CN114106224A - Method for preparing PTFE (polytetrafluoroethylene) by suspension polymerization - Google Patents
Method for preparing PTFE (polytetrafluoroethylene) by suspension polymerization Download PDFInfo
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- CN114106224A CN114106224A CN202111362912.XA CN202111362912A CN114106224A CN 114106224 A CN114106224 A CN 114106224A CN 202111362912 A CN202111362912 A CN 202111362912A CN 114106224 A CN114106224 A CN 114106224A
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- suspension polymerization
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 64
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 41
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 41
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 24
- KQNSPSCVNXCGHK-UHFFFAOYSA-N [3-(4-tert-butylphenoxy)phenyl]methanamine Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1=CC=CC(CN)=C1 KQNSPSCVNXCGHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 115
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 30
- 229920000570 polyether Polymers 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 28
- 125000003342 alkenyl group Chemical group 0.000 claims description 26
- 239000002608 ionic liquid Substances 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 24
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229920002545 silicone oil Polymers 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002671 adjuvant Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000005048 methyldichlorosilane Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- VBDMVWQNRXVEGC-UHFFFAOYSA-N dichloro-methyl-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound C[Si](Cl)(Cl)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBDMVWQNRXVEGC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 22
- 229920005989 resin Polymers 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 13
- 239000000725 suspension Substances 0.000 abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 4
- 239000012498 ultrapure water Substances 0.000 abstract description 4
- 238000012824 chemical production Methods 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 abstract description 2
- 239000011164 primary particle Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004341 Octafluorocyclobutane Substances 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/26—Tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of chemical production, in particular to a method for preparing PTFE by suspension polymerization; the method for preparing PTFE by suspension polymerization uses high-purity water as a medium, primary polytetrafluoroethylene particles with small particle size are prepared by a suspension method, a small amount of emulsifier perfluorohexanoic acid is added into the primary particles, a synergist further enables the solution to be in a micro-emulsification phenomenon, and the obtained resin is small in molecular weight and proper in particle size and can be dried by airflow drying equipment. In addition, the residual quantity of the fluorine-containing emulsifier in the PTFE resin prepared by the method is less than 25ppb, and the residual quantity does not cause harm to the environment and human bodies.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a method for preparing PTFE (polytetrafluoroethylene) by suspension polymerization.
Background
The suspension process is to suspension polymerize tetrafluoroethylene in water medium and persulfate as initiator, and to prepare white powdered resin with excellent performance similar to that of polytetrafluoroethylene through crushing, grinding, washing and drying. The suspension resin has various grades with different particle sizes and different apparent densities, is respectively suitable for different processing and forming methods such as molding, hydraulic pressure, plunger extrusion and the like, and can be processed into various sections such as plates, rods, pipes and the like. It can also be made into insulating film, liner and various complex products by secondary processing.
CN201610716569.7 discloses a polytetrafluoroethylene suspension resin and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out suspension polymerization reaction on tetrafluoroethylene monomer under the action of a free radical initiator and a molecular weight promoter to obtain the tetrafluoroethylene monomer; wherein the molecular weight promoter is perfluorobutyl ethylene. The SSG range of the suspension resin produced by the method is 2.140-2.159, the average molecular weight range is 1012.2-1565.1 ten thousand, and the strength is excellent. The resin can be used for processing molded products with excellent, neat, smooth and high strength, and can be used in the application fields of mechanical equipment, building bridges, anticorrosive materials and the like.
CN201911074884.4 discloses a method for preparing tetrafluoroethylene homopolymerized resin by ultra-high molecular weight suspension method, in which high-purity water is used as reaction medium in a polymerization kettle after deoxygenation, tetrafluoroethylene is continuously charged for polymerization in the presence of pH regulator, initiator and molecular weight regulator, and the polymerization reaction adopts constant pressure heating reaction. The suspension-method tetrafluoroethylene homopolymerization resin prepared by the method has the advantages that the number average molecular weight can reach more than 2000 ten thousand, the molecular weight distribution is narrow, the resin has excellent mechanical strength and high temperature resistance, the shrinkage after sintering is small, the shrinkage is uniform, and the suspension-method tetrafluoroethylene homopolymerization resin can be used for processing products such as films, sealing elements and the like with excellent characteristics of high strength, high temperature resistance, small shrinkage and the like.
The applicant's prior application, patent CN201510688758.3, relates to a process for the preparation of low molecular weight polytetrafluoroethylene resins comprising the steps of: adding high-purity water into a polymerization container, and deoxidizing the polymerization container by adopting a vacuum pumping and nitrogen filling mode; adding methanol into a polymerization container, introducing a tetrafluoroethylene monomer, adding succinyl peroxide to initiate polymerization reaction after the polymerization container reaches a reaction temperature T1 and a reaction pressure P1 at a stirring rotation speed of V1, adding a fluorine-containing emulsifier into the polymerization container at a stirring rotation speed of V2, and adding octafluorocyclobutane and ammonium persulfate into the reaction container after the polymerization container reaches a reaction temperature T2 and a reaction pressure T2; and washing and drying the reaction product to obtain the catalyst. The method solves the problems that the suspension float method in the prior art needs to crush the low molecular weight polytetrafluoroethylene particles for multiple times and the obtained resin has larger molecular weight.
The following technical problems exist:
the resin has small molecular weight and uneven particle size, the residual quantity of the fluorine-containing emulsifier in the obtained resin is high, and the residual quantity causes harm to the environment and human bodies.
Disclosure of Invention
The invention discloses a method for preparing PTFE (polytetrafluoroethylene) by suspension polymerization, belonging to the technical field of chemical production. The PTFE resin prepared by the method has small molecular weight and proper particle size, and meanwhile, the residual amount of the fluorine-containing emulsifier in the PTFE resin is less than 25ppb, so that the residual amount cannot cause harm to the environment and human bodies.
A method for preparing PTFE by suspension polymerization comprises the following operation steps:
(1) adding 2500 parts of 1500 and 2500 parts of deionized water into the polymerization kettle after the polymerization kettle is vacuumized;
(2) adding synergist 5 x 10 into the adjuvant tank-6-1*10-4Preparing; emulsifier 7 x 10-7-1*10-5Adding the mixture into a polymerization kettle after nitrogen purging and replacement, and taking an initiator 3 x 10 after the mixture is added into the polymerization kettle-6-10*10-6Adding the components into a polymerization kettle; introducing hot water into a jacket of the polymerization kettle through a jacket water inlet valve of the polymerization kettle to heat the polymerization kettle to 65-71 ℃; vacuumizing the polymerization kettle and replacing nitrogen for three times, pressurizing the polymerization kettle to 280-320kPa, and sampling to analyze the oxygen content in the polymerization kettle; after the oxygen content in the polymerization kettle is qualified, the polymerization kettle is decompressed to 130-150kPa, and an initiator is added into the polymerization kettle; pressurizing a tetrafluoroethylene storage tank to 1700-1800MPa, adding 550-800 parts of tetrafluoroethylene, and obtaining modified polytetrafluoroethylene polymer liquid after the reaction is finished; and carrying out vacuum concentration on the modified polytetrafluoroethylene monomer polymerization solution to obtain a modified polytetrafluoroethylene dispersion concentrated solution.
Further: the synergist is obtained by carrying out hydrosilylation reaction on polyether-based monomer, hydrofluoro silicone oil and alkenyl ionic liquid, and the preparation method comprises the following steps:
adding 15-30 parts of polyether-based monomer, 52-75 parts of hydrofluorosilicone oil, 0.1-0.5 part of chloroplatinic acid isopropanol solution and 0.5-2.7 parts of alkenyl ionic liquid into a reaction kettle according to the parts by mass, heating to 50-60 ℃, and stirring for 2-5 hours; thus obtaining the synergist.
Further, the polyether-based monomer is allyl epoxy polyether.
Further, the hydrofluorosilicone oil is one of (1H,1H,2H, 2H-perfluorohexyl) methyldichlorosilane, (1H,1H,2H, 2H-perfluorooctyl) methyldichlorosilane, and (1H,1H,2H, 2H-perfluorodecyl) methyldichlorosilane.
Further, the mass percentage content of the chloroplatinic acid isopropanol solution is 5-10%.
Further, the cation of the alkenyl ionic liquid is imidazolium, quaternary ammonium salt or quaternary phosphonium salt, and the anion is at least one of halogen anion, carboxylate, nitrate and sulfate, and sulfimide.
Further, the cationic substituent on the alkenyl ionic liquid is at least one of methyl, ethyl, propyl, butyl, hexyl, octyl, hydroxyethyl, dihydroxypropyl and long-chain substituent containing hydroxyl and ether bond.
Further, the alkenyl ionic liquid is selected from 1-allyl-3-ethylimidazole bis (trifluoromethanesulfonyl) imide salt and 1-vinyl-3-hydroxyethyl imidazolium acrylate.
Further, the weight portion of the synergist is preferably 1-10-6-5*10-5And (4) portions are obtained.
Further, the emulsifier is preferably perfluorohexanoic acid.
Further, the mass fraction of the emulsifier is preferably 2 x 10-7-5*10-6And (4) portions are obtained.
Further, the initiator is preferably ammonium persulfate.
The reaction mechanism is as follows:
the tetrafluoroethylene monomer, the allyl epoxy polyether, the hydrofluoro silicone oil and the alkenyl ionic liquid are subjected to hydrosilylation reaction, so that the obtained silicon-containing polyether has an increased emulsifying effect, particle size dispersion of a polymer product is optimized to a certain extent, and mechanical strength and compressive capacity are improved.
The technical effects are as follows:
firstly, high-purity water is used as a medium, primary polytetrafluoroethylene particles with small particle size are prepared by a suspension method, a small amount of emulsifier perfluorohexanoic acid is added into the primary particles, a synergist is added to further enable the solution to be in a micro-emulsification phenomenon, and the obtained resin has small molecular weight and proper particle size and can be dried by airflow drying equipment. In addition, the residual quantity of the fluorine-containing emulsifier in the PTFE resin prepared by the method is less than 25ppb, and the residual quantity does not cause harm to the environment and human bodies.
Drawings
FIG. 1 is an SEM photograph of a PTFE sample prepared in example 3.
FIG. 2 is an infrared spectrum of a PTFE sample prepared in example 3.
Detailed Description
1. Tensile Strength and elongation Properties test
The test was carried out according to the test method for tensile Properties of plastics GB/T1040-92.
2. Particle size analysis
The PTFE resin prepared in the example was added to absolute ethanol and subjected to particle size analysis using a Mastersizer 3000 laser diffraction particle size analyzer.
DSC analysis
Under the condition of program control temperature, the power difference of the sample and the reference substance of the embodiment is measured and related to the temperature.
The invention is further illustrated by the following specific examples:
example 1
A method for preparing PTFE by suspension polymerization comprises the following operation steps:
(1) after the polymerization kettle is vacuumized, adding 1500kg of deionized water into the polymerization kettle;
(2) adding synergist 1 x 10 into the adjuvant tank-6kg; emulsifier 2 x 10-7kg, adding into a polymerization kettle after nitrogen purging and replacement, and taking an initiator 3 x 10 after adding into the polymerization kettle-6kg, adding into a polymerization kettle; introducing hot water into a jacket of the polymerization kettle through a jacket water inlet valve of the polymerization kettle to heat the polymerization kettle to 65 ℃; vacuumizing the polymerization kettle and replacing nitrogen for three times, pressurizing the polymerization kettle to 280kPa, and sampling to analyze the oxygen content in the polymerization kettle; after the oxygen content in the polymerization kettle is qualified, releasing the pressure of the polymerization kettle to 130kPa, and adding an initiator into the polymerization kettle; pressurizing a tetrafluoroethylene storage tank to 1800MPa, adding 550kg of tetrafluoroethylene, and obtaining modified polytetrafluoroethylene polymer liquid after the reaction is finished; and carrying out vacuum concentration on the modified polytetrafluoroethylene monomer polymerization solution to obtain a modified polytetrafluoroethylene dispersion concentrated solution.
The synergist is obtained by carrying out hydrosilylation reaction on polyether-based monomer, fluorosilicone oil and alkenyl ionic liquid, and the preparation method comprises the following steps:
adding 15kg of polyether-based monomer, 52kg of hydrofluorosilicone oil, 0.1kg of chloroplatinic acid isopropanol solution and 0.5kg of alkenyl ionic liquid into a reaction kettle, heating to 50 ℃, and stirring for 2 hours; thus obtaining a synergist;
the polyether-based monomer is allyl epoxy polyether;
the hydrofluoro silicone oil is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane;
the mass percentage content of the chloroplatinic acid isopropanol solution is 5%;
the alkenyl ionic liquid is 1-allyl-3-ethylimidazole bis (trifluoromethanesulfonyl) imide salt;
the emulsifier is perfluorohexanoic acid;
the initiator is ammonium persulfate.
Example 2
A method for preparing PTFE by suspension polymerization comprises the following operation steps:
(1) adding 1600kg of deionized water into the polymerization kettle after the polymerization kettle is vacuumized;
(2) adding synergist 1 x 10 into the adjuvant tank-5kg; emulsifier 1.5 x 10-6kg, adding into a polymerization kettle after nitrogen purging and replacement, and taking an initiator 2 x 10 after adding into the polymerization kettle-6kg, adding into a polymerization kettle; introducing hot water into a jacket of the polymerization kettle through a jacket water inlet valve of the polymerization kettle to heat the polymerization kettle to 67 ℃; vacuumizing the polymerization kettle and replacing nitrogen for three times, pressurizing the polymerization kettle to 290kPa, and sampling to analyze the oxygen content in the polymerization kettle; after the oxygen content in the polymerization kettle is qualified, releasing the pressure of the polymerization kettle to 135kPa, and adding an initiator into the polymerization kettle; pressurizing a tetrafluoroethylene storage tank to 1720MPa, adding 650kg of tetrafluoroethylene, and obtaining modified polytetrafluoroethylene polymer liquid after the reaction is finished; and carrying out vacuum concentration on the modified polytetrafluoroethylene monomer polymerization solution to obtain a modified polytetrafluoroethylene dispersion concentrated solution.
The synergist is obtained by carrying out hydrosilylation reaction on polyether-based monomer, hydrofluoro silicone oil and alkenyl ionic liquid, and the preparation method comprises the following steps:
adding 18kg of polyether-based monomer, 58kg of hydrofluorosilicone oil, 0.4kg of chloroplatinic acid isopropanol solution and 0.8kg of alkenyl ionic liquid into a reaction kettle, heating to 53 ℃, and stirring for 3 hours; thus obtaining a synergist;
the polyether-based monomer is allyl epoxy polyether;
the hydrofluoro silicone oil is (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane;
the mass percentage content of the chloroplatinic acid isopropanol solution is 6%;
the alkenyl ionic liquid is 1-vinyl-3-hydroxyethyl imidazolium acrylate;
the emulsifier is perfluorohexanoic acid;
the initiator is ammonium persulfate.
Example 3
A method for preparing PTFE by suspension polymerization comprises the following operation steps:
(1) after the polymerization kettle is vacuumized, 2000kg of deionized water is added into the polymerization kettle;
(2) adding synergist 3 x 10 into the adjuvant tank-5kg, emulsifier 2.5 x 10-6kg, adding into a polymerization kettle after nitrogen purging and replacement, and taking an initiator 6 x 10 after adding into the polymerization kettle-6kg, adding into a polymerization kettle; introducing hot water into a jacket of the polymerization kettle through a jacket water inlet valve of the polymerization kettle to heat the polymerization kettle to 68 ℃; vacuumizing the polymerization kettle and replacing nitrogen for three times, pressurizing the polymerization kettle to 300kPa, and sampling to analyze the oxygen content in the polymerization kettle; after the oxygen content in the polymerization kettle is qualified, releasing the pressure of the polymerization kettle to 140kPa, and adding an initiator into the polymerization kettle; pressurizing a tetrafluoroethylene storage tank to 1750MPa, adding 700kg of tetrafluoroethylene, and obtaining modified polytetrafluoroethylene polymer liquid after the reaction is finished; and carrying out vacuum concentration on the modified polytetrafluoroethylene monomer polymerization solution to obtain a modified polytetrafluoroethylene dispersion concentrated solution.
The synergist is obtained by carrying out hydrosilylation reaction on polyether-based monomer, hydrofluoro silicone oil and alkenyl ionic liquid, and the preparation method comprises the following steps:
adding 24kg of polyether-based monomer, 65kg of hydrofluorosilicone oil, 0.3kg of chloroplatinic acid isopropanol solution and 1.2kg of alkenyl ionic liquid into a reaction kettle, heating to 56 ℃, and stirring for 3 hours; thus obtaining a synergist;
the polyether-based monomer is allyl epoxy polyether;
the hydrofluoro silicone oil is (1H,1H,2H, 2H-perfluorodecyl) methyl dichlorosilane;
the mass percentage content of the chloroplatinic acid isopropanol solution is 7%;
the alkenyl ionic liquid is 1-allyl-3-ethylimidazole bis (trifluoromethanesulfonyl) imide salt;
the emulsifier is perfluorohexanoic acid;
the initiator is ammonium persulfate.
Example 4
A method for preparing PTFE by suspension polymerization comprises the following operation steps:
(1) after the polymerization kettle is vacuumized, 2200kg of deionized water is added into the polymerization kettle;
(2) adding synergist 4 x 10 into the adjuvant tank-5kg; emulsifier 4 x 10-6kg, adding into a polymerization kettle after nitrogen purging and replacement, and taking an initiator 8 x 10 after adding into the polymerization kettle-6kg, adding into a polymerization kettle; introducing hot water into a jacket of the polymerization kettle through a jacket water inlet valve of the polymerization kettle to heat the polymerization kettle to 69 ℃; vacuumizing the polymerization kettle and replacing nitrogen for three times, pressurizing the polymerization kettle to 320kPa, and sampling to analyze the oxygen content in the polymerization kettle; after the oxygen content in the polymerization kettle is qualified, releasing the pressure of the polymerization kettle to 150kPa, and adding an initiator into the polymerization kettle; pressurizing a tetrafluoroethylene storage tank to 1800MPa, adding 750kg of tetrafluoroethylene, and obtaining modified polytetrafluoroethylene polymer liquid after the reaction is finished; and carrying out vacuum concentration on the modified polytetrafluoroethylene monomer polymerization solution to obtain a modified polytetrafluoroethylene dispersion concentrated solution.
The synergist is obtained by carrying out hydrosilylation reaction on polyether-based monomer, hydrofluoro silicone oil and alkenyl ionic liquid, and the preparation method comprises the following steps:
adding 27kg of polyether-based monomer, 70kg of hydrofluorosilicone oil, 0.4kg of chloroplatinic acid isopropanol solution and 2.4kg of alkenyl ionic liquid into a reaction kettle, heating to 58 ℃, and stirring for 4 hours; thus obtaining a synergist;
the polyether-based monomer is allyl epoxy polyether;
the hydrofluoro silicone oil is (1H,1H,2H, 2H-perfluorodecyl) methyl dichlorosilane;
the mass percentage content of the chloroplatinic acid isopropanol solution is 8%;
the alkenyl ionic liquid is 1-allyl-3-ethylimidazole bis (trifluoromethanesulfonyl) imide salt;
the emulsifier is perfluorohexanoic acid;
the initiator is ammonium persulfate.
Example 5
(1) Adding 2500kg of deionized water into the polymerization kettle after the polymerization kettle is vacuumized;
(2) adding synergist 5 x 10 into the adjuvant tank-5kg; emulsifier 5 x 10-6kg, adding into a polymerization kettle after nitrogen purging and replacement, and taking 10 x 10 initiator after adding into the polymerization kettle-6kg, adding into a polymerization kettle; introducing hot water into a jacket of the polymerization kettle through a jacket water inlet valve of the polymerization kettle to heat the polymerization kettle to 71 ℃; vacuumizing the polymerization kettle and replacing nitrogen for three times, pressurizing the polymerization kettle to 320kPa, and sampling to analyze the oxygen content in the polymerization kettle; after the oxygen content in the polymerization kettle is qualified, releasing the pressure of the polymerization kettle to 150kPa, and adding an initiator into the polymerization kettle; pressurizing a tetrafluoroethylene storage tank to 1800MPa, adding 800kg of tetrafluoroethylene, and obtaining modified polytetrafluoroethylene polymer liquid after the reaction is finished; and carrying out vacuum concentration on the modified polytetrafluoroethylene monomer polymerization solution to obtain a modified polytetrafluoroethylene dispersion concentrated solution.
The synergist is obtained by carrying out hydrosilylation reaction on polyether-based monomer, hydrofluoro silicone oil and alkenyl ionic liquid, and the preparation method comprises the following steps:
adding 30kg of polyether-based monomer, 75kg of hydrofluorosilicone oil, 0.5kg of chloroplatinic acid isopropanol solution and 2.7kg of alkenyl ionic liquid into a reaction kettle, heating to 60 ℃, and stirring for 5 hours; thus obtaining a synergist;
the polyether-based monomer is allyl epoxy polyether;
the hydrofluoro silicone oil is (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane;
the mass percentage content of the chloroplatinic acid isopropanol solution is 10 percent;
the alkenyl ionic liquid is 1-vinyl-3-hydroxyethyl imidazolium acrylate;
the emulsifier is perfluorohexanoic acid;
the initiator is ammonium persulfate.
The results of the performance testing of all the above examples are shown in the following table:
the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained desirable results. As can be seen from the table, the method for preparing PTFE by suspension polymerization in the preferred embodiments 1 to 5 of the application can obtain the PTFE resin with small molecular weight and proper particle size, and can ensure the excellent mechanical properties of the PTFE resin. In addition, the residual amount of the fluorine-containing emulsifier in the method is less than 25ppb, and the residual amount does not cause harm to the environment and human bodies.
Claims (12)
1. A method for preparing PTFE by suspension polymerization comprises the following operation steps:
according to the weight portion of the components,
(1) adding 2500 parts of 1500 and 2500 parts of deionized water into the polymerization kettle after the polymerization kettle is vacuumized;
(2) adding synergist 5 x 10 into the adjuvant tank-6-1*10-4Preparing; emulsifier 7 x 10-7-1*10-5Adding the mixture into a polymerization kettle after nitrogen purging and replacement, and taking an initiator 3 x 10 after the mixture is added into the polymerization kettle-6-10*10-6Adding the components into a polymerization kettle; introducing hot water into a jacket of the polymerization kettle through a jacket water inlet valve of the polymerization kettle to heat the polymerization kettle to 65-71 ℃; vacuumizing the polymerization kettle and replacing nitrogen for three times, pressurizing the polymerization kettle to 280-320kPa, and sampling to analyze the oxygen content in the polymerization kettle;after the oxygen content in the polymerization kettle is qualified, the polymerization kettle is decompressed to 130-150kPa, and an initiator is added into the polymerization kettle; pressurizing a tetrafluoroethylene storage tank to 1700-1800MPa, adding 550-800 parts of tetrafluoroethylene, and obtaining modified polytetrafluoroethylene polymer liquid after the reaction is finished; and carrying out vacuum concentration on the modified polytetrafluoroethylene monomer polymerization solution to obtain a modified polytetrafluoroethylene dispersion concentrated solution.
2. A method of preparing PTFE by suspension polymerization according to claim 1, wherein: the synergist is obtained by carrying out hydrosilylation reaction on polyether-based monomer, hydrofluoro silicone oil and alkenyl ionic liquid, and the preparation method comprises the following steps:
adding 15-30 parts of polyether-based monomer, 52-75 parts of hydrofluorosilicone oil, 0.1-0.5 part of chloroplatinic acid isopropanol solution and 0.5-2.7 parts of alkenyl ionic liquid into a reaction kettle according to the parts by mass, heating to 50-60 ℃, and stirring for 2-5 hours; thus obtaining the synergist.
3. A method of preparing PTFE by suspension polymerization according to claim 2, wherein: the polyether-based monomer is allyl epoxy polyether.
4. A method of preparing PTFE by suspension polymerization according to claim 2, wherein: the hydrofluoro silicone oil is one of (1H,1H,2H, 2H-perfluorohexyl) methyldichlorosilane, (1H,1H,2H, 2H-perfluorooctyl) methyldichlorosilane and (1H,1H,2H, 2H-perfluorodecyl) methyldichlorosilane.
5. A method of preparing PTFE by suspension polymerization according to claim 2, wherein: the mass percentage content of the chloroplatinic acid isopropanol solution is 5-10%.
6. A method of preparing PTFE by suspension polymerization according to claim 2, wherein: the cation of the alkenyl ionic liquid is imidazolium, quaternary ammonium salt or quaternary phosphonium salt, and the anion is at least one of halogen anion, carboxylate radical, nitrate radical, sulfate radical and sulfimide.
7. A method of preparing PTFE by suspension polymerization according to claim 2, wherein: and the cationic substituent on the alkenyl ionic liquid is at least one of methyl, ethyl, propyl, butyl, hexyl, octyl, hydroxyethyl, dihydroxypropyl and long-chain substituent containing hydroxyl and ether bond.
8. A method of preparing PTFE by suspension polymerization according to claim 2, wherein: the alkenyl ionic liquid is selected from 1-allyl-3-ethylimidazole bis (trifluoromethanesulfonyl) imide salt and 1-vinyl-3-hydroxyethyl imidazolium acrylate.
9. A method of preparing PTFE by suspension polymerization according to claim 1, wherein: the synergist is preferably 1-10 parts by weight-6-5*10-5And (4) portions are obtained.
10. A method of preparing PTFE by suspension polymerization according to claim 1, wherein: the emulsifier is preferably perfluorohexanoic acid.
11. A method of preparing PTFE by suspension polymerization according to claim 1, wherein: the mass fraction of the emulsifier is preferably 2 x 10-7-5*10-6And (4) portions are obtained.
12. A method of preparing PTFE by suspension polymerization according to claim 1, wherein: the initiator is preferably ammonium persulfate.
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| CN105315395A (en) * | 2015-10-22 | 2016-02-10 | 浙江巨圣氟化学有限公司 | Preparation method of high-performance suspension PTFE |
| CN108339410A (en) * | 2018-03-08 | 2018-07-31 | 华东师范大学 | A kind of the three-dimensional structure nethike embrane and preparation method and application of poly ion liquid modification |
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| CN105315395A (en) * | 2015-10-22 | 2016-02-10 | 浙江巨圣氟化学有限公司 | Preparation method of high-performance suspension PTFE |
| CN108339410A (en) * | 2018-03-08 | 2018-07-31 | 华东师范大学 | A kind of the three-dimensional structure nethike embrane and preparation method and application of poly ion liquid modification |
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