CN104448099B - A kind of long-chain fluorinated olefin polymer and preparation method thereof - Google Patents
A kind of long-chain fluorinated olefin polymer and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of long-chain fluorinated olefin polymer and preparation method thereof, and its preparation method is 1) add its volume 60～deionized water of 70% in a kettle., in deionized water, add the reaction promoters such as emulsifying agent simultaneously；By evacuation and nitrogen charging by the Control for Oxygen Content in reactor at 30 below ppm, it is warmed up to 20～160 DEG C；2) in reactor, polymerization monomer is added, until pressure reaches 0.5～6.0 MPa in still；Adding radical initiator in reactor, reaction adds modified monomer R while startingfCX1=CX2X3, course of reaction is added the described polymerization monomer of same ratio, maintains reactor pressure constant；3) add after polymerization monomer reaches predetermined quality and stop adding, after reaction stops, releasing emulsion；To described emulsion by being condensed, wash, be dehydrated, be dried to obtain powdery long-chain fluorinated olefin polymer.The present invention provide monomer long chain fluorine-containing alkene prepare polymer, heat-resist, light transmittance is high, preparation technology is simple and environmentally-friendly, has broad application prospects.
Description
Technical field
The present invention relates to the preparation method of a kind of long chain fluorine-containing olefin polymer, belong to macromolecule material
Material field.
Background technology
Traditional fluoropolymer, as politef (referred to hereinafter as PCTFE), poly-trifluoro chlorine
Ethylene (referred to hereinafter as PCTFE), Kynoar (referred to hereinafter as PVDF) and perfluoroethylene
Propylene (referred to hereinafter as FEP), ethylene-tetrafluoroethylene copolymer (referred to hereinafter as ETFE), ethylene-
Chlorotrifluoroethylene (ECTFE), owing to fusing point is high, degree of crystallinity is high, causes processing temperature
Degree is high, light transmittance is low, stress is high, causes product variable color, appearance poor, stress cracking, limit
Make its range of application, reduced quality, add cost.
In order to improve the performance of fluoropolymer, the modified monomer to fluoropolymer both at home and abroad
Carried out substantial amounts of exploration, it was recently reported that a large amount of as hydroxy butyl vinyl ethers, vinylacetate,
Trifluoromethyl propylene, perfluoro methyl vinyl ether (referred to hereinafter as PMVE), perfluor n-pro-pyl second
Alkene ether (referred to hereinafter as PPVE), 1,1,5-tri-hydrogen perfluor amylene-1, perfluorobutyl ethylene
(C4F9CH=CH2) etc. particular monomers be used for the modification by copolymerization of all kinds of fluoropolymer.Japan
Big King Company's patent EP0162455B1 and Asahi Glass house journal US4123602 are respectively adopted
1,1,5-tri-hydrogen perfluor amylene-1, C4F9CH=CH2As modified monomer, effectively improve
The processing characteristics of ETFE, but owing to the two uses the modified monomer containing nonfluorinated double bond,
Copolymerization activity is low, affects reaction rate, it is necessary to use the special solvent of this patent report to gather
Legal it is polymerized, has that post processing is complicated, pollute the problem such as environment, high cost.
Summary of the invention
Utilize the reaction monomers synthesis containing nonfluorinated double bond poly-present in prior art
The defect that compound Copolymerization activity is low, reaction rate is slow, the invention provides a kind of utilization modification
The method of monomer synthetic polymer, the method synthetic polymer technique is simple and environmentally-friendly, low cost,
Described method comprises the steps:
1) its volume 60～deionized water of 70% is added in a kettle., simultaneously to deionization
Water adds the reaction promoters such as emulsifying agent；By evacuation and nitrogen charging by the oxygen content in reactor
Control at below 30ppm, be warmed up to 20～160 DEG C, preferably 40～120 DEG C；
2) in reactor, polymerization monomer is added, until pressure reaches 0.5～6.0MPa in still,
Preferably 1.0～5.0MPa；Described polymerization monomer is fluorochemical monomer or fluorochemical monomer and non-fluorine-containing list
The mixture of body；Adding radical initiator in reactor, reaction adds and changes while starting
Property monomer RfCX1=CX2X3, described RfCX1=CX2X3R in monomerfExist for carbon number
Perfluorinated alkyl group between 2～8, X1、X2、X3Selected from halogen atom or hydrogen atom, its
In at least one be fluorine atom；Course of reaction is added the described polymerization monomer of same ratio,
Maintain reactor pressure constant；
3) add after polymerization monomer reaches predetermined quality and stop adding, after reaction stops, reclaiming
Unreacted monomer, releases emulsion；To described emulsion by being condensed, wash, be dehydrated,
It is dried to obtain powdery long-chain fluorinated olefin polymer.
The heretofore described predetermined quality adding polymerization monomer, according to containing of final required synthesis
Depending on the quality of fluoropolymer.
R of the present inventionfCX1=CX2X3R in monomerfFor complete between 2～8 of carbon number
Fluorinated alkyl group, X1、X2、X3For halogen atom, hydrogen atom etc., at least one is
Fluorine atom.RfCX1=CX2X3For example it may be that but be not limited only to example below:
CHF=CHC2F5, CHF=CHC3F7, CHF=CHC4F9, CHF=CHC5F11、
CHF=CFC6F13, CHF=CFC2F5, CHF=CFC3F7, CHF=CFC4F9、
CHF=CFC5F11, CHF=CFC6F13, CF2=CHC2F5、CF2=CHC3F7、
CF2=CHC4F9、CF2=CHC5F11、CF2=CHC6F13, CF2=CClC2F5、
CF2=CClC3F7、CF2=CClC4F9、CF2=CClC5F11、CF2=CClC6F13,
CF2=CFC2F5、CF2=CFC3F7、CF2=CFC4F9、CF2=CFC5F11、CF2=CFC6F13,
Preferably CHF=CHC4F9, CHF=CFC4F9、CF2=CHC4F9、CF2=CClC4F9。
Fluorochemical monomer of the present invention can be tetrafluoroethene (referred to hereinafter as TFE), vinylidene
(referred to hereinafter as VDF), CTFE (referred to hereinafter as CTFE), hexafluoropropene are (referred to hereinafter as
HFP), fluorothene (referred to hereinafter as VF), perfluor (n-propyl vinyl) ether (PPVE)
Deng one or more.
The present invention is with modified monomer RfCX1=CX2X3It is base with the molal quantity sum of fluorochemical monomer
Standard, modified monomer RfCX1=CX2X3Molar fraction in the range of 0.01～9.9%, preferably
0.1～9.0%.RfCX1=CX2X3To fluorine-containing poly-when the molar fraction of monomer is less than 0.1%
The processing characteristics of compound, creep resistance and light transmission impact are inconspicuous, must not be higher than
9.0%, the machinery being normally carried out simultaneously affecting fluoropolymer otherwise affecting polyreaction is strong
Degree and resistance to elevated temperatures.
Except the above modified monomer RfCX1=CX2X3Gather with two kinds that fluorochemical monomer is base
Outside conjunction unit, it is the polymerization of base that the polymer of the present invention can also comprise a kind of non-fluorochemical monomer
Unit.This monomer can be ethylene (hereinafter referred to as E), the one of propylene (hereinafter referred to as P)
Or two kinds.If containing this monomer, then modified monomer RfCX1=CX2X3Rub with fluorochemical monomer
The mol ratio of that number sum and non-fluorochemical monomer is between 1:1～10, preferable 1:1～9,
When higher than 9, the modifying function of non-fluorochemical monomer is inconspicuous, must not be the most fluorine-containing poly-less than 1
Resistance to elevated temperatures and the resistance to chemical corrosion of compound are affected.
Emulsifying agent selected by this patent is prepared by patent CN101648122 institute provider's method, formula
For
Wherein A, B represent CF respectively3, COOM or CF2Any one in COOM, M
Represent H, NH4Or any one of alkali metal；Rf‘Represent F or CF3Deng；P represents
CF2、CH2、CFCl、CClH、CFBr、CF(CF3) etc.；GfRepresent CF2CF2、
CF2CH2、CF2CF(CF3)、CF2CFCl、CF2CHF、CF2CH(CF3)、
CH2CHCF(CF3)、CF2CHCl、CF2CFBr etc.；M, n, q, r, s meet following bar
Part:
F) m, n, q, r, s are the integer not less than 0；
g)n+r≥1；
h)n+r≤m+q+s；
i)m≥n+q+r+s；
J) molecular weight is 300～20000, preferably 1000～5000.
The example of perfluorocarboxylic acid base polyethers includes but are not limited to:
CF3-O-[-CF(OCF3)-CF2-O-]2-CF2-O-O-COOM
CF3O-[-CF(OCF3)-CClH-O-]2-CF2-O-O-COOM
CF3O-[-CF(OCF3)-CFCl-O-]2-CF2-O-O-COOM
CF3O-[-CF(OCF3)-CFBr-O-]2-CF2-O-O-COOM
CF3O-[-CF(OCF3)-CF(CF3)-O-]2-CF2-O-O-COOM
CF3O-[-CF(OCF3)-CF2-O-]3-CF2-CF2-O-O-CF2-O-CF(CF3)-O-CF2-CO
OM
CF3O-[-CF(OCF3)-CH2-O-]3-CF2-CH2-O-O-CF2-O-CF(CF3)-O-CF2-CO
OM
CF3O-[-CF(OCF3)-CF2-O-]4-CF2-CF2-O-O-CF2-O-CF2-O-O-CF(CF3)-O
-CF2-COOM
CF3O-[CF(OCF3)-CH2-O-]4-CF2-CH2-O-O-CF2-O-CF2-O-O-CF(CF3)-O
-CF2-COOM
CF3O-[CF2-CF(CF3)-O]4-CF2-CF(CF3)-OO-CF2-O-CF2-OO-CF(CF3)-O-
CF2-COOM
MOOCO-[-CF(OCF3)-CF2-O-]3-CF2-CF2-O-O-[CF(CF3)-O]2-CF2-COO
M
MOOCO-[-CF(OCF3)-CH2-O-]3-CF2-CH2-O-O-[CF(CF3)-O]2-CF2-COO
M
MOOCO-[-CF2-CF(CF3)-O-]3-CF2-CF(CF3)-O-O-[CF(CF3)-O]2-CF2-CO
OM
CF3-O-CF(OCF3)-CF2-O-CF2-CF2-O-O-COOM
CF3-O-CF(OCF3)-CF2-O-CF2-CH2-O-O-COOM
CF3-O-CF(OCF3)-CF2-O-CF2-CF(CF3)-O-O-COOM
Application claims, in terms of every 100 mass parts fluoropolymers, the consumption of emulsifying agent is
0.001～5.0 part, preferably 0.01～2.0 part.
The radical initiator that the present invention selects is inorganic peroxide or organic peroxy
Thing.The example of organic peroxide includes but are not limited to: azo-compound such as nitrogen two isobutyl
Nitrile；Two perfluoroalkyl peroxide such as two perfluor n-pro-pyl peroxide, two perfluoro capryl mistakes
Oxide, two perfluorocyclohexyl peroxide；Perfluor diacyl peroxide such as perfluor dipropyl
Acyl peroxide, perfluor two decoyl peroxide, perfluor two hexanoyl peroxide, perfluor two
Hexamethylene acyl peroxide；Floride-free dialkyl peroxide such as diisopropyl peroxide, peroxidating
Di-t-butyl (DTBP)；Floride-free diacyl peroxide such as diacetyl peroxide, peroxidating
Two propionyl, dibutyrylperoxide, dibenzoyl peroxide, benzoylperoxy acetyl, mistake
Oxidation succinic acid；Floride-free peroxy dicarbonate such as peroxy dicarbonate methyl ester, peroxidating two
Propylene carbonate (hereinafter referred to as IPP), peroxy dicarbonate tertiary butyl ester.Inorganic peroxygen
The example of thing have potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate., potassium peroxydisulfate/sodium sulfite,
Potassium peroxydisulfate/sodium metabisulfite.In terms of every 100 mass parts fluoropolymers, the present invention selects
Selecting initiator amount is 0.001～5.0 part, preferably 0.01～2.0 part.
Step 1) in also can add chain-transferring agent further to adjust the molecular weight of product, to reach
To target molecular weight product, improve mobile performance.Described chain-transferring agent is selected from alkanes, alcohol
Class, fluorochlorohydrocarbon class or esters chain-transferring agent；Described alkanes chain-transferring agent be preferably pentane,
Hexane or hexamethylene；Described alcohols chain-transferring agent is preferably methanol, ethanol, ethylene glycol or third
Glycol；Described fluorochlorohydrocarbon class chain-transferring agent is preferably CCl4、CH2Cl2、CF2ClCF2CFClH
Or CFCl2CH3, esters chain-transferring agent is preferably methyl acetate, ethyl acetate, malonic acid two
Ethyl ester；In terms of every 100 mass parts fluoropolymers, described chain-transferring agent consumption is 0.001～5.0
Part, preferably 0.01～3.0 part.
For ensureing emulsion intercalation method and reducing material wall sticking phenomenon, step 1) in also can be to
Adding paraffin in reactor, the paraffin melting point of selection is 20～100 DEG C, preferably 30～70 DEG C,
In terms of every 100 mass parts fluoropolymers, the addition of paraffin is 0.1～5.0 part, preferably
0.5～3.0 part.
Selective polymerization reaction pressure of the present invention is 0.5～6.0MPa, preferably 1.0～5.0MPa.
Selective polymerization reaction temperature of the present invention is 20～160 DEG C, preferably 40～120 DEG C.
The polymerization time of the present invention is 1.0～8.0h, preferably 3.0～5.0h.
Prepare the free radical under the method choice water-based system of fluoropolymer of the present invention and cause poly-
Conjunction mode, can be emulsion polymerization or suspension polymerisation.
The semi-continuous polymerization mode that the present invention selects is reacted, and ties up by constantly adding monomer
Hold reaction system pressure, until reaching to react the quality requiring polymer.
The preferred object lesson of fluoropolymer of the present invention includes but are not limited to: TFE/
CHF=CHC4F9, TFE/CHF=CFC4F9/E、TFE/CF2=CFC4F9、TFE/
CF2=CClC4F9, CTFE/CHF=CHC4F9, CTFE/CHF=CFC4F9、CTFE/
CF2=CFC4F9、CTFE/CF2=CClC4F9, VDF/CHF=CHC4F9、VDF/
CHF=CFC4F9、VDF/CF2=CFC4F9、VDF/CF2=CClC4F9、TFE/HFP/
CHF=CHC4F9, TFE/HFP/CHF=CFC4F9、TFE/HFP/CF2=CFC4F9、
TFE/HFP/CF2=CClC4F9, VDF/HFP/CHF=CHC4F9、VDF/HFP/
CHF=CFC4F9、VDF/HFP/CF2=CFC4F9、VDF/HFP/CF2=CClC4F9、
TFE/PPVE/CHF=CHC4F9, TFE/PPVE/CHF=CFC4F9、TFE/PPVE/
CF2=CFC4F9、TFE/PPVE/CF2=CClC4F9, TFE/CHF=CHC4F9/E、TFE/
CHF=CFC4F9/E、TFE/CF2=CFC4F9/E、TFE/CF2=CClC4F9/E、CTFE/
CHF=CHC4F9/ E, CTFE/CHF=CFC4F9/E、CTFE/CF2=CFC4F9/E、
CTFE/CF2=CClC4F9/E。
As the modified monomer of fluoropolymer, long chain fluorine-containing alkene has raising fluoropolymer
The moulding processability of thing, creep resistance, resistance to cracking energy and light transmission, simultaneously
Do not affect fluoropolymer distinctive high temperature resistant, fire resistance, solvent resistant, resistance to chemical attack
The effect of performance.
The present invention carries out copolymerization by the long-chain fluoroolefin that addition uses to fluorinated copolymer and changes
Property, reduces the processing temperature of polymer, improve the mobility of polymer, light transmittance and
High temperature resistance to cracking energy, the free radical polymerization under this building-up process is water-based system simultaneously
Mode, can be emulsion polymerization or suspension polymerisation, not use solvent polymeric, production process
It is simple and environmentally-friendly, it is easy to accomplish.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
The present invention is as follows to the performance test methods of product:
Fusing point
According to ASTM D 3418, by the fusing point of differential scanning calorimetry detection sample.
Melt index
According to ASTM D 1238, measure its melt flow index according to the fusing point of polymer
(MFI, unit g/10min).
High temperature Cracking Temperature
Test sample is pressed into the notched of a size of 38mm × 13mm × 2mm
Plate, in the bent state, starts to heat up with the speed of 2 DEG C/min from 50 DEG C, records out
The temperature (US4513129) of existing crackle.
Light transmittance
According to ASTM D1003-2011e1, detect 100mm × 100mm × 1mm size
The visible light transmissivity of polymer sheet.
By embodiment in detail below, the present invention is described, but the present invention is not limited only to following reality
Execute example:
Embodiment 1
1) in the 10L stainless steel cauldron with agitator, 6L deionized water is added,
20g molecular weight be 1200 concentration be the aqueous solution of the perfluorocarboxylic acid base polyethers ammonium salt of 10wt%,
30g fusing point is the paraffin of 40 DEG C, 40g hexamethylene.
2) with air in vacuum pump extraction still, then replace with nitrogen, repeat nitrogen charging and
Evacuate degassing, until oxygen content reaches below 30ppm.Then heat to 70 DEG C, pass through
Pipeline carries TFE monomer to reactor, until still pressure reaches 2.5MPa.
3), after treating that temperature and pressure is stable, 10g mass concentration is added by Micro-metering Pumps
It is the persulfate aqueous solution of 10%, starts reaction.Reaction passes through microflowmeter while starting
Amount pump is continuously added the CF being cooled to 0 DEG C with the speed of 150g/h2=CHC4F9, Zong Gongjia
Enter 300g.Being continuously replenished TFE monomer in course of reaction, maintaining reactor pressure is 2.5MPa.
Reaction is until monomer storage tank quality reduces stopped reaction after 2.1kg.Cool to room temperature, reclaim not
The monomer of reaction, releases emulsion, reclaims the paraffin in reactor.
Reaction there are 8100g emulsion, and emulsion is condensed by cohesion bucket breakdown of emulsion at a high speed, washing,
Dehydration, is dried 12h at 150 DEG C and obtains powdery polymer product.Record the fusing point of product
Be 285 DEG C, 370 DEG C, to record MFI under conditions of 5.0kg be 4.5g/10min,
Light transmittance is 92%, by the high temperature resistance to cracking the most cracking phenomenon of energy test experience.
Embodiment 2
1) in the 10L stainless steel cauldron with agitator, 6L deionized water is added,
20g molecular weight be 1200 concentration be the aqueous solution of the perfluorocarboxylic acid base polyethers ammonium salt of 10wt%,
30g fusing point is the paraffin of 60 DEG C, 40g hexamethylene.
2) with air in vacuum pump extraction still, then replace with nitrogen, repeat nitrogen charging and
Evacuate degassing, until oxygen content reaches below 30ppm.Then heat to 80 DEG C, pass through
Compressor adds the TFE/HFP mix monomer of mol ratio 50:50 in reactor, until
Still pressure reaches 4.0MPa.
3), after treating that temperature and pressure is stable, 10g mass concentration is added by Micro-metering Pumps
It is the persulfate aqueous solution of 10%, starts reaction.Reaction passes through microflowmeter while starting
Amount pump is continuously added the CF being cooled to 0 DEG C with the speed of 100g/h2=CHC4F9, Zong Gongjia
Enter 300g.Being continuously replenished phase mol ratio by compressor in course of reaction is 90:10's
TFE/HFP mix monomer, maintaining reactor pressure is 4.0MPa.Reaction is until monomer storage tank
Quality reduces stopped reaction after 2.2kg.Cool to room temperature, reclaim unreacted monomer, release
Emulsion, reclaims the paraffin in reactor.
Reaction there are 8150g emulsion, and emulsion is condensed by cohesion bucket breakdown of emulsion at a high speed, washing,
Dehydration, is dried 12h at 150 DEG C and obtains powdery polymer product.By detection, product
Fusing point be 235 DEG C, 300 DEG C, to record MFI under conditions of 5.0kg be 6.5g/10
Min, light transmittance is 94%, the most cracking existing by high temperature resistance to cracking energy test experience
As.
Embodiment 3
According to the method for embodiment 1, same to CF2=CHC4F9Add 250gPPVE together, instead
Storage tank quality is answered to reduce stopped reaction after 2.0kg.Finally give 8080g product emulsion.
By detection, the fusing point of product is 205 DEG C, 265 DEG C, under conditions of 5.0kg
Recording MFI is 8.9g/10min, and light transmittance is 95%, can be examined by high temperature resistance to cracking
Survey and test the most cracking phenomenon.
Embodiment 4
1) in the 10L stainless steel cauldron with agitator, 6L deionized water is added,
20g molecular weight be 1200 concentration be the aqueous solution of the perfluorocarboxylic acid base polyethers ammonium salt of 10wt%,
30g fusing point is the paraffin of 60 DEG C, 20g hexamethylene.
2) with air in vacuum pump extraction still, then replace with nitrogen, repeat nitrogen charging and
Evacuate degassing, until oxygen content reaches below 30ppm.Then heat to 90 DEG C, pass through
Compressor adds VDF monomer in reactor, until still pressure reaches 4.0MPa.
3), after treating that temperature and pressure is stable, 10g mass concentration is added by Micro-metering Pumps
It is the persulfate aqueous solution of 10%, starts reaction.Reaction passes through microflowmeter while starting
Amount pump is continuously added the CHF=CFC being cooled to 0 DEG C with the speed of 150g/h4F9, Zong Gongjia
Enter 300g CHF=CFC4F9.It is continuously replenished VDF monomer by compressor, maintains reactor
Pressure is 4.0MPa.Reaction is until monomer storage tank quality reduces stopped reaction after 1.4kg.Fall
Temperature, to room temperature, reclaims unreacted monomer, releases emulsion, reclaims the paraffin in reactor.
Reaction there are 7560g emulsion, and emulsion is condensed by cohesion bucket breakdown of emulsion at a high speed, washing,
Dehydration, is dried 12h at 150 DEG C and obtains powdery polymer product.By detection, product
Fusing point be 135 DEG C, 232 DEG C, to record MFI under conditions of 5.0kg be 7.3g/10
Min, light transmittance is 96%, the most cracking existing by high temperature resistance to cracking energy test experience
As.
Embodiment 5
According to embodiment 4, replace VDF with the VDF/HFP mix monomer that mol ratio is 95:5
Monomer, reaction storage tank quality reduces stopped reaction after 1.5kg.Finally give 7620g emulsion
Product.
By detection, the fusing point of product is 115 DEG C, 232 DEG C, under conditions of 5.0kg
Recording MFI is 12.8g/10min, and light transmittance is 96%, can be examined by high temperature resistance to cracking
Survey and test the most cracking phenomenon.
Embodiment 6
1) in the 10L stainless steel cauldron with agitator, 6L deionized water is added,
20g molecular weight be 1200 concentration be the aqueous solution of the perfluorocarboxylic acid base polyethers ammonium salt of 10wt%,
30g fusing point is the paraffin of 30 DEG C.
2) with air in vacuum pump extraction still, then replace with nitrogen, repeat nitrogen charging and
Evacuate degassing, until oxygen content reaches below 30ppm.Then heat to 50 DEG C, pass through
Compressor adds CTFE monomer in reactor, until still pressure reaches 1.2MPa.
3), after temperature and pressure is stable, 20g mass is successively added by Micro-metering Pumps dense
Degree is the persulfate aqueous solution of 10% and sodium sulfite water that 10g mass concentration is 10%
Solution, starts reaction.The Micro-metering Pumps speed with 150g/h is passed through in reaction while starting
It is continuously added the CF being cooled to 0 DEG C2=CFC4F9, altogether add 300g's
CF2=CFC4F9.Being continuously replenished CTFE monomer by compressor, maintenance reactor pressure is
1.2MPa.Reaction is until monomer storage tank quality reduces stopped reaction after 2.5kg.Cool to room
Temperature, reclaims unreacted monomer, releases emulsion, reclaims the paraffin in reactor.
Reaction there are 8210g emulsion, and emulsion is put into freezing 48h in the refrigerator of-25 DEG C,
Wash after at room temperature melting, be dehydrated, at 150 DEG C, be dried 12h obtain powdery polymer
Product.By detection, the fusing point of product is 195 DEG C, 265 DEG C, the condition of 5.0kg
Under to record MFI be 7.3g/10min, light transmittance is 96%, by high temperature resistance to cracking energy
165 DEG C of cracking phenomenons of test experience.165 DEG C of cracking phenomenons of test experience.
Embodiment 7
1) in the 10L stainless steel cauldron with agitator, 6L deionized water is added,
20g molecular weight be 1000 concentration be the aqueous solution of the perfluorocarboxylic acid base polyethers ammonium salt of 10wt%,
30g fusing point is the paraffin of 60 DEG C
2) with air in vacuum pump extraction still, then replace with nitrogen, repeat nitrogen charging and
Evacuate degassing, until oxygen content reaches below 30ppm.Then heat to 80 DEG C, pass through
Compressor adds the TFE/E mix monomer that mol ratio is 60:40 in reactor, until still
Pressure reaches 4.0MPa.
3), after treating that temperature and pressure is stable, 20g mass is successively added by Micro-metering Pumps
Concentration is the persulfate aqueous solution of 10%, starts reaction.Reaction is passed through micro-while starting
Amount dosing pump is continuously added the CF being cooled to 0 DEG C with the speed of 150g/h2=CFC4F9, altogether
Add the CF of 300g2=CFC4F9.The TFE/E being continuously replenished same ratio by compressor is mixed
Closing monomer, maintaining reactor pressure is 4.0MPa.Reaction is until monomer storage tank quality reduces
Stopped reaction after 1.5kg.Cool to room temperature, reclaim unreacted monomer, release emulsion, return
Receive the paraffin in reactor.
Reaction there are 7650g emulsion, and emulsion is condensed by cohesion bucket breakdown of emulsion at a high speed, washing,
Dehydration, is dried 12h at 150 DEG C and obtains powdery polymer product.By detection, product
Fusing point be 235 DEG C, 300 DEG C, to record MFI under conditions of 5.0kg be 3.3g/10
Min, light transmittance is 91%, is occurred out by high temperature resistance to cracking energy test experience 179 DEG C
Split phenomenon.
Embodiment 8
1) in the 10L stainless steel cauldron with agitator, 6L deionized water is added,
20g molecular weight be 1200 concentration be the aqueous solution of the perfluorocarboxylic acid base polyethers ammonium salt of 10wt%,
30g fusing point is the paraffin of 30 DEG C
2) with air in vacuum pump extraction still, then replace with nitrogen, repeat nitrogen charging and
Evacuate degassing, until oxygen content reaches below 30ppm.Then heat to 50 DEG C, pass through
Compressor adds the CTFE/E mix monomer that mol ratio is 60:40 in reactor, until
Still pressure reaches 2.0MPa.
3), after treating that temperature and pressure is stable, 20g mass is successively added by Micro-metering Pumps
Concentration be 10% persulfate aqueous solution and 10g mass concentration be the sodium sulfite of 10%
Aqueous solution, starts reaction.The Micro-metering Pumps speed with 150g/h is passed through in reaction while starting
Degree is continuously added the CF being cooled to 0 DEG C2=CClC4F9, altogether add 300g's
CF2=CClC4F9.The CTFE/E mix monomer of same ratio it is continuously replenished by compressor,
Maintaining reactor pressure is 2.0MPa.Reaction is until monomer storage tank quality is stopped after reducing 1.7kg
Only reaction.Cool to room temperature, reclaim unreacted monomer, release emulsion, reclaim reactor
Interior paraffin.
Reaction there are 7810g emulsion, and emulsion is put into freezing 48h in the refrigerator of-25 DEG C,
Wash after at room temperature melting, be dehydrated, at 150 DEG C, be dried 12h obtain powdery polymer
Product.By detection, the fusing point of product is 216 DEG C, 265 DEG C, the condition of 5.0kg
Under to record MFI be 4.3g/10min, light transmittance is 93%, by high temperature resistance to cracking energy
175 DEG C of cracking phenomenons of test experience.
Embodiment 9
According to embodiment 8, potassium persulfate solution and sodium sulfite solution by 10% become cold
But the trifluoro of the perfluor dicyclohexyl formyl peroxide that mass fraction is 10% of extremely-20 DEG C
Trichloroethane solution, reaction temperature is down to 20 DEG C, is cancelled and use paraffin.Finally give emulsion
Quality is 7915g.By detection, the fusing point of product is 186 DEG C, at 265 DEG C, 5.0kg
Under conditions of to record MFI be 11.4g/10min, light transmittance is 96%, opens by high temperature is resistance to
The most cracking phenomenon of fragility energy test experience.
Embodiment 10
According to embodiment 8, by CF2=CClC4F9Addition increased to 450g by 300g,
Finally giving quality of the emulsion is 7875g.By detection, the fusing point of product is 196 DEG C,
265 DEG C, to record MFI under conditions of 5.0kg be 8.3g/10min, light transmittance is 94%,
By the high temperature resistance to cracking the most cracking phenomenon of energy test experience.
Embodiment 11
According to embodiment 8, by CF2=CClC4F9Addition by 300g reduce to 150g,
Finally giving quality of the emulsion is 7810g.By detection, the fusing point of product is 231 DEG C,
265 DEG C, to record MFI under conditions of 5.0kg be 3.2g/10min, light transmittance is 91%,
By high temperature 158 DEG C of cracking phenomenons of resistance to cracking energy test experience.
Comparative example 1
According to the method for embodiment 1, by CF2=CHC4F9Addition reduced to 0g by 300g,
Other are constant.Finally give 8020g product emulsion.By detection, the fusing point of product is
335 DEG C, 370 DEG C, detect MFI under conditions of 5.0kg time do not flow, it is impossible to be hot pressed into
Type light transmittance cannot detect, by the high temperature resistance to cracking the most cracking phenomenon of energy test experience.
Comparative example 2
According to embodiment 2, by CF2=CHC4F9Addition reduced to 0g by 300g, other
Constant, finally give quality of the emulsion 7910g.By detection, the fusing point of product is 268 DEG C,
370 DEG C, to record MFI under conditions of 5.0kg be 3.9g/10min, light transmittance is 92%,
By the high temperature resistance to cracking the most cracking phenomenon of energy test experience.
Comparative example 3
According to embodiment 4, by CHF=CFC4F9Addition reduced to 0g by 300g, other
Constant.Finally give quality of the emulsion 7450g.By detection, the fusing point of product is 169 DEG C,
232 DEG C, to record MFI under conditions of 5.0kg be 1.3g/10min, light transmittance is 86%,
By the high temperature resistance to cracking the most cracking phenomenon of energy test experience.
Comparative example 4
According to embodiment 7, by CF2=CFC4F9Addition reduced to 0g by 300g, other
Constant.Finally give quality of the emulsion 7540g.Reaction there are 7650g emulsion.By inspection
Surveying, the fusing point of product is 263 DEG C, 370 DEG C, record MFI under conditions of 5.0kg and be
1.3g/10min, light transmittance is 78%, by high temperature resistance to cracking energy test experience 139 DEG C
Cracking phenomenon.
Can be drawn by above example, add modified fluoride-containing monomer and carry out polyreaction, one
Aspect, reaction is prone to carry out, and is not required to use solvent polymeric, and method is simple and environmentally-friendly, product
Yield is higher；Polymer synthesized by Ling Yifangmian has higher light transmittance, and high temperature is resistance to be opened
Fragility can be good, is a kind of well-behaved macromolecule polymeric material, before having wide application
Scape.
Although, the most with a general description of the specific embodiments the present invention is made
Detailed description, but on the basis of the present invention, it can be made some modifications or improvements, this
Will be apparent to those skilled in the art.Therefore, without departing from present invention spirit
On the basis of these modifications or improvements, belong to the scope of protection of present invention.
Claims (18)
1. a preparation method for long-chain fluorinated olefin polymer, comprises the steps:
1) its volume 60～deionized water of 70% is added in a kettle., simultaneously to deionization
Water adds the reaction promoter including emulsifying agent；By evacuation and nitrogen charging by the oxygen in reactor
Content controls at below 30ppm, is warmed up to 20～160 DEG C；
2) in reactor, polymerization monomer is added, until pressure reaches 0.5～6.0MPa in still,；
Described polymerization monomer is fluorochemical monomer or fluorochemical monomer and the mixture of non-fluorochemical monomer；To reaction
Adding radical initiator in still, reaction adds modified monomer while starting
RfCX1=CX2X3, described RfCX1=CX2X3R in monomerfFor carbon number between 2～8
Perfluorinated alkyl group, X1、X2、X3Selected from halogen atom or hydrogen atom, at least a part of which has
One is fluorine atom；Course of reaction is added the described polymerization monomer of same ratio, maintains reaction
Still pressure is constant；
3) add after polymerization monomer reaches predetermined quality and stop adding, after reaction stops, reclaiming
Unreacted monomer, releases emulsion；To described emulsion by being condensed, wash, be dehydrated,
It is dried to obtain powdery long-chain fluorinated olefin polymer.
Long-chain fluorinated olefin polymer preparation method the most according to claim 1, its feature
Be, described step 1) in be warmed up to 40～120 DEG C, described step 2) in still pressure reach
1.0～5.0MPa.
Long-chain fluorinated olefin polymer preparation method the most according to claim 1, it is special
Levy and be, described fluorochemical monomer selected from tetrafluoroethene, vinylidene, CTFE, six
One or more in fluoropropene, fluorothene, perfluor (n-propyl vinyl) ether.
Long-chain fluorinated olefin polymer preparation method the most according to claim 3, it is special
Levy and be, with modified monomer RfCX1=CX2X3On the basis of the molal quantity sum of fluorochemical monomer,
Described modified monomer RfCX1=CX2X3Molar fraction in the range of 0.01～9.9%.
Long-chain fluorinated olefin polymer preparation method the most according to claim 4, it is special
Levy and be, with modified monomer RfCX1=CX2X3On the basis of the molal quantity sum of fluorochemical monomer,
Described modified monomer RfCX1=CX2X3Molar fraction in the range of 0.1～9.0%.
Long-chain fluorinated olefin polymer preparation method the most according to claim 3, it is special
Levying and be, described polymerization monomer is the mixture of fluorochemical monomer and non-fluorochemical monomer, described non-
Fluorochemical monomer is ethylene and/or propylene, modified monomer RfCX1=CX2X3With fluorochemical monomer mole
The mol ratio of number sum and non-fluorochemical monomer is between 1～10:1,.
Long-chain fluorinated olefin polymer preparation method the most according to claim 6, it is special
Levy and be, described modified monomer RfCX1=CX2X3Contain with non-with fluorochemical monomer molal quantity sum
The mol ratio of fluorine monomer is between 1～9:1.
8. according to the long-chain fluorinated olefin polymer preparation side described in any one of claim 1-7
Method, it is characterised in that described emulsifying agent is perfluorocarboxylic acid base polyethers, and formula is:
Wherein A, B represent CF respectively3, COOM or CF2Any one in COOM, M
Represent H, NH4Or any one of alkali metal；Rf‘Represent F or CF3；P generation
Table CF2、CH2, CFCl, CClH, CFBr or CF (CF3)；GfRepresent CF2CF2、
CF2CH2、CF2CF(CF3)、CF2CFCl、CF2CHF、CF2CH(CF3)、
CH2CHCF(CF3)、CF2CHCl or CF2CFBr；M, n, q, r, s meet following bar
Part:
A) m, n, q, r, s are the integer not less than 0；
b)n+r≥1；
c)n+r≤m+q+s；
d)m≥n+q+r+s；
E) molecular weight is 300～20000；
In terms of every 100 mass parts fluoropolymers, the consumption of emulsifying agent is 0.001～5.0 part.
Long-chain fluorinated olefin polymer preparation method the most according to claim 8, it is special
Levying and be, the molecular weight of described emulsifying agent is 1000～5000, and the consumption of described emulsifying agent is
0.01～2.0 part.
10. prepare according to the long-chain fluorinated olefin polymer described in any one of claim 1-7
Method, it is characterised in that described radical initiator is inorganic peroxide or organic mistake
Oxide；In terms of every 100 mass parts fluoropolymers, described radical initiator consumption is
0.001～5.0 part.
11. according to the long-chain fluorinated olefin polymer preparation method described in right 10, its feature
Being, the consumption of described radical initiator is 0.01～2.0 part.
12. prepare according to the long-chain fluorinated olefin polymer described in any one of claim 1-7
Method, it is characterised in that step 1) in further to reactor add chain-transferring agent, described
Chain-transferring agent is selected from alkanes, alcohols, fluorochlorohydrocarbon class or esters chain-transferring agent；Described chain turns
Moving agent consumption is 0.001～5.0 part.
13. long-chain fluorinated olefin polymer preparation methoies according to claim 12, its
Being characterised by, described alkanes chain-transferring agent is pentane, hexane or hexamethylene；Described alcohols
Chain-transferring agent is methanol, ethanol, ethylene glycol or propylene glycol；Described fluorochlorohydrocarbon class chain-transferring agent
For CCl4、CH2Cl2、CF2ClCF2CFClH or CFCl2CH3, described esters chain tra nsfer
Agent is methyl acetate, ethyl acetate, diethyl malonate；Described chain-transferring agent consumption is
0.01～3.0 part.
14. prepare according to the long-chain fluorinated olefin polymer described in any one of claim 1-7
Method, it is characterised in that step 1) in further in reactor add paraffin, described stone
Wax fusing point is 20～100 DEG C.
15. long-chain fluorinated olefin polymer preparation methoies according to claim 14, its
Being characterised by, described melting point of paraffin wax is 30～70 DEG C.
16. long-chain fluorinated olefin polymer preparation methoies according to claim 14, its
Being characterised by, in terms of every 100 mass parts fluoropolymers, the addition of paraffin is 0.1～5.0
Part.
17. long-chain fluorinated olefin polymer preparation methoies according to claim 16, its
Being characterised by, the addition of described paraffin is 0.5～3.0 part.
The long-chain fluoroolefin that method described in 18. any one of claim 1-17 prepares gathers
Compound.
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