CN104945549B - Ethene chlorotrifluoroethylene, its preparation method and application with stable end groups structure - Google Patents
Ethene chlorotrifluoroethylene, its preparation method and application with stable end groups structure Download PDFInfo
- Publication number
- CN104945549B CN104945549B CN201410116255.4A CN201410116255A CN104945549B CN 104945549 B CN104945549 B CN 104945549B CN 201410116255 A CN201410116255 A CN 201410116255A CN 104945549 B CN104945549 B CN 104945549B
- Authority
- CN
- China
- Prior art keywords
- ethylene
- chlorotrifluoro
- reactor
- ethylene copolymer
- end groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CC(*)(C1=NCCN1)N Chemical compound CC(*)(C1=NCCN1)N 0.000 description 8
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N C1CCNCCC1 Chemical compound C1CCNCCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- PDXOCTDFIXPYNW-UHFFFAOYSA-N CC(C)C(NC1CCCCCC1)=C Chemical compound CC(C)C(NC1CCCCCC1)=C PDXOCTDFIXPYNW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of ethene chlorotrifluoroethylene with stable end groups structure, its end-group structure isOr
Description
Technical field
The invention belongs to fluoro-containing macromolecule material field, it is related to a kind of ethene with stable end groups structure-trifluoro chloroethene
Alkene copolymer, its preparation method and application.
Background technology
Ethylene-chlorinated（ECTFE or F30）Fluororesin, is synthesized by du pont company earliest, is a kind of thermoplastic
Property fluorinated copolymer, has outstanding resistance to corrosion to the inorganic of thumping majority, organic chemicals and organic solvent.With other
Thermoplastic is compared, and the performance of ECTFE chlorine-resistant at high temperature and chlorine derivative is particularly pertinent；Its good toughness, hardness is high,
There is prominent shock resistance, the surface of its finished-product material is extremely smooth, and similar glass can prevent the hyperplasia of microorganism, be used for
Food and drinking-water field；ECTFE electric properties are excellent, and made electric wire belongs to highest safe class, electric
Commercial Application is more, is made the electric equipment parts such as electric wire insulation layer, cable cover(ing), communications satellite, nuclear reactor, micro electric
Position device positive/negative thread slider, battery case, electrical equipment collapsible tube etc., can be in low temperature to making safely within the temperature range of 149 DEG C
With；A mostly important feature is exactly that it has extremely low permeance property to vapor and other gases, is widely used in electricity
The spraying inside and outside of son and pharmaceuticals industry dust-free sterile airduct, the preservative treatment of chemical industry and other industry anticorrosion equipments, solar energy envelope
Dress membrane material and other field film application.
Fluorinated surfactant is that surface-active highest is a kind of so far in surfactant, and it is in fluoropolymer
Application in thing manufacture is long-standing, and Main Function is the polymerization process stabilization for ensureing fluoropolymer, the surface for reducing water
Power, increase reaction monomers solubility, construction primary particle state and reactor cleannes in water, are the fluorine-containing trees of industrialized production
The necessary assistant of fat.In the past few decades, with perfluorooctanoic acid compound（It is abbreviated as PFOA）, perfluor sulfonyl compound
（It is abbreviated as PFOS）It is the fluorine-containing surfactant for representing, important function has been played in the manufacturing of fluoropolymer.But
Because latter stage in last century scientist has found that PFOA or PFOS may have carcinogenic risk, therefore PFOA is put into the organic dirt of persistence
Dye thing（POPs）Material register.On November 11st, 2004, it is intended to reduce and eliminate lasting pollutant（POPs）Anthropogenic discharge
's《Convention of Stockholm on persistence organic pollutant》Formally China is come into force.Countries in the world fluorination work manufacturing enterprise
All actively seek, develop PFOA green substitutes.
ECTFE resins can be prepared using polymerisation in solution, emulsion polymerization, micro-emulsion polymerization and suspension polymerisation.Solution
Polymerization such as patent CA902848A, EP0612767B1, US4053445, US5182342, US5434229.Micro-emulsion polymerization is such as
Patent EP0712882B1.Suspension polymerisation such as patent EP0747404B1, EP1067145B1.Emulsion polymerization such as patent
US2559752、US4426501、US4789717、US5498680、US4482685、US3767634、US3857827、
US4025709, US4225482, US6395848B1, US3006881, US3043823, US6869997, CA1235549 etc..This
A little patents are using fluorine-containing（Chlorine）Class carboxylic acid or sulfosalt surfactant or fluorine-containing alkyl ether class carboxylic acid and Sulfonates surface
Activating agent.
Accordingly, it would be desirable to new initiator is developed, not only environmental protection, and the ethylene-chlorinated of preparation can be made
Copolymer end group stabilization, function admirable.
The content of the invention
It is an object of the invention to provide a kind of ethylene-chlorotrifluoro-ethylene copolymer with end group stabilization, function admirable,
Its preparation method and application.
It is to reach goal of the invention the technical solution adopted by the present invention：
A kind of ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure, the ethylene-chlorotrifluoro-ethylene copolymer
End-group structure beOr
The R is-NHxR1, wherein：
X=0 or 1；
R1Replaced by O selected from H, C1-C12 straight chained alkyl, branched alkyl or cycloalkyl, phenyl, at least one carbon atom
C1-C12 straight chained alkyls, branched alkyl or cycloalkyl；
The 1% weight decomposition temperature Td of the ethylene-chlorotrifluoro-ethylene copolymer TGA is 380~450 DEG C.
As preferred embodiment, above-mentioned end-group structureIt is preferably selected from following structural formula one
Kind：
Above-mentioned ethylene-chlorotrifluoro-ethylene copolymer can further containing selected from the one kind in following monomer, two kinds
Or three kinds of combination of the above：CF2=CF-CF3、CHF=CH-CF3、CH2=CF-CF3Or CH2=CH-CF3。
Present invention also offers the preparation method of above-mentioned ethylene-chlorotrifluoro-ethylene copolymer.Above-mentioned ethylene-chlorinated
Copolymer is preferably by ethene and CTFE in the case where end group after water-soluble azo class hydrochloric acid salt initiators trigger is self-emulsified
Prepared by emulsion copolymerization reaction, the water-soluble azo class hydrochloric acid salt initiators are selected from the one kind in following structural formula：
Above-mentioned R group and preferably it is the same as those described above, i.e.,：
（1）The R is-NHxR1, wherein：
X=0 or 1；
R1Replaced by O selected from H, C1-C12 straight chained alkyl, branched alkyl or cycloalkyl, phenyl, at least one carbon atom
C1-C12 straight chained alkyls, branched alkyl or cycloalkyl；
（2）The R preferably is selected from the one kind in following structural formula：
The consumption of above-mentioned water-soluble azo class hydrochloride is preferably reaction monomers ethene and CTFE mole total amount
0.01~5%.Polymerization temperature is preferably 10~70 DEG C, more preferably 30~55 DEG C；Polymerization pressure is preferably 0.2~5MPa,
More preferably 0.5~3MPa.
Ethylene-chlorotrifluoro-ethylene copolymer of the present invention is preferably carried out by ethene and CTFE in water phase
The reaction of self-emulsifying type emulsion copolymerization is obtained, and comprises the following steps：
（1）Pure water is added toward reactor, starts stirring at low speed, reactor is vacuumized, be less than oxygen content in kettle
30ppm；
（2）Part CTFE monomer and vinyl monomer are added toward reactor, make pressure in kettle reach 0.2~
5MPa；
（3）Heating makes reactor temperature rise to 10~70 DEG C, improves reactor speed of agitator, is added toward reactor water-soluble
Azo hydrochloric acid salt initiator initiation reaction is carried out；
（4）Remaining CTFE monomer and vinyl monomer are continuously added into toward reactor, reacting kettle inner pressure is kept
In ± 0.01MPa the scopes of setting polymerization pressure；
（5）Reaction obtains final product ethylene-chlorotrifluoro-ethylene copolymer after terminating.
Oxygen content is preferably shorter than 10ppm in aforesaid reaction vessel；Vinyl monomer and CTFE monomer can first mix
Reactor is added after even, it is also possible to add reactor independently of one another；The water-soluble azo class hydrochloric acid salt initiator can be with
It is disposable to add, it is also possible to be dividedly in some parts.
The ethylene-chlorotrifluoro-ethylene copolymer end group stabilization of present invention preparation, function admirable, resin height are pure, inside
Surfactant-free is remained, and is suitable for anti-corrosion or is prevented microorganism adhesion equipment from protecting；It is especially suitable for use as chemical anticorrosion painting
Layer or liner, semiconductor air pipeline system corrosion-inhibiting coating, food, high purity water, medical equipment, electric wire and electric anti-
Only microorganism adhesion equipment protection.
Ethylene-chlorotrifluoro-ethylene copolymer of the present invention and preparation method thereof compared to existing technology, with following excellent
Point：（1）Polymerization eliminates the disturbing factor that dispersant brings relative to conventional method, saves a large amount of slurries；（2）System
Standby polymer terminal group stabilization, temperature resistant grade high, mechanical performance and excellent electrical property；（3）Tree is assigned by the way of self-emulsifying
Fat high cleanliness, is allowed to can be applied to food, medicine and high pure electronic electric field.
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body implementation method.One skilled in the art would recognize that present invention encompasses being potentially included in Claims scope
All alternatives, improvement project and equivalents.
Embodiment 1：Azo diisobutyl amidine dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to, by metering device to 2500g CTFEs are added in reactor, is stirred for -0.1MPa
45 DEG C are mixed and be warming up to, after system temperature is constant, with compressor to adding ethene to pressure as 3.8MPa in reactor, is used tricks
To the 200ml diisobutyl amidine dihydrochloride aqueous solution of azo containing 23.5g is added in reactor, initiation reaction starts polymerization to amount pump.
At 45 DEG C, be continually fed into ethylene gas maintenance pressure makes reaction constantly carry out to maintenance reaction temperature in 3.8MPa, reacts 6 hours
Afterwards, stop ethylene gas adding, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by discharging valve of reaction kettle goalkeeper
White emulsion material is put into cohesion bucket, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white powder.
Further white powder is vacuum dried 8 hours in 100~120 DEG C, 1960gECTFE resins are obtained.
Contain through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation fluororesin
Measure is 48.82%；Molar content shared by ethylene unit unit is 51.18%.
ECTFE polymer datas：The melt index for determining ECTFE resins by fusion index instrument is 6.5g/10mim (275
℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 399.25 DEG C；DSC data display copolymer fusing point exists
228.9℃。
Embodiment 2：Azo diisobutyl amidine dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to, by metering device to 2500g CTFEs are added in reactor, is stirred for -0.1MPa
65 DEG C are mixed and be warming up to, after system temperature is constant, with compressor to adding ethene to pressure as 2.6MPa in reactor, is used tricks
To the 100ml diisobutyl amidine dihydrochloride aqueous solution of azo containing 7.5g is added in reactor, initiation reaction starts polymerization to amount pump.Dimension
Reaction temperature is held at 65 DEG C, be continually fed into ethylene gas maintenance pressure makes reaction constantly carry out in 2.6MPa, after reacting 8 hours,
Stop ethylene gas adding, lower the temperature, reclaim unreacted ethene, CTFE monomer, goalkeeper is white by discharging valve of reaction kettle
Color emulsion material is put into cohesion bucket, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white powder.Enter
In 100-120 DEG C be vacuum dried 8 hours white powder by one step, obtains 2180gECTFE resins.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 50.02%；Molar content shared by ethylene unit unit is 49.98%.
ECTFE polymer datas：The melt index for determining ECTFE resins by fusion index instrument is 10.5g/10mim (275
℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 412.1 DEG C；DSC data display copolymer fusing point exists
218.56℃。
Embodiment 3：Azo diisobutyl amidine dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to, by metering device to 2500g CTFEs are added in reactor, is stirred for -0.1MPa
25 DEG C are mixed and be warming up to, after system temperature is constant, with compressor to adding ethene to pressure as 0.85MPa in reactor, is used
To the 300ml diisobutyl amidine dihydrochloride aqueous solution of azo containing 28.35g is added in reactor, initiation reaction starts to gather measuring pump
Close.At 25 DEG C, be continually fed into ethylene gas maintenance pressure makes reaction constantly carry out to maintenance reaction temperature in 0.85MPa, reaction 12
After hour, stop ethylene gas and add, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by discharging valve of reaction kettle
Goalkeeper's white emulsion material is put into cohesion bucket, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white powder
End.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1960gECTFE resins are obtained.
Through shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation white powder resin moles
Percentage composition is 50.8%；Molar content shared by ethylene unit unit is 49.2%.
White powder polymer data：The melt index for determining white powder resin by fusion index instrument is 10.5g/
10mim(275℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 412.25 DEG C；DSC data shows copolymerization
Thing fusing point is at 238.9 DEG C.
Embodiment 4：Azo diimidazole quinoline base propane dihydrochloride
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 5.5L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm,
Continue to be evacuated to reacting kettle inner pressure for -0.1MPa, by metering device to addition 2500g CTFEs in reactor,
45 DEG C are stirred and be warming up to, after system temperature is constant, with compressor to adding ethene to pressure as 3.8MPa in reactor, is used
Measuring pump to the 400ml diimidazole quinoline base propane dihydrochloride aqueous solution of azo containing 28.05g is added in reactor, open by initiation reaction
Begin to be polymerized.At 45 DEG C, be continually fed into ethylene gas maintenance pressure makes reaction constantly carry out to maintenance reaction temperature in 3.8MPa, reacts
After 6 hours, stop ethylene gas and add, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by reactor blowing
Be put into white emulsion material in cohesion bucket by valve, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white
Powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1960gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 48.83%；Molar content shared by ethylene unit unit is 51.17%.
ECTFE polymer datas：The melt index for determining ECTFE resins by fusion index instrument is 7.05g/10mim (275
℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 402.5 DEG C；DSC data display copolymer fusing point exists
229.5℃。
Embodiment 5：Azo diimidazole quinoline base propane dihydrochloride
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 5.5L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm,
Continue to be evacuated to reacting kettle inner pressure for -0.1MPa, by metering device to addition 2500g CTFEs in reactor,
65 DEG C are stirred and be warming up to, after system temperature is constant, with compressor to adding ethene to pressure as 2.6MPa in reactor, is used
To the 150ml diimidazole quinoline base propane dihydrochloride aqueous solution of azo containing 9.1g is added in reactor, initiation reaction starts measuring pump
Polymerization.At 65 DEG C, be continually fed into ethylene gas maintenance pressure makes reaction constantly carry out to maintenance reaction temperature in 2.6MPa, reaction 8
After hour, stop ethylene gas and add, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by discharging valve of reaction kettle
Goalkeeper's white emulsion material is put into cohesion bucket, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white powder
End.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 2180gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 50.03%；Molar content shared by ethylene unit unit is 49.97%.
ECTFE polymer datas：The melt index for determining ECTFE resins by fusion index instrument is 9.5g/10mim (275
℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 411.1 DEG C；DSC data display copolymer fusing point exists
219.6℃。
Embodiment 6：Azo diimidazole quinoline base propane dihydrochloride
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 5.5L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm,
Continue to be evacuated to reacting kettle inner pressure for -0.1MPa, by metering device to addition 2500g CTFEs in reactor,
Stir and be warming up to 25 DEG C, after system temperature is constant, with compressor in reactor add ethene to pressure as 1.05MPa,
With measuring pump to the 300ml diimidazole quinoline base propane dihydrochloride aqueous solution of azo containing 33.7g is added in reactor, initiation reaction is opened
Begin to be polymerized.At 25 DEG C, be continually fed into ethylene gas maintenance pressure makes reaction constantly carry out to maintenance reaction temperature in 1.05MPa, instead
After answering 12 hours, stop ethylene gas and add, lower the temperature, reclaim unreacted ethene, CTFE monomer, put by reactor
Be put into white emulsion material in cohesion bucket by material valve, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white
Color powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 2160gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 50.76%；Molar content shared by ethylene unit unit is 49.24%.
ECTFE polymer datas：The melt index for determining ECTFE resins by fusion index instrument is 16.5g/10mim (275
℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 422.46 DEG C；DSC data display copolymer fusing point exists
240.05℃。
Embodiment 7：The tertiary fourth imines methyl ether hydrochloride of azoInitiator, ternary polymerization
Thing
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to for -0.1MPa, by metering device to added in reactor 2500g CTFEs,
250g hexafluoropropenes, stir and are warming up to 45 DEG C, after system temperature is constant, with compressor to addition ethene in reactor to pressure
Power is 3.85MPa, with measuring pump to the tertiary fourth imines methyl ether hydrochloride aqueous solution of 250ml azos containing 20.9g is added in reactor, is drawn
Hair reaction starts polymerization.At 45 DEG C, be continually fed into ethylene gas maintenance pressure makes reaction continuous to maintenance reaction temperature in 3.85MPa
Carry out, after reacting 6 hours, stop ethylene gas and add, lower the temperature, reclaim unreacted ethene, CTFE and hexafluoropropene
Monomer, is put into cohesion bucket by discharging valve of reaction kettle goalkeeper's white emulsion material, many with the deionized water of heat after cohesion, dehydration
Secondary washing material, obtains white powder.Further white powder is vacuum dried 8 hours in 100~120 DEG C, is obtained
2060gECTFE resins.
Contain through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation fluororesin
Measure is 50.2%；Molar content shared by hexafluoropropene construction unit is 1.7%；Molar content shared by ethylene unit unit
It is 48.1%.
Polymer data：The melt index for determining resin by fusion index instrument is 11.5g/10mim (275 DEG C, 2.16kg)；
TGA tests 1% weight decomposition temperature of resin（Td）It is 401.2 DEG C；DSC data shows copolymer fusing point at 215.8 DEG C.
Embodiment 8：Azo tert-Butyl-cyclohexyl narrows hydrochlorideInitiator, three
Membered copolymer
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to for -0.1MPa, by metering device to added in reactor 2500g CTFEs,
150g3,3,3- trifluoromethyl propylene, stirs and is warming up to 40 DEG C, after system temperature is constant, is added in reactor with compressor
It is 3.85MPa to enter ethene to pressure, and salt is narrowed to the addition 500ml tert-Butyl-cyclohexyls of azo containing 50.6g in reactor with measuring pump
Acid salt aqueous solution, initiation reaction starts polymerization.Maintenance reaction temperature is continually fed into ethylene gas and maintains pressure to exist at 40 DEG C
3.85MPa makes reaction constantly carry out, and after reacting 6 hours, stops ethylene gas and adds, and lowers the temperature, reclaims unreacted ethene, trifluoro
Vinyl chloride and 3,3,3- trifluoromethyl propylene monomers are put into cohesion bucket by discharging valve of reaction kettle goalkeeper's white emulsion material,
With the multiple washing material of deionized water of heat after cohesion, dehydration, white powder is obtained.Further by white powder in 100~120
DEG C vacuum drying 8 hours, obtain 1960gECTFE resins.
Contain through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation fluororesin
Measure is 49.52%；Molar content shared by 3,3,3- trifluoromethyl propylene construction units is 1.08%；Shared by ethylene unit unit
Molar content is 49.4%.
Polymer data：The melt index for determining resin by fusion index instrument is 15.5g/10mim (275 DEG C, 2.16kg)；
TGA tests 1% weight decomposition temperature of resin（Td）It is 403.5 DEG C；DSC data shows copolymer fusing point at 215.5 DEG C.
Embodiment 9：The azo tert-butyl group-propyl group narrows hydrochlorideInitiator,
Terpolymer
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to for -0.1MPa, by metering device to added in reactor 2500g CTFEs,
180g2,3,3,3- tetrafluoropropenes stir and are warming up to 50 DEG C, after system temperature is constant, are added in reactor with compressor
Ethene to pressure is 3.9MPa, and hydrochloride is narrowed to addition 500ml azos containing the 41.6g tert-butyl group-propyl group in reactor with measuring pump
The aqueous solution, initiation reaction starts polymerization.At 50 DEG C, be continually fed into ethylene gas maintenance pressure makes maintenance reaction temperature in 3.9MPa
Reaction constantly carry out, reaction 6 hours after, stop ethylene gas addition, lower the temperature, reclaim unreacted ethene, CTFE and
2,3,3,3- tetrafluoropropene monomers, are put into cohesion bucket by discharging valve of reaction kettle goalkeeper's white emulsion material, after cohesion, dehydration
With the multiple washing material of deionized water of heat, white powder is obtained.White powder is further vacuum dried 8 in 100~120 DEG C
Hour, obtain 1560gECTFE resins.
Contain through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation fluororesin
Measure is 50.63%；Molar content shared by 2,3,3,3- tetrafluoropropene construction units is 0.88%；Rubbed shared by ethylene unit unit
Your percentage composition is 48.49%.
Polymer data：The melt index for determining resin by fusion index instrument is 23.5g/10mim (275 DEG C, 2.16kg)；
TGA tests 1% weight decomposition temperature of resin（Td）It is 392.5 DEG C；DSC data shows copolymer fusing point at 215.3 DEG C.
Example 10 below~17 are polymerized in mixed ethylene-CTFE gas feed mode, in reaction unit
Need to be equipped with two gas mixers, ethene and CTFE monomer mole ratio are between 25-40 in No. 1 gas mixer：75-
60；Ethene is matched between 45-55 with CTFE in No. 2 gas mixers：Between 55-45.
Embodiment 10：Azo diisobutyl amidine dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to stirs and is warming up to 35 DEG C, by compressor by No. 1 gas mixer for -0.1MPa
Gas is passed through in reactor, is 1.65MPa to pressure, after system temperature is constant, with measuring pump to adding 100ml in reactor
The diisobutyl amidine dihydrochloride aqueous solution initiation reaction of azo containing 3.5g is carried out, with compressor to No. 2 mixing of addition in reactor
Mixed gas in gas, maintenance reaction pressure is 1.65MPa.Being continually fed into No. 2 gaseous mixtures makes reaction constantly carry out, at interval of reaction
2 hours, by measuring pump to 50ml azos containing the 1.5g diisobutyl amidine dihydrochloride aqueous solution is added in reactor, continue to react
After 8 hours, stop No. 2 groove gases and add, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by reactor blowing
Be put into white emulsion material in cohesion bucket by valve, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white
Powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1764gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 50.03%；Molar content shared by ethylene unit unit is 49.97%.
ECTFE polymer datas：By fusion index instrument determine resin melt index for 12.5g/10mim (275 DEG C,
2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 402.75 DEG C；DSC data display copolymer fusing point exists
235.9℃。
Embodiment 11：Azo diisobutyl amidine dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to stirs and is warming up to 35 DEG C, by compressor by No. 1 gas mixer for -0.1MPa
Gas is passed through in reactor, is 1.65MPa to pressure, after system temperature is constant, with measuring pump to adding 100ml in reactor
The diisobutyl amidine dihydrochloride aqueous solution initiation reaction of azo containing 6.5g is carried out, with compressor to No. 2 mixing of addition in reactor
Mixed gas in gas, maintenance reaction pressure is 1.65MPa.Being continually fed into No. 2 gaseous mixtures makes reaction constantly carry out, at interval of reaction
2 hours, by measuring pump to 50ml azos containing the 2g diisobutyl amidine dihydrochloride aqueous solution is added in reactor, continue to react 8
After hour, stop No. 2 groove gases and add, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by reactor blowing
Be put into white emulsion material in cohesion bucket by valve, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white
Powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1856gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 50.24%；Molar content shared by ethylene unit unit is 49.76%.
ECTFE polymer datas：By fusion index instrument determine resin melt index for 24.5g/10mim (275 DEG C,
2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 401.05 DEG C；DSC data shows copolymer fusing point 236
℃。
Embodiment 12：Azo diisobutyl amidine dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to stirs and is warming up to 65 DEG C, by compressor by No. 1 gas mixer for -0.1MPa
Gas is passed through in reactor, is 2.45MPa to pressure, after system temperature is constant, with measuring pump to adding 100ml in reactor
The diisobutyl amidine dihydrochloride aqueous solution initiation reaction of azo containing 2.5g is carried out, with compressor to No. 2 mixing of addition in reactor
Mixed gas in gas, maintenance reaction pressure is 2.45MPa.Being continually fed into No. 2 gaseous mixtures makes reaction constantly carry out, at interval of reaction
1 hour, by measuring pump to 50ml azos containing the 1g diisobutyl amidine dihydrochloride aqueous solution is added in reactor, continue to react 8
After hour, stop No. 2 groove gases and add, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by reactor blowing
Be put into white emulsion material in cohesion bucket by valve, with the multiple washing material of deionized water of heat after cohesion, dehydration, obtains white
Powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1854gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 48.94%；Molar content shared by ethylene unit unit is 51.06%.
ECTFE polymer datas：By fusion index instrument determine resin melt index for 18.5g/10mim (275 DEG C,
2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 399.08 DEG C；DSC data display copolymer fusing point exists
226.3℃。
Embodiment 13：Azo diimidazole quinoline base propane dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to stirs and is warming up to 35 DEG C, by compressor by No. 1 gas mixer for -0.1MPa
Gas is passed through in reactor, is 1.65MPa to pressure, after system temperature is constant, with measuring pump to adding 100ml in reactor
The diimidazole quinoline base propane dihydrochloride aqueous solution initiation reaction of azo containing 4.1g is carried out, with compressor to addition 2 in reactor
Mixed gas in gaseous mixture, maintenance reaction pressure is 1.65MPa.Being continually fed into No. 2 gaseous mixtures makes reaction constantly carry out, at interval of
Reaction 2 hours, it is water-soluble to 50ml azos containing 1.75g diimidazole quinoline base propane dihydrochloride is added in reactor by measuring pump
Liquid, after continuing to react 8 hours, stops No. 2 groove gases and adds, and lowers the temperature, reclaims unreacted ethene, CTFE monomer, leads to
Cross discharging valve of reaction kettle goalkeeper's white emulsion material to be put into cohesion bucket, repeatedly washed with the deionized water of heat after cohesion, dehydration
Material, obtains white powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1764gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 50.05%；Molar content shared by ethylene unit unit is 49.95%.
ECTFE polymer datas：The melt index for determining ECTFE resins by fusion index instrument is 15.5g/10mim (275
℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 412.65 DEG C；DSC data display copolymer fusing point exists
237.9℃。
Embodiment 14：Azo diimidazole quinoline base propane dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to stirs and is warming up to 35 DEG C, by compressor by No. 1 gas mixer for -0.1MPa
Gas is passed through in reactor, is 1.65MPa to pressure, after system temperature is constant, with measuring pump to adding 100ml in reactor
The diimidazole quinoline base propane dihydrochloride aqueous solution initiation reaction of azo containing 7.7g is carried out, with compressor to addition 2 in reactor
Mixed gas in gaseous mixture, maintenance reaction pressure is 1.65MPa.Being continually fed into No. 2 gaseous mixtures makes reaction constantly carry out, at interval of
Reaction 2 hours, by measuring pump to adding 50ml azos containing the 2.4g diimidazole quinoline base propane dihydrochloride aqueous solution in reactor,
After continuing to react 8 hours, stop No. 2 groove gases and add, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by anti-
Answer kettle dispensing valve that white emulsion material is put into cohesion bucket, with the multiple washing material of deionized water of heat after cohesion, dehydration,
Obtain white powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1956gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 50.32%；Molar content shared by ethylene unit unit is 49.68%.
ECTFE polymer datas：The melt index for determining ECTFE resins by fusion index instrument is 23.8g/10mim (275
℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 411.05 DEG C；DSC data display copolymer fusing point exists
234.5℃。
Embodiment 15：Azo diimidazole quinoline base propane dihydrochloride initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
The continuous reacting kettle inner pressure that is evacuated to stirs and is warming up to 65 DEG C, by compressor by No. 1 gas mixer for -0.1MPa
Gas is passed through in reactor, is 2.45MPa to pressure, after system temperature is constant, with measuring pump to adding 100ml in reactor
The diimidazole quinoline base propane dihydrochloride aqueous solution initiation reaction of azo containing 2.97g is carried out, with compressor to addition 2 in reactor
Mixed gas in gaseous mixture, maintenance reaction pressure is 2.45MPa.Being continually fed into No. 2 gaseous mixtures makes reaction constantly carry out, at interval of
Reaction 1 hour, by measuring pump to adding 50ml azos containing the 1.2g diimidazole quinoline base propane dihydrochloride aqueous solution in reactor,
After continuing to react 8 hours, stop No. 2 groove gases and add, lower the temperature, unreacted ethene, CTFE monomer are reclaimed, by anti-
Answer kettle dispensing valve that white emulsion material is put into cohesion bucket, with the multiple washing material of deionized water of heat after cohesion, dehydration,
Obtain white powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1960gECTFE resins are obtained.
Through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation ECTFE resins
Content is 48.64%；Molar content shared by ethylene unit unit is 51.36%.
ECTFE polymer datas：The melt index for determining ECTFE resins by fusion index instrument is 28.5g/10mim (275
℃,2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 398.08 DEG C；DSC data display copolymer fusing point exists
223.3℃。
Embodiment 16：The azo tert-butyl group-butyl narrows hydrochloride
Initiator
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
, for -0.1MPa, with Metering pump to hexafluoropropene 300g is added in reactor, stirring is simultaneously for the continuous reacting kettle inner pressure that is evacuated to
35 DEG C are warming up to, by compressor by gas in No. 1 gas mixer（Ethene:CTFE=25:75）It is passed through reactor
In, it is 1.68MPa to pressure, after system temperature is constant, with measuring pump to the addition tertiary fourth of 200ml azos containing 6.8g in reactor
Base-butyl is narrowed the initiation reaction of hydrochloric acid saline solution and is carried out, with compressor to No. 2 gaseous mixtures of addition in reactor（Ethene:Trifluoro chlorine
Ethene=50:50）Interior mixed gas, maintenance reaction pressure is 1.68MPa.Being continually fed into No. 2 gaseous mixtures makes reaction constantly carry out,
At interval of reaction 2 hours, hydrochloric acid salt solution is narrowed to 100ml azos containing the 3.0g tert-butyl group-butyl is added in reactor by measuring pump
Solution, after continuing to react 8 hours, stops No. 2 groove gases and adds, and lowers the temperature, reclaims unreacted ethene, CTFE, hexafluoro
Propylene monomer, is put into cohesion bucket by discharging valve of reaction kettle goalkeeper's white emulsion material, with the deionization of heat after cohesion, dehydration
The multiple washing material of water, obtains white powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C, 1964g is obtained
Fluororesin.
Contain through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation fluororesin
Measure is 50.43%；Molar content shared by hexafluoropropene construction unit is 1.77%；Mole percent shared by ethylene unit unit contains
Measure is 47.8%.
Polymer data：By fusion index instrument determine fluororesin melt index for 16.5g/10mim (275 DEG C,
2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 402.5 DEG C；DSC data shows copolymer fusing point 219.2
℃。
Embodiment 17：The azo tert-butyl group-diethyl narrows hydrochlorideInitiator, three
First copolymerization
10L stainless steel autoclaves equipped with mechanical agitation, temperature regulating device, circulating-heating, recirculated cooling water are washed
Only, to adding 6L high purity deionized waters, vacuum nitrogen gas to replace in reactor three times, oxygen content is determined in below 10ppm, after
, for -0.1MPa, with Metering pump to hexafluoropropene 300g is added in reactor, stirring is simultaneously for the continuous reacting kettle inner pressure that is evacuated to
35 DEG C are warming up to, by compressor by gas in No. 1 gas mixer（Ethene:CTFE=30:70）It is passed through reactor
In, it is 1.68MPa to pressure, after system temperature is constant, with measuring pump to the addition tertiary fourth of 200ml azos containing 7.0g in reactor
Base-diethyl is narrowed the initiation reaction of hydrochloric acid saline solution and is carried out, with compressor to No. 2 gaseous mixtures of addition in reactor（Ethene:Trifluoro
Vinyl chloride=49.5:50.5）Interior mixed gas, maintenance reaction pressure is 1.68MPa.Being continually fed into No. 2 gaseous mixtures makes reaction continuous
Carry out, at interval of reaction 2 hours, salt is narrowed to 150ml azos containing the 3.5g tert-butyl group-diethyl is added in reactor by measuring pump
Acid salt aqueous solution, after continuing to react 8 hours, stops No. 2 groove gases and adds, and lowers the temperature, reclaims unreacted ethene, trifluoro chloroethene
Alkene, hexafluoropropene monomer, are put into cohesion bucket by discharging valve of reaction kettle goalkeeper's white emulsion material, with heat after cohesion, dehydration
The multiple washing material of deionized water, obtain white powder.Further white powder is vacuum dried 8 hours in 100-120 DEG C,
Obtain 2004g fluororesin.
Contain through Mole percent shared by CTFE construction unit in elementary analysis, F19NMR, IR analysis confirmation fluororesin
Measure is 50.93%；Molar content shared by hexafluoropropene construction unit is 1.67%；Mole percent shared by ethylene unit unit contains
Measure is 47.4%.
Polymer data：By fusion index instrument determine fluororesin melt index for 14.5g/10mim (275 DEG C,
2.16kg)；TGA tests 1% weight decomposition temperature of resin（Td）It is 412.5 DEG C；DSC data shows copolymer fusing point 217.6
℃。
Claims (13)
1. a kind of ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure, it is characterised in that the ethene-trifluoro chloroethene
The end-group structure of alkene copolymer is
The R is selected from-NHxR1、In one kind, wherein：
X=1；
R1Selected from the C1-C12 that H, C1-C12 straight chained alkyl, branched alkyl or cycloalkyl, phenyl, at least one carbon atom are replaced by O
Straight chained alkyl, branched alkyl or cycloalkyl；
The 1% weight decomposition temperature Td of the ethylene-chlorotrifluoro-ethylene copolymer TGA is 380~450 DEG C.
2. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 1, it is characterised in that institute
State one kind that the end-group structure of ethylene-chlorotrifluoro-ethylene copolymer is selected from following structural formula：
3. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 1, it is characterised in that institute
Stating ethylene-chlorotrifluoro-ethylene copolymer can further containing selected from one kind, more than two or three group in following monomer
Close：CF2=CF-CF3, CHF=CH-CF3、CH2=CF-CF3Or CH2=CH-CF3。
4. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 1, it is characterised in that institute
State ethylene-chlorotrifluoro-ethylene copolymer by ethene and CTFE the end group after the initiation of water-soluble azo class hydrochloric acid salt initiators
Prepared by the emulsion copolymerization reaction under self-emulsified, the water-soluble azo class hydrochloric acid salt initiators are selected from following structural formula
It is a kind of：
The R group is with claim 1.
5. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 4, it is characterised in that institute
State the one kind during R is selected from following structural formula：
6. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 4, it is characterised in that institute
The consumption for stating water-soluble azo class hydrochloride is the 0.01~5% of reaction monomers ethene and CTFE mole total amount.
7. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 4, it is characterised in that poly-
It is 10~70 DEG C to close temperature, and polymerization pressure is 0.2~5MPa.
8. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 7, it is characterised in that poly-
It is 30~55 DEG C to close temperature, and polymerization pressure is 0.5~3MPa.
9. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 4, it is characterised in that institute
State ethylene-chlorotrifluoro-ethylene copolymer carries out self-emulsifying type emulsion copolymerization reaction by ethene and CTFE in water phase
It is obtained, comprises the following steps：
(1) toward pure water is added in reactor, start stirring at low speed, reactor is vacuumized, oxygen content in kettle is less than 30ppm；
(2) toward addition part CTFE monomer and vinyl monomer in reactor, pressure in kettle is made to reach 0.2~5MPa；
(3) heating makes reactor temperature rise to 10~70 DEG C, improves reactor speed of agitator, and water-soluble azo is added toward reactor
Class hydrochloric acid salt initiator initiation reaction is carried out；
(4) toward remaining CTFE monomer and vinyl monomer is continuously added into reactor, reacting kettle inner pressure is kept to set
Determine ± 0.01MPa the scopes of polymerization pressure；
(5) reaction obtains final product ethylene-chlorotrifluoro-ethylene copolymer after terminating.
10. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 9, it is characterised in that
Oxygen content is less than 10ppm in the reactor；Vinyl monomer and CTFE monomer can first be well mixed and add afterwards reaction
Kettle, it is also possible to add reactor independently of one another；The water-soluble azo class hydrochloric acid salt initiator can be added disposably,
Can be dividedly in some parts.
11. according to the described ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure of one of claim 1 to 10, its
The ethylene-chlorotrifluoro-ethylene copolymer is characterised by for anti-corrosion or prevents microorganism adhesion equipment from protecting.
12. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 11, it is characterised in that
The ethylene-chlorotrifluoro-ethylene copolymer is used as chemical anticorrosion coating or liner, semiconductor air pipeline system corrosion-inhibiting coating, food
Product, high purity water, medical equipment, electric wire and it is electric prevent microorganism adhesion equipment protect.
13. according to the ethylene-chlorotrifluoro-ethylene copolymer with stable end groups structure described in claim 1, it is characterised in that
The melt index of the ethylene-chlorotrifluoro-ethylene copolymer is 0.1~50g/10min, fusing point under the conditions of 275 DEG C, 2.16kg
At 200~240 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410116255.4A CN104945549B (en) | 2014-03-26 | 2014-03-26 | Ethene chlorotrifluoroethylene, its preparation method and application with stable end groups structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410116255.4A CN104945549B (en) | 2014-03-26 | 2014-03-26 | Ethene chlorotrifluoroethylene, its preparation method and application with stable end groups structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104945549A CN104945549A (en) | 2015-09-30 |
| CN104945549B true CN104945549B (en) | 2017-06-06 |
Family
ID=54160657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410116255.4A Active CN104945549B (en) | 2014-03-26 | 2014-03-26 | Ethene chlorotrifluoroethylene, its preparation method and application with stable end groups structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104945549B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10435580B2 (en) | 2015-11-20 | 2019-10-08 | Honeywell International Inc. | Gloss retentive fluorocopolymers for coating applications |
| CN105829367A (en) | 2013-10-22 | 2016-08-03 | 霍尼韦尔国际公司 | Curable fluorocopolymer formed from tetrafluoropropene |
| WO2017087806A2 (en) * | 2015-11-20 | 2017-05-26 | Honeywell International Inc. | Gloss retentive fluorocopolymers for coating applications |
| US11015005B2 (en) | 2015-11-20 | 2021-05-25 | Honeywell International Inc. | Fluorocopolymers for coating applications |
| CN110240836B (en) * | 2018-03-09 | 2022-02-01 | 浙江省化工研究院有限公司 | Fluorocarbon anticorrosive paint |
| CN110078855B (en) * | 2019-04-22 | 2020-07-14 | 中昊晨光化工研究院有限公司 | Fluorine-containing polymer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3624250A (en) * | 1970-01-20 | 1971-11-30 | Du Pont | Copolymers of ethylene/tetrafluoroethylene and of ethylene/chlorotrifluoroethylene |
| US4053445A (en) * | 1976-11-01 | 1977-10-11 | Allied Chemical Corporation | Solutions of ethylene-chlorotrifluoroethylene copolymers |
| US5434229A (en) * | 1993-02-23 | 1995-07-18 | Ausimont S.P.A. | Radical (co)polymerization process of fluorinated olefinic monomers |
| CN1587287A (en) * | 2004-08-09 | 2005-03-02 | 大连振邦氟涂料股份有限公司 | Process for preparing ethylene-trifluoro vinyl chloride copolymer |
| CN102558419A (en) * | 2011-12-26 | 2012-07-11 | 山东华夏神舟新材料有限公司 | Melt-processable modified polyvinyl fluoride resin and preparation method thereof |
-
2014
- 2014-03-26 CN CN201410116255.4A patent/CN104945549B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3624250A (en) * | 1970-01-20 | 1971-11-30 | Du Pont | Copolymers of ethylene/tetrafluoroethylene and of ethylene/chlorotrifluoroethylene |
| US4053445A (en) * | 1976-11-01 | 1977-10-11 | Allied Chemical Corporation | Solutions of ethylene-chlorotrifluoroethylene copolymers |
| US5434229A (en) * | 1993-02-23 | 1995-07-18 | Ausimont S.P.A. | Radical (co)polymerization process of fluorinated olefinic monomers |
| CN1587287A (en) * | 2004-08-09 | 2005-03-02 | 大连振邦氟涂料股份有限公司 | Process for preparing ethylene-trifluoro vinyl chloride copolymer |
| CN102558419A (en) * | 2011-12-26 | 2012-07-11 | 山东华夏神舟新材料有限公司 | Melt-processable modified polyvinyl fluoride resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 乙烯-三氟氯乙烯共聚物(ECTFE)的研究进展;王文贵等;《有机氟工业》;20070615(第2期);28-32 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104945549A (en) | 2015-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104945549B (en) | Ethene chlorotrifluoroethylene, its preparation method and application with stable end groups structure | |
| CN104892811B (en) | A kind of ethene chlorotrifluoroethylene, its preparation method and application | |
| EP1904538B1 (en) | Aqueous emulsion polymerization of fluorinated monomers using a perfluoropolyether surfactant | |
| US7294668B2 (en) | Aqueous dispersions of polytetrafluoroethylene having a low amount of fluorinated surfactant | |
| EP1904539B1 (en) | Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant | |
| EP1556426B1 (en) | Emulsifier free aqueous emulsion polymerization to produce copolymers of a fluorinated olefin and hydrocarbon olefin | |
| CN104797609B (en) | The synthesis of trans-1,3,3,3-tetrafluoropropene/vinylidene fluoride copolymer and purposes | |
| US20170037166A1 (en) | Fluorinated surfactants for making fluoropolymers | |
| EP2651989A1 (en) | Microemulsions and fluoropolymers made using microemulsions | |
| JP2009517502A (en) | Fluorinated surfactants used to produce fluoropolymers | |
| CN109721675B (en) | Ethylene-tetrafluoroethylene copolymer and preparation method thereof | |
| CN101506250B (en) | Process for producing fluoropolymers | |
| EP0648787B1 (en) | Process for preparing tetrafluoroethylene copolymers with other perfluorinated monomers | |
| WO2008026707A1 (en) | Perfluorocarboxylic acid salt and method for producing the same | |
| US20180312678A1 (en) | Composition including amorphous fluoropolymer and fluoroplastic particles and methods of making the same | |
| CA2589339A1 (en) | Fluoropolymer for making a fluoroelastomer | |
| CN102174139B (en) | Method for preparing polytetrafluoroethylene resin for coating | |
| JP2001270969A (en) | Thermoplastic fluoropolymer | |
| CN103193904B (en) | A kind of dispersion method prepares the method for fluoropolymer | |
| CN106854253A (en) | A kind of new low temperature resistant fluorubber and preparation method thereof | |
| CN101302263B (en) | Ethylene-tetrafluoroethylene copolymer | |
| CN107540777A (en) | A kind of modified daiflon, its preparation method and application | |
| CN106832256A (en) | A kind of preparation method of fluorine-containing nonionic surfactant | |
| CN104945551A (en) | Application of environment-friendly surfactant in synthesis of fluorine-containing polymer | |
| WO2008024601A1 (en) | Solvent slurry process for producing high solids fluoropolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Ethylene chlorotrifluoroethylene copolymer with stable end group structure, its preparation method and Application Effective date of registration: 20220628 Granted publication date: 20170606 Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch Pledgor: SINOCHEM LANTIAN Co.,Ltd. Registration number: Y2022330001143 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230308 Granted publication date: 20170606 Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch Pledgor: SINOCHEM LANTIAN Co.,Ltd. Registration number: Y2022330001143 |