CN102336858B - A kind of ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin - Google Patents
A kind of ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 87
- 229920005989 resin Polymers 0.000 title claims abstract description 87
- 239000006185 dispersion Substances 0.000 title claims abstract description 68
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 45
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 22
- 239000011737 fluorine Substances 0.000 claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000005484 gravity Effects 0.000 claims abstract description 12
- 239000011164 primary particle Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000004698 Polyethylene Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VIBRUMXTFSYBCG-UHFFFAOYSA-N [F].C=CCCCC Chemical compound [F].C=CCCCC VIBRUMXTFSYBCG-UHFFFAOYSA-N 0.000 claims description 4
- DHJCMDIDXIUWQC-UHFFFAOYSA-N 8,8,8-trifluorooct-1-ene Chemical group FC(F)(F)CCCCCC=C DHJCMDIDXIUWQC-UHFFFAOYSA-N 0.000 claims description 3
- CRYGDJJVXSOLHR-UHFFFAOYSA-N C=CCCCCC.[F] Chemical compound C=CCCCCC.[F] CRYGDJJVXSOLHR-UHFFFAOYSA-N 0.000 claims description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 abstract description 3
- 238000003490 calendering Methods 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 21
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 14
- 239000012286 potassium permanganate Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000004513 sizing Methods 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 239000012982 microporous membrane Substances 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 210000004379 membrane Anatomy 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Abstract
A kind of ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin, by ultra-high purity tetrafluoroethylene monomer and special modified monomer, in autoclave, copolymerization forms dispersion emulsion, the size of primary particle is in 120 ~ 280 nanometers, after dry, the standard specific gravity SSG of resin is between 2.14 ~ 2.16, described modified polytetrafluoroethylresin resin modified monomer used is that a kind of fluorine-containing hydrogeneous monomer can have 2-10 carbon and have an insatiable hunger conjunction bond energy to carry out free-radical polymerized, and modified monomer consumption used accounts for 0.001% ~ 0.1% of the gross dry weight amount ratio of polytetrafluoroethyldispersion dispersion resin.Modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin cost provided by the invention is lower, and can be passed through paste and extrude, calendering, unidirectional or two-way stretch becomes the expanded PTFE having micropore, and its physical mechanical strength is as higher in tension stress etc., can be made into high strength microporous film for clothes and filter, fiber, sealing-ring, pad, tubing etc.
Description
Technical field
The present invention relates to a kind of ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin material
.
Background technology
Fluorine resin especially teflon resin is invented during World War II by du pont company the earliest.Because having excellent physical and mechanical properties and chemical stability, be obtained for widespread use in each fields such as chemical, mechano-electronic, space flight military project, novel material and new forms of energy.Adopted by polytetrafluoroethyldispersion dispersion resin paste to extrude and extrude and de-oiling, again through unidirectional or two-way stretch, the polytetrafluoroethylcellular cellular material according to there being micropore can be obtained, due to its property, this material has become a kind of high-end functional fluoropolymer material, such as, be used as filtering membrane, garment film, artificial organ, wire-insulating material and sealing material etc.
Expanded PTFE poromerics is because having excellent mechanical property, water-proof breathable properties, and chemical stability, and firm being used to once coming out of late nineteen seventies does wire cable insulating material, artificial blood vessel, seal strip, filtering membrane, and garment film.Industrial usual employing high purity tetrafluoroethylene monomer, carries out being polymerized or the dispersion polymerization processes of copolymerization prepares dispersion resin.Because polytetrafluoroethyldispersion dispersion resin can not carry out molten thermoplastic processing, but extrude by paste, extrude, de-oiling, more unidirectional or two-way stretch, becomes the excellent material with micro-porous.
Modified polytetrafluoroethyldispersion dispersion resin has instruction in U.S. Patent number 3819594 and 5756620, du pont company's modified monomer used is here perfluor (alkyl vinyl ether), as perfluor (propyl vinyl ether), and R 1216, but prepare the resin that obtains and cannot process and make expanded PTFE.Japanese Patent 26242/1981 instruction trifluorochloroethylene does modified polytetrafluoroethyldispersion dispersion resin, but its thermostability can not show a candle to the resin polytetrafluoroethyldispersion dispersion resin of not modification.Great Jing company of Japan also instructs the preparation method of modified polytetrafluoroethyldispersion dispersion resin in U.S. Patent number 4840998 and 5176958, and modified monomer wherein used has following structure: X-(CF
2)
noCF=CF
2and C
3f
7(OCF
2cF
2cF
2)
m(OCF (CF
3) CF
2)
loCF=CF
2; But these modified monomers used are too expensive.
Expanded PTFE adopts the patent No. to prepare for the preparation method disclosed in the United States Patent (USP) of US 3953566 and US 4187390 usually, this preparation method mainly comprises the following steps: by polytetrafluoroethyldispersion dispersion resin and kerosene blended after, paste is extruded, de-oiling, under tetrafluoroethylene fusing point, carry out unidirectional or two-way stretch again, obtain expanded PTFE microporous membrane.
The patent No. of great Jing company is the preparation method U.S. patents disclosing another kind of expanded PTFE microporous membrane of US 5234739, its be by polytetrafluoroethyldispersion dispersion resin and kerosene blended after, paste is extruded, de-oiling, sintering sizing is first carried out again more than tetrafluoroethylene fusing point, then below tetrafluoroethylene fusing point, carry out unidirectional or two-way stretch, obtain the microporous teflon membran of micropore multifilament.The aperture of the microporous membrane of the method gained is greater than 100 nanometers, how between 200 ~ 500 nanometers.
The patent No. is the preparation method U.S. patents disclosing another expanded PTFE microporous membrane of US 5814405: by polytetrafluoroethyldispersion dispersion resin and kerosene blended after, paste is extruded, de-oiling, longitudinal stretching is carried out again below tetrafluoroethylene fusing point, sintering sizing is first carried out again more than tetrafluoroethylene fusing point, then below tetrafluoroethylene fusing point, cross directional stretch is carried out, obtain the microporous teflon membran of micropore multifilament, the aperture of the microporous membrane of the method gained is greater than 200 nanometers, how at 1000 ran.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, a kind of preparation method of ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin is provided, the ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin obtained in this approach can be used for preparation high strength expanded PTFE poromerics, can meet the application that tensile strength is higher.
For solving above technical problem, the present invention takes following technical scheme:
A kind of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin, resin is by ultra-high purity tetrafluoroethylene and special modified monomer, in autoclave, copolymerization forms dispersion emulsion, the size of primary particle is in 120 ~ 280 nanometers, the standard specific gravity SSG of dry powder resin is between 2.14 ~ 2.16, melting point resin is between 325-350 degree, described modified Teflon modifying comonomer used is that not only fluorine-containing but also hydrogeneous monomer has 2-10 carbon and has an insatiable hunger to close bond energy and tetrafluoroethylene carries out free-radical polymerized, the consumption of modifying comonomer used accounts for 0.001% ~ 0.1% of the gross dry weight amount of polytetrafluoroethyldispersion dispersion resin.
A preparation method for modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin, the main raw material adopted in preparation process is ultra-high purity tetrafluoroethylene and modified monomer, and preparation process is as follows:
1., autoclave vacuumizes deoxygenation: in autoclave, add pure water, after reactor good seal, vacuumize deoxygenation, until oxygen level is lower than 30 ppm;
2., high pressure polymerisation reaction: pass into tetrafluoroethylene monomer in reactor and add a small amount of above-mentioned modified monomer, add a small amount of radical initiator and fluorine-containing dispersion agent, temperature of reaction controls between 20 ~ 130 DEG C, reaction pressure controls at 1 ~ 3 MPa, in 0.5 ~ 8 hour reaction times, obtain dispersion emulsion;
3., dispersion emulsion process: obtain modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin after the cohesion of obtained dispersion emulsion being dried.
Step 1. in, in autoclave, when adding pure water, also add low molecular weight polyethylene wax.
Described low molecular weight polyethylene wax fusing point is between 50 ~ 90 degree.
Step 2. in, described modified monomer is fluorine-containing monomer hydrogeneous again, has 2-10 carbon, and has insatiable hunger to close bond energy and tetrafluoroethylene carries out free-radical polymerized, and has following structure: R
1-CH=C(R
2) R
3, wherein R
1f or H or R
f; R
fit is the fluoroalkyl containing 1-8 carbon; R
2f or H; R
3f or H.
The consumption of modified monomer accounts for 0.002% ~ 0.08% of the gross weight of polytetrafluoroethyldispersion dispersion resin.
Described modified monomer, by vinyl fluoride, difluoroethylene, trifluoro-ethylene, 3,3,3-trifluoro propene, 3,3,4,4,4-five fluorine butylene, 3,3,4,4,5,5,5-seven fluorine amylene, 3,3,4,4,5,5,6,6,6-nine fluorine hexene, 3,3,4,4,5,5,6,6,7,7,7-11 fluorine heptene or 3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octene forms.
Step 2. in, described radical initiator is persulphate, the redox system of permanganate, or its miscellany, radical initiator consumption be account for total resin heavy 0.0001% ~ 0.01%.
Step 2. in, described fluorine-containing dispersion agent be fluorine-containing have 6 ~ 12 carbon carboxylic acid or sulfonate or its miscellany.The consumption of fluorine-containing dispersion agent be account for total resin heavy 0.05% ~ 1.0%.
Described its purity of ultra-high purity tetrafluoroethylene at least reaches 99.999%.
The modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin obtained by the present invention is compared with prior art had the following advantages: produced modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin cost is lower, and can be passed through paste and extrude, calendering, unidirectional or two-way stretch becomes the expanded PTFE having micropore, and its physical mechanical strength is as higher in tension stress etc., can be made into high strength microporous film for clothes and filter, fiber, sealing-ring, pad, tubing etc.
Gained dispersion emulsion solid content is 10 ~ 45%, and primary particle particle mean size is between 120 ~ 280 nanometers, and the resin after cohesion oven dry, its standard specific gravity is between 2.14 ~ 2.16, represents that the molecular weight of this resin is at least 10
7above.
Embodiment
Below in conjunction with specific embodiment, the present invention is further detailed explanation, but the invention is not restricted to these embodiments.
A is implemented in contrast
Substantially the embodiment one of the patent 5756620 li of du pont company is repeated:
Can lead in the autoclave of cold water/steam at horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed, still internal volume is about 36 liters, there are four blades, add 21 kilograms of deionized waters, 600 grams of paraffin (fusing point is about 56-58 degree), 1 gram of succinic acid, 0.5 gram of oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Reactor is sealed, rotating speed is raised to 65 rpm, in still, temperature rise is to after 65 degree, vacuumize deoxygenation, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, vacuumize deoxygenation again, logical tetrafluoroethylene, vacuumize deoxygenation again, until oxygen level < 25ppm in still, under micro-vacuum state, perfluor (propyl vinyl ether) modified monomer of 30 milliliters is sucked in still, then temperature rise in still to 80 degree, rotating speed is transferred to 70 rpm, the tetrafluoroethylene monomer about 1.7 kilograms of purity at least 99.999% is passed in still, still internal pressure reaches about 2.72 MPa, then the octarius that starts to use tricks squeezes into initiator in still: the potassium permanganate solution of 0.1 grams per liter water, squeeze into the speed of per minute 25 milliliters, the amount being equivalent to per minute 2.5 milligrams of potassium permanganate is squeezed into.After reaction starts, in still, tetrafluoroethylene monomer has pin to consume, tetrafluoroethylene monomer is passed into again in still, making still internal pressure maintain about 2.6-2.7 MPa. reacts after about 10 minutes, the tetrafluoroethylene monomer of 1.4 kilograms also passes in still again, at this moment using tricks, in still, squeeze into concentration be 27.5 grams of Perfluorocaprylic Acid ammonia/aqueous solution to octarius, squeeze into the speed of 50 ml/min, within 20 minutes, altogether squeeze into 1000 milliliters, pass in still Deng the tetrafluoroethylene monomer of 11.8 kilograms altogether, the amount of initiator changes 1 ml/min into, pass into after in still Deng the tetrafluoroethylene monomer of 15.4 kilograms altogether, cooling stops stirring, stopped reaction, about 108 minutes reaction times.The emulsion solid content obtained about 41%, primary particle particle mean size about 0.18 micron, modified monomer accounts for 0.097% of the total amount of dried resin, the standard specific gravity SSG=2.165 of dried resin.
Expanded PTFE stretching experiment: the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dried polytetrafluoroethyldispersion dispersion resin of the present embodiment gained with boiling point 180-200 DEG C is mixed mutually with the weight ratio of 100:18, gentle stir after be first pressed into cylinder in advance, at 30 DEG C, high pressure is extruded into paste rod again, and compression ratio is about 200:1.The de-oiling in the baking oven of 220 DEG C of this wet rod is obtained dry rod.This dry rod is carried out longitudinal stretching under the hot conditions of 250 DEG C: draw speed is when 10%/second, and rod is just pulled off once, the micropore bar of expanded PTFE cannot be obtained; Draw speed when 100%/second, rod move to about 50% elongation time be just pulled off, also cannot obtain the micropore bar of desirable expanded PTFE.So this modified polytetrafluoroethylresin resin cannot bring the materials application doing expanded PTFE.
Comparative example B
Ultra-high molecular weight tetrafluoroethylene homopolymer dispersion resin (not having modification):
Can lead in the autoclave of cold water/steam at horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed, still internal volume is about 36 liters, there are four blades, add 21 kilograms of deionized waters, 600 grams of paraffin (fusing point 56-58 degree), 1 gram of succinic acid, 0.5 gram of oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Reactor is sealed, rotating speed is raised to 65 rpm, in still, temperature rise is to after 65 degree, vacuumize deoxygenation, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, vacuumize deoxygenation again, logical tetrafluoroethylene, vacuumize deoxygenation again, until oxygen level < 25ppm in still, then temperature rise in still to 80 degree, rotating speed is transferred to 70 rpm, the tetrafluoroethylene monomer about 1.7 kilograms of purity at least 99.999% is passed in still, still internal pressure reaches about 2.72 MPa, then the octarius that starts to use tricks squeezes into initiator in still: the potassium permanganate solution of 0.1 grams per liter water, squeeze into the speed of per minute 20 milliliters, the amount being equivalent to per minute 2 milligrams of potassium permanganate is squeezed into.After reaction starts, in still, tetrafluoroethylene monomer has pin to consume, tetrafluoroethylene monomer is passed into again in still, making still internal pressure maintain about 2.6-2.7 MPa. reacts after about 15 minutes, the tetrafluoroethylene monomer of 1.5 kilograms also passes in still again, at this moment using tricks, in still, squeeze into concentration be 27.5 grams of Perfluorocaprylic Acid ammonia/aqueous solution to octarius, squeeze into the speed of 50 ml/min, within 20 minutes, altogether squeeze into 1000 milliliters, pass in still Deng the tetrafluoroethylene monomer of about 10 kilograms altogether, initiator stops squeezing in still, pass into after in still Deng the tetrafluoroethylene monomer of 12.5 kilograms altogether, cooling stops stirring, stopped reaction, about 128 minutes reaction times.The emulsion solid content obtained about 35%, primary particle particle mean size about 0.3 micron, the standard specific gravity SSG=2.168 of dried resin.
Expanded PTFE stretching experiment: the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dried polytetrafluoroethyldispersion dispersion resin of the present embodiment gained with boiling point 180-200 DEG C is mixed mutually with the weight ratio of 100:18, gentle stir after be first pressed into cylinder in advance, at 30 DEG C, high pressure is extruded into paste rod again, and compression ratio is about 200:1.The de-oiling in the baking oven of 220 DEG C of this wet rod is obtained dry rod.This dry rod is carried out longitudinal stretching under the hot conditions of 250 DEG C: draw speed, when 10%/second, can stretch 500%, obtain the micropore bar of expanded PTFE; Draw speed is when 100%/second, and also can stretch 500% elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained is shaped 30 seconds under 360 degree of high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after sizing is about 7 newton.So this ultra-high molecular weight polytetrafluoroethyl-ne polyamino alkenyl resin can bring the application doing expanded PTFE, but tensile strength is necessary to improve again.
Embodiment 1
Ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin:
The autoclave of cold water/steam can be led at horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed, still internal volume is about 36 liters, there are four blades, add 21 kilograms of deionized waters, 600 grams of low molecular weight polyethylene waxes (fusing point 56-58 degree), 1 gram of succinic acid, 0.5 gram of oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Reactor is sealed, rotating speed is raised to 65 rpm, in still, temperature rise is to after 65 degree, vacuumize deoxygenation, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, vacuumize deoxygenation again, logical tetrafluoroethylene, vacuumize deoxygenation again, until oxygen level < 25ppm in still, under micro-vacuum state, 5 grams 3 are sucked in still, 3, 4, 4, 4-five fluorine butylene, for modified monomer, then temperature rise in still to 80 degree, rotating speed is transferred to 70 rpm, the tetrafluoroethylene monomer about 1.7 kilograms of purity at least 99.999% is passed in still, still internal pressure reaches about 2.72 MPa, then the octarius that starts to use tricks squeezes into initiator in still: the potassium permanganate solution of 0.1 grams per liter water, squeeze into the speed of per minute 20 milliliters, the amount being equivalent to per minute 2 milligrams of potassium permanganate is squeezed into.After reaction starts, in still, tetrafluoroethylene monomer has pin to consume, tetrafluoroethylene monomer is passed into again in still, making still internal pressure maintain about 2.6-2.7 MPa. reacts after about 12 minutes, the tetrafluoroethylene monomer of 1.5 kilograms also passes in still again, at this moment using tricks, in still, squeeze into concentration be 27.5 grams of Perfluorocaprylic Acid ammonia/aqueous solution to octarius, squeeze into the speed of 50 ml/min, within 20 minutes, altogether squeeze into 1000 milliliters, pass into after in still Deng the tetrafluoroethylene monomer of about 7 kilograms altogether, initiator stops squeezing in still, pass into after in still Deng the tetrafluoroethylene monomer of 12.5 kilograms altogether, cooling stops stirring, stopped reaction, about 111 minutes reaction times.The emulsion solid content obtained about 35%, primary particle particle mean size about 0.19 micron (190 nanometer), modified monomer accounts for 0.042% of the total amount of dried resin, the standard specific gravity SSG=2.148 of dried resin.
Expanded PTFE stretching experiment: the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dried polytetrafluoroethyldispersion dispersion resin of the present embodiment gained with boiling point 180-200 DEG C is mixed mutually with the weight ratio of 100:18, gentle stir after be first pressed into cylinder in advance, at 30 DEG C, high pressure is extruded into paste rod again, and compression ratio is about 200:1.The de-oiling in the baking oven of 220 DEG C of this wet rod is obtained dry rod.This dry rod is carried out longitudinal stretching under the hot conditions of 250 DEG C: draw speed, when 10%/second, can stretch 500%, obtain the micropore bar of expanded PTFE; Draw speed is when 100%/second, and also can stretch 500% elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained is shaped 30 seconds under 360 degree of high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after sizing is about 14 newton.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can bring the application doing high strength expanded PTFE, its tensile strength can meet many high-end application.
Embodiment 2
Ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin:
Can lead in the autoclave of cold water/steam at horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed, still internal volume is about 36 liters, there are four blades, add 21 kilograms of deionized waters, 600 grams of low molecular weight polyethylene waxes (fusing point 56-58 degree), 1 gram of succinic acid, 0.5 gram of oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Reactor is sealed, rotating speed is raised to 65 rpm, in still, temperature rise is to after 65 degree, vacuumize deoxygenation, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, vacuumize deoxygenation again, logical tetrafluoroethylene, vacuumize deoxygenation again, until oxygen level < 25ppm in still, under micro-vacuum state, 0.5 gram 3 are sucked in still, 3, 4, 4, 5, 5, 5-seven fluorine amylene, for modified monomer, then temperature rise in still to 80 degree, rotating speed is transferred to 70 rpm, the tetrafluoroethylene monomer about 1.7 kilograms of purity at least 99.999% is passed in still, still internal pressure reaches about 2.72 MPa, then the octarius that starts to use tricks squeezes into initiator in still: the potassium permanganate solution of 0.1 grams per liter water, squeeze into the speed of per minute 20 milliliters, the amount being equivalent to per minute 2 milligrams of potassium permanganate is squeezed into.After reaction starts, in still, tetrafluoroethylene monomer has pin to consume, tetrafluoroethylene monomer is passed into again in still, making still internal pressure maintain about 2.6-2.7 MPa. reacts after about 14 minutes, the tetrafluoroethylene monomer of 1.5 kilograms also passes in still again, at this moment using tricks, in still, squeeze into concentration be 27.5 grams of Perfluorocaprylic Acid ammonia/aqueous solution to octarius, squeeze into the speed of 50 ml/min, within 20 minutes, altogether squeeze into 1000 milliliters, pass in still Deng the tetrafluoroethylene monomer of about 7 kilograms altogether, initiator stops squeezing in still, pass into after in still Deng the tetrafluoroethylene monomer of 12 kilograms altogether, cooling stops stirring, stopped reaction, about 118 minutes reaction times.The emulsion solid content obtained about 33%, primary particle particle mean size about 0.25 micron (250 nanometer), modified monomer accounts for 0.004% of the total amount of dried resin, the standard specific gravity SSG=2.158 of dried resin.
Expanded PTFE stretching experiment: the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dried polytetrafluoroethyldispersion dispersion resin of the present embodiment gained with boiling point 180-200 DEG C is mixed mutually with the weight ratio of 100:18, gentle stir after be first pressed into cylinder in advance, at 30 DEG C, high pressure is extruded into paste rod again, and compression ratio is about 200:1.The de-oiling in the baking oven of 220 DEG C of this wet rod is obtained dry rod.This dry rod is carried out longitudinal stretching under the hot conditions of 250 DEG C: draw speed, when 10%/second, can stretch 500%, obtain the micropore bar of expanded PTFE; Draw speed is when 100%/second, and also can stretch 500% elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained is shaped 30 seconds under 360 degree of high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after sizing is about 14 newton.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can bring the application doing high strength expanded PTFE, its tensile strength can meet many high-end application.
Embodiment 3
Ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin:
Can lead in the autoclave of cold water/steam at horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed, still internal volume is about 36 liters, there are four blades, add 21 kilograms of deionized waters, 600 grams of low molecular weight polyethylene waxes (fusing point 56-58 degree), 1 gram of succinic acid, 0.5 gram of oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Reactor is sealed, rotating speed is raised to 65 rpm, in still, temperature rise is to after 65 degree, vacuumize deoxygenation, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, vacuumize deoxygenation again, logical tetrafluoroethylene, vacuumize deoxygenation again, until oxygen level < 25ppm in still, under micro-vacuum state, 12 grams 3 are sucked in still, 3, 4, 4, 5, 5, 6, 6, 6-nine fluorine hexene, for modified monomer, then temperature rise in still to 80 degree, rotating speed is transferred to 70 rpm, the tetrafluoroethylene monomer about 1.7 kilograms of purity at least 99.999% is passed in still, still internal pressure reaches about 2.72 MPa, then the octarius that starts to use tricks squeezes into initiator in still: the potassium permanganate solution of 0.1 grams per liter water, squeeze into the speed of per minute 20 milliliters, the amount being equivalent to per minute 2 milligrams of potassium permanganate is squeezed into.After reaction starts, in still, tetrafluoroethylene monomer has pin to consume, tetrafluoroethylene monomer is passed into again in still, making still internal pressure maintain about 2.6-2.7 MPa. reacts after about 11 minutes, the tetrafluoroethylene monomer of 1.5 kilograms also passes in still again, at this moment using tricks, in still, squeeze into concentration be 27.5 grams of Perfluorocaprylic Acid ammonia/aqueous solution to octarius, squeeze into the speed of 50 ml/min, within 20 minutes, altogether squeeze into 1000 milliliters, pass in still Deng the tetrafluoroethylene monomer of about 7 kilograms altogether, initiator stops squeezing in still, pass into after in still Deng the tetrafluoroethylene monomer of 12.8 kilograms altogether, cooling stops stirring, stopped reaction, about 111 minutes reaction times.The emulsion solid content obtained about 36%, primary particle particle mean size about 0.18 micron (180 nanometer), modified monomer accounts for 0.099% of the total amount of dried resin, the standard specific gravity SSG=2.14 of dried resin.
Expanded PTFE stretching experiment: the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dried polytetrafluoroethyldispersion dispersion resin of the present embodiment gained with boiling point 180-200 DEG C is mixed mutually with the weight ratio of 100:18, gentle stir after be first pressed into cylinder in advance, at 30 DEG C, high pressure is extruded into paste rod again, and compression ratio is about 200:1.The de-oiling in the baking oven of 220 DEG C of this wet rod is obtained dry rod.This dry rod is carried out longitudinal stretching under the hot conditions of 250 DEG C: draw speed, when 10%/second, can stretch 500%, obtain the micropore bar of expanded PTFE; Draw speed is when 100%/second, and also can stretch 500% elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained is shaped 30 seconds under 360 degree of high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after sizing is about 15 newton.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can bring the application doing high strength expanded PTFE, its tensile strength can meet many high-end application.
Embodiment 4
Ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin:
Can lead in the autoclave of cold water/steam at horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed, still internal volume is about 36 liters, there are four blades, add 21 kilograms of deionized waters, 600 grams of low molecular weight polyethylene waxes (fusing point 56-58 degree), 1 gram of succinic acid, 0.5 gram of oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Reactor is sealed, rotating speed is raised to 65 rpm, in still, temperature rise is to after 65 degree, vacuumize deoxygenation, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, vacuumize deoxygenation again, logical tetrafluoroethylene, vacuumize deoxygenation again, until oxygen level < 25ppm in still, under micro-vacuum state, 5 grams 3 are sucked in still, 3, 3-trifluoro propene, for modified monomer, then temperature rise in still to 80 degree, rotating speed is transferred to 70 rpm, the tetrafluoroethylene monomer about 1.7 kilograms of purity at least 99.999% is passed in still, still internal pressure reaches about 2.72 MPa, then the octarius that starts to use tricks squeezes into initiator in still: the potassium permanganate solution of 0.1 grams per liter water, squeeze into the speed of per minute 20 milliliters, the amount being equivalent to per minute 2 milligrams of potassium permanganate is squeezed into.After reaction starts, in still, tetrafluoroethylene monomer has pin to consume, tetrafluoroethylene monomer is passed into again in still, making still internal pressure maintain about 2.6-2.7 MPa. reacts after about 12 minutes, the tetrafluoroethylene monomer of 1.5 kilograms also passes in still again, at this moment using tricks, in still, squeeze into concentration be 27.5 grams of Perfluorocaprylic Acid ammonia/aqueous solution to octarius, squeeze into the speed of 50 ml/min, within 20 minutes, altogether squeeze into 1000 milliliters, pass in still Deng the tetrafluoroethylene monomer of about 7 kilograms altogether, initiator stops squeezing in still, pass into after in still Deng the tetrafluoroethylene monomer of 12.5 kilograms altogether, cooling stops stirring, stopped reaction, about 115 minutes reaction times.The emulsion solid content obtained about 35%, primary particle particle mean size about 0.20 micron (200 nanometer), modified monomer accounts for 0.043% of the total amount of dried resin, the standard specific gravity SSG=2.15 of dried resin.
Expanded PTFE stretching experiment: the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dried polytetrafluoroethyldispersion dispersion resin of the present embodiment gained with boiling point 180-200 DEG C is mixed mutually with the weight ratio of 100:18, gentle stir after be first pressed into cylinder in advance, at 30 DEG C, high pressure is extruded into paste rod again, and compression ratio is about 200:1.The de-oiling in the baking oven of 220 DEG C of this wet rod is obtained dry rod.This dry rod is carried out longitudinal stretching under the hot conditions of 250 DEG C: draw speed, when 10%/second, can stretch 500%, obtain the micropore bar of expanded PTFE; Draw speed is when 100%/second, and also can stretch 500% elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained is shaped 30 seconds under 360 degree of high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after sizing is about 13 newton.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin can bring the application doing high strength expanded PTFE, its tensile strength can meet many high-end application.
Embodiment 5
Ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin:
Can lead in the autoclave of cold water/steam at horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed, still internal volume is about 36 liters, there are four blades, add 21 kilograms of deionized waters, 600 grams of low molecular weight polyethylene waxes (fusing point 56-58 degree), 1 gram of succinic acid, 0.5 gram of oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Reactor is sealed, rotating speed is raised to 65 rpm, in still, temperature rise is to after 65 degree, vacuumize deoxygenation, reactor is boosted to normal pressure by logical tetrafluoroethylene monomer, vacuumize deoxygenation again, logical tetrafluoroethylene, vacuumize deoxygenation again, until oxygen level < 25ppm in still, under micro-vacuum state, 5 grams 1 is sucked in still, 2-difluoroethylene, for modified monomer, then temperature rise in still to 80 degree, rotating speed is transferred to 70 rpm, the tetrafluoroethylene monomer about 1.7 kilograms of purity at least 99.999% is passed in still, still internal pressure reaches about 2.72 MPa, then the octarius that starts to use tricks squeezes into initiator in still: the potassium permanganate solution of 0.1 grams per liter water, squeeze into the speed of per minute 20 milliliters, the amount being equivalent to per minute 2 milligrams of potassium permanganate is squeezed into.After reaction starts, in still, tetrafluoroethylene monomer has pin to consume, tetrafluoroethylene monomer is passed into again in still, making still internal pressure maintain about 2.6-2.7 MPa. reacts after about 15 minutes, the tetrafluoroethylene monomer of 1.5 kilograms also passes in still again, at this moment using tricks, in still, squeeze into concentration be 27.5 grams of Perfluorocaprylic Acid ammonia/aqueous solution to octarius, squeeze into the speed of 50 ml/min, within 20 minutes, altogether squeeze into 1000 milliliters, pass in still Deng the tetrafluoroethylene monomer of about 7 kilograms altogether, initiator stops squeezing in still, pass into after in still Deng the tetrafluoroethylene monomer of 12.5 kilograms altogether, cooling stops stirring, stopped reaction, about 122 minutes reaction times.The emulsion solid content obtained about 34%, primary particle particle mean size about 0.28 micron (280 nanometer), modified monomer accounts for 0.04% of the total amount of dried resin, the standard specific gravity SSG=2.16 of dried resin.
[0035]expanded PTFE stretching experiment: the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dried polytetrafluoroethyldispersion dispersion resin of the present embodiment gained with boiling point 180-200 DEG C is mixed mutually with the weight ratio of 100:18, gentle stir after be first pressed into cylinder in advance, at 30 DEG C, high pressure is extruded into paste rod again, and compression ratio is about 200:1.The de-oiling in the baking oven of 220 DEG C of this wet rod is obtained dry rod.This dry rod is carried out longitudinal stretching under the hot conditions of 250 DEG C: draw speed, when 10%/second, can stretch 500%, obtain the micropore bar of expanded PTFE; Draw speed is when 100%/second, and also can stretch 500% elongation, obtains the micropore bar of expanded PTFE, and the micropore bar of the expanded PTFE of gained is shaped 30 seconds under 360 degree of high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after sizing is about 12 newton.So this ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin also can bring the application doing high strength expanded PTFE, its tensile strength also can meet many high-end application.
Can be found out by embodiment 1-5 and Comparative Examples A-B, adopt ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin out made by the modified monomer recommended of present patent application, cost is lower, and making high strength expanded PTFE material can be brought, its tensile strength can meet many high-end application.
The lubricating oil that above embodiment adopts can adopt the analogous products of Exxon Mobile company of the U.S..
The testing method of the data foundation in above embodiment or the instrument adopted are respectively: emulsion primary particle granular size goes to calculate Average Particle Diameters with computer with after electron microscope (SEM) shooting.The solid content of emulsion calculates dry weight and weight in wet base ratio by weighting method.The mensuration of dried resin standard specific gravity SSG is according to ASTM D-4895 method.Tensile strength surveyed with tension intensity machine (Instron).
In above embodiment, modified monomer, also can adopt vinyl fluoride, difluoroethylene, trifluoro-ethylene, 3,3,3-trifluoro propene, 3,3,4,4,4-five fluorine butylene, 3,3,4,4,5,5,5-seven fluorine amylene, 3,3,4,4,5,5,6,6,6-nine fluorine hexene, 3,3,4,4,5,5,6,6,7,7,7-11 fluorine heptene or 3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octene.
In more than implementing, radical initiator is persulphate, the redox system of permanganate, or its miscellany.
In above embodiment, fluorine-containing dispersion agent be fluorine-containing have 6 ~ 12 carbon carboxylic acid or sulfonate or its miscellany.
Claims (5)
1. a ultrahigh-molecular-weight modified polytetrafluoroethyldispersion dispersion resin, it is characterized in that: resin at least reaches the tetrafluoroethylene of 99.999% and special modified monomer by purity, in autoclave, copolymerization forms dispersion emulsion, the size of primary particle is in 120 ~ 280 nanometers, the standard specific gravity SSG of dry powder resin is between 2.14 ~ 2.16, melting point resin is between 325-350 degree, and the molecular weight of resin is at least 10
7above, described special modified monomer has following structure R
1-CH=CH2, wherein R
1f or R
f, R
fbe the fluoroalkyl containing 1-8 carbon, the consumption of special modified monomer used accounts for the gross dry weight amount 0.001% ~ 0.1% of polytetrafluoroethyldispersion dispersion resin, and described resin is for the preparation of expanded PTFE poromerics.
2. modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 1, is characterized in that: described special modified monomer by vinyl fluoride, 3,3,3-trifluoro propene, 3,3,4,4,4-five fluorine butylene, 3,3,4,4,5,5,5-seven fluorine amylene, 3,3,4,4,5,5,6,6,6-nine fluorine hexene, 3,3,4,4,5,5,6,6,7,7,7-11 fluorine heptene or 3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octene forms.
3. prepare a method for modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin as claimed in claim 1, it is characterized in that: the main raw material adopted in preparation process is tetrafluoroethylene and the modified monomer that purity at least reaches 99.999%, and preparation process is as follows:
1., autoclave vacuumizes deoxygenation: in autoclave, add pure water, after reactor good seal, vacuumize deoxygenation, until oxygen level is lower than 30ppm;
2., high pressure polymerisation reaction: pass into tetrafluoroethylene monomer in reactor and add described modified monomer, add a small amount of radical initiator and fluorine-containing dispersion agent, temperature of reaction controls between 20 ~ 130 DEG C, and reaction pressure controls at 1 ~ 3MPa, in 0.5 ~ 8 hour reaction times, obtain dispersion emulsion;
3., dispersion emulsion process: obtain modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin after the cohesion of obtained dispersion emulsion being dried;
Step 1. in, in autoclave, when adding pure water, also add low molecular weight polyethylene wax;
Described low molecular weight polyethylene wax fusing point is between 50 ~ 90 degree.
4. the preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 3, it is characterized in that: step 2. in, described radical initiator is persulphate, the redox system of permanganate, or its miscellany, radical initiator consumption be account for total resin heavy 0.0001% ~ 0.01%.
5. the preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 3, is characterized in that: step 2. in, described fluorine-containing dispersion agent be fluorine-containing have 6 ~ 12 carbon carboxylic acid or sulfonate or its miscellany; The consumption of fluorine-containing dispersion agent be account for total resin heavy 0.05% ~ 1.0%.
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| CN106883337B (en) * | 2015-12-15 | 2019-10-01 | 浙江汉丞科技有限公司 | Dispersion resin can be copolymerized by the high molecular weight tetrafluoroethene of extruding |
| CN108297326B (en) * | 2018-02-05 | 2020-03-13 | 大连盛泰密封件有限公司 | Preparation method of soft polytetrafluoroethylene gasket |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756620A (en) * | 1995-11-15 | 1998-05-26 | E. I. Du Pont De Nemours And Company | Tetrafluoroethylene polymer for improved paste extrusion |
| CN1202179A (en) * | 1995-11-09 | 1998-12-16 | 大金工业株式会社 | Fine polytetrafluoroethylene powder and production and uses thereof |
| CN101076445A (en) * | 2003-12-17 | 2007-11-21 | 大金工业株式会社 | Fire-retardant composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1202179A (en) * | 1995-11-09 | 1998-12-16 | 大金工业株式会社 | Fine polytetrafluoroethylene powder and production and uses thereof |
| US5756620A (en) * | 1995-11-15 | 1998-05-26 | E. I. Du Pont De Nemours And Company | Tetrafluoroethylene polymer for improved paste extrusion |
| CN101076445A (en) * | 2003-12-17 | 2007-11-21 | 大金工业株式会社 | Fire-retardant composite material |
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