CN107868162A - A kind of high molecular weight polytetrafluoroethyldispersions dispersion resin and preparation method thereof - Google Patents
A kind of high molecular weight polytetrafluoroethyldispersions dispersion resin and preparation method thereof Download PDFInfo
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- CN107868162A CN107868162A CN201610849293.XA CN201610849293A CN107868162A CN 107868162 A CN107868162 A CN 107868162A CN 201610849293 A CN201610849293 A CN 201610849293A CN 107868162 A CN107868162 A CN 107868162A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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Abstract
The present invention relates to chemical field, specifically discloses a kind of high molecular weight polytetrafluoroethyldispersions dispersion resin and preparation method thereof.Stabilizer, dispersant, antitack agent etc. are added in aqueous medium, pass through redox initiation system, under modifying agent effect, add tetrafluoroethylene monomer and carry out dispersin polymerization under certain temperature and pressure, obtain the polytetrafluoroethyldispersion dispersion resin that SSG is 2.14~2.15.The present invention obtains polytetrafluoroethyldispersion dispersion resin molecular weight height, narrow molecular weight distribution and is uniformly distributed, and it is used for spinning, high into silk rate, is not easy fracture of wire；There is film-strength height, appearance uniform, good permeability for preparing microporous barrier.
Description
Technical field
The present invention relates to chemical field, specifically, is related to a kind of high molecular weight polytetrafluoroethyldispersions dispersion resin and its system
Preparation Method.
Background technology
The excellent chemical resistance of polytetrafluoroethylene (PTFE), resistant of high or low temperature, resistance to ag(e)ing, low frictional properties, non-stick, physiology
Inertia, it is set to turn into indispensable special material in fields such as chemical industry, machinery, electric, building, medical treatment, it is -250~250
It is long-term use of in DEG C temperature range.Progress and polyflon application with dispersion resin forming processing technology
Widen, promote extrusion type polytetrafluoroethyldispersion dispersion resin Quality advance and to high-end development.High molecular weight polytetrafluoroethyldispersions are disperseed
Molecular resin amount is high, narrow molecular weight distribution, prepares polytetrafluoroethylene fibre cotton available for processing and is prepared through biaxial tension micro-
Pore membrane, microporous barrier have extensive purposes, available for making wind-proof warming fabric, environmentally friendly filtering material etc..
Publication No. CN1145600A Chinese patent application discloses a kind of porous polyetetrafluoroethycomposition composition, its feature
It is that a kind of homopolymer of polytetrafluoroethylene (PTFE) and a kind of copolymer of polytetrafluoroethylene (PTFE) are mixed according to a certain percentage, passes through machinery
Stirring condenses dispersion blend, and the powder of gained is dried several days in 50 DEG C of baking oven.Dry solid is lubricated, thickener
Extruding, roll heat drying, then rapid stretching is obtained uniformly and constitutionally stable under higher than homopolymer melting temperature contained
The very open micro-structural of major node and long fibril.The patent introduction be two kinds of polyflons mixture, and
Its preparation method is not described.
Publication No. CN1107383A Chinese patent application discloses a kind of method that perforated membrane is prepared with tetrafluoroethene,
It is characterized in that using being mixed between different trade mark low-molecular-weight resins and surface tension compole fine difference, by them by certain ratio
Example mixing, expansion is then carried out at -10 DEG C~1000 DEG C of temperature with physical dilatation method and formed.But the patent is only applicable to low point
Son amount resin, is not referred to high molecular weight resin.
Publication No. CN101421319A Chinese patent application discloses a kind of tetrafluoro ethylene polymer and its water-based point
The preparation method of dispersion liquid, it is characterized in, in aqueous phase, adding paraffin, perfluorooctanoic acid, the quinhydrones aqueous solution, being warming up to 70 DEG C,
Tetrafluoroethylene monomer is passed through, starts polymerisation, constant reaction pressure is in 70 ± 2 DEG C of 0.80MPa, reaction temperature, four obtained
Fluorine emulsion separation cohesion PTFE fine powder end, is dried to obtain PTFE fine powder end, product is obtained by the stretching after extrusion molding.Pass through
The dispersion resin SSG that this method obtains is 2.140~2.160.Its purposes and its product properties are not introduced for the patent.
Publication No. is that CN103665240B Chinese patent discloses a kind of preparation method of polytetrafluoroethyldispersion dispersion resin,
The patent uses persulfate or the peroxide of alkali metal as initiator, into reactor add deionized water, pH adjusting agent,
Perfluorobutyl ethylene, dispersant and stabilizer, it is 1.5~3.0MPa to control reactor pressure, and temperature is 70~105 DEG C, is obtained
SSG is 2.16~2.17 polytetrafluoroethyldispersion dispersion resins.The molecular weight levels of resin are general, it is hard to meet high intensity in the patent
The demand of massive article process equipment.
The content of the invention
In order to solve problems of the prior art, it is an object of the invention to provide a kind of high molecular weight polytetrafluoroethyldispersions
Dispersion resin, its preparation method comprise the following steps：
S1, deionized water, stabilizer, dispersant, antitack agent and oxidative initiator are added into reactor；Confined reaction
Kettle carries out nitrogen displacement, makes oxygen content≤30ppm；
S2, perfluorobutyl ethylene is added, and it is 2.0~3.0MPa to put into pressure in gas phase tetrafluoroethylene monomer to kettle, dimension
Hold pressure in kettle and polymerisation is carried out under conditions of 68~78 DEG C；In course of reaction, reproducibility is added into reaction system
Initiator；
S3, when reacting fluid solid content and reaching 30 ± 1%, after reaction terminates, polytetrafluoroethylene (PTFE) polymer fluid is collected, through solidifying
Poly-, clean, drying, obtain the polytetrafluoroethyldispersion dispersion resin that SSG is 2.14~2.15.
The present invention forms oxidationreduction by adding reproducibility initiator into reaction system, with oxidative initiator and drawn
Hair system, the decomposition activation energy of peroxide can be reduced, trigger monomer polymerization under lower temperature conditions；It can also increase
The decomposition rate of oxide, so as to increase rate of polymerization.So as to which the resin for making to obtain has higher molecular weight.
Further, the oxidative initiator includes but is not limited to the persulfate, potassium permanganate, potassium bromate of alkali metal
Or potassium chlorate；The reproducibility initiator includes but is not limited to ferrous ion, sulphite or oxalic acid.
Preferably, the oxidative initiator is potassium bromate, the reproducibility initiator is sodium sulfite.Under the combination
Oxidation-reduction trigger system can ensure the progress of polymerisation continuous and effective, and reaction rate smoothly accelerates, and is not in
Suddenly slow phenomenon is neglected soon.
Further, the addition of the oxidative initiator is the 0.0003~0.0025% of deionized water weight, excellent
Select 0.0009~0.002%；The addition of the reproducibility initiator is the 0.003~0.006% of deionized water weight, preferably
0.004~0.005%.
Preferably, the reproducibility initiator is with 1:6 ratio is successively added portionwise, and first is in gas phase tetrafluoroethene
Monomer adds after putting into, and second batch is persistently added dropwise during the course of the reaction.
Concentration when first reproducibility initiator adds is 0.04~0.06g/L, preferably 0.05g/L.
Concentration when second batch reproducibility initiator is added dropwise is 0.4~0.6g/L, preferably 0.5g/L.
Further, the use of hydrochloric acid regulation system pH is 5~6 before closed reactor in S1.In S2, reaction pressure be
2.2~2.7Mpa, reaction temperature are 70~75 DEG C.
Further,
The dosage of deionized water is the 50-70%, preferably 60-70% of reactor volume；
The dosage of stabilizer is 1.0~8.0%, preferably the 3.0~6.0% of deionized water quality；
The dosage of dispersant is 0.01~0.15%, preferably the 0.05~0.1% of deionized water quality；
The dosage of antitack agent is 0.003~0.015%, preferably the 0.006~0.009% of deionized water quality；
The addition of perfluorobutyl ethylene is 0.003~0.02%, preferably the 0.007~0.016% of deionized water quality.
Wherein, stabilizer is solid paraffin or the saturated hydrocarbons of carbon number >=12；Dispersant is perfluor/fluorochemical polyether carboxylic acid
Salt or perfluor/fluorine-containing alkyl carboxylate, preferably perfluorooctanoic acid；Antitack agent is succinic acid.
Invention also provides a kind of preparation method of high molecular weight polytetrafluoroethyldispersions dispersion resin as described above.
The beneficial effects of the present invention are：
The invention provides a kind of high molecular weight polytetrafluoroethyldispersions dispersion resin and preparation method thereof, obtains molecular weight height,
Narrow molecular weight distribution and equally distributed polytetrafluoroethyldispersion dispersion resin, it is used for spinning, high into silk rate, is not easy fracture of wire；For
Preparing microporous barrier has the characteristics that film-strength height, appearance uniform, good permeability.
Embodiment
The preferred embodiment of the present invention is described in detail below in conjunction with embodiment.It is it will be appreciated that following real
Providing merely to play the purpose of explanation for example is applied, is not used to limit the scope of the present invention.The skill of this area
Art personnel can carry out various modifications and replacement in the case of without departing substantially from spirit of the invention and spirit to the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
Embodiment 1
50L stainless steel cauldrons, clean, add deionized water 32L, potassium bromate 0.15g, succinic acid 2g, perfluorooctanoic acid 8g,
After paraffin 2kg, regulation pH is 5~6, and kettle is closed, evacuates and after nitrogen displacement, oxygen content is analyzed, as oxygen content≤30ppm
To be qualified.After oxygen analysis is qualified, perfluorobutyl ethylene (modifying agent) 5g is added by measuring pump.Reactor is warming up to 70 ± 1 DEG C,
Put into gaseous monomer tetrafluoroethene, to kettle in pressure 2.5MPa, pass through measuring pump add sodium sulfite (reproducibility initiator)
0.1g (is diluted) with 2L deionized waters, and the sodium sulfite that concentration is 0.5g/L is persistently added dropwise in another measuring pump, and 0.6g is added dropwise altogether.
Pressure 2.5MPa in kettle, 70~75 DEG C of temperature are maintained during reaction.Changed according to polymerization rate, reducing agent is added dropwise in control
Speed.When tetrafluoroethene inventory reaches 3Kg, remaining dispersant 42g is continuously added to polymerization system.When tetrafluoroethene feeds intake
When amount reaches 12.8Kg, stop that reducing agent is added dropwise.When tetrafluoroethene inventory reaches 15Kg (solid content about 30%), reaction knot
Beam, gaseous monomer is reclaimed, cooling discharge, separating paraffin, obtains polytetrafluoroethylene (PTFE) polymer fluid.Post-treated cohesion, clean, dry
It is dry, obtain polytetrafluoroethyldispersion dispersion resin.
Embodiment 2
50L stainless steel cauldrons, clean, add deionized water 32L, potassium bromate 0.15g, succinic acid 2g, perfluorooctanoic acid 8g,
After paraffin 2kg, regulation pH is 5~6, and kettle is closed, evacuates and after nitrogen displacement, oxygen content is analyzed, as oxygen content≤30ppm
To be qualified.After oxygen analysis is qualified, perfluorobutyl ethylene (modifying agent) 2.5g is added by measuring pump.Reactor is warming up to 70 ± 1
DEG C, put into gaseous monomer tetrafluoroethene, to kettle in pressure 2.5MPa, pass through measuring pump add sodium sulfite (reproducibility initiator)
0.1g (is diluted) with 2L deionized waters, and the sodium sulfite that concentration is 0.5g/L is persistently added dropwise in another measuring pump, and 0.6g is added dropwise altogether.
Pressure 2.5MPa in kettle, 70~75 DEG C of temperature are maintained during reaction.Changed according to polymerization rate, reducing agent is added dropwise in control
Speed.When tetrafluoroethene inventory reaches 3Kg, remaining dispersant 42g is continuously added to polymerization system.When tetrafluoroethene feeds intake
When amount reaches 12.8Kg, stop that reducing agent is added dropwise.When tetrafluoroethene inventory reaches 15Kg (solid content about 30%), reaction knot
Beam, gaseous monomer is reclaimed, cooling discharge, separating paraffin, obtains polytetrafluoroethylene (PTFE) polymer fluid.Post-treated cohesion, clean, dry
It is dry, obtain polytetrafluoroethyldispersion dispersion resin.
Embodiment 3
50L stainless steel cauldrons, clean, add deionized water 32L, potassium bromate 0.15g, succinic acid 2g, perfluorooctanoic acid 8g,
After paraffin 2kg, regulation pH is 5~6, and kettle is closed, evacuates and after nitrogen displacement, oxygen content is analyzed, as oxygen content≤30ppm
To be qualified.After oxygen analysis is qualified, perfluorobutyl ethylene (modifying agent) 1g is added by measuring pump.Reactor is warming up to 70 ± 1 DEG C,
Put into gaseous monomer tetrafluoroethene, to kettle in pressure 2.5MPa, pass through measuring pump add sodium sulfite (reproducibility initiator)
0.1g (is diluted) with 2L deionized waters, and the sodium sulfite that concentration is 0.5g/L is persistently added dropwise in another measuring pump, and 0.6g is added dropwise altogether.
Pressure 2.5MPa in kettle, 70~75 DEG C of temperature are maintained during reaction.Changed according to polymerization rate, reducing agent is added dropwise in control
Speed.When tetrafluoroethene inventory reaches 3Kg, remaining dispersant 42g is continuously added to polymerization system.When tetrafluoroethene feeds intake
When amount reaches 12.8Kg, stop that reducing agent is added dropwise.When tetrafluoroethene inventory reaches 15Kg (solid content about 30%), reaction knot
Beam, gaseous monomer is reclaimed, cooling discharge, separating paraffin, obtains polytetrafluoroethylene (PTFE) polymer fluid.Post-treated cohesion, clean, dry
It is dry, obtain polytetrafluoroethyldispersion dispersion resin.
Embodiment 4
The present embodiment and the difference of embodiment 1 are, sodium sulfite is replaced with into oxalic acid.
Embodiment 5
The present embodiment and the difference of embodiment 1 are that reactor is warming up to 70 ± 1 DEG C, put into gaseous monomer tetrafluoroethene,
Pressure 2.5MPa in kettle, sodium sulfite 0.08g (being diluted with 2L deionized waters) is added by measuring pump, another measuring pump is held
It is continuous that the sodium sulfite that concentration is 0.5g/L is added dropwise, 1g is added dropwise altogether.
Comparative example 1
The present embodiment and the difference of embodiment 1 are, are added without perfluorobutyl ethylene.
Comparative example 2
Using tetrafluoroethylene polymerization process disclosed in China Patent Publication No. CN103665240B, polytetrafluoroethylene (PTFE) point is obtained
Dissipate resin.
The performance test data of table 1 (film tentering standard：20 times of cross directional stretch, 4 times of longitudinal stretching)
With the increase of film tentering equipment, patent CN103665240B can not meet use or the product of large-scale stenter
Degradation.
Although above the present invention is described in detail with a general description of the specific embodiments,
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.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of high molecular weight polytetrafluoroethyldispersions dispersion resin, it is characterised in that its preparation method comprises the following steps：
S1, deionized water, stabilizer, dispersant, antitack agent and oxidative initiator are added into reactor；Closed reactor enters
Row nitrogen displacement, make oxygen content≤30ppm；
S2, perfluorobutyl ethylene is added, and it is 2.0~3.0MPa to put into pressure in gas phase tetrafluoroethylene monomer to kettle, maintains kettle
Interior pressure simultaneously carries out polymerisation under conditions of 68~78 DEG C；In course of reaction, reproducibility initiation is added into reaction system
Agent；
S3, when react fluid solid content reach 30 ± 1% when, reaction terminate after, collect polytetrafluoroethylene (PTFE) polymer fluid, through condensing, washing
Only, dry, obtain polytetrafluoroethyldispersion dispersion resin.
2. high molecular weight polytetrafluoroethyldispersions dispersion resin according to claim 1, it is characterised in that the oxidisability triggers
Agent includes but is not limited to persulfate, potassium permanganate, potassium bromate or the potassium chlorate of alkali metal；The reproducibility initiator include but
It is not limited to ferrous ion, sulphite or oxalic acid.
3. high molecular weight polytetrafluoroethyldispersions dispersion resin according to claim 2, it is characterised in that the oxidisability triggers
Agent is potassium bromate, and the reproducibility initiator is sodium sulfite.
4. high molecular weight polytetrafluoroethyldispersions dispersion resin according to claim 3, it is characterised in that the oxidisability triggers
The addition of agent is 0.0003~0.0025%, preferably the 0.0009~0.002% of deionized water weight；The reproducibility triggers
The addition of agent is 0.003~0.006%, preferably the 0.004~0.005% of deionized water weight.
5. the high molecular weight polytetrafluoroethyldispersions dispersion resin according to any one of Claims 1 to 4, it is characterised in that described
Reproducibility initiator is with 1:3~8 ratio is successively added portionwise, and first adds after gas phase tetrafluoroethylene monomer is put into
Add, second batch is persistently added dropwise during the course of the reaction.
6. high molecular weight polytetrafluoroethyldispersions dispersion resin according to claim 5, it is characterised in that second batch reproducibility is drawn
The concentration sent out when agent is added dropwise is 0.4~0.6g/L.
7. high molecular weight polytetrafluoroethyldispersions dispersion resin according to claim 6, it is characterised in that in S2, reaction pressure
For 2.2~2.7Mpa, reaction temperature is 70~75 DEG C.
8. high molecular weight polytetrafluoroethyldispersions dispersion resin according to claim 7, it is characterised in that in S1, confined reaction
Before kettle, regulation system pH is 5~6.
9. according to the high molecular weight polytetrafluoroethyldispersions dispersion resin described in Claims 1 to 4 or 6~8 any one, its feature exists
In,
The dosage of deionized water is the 50-70%, preferably 60-70% of reactor volume；
The dosage of stabilizer is 1.0~8.0%, preferably the 3.0~6.0% of deionized water quality；
The dosage of dispersant is 0.01~0.15%, preferably the 0.05~0.1% of deionized water quality；
The dosage of antitack agent is 0.003~0.015%, preferably the 0.006~0.009% of deionized water quality；
The addition of perfluorobutyl ethylene is 0.003~0.02%, preferably the 0.007~0.016% of deionized water quality.
10. high molecular weight polytetrafluoroethyldispersions dispersion resin according to claim 9, it is characterised in that
Stabilizer is solid paraffin or the saturated hydrocarbons of carbon number >=12；
Dispersant is perfluor/fluorochemical polyether carboxylate or perfluor/fluorine-containing alkyl carboxylate, preferably perfluorooctanoic acid；
Antitack agent is succinic acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285954A (en) * | 2020-03-16 | 2020-06-16 | 山东东岳高分子材料有限公司 | Preparation method of high molecular weight modified polytetrafluoroethylene dispersion resin and dispersion concentrated solution |
| CN111627606A (en) * | 2020-05-25 | 2020-09-04 | 浙江德通科技有限公司 | High-flame-retardancy coaxial radio frequency cable and preparation method thereof |
| CN113388057A (en) * | 2020-03-12 | 2021-09-14 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene resin and preparation method and application thereof |
| CN114127131A (en) * | 2019-07-23 | 2022-03-01 | 大金工业株式会社 | Method for producing fluoropolymer, polytetrafluoroethylene composition, and polytetrafluoroethylene powder |
| CN116217765A (en) * | 2021-12-03 | 2023-06-06 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene dispersion resin for dry electrode binder and preparation method thereof |
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| CN105884946A (en) * | 2011-08-25 | 2016-08-24 | 大金工业株式会社 | Method for producing aqueous polytetrafluoroethylene dispersion |
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| CN105884946A (en) * | 2011-08-25 | 2016-08-24 | 大金工业株式会社 | Method for producing aqueous polytetrafluoroethylene dispersion |
| CN103665240A (en) * | 2013-12-11 | 2014-03-26 | 中昊晨光化工研究院有限公司 | Preparation method of polytetrafluoroethylene dispersion resin |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114127131A (en) * | 2019-07-23 | 2022-03-01 | 大金工业株式会社 | Method for producing fluoropolymer, polytetrafluoroethylene composition, and polytetrafluoroethylene powder |
| EP4006063A4 (en) * | 2019-07-23 | 2023-10-25 | Daikin Industries, Ltd. | Method for producing fluoropolymer, polytetrafluoroethylene composition, and polytetrafluoroethylene powder |
| CN114127131B (en) * | 2019-07-23 | 2024-04-02 | 大金工业株式会社 | Method for producing fluorine-containing polymer, polytetrafluoroethylene composition, and polytetrafluoroethylene powder |
| CN113388057A (en) * | 2020-03-12 | 2021-09-14 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene resin and preparation method and application thereof |
| CN111285954A (en) * | 2020-03-16 | 2020-06-16 | 山东东岳高分子材料有限公司 | Preparation method of high molecular weight modified polytetrafluoroethylene dispersion resin and dispersion concentrated solution |
| CN111627606A (en) * | 2020-05-25 | 2020-09-04 | 浙江德通科技有限公司 | High-flame-retardancy coaxial radio frequency cable and preparation method thereof |
| CN116217765A (en) * | 2021-12-03 | 2023-06-06 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene dispersion resin for dry electrode binder and preparation method thereof |
| CN116217765B (en) * | 2021-12-03 | 2024-04-02 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene dispersion resin for dry electrode binder and preparation method thereof |
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