CN109517096A - A kind of shelf-stable polytetrafluoroethylene (PTFE) concentration dispersion liquid and preparation method thereof - Google Patents
A kind of shelf-stable polytetrafluoroethylene (PTFE) concentration dispersion liquid and preparation method thereof Download PDFInfo
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- CN109517096A CN109517096A CN201710840810.1A CN201710840810A CN109517096A CN 109517096 A CN109517096 A CN 109517096A CN 201710840810 A CN201710840810 A CN 201710840810A CN 109517096 A CN109517096 A CN 109517096A
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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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/20—Concentration
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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
- C08F114/00—Homopolymers 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
- C08F114/18—Monomers containing fluorine
- C08F114/26—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
- C08F214/26—Tetrafluoroethene
Abstract
The present invention relates to a kind of preparation methods of shelf-stable polytetrafluoroethylene (PTFE) concentration dispersion liquid, and nonionic surface active agent and anionic surfactant is added in this method in polytetrafluoroethyldispersion dispersion, be concentrated to get；The anionic surfactant is mixed by Brij 35 carboxylic acid sodium and sodium laurate.Dispersion liquid is concentrated in the polytetrafluoroethylene (PTFE) of method production provided by the invention, has excellent storage stability, is monthly once stirred evenly, the Storage period of lotion reaches 1 year, the condition of storage and operation difficulty for reducing user, extend the service life of product, better meet process requirements.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of shelf-stable polytetrafluoroethyldispersion dispersion and its preparation side
Method.
Background technique
The excellent chemical corrosion resistance of polytetrafluoroethylene (PTFE), resistant of high or low temperature, resistance to ag(e)ing, low frictional properties, non-stick, physiology
Inertia makes it become indispensable special material in fields such as chemical industry, machinery, electrical, building, medical treatment, instead of previous tradition
Material, wherein dispersion liquid is concentrated in polytetrafluoroethylene (PTFE), general solid content 60% or so, can be used for fabric and porous metals dipping,
Form film, metal coating and coating of other substrates etc..
Stable micella is formed by non-ionic size in polytetrafluoroethylene (PTFE) concentration dispersion liquid, suspend balling-up in water
Shape, average grain diameter generally in 0.18-0.30um, there is longer storage period at 20 DEG C, but meeting precipitating is generally put in container bottom
Setting need to be slowly stirred uniformly for one week, avoid generating irreversible condensation, and wherein the average grain diameter of dispersion liquid is bigger, form coating
Function admirable, but it is more easily settled.Dispersion liquid once generates irreversible condensation, under will lead to the solid content of dispersion liquid sharply
Drop, loses a large amount of materials, while the use of remaining low-solid content dispersion liquid is very limited, the performance of application product is difficult to
Guarantee.
Patent document CN1754894A discloses a kind of modified Teflon and its manufacturing method, it is characterized in that tetrafluoro second
Alkene and comonomer polymerize to obtain modified Teflon, and control modified monomer dosage accounts for the 0.1- of modified Teflon
1.0%, and the average primary particle diameter of modified Teflon is 0.22-0.5um, and a large amount of non-ionic sizes are added, pass through
Chemical concentration obtains the dispersion liquid that emulsifier content reaches 13%, and dispersion liquid film forming is excellent, and light transmittance is good, but to dispersion liquid
There are common fault in terms of storage stability, big partial size is easily settled, and is needed to stir weekly once, be wanted to the condition of storage of dispersion liquid
Ask higher.
Patent document CN1642995A discloses a kind of preparation method of aqueous polytetrafluoroethyldispersion dispersion composition, special
Sign is to be carried out the polymerization reaction of tetrafluoroethene as dispersing agent using perfluorocarboxylic acid salt analog anion surfactants, obtained
Dispersion liquid is added a certain amount of nonionic surfactant and carries out chemical settling, obtains the concentration dispersion liquid of certain solid content, leads to
It crosses and is arranged in pairs or groups using inorganic nature/Organic certain proportion, perfluorocarboxylic acid salt analog anion surfactants is dense in reduction dispersion liquid
Degree, but dispersion liquid Shortcomings in terms of storage stability are concentrated, it needs to stir weekly once, the condition of storage of dispersion liquid is wanted
Ask higher.
Patent document CN1876709A discloses a kind of preparation method of high concentration aqueous's PTFE dispersion, by using strong
Alkalescence anion-exchange resin removes perfluorooctanoic acid content, and ammonium laurate solution is added, and electrophoresis concentration is carried out, to obtain height
Concentration PTFE dispersion adds a certain amount of nonionic surface active agent, and it is good to obtain friction stability, non-coloring, without miscellaneous
Matter elution aqueous PTFE dispersion, lotion average grain diameter be 0.25um, but dispersion storage stability in terms of Shortcomings,
It is short to place the period.
In patent document CN1125131, using a kind of emulsifier of the cloud point between 45~85 DEG C, method for concentration is used
Chemical concentration, obtains that impregnation performance is preferable, and dispersion liquid is concentrated in the thicker PTFE of coating, but it has been investigated that dispersion liquid storage is concentrated in it
It is poor to deposit stability, easily settles, generates irreversible condensation.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of shelf-stable polytetrafluoroethylene (PTFE) concentration dispersion liquid, to improve poly- four
The problems such as vinyl fluoride concentration dispersion liquid is easily settled during storage, and irreversible condensation occurs.
Specifically, the preparation method of shelf-stable polytetrafluoroethylene (PTFE) concentration dispersion liquid provided by the invention includes following step
It is rapid: in the concentration process of polytetrafluoroethyldispersion dispersion, nonionic surface active agent and anionic surfactant is added；
Wherein, the anionic surfactant by Brij 35 carboxylic acid sodium and sodium laurate mixing and
At.
The present invention by concentration dispersion liquid resin be concentrated production process in, be added by specific components mix yin from
Sub- surfactant forms the protection to polytetrafluoroethylparticle particle, reduces polytetrafluoroethylene (PTFE) concentration dispersion liquid and stored in transport
The problems such as Cheng Zhong, stability is poor, easily settles, generates irreversible condensation, and the anionic surfactant group being added
It closes, in post-production application, pyrolytic noresidue, on downstream product quality without influence.In order to further increase the effect
The mass ratio of fruit, the preferably described Brij 35 carboxylic acid sodium of the present invention and sodium laurate is 1:1~2:
1.And when the dosage of the anionic surfactant is 0.1~0.4% of polytetrafluoroethylene solids quality in dispersion liquid,
The resultant effect of products obtained therefrom is best.Other anionoid type surfactants, as sulfonate surfactants or sulfate type are living
Property agent, in lotion process, high-temperature residual causes product to turn to be yellow or burnt hair, limits application range, and deposits for a long time to lotion
The maintenance effect of stability can not show a candle to the certain types of anionic surfactant that the present invention uses during storage.
In order to generate synergistic effect with the anionic surfactant, it is ensured that dispersion liquid is concentrated in long-term storing process
With good stability, nonionic surface active agent is added in the present invention simultaneously in the polytetrafluoroethyldispersion dispersion.Institute
Stating nonionic surfactant can be selected common type known in the art.In order to realize and specific anion table of the present invention
The optimal synergy of face activating agent combination, the preferably described nonionic surface active agent of the present invention are nonylphenol polyoxyethylene ether
(NP12) or isomeric alcohol polyethenoxy ether (TMN-10).When the dosage of the nonionic surface active agent is poly- four in dispersion liquid
Vinyl fluoride solid masses 4~8% when resultant effect it is optimal.
Polytetrafluoroethyldispersion dispersion before being concentrated in the present invention is prepared using known conventional polymerization, such as cream
Liquid polymerization, co-polymeric etc..
The dispersion liquid can be modified Teflon dispersion liquid, be also possible to non-modified polytetrafluoroethyldispersion dispersion.
The dispersion liquid is during the preparation process, it is preferred to use deionized water as reaction medium, using perfluorooctanoic acid or
Perfluorooctanoic acid substitute is as dispersing agent.
As a preferred solution of the present invention, the polytetrafluoroethyldispersion dispersion is using the method system included the following steps
It is standby to form:
In the reaction kettle for being previously added deionized water, stabilizer, pH adjusting agent and dispersing agent, it is passed through tetrafluoroethene list
Initiator is added in body, and control reaction pressure is 1~3MPa and temperature is 60~100 DEG C, stop after reaction 1~3 hour to get.
Preferably, the mass percent of polytetrafluoroethylene (PTFE) is 25~35% in the polytetrafluoroethyldispersion dispersion that the present invention uses.
Wherein, dispersing agent is preferably that fluorine-containing surfactant, further preferably perfluorooctanoic acid or perfluorooctanoic acid replace
Dai Pin, dosage are the 0.05~0.1% of deionized water quality.Stabilizer is preferably 56~58 DEG C of fusing point of solid paraffin, dosage
It is the 1~3% of deionized water quality.PH adjusting agent is preferably succinic acid, and dosage is the 100-300ppm of deionized water quality.Draw
Hair agent is preferably persulfuric acid salt initiator, and additional amount is the 3-5ppm of deionized water quality.
Copolymerization method is such as used, hexafluoropropene, perfluoro methyl vinyl ether, perfluoro propyl vinyl base can be selected in comonomer
One kind of ether, chlorotrifluoroethylene, additional amount are the 0.05~0.15% of deionized water quality.
The method for concentration that the present invention uses is conventionally known method for concentration, such as vacuum concentration, chemical precipitation method.
In order to further increase the stability of the concentration dispersion liquid, the present invention controls polytetrafluoroethylene (PTFE) in concentration dispersion liquid
Mass percent be 50~70%.
In order to improve the stability of final concentration dispersion liquid, the present invention is preferably in concentrated preceding first removal polytetrafluoroethylene (PTFE) point
Dispersing agent in dispersion liquid.By taking the dispersing agent perfluorooctanoic acid that the present invention uses as an example, strong basic ion can first be added before concentration
Exchanger resin adsorbs it, then will be adsorbed with the ion exchange resin filtering removal of dispersing agent, then be concentrated.It is described
The additional amount of ion exchange resin is preferably 6~10% of polytetrafluoroethylene (PTFE) weight in dispersion liquid.
Preferably, the present invention using tetrafluoroethylene monomer in perfluorooctanoic acid or its substitute as dispersing agent,
Obtain polytetrafluoroethyldispersion dispersion by homopolymerization or modified copolymer, be added in the dispersion liquid in concentration process it is a certain amount of it is non-from
It is pungent to add ion exchange resin progress perfluor for the anionic surfactant combination of sub- surfactant and certain proportion collocation
Sour ammonium or the removal of its substitute, or the processes such as vacuum concentration or chemical precipitating are directly carried out, pass through consolidating for control polytetrafluoroethylene (PTFE)
Content obtains shelf-stable polytetrafluoroethylene (PTFE) concentration dispersion liquid.
The polytetrafluoroethylene (PTFE) concentration dispersion liquid that the present invention protects the above method to be prepared simultaneously.
Dispersion liquid is concentrated in the polytetrafluoroethylene (PTFE) of method production provided by the invention, has excellent storage stability, monthly carries out one
Secondary to stir evenly, the Storage period of lotion reaches 1 year, reduces the condition of storage and operation difficulty of user, extends the validity period of product
Limit, better meets process requirements.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The preparation of polytetrafluoroethyldispersion dispersion: in the 5L stainless steel autoclave equipped with collet and stirring, cleans and add
Enter 2.8L deionized water, 84g solid paraffin, 0.84g succinic acid, 2.8g perfluorooctanoic acid dispersant cover kettle cover, and unlatching is stirred
It mixes, vacuumizes, nitrogen displacement.Until oxygen content is less than 30ppm, temperature in the kettle is controlled to 70 DEG C, tetrafluoroethylene monomer is passed through, adds
Enter 0.01g ammonium persulfate initiator, control reaction pressure is 2.5MPa, starts to react, and the highest temperature in kettle is controlled in reaction process
Degree be 90 DEG C, when react 1.5 it is small when after, stop reaction, obtain solid content be 30% polytetrafluoroethyldispersion dispersion.
The preparation of polytetrafluoroethylene (PTFE) concentration dispersion liquid: in above-mentioned gained polytetrafluoroethyldispersion dispersion, it is added
61.9gNP12,1.2g Brij 35 carboxylic acid sodium and 1.2g sodium laurate, stir evenly, add
99.1g strong basic ion exchange resin stirs 24 hours, filters out ion exchange resin, lotion is concentrated in vacuo, obtain
Dispersion liquid is concentrated in the polytetrafluoroethylene (PTFE) that solid content is 60%.
Embodiment 2
The preparation of polytetrafluoroethyldispersion dispersion: in the 5L stainless steel autoclave equipped with collet and stirring, cleans and add
Enter 2.8L deionized water, 84g solid paraffin, 0.84g succinic acid, 1.4g perfluorooctanoic acid dispersant cover kettle cover, and unlatching is stirred
It mixes, vacuumizes, nitrogen displacement.Until oxygen content is less than 30ppm, 4.2g hexafluoropropene is added, controls temperature in the kettle to 70 DEG C, leads to
Enter tetrafluoroethylene monomer, 0.01g ammonium persulfate initiator is added, control reaction pressure is 2.5MPa, starts to react, reaction process
In middle control kettle maximum temperature be 90 DEG C, when react 2 it is small when after, stop reaction, obtain emulsion solid content be 31%.
The preparation of polytetrafluoroethylene (PTFE) concentration dispersion liquid: in above-mentioned gained polytetrafluoroethyldispersion dispersion, it is added
61.9gNP12,1.2g Brij 35 carboxylic acid sodium and 1.2g sodium laurate, stir evenly, and are added
99.1g strong basic ion exchange resin stirs 24 hours, filters out ion exchange resin, lotion is concentrated in vacuo, obtain
Dispersion liquid is concentrated in the PTFE that solid content is 60%, and emulsion property and storage stability are detected.
Embodiment 3
Compared with Example 1, difference is only that:
?The preparation of polytetrafluoroethyldispersion dispersionIn: addition 0.28g succinic acid, 2.8g perfluorooctanoic acid dispersant,
0.0084g ammonium persulfate initiator；
?The preparation of polytetrafluoroethylene (PTFE) concentration dispersion liquidIn: 52gNP12,2.4g Brij 35 carboxylic is added
Sour sodium and 1.2g sodium laurate.
Embodiment 4
Compared with Example 2, difference is only that:
?The preparation of polytetrafluoroethyldispersion dispersionIn: 0.28g succinic acid, 2.8g perfluorooctanoic acid dispersant, 1.4g is added
Hexafluoropropene, 0.0084g ammonium persulfate initiator；
?The preparation of polytetrafluoroethylene (PTFE) concentration dispersion liquidIn: 104gNP12,2.4g Brij 35 is added
Carboxylic acid sodium and 1.2g sodium laurate.
Embodiment 5
Compared with Example 3, difference is only that:
?The preparation of polytetrafluoroethyldispersion dispersionIn: 0.5g succinic acid is added, 2.4g perfluorooctanoic acid substitute, which is used as, divides
Powder, 0.014g ammonium persulfate initiator；
?The preparation of polytetrafluoroethylene (PTFE) concentration dispersion liquidIn: 104gTMN-10,0.65g dodecyl alcohol polyoxyethylene is added
Ether carboxylic acid sodium and 0.65g sodium laurate；Use 78g strong basic ion exchange resin.
Embodiment 6
Compared with Example 4, difference is only that:
?The preparation of polytetrafluoroethyldispersion dispersionIn: 0.68g succinic acid, 2.4g perfluorooctanoic acid dispersant, 3.6g is added
Perfluoro propyl vinyl ether, 0.01g ammonium persulfate initiator；
?The preparation of polytetrafluoroethylene (PTFE) concentration dispersion liquidIn: 74gTMN-10,2.6g Brij 35 is added
Carboxylic acid sodium and 2.6g sodium laurate；Use 130g strong basic ion exchange resin.
Embodiment 7
Compared with Example 3, difference is only that: strong basic ion exchange resin is not used before concentration, and dense using chemistry
Contracting.
Embodiment 8
Compared with Example 1, difference is only that: in the preparation process of polytetrafluoroethylene (PTFE) concentration dispersion liquid, 1.2g is added
Brij 35 carboxylic acid sodium and 2.4g sodium laurate (i.e. the ratio between the two is 1:2).
Embodiment 9
Compared with Example 1, difference is only that: in the preparation process of polytetrafluoroethylene (PTFE) concentration dispersion liquid, 5g ten is added
Dialkyl group alcohol polyoxyethylene ether carboxylic acid sodium and 5g sodium laurate.
Comparative example 1
Compared with Example 1, difference is only that: in the preparation process of polytetrafluoroethylene (PTFE) concentration dispersion liquid, being added without ten
Dialkyl group alcohol polyoxyethylene ether carboxylic acid sodium and sodium laurate.
Comparative example 2
Compared with Example 2, difference is only that: in the preparation process of polytetrafluoroethylene (PTFE) concentration dispersion liquid, being used
104gTX100 replaces 61.9gNP12, and is added without Brij 35 carboxylic acid sodium and sodium laurate.
Comparative example 3
Compared with Example 1, difference is only that: in the preparation process of polytetrafluoroethylene (PTFE) concentration dispersion liquid, being only added ten
Dialkyl group alcohol polyoxyethylene ether carboxylic acid sodium and be added without sodium laurate.
Comparative example 4
Compared with Example 1, difference is only that: in the preparation process of polytetrafluoroethylene (PTFE) concentration dispersion liquid, being added without ten
Dialkyl group alcohol polyoxyethylene ether carboxylic acid sodium and sodium laurate is only added.
Comparative example 5
Compared with Example 1, difference is only that: anionic surfactant is using dodecyl sodium sulfate (i.e. with 12
Sodium alkyl sulfonate replaces the combination of the Brij 35 carboxylic acid sodium and sodium laurate).
Comparative example 6
Compared with Example 1, difference is only that: anionic surfactant is using lauryl sodium sulfate (i.e. with 12
Sodium alkyl sulfate replaces the combination of the Brij 35 carboxylic acid sodium and sodium laurate).
Comparative example 7
Compared with Example 1, difference is only that: in the preparation process of polytetrafluoroethylene (PTFE) concentration dispersion liquid, being added without non-
Ionic surfactant NP12.
Experimental example: emulsion property and storage stability are detected
The detection of dispersion liquid storage stability is concentrated in polytetrafluoroethylene (PTFE) are as follows: monthly carries out uniform stirring 1 time, Storage period reaches one
Nian Hou is filtered using 300 mesh stainless steel filter screens, calculates loss amount.
Dispersion liquid test result such as 1 institute of table is concentrated in the polytetrafluoroethylene (PTFE) that Examples 1 to 9 and comparative example 1~7 are prepared
Show.
Table 1: dispersion liquid experimental test data are concentrated in polytetrafluoroethylene (PTFE)
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of preparation method of shelf-stable polytetrafluoroethylene (PTFE) concentration dispersion liquid, which is characterized in that in polytetrafluoroethyldispersion dispersion
Middle addition nonionic surface active agent and anionic surfactant, be concentrated to get；
The anionic surfactant by Brij 35 carboxylic acid sodium and sodium laurate mixing and
At.
2. the method according to claim 1, wherein the Brij 35 carboxylic acid sodium and 12
The mass ratio of sodium carboxylate is 1:1~2:1.
3. method according to claim 1 or 2, which is characterized in that the dosage of the anionic surfactant is point
The 0.1~0.4% of polytetrafluoroethylene solids quality in dispersion liquid.
4. method according to any one of claims 1 to 3, which is characterized in that the nonionic surface active agent is
Nonylphenol polyoxyethylene ether or isomeric alcohol polyethenoxy ether.
5. method according to claim 1 or 4, which is characterized in that the dosage of the nonionic surface active agent is point
The 4~8% of polytetrafluoroethylene solids quality in dispersion liquid.
6. method described in any one according to claim 1~5, which is characterized in that gather in gained concentration dispersion liquid after concentration
The mass percent of tetrafluoroethene is 50~70%.
7. method described in any one according to claim 1~6, which is characterized in that the concentration is vacuum concentration or chemistry
Precipitating.
8. the method according to the description of claim 7 is characterized in that the first spent ion exchange resin removal poly- four before the concentration
The dispersing agent contained in vinyl fluoride dispersion liquid.
9. according to claim 1, method described in 7 or 8, which is characterized in that it includes such as that the polytetrafluoroethyldispersion dispersion, which uses,
The method of lower step is prepared:
In the reaction kettle for being previously added deionized water, stabilizer, pH adjusting agent and dispersing agent, it is passed through tetrafluoroethylene monomer, is added
Enter initiator, control reaction pressure is 1~3MPa and temperature is 60~100 DEG C, stop after reaction 1~3 hour to get；
Preferably, the mass percent of polytetrafluoroethylene (PTFE) is 25~35% in the polytetrafluoroethyldispersion dispersion.
10. dispersion liquid is concentrated in the polytetrafluoroethylene (PTFE) that any one the method is prepared according to claim 1~9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114381013A (en) * | 2022-01-30 | 2022-04-22 | 广州熵能创新材料股份有限公司 | Concentrated aqueous dispersion of fluorine-containing polymer, preparation method and application thereof |
| CN116199905A (en) * | 2022-11-11 | 2023-06-02 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene concentrated dispersion |
| CN116515221A (en) * | 2023-07-03 | 2023-08-01 | 山东东岳高分子材料有限公司 | Interface modified polytetrafluoroethylene suspension and method for preparing polytetrafluoroethylene film by using same |
| CN116199905B (en) * | 2022-11-11 | 2024-05-14 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene concentrated dispersion |
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| WO2002002647A1 (en) * | 2000-06-30 | 2002-01-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Improved microgels and films |
| CN1642995A (en) * | 2002-03-20 | 2005-07-20 | 旭硝子株式会社 | Aqueous polytetrafluoroethylene dispersion composition and process for its production |
| CN1876709A (en) * | 2005-06-06 | 2006-12-13 | 旭硝子株式会社 | Aqueous dispersion of polytetrafluorethylene and process for its production |
| CN104220517A (en) * | 2012-03-27 | 2014-12-17 | 大金工业株式会社 | Aqueous fluoropolymer dispersion |
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| WO2002002647A1 (en) * | 2000-06-30 | 2002-01-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Improved microgels and films |
| CN1642995A (en) * | 2002-03-20 | 2005-07-20 | 旭硝子株式会社 | Aqueous polytetrafluoroethylene dispersion composition and process for its production |
| CN1876709A (en) * | 2005-06-06 | 2006-12-13 | 旭硝子株式会社 | Aqueous dispersion of polytetrafluorethylene and process for its production |
| CN104220517A (en) * | 2012-03-27 | 2014-12-17 | 大金工业株式会社 | Aqueous fluoropolymer dispersion |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114381013A (en) * | 2022-01-30 | 2022-04-22 | 广州熵能创新材料股份有限公司 | Concentrated aqueous dispersion of fluorine-containing polymer, preparation method and application thereof |
| CN114381013B (en) * | 2022-01-30 | 2023-11-07 | 熵能创新材料(珠海)有限公司 | Concentrated aqueous dispersion of fluorine-containing polymer, preparation method and application thereof |
| CN116199905A (en) * | 2022-11-11 | 2023-06-02 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene concentrated dispersion |
| CN116199905B (en) * | 2022-11-11 | 2024-05-14 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene concentrated dispersion |
| CN116515221A (en) * | 2023-07-03 | 2023-08-01 | 山东东岳高分子材料有限公司 | Interface modified polytetrafluoroethylene suspension and method for preparing polytetrafluoroethylene film by using same |
| CN116515221B (en) * | 2023-07-03 | 2023-11-14 | 山东东岳高分子材料有限公司 | Interface modified polytetrafluoroethylene suspension and method for preparing polytetrafluoroethylene film by using same |
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| CN109517096B (en) | 2020-03-20 |
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