CN102336858A - Ultrahigh-molecular-weight modified polytetrafluoroethylene dispersion resin - Google Patents
Ultrahigh-molecular-weight modified polytetrafluoroethylene dispersion resin Download PDFInfo
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- CN102336858A CN102336858A CN2011101913155A CN201110191315A CN102336858A CN 102336858 A CN102336858 A CN 102336858A CN 2011101913155 A CN2011101913155 A CN 2011101913155A CN 201110191315 A CN201110191315 A CN 201110191315A CN 102336858 A CN102336858 A CN 102336858A
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- 239000011347 resin Substances 0.000 title claims abstract description 93
- 229920005989 resin Polymers 0.000 title claims abstract description 93
- 239000006185 dispersion Substances 0.000 title claims abstract description 76
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 49
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 49
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 35
- 239000011737 fluorine Substances 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000005484 gravity Effects 0.000 claims abstract description 12
- 239000011164 primary particle Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 25
- 239000004809 Teflon Substances 0.000 claims description 24
- 229920006362 Teflon® Polymers 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 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
- 239000012188 paraffin wax Substances 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
- VIBRUMXTFSYBCG-UHFFFAOYSA-N [F].C=CCCCC Chemical class [F].C=CCCCC VIBRUMXTFSYBCG-UHFFFAOYSA-N 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- DHJCMDIDXIUWQC-UHFFFAOYSA-N 8,8,8-trifluorooct-1-ene Chemical class FC(F)(F)CCCCCC=C DHJCMDIDXIUWQC-UHFFFAOYSA-N 0.000 claims description 4
- CRYGDJJVXSOLHR-UHFFFAOYSA-N C=CCCCCC.[F] Chemical compound C=CCCCCC.[F] CRYGDJJVXSOLHR-UHFFFAOYSA-N 0.000 claims description 4
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 4
- 235000003642 hunger Nutrition 0.000 claims description 4
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 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
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000007634 remodeling Methods 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000003490 calendering Methods 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 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
- 238000000034 method Methods 0.000 description 14
- 239000012286 potassium permanganate Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 238000013461 design Methods 0.000 description 6
- 239000012982 microporous membrane Substances 0.000 description 5
- 210000004379 membrane Anatomy 0.000 description 4
- 239000003350 kerosene 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
- 239000011810 insulating material Substances 0.000 description 2
- 239000012528 membrane 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
- 239000002473 artificial blood Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 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
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to ultrahigh-molecular-weight modified polytetrafluoroethylene dispersion resin. According to the invention, an ultrahigh-purity tetrafluoroethylene monomer and a special modifying monomer are copolymerized in a high-pressure reaction kettle to form a dispersion emulsion with primary particle size of 120-280 nm; the standard specific gravity (SSG) of the dried resin is 2.14-2.16; the modifying monomer for modifying polytetrafluoroethylene resin is a fluorine-containing hydrogen-containing monomer which has 2-10 carbon atoms and an unsaturated bond to carry out free radical copolymerization; and the use amount of the modifying monomer is 0.001-0.1% of the total dry weight of the polytetrafluoroethylene dispersion resin. The modified ultrahigh-molecular-weight polytetrafluoroethylene dispersion resin provided by the invention has lower cost, can be processed into microporous expanded polytetrafluoroethylene through paste extrusion, calendering, and unidirectional or biaxial drawing, has higher physical mechanical strength such as tensile stress and the like, can be made into high-strength microporous thin film for clothes and filtration, and also can be made into fibers, sealing rings, gaskets, pipes and the like.
Description
Technical field
The present invention relates to a kind of ultra-high molecular weight modified Teflon dispersion resin material
.
Background technology
Fluorine resin especially teflon resin is invented during World War II by du pont company the earliest.Because of having excellent physical and mechanical performance and chemicalstability, all obtained widespread use in each fields such as chemical, mechano-electronic, space flight military project, novel material and new forms of energy.Polytetrafluoroethyldispersion dispersion resin is adopted the paste extruding and extrudes also de-oiling; Pass through unidirectional or two-way stretch again; Can obtain according to the tetrafluoroethylene poromerics that micropore is arranged; Because its property, this material has become a kind of high-end functional fluoropolymer property material, for example as filtering membrane, clothes film, artificial organ, wire-insulating material and sealing material etc.
The expanded PTFE poromerics is because of having good mechanical property, water-proof breathable properties, and chemicalstability, and late nineteen seventies is firm to be used to do wire cable insulating material, artificial blood vessel, seal strip, filtering membrane, and clothes film once coming out.Usually adopt the high purity tetrafluoroethylene monomer in the industry, the dispersion polymerization processes of carrying out polymerization or copolymerization prepares dispersion resin.Because polytetrafluoroethyldispersion dispersion resin can not carry out molten thermoplastic processing, but can push through paste, extrude, de-oiling, unidirectional again or two-way stretch becomes and has little porous excellent material.
The modified Teflon dispersion resin all has instruction U.S. Patent number 3819594 and 5756620 li; The used here modified monomer of du pont company is perfluor (alkyl vinyl ether); Like perfluor (propyl vinyl ether); And R 1216, can't process and make expanded PTFE but prepare resulting resin.Japanese Patent 26242/1981 instruction is done the modified Teflon dispersion resin with trifluorochloroethylene, but its thermostability can not show a candle to not modified resins polytetrafluoroethyldispersion dispersion resin.The big capital company of Japan is in U.S. Patent number 4840998 and 5176958 li preparing methods that also instruct the modified Teflon dispersion resin, and wherein used modified monomer 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 used modified monomers are too expensive.
It is that the disclosed preparation method of USP of US 3953566 and US 4187390 prepares that expanded PTFE adopts the patent No. usually; This preparation method mainly may further comprise the steps: after polytetrafluoroethyldispersion dispersion resin and kerosene blend; Paste is extruded; Unidirectional or two-way stretch is carried out in de-oiling again under the tetrafluoroethylene fusing point, promptly get the expanded PTFE microporous membrane.
The patent No. of big capital company is the preparation method that the USP of US 5234739 discloses another kind of expanded PTFE microporous membrane; It is with after polytetrafluoroethyldispersion dispersion resin and the kerosene blend; Paste is extruded, and the sintering typing is carried out in de-oiling more earlier more than the tetrafluoroethylene fusing point; Below the tetrafluoroethylene fusing point, carry out unidirectional or two-way stretch then, obtain the microporous teflon membran of micropore multifilamentization.The aperture of the microporous membrane of this method gained is greater than 100 nanometers, how between 200 ~ 500 nanometers.
The patent No. is the preparation method that the USP of US 5814405 discloses another expanded PTFE microporous membrane: after polytetrafluoroethyldispersion dispersion resin and kerosene blend; Paste is extruded; Longitudinal stretching is carried out in de-oiling again below the tetrafluoroethylene fusing point, more than the tetrafluoroethylene fusing point, carry out the sintering typing more earlier; Below the tetrafluoroethylene fusing point, carry out cross directional stretch then; Obtained the microporous teflon membran of micropore multifilamentization, the aperture of the microporous membrane of this method gained is greater than 200 nanometers, how about 1000 nanometers.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes prior art; A kind of preparation method of ultra-high molecular weight modified Teflon dispersion resin is provided; The ultra-high molecular weight modified Teflon dispersion resin that obtains with this method can be used for preparing HS expanded PTFE poromerics, can satisfy the higher application of tensile strength.
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; Copolymerization forms dispersion emulsion in autoclave; The size of primary particle is in 120 ~ 280 nanometers, and the standard specific gravity SSG of dry powder resin is between 2.14 ~ 2.16, and melting point resin is between the 325-350 degree; The used modified copolymer monomer of said modified Teflon is that not only fluorine-containing but also hydrogenous monomer can have 2-10 carbon and have an insatiable hunger to close bond energy and tetrafluoroethylene carries out free machine copolymerization, the consumption of used remodeling comonomer account for polytetrafluoroethyldispersion dispersion resin the gross dry weight amount 0.001% ~ 0.1%.
A kind of preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin, the main raw material that is adopted in the preparation process is ultra-high purity tetrafluoroethylene and modified monomer, preparation process is following:
1., autoclave vacuumizes deoxygenation: in autoclave, add pure water, behind the reaction kettle good seal, vacuumize deoxygenation, be lower than 30 ppm up to oxygen level;
2., high pressure polymerisation reaction: feed tetrafluoroethylene monomer in the reaction kettle and add a spot of above-mentioned modified monomer; Add a small amount of radical initiator and fluorine-containing dispersion agent; Temperature of reaction is controlled between 20 ~ 130 ℃; Reaction pressure is controlled at 1 ~ 3 MPa, in 0.5 ~ 8 hour reaction times, obtains dispersion emulsion;
3., dispersion emulsion is handled: with obtaining the modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin after the resulting dispersion emulsion cohesion oven dry.
Step ①, in the autoclave, the purified water is also joined Stone Que.
Described paraffin is low molecular weight polyethylene wax, and fusing point is between 50 ~ 90 degree.
Step 2. in, described modified monomer is fluorine-containing hydrogenous again monomer, has 2-10 carbon, and has an insatiable hunger to close bond energy and tetrafluoroethylene carries out free machine copolymerization, and following structure: R is arranged
1-CH=C (R
2) R
3, R wherein
1Be F or H or R
f(contain fluoroalkyl 1-8 carbon can be arranged); R
2Be F or H; R
3Be F or H.
The consumption of modified monomer account for polytetrafluoroethyldispersion dispersion resin gross weight 0.002% ~ 0.08%.
Described modified monomer adopts 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 amylenes, 3,3,4,4,5,5,6; 6,6-nine fluorine hexenes, 3,3,4,4,5,5,6,6,7,7,7;-ten one fluorine heptene or 3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octenes.
Step 2. in, described radical initiator is a persulphate, the redox system of permanganate, or its miscellany, the radical initiator consumption be account for total resin heavy 0.0001% ~ 0.01%.
Step 2. in, said fluorine-containing dispersion agent is fluorine-containing carboxylic acid or sulphonate or its miscellany that 6 ~ 12 carbon are arranged.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 reaches 99.999% at least.
The modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin that obtains through the present invention compared with prior art has the following advantages: produced modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin cost is lower, and can pass through paste and extrude, calendering; Unidirectional or two-way stretch becomes the expanded PTFE that micropore is arranged, and its physical mechanical strength such as tension stress etc. are higher, can be made into high strength microporous film and supply clothes and filter usefulness; Fiber; Sealing-ring, pad, tubing etc.
Gained dispersion emulsion solid content is 10 ~ 45%, and primary particle particle mean size condenses the resin after drying between 120 ~ 280 nanometers, and its standard specific gravity is between 2.14 ~ 2.16, and the molecular weight of representing this resin is at least 10
7More than.
Embodiment
Below in conjunction with concrete embodiment the present invention is done further detailed explanation, but the invention is not restricted to these embodiment.
A is implemented in contrast
Basically repeat the embodiment one of 5756620 li of the patents of du pont company:
Can lead in the autoclave of cold water/steam in a horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed; The still internal volume is about 36 liters, and four blades are arranged, and adds 21 kilograms of deionized waters; 600 gram paraffin (the about 56-58 degree of fusing point); 1 gram Succinic Acid, 0.5 gram oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Seal reaction kettle, rotating speed is raised to 65 rpm, after temperature rise to 65 is spent in the still; Vacuumize deoxygenation, logical tetrafluoroethylene monomer boosts to normal pressure with reaction kettle, vacuumizes deoxygenation again; Logical tetrafluoroethylene vacuumizes deoxygenation, oxygen level < 25ppm in still again; Under the micro-vacuum state, suck 30 milliliters perfluor (propyl vinyl ether) modified monomer in the still, then temperature rise to 80 degree in the still; Rotating speed is transferred to 70 rpm, feeds about 1.7 kilograms of the tetrafluoroethylene monomer of purity at least 99.999% in the still, and the still internal pressure reaches about 2.72 MPa; The octarius that begins then to use tricks is squeezed into initiator in the still: the potassium permanganate solution of 0.1 grams per liter water, to squeeze into the speed of 25 milliliters of PMs, and the amount that is equivalent to 2.5 milligrams of potassium permanganate of PM is squeezed into.After the reaction beginning, tetrafluoroethylene monomer has the pin consumption in the still, feeds tetrafluoroethylene monomer in the still again; After making the still internal pressure maintain about 2.6-2.7 MPa. to react about 10 minutes, 1.4 kilograms tetrafluoroethylene monomer also feeds in the still again, and it is 27.5 gram Perfluorocaprylic Acid ammonia/>premium on currency solution that the octarius of at this moment using tricks is squeezed into concentration in the still; Speed with 50 ml/min is squeezed into, and squeezes into 1000 milliliters altogether in 20 minutes, and waiting altogether, 11.8 kilograms tetrafluoroethylene monomer feeds in the still; The amount of initiator changes 1 ml/min into, wait altogether 15.4 kilograms tetrafluoroethylene monomer to feed in the still after, cooling stops stirring; Stopped reaction, about 108 minutes of reaction times.The emulsion solid content that obtains is about 41%, about 0.18 micron of primary particle particle mean size, modified monomer account for dried resin total amount 0.097%, the standard specific gravity SSG=2.165 of dried resin.
Expanded PTFE stretching experiment: mix the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dry good polytetrafluoroethyldispersion dispersion resin of present embodiment gained mutually with the weight ratio of 100:18 with boiling point 180-200 ℃; The gentle first precompressed in back that stirs becomes cylinder; Be extruded into the paste rod at 30 ℃ of following high pressure again, compression ratio is about 200:1.The de-oiling in 220 ℃ baking oven of this wet rod is obtained dried rod.This dried rod is being carried out longitudinal stretching under 250 ℃ the hot conditions: draw speed is under the situation of 10%/second, and rod is once just broken, and can't obtain the micropore bar of expanded PTFE; Draw speed 100%/second situation under, just broken when rod is moved about 50% elongation to, also can't obtain the micropore bar of ideal expanded PTFE.So this modified polytetrafluoroethylresin resin can't be brought the material of doing expanded PTFE and use.
Comparative example B
Ultra-high molecular weight tetrafluoroethylene homopolymer dispersion resin (not having modification):
Can lead in the autoclave of cold water/steam in a horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed; The still internal volume is about 36 liters, and four blades are arranged, and adds 21 kilograms of deionized waters; 600 gram paraffin (fusing point 56-58 degree); 1 gram Succinic Acid, 0.5 gram oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Seal reaction kettle, rotating speed is raised to 65 rpm, behind temperature rise to 65 degree, vacuumizes deoxygenation in the still; Logical tetrafluoroethylene monomer boosts to normal pressure with reaction kettle, vacuumizes deoxygenation again, logical tetrafluoroethylene; Vacuumize deoxygenation again, < 25ppm is then temperature rise to 80 degree in the still for oxygen level in still; Rotating speed is transferred to 70 rpm, feeds about 1.7 kilograms of the tetrafluoroethylene monomer of purity at least 99.999% in the still, and the still internal pressure reaches about 2.72 MPa; The octarius that begins then to use tricks is squeezed into initiator in the still: the potassium permanganate solution of 0.1 grams per liter water, to squeeze into the speed of 20 milliliters of PMs, and the amount that is equivalent to 2 milligrams of potassium permanganate of PM is squeezed into.After the reaction beginning, tetrafluoroethylene monomer has the pin consumption in the still, feeds tetrafluoroethylene monomer in the still again; After making the still internal pressure maintain about 2.6-2.7 MPa. to react about 15 minutes, 1.5 kilograms tetrafluoroethylene monomer also feeds in the still again, and it is 27.5 gram Perfluorocaprylic Acid ammonia/>premium on currency solution that the octarius of at this moment using tricks is squeezed into concentration in the still; Speed with 50 ml/min is squeezed into, and squeezes into 1000 milliliters altogether in 20 minutes, waits about altogether 10 kilograms tetrafluoroethylene monomer to feed in the still; Initiator stops to squeeze in the still, wait altogether 12.5 kilograms tetrafluoroethylene monomer to feed in the still after, cooling stops stirring; Stopped reaction, about 128 minutes of reaction times.The emulsion solid content that obtains is about 35%, about 0.3 micron of primary particle particle mean size, the standard specific gravity SSG=2.168 of dried resin.
Expanded PTFE stretching experiment: mix the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dry good polytetrafluoroethyldispersion dispersion resin of present embodiment gained mutually with the weight ratio of 100:18 with boiling point 180-200 ℃; The gentle first precompressed in back that stirs becomes cylinder; Be extruded into the paste rod at 30 ℃ of following high pressure again, compression ratio is about 200:1.The de-oiling in 220 ℃ baking oven of this wet rod is obtained dried rod.This dried rod is being carried out longitudinal stretching under 250 ℃ the hot conditions: draw speed can stretch 500% under the situation of 10%/second, obtain the micropore bar of expanded PTFE; Draw speed 100%/second situation under, 500% elongation that also can stretch obtains the micropore bar of expanded PTFE, the micropore bar of the expanded PTFE of gained was finalized the design 30 seconds down at 360 degree high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after the process typing is about 7 newton.So this ultra-high molecular weight polytetrafluoroethyl-ne polyamino alkenyl resin can be brought the application of doing expanded PTFE, but tensile strength is necessary to improve again.
Embodiment 1
Ultra-high molecular weight modified Teflon dispersion resin:
The autoclave that can lead to cold water/steam in a horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed; The still internal volume is about 36 liters, and four blades are arranged, and adds 21 kilograms of deionized waters; 600 gram paraffin (fusing point 56-58 degree); 1 gram Succinic Acid, 0.5 gram oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Seal reaction kettle, rotating speed is raised to 65 rpm, behind temperature rise to 65 degree, vacuumizes deoxygenation in the still; Logical tetrafluoroethylene monomer boosts to normal pressure with reaction kettle, vacuumizes deoxygenation again, and logical tetrafluoroethylene vacuumizes deoxygenation again; < 25ppm under the micro-vacuum state, sucks 3,3 of 5 grams to oxygen level in still in the still; 4,4,4-five fluorine butylene are modified monomer; Temperature rise to 80 degree in the still, rotating speed is transferred to 70 rpm then, about 1.7 kilograms of the tetrafluoroethylene monomer of feeding purity at least 99.999% in the still, and the still internal pressure reaches about 2.72 MPa; The octarius that begins then to use tricks is squeezed into initiator in the still: the potassium permanganate solution of 0.1 grams per liter water, to squeeze into the speed of 20 milliliters of PMs, and the amount that is equivalent to 2 milligrams of potassium permanganate of PM is squeezed into.After the reaction beginning, tetrafluoroethylene monomer has the pin consumption in the still, feeds tetrafluoroethylene monomer in the still again; After making the still internal pressure maintain about 2.6-2.7 MPa. to react about 12 minutes, 1.5 kilograms tetrafluoroethylene monomer also feeds in the still again, and it is 27.5 gram Perfluorocaprylic Acid ammonia/>premium on currency solution that the octarius of at this moment using tricks is squeezed into concentration in the still; Speed with 50 ml/min is squeezed into, and squeezes into 1000 milliliters altogether in 20 minutes, wait about altogether 7 kilograms tetrafluoroethylene monomer to feed in the still after; Initiator stops to squeeze in the still, wait altogether 12.5 kilograms tetrafluoroethylene monomer to feed in the still after, cooling stops stirring; Stopped reaction, about 111 minutes of reaction times.The emulsion solid content that obtains is about 35%, about 0.19 micron of primary particle particle mean size (190 nanometer), modified monomer account for dried resin total amount 0.042%, the standard specific gravity SSG=2.148 of dried resin.
Expanded PTFE stretching experiment: mix the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dry good polytetrafluoroethyldispersion dispersion resin of present embodiment gained mutually with the weight ratio of 100:18 with boiling point 180-200 ℃; The gentle first precompressed in back that stirs becomes cylinder; Be extruded into the paste rod at 30 ℃ of following high pressure again, compression ratio is about 200:1.The de-oiling in 220 ℃ baking oven of this wet rod is obtained dried rod.This dried rod is being carried out longitudinal stretching under 250 ℃ the hot conditions: draw speed can stretch 500% under the situation of 10%/second, obtain the micropore bar of expanded PTFE; Draw speed 100%/second situation under, 500% elongation that also can stretch obtains the micropore bar of expanded PTFE, the micropore bar of the expanded PTFE of gained was finalized the design 30 seconds down at 360 degree high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after the process typing is about 14 newton.So this ultra-high molecular weight modified Teflon dispersion resin can be brought the application of doing the HS expanded PTFE, its tensile strength can satisfy many high-end application.
Embodiment 2
Ultra-high molecular weight modified Teflon dispersion resin:
Can lead in the autoclave of cold water/steam in a horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed; The still internal volume is about 36 liters, and four blades are arranged, and adds 21 kilograms of deionized waters; 600 gram paraffin (fusing point 56-58 degree); 1 gram Succinic Acid, 0.5 gram oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Seal reaction kettle, rotating speed is raised to 65 rpm, behind temperature rise to 65 degree, vacuumizes deoxygenation in the still, and logical tetrafluoroethylene monomer boosts to normal pressure with reaction kettle; Vacuumize deoxygenation again, logical tetrafluoroethylene vacuumizes deoxygenation, oxygen level < 25ppm in still again; Under the micro-vacuum state, suck 3,3,4 of 0.5 gram in the still; 4,5,5,5-seven fluorine amylenes; Be modified monomer, temperature rise to 80 degree in the still, rotating speed is transferred to 70 rpm then, about 1.7 kilograms of the tetrafluoroethylene monomer of feeding purity at least 99.999% in the still; The still internal pressure reaches about 2.72 MPa, and the octarius that begins then to use tricks is squeezed into initiator in the still: the potassium permanganate solution of 0.1 grams per liter water, to squeeze into the speed of 20 milliliters of PMs, and the amount that is equivalent to 2 milligrams of potassium permanganate of PM is squeezed into.After the reaction beginning, tetrafluoroethylene monomer has the pin consumption in the still, feeds tetrafluoroethylene monomer in the still again; After making the still internal pressure maintain about 2.6-2.7 MPa. to react about 14 minutes, 1.5 kilograms tetrafluoroethylene monomer also feeds in the still again, and it is 27.5 gram Perfluorocaprylic Acid ammonia/>premium on currency solution that the octarius of at this moment using tricks is squeezed into concentration in the still; Speed with 50 ml/min is squeezed into, and squeezes into 1000 milliliters altogether in 20 minutes, waits about altogether 7 kilograms tetrafluoroethylene monomer to feed in the still; Initiator stops to squeeze in the still, wait altogether 12 kilograms tetrafluoroethylene monomer to feed in the still after, cooling stops stirring; Stopped reaction, about 118 minutes of reaction times.The emulsion solid content that obtains is about 33%, about 0.25 micron of primary particle particle mean size (250 nanometer), modified monomer account for dried resin total amount 0.004%, the standard specific gravity SSG=2.158 of dried resin.
Expanded PTFE stretching experiment: mix the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dry good polytetrafluoroethyldispersion dispersion resin of present embodiment gained mutually with the weight ratio of 100:18 with boiling point 180-200 ℃; The gentle first precompressed in back that stirs becomes cylinder; Be extruded into the paste rod at 30 ℃ of following high pressure again, compression ratio is about 200:1.The de-oiling in 220 ℃ baking oven of this wet rod is obtained dried rod.This dried rod is being carried out longitudinal stretching under 250 ℃ the hot conditions: draw speed can stretch 500% under the situation of 10%/second, obtain the micropore bar of expanded PTFE; Draw speed 100%/second situation under, 500% elongation that also can stretch obtains the micropore bar of expanded PTFE, the micropore bar of the expanded PTFE of gained was finalized the design 30 seconds down at 360 degree high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after the process typing is about 14 newton.So this ultra-high molecular weight modified Teflon dispersion resin can be brought the application of doing the HS expanded PTFE, its tensile strength can satisfy many high-end application.
Embodiment 3
Ultra-high molecular weight modified Teflon dispersion resin:
Can lead in the autoclave of cold water/steam in a horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed; The still internal volume is about 36 liters, and four blades are arranged, and adds 21 kilograms of deionized waters; 600 gram paraffin (fusing point 56-58 degree); 1 gram Succinic Acid, 0.5 gram oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Seal reaction kettle, rotating speed is raised to 65 rpm, behind temperature rise to 65 degree, vacuumizes deoxygenation in the still, and logical tetrafluoroethylene monomer boosts to normal pressure with reaction kettle; Vacuumize deoxygenation again, logical tetrafluoroethylene vacuumizes deoxygenation again, and < 25ppm is under the micro-vacuum state for oxygen level in still; Suck 3,3,4,4,5 of 12 grams in the still; 5,6,6,6-nine fluorine hexenes; Be modified monomer, temperature rise to 80 degree in the still, rotating speed is transferred to 70 rpm then, about 1.7 kilograms of the tetrafluoroethylene monomer of feeding purity at least 99.999% in the still; The still internal pressure reaches about 2.72 MPa, and the octarius that begins then to use tricks is squeezed into initiator in the still: the potassium permanganate solution of 0.1 grams per liter water, to squeeze into the speed of 20 milliliters of PMs, and the amount that is equivalent to 2 milligrams of potassium permanganate of PM is squeezed into.After the reaction beginning, tetrafluoroethylene monomer has the pin consumption in the still, feeds tetrafluoroethylene monomer in the still again; After making the still internal pressure maintain about 2.6-2.7 MPa. to react about 11 minutes, 1.5 kilograms tetrafluoroethylene monomer also feeds in the still again, and it is 27.5 gram Perfluorocaprylic Acid ammonia/>premium on currency solution that the octarius of at this moment using tricks is squeezed into concentration in the still; Speed with 50 ml/min is squeezed into, and squeezes into 1000 milliliters altogether in 20 minutes, waits about altogether 7 kilograms tetrafluoroethylene monomer to feed in the still; Initiator stops to squeeze in the still, wait altogether 12.8 kilograms tetrafluoroethylene monomer to feed in the still after, cooling stops stirring; Stopped reaction, about 111 minutes of reaction times.The emulsion solid content that obtains is about 36%, about 0.18 micron of primary particle particle mean size (180 nanometer), modified monomer account for dried resin total amount 0.099%, the standard specific gravity SSG=2.14 of dried resin.
Expanded PTFE stretching experiment: mix the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dry good polytetrafluoroethyldispersion dispersion resin of present embodiment gained mutually with the weight ratio of 100:18 with boiling point 180-200 ℃; The gentle first precompressed in back that stirs becomes cylinder; Be extruded into the paste rod at 30 ℃ of following high pressure again, compression ratio is about 200:1.The de-oiling in 220 ℃ baking oven of this wet rod is obtained dried rod.This dried rod is being carried out longitudinal stretching under 250 ℃ the hot conditions: draw speed can stretch 500% under the situation of 10%/second, obtain the micropore bar of expanded PTFE; Draw speed 100%/second situation under, 500% elongation that also can stretch obtains the micropore bar of expanded PTFE, the micropore bar of the expanded PTFE of gained was finalized the design 30 seconds down at 360 degree high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after the process typing is about 15 newton.So this ultra-high molecular weight modified Teflon dispersion resin can be brought the application of doing the HS expanded PTFE, its tensile strength can satisfy many high-end application.
Embodiment 4
Ultra-high molecular weight modified Teflon dispersion resin:
Can lead in the autoclave of cold water/steam in a horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed; The still internal volume is about 36 liters, and four blades are arranged, and adds 21 kilograms of deionized waters; 600 gram paraffin (fusing point 56-58 degree); 1 gram Succinic Acid, 0.5 gram oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Seal reaction kettle, rotating speed is raised to 65 rpm, behind temperature rise to 65 degree, vacuumizes deoxygenation in the still; Logical tetrafluoroethylene monomer boosts to normal pressure with reaction kettle, vacuumizes deoxygenation again, and logical tetrafluoroethylene vacuumizes deoxygenation again; < 25ppm under the micro-vacuum state, sucks 3,3 of 5 grams to oxygen level in still in the still; The 3-trifluoro propene is modified monomer, then temperature rise to 80 degree in the still; Rotating speed is transferred to 70 rpm, feeds about 1.7 kilograms of the tetrafluoroethylene monomer of purity at least 99.999% in the still, and the still internal pressure reaches about 2.72 MPa; The octarius that begins then to use tricks is squeezed into initiator in the still: the potassium permanganate solution of 0.1 grams per liter water, to squeeze into the speed of 20 milliliters of PMs, and the amount that is equivalent to 2 milligrams of potassium permanganate of PM is squeezed into.After the reaction beginning, tetrafluoroethylene monomer has the pin consumption in the still, feeds tetrafluoroethylene monomer in the still again; After making the still internal pressure maintain about 2.6-2.7 MPa. to react about 12 minutes, 1.5 kilograms tetrafluoroethylene monomer also feeds in the still again, and it is 27.5 gram Perfluorocaprylic Acid ammonia/>premium on currency solution that the octarius of at this moment using tricks is squeezed into concentration in the still; Speed with 50 ml/min is squeezed into, and squeezes into 1000 milliliters altogether in 20 minutes, waits about altogether 7 kilograms tetrafluoroethylene monomer to feed in the still; Initiator stops to squeeze in the still, wait altogether 12.5 kilograms tetrafluoroethylene monomer to feed in the still after, cooling stops stirring; Stopped reaction, about 115 minutes of reaction times.The emulsion solid content that obtains is about 35%, about 0.20 micron of primary particle particle mean size (200 nanometer), modified monomer account for dried resin total amount 0.043%, the standard specific gravity SSG=2.15 of dried resin.
Expanded PTFE stretching experiment: mix the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dry good polytetrafluoroethyldispersion dispersion resin of present embodiment gained mutually with the weight ratio of 100:18 with boiling point 180-200 ℃; The gentle first precompressed in back that stirs becomes cylinder; Be extruded into the paste rod at 30 ℃ of following high pressure again, compression ratio is about 200:1.The de-oiling in 220 ℃ baking oven of this wet rod is obtained dried rod.This dried rod is being carried out longitudinal stretching under 250 ℃ the hot conditions: draw speed can stretch 500% under the situation of 10%/second, obtain the micropore bar of expanded PTFE; Draw speed 100%/second situation under, 500% elongation that also can stretch obtains the micropore bar of expanded PTFE, the micropore bar of the expanded PTFE of gained was finalized the design 30 seconds down at 360 degree high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after the process typing is about 13 newton.So this ultra-high molecular weight modified Teflon dispersion resin can be brought the application of doing the HS expanded PTFE, its tensile strength can satisfy many high-end application.
Embodiment 5
Ultra-high molecular weight modified Teflon dispersion resin:
Can lead in the autoclave of cold water/steam in a horizontal garden column type (length-to-diameter ratio 1.5:1) jacketed; The still internal volume is about 36 liters, and four blades are arranged, and adds 21 kilograms of deionized waters; 600 gram paraffin (fusing point 56-58 degree); 1 gram Succinic Acid, 0.5 gram oxalic acid, the Perfluorocaprylic Acid ammonia soln of 25 ml concns 20%.Seal reaction kettle, rotating speed is raised to 65 rpm, behind temperature rise to 65 degree, vacuumizes deoxygenation in the still; Logical tetrafluoroethylene monomer boosts to normal pressure with reaction kettle, vacuumizes deoxygenation again, and logical tetrafluoroethylene vacuumizes deoxygenation again; < 25ppm under the micro-vacuum state, sucks 1 of 5 grams to oxygen level in still in the still; The 2-difluoroethylene is modified monomer, then temperature rise to 80 degree in the still; Rotating speed is transferred to 70 rpm, feeds about 1.7 kilograms of the tetrafluoroethylene monomer of purity at least 99.999% in the still, and the still internal pressure reaches about 2.72 MPa; The octarius that begins then to use tricks is squeezed into initiator in the still: the potassium permanganate solution of 0.1 grams per liter water, to squeeze into the speed of 20 milliliters of PMs, and the amount that is equivalent to 2 milligrams of potassium permanganate of PM is squeezed into.After the reaction beginning, tetrafluoroethylene monomer has the pin consumption in the still, feeds tetrafluoroethylene monomer in the still again; After making the still internal pressure maintain about 2.6-2.7 MPa. to react about 15 minutes, 1.5 kilograms tetrafluoroethylene monomer also feeds in the still again, and it is 27.5 gram Perfluorocaprylic Acid ammonia/>premium on currency solution that the octarius of at this moment using tricks is squeezed into concentration in the still; Speed with 50 ml/min is squeezed into, and squeezes into 1000 milliliters altogether in 20 minutes, waits about altogether 7 kilograms tetrafluoroethylene monomer to feed in the still; Initiator stops to squeeze in the still, wait altogether 12.5 kilograms tetrafluoroethylene monomer to feed in the still after, cooling stops stirring; Stopped reaction, about 122 minutes of reaction times.The emulsion solid content that obtains is about 34%, about 0.28 micron of primary particle particle mean size (280 nanometer), modified monomer account for dried resin total amount 0.04%, the standard specific gravity SSG=2.16 of dried resin.
Expanded PTFE stretching experiment: mix the U.S. Exxon Mobile senior lubricant (trade mark Isopar K) of the dry good polytetrafluoroethyldispersion dispersion resin of present embodiment gained mutually with the weight ratio of 100:18 with boiling point 180-200 ℃; The gentle first precompressed in back that stirs becomes cylinder; Be extruded into the paste rod at 30 ℃ of following high pressure again, compression ratio is about 200:1.The de-oiling in 220 ℃ baking oven of this wet rod is obtained dried rod.This dried rod is being carried out longitudinal stretching under 250 ℃ the hot conditions: draw speed can stretch 500% under the situation of 10%/second, obtain the micropore bar of expanded PTFE; Draw speed 100%/second situation under, 500% elongation that also can stretch obtains the micropore bar of expanded PTFE, the micropore bar of the expanded PTFE of gained was finalized the design 30 seconds down at 360 degree high temperature.The tensile strength of the micropore bar of the tetrafluoroethylene after the process typing is about 12 newton.So this ultra-high molecular weight modified Teflon dispersion resin also can be brought the application of doing the HS expanded PTFE, its tensile strength also can satisfy many high-end application.
Can find out by embodiment 1-5 and Comparative Examples A-B; The ultra-high molecular weight modified Teflon dispersion resin that the modified monomer made that adopts present patent application to recommend comes out; Cost is lower; And can bring and make HS expanded PTFE material, its tensile strength can satisfy many high-end application.
The lubricating oil that above embodiment adopted can adopt the analogous products of U.S. Exxon Mobile company.
The testing method of the data foundation among the above embodiment or the instrument that is adopted are respectively: emulsion primary particle particle size is to take the back with electron microscope (SEM) to go to calculate average size with computer.The solid content of emulsion is to calculate dry weight and weight in wet base ratio with weighting method.The mensuration of dried resin standard specific gravity SSG is according to ASTM D-4895 method.Tensile strength is to survey with tension intensity machine (Instron).
Among the 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 amylenes, 3,3,4,4,5,5,6; 6,6-nine fluorine hexenes, 3,3,4,4,5,5,6,6,7,7,7;-ten one fluorine heptene or 3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octenes.
In more than implementing, radical initiator is a persulphate, the redox system of permanganate, or its miscellany.
Among the above embodiment, fluorine-containing dispersion agent is fluorine-containing carboxylic acid or sulphonate or its miscellany that 6 ~ 12 carbon are arranged.
Claims (12)
1. ultra-high molecular weight modified Teflon dispersion resin; It is characterized in that: resin is by ultra-high purity tetrafluoroethylene and special modified monomer; Copolymerization forms dispersion emulsion in autoclave; The size of primary particle is in 120 ~ 280 nanometers, and the standard specific gravity SSG of dry powder resin is between 2.14 ~ 2.16, and melting point resin is between the 325-350 degree; The used modified copolymer monomer of said modified Teflon is that not only fluorine-containing but also hydrogenous monomer can have 2-10 carbon and have an insatiable hunger to close bond energy and tetrafluoroethylene carries out free machine copolymerization, the consumption of used remodeling comonomer account for polytetrafluoroethyldispersion dispersion resin the gross dry weight amount 0.001% ~ 0.1%.
2. the preparation method of a modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin, it is characterized in that: the main raw material that is adopted in the preparation process is ultra-high purity tetrafluoroethylene and modified monomer, and preparation process is following:
1., autoclave vacuumizes deoxygenation: in autoclave, add pure water, behind the reaction kettle good seal, vacuumize deoxygenation, be lower than 30 ppm up to oxygen level;
2., high pressure polymerisation reaction: feed tetrafluoroethylene monomer in the reaction kettle and add a spot of above-mentioned modified monomer; Add a small amount of radical initiator and fluorine-containing dispersion agent; Temperature of reaction is controlled between 20 ~ 130 ℃; Reaction pressure is controlled at 1 ~ 3 MPa, in 0.5 ~ 8 hour reaction times, obtains dispersion emulsion;
3., dispersion emulsion is handled: with obtaining the modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin after the resulting dispersion emulsion cohesion oven dry.
3 according to claim 2, wherein a modified high molecular weight PTFE dispersion resin preparation, characterized in that: step ① in the high pressure reaction kettle, purified water was added when adding graphite Que.
4. the preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 3 is characterized in that: described paraffin is low molecular weight polyethylene wax, and fusing point is between 50 ~ 90 degree.
5. the preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 2; It is characterized in that: step 2. in; Described modified monomer is fluorine-containing hydrogenous again monomer; Have 2-10 carbon, and have an insatiable hunger to close bond energy and tetrafluoroethylene carries out free machine copolymerization, and following structure: R is arranged
1-CH=C (R
2) R
3, R wherein
1Be F or H or R
f(contain fluoroalkyl 1-8 carbon can be arranged); R
2Be F or H; R
3Be F or H.
6. according to the preparation method of claim 2 or 5 described modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resins, it is characterized in that: the consumption of modified monomer account for polytetrafluoroethyldispersion dispersion resin gross weight 0.002% ~ 0.08%.
7. the preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 6 is characterized in that: described modified monomer, 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 amylenes, 3,3,4,4,5,5,6; 6,6-nine fluorine hexenes, 3,3,4,4,5,5,6,6,7,7,7;-ten one fluorine heptene or 3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octenes.
8. the preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 2; It is characterized in that: step 2. in; Described radical initiator is a persulphate; The redox system of permanganate, or its miscellany, radical initiator consumption be account for total resin heavy 0.0001% ~ 0.01%.
9. the preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 2 is characterized in that: step 2. in, said fluorine-containing dispersion agent is fluorine-containing carboxylic acid or sulphonate or its miscellany that 6 ~ 12 carbon are arranged; The consumption of fluorine-containing dispersion agent be account for total resin heavy 0.05% ~ 1.0%.
10. the preparation method of modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 2 is characterized in that: described its purity of ultra-high purity tetrafluoroethylene reaches 99.999% at least.
11. modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 1 is characterized in that: described special modified monomer has following structure: R
1-CH=C (R
2) R
3, R wherein
1Be F or H or R
f(contain fluoroalkyl 1-8 carbon can be arranged); R
2Be F or H; R
3Be F or H.
12. modified ultra-high molecular mass polytetrafluoroethyldispersion dispersion resin according to claim 1 is characterized in that: described special modified monomer, 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 amylenes, 3,3,4,4,5,5,6; 6,6-nine fluorine hexenes, 3,3,4,4,5,5,6,6,7,7,7;-ten one fluorine heptene or 3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octenes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632796A (en) * | 2015-12-15 | 2017-05-10 | 浙江汉丞科技有限公司 | Bulk micro-porous material for high molecular weight tetrafluoroethylene copolymerizing dispersion resin |
| CN106883337A (en) * | 2015-12-15 | 2017-06-23 | 浙江汉丞科技有限公司 | Can be by expanded HMW tetrafluoroethene copolymerization dispersion resin |
| CN108297326A (en) * | 2018-02-05 | 2018-07-20 | 大连盛泰密封件有限公司 | A kind of preparation method of soft teflon 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 |
-
2011
- 2011-07-08 CN CN201110191315.5A patent/CN102336858B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632796A (en) * | 2015-12-15 | 2017-05-10 | 浙江汉丞科技有限公司 | Bulk micro-porous material for high molecular weight tetrafluoroethylene copolymerizing dispersion resin |
| CN106883337A (en) * | 2015-12-15 | 2017-06-23 | 浙江汉丞科技有限公司 | Can be by expanded HMW tetrafluoroethene copolymerization dispersion resin |
| CN106632796B (en) * | 2015-12-15 | 2019-02-05 | 浙江汉丞科技有限公司 | The poromerics of varicosity high molecular weight tetrafluoroethene copolymerization dispersion resin |
| CN108297326A (en) * | 2018-02-05 | 2018-07-20 | 大连盛泰密封件有限公司 | A kind of preparation method of soft teflon gasket |
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