CN109762091A - Tetrafluoroethene base co-polymer and preparation method thereof - Google Patents
Tetrafluoroethene base co-polymer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to fluoro-containing macromolecule material fields, and in particular to a kind of tetrafluoroethene base co-polymer and preparation method thereof.The tetrafluoroethene base co-polymer is the tetrafluoroethene comprising 90~98wt%, and the perfluoropropylvinylether of 1~7wt% and 1~3wt%'s has CF2=CFCF2[OCF2CF(CF3)]nORfThe hexafluoropropylene-based alkoxy ether of structure or its terpolymer containing hydroperoxide derivative, wherein n is 0~5 integer, RfIt is the derivative of the perfluoroalkyl or hydrogen atoms with 1~5 carbon atom；The tetrafluoroethene base co-polymer has good melt fluidity and thermal stability, and flexibility is strong, and transparency is high, and surface smoothness is high；The preparation method avoids the destruction to atmospheric ozone layer, energy conservation and environmental protection using green and environment-friendly solvent.
Description
Technical field
The invention belongs to fluoro-containing macromolecule material fields, and in particular to a kind of tetrafluoroethene base co-polymer and its preparation side
Method.
Background technique
Meltability polytetrafluorethyletubular was announced in United States Patent (USP) US3635926 for the first time by 1972, trade name
Teflon PFA.It is the copolymer of tetrafluoroethene and a small amount of perfluoro propyl vinyl ether, and backbone structure assigns itself and poly- four
The very similar performance of vinyl fluoride has excellent chemical stability, physical mechanical property, electrical insulation capability, lubricity, does not glue
Property, resistance to ag(e)ing, noninflammability and thermal stability.Because containing perfluoro alkoxy side group in main chain, the flexibility of chain is increased, is improved
The melt viscosity of polymer enables it that general processing technology to be used to carry out hot-working.
Meltability polytetrafluorethyletubular has many applications in engineering field, and early stage, Melt-Processable Polytetrafluoroethylene was in chemical industry
Aspect is applied to the reaction vessels and reaction kettle, rectifying column, storage tank, pipeline, pipe fitting and hose etc. such as beaker for experiment, flask.
With the development of industry, nowadays application range is wider, can be used as the element in semiconductor process, and electronic component is release
Film, equipment protection film, heating wires, insulating layer of special electric wire etc..
Polymerization of the existing technical literature than describing Meltability polytetrafluorethyletubular in more detail, but mainly tetrafluoro second
Two membered copolymers of alkene and perfluoroalkyl vinyl ether, few patent literature reports are in polymerization reaction with Third monomer to can
Fusibleness polytetrafluoroethylene (PTFE) is modified, Lai Tigao Meltability polytetrafluorethyletubular a certain kind or a variety of specific performances.
Daikin company discloses a kind of comprising tetrafluoro second in patent JP2003246823A and JP2007197561A
Alkene, the terpolymer of P PVE and perfluoroethylvinyl ether (PEVE), the terpolymer are shown under room temperature and higher temperature
Excellent transparency and intensity are shown, but the side chain of comonomer is relatively short, it is flexible poor, it is prepared relative to common two-spot monomer
Melt-Processable Polytetrafluoroethylene product flexibility improve it is not significant.
Big King Company discloses a kind of tetrafluoroethene and perfluoroalkyl vinyl ether two-spot in United States Patent (USP) US4499249
The preparation method of copolymer.This method uses suspension polymerisation, withFor initiator, perfluoroalkyl vinyl
Ether has the following structure formula:
Wherein, X is F atom or H atom, and a is 0~4 integer, and b is 0~7 integer, typical example such as PMVE,
PEVE and PPVE.The tetrafluoroethene and perfluoroalkyl vinyl ether copolymer prepared by this method has lower unstable fixed end
Base content and excellent folding service life.But it is higher to polymerize initiator efficiency of initiation used, polymerize and needs to accurately control initiator
Additional amount, melt index are more sensitive to the additional amount variation of initiator.
3M company discloses a kind of CF in United States Patent (USP) US20040024155A12=CFO (CF2)nORfStructures alone,
Wherein n is 2~6 integer, and f is the perfluoro alkyl group with 1~6 carbon atom.Using tetrafluoroethene and less in the patent
Measure CF2=CFO (CF2)nORfThe derived units of structures alone are copolymerized, then are suitably added conventional olefin monomer, such as hexafluoropropene, by
It is long flexible linear chain in the side chain of comonomer, significantly improves the bending fatigue strength of product, flexibility, light transmittance,
Chemically and thermally stress cracking performance.Shortcoming is that product fusing point is low, and 160 DEG C of fusing point lower bound, thermal stability is relatively poor.
E.I.Du Pont Company discloses a kind of PTFE and tetrafluoroethene and perfluor alkane in United States Patent (USP) US2013/0161873A1
The method that base vinyl ether co-polymer is blended, wherein perfluoroalkyl vinyl ether has with above formula (1) identical structural formula.It is logical
The blend for crossing this method preparation has excellent chemically-resistant permeability and good durability, can be used for being injection moulded complex shape
The component of shape, melt index are greater than 12g/10min, and the folding service life is greater than 20000 circulations, and nitrogen infiltration coefficient is less than 0.8
×10-10cm3(STP).cm/cm2.sec.cmHg.The disadvantage is that the ratio of accurate control PTFE and PFA is needed when mixing, if PTFE
It cannot be uniformly mixed in composition, then the durability of composition can reduce.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of tetrafluoroethene base co-polymers, have good
Melt fluidity and thermal stability, flexibility is strong, and transparency is high, and surface smoothness is high；The present invention also provides its preparations simultaneously
Method, scientific and reasonable, energy conservation and environmental protection.
Tetrafluoroethene base co-polymer of the present invention is the tetrafluoroethene comprising 90~98wt%, the perfluor of 1~7wt%
The hexafluoropropylene-based alkoxy ether or its terpolymer containing hydroperoxide derivative of n-propyl vinyl ether (PPVE) and 1~3wt%；
The hexafluoropropylene-based alkoxy ether or its containing hydroperoxide derivative have CF2=CFCF2[OCF2CF(CF3)]nORfKnot
Structure, wherein n is 0~5 integer, RfIt is the derivative of the perfluoroalkyl or hydrogen atoms with 1~5 carbon atom.
Preferably, described that there is CF2=CFCF2[OCF2CF(CF3)]nORfThe hexafluoropropylene-based alkoxy ether of structure or
Hydrogen atoms derivative is CF2=CFCF2OCF2CF(CF3)OCF3、CF2=CFCF2OCF2CF(CF3)OC2F5、CF2=
CFCF2OCF2CF(CF3)OC3F7、CF2=CFCF2OC3F7、CF2=CFCF2OCF2CH2CF3Or CF2=CFCF2OCF2CF(CF3)
OCF2CH2CF3。
The preparation method of tetrafluoroethene base co-polymer of the present invention, comprising the following steps:
(1) solvent and emulsifier are added in anaerobic polymerization kettle, auxiliary agent, perfluoro n-propyl vinyl base is added after vacuumizing
Ether, hexafluoropropylene-based alkoxy ether or its contain hydroperoxide derivative and chain-transferring agent, at 50~100 DEG C, under 1.5~4.5MPa be added draw
It sends out agent and carries out polymerization reaction；
(2) tetrafluoroethene is continuously added in reaction process into polymeric kettle, maintains temperature and pressure in polymeric kettle constant；
(3) in step (2) after tetrafluoroethene addition, polymeric kettle cooling emptying by gained emulsion coagulation, washing, is done
Dry, granulation is to get tetrafluoroethene base co-polymer.
Wherein:
Solvent described in step (1) is deionized water, and dosage and the mass ratio of tetrafluoroethene used in step (2) are
3.67~4.33:1.
Emulsifier described in step (1) is perfluoropolyether carboxylic acid or its salt, structural formula CF3CF2OCF2(OCF2)n-
X, X is carboxylic acid group or its salt in formula, and n is 0~3 integer, preferably CF3CF2OCF2OCF2COONH4Or
CF3CF2OCF2OCF2COONa, dosage are the 1.07~1.6% of tetrafluoroethene gross mass used in step (2).
Auxiliary agent described in step (1) is perfluoro alkane or perfluorinated cycloalkanes, is selected from perfluorooctane, PF 5070 or perfluor
One of hexamethylene, two or more, two or more when arbitrary proportion mix, dosage be solvent quality 1~10%.
Perfluoro alkane or perfluorinated cycloalkanes are colorless and transparent, odorless nontoxic, non-ignitable, the green solvents of no pollution to the environment.Polymerization system
Middle addition perfluoro alkane or perfluorinated cycloalkanes, can be improved PPVE and CF2=CFCF2[OCF2CF(CF3)]nORfIn a solvent
Solubility accelerates polymerization rate.
Hexafluoropropylene-based alkoxy ether described in step (1) or its dosage containing hydroperoxide derivative are used four in step (2)
The 1.33~4% of vinyl fluoride gross mass；The perfluoropropylvinylether dosage is that tetrafluoroethene used is total in step (2)
The 3.33~10% of quality.
Chain-transferring agent described in step (1) be methanol, ethyl alcohol, isopropanol, acetone, ethyl acetate, methane, n-hexane,
Thiacyclohexane, chloroform, methylene chloride or hydrogen, optimization methane, pressure increase 0.4 in the chain-transferring agent to polymeric kettle of addition~
0.8MPa。
The initiator is peroxide initiator, is selected from perfluoroacyl peroxides, potassium peroxydisulfate or ammonium persulfate
One of, two or more, two or more when arbitrary proportion mix, the preferred mixture of potassium peroxydisulfate and ammonium persulfate,
Additive amount can be depending on required melt index.
Washing times described in step (3) are 4~6 times, and wash time is 2~4 hours, and drying temperature is 120~200
DEG C, drying time is 4~6 hours.
Preferably, reaction temperature is 50~90 DEG C in step (1), and pressure is 2.0~4.5MPa.
It is highly preferred that reaction temperature is 80~90 DEG C in step (1), pressure is 2.7~3.0MPa.
Preferably, the preparation method of tetrafluoroethene base co-polymer of the present invention, comprising the following steps:
(1) solvent and emulsifier are added in anaerobic polymerization kettle, auxiliary agent, perfluoropropylvinylether is added after vacuumizing
With hexafluoropropylene-based alkoxy ether or its contain hydroperoxide derivative, then be added chain-transferring agent to polymeric kettle in pressure increase 0.4~
0.8MPa is added initiator at 50~90 DEG C, under 2.0~4.5MPa and carries out polymerization reaction；
(2) tetrafluoroethene is continuously added in reaction process into polymeric kettle, maintains temperature and pressure in polymeric kettle constant；
(3) in step (2) after tetrafluoroethene addition, polymeric kettle cooling emptying, by gained emulsion coagulation, using go from
Sub- water washing 4~6 times, wash 2~4 hours, then dry 4~6 hours at 120~200 DEG C, through pelletizer granulation to get
Tetrafluoroethene base co-polymer.
It is highly preferred that the preparation method of tetrafluoroethene base co-polymer of the present invention, comprising the following steps:
(1) solvent of metering and emulsifier are added in anaerobic polymerization kettle, auxiliary agent, perfluor n-propyl second is added after vacuumizing
Alkene ether and hexafluoropropylene-based alkoxy ether or its contain hydroperoxide derivative, then be added chain-transferring agent to polymeric kettle in pressure increase
0.4~0.8M Pa is gathered under 2.7~3.0MPa according to the initiator that metering is added in required melt index at 80~90 DEG C
Close reaction；
(2) tetrafluoroethene is continuously added in reaction process into polymeric kettle, maintains temperature and pressure in polymeric kettle constant；
(3) in step (2) after tetrafluoroethene addition, polymeric kettle cooling emptying, by gained emulsion coagulation, using go from
Sub- water washing 4~6 times, wash 2~4 hours, then dry 4~6 hours at 120~200 DEG C, through pelletizer granulation to get
Tetrafluoroethene base co-polymer.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) polytetrafluoroethylene (PTFE) base co-polymer prepared by the present invention, by hexafluoropropylene-based alkoxy ether being added or its is hydrogeneous
Derivative can be modified polytetrafluoroethylene (PTFE) because it contains longer side chain, enhance the flexility of product, transparency
It improves, the folding service life is greater than 200000 circulations, and light transmittance is greater than 92%；
(2) polytetrafluoroethylene (PTFE) base co-polymer prepared by the present invention has good melt fluidity and thermal stability, melts
Melting index is 2~32g/10min, and fusing point is 300~310 DEG C；
(3) the auxiliary agent perfluoro alkane or perfluorinated cycloalkanes that preparation method of the present invention uses is green and environment-friendly solvents, with tradition
FC-113 solvent used in PFA polymerization system is compared, and is avoided because using traditional FC-113 solvent to atmospheric ozone layer
It destroys, energy conservation and environmental protection.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the present invention is not limited thereto.
Used in embodiment it is raw materials used unless otherwise specified, be commercially available.
Embodiment 1
(1) into the 100L stainless steel polymeric kettle of anaerobic, the deionized water of 60L, the perfluoropolyether carboxylic acid ammonium C of 500g is added
F3CF2OCF2OCF2COONH4The perfluorooctane of 3kg, PF 5070 and complete is added after being evacuated in polymeric kettle in (40wt%)
The mixture of fluorine hexamethylene, the hexafluoropropylene-based alkoxy ether CF of the PPVE and 600g of 1000g2=CFCF2OCF2C F(CF3)
OC3F7, being then charged with methane makes pressure increase 0.5MPa in polymeric kettle, by polymerization kettle temperature raising to 90 DEG C, when pressure reaches 2.7MPa
Quickly prepared 45g potassium peroxydisulfate and ammonium persulfate mixed liquor are squeezed into polymeric kettle through auxiliary agent pump, what polymerization reaction started
Mark is that pressure is begun to decline in polymeric kettle；
(2) tetrafluoroethylene monomer is added continuously in the course of the polymerization process to maintain temperature and pressure in polymeric kettle constant；
(3) stop addition when consuming 15kg to tetrafluoroethylene monomer, unreacted monomer is vented, it will after being replaced with nitrogen
Lotion is condensed, and water washing 4 times of 40 DEG C of 300L is then used, after washing 3 hours, by polymer powders at 150 DEG C
5h is dried in baking oven, obtains polytetrafluoroethylene (PTFE) base co-polymer powder, is granulated through pelletizer to get tetrafluoroethene base co-polymer.
Embodiment 2
(1) into the 100L stainless steel polymeric kettle of anaerobic, the deionized water of 60L, the perfluoropolyether carboxylic acid ammonium C of 500g is added
F3CF2OCF2OCF2COONH4The perfluorooctane of 5kg, PF 5070 and complete is added after being evacuated in polymeric kettle in (40wt%)
The mixture of fluorine hexamethylene, the hexafluoropropylene-based alkoxy ether CF of the PPVE and 300g of 800g2=CFCF2OCF2CF(CF3)
OC3F7, being then charged with methane makes pressure increase 0.6MPa in polymeric kettle, by polymerization kettle temperature raising to 85 DEG C, when pressure reaches 2.7MPa
Quickly prepared 100g potassium peroxydisulfate and ammonium persulfate mixed liquor are squeezed into polymeric kettle through auxiliary agent pump, what polymerization reaction started
Mark is that pressure is begun to decline in polymeric kettle；
(2) tetrafluoroethylene monomer is added continuously in the course of the polymerization process to maintain temperature and pressure in polymeric kettle constant；
(3) stop addition when consuming 15kg to tetrafluoroethylene monomer, unreacted monomer is vented, it will after being replaced with nitrogen
Lotion is condensed, and water washing 5 times of 40 DEG C of 300L is then used, after washing 3 hours, by polymer powders at 160 DEG C
6h is dried in baking oven, obtains polytetrafluoroethylene (PTFE) base co-polymer powder, is granulated through pelletizer to get tetrafluoroethene base co-polymer.
Embodiment 3
(1) into the 100L stainless steel polymeric kettle of anaerobic, the deionized water of 60L, the perfluoropolyether carboxylic acid ammonium C of 500g is added
F3CF2OCF2OCF2COONH4The perfluorooctane of 5kg, PF 5070 and complete is added after being evacuated in polymeric kettle in (40wt%)
The mixture of fluorine hexamethylene, the hexafluoropropylene-based alkoxy ether CF of the PPVE and 200g of 600g2=CFCF2OCF2CF(CF3)
OC3F7, being then charged with methane makes pressure increase 0.6MPa in polymeric kettle, by polymerization kettle temperature raising to 85 DEG C, when pressure reaches 2.7MPa
Quickly prepared 200g potassium peroxydisulfate and ammonium persulfate mixed liquor are squeezed into polymeric kettle through auxiliary agent pump, what polymerization reaction started
Mark is that pressure is begun to decline in polymeric kettle；
(2) tetrafluoroethylene monomer is added continuously in the course of the polymerization process to maintain temperature and pressure in polymeric kettle constant；
(3) stop addition when consuming 15kg to tetrafluoroethylene monomer, unreacted monomer is vented, it will after being replaced with nitrogen
Lotion is condensed, and water washing 6 times of 40 DEG C of 300L is then used, after washing 4 hours, by polymer powders at 160 DEG C
6h is dried in baking oven, obtains polytetrafluoroethylene (PTFE) base co-polymer powder, is granulated through pelletizer to get tetrafluoroethene base co-polymer.
Embodiment 4
(1) into the 100L stainless steel polymeric kettle of anaerobic, the deionized water of 60L, the perfluoropolyether carboxylic acid ammonium C of 500g is added
F3CF2OCF2OCF2COONH4The perfluorooctane of 5kg, PF 5070 and complete is added after being evacuated in polymeric kettle in (40wt%)
The mixture of fluorine hexamethylene, the hexafluoropropylene-based alkoxy ether CF of the PPVE and 300g of 800g2=CFCF2OCF2CF(CF3)
OCF2CH2CF3, being then charged with methane makes pressure increase 0.6MPa in polymeric kettle, and by polymerization kettle temperature raising to 85 DEG C, pressure reaches
Quickly prepared 100g potassium peroxydisulfate and ammonium persulfate mixed liquor are squeezed into polymeric kettle through auxiliary agent pump when 2.7MPa, polymerization is anti-
The mark that should start is that pressure is begun to decline in polymeric kettle；
(2) tetrafluoroethylene monomer is added continuously in the course of the polymerization process to maintain temperature and pressure in polymeric kettle constant；
(3) stop addition when consuming 15kg to tetrafluoroethylene monomer, unreacted monomer is vented, it will after being replaced with nitrogen
Lotion is condensed, and water washing 6 times of 40 DEG C of 300L is then used, after washing 4 hours, by polymer powders at 160 DEG C
6h is dried in baking oven, obtains tetrafluoroethene base co-polymer powder, is granulated through pelletizer to get tetrafluoroethene base co-polymer.
Comparative example
(1) into the 100L stainless steel polymeric kettle of anaerobic, the deionized water of 60L, the perfluoropolyether carboxylic acid ammonium C of 500g is added
F3CF2OCF2OCF2COONH4The perfluorooctane of 5kg, PF 5070 and complete is added after being evacuated in polymeric kettle in (40wt%)
The mixture of fluorine hexamethylene, the PPVE of 800g, being then charged with methane makes pressure increase 0.6MPa in polymeric kettle, by polymerization kettle temperature raising
To 90 DEG C, quickly prepared 100g potassium peroxydisulfate and ammonium persulfate mixed liquor are squeezed into through auxiliary agent pump when pressure reaches 2.7MPa
In polymeric kettle, the mark that polymerization reaction starts is that pressure is begun to decline in polymeric kettle；
(2) tetrafluoroethylene monomer is added continuously in the course of the polymerization process to maintain temperature and pressure in polymeric kettle constant；
(3) stop addition when consuming 15kg to tetrafluoroethylene monomer, unreacted monomer is vented, it will after being replaced with nitrogen
Lotion is condensed, and water washing 5 times of 40 DEG C of 300L is then used, after washing 3 hours, by polymer powders at 150 DEG C
5h is dried in baking oven, obtains polytetrafluoroethylene (PTFE) base co-polymer powder, is granulated through pelletizer to get tetrafluoroethene base co-polymer.
Performance test
By tetrafluoroethene base co-polymer prepared by Examples 1 to 3 and comparative example carry out unstable end-group processing, then into
Product press mold is carried out the test of light transmittance and folding service life, test result such as 1 institute of table by the test of row melt index and fusing point
Show.
Table 1
Claims (10)
1. a kind of tetrafluoroethene base co-polymer, it is characterised in that: the tetrafluoroethene base co-polymer is comprising 90~98wt%
Tetrafluoroethene, the perfluoropropylvinylether of 1~7wt% and the hexafluoropropylene-based alkoxy ether of 1~3wt% or its is hydrogeneous
The terpolymer of derivative；
The hexafluoropropylene-based alkoxy ether or its containing hydroperoxide derivative have CF2=CFCF2[OCF2CF(CF3)]nORfStructure,
Wherein, n is 0~5 integer, RfIt is the derivative of the perfluoroalkyl or hydrogen atoms with 1~5 carbon atom.
2. tetrafluoroethene base co-polymer according to claim 1, it is characterised in that: described has CF2=CFCF2
[OCF2CF(CF3)]nORfThe hexafluoropropylene-based alkoxy ether or hydrogen atoms derivative of structure are CF2=CFCF2OCF2CF(CF3)
OCF3、CF2=CFCF2OCF2CF(CF3)OC2F5、CF2=CFCF2OCF2CF(CF3)OC3F7、CF2=CFCF2OC3F7、CF2=
CFCF2OCF2CH2CF3Or CF2=CFCF2OCF2CF(CF3)OCF2CH2CF3。
3. a kind of preparation method of tetrafluoroethene base co-polymer described in claim 1, it is characterised in that: the following steps are included:
(1) solvent and emulsifier are added in anaerobic polymerization kettle, auxiliary agent, perfluoropropylvinylether, complete is added after vacuumizing
Fluoropropene base alkoxy ether or its contain hydroperoxide derivative and chain-transferring agent, initiator is added under 50~100 DEG C, 1.5~4.5MPa
Carry out polymerization reaction；
(2) tetrafluoroethene is continuously added in reaction process into polymeric kettle, maintains temperature and pressure in polymeric kettle constant；
(3) in step (2) after tetrafluoroethene addition, polymeric kettle cooling emptying by gained emulsion coagulation, washing, drying, is made
Grain is to get tetrafluoroethene base co-polymer.
4. the preparation method of tetrafluoroethene base co-polymer according to claim 3, it is characterised in that: described in step (1)
Solvent be deionized water, the mass ratio of tetrafluoroethene used is 3.67~4.33:1 in dosage and step (2).
5. the preparation method of tetrafluoroethene base co-polymer according to claim 3, it is characterised in that: described in step (1)
Emulsifier be perfluoropolyether carboxylic acid or its salt, structural formula CF3CF2OCF2(OCF2)n- X, in formula X be carboxylic acid group or its
Salt, n are 0~3 integers, and dosage is the 1.07~1.6% of tetrafluoroethene gross mass used in step (2).
6. the preparation method of tetrafluoroethene base co-polymer according to claim 3, it is characterised in that: described in step (1)
Auxiliary agent be perfluoro alkane or perfluorinated cycloalkanes, selected from one of perfluorooctane, PF 5070 or perfluorocyclohexane, two kinds or
A variety of, dosage is the 1~10% of solvent quality.
7. the preparation method of tetrafluoroethene base co-polymer according to claim 3, it is characterised in that: described in step (1)
Hexafluoropropylene-based alkoxy ether or its dosage containing hydroperoxide derivative be tetrafluoroethene gross mass used in step (2) 1.33~
4%；Perfluoropropylvinylether dosage is the 3.33~10% of tetrafluoroethene gross mass used in step (2).
8. the preparation method of tetrafluoroethene base co-polymer according to claim 3, it is characterised in that: described in step (1)
Chain-transferring agent be methanol, ethyl alcohol, isopropanol, acetone, ethyl acetate, methane, n-hexane, thiacyclohexane, chloroform, dichloromethane
Alkane or hydrogen, 0.4~0.8MPa of pressure increase in the chain-transferring agent to polymeric kettle of addition.
9. the preparation method of tetrafluoroethene base co-polymer according to claim 3, it is characterised in that: the initiator is
Peroxide initiator, selected from one of perfluoroacyl peroxides, potassium peroxydisulfate or ammonium persulfate, two or more.
10. the preparation method of tetrafluoroethene base co-polymer according to claim 3, it is characterised in that: described in step (3)
Washing times be 4~6 times, wash time is 2~4 hours, and drying temperature is 120~200 DEG C, and drying time is 4~6 small
When.
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| CN110790854A (en) * | 2019-10-29 | 2020-02-14 | 金华永和氟化工有限公司 | Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and preparation method thereof |
| CN114957520A (en) * | 2022-05-09 | 2022-08-30 | 江苏梅兰化工有限公司 | Preparation method of suspended PTFE resin spherical medium particle molding material |
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| US20180371121A1 (en) * | 2017-06-23 | 2018-12-27 | 3M Innovative Properties Company | Fluoropolymer dispersion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110790854A (en) * | 2019-10-29 | 2020-02-14 | 金华永和氟化工有限公司 | Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and preparation method thereof |
| CN110790854B (en) * | 2019-10-29 | 2021-06-29 | 金华永和氟化工有限公司 | Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and preparation method thereof |
| CN113402650A (en) * | 2019-10-29 | 2021-09-17 | 金华永和氟化工有限公司 | Process for preparing fusible polytetrafluoroethylene |
| CN114957520A (en) * | 2022-05-09 | 2022-08-30 | 江苏梅兰化工有限公司 | Preparation method of suspended PTFE resin spherical medium particle molding material |
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