CN107540777A - A kind of modified daiflon, its preparation method and application - Google Patents
A kind of modified daiflon, its preparation method and application Download PDFInfo
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- CN107540777A CN107540777A CN201610479992.XA CN201610479992A CN107540777A CN 107540777 A CN107540777 A CN 107540777A CN 201610479992 A CN201610479992 A CN 201610479992A CN 107540777 A CN107540777 A CN 107540777A
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- polytrifluorochloroethylene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a kind of modified daiflon, and it is formed as compound (structural formula is shown in specification) copolymerization shown in including CTFE and structure formula (I).Modification polytrifluorochloroethylene diaphragm prepared by modified daiflon provided by the present invention has good barrier for steam and/or oxygen, is suitable for the fields such as medical packaging, electric component encapsulation and solar cell package.
Description
Technical field
The invention belongs to fluoro-containing macromolecule material field, and in particular to a kind of modified daiflon.
Background technology
Polytrifluorochloroethylene (PCTFE) is thermoplastic fluoroelastomer plastics of the earliest exploitation for industrialized production.Nineteen thirty-seven Germany
I.G.Farben industrie companies report PCTFE preparation first.Nineteen forty-six United States Non-Provisional builds up PCTFE production dress
Put and go into operation.Nineteen fifty-seven, Minnesota Mining and Manufacturing Company started largely to sell PCTFE with " Kel-F " trade mark.
PCTFE is to be formed by CTFE (CTFE) for polymerizable raw material, have excellent chemical stability, insulating properties and
Weatherability, can be long-term use of at -196~125 DEG C, and mechanical strength and hardness are better than polytetrafluoroethylene (PTFE), and manufactured film then has
Preferable transparency and splendid water vapor barrier property, it is widely used in electroluminescent electronic component, electrically as encapsulating film
The fields such as component, electronic building brick, medical material and medicament.
Wherein with regard to medical material and pharmaceutical arts, modern medicines are more and more stronger for the sensitiveness of steam and oxygen,
This is for proposing higher requirement for the polymer membrane of packaging, it is desirable to which polymer membrane both has high water vapor rejection
Property, there is high oxygen-barrier property again.Existing PCTFE films have splendid water vapor barrier property, but its oxygen-barrier property omits
It is inadequate.Therefore, at present in drug packing material, PCTFE films need to cooperate with adhesive to carry out compound, ability with other materials
The requirement for having both steam and oxygen-barrier property can be reached.
In order to improve the oxygen-barrier property of PCTFE films, however, it would be possible to by increase film thickness or with other films
Compound method is realized, but is found in actual applications, and the thickness of increase PCTFE films might not can improve the oxygen of film
Gas barrier, and it is also uneconomical in cost.
Therefore, it is in need that polytrifluorochloroethylene is further improved, so that its film can have preferable oxygen blocking
Every property and water vapor barrier property.
The content of the invention
It is an object of the invention to provide a kind of daiflon, is prepared into polytrifluorochloroethylene film
When, there is preferable oxygen-barrier property and water vapor barrier property.
To realize goal of the invention, the present invention is copolymerized with CTFE by adding feature monomer, made
Feature functional group is carried in daiflon main chain so that polytrifluorochloroethylene film can between adhesive shape
Into stronger intermolecular force, so as to improve the adhesion strength between polytrifluorochloroethylene film and other films, reduce and apply
The usage amount of adhesive in cloth.
The present invention provides following technical scheme：
A kind of modified daiflon, the monomer for preparing modified daiflon include trifluoro chlorine
Compound shown in ethene and structure formula (I),
Wherein：RfContain fluoroalkyl selected from C1~C6；
Quality percentage of the construction unit that the structure formula (I) is formed in modified daiflon segmented structure
Than for 0.1~10%.
Compound shown in structure formula (I) provided by the invention, wherein RfContain fluoroalkyl selected from C1~C6.Preferably
It is the RfContain fluoroalkyl selected from C1~C4.
Modified daiflon provided by the invention, the construction unit that the structure formula (I) is formed is modified poly-
Mass percent in trifluorochlorethylene resin segmented structure is 0.1~10%.Preferably, the structure formula (I) is formed
Mass percent of the construction unit in modified daiflon segmented structure is 1~5%.
Present invention also offers the preparation method of the modified daiflon.The modified polytrifluorochloroethylene
Resin is obtained by emulsion polymerization, and the emulsion polymer method includes：
In blending agent, in the presence of fluorine-containing surfactant and initiator, shown in CTFE and structure formula (I)
Compound obtain described modification daiflon through emulsion polymerization；
The blending agent contains organic solvent and water, and mass percent of the organic solvent in blending agent is 5
~25%.
In emulsion polymerization of the present invention, the blending agent contains organic solvent and water.The organic solvent can be with
It is organic solvent commonly used in the art.Preferably, the organic solvent be selected from dimethylbenzene, methyl iso-butyl ketone (MIBK), ethyl acetate,
At least one of butyl acetate, propylene glycol methyl ether acetate and n-hexane.
In emulsion polymerization of the present invention, the fluorine-containing surfactant can be organic solvent commonly used in the art.
Preferably, the fluorine-containing surfactant is selected from RFCOOM and RFSO3At least one of M, and RFIndependently selected from CnFn+1(n
=6~10) or F (CFCF3CF2O)nCFCF3(n=2~5), M is independently selected from H+、NH4 +、Na+Or K+。
The dosage of fluorine-containing surfactant meets to be smoothed out polymerisation.Preferably, the fluorochemical surface
Mass percent concentration of the activating agent in aqueous phase is 0.01~5%.
In emulsion polymerization of the present invention, the initiator can be initiator commonly used in the art.Preferably, institute
State initiator and be selected from least one of azo and peroxy dicarbonates oil-soluble initiator.It may further be preferable that
The azo-initiator is selected from azodiisobutyronitrile, ABVN, azobis methylbutyronitrile, two different caprylic nitrile of azo, idol
At least one of two different pelargonitrile of nitrogen and the isodecyl nitrile of azo two.It may further be preferable that the peroxy dicarbonates triggers
Agent is selected from dicetyl peroxydicarbonate dibutyl ester, dicetyl peroxydicarbonate diisobutyl ester, di-isopropyl peroxydicarbonate, the carbon of peroxidating two
Sour at least one of two (2- ethylhexyls) esters and dicetyl peroxydicarbonate two (3- methoxybutyls).
The dosage of initiator meets to be smoothed out polymerisation.Preferably, the initiator is in blending agent
In mass percent concentration be 0.01~2%.
In emulsion polymerization of the present invention, polymerization temperature meets to be smoothed out polymerisation.Preferably, polymerization temperature
Spend for 30~80 DEG C.
In emulsion polymerization of the present invention, polymerization pressure meets to be smoothed out polymerisation.Preferably, it is described poly-
Resultant pressure is 0.5~2.5MPa.
Present invention also offers a kind of modified polytrifluorochloroethylene diaphragm, the modified polytrifluorochloroethylene diaphragm is by being modified
It is prepared by daiflon.
The modified polytrifluorochloroethylene diaphragm, its hydroxyl value are 3~20mgKOH/g.Preferably, the hydroxyl value be 5~
15mgKOH/g。
The modified polytrifluorochloroethylene diaphragm, it coats 3~15N/cm of initial bonding strength of 3 μm of adhesive and PVC film piece.It is excellent
Choosing, the modified polytrifluorochloroethylene diaphragm coat 5~10N/cm of initial bonding strength of 3 μm of adhesive and PVC film piece.
Present invention also offers the preparation method of modified polytrifluorochloroethylene diaphragm, the preparation method includes：
(1) make to be modified that daiflon is melt processed to obtain diaphragm；
(2) diaphragm is placed in in the methanol solution of sodium hydroxide alcoholysis 1~2 hour at 30~50 DEG C, obtained after scrubbed
To the modified polytrifluorochloroethylene diaphragm.
Modified polytrifluorochloroethylene diaphragm provided by the invention, is suitable for steam and/or oxygen obstruction.
Modified polytrifluorochloroethylene diaphragm provided by the invention, be suitable for medical packaging, electric component encapsulation or
Solar cell package.
Embodiment
The present invention is further described with reference to specific embodiment, 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 equivalents.
Embodiment 1
Azodiisobutyronitrile 2.4g is dissolved in 240g ethyl acetate and is configured to initiator solution.Take CF3(CF2)6COONH4
3.6g and 3L deionized waters be together added to mechanical agitation, temperature regulating device, circulating-heating cooling device 5L reactors
In, vacuum nitrogen gas is replaced three times, measure oxygen content in below 10ppm, continue to be evacuated to reacting kettle inner pressure for-
0.1MPa.CTFE 1200g and CH are added into reactor by metering device2=C (CF3)OCOCH345g, stirring speed
Rate 500rpm, 65 DEG C are warming up to, after system temperature is constant, initiator solution is added into reactor with measuring pump, keeps anti-
It is 1.68MPa to answer polymerization pressure in kettle, is reacted 8 hours.Polymerizate is repeatedly less than 10 μ by deionized water washing to electrical conductivity
S/cm, further product is dried in vacuo 24 hours in 100-120 DEG C, obtains the modified daiflon 1053g of white.
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 2 hours at 35 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 11.58mgKOH/g.
Embodiment 2
ABVN 3.6g is dissolved in 240g butyl acetates and is configured to initiator solution.Take CF3(CF2)7SO3NH4
3.6g and 3L deionized waters be together added to mechanical agitation, temperature regulating device, circulating-heating cooling device 5L reactors
In, vacuum nitrogen gas is replaced three times, measure oxygen content in below 10ppm, continue to be evacuated to reacting kettle inner pressure for-
0.1MPa.CTFE 1200g and CH are added into reactor by metering device2=C (CF2CF3)OCOCH360g, stir
Speed 500rpm is mixed, is warming up to 55 DEG C, after system temperature is constant, initiator solution is added into reactor with measuring pump, is protected
It is 1.32MPa to hold polymerization pressure in reactor, is reacted 8 hours.Polymerizate is washed repeatedly small to electrical conductivity by deionized water
In 10 μ S/cm, further product is dried in vacuo 24 hours in 100-120 DEG C, obtains the modified daiflon of white
982g。
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 2 hours at 35 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 9.73mgKOH/g.
Embodiment 3
Di-isopropyl peroxydicarbonate 6g is dissolved in 360g n-hexanes and is configured to initiator solution.Take F
(CFCF3CF2O)3CFCF3COONH46g and 3L deionized waters be together added to mechanical agitation, temperature regulating device, circulating-heating
In the 5L reactors of cooling device, vacuum nitrogen gas is replaced three times, and measure oxygen content continues to be evacuated in below 10ppm
Reacting kettle inner pressure is -0.1MPa.CTFE 1200g and CH are added into reactor by metering device2=C
(CF2CF2CF3)OCOCH390g, stir speed (S.S.) 500rpm, 55 DEG C are warming up to, after system temperature is constant, with measuring pump to anti-
Answer and initiator solution is added in kettle, it is 1.32MPa to keep polymerization pressure in reactor, is reacted 8 hours.Polymerizate by go from
Sub- water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo product 24 hours in 100-120 DEG C, obtains white
Color is modified daiflon 997g.
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 2 hours at 35 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 8.95mgKOH/g.
Embodiment 4
Dicetyl peroxydicarbonate two (2- ethylhexyls) ester 9g is dissolved in 390g butyl acetates and is configured to initiator solution.Take
F(CFCF3CF2O)4CFCF3COONH46g and 3L deionized waters are together added to be added with mechanical agitation, temperature regulating device, circulation
It is hot cooling device 5L reactors in, vacuum nitrogen gas is replaced three times, and measure oxygen content continues to vacuumize in below 10ppm
It is -0.1MPa to reacting kettle inner pressure.CTFE 1200g and CH are added into reactor by metering device2=C
(CF3CFCF3)OCOCH390g, stir speed (S.S.) 500rpm, 50 DEG C are warming up to, after system temperature is constant, with measuring pump to reaction
Initiator solution is added in kettle, it is 1.17MPa to keep polymerization pressure in reactor, is reacted 8 hours.Polymerizate passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, and further product is dried in vacuo 24 hours in 100-120 DEG C, obtains white
Modified daiflon 936g.
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 2 hours at 35 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 8.31mgKOH/g.
Embodiment 5
Dicetyl peroxydicarbonate diisobutyl ester 12g is dissolved in 510g ethyl acetate and is configured to initiator solution.Take CF3
(CF2)6COONa 6g and 3L deionized water be together added to mechanical agitation, temperature regulating device, circulating-heating cooling device
In 5L reactors, vacuum nitrogen gas is replaced three times, and measure oxygen content continues to be evacuated to reactor internal pressure in below 10ppm
Power is -0.1MPa.CTFE 1200g and CH are added into reactor by metering device2=C (CF2CF2CF2CF3)
OCOCH3120g, stir speed (S.S.) 700rpm, 45 DEG C are warming up to, after system temperature is constant, are added with measuring pump into reactor
Initiator solution, it is 1.04MPa to keep polymerization pressure in reactor, is reacted 12 hours.Polymerizate is washed by deionized water
Repeatedly it is less than 10 μ S/cm to electrical conductivity, is further dried in vacuo product 24 hours in 100-120 DEG C, it is modified poly- obtains white
Trifluorochlorethylene resin 882g.
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 1.5 hours at 45 DEG C.By surface alcoholization processing modification polytrifluorochloroethylene diaphragm by go from
Sub- water washing is repeatedly less than 10 μ S/cm to electrical conductivity, and further diaphragm is dried in vacuo 12 hours in 80-100 DEG C, is modified
Polytrifluorochloroethylene diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 7.35mgKOH/g.
Embodiment 6
Azodiisobutyronitrile 15g is dissolved in 540g butyl acetates and is configured to initiator solution.Take F (CFCF3CF2O)4CFCF3COOH 9g and 3L deionized water be together added to mechanical agitation, temperature regulating device, circulating-heating cooling device 5L
In reactor, vacuum nitrogen gas is replaced three times, and measure oxygen content continues to be evacuated to reacting kettle inner pressure in below 10ppm
For -0.1MPa.CTFE 1200g and CH2=C (C (CF are added into reactor by metering device3)3)OCOCH3
120g, stir speed (S.S.) 700rpm, 70 DEG C are warming up to, after system temperature is constant, initiator is added into reactor with measuring pump
Solution, it is 1.87MPa to keep polymerization pressure in reactor, is reacted 6.5 hours.Polymerizate is washed repeatedly extremely by deionized water
Electrical conductivity is less than 10 μ S/cm, is further dried in vacuo product 24 hours in 100-120 DEG C, obtains the modified poly- trifluoro chlorine of white
Vinyl 1093g.
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 2 hours at 50 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 7.65mgKOH/g.
Embodiment 7
Dicetyl peroxydicarbonate two (2- ethylhexyls) ester 12g is dissolved in 510g n-hexanes and is configured to initiator solution.Take F
(CFCF3CF2O)4CFCF3COONH418g and 3L deionized waters are together added to be added with mechanical agitation, temperature regulating device, circulation
It is hot cooling device 5L reactors in, vacuum nitrogen gas is replaced three times, and measure oxygen content continues to vacuumize in below 10ppm
It is -0.1MPa to reacting kettle inner pressure.CTFE 900g and CH are added into reactor by metering device2=C (CF3)
OCOCH345g, stir speed (S.S.) 500rpm, 40 DEG C are warming up to, after system temperature is constant, are added with measuring pump into reactor
Initiator solution, it is 0.91MPa to keep polymerization pressure in reactor, is reacted 16 hours.Polymerizate is washed by deionized water
Repeatedly it is less than 10 μ S/cm to electrical conductivity, is further dried in vacuo product 24 hours in 100-120 DEG C, it is modified poly- obtains white
Trifluorochlorethylene resin 633g.
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 1 hour at 30 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 9.33mgKOH/g.
Embodiment 8：The preparation of modified polytrifluorochloroethylene emulsion
Dicetyl peroxydicarbonate diisobutyl ester 9g is dissolved in 480g ethyl acetate and is configured to initiator solution.Take F
(CFCF3CF2O)3CFCF3COOH 7.5g and 3L deionized water are together added to be added with mechanical agitation, temperature regulating device, circulation
It is hot cooling device 5L reactors in, vacuum nitrogen gas is replaced three times, and measure oxygen content continues to vacuumize in below 10ppm
It is -0.1MPa to reacting kettle inner pressure.CTFE 900g and CH are added into reactor by metering device2=C
(CF2CF3)OCOCH360g, stir speed (S.S.) 500rpm, 50 DEG C are warming up to, after system temperature is constant, with measuring pump to reactor
Interior addition initiator solution, it is 1.17MPa to keep polymerization pressure in reactor, is reacted 10 hours.Polymerizate passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, and further product is dried in vacuo 24 hours in 100-120 DEG C, obtains white
Modified daiflon 721g.
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 2 hours at 40 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 10.37mgKOH/g.
Embodiment 9：The preparation of modified polytrifluorochloroethylene emulsion
ABVN 12g is dissolved in 330g butyl acetates and is configured to initiator solution.Take CF3(CF2)9SO3NH4
7.5g and 3L deionized waters be together added to mechanical agitation, temperature regulating device, circulating-heating cooling device 5L reactors
In, vacuum nitrogen gas is replaced three times, measure oxygen content in below 10ppm, continue to be evacuated to reacting kettle inner pressure for-
0.1MPa.CTFE 1500g and CH are added into reactor by metering device2=C (CF2CF2CF3)OCOCH390g,
Stir speed (S.S.) 700rpm, 55 DEG C are warming up to, after system temperature is constant, initiator solution are added into reactor with measuring pump,
It is 1.32MPa to keep polymerization pressure in reactor, is reacted 8 hours.Polymerizate is washed repeatedly to electrical conductivity by deionized water
Less than 10 μ S/cm, further product is dried in vacuo 24 hours in 100-120 DEG C, obtains the modified polytrifluorochloroethylene tree of white
Fat 1265g.
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 2 hours at 40 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 9.02mgKOH/g.
Embodiment 10：The preparation of modified polytrifluorochloroethylene emulsion
Azodiisobutyronitrile 12g is dissolved in 510g butyl acetates and is configured to initiator solution.Take CF3(CF2)8COOK
12g and 3L deionized waters be together added to mechanical agitation, temperature regulating device, circulating-heating cooling device 5L reactors in,
Vacuum nitrogen gas is replaced three times, and for measure oxygen content in below 10ppm, it is -0.1MPa to continue to be evacuated to reacting kettle inner pressure.
CTFE 1500g and CH are added into reactor by metering device2=C (CF2CF2CF2CF3)OCOCH3120g, stirring
Speed 700rpm, 70 DEG C are warming up to, after system temperature is constant, initiator solution is added into reactor with measuring pump, kept
Polymerization pressure is 1.87MPa in reactor, is reacted 8 hours.Polymerizate is repeatedly less than by deionized water washing to electrical conductivity
10 μ S/cm, further product is dried in vacuo 24 hours in 100-120 DEG C, obtains the modified daiflon of white
1402g。
The modification daiflon of preparation is prepared into the diaphragm of 100 μm of thickness.300g sodium hydroxides are dissolved
In 3L methanol, sodium hydroxide-methanol solution is prepared.Modified polytrifluorochloroethylene diaphragm is added into sodium hydroxide-methanol solution
In, temperature control stirs 2 hours at 50 DEG C.Modification polytrifluorochloroethylene diaphragm by surface alcoholization processing passes through deionization
Water washing is repeatedly less than 10 μ S/cm to electrical conductivity, is further dried in vacuo diaphragm 12 hours in 80-100 DEG C, obtains modified poly-
CTFE diaphragm.
After tested, the hydroxyl value of the modification polytrifluorochloroethylene diaphragm of preparation is 7.47mgKOH/g.
Embodiment 11
Modification polytrifluorochloroethylene diaphragm prepared by embodiment 1 to 10, adhesive coating (3 μm) is compound with PVC film piece,
The initial bonding strength of the modified polytrifluorochloroethylene diaphragm of test and PVC film piece.As a result such as table 1 below.
Simultaneously by non-modified polytrifluorochloroethylene diaphragm, after the same method, adhesive coating (3 μm) and PVC
Diaphragm is compound, the initial bonding strength of test polytrifluorochloroethylene diaphragm and PVC film piece.As a result also represented such as table 1 below with comparative example.
Table 1
Claims (11)
1. a kind of modified daiflon, it is characterised in that for preparing the monomer bag of modified daiflon
CTFE and the compound shown in structure formula (I) are included,
Wherein：RfContain fluoroalkyl selected from C1~C6；
Mass percent of the construction unit that the structure formula (I) is formed in modified daiflon segmented structure be
0.1~10%.
2. according to the modification daiflon described in claim 1, it is characterised in that the RfSelected from the fluorine-containing of C1~C4
Alkyl, mass percent of the construction unit that the structure formula (I) is formed in modified daiflon segmented structure
For 1~5%.
3. according to the modification daiflon described in claim 1, it is characterised in that the modified polytrifluorochloroethylene
Resin is obtained by emulsion polymerization, and the emulsion polymer method includes：
In blending agent, in the presence of fluorine-containing surfactant and initiator, the change shown in CTFE and structure formula (I)
Compound obtains described modification daiflon through emulsion polymerization；
The blending agent contains organic solvent and water, and mass percent of the organic solvent in blending agent be 5~
25%.
4. according to the modification daiflon described in claim 3, it is characterised in that：
The organic solvent be selected from dimethylbenzene, methyl iso-butyl ketone (MIBK), ethyl acetate, butyl acetate, propylene glycol methyl ether acetate and
At least one of n-hexane；
The fluorine-containing surfactant is selected from RFCOOM and RFSO3At least one of M, and RFIndependently selected from CnFn+1(n=6~
Or F (CFCF 10)3CF2O)nCFCF3(n=2~5), M is independently selected from H+、NH4 +、Na+Or K+, and fluorine-containing surfactant is in water
Mass percent concentration in phase is 0.01~5%；
The initiator is selected from least one of azo and peroxy dicarbonates oil-soluble initiator, and initiator exists
Mass percent concentration in blending agent is 0.01~2%.
5. according to the modification daiflon described in claim 4, it is characterised in that：
It is different pungent that the azo-initiator is selected from azodiisobutyronitrile, ABVN, azobis methylbutyronitrile, azo two
At least one of nitrile, two different pelargonitrile of azo and the isodecyl nitrile of azo two；
The peroxy dicarbonates initiator is selected from dicetyl peroxydicarbonate dibutyl ester, dicetyl peroxydicarbonate diisobutyl ester, mistake
Aoxidize two diisopropyl carbonates, (2- ethylhexyls) ester of dicetyl peroxydicarbonate two and dicetyl peroxydicarbonate two (3- methoxybutyls)
At least one of；
Polymerization temperature is 30~80 DEG C, and polymerization pressure is 0.5~2.5MPa.
6. a kind of modified polytrifluorochloroethylene diaphragm, it is characterised in that the modified polytrifluorochloroethylene diaphragm is by being modified poly- trifluoro
It is prepared by vinyl chloride resin.
7. according to the modification polytrifluorochloroethylene diaphragm described in claim 6, it is characterised in that the modified polytrifluorochloroethylene
Diaphragm, its hydroxyl value is 3~20mgKOH/g, the 3~15N/cm of initial bonding strength of 3 μm of adhesive of coating and PVC film piece.
8. according to the modification polytrifluorochloroethylene diaphragm described in claim 7, it is characterised in that the modified polytrifluorochloroethylene
Diaphragm, its hydroxyl value is 5~15mgKOH/g, the 5~10N/cm of initial bonding strength of 3 μm of adhesive of coating and PVC film piece.
9. according to the modification polytrifluorochloroethylene diaphragm described in claim 6, it is characterised in that the modified polytrifluorochloroethylene
Resin, its preparation method include：
(1) make to be modified that daiflon is melt processed to obtain diaphragm；
(2) diaphragm is placed in in the methanol solution of sodium hydroxide alcoholysis 1~2 hour at 30~50 DEG C, institute is obtained after scrubbed
State modified polytrifluorochloroethylene diaphragm.
10. according to the modification polytrifluorochloroethylene diaphragm described in claim 6, it is characterised in that the modified polytrifluorochloroethylene
Diaphragm is used for steam and/or oxygen obstruction.
11. according to the modification polytrifluorochloroethylene diaphragm described in claim 10, it is characterised in that the poly- trifluoro chloroethene of modification
Alkene diaphragm is used for medical packaging, electric component encapsulation or solar cell package.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112979857A (en) * | 2019-12-16 | 2021-06-18 | 浙江省化工研究院有限公司 | Modified polychlorotrifluoroethylene and preparation method thereof |
| CN114106622A (en) * | 2020-08-31 | 2022-03-01 | 浙江省化工研究院有限公司 | Aqueous dispersion coating |
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| CN1867619A (en) * | 2003-10-17 | 2006-11-22 | 霍尼韦尔国际公司 | Method of making oriented polychlorotrifluoroethylene films |
| CN102066470A (en) * | 2008-06-19 | 2011-05-18 | 斯泰拉化工公司 | Method for modifying fluorine resin film |
| CN103304712A (en) * | 2013-05-07 | 2013-09-18 | 山东森福新材料有限公司 | Manufacturing method of beaded polytrifluorochloroethylene resins |
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| CN1867619A (en) * | 2003-10-17 | 2006-11-22 | 霍尼韦尔国际公司 | Method of making oriented polychlorotrifluoroethylene films |
| CN102066470A (en) * | 2008-06-19 | 2011-05-18 | 斯泰拉化工公司 | Method for modifying fluorine resin film |
| CN103304712A (en) * | 2013-05-07 | 2013-09-18 | 山东森福新材料有限公司 | Manufacturing method of beaded polytrifluorochloroethylene resins |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112979857A (en) * | 2019-12-16 | 2021-06-18 | 浙江省化工研究院有限公司 | Modified polychlorotrifluoroethylene and preparation method thereof |
| CN112979857B (en) * | 2019-12-16 | 2022-09-02 | 浙江省化工研究院有限公司 | Modified polychlorotrifluoroethylene and preparation method thereof |
| CN114106622A (en) * | 2020-08-31 | 2022-03-01 | 浙江省化工研究院有限公司 | Aqueous dispersion coating |
| CN114106622B (en) * | 2020-08-31 | 2022-09-06 | 浙江省化工研究院有限公司 | Aqueous dispersion coating |
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Denomination of invention: A modified polytrifluoroethylene chloride resin, its preparation method and Application Effective date of registration: 20220628 Granted publication date: 20200609 Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch Pledgor: SINOCHEM LANTIAN Co.,Ltd. Registration number: Y2022330001143 |
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