CN102443086B - Preparation method of low molecular weight polytetrafluoroethylene resin - Google Patents
Preparation method of low molecular weight polytetrafluoroethylene resin Download PDFInfo
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Abstract
The invention discloses a preparation method of a low molecular weight polytetrafluoroethylene resin. The preparation method comprises the following steps: 1, adding 14 parts by weight of deionized water and 0.28-1.4 parts by weight of a paraffin stabilizing agent to a reactor with a stirrer, sealing the reactor, evacuating, displacing with high purity nitrogen until the oxygen content is less than 20pm, and sucking 0.35-0.6 parts by weight of a perfluoroalkoxy carboxylate emulsifier; 2, adding a tetrafluoroethylene monomer to the reactor until the reactor pressure is 0.5MPa, starting stirring, adding the tetrafluoroethylene monomer until the pressure is 0.7-3.0MPa after the reactor is heated to 70-75DEG C, adding 0.14-0.28 parts by weight of an ammonium persulfate initiator, starting a polymerization reaction, maintaining the reaction temperature at 70-100DEG C and the reaction pressure at 0.7-3.0MPa, terminating the reaction after continuously reacting for 50-60min; and 3, recovering the tetrafluoroethylene monomer to obtain a polytetrafluoroethylene polymerization emulsion with the microemulsion particle size of 20-100nm, conglomerating the emulsion, washing, and drying to obtain the fine powdery polytetrafluoroethylene resin with the particle size of 5-14mum. The preparation method has the advantages of stable polymerization speed, short polymerization time, and no agglomeration product in the reactor.
Description
Technical field
The present invention relates to a kind of preparation method of teflon resin, especially relate to a kind of preparation method of low molecular weight tetrafluoro ethylene resin.
Background technology
Teflon resin is owing to having good mechanical property, electrical property, chemical resistance, weathering resistance and non-viscosity and oilness, in the industry such as nuclear power, national defence, space flight, electronics, electric, chemical industry, machinery, building, weaving, metal finishing, pharmacy, medical treatment, weaving, be widely used as high-low temperature resistant, corrosion resistant material, insulating material, anti-stick coatings etc., make it to become the product of not replacing.Tetrafluoroethylene relative molecular mass is larger, and low is hundreds thousand of, and high reaches more than 10,000,000, is generally millions of.Its degree of crystallinity is generally 90～95%, and melt temperature is 327～342 DEG C.
Low molecular weight polytetrafluoroethylene can be described as PTFE micro mist, PTFE wax, PTFE Dry-powder Lubricant etc.Its molecular weight of lower molecular weight PTFE generally only has 3～200,000, even have less than 10,000, median size is 1～20 μ m.Because its molecular weight is low, fusing point is generally at 315～320 DEG C, because itself and high molecular weight polytetrafluoroethyldispersions resin have identical chemical structure form, therefore its weathering resistance, chemical proofing, self lubricity and not cementability and general PTFE molecular weight as broad as long.Because the molecular weight of lower molecular weight PTFE is low, thus particle size thin and soft, have good dispersive ability, can be scattered in equably and in other base materials, change its characteristic.Therefore, its main application is in other materials, to be used as additive, improves oilness, increases separability, improves wear resistance, gives pollution resistance and resistance to scratch, improves flame retardant resistance and increases water repellency.The preparation method of lower molecular weight PTFE has the methods such as TFE polymerization, high molecular PTFE thermo-cracking and radiation cleavage.Preparation method has determined structural form, molecular weight and the distribution thereof of lower molecular weight PTFE powder.
The methods such as high molecular PTFE thermo-cracking and radiation cleavage can change the structure of molecular chain, make product introduce unstable end group, thereby reduce the performance of product.And the method that adopts emulsion to telomerize just can be avoided above problem.
In PTFE emulsion preparation process, conventionally add fluorinated surfactant and chain-transfer agent.Conventional fluorinated surfactant is mainly Perfluorocaprylic Acid (PFOS), ammonium perfluorocaprylate (PFOA), their biological degradability is poor, be difficult for being discharged to external, easily accumulation in vivo, and biological liver is had to higher bio-toxicity, to be prohibited from using, must eliminate.Therefore, adopt other fluorine-containing emulsifier to replace Perfluorocaprylic Acid series emulsifying agent extremely urgent.
Adding chain-transfer agent is the another kind of method of preparation lower molecular weight PTFE.CN101215348 carries out polymerization and prepares ptfe emulsion taking difluorochloromethane as chain-transfer agent.It is chain-transfer agent that CN1948355 adopts methylene dichloride, at 75-100 DEG C, and under 0.1-1.0Mpa condition, polymerization 5-6 hour, obtaining solid content is 20% polymerized emulsion.CN101215348 adopts ammonium perfluorocaprylate and hc-surfactant TX-4 as compound emulsifying agent, and ether has been prepared PTFE emulsion as molecular weight regulator.Dupont company of the U.S. and Japanese Dakin company also all adopt and add the method for molecular weight regulator to prepare corresponding emulsion.Because difluorochloromethane, methylene dichloride, ether are all low boiling point solvents, easily volatilization, after reaction, can remain in gas phase, to gas recovery utilization bring unfavorable, cause monomer purity decline, affect quality.After telomerizing, can make the perfluor chain change of PTFE elementary composition, also can form new free radical, continue polymerization meeting and introduce other elements.In addition, CN1948355 technique polymerization time is long, and the solid content of gained emulsion is lower; CN101215348 technique has still been used ammonium perfluorocaprylate as emulsifying agent.
Adopting letex polymerization to prepare in the lower molecular weight PTFE emulsion process telomerizing, tend to occur coacervation, thereby make reactor produce sticky still phenomenon., all there is this phenomenon in PTFE emulsion preparation process as disclosed in CN101291987, condensation product is greater than 0.5% after the various formulas of employing.The sticky still phenomenon that cohesion causes causes heat-transfer effect and throughput to decline, and labour intensity strengthens, and safety, quality are caused to detrimentally affect.Must carry out still clearly if carry out next step reaction, make troubles to production.Document " dispersion polymerization process is prepared tetrafluoroethylene and performance study thereof " (engineering plastics application, 2005,33 (7): 13-15) although also there is formula to solve the sticky still problem in PTFE emulsion polymerization process in research, but still adopt PFOA emulsifying agent, in addition, the add-on of paraffin is very high is 15%.Therefore, up to the present also do not occur filling a prescription and solve the sticky still problem that emulsion is prepared lower molecular weight PTFE nanoemulsions.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of chain-transfer agent that do not adopt, substitute Perfluorocaprylic Acid and derivative series emulsifying agent thereof taking perfluoro alkoxy carboxylate salt as emulsifying agent, prepare high solids content, size distribution is even, without condensation product, do not glue still, be conducive to the preparation method of suitability for industrialized production low molecular weight polytetrafluoroethylene nanoemulsions.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of low molecular weight tetrafluoro ethylene resin, comprises the following steps:
(1) in the reactor with agitator, add 14 parts by weight of deionized water, 0.28～14 weight part paraffin stablizer, closed reactor, vacuumize and replace to oxygen level and be less than after 20ppm with High Purity Nitrogen, then suck 0.35～0.6 weight part perfluoro alkoxy carboxylate salt emulsifying agent;
(2) adding tetrafluoroethylene monomer to reactor pressure is 0.5MPa, open and stir, when reactor is warming up to after 70～75 DEG C, while adding again tetrafluoroethylene monomer to pressure to be 0.7～3.0Mpa, add the ammonium persulfate initiator of 0.14～0.28 weight part, start polyreaction, maintaining temperature of reaction is 70～100 DEG C, reaction pressure is 0.7～3.0Mpa, termination reaction after successive reaction 50～60min;
(3) reclaim tetrafluoroethylene monomer, obtaining microemulsion particle diameter is the PTFE polymerized emulsion of 20～100nm, after cohesion emulsion, washing, oven dry, obtains the teflon resin that fine powder particle diameter is 5～14 μ m.
Perfluoro alkoxy carboxylate salt emulsifying agent described in step (1) is selected from perfluor methoxypropionic acid (CF
3oCF
2cF
2cOOH), the sub-isopropoxy methane amide of perfluor oxyethyl group (CF
3cF
2oCF (CF
3) CF
2oCONH
4), perfluor oxyethyl group inferior ethoxyl sodium acetate (C
2f
5oC
2f
4oCF
2cOONa), the sub-isopropoxy propionic acid amide of perfluor oxyethyl group two (C
2f
5oCF (CF
3) CF
2oCF (CF
3) CF
2oCF
2cF
2oCF
2cF
2cOONH
4), perfluor oxyethyl group inferior ethoxyl ammonium formate (C
2f
5oC
2f
4oCOONH
4), perfluor oxyethyl group two inferior ethoxyl formyl fluoride (C
2f
5oC
2f
4oC
2f
4oCOF).
Stirring velocity described in step (2) is 300～800r/min.
Ptfe emulsion solid content described in step (3) is 25～40%.
In above-mentioned steps, TFE polymerization starts from lower temperature, after polymerization starts, can pass through the polymerization exotherm process of TFE, make reaction heat that still temperature rise is arrived to comparatively high temps, also can promote by heating the rising of temperature, substantially complete polymerization under higher temperatures, polymerization temperature of the present invention is 70～100 DEG C, be raised to after higher temperatures section in temperature, application cooling system is controlled the polymerization temperature variations that reaction heat causes, and it is stabilized in this constant scope, is convenient to control speed of reaction.
In PTFE emulsion polymerization process, the long-chain free radical of PTFE and formation is water insoluble, with solid-state precipitating, forms solid phase, and gradually grows up as PTFE primary particle.Because the degree of crystallinity of PTFE is high, the TFE monomer in water is difficult to diffuse into PTFE inside particles, and polymerization mainly occurs in PTFE particle surface.PTFE particle, under emulsifying agent protection, exists in water with primary particle form substantially.Along with the growth in reaction times, TFE monomer reaction amount is more, and the particle diameter of particle increases, and the molecular weight of PTFE is also larger.Therefore, the size of primary particle has been reacted the size of PTFE molecular weight substantially.Except Reaction time shorten, control outside particle increase, can also pass through to select the low emulsifying agent of micelle-forming concentration, and control the consumption of emulsifying agent, control form, quantity and the size of micella.The quantity of the general more micellas of emulsifier is more, and the particle diameter of micella is less.Also can realize so control the consumption of emulsifying agent the molecular weight that reduces PTFE.The consumption of emulsifying agent of the present invention is 2.5%～5% of tetrafluoroethylene monomer consumption, and the reaction times is 50～60min.
In polymerization process, each PTFE molecule is with the end group from initiator.Under the same prerequisite of TFE monomer reaction amount, add the consumption of initiator more, just mean that the quantity of PTFE molecule is more.Therefore be, also a kind of method of the PTFE of reduction molecular weight by the consumption that increases initiator.In emulsion polymerization process, employing be inorganic peroxide initiator, as ammonium persulphate, Potassium Persulphate, expand after the consumption of initiator, the ionic concn in polymerization system increases, and can reduce the stability of system.The amount of the initiator therefore, adding is suitable.The present invention adopts ammonium persulphate as initiator, and its consumption is 1%～2% of tetrafluoroethylene monomer consumption.
The present invention is taking deoxidation de-mineralized water as polymerisation medium, and perfluoro alkoxy carboxylate salt is emulsifying agent, and persulphate is initiator, and paraffin is stablizer, prepares lower molecular weight PTFE nanoemulsions, finally by cohesion, and the dry PTFE ultrafine powder that obtains.The invention has the advantages that: in preparation lower molecular weight PTFE emulsion technique, adopting perfluoro alkoxy is that emulsifying agent substitutes Perfluorocaprylic Acid series emulsifying agent, do not adopt chain-transfer agent, prepared lower molecular weight PTFE nanoemulsions size distribution is even, in preparation process without condensation product, not sticky still, the reaction times is short, is conducive to suitability for industrialized production low molecular weight tetrafluoro ethylene resin.
The performance test methods of ptfe emulsion and ultrafine powder resin thereof is as follows:
(1) solid content in PTFE dispersion system is measured by weighting method: dispersion system is divided into some sample evaporations of having weighed dry, takes the weight of drying solid.Solids content refers to the per-cent of PTFE with respect to PTFE and water gross weight.
(2) discrete particles size (RDPS) is measured with Photon Correlation Spectrum, measures according to GBT 19627-2005 method.
(3) fusing point of PTFE micro mist resin and crystallization Heat of Formation are with differential scanning instrument (DSC), according to ASTMD4591-2001DSC standard test.
(4) mensuration of the molecular weight of PTFE micro mist.PTFE, because the hydro-oleophobicity of fluorine element is insoluble to any organic solvent, can not pass through conventional GPC and viscosity measurement PTFE molecular weight.It is the molecular weight by corresponding physical index indirect measurement PTFE that current mensuration PTFE molecule measuring is established a capital, and concrete grammar has melting index method, SSG, DCS method, rheological method and light scattering method etc.But because lower molecular weight PTFE resin exists defect in respective sample preparation process, such as the easy curtain coating of sintering, molecular weight ranges is outside classical formulas etc., and above-mentioned several testing method are not also suitable for lower molecular weight PTFE test.Document (J.Polym.Sci.:Polym.Chem.Ed., 1978,16,2931-2944.) report crystalline melt temperature and melting enthalpy, Tc and the heat of crystallization of different molecular weight PTFE sample (former powder or sintered sample) at difference intensification, rate of temperature fall, along with PTFE molecular weight increases, crystallization Heat of Formation reduces.The scope of the PTFE molecular weight of reporting in article is 2～4,500 ten thousand.Molecular weight is larger, and the motor capacity of molecule segment is less, is unfavorable for crystallization, and crystallization Heat of Formation reduces; Contrary molecular weight is less, and the motor capacity of molecule segment increases, and is conducive to crystallization, thereby crystallization Heat of Formation increases.And crystallization Heat of Formation can be tested by DCS and obtains, the molecular weight ranges of judgement PTFE micro mist that can be very fast in conjunction with the data results of above-mentioned document.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The preparation method of low molecular weight tetrafluoro ethylene resin, concrete grammar is as follows:
(1) in the 25L reactor with agitator, add the deionized water of 14kg and the paraffin stablizer of 0.28kg, closed reactor, vacuumizes and replaces to the emulsifying agent CF that adds again 0.35kg after oxygen level is less than 20ppm with High Purity Nitrogen
3oCF
2cF
2cOOH;
(2) adding polytetrafluoroethyl-ne alkene monomer to reactor pressure is 0.5MPa, under the rotating speed of 300r/min, reactor is warming up to after 70 DEG C, add again polytetrafluoroethyl-ne alkene monomer in the time that pressure is 0.7MPa, to add the ammonium persulfate initiator of 0.14kg, start polyreaction, maintaining temperature of reaction is 70 DEG C, and reaction pressure is termination reaction after 0.7MPa successive reaction 60min;
(3) reclaim tetrafluoroethylene monomer, obtaining microemulsion particle diameter is the PTFE polymerized emulsion of 20nm, and its PTFE solids content is 35%, after cohesion emulsion, washing, oven dry, obtains the teflon resin that fine powder particle diameter is 14 μ m, its fusing point is 325 DEG C, and crystallization Heat of Formation is 17.5cal/g.
Embodiment 2
The preparation method of low molecular weight tetrafluoro ethylene resin, concrete grammar is as follows:
(1) in the 25L reactor with agitator, add the paraffin stablizer of 14kg deionized water and 1.4kg, closed reactor, vacuumizes and replaces to the emulsifying agent CF that adds again 0.6kg after oxygen level is less than 20ppm with High Purity Nitrogen
3cF
2oCF (CF
3) CF
2oCONH
4;
(2) adding in advance polytetrafluoroethyl-ne alkene monomer to reactor pressure is 0.5MPa, under the rotating speed of 450r/min, reactor is warming up to after 70 DEG C, add again polytetrafluoroethyl-ne alkene monomer in the time that pressure is 1.0MPa, to add the ammonium persulfate initiator of 0.28kg, start polyreaction, maintaining temperature of reaction is 100 DEG C, and reaction pressure is termination reaction after 1.0MPa successive reaction 50min;
(3) reclaim tetrafluoroethylene monomer, obtaining microemulsion particle diameter is the PTFE polymerized emulsion of 100nm, and its PTFE solids content is 25%, after cohesion emulsion, washing, oven dry, obtains the teflon resin that fine powder particle diameter is 8 μ m, fusing point is 325.5 DEG C, and crystallization Heat of Formation is 15.8cal/g.
Embodiment 3
The preparation method of low molecular weight tetrafluoro ethylene resin, concrete grammar is as follows:
(1) in the 25L reactor with agitator, add the deionized water of 14kg and the paraffin stablizer of 0.42kg, closed reactor, vacuumizes and replaces to the emulsifying agent C that adds again 0.42kg after oxygen level is less than 20ppm with High Purity Nitrogen
2f
5oC
2f
4oCF
2cOONa;
(2) adding in advance polytetrafluoroethyl-ne alkene monomer to reactor pressure is 0.5MPa, under the rotating speed of 500r/min, reactor is warming up to after 70 DEG C, add again polytetrafluoroethyl-ne alkene monomer in the time that pressure is 2.0MPa, to add the ammonium persulfate initiator of 0.21kg, start polyreaction, maintaining temperature of reaction is 80 DEG C, and reaction pressure is termination reaction after 2.0MPa successive reaction 50min;
(3) reclaim tetrafluoroethylene monomer, obtaining microemulsion particle diameter is the PTFE polymerized emulsion of 70nm, and its PTFE solids content is 30%, after cohesion emulsion, washing, oven dry, obtains the teflon resin that fine powder particle diameter is 5 μ m, fusing point is 326.0 DEG C, and crystallization Heat of Formation is 17.8cal/g.
Embodiment 4
The preparation method of low molecular weight tetrafluoro ethylene resin, concrete grammar is as follows:
(1) in the 25L reactor with agitator, add the deionized water of 14kg and the paraffin stablizer of 0.7kg, closed reactor, vacuumizes and replaces to the emulsifying agent C that adds again 0.42kg after oxygen level is less than 20ppm with High Purity Nitrogen
2f
5oCF (CF
3) CF
2oCF (CF
3) CF
2oCF
2cF
2oCF
2cF
2cOONH
4;
(2) adding in advance polytetrafluoroethyl-ne alkene monomer to reactor pressure is 0.5MPa, under the rotating speed of 800r/min, reactor is warming up to after 70 DEG C, add again polytetrafluoroethyl-ne alkene monomer in the time that pressure is 2.5MPa, to add the ammonium persulfate initiator of 0.21kg, start polyreaction, maintaining temperature of reaction is 85 DEG C, and reaction pressure is termination reaction after 2.5MPa successive reaction 50min;
(3) reclaim tetrafluoroethylene monomer, obtaining microemulsion particle diameter is the PTFE polymerized emulsion of 70nm, and its PTFE solids content is 25%, after cohesion emulsion, washing, oven dry, obtains the teflon resin that fine powder particle diameter is 5 μ m, fusing point is 326.0 DEG C, and crystallization Heat of Formation is 15.4cal/g.
Embodiment 5
The preparation method of low molecular weight tetrafluoro ethylene resin, concrete grammar is as follows:
(1) in the 25L reactor with agitator, add the paraffin stablizer of 14kg deionized water and 0.98kg, closed reactor, vacuumizes and replaces to the emulsifying agent C that adds again 0.35kg after oxygen level is less than 20ppm with High Purity Nitrogen
2f
5oC
2f
4oCOONH
4;
(2) adding in advance polytetrafluoroethyl-ne alkene monomer to reactor pressure is 0.5MPa, under the rotating speed of 600r/min, reactor is warming up to after 75 DEG C, add again polytetrafluoroethyl-ne alkene monomer in the time that pressure is 3.0MPa, to add the ammonium persulfate initiator of 0.14kg, start polyreaction, maintaining temperature of reaction is 90 DEG C, and reaction pressure is termination reaction after 3.0MPa successive reaction 60min;
(3) reclaim tetrafluoroethylene monomer, obtaining microemulsion particle diameter is the PTFE polymerized emulsion of 80nm, and its PTFE solids content is 35%, after cohesion emulsion, washing, oven dry, obtains the teflon resin that fine powder particle diameter is 10 μ m, fusing point is 325.6 DEG C, and crystallization Heat of Formation is 15.Ocal/g.
Embodiment 6
The preparation method of low molecular weight tetrafluoro ethylene resin, concrete grammar is as follows:
(1) in the 25L reactor with agitator, add the paraffin stablizer of 14kg deionized water and 1.05kg, closed reactor, vacuumizes and replaces to the emulsifying agent C that adds again 0.6kg after oxygen level is less than 20ppm with High Purity Nitrogen
2f
5oC
2f
4oC
2f
4oCOF;
(2) adding in advance polytetrafluoroethyl-ne alkene monomer to reactor pressure is 0.5MPa, under the rotating speed of 400r/min, reactor is warming up to after 75 DEG C, add again polytetrafluoroethyl-ne alkene monomer in the time that pressure is 1.5MPa, to add the ammonium persulfate initiator of 0.14kg, start polyreaction, maintaining temperature of reaction is 80 DEG C, and reaction pressure is termination reaction after 1.5MPa successive reaction 60min;
(3) reclaim tetrafluoroethylene monomer, obtaining microemulsion particle diameter is the PTFE polymerized emulsion of 80nm, and its PTFE solids content is 40%, after cohesion emulsion, washing, oven dry, obtains the teflon resin that fine powder particle diameter is 10 μ m, fusing point is 325.7 DEG C, and crystallization Heat of Formation is 16.8cal/g.
Claims (2)
1. a preparation method for low molecular weight tetrafluoro ethylene resin, is characterized in that comprising the following steps:
(1) in the reactor with agitator, add 14 parts by weight of deionized water, 0.28～1.4 weight part paraffin stablizer, closed reactor, vacuumize and replace to oxygen level and be less than after 20ppm with High Purity Nitrogen, suck 0.35～0.6 weight part perfluoro alkoxy carboxylate salt emulsifying agent, described perfluoro alkoxy carboxylate salt emulsifying agent is selected from C again
2f
5oC
2f
4oCF
2cOONa, C
2f
5oC
2f
4oCOONH
4in one;
(2) adding tetrafluoroethylene monomer to reactor pressure is 0.5MPa, open and stir, when reactor is warming up to after 70～75 DEG C, while adding again tetrafluoroethylene monomer to pressure to be 0.7～3.0MPa, add the ammonium persulfate initiator of 0.14～0.28 weight part, start polyreaction, maintaining temperature of reaction is 70～100 DEG C, reaction pressure is 0.7～3.0MPa, termination reaction after successive reaction 50～60min;
(3) reclaim tetrafluoroethylene monomer, obtaining microemulsion particle diameter is the tetrafluoroethylene polymerized emulsion of 20～100nm, described tetrafluoroethylene polymerized emulsion solid content is 30～40%, and after cohesion emulsion, washing, oven dry, obtaining particle diameter is the finely powdered teflon resin of 5～14 μ m.
2. the preparation method of a kind of low molecular weight tetrafluoro ethylene resin according to claim 1, is characterized in that the stirring velocity described in step (2) is 300～800r/min.
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| CN105315395A (en) * | 2015-10-22 | 2016-02-10 | 浙江巨圣氟化学有限公司 | Preparation method of high-performance suspension PTFE |
| CN105367692B (en) * | 2015-12-07 | 2017-11-24 | 上海三爱富新材料股份有限公司 | The preparation method of low molecular weight tetrafluoro ethylene resin |
| CN106243256B (en) * | 2016-08-05 | 2018-09-25 | 云南宏创新材料科技有限公司 | A kind of preparation method of nano-calcium carbonate/polytetrafluoroethylene (PTFE) composite polymer material |
| CN107459670A (en) * | 2017-08-22 | 2017-12-12 | 成都新柯力化工科技有限公司 | A kind of enhanced expandable microspheres foaming agent and preparation method for ASA plastic foaming |
| CN113844074A (en) * | 2021-08-23 | 2021-12-28 | 绍兴市科宏仪器有限公司 | Processing method of polytetrafluoroethylene reagent bottle |
| CN115124639B (en) * | 2022-08-19 | 2024-05-24 | 江西中氟化学材料科技股份有限公司 | Preparation method of low molecular weight polytetrafluoroethylene emulsion |
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| CN101215348A (en) * | 2007-12-29 | 2008-07-09 | 山东东岳高分子材料有限公司 | Polymerization method for low molecule polytetrafluoroethylene resin |
| CN101291987A (en) * | 2005-10-20 | 2008-10-22 | 旭硝子株式会社 | Aqueous polytetrafluoroethylene dispersion and product made from same |
| CN101998968A (en) * | 2008-04-14 | 2011-03-30 | 旭硝子株式会社 | Production method of polytetrafluoroethylene fine powder |
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| CN101291987A (en) * | 2005-10-20 | 2008-10-22 | 旭硝子株式会社 | Aqueous polytetrafluoroethylene dispersion and product made from same |
| CN101215348A (en) * | 2007-12-29 | 2008-07-09 | 山东东岳高分子材料有限公司 | Polymerization method for low molecule polytetrafluoroethylene resin |
| CN101998968A (en) * | 2008-04-14 | 2011-03-30 | 旭硝子株式会社 | Production method of polytetrafluoroethylene fine powder |
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