbonate (vv10) 163.9g,
Hydroxy butyl vinyl ether 112.0g, dimethylaminoethyl propyl ester 9.4g, undecenoic acid 25.3g, dimethylbenzene 600g, acetic acid
Butyl ester 1400g, di-isopropyl peroxydicarbonate 6g are sequentially added in autoclave, are vacuumized to reaction kettle, nitrogen
Displacement 3 times, it is spare after displacement is qualified, chilled brine cooling is led to jacket of polymerization, is down to 0 DEG C hereinafter, to polymeric kettle to temperature
Middle addition 900g chlorotrifluoroethylene monomer, stirs and heats reaction kettle, controls 52 DEG C of temperature, reaction time in reaction kettle
9h after polymerization, stops stirring and is simultaneously cooled to room temperature, recycles remaining chlorotrifluoroethylene monomer, releases polymer material to dense
Contracting kettle, is concentrated resin solution, is concentrated into solid content 50% or so and obtains finished product, i.e. trifluorochlorethylene resin.
Embodiment 13
By vinyl acetate 498.2g, hydroxyethyl vinylethers 109.3g, N- (3- dimethylaminoethyl) ethyl propylene acyl
Amine 48.0g, undecenoic acid 38.0g, dimethylbenzene 400g, butyl acetate 1600g, di-isopropyl peroxydicarbonate 7g are sequentially added
In autoclave, reaction kettle is vacuumized, nitrogen displacement 3 times, it is spare after displacement is qualified, to the logical freezing of jacket of polymerization
Salt water cooling, to temperature be down to 0 DEG C hereinafter, into polymeric kettle be added 810g chlorotrifluoroethylene monomer, reaction kettle is stirred
And heating, 60 DEG C, reaction time 8h of temperature in reaction kettle is controlled, after polymerization, stops stirring and being cooled to room temperature, recycling is remaining
Chlorotrifluoroethylene monomer, release polymer material to concentration kettle, resin solution is concentrated, solid content 50% or so is concentrated into
Obtain finished product, i.e. trifluorochlorethylene resin.
Embodiment 14
By vinyl acetate 427.0g, hydroxyethyl vinylethers 97.1g, N- (3- dimethylaminoethyl) tert-butyl acryloyl
Amine 11.7g, undecenoic acid 2.8g, dimethylbenzene 500g, butyl acetate 1500g, di-isopropyl peroxydicarbonate 7g are sequentially added
In autoclave, reaction kettle is vacuumized, nitrogen displacement 3 times, it is spare after displacement is qualified, to the logical freezing of jacket of polymerization
Salt water cooling, to temperature be down to 0 DEG C hereinafter, into polymeric kettle be added 990g chlorotrifluoroethylene monomer, reaction kettle is stirred
And heating, 48 DEG C, reaction time 10h of temperature in reaction kettle is controlled, after polymerization, stops stirring and being cooled to room temperature, recycle residual
Remaining chlorotrifluoroethylene monomer releases polymer material to concentration kettle, is concentrated to resin solution, it is left to be concentrated into solid content 50%
The right side obtains finished product, i.e. trifluorochlorethylene resin.
Comparative example 1
By vinyl acetate 467.4g, hydroxy butyl vinyl ether 160.0g, undecenoic acid 15.2g, dimethylbenzene 800g, acetic acid
Butyl ester 1200g, di-isopropyl peroxydicarbonate 8g are sequentially added in autoclave, are vacuumized to reaction kettle, nitrogen
Displacement 3 times, it is spare after displacement is qualified, chilled brine cooling is led to jacket of polymerization, is down to 0 DEG C hereinafter, to polymeric kettle to temperature
Middle addition 900g chlorotrifluoroethylene monomer, stirs and heats reaction kettle, controls 52 DEG C of temperature, reaction time in reaction kettle
8h after polymerization, stops stirring and is simultaneously cooled to room temperature, recycles remaining chlorotrifluoroethylene monomer, releases polymer material to dense
Contracting kettle, is concentrated resin solution, is concentrated into solid content 50% or so and obtains finished product, i.e. trifluorochlorethylene resin.
Comparative example 2
By ethyl vinyl ether 258.2g, cyclohexyl vinyl ether 243.3g, hydroxy butyl vinyl ether 160.0g, dimethylbenzene
1500g, butyl acetate 500g, di-isopropyl peroxydicarbonate 8g are sequentially added in autoclave, are taken out to reaction kettle
Vacuum, nitrogen are replaced 3 times, spare after displacement is qualified, lead to chilled brine cooling to jacket of polymerization, to temperature be down to 0 DEG C hereinafter,
900g chlorotrifluoroethylene monomer is added into polymeric kettle, reaction kettle is stirred and heated, controls 55 DEG C of temperature in reaction kettle, instead
10h between seasonable after polymerization, stops stirring and is cooled to room temperature, recycle remaining chlorotrifluoroethylene monomer, release polymer
Material is concentrated resin solution, is concentrated into solid content 50% or so and obtains finished product, i.e. trifluorochlorethylene resin to concentration kettle.
Trifluorochlorethylene resin made from embodiment 1-14 and comparative example 1-2 is tested for the property, the results are shown in Table
1。
Table 1
From above embodiments and comparative example data it is found that the present invention passes through addition structural unit A to chlorotrifluoroethylene
In resin, the viscosity change ratio for the trifluorochlorethylene resin being prepared can be made to be respectively less than 1.15, storage stability is good.
The rate of viscosity increase for being not added with the trifluorochlorethylene resin of structural unit A is all larger than 1.3.
Claims (10)
1. a kind of trifluorochlorethylene resin, it is characterised in that the trifluorochlorethylene resin include chlorotrifluoroethylene structural unit and
Structural unit A, wherein structural unit A is selected from following structural formula (A1) and/or (A2):
Wherein: R1Selected from hydrogen, C1~C4 alkyl, R2Selected from hydrogen, C1~C4 alkyl, n1And n2Independently selected from 1~6 integer.
2. trifluorochlorethylene resin described in accordance with the claim 1, it is characterised in that in the structural formula (A1) and (A2), R1Choosing
From hydrogen, methyl, ethyl, tert-butyl, R2Selected from hydrogen, methyl, ethyl, isopropyl, n1And n2Independently selected from 2~4 integer.
3. trifluorochlorethylene resin according to claim 2, it is characterised in that in the structural formula (A1) and (A2), R1Choosing
From hydrogen, methyl, R2Selected from hydrogen, methyl, n1And n2Independently selected from 2~3 integer.
4. trifluorochlorethylene resin described in accordance with the claim 1, it is characterised in that the structural unit A and chlorotrifluoroethylene knot
The mol ratio of structure unit is 1:25~1:500.
5. trifluorochlorethylene resin according to claim 4, it is characterised in that the structural unit A and chlorotrifluoroethylene knot
The mol ratio of structure unit is 1:50~1:150.
6. trifluorochlorethylene resin described in accordance with the claim 1, it is characterised in that the trifluorochlorethylene resin includes following
Structural unit:
(1) chlorotrifluoroethylene structural unit, and molar content of the chlorotrifluoroethylene structural unit in trifluorochlorethylene resin is
45~55%；
(2) vinyl esters or alkyl vinyl ether structural unit, and vinyl esters or alkyl vinyl ether structural unit are in trifluoro
Molar content in vinyl chloride resin is 34~42%；
(3) hydroxyalkyl vinylether structural unit, and hydroxyalkyl vinylether structural unit rubbing in trifluorochlorethylene resin
Your content is 6~12%；
(4) undecenoic acid structural unit, and molar content of the undecenoic acid structural unit in trifluorochlorethylene resin be 0~
2%；
(5) structural unit A, and molar content of the structural unit A in trifluorochlorethylene resin is 0.1~3%.
7. trifluorochlorethylene resin according to claim 6, it is characterised in that:
The vinyl esters is selected from vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate and tertiary ethylene carbonate
At least one of；
The alkyl vinyl ether is selected from ethyl vinyl ether, cyclohexyl vinyl ether, isopropyl-ethylene base ether and butylethylene
At least one of base ether；
The hydroxyalkyl vinylether is selected from one of hydroxyethyl vinylethers and 4- hydroxy butyl vinyl ether.
8. trifluorochlorethylene resin according to claim 7, it is characterised in that:
The vinyl esters is selected from least one of vinyl acetate and tertiary ethylene carbonate；
The alkyl vinyl ether is selected from least one of ethyl vinyl ether and cyclohexyl vinyl ether.
9. trifluorochlorethylene resin according to claim 6, it is characterised in that:
Molar content of the chlorotrifluoroethylene structural unit in trifluorochlorethylene resin is 48-52%；
The molar content of vinyl esters or alkyl vinyl ether structural unit in trifluorochlorethylene resin is 36~40%；
Molar content of the hydroxyalkyl vinylether structural unit in trifluorochlorethylene resin is 8~10%；
Molar content of the undecenoic acid structural unit in trifluorochlorethylene resin is 0~1.5%；
Molar content of the structural unit A in trifluorochlorethylene resin is 0.3-2%.
10. trifluorochlorethylene resin described in accordance with the claim 1, it is characterised in that the trifluorochlorethylene resin, structure
Middle fluorine element content is greater than 24%, and the glass transition temperature of trifluorochlorethylene resin is 30~40 DEG C.
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