CN103951772B - A kind of being applicable to is prepared without perfluoro caprylic acid or the method for the fluoropolymer of perfluorooctane sulfonate - Google Patents
A kind of being applicable to is prepared without perfluoro caprylic acid or the method for the fluoropolymer of perfluorooctane sulfonate Download PDFInfo
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- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 51
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 51
- SNGREZUHAYWORS-UHFFFAOYSA-N Perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N Perfluorooctanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 190
- 239000002253 acid Substances 0.000 claims abstract description 117
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 55
- 150000003839 salts Chemical class 0.000 claims abstract description 52
- 239000011780 sodium chloride Substances 0.000 claims abstract description 52
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- UUAGAQFQZIEFAH-UHFFFAOYSA-N Chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 24
- BFKJFAAPBSQJPD-UHFFFAOYSA-N Tetrafluoroethylene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 22
- -1 Alkoxyl ether Chemical compound 0.000 claims description 18
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- HCDGVLDPFQMKDK-UHFFFAOYSA-N Hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910006069 SO3H Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 239000000693 micelle Substances 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 55
- 229910052731 fluorine Inorganic materials 0.000 abstract description 35
- 239000011737 fluorine Substances 0.000 abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 32
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 239000000839 emulsion Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000003999 initiator Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000007792 addition Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229950000845 Politef Drugs 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 235000021050 feed intake Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000000977 initiatory Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- DAVCAHWKKDIRLY-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC=C DAVCAHWKKDIRLY-UHFFFAOYSA-N 0.000 description 3
- 210000004080 Milk Anatomy 0.000 description 3
- JGTNAGYHADQMCM-UHFFFAOYSA-N Perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N Tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000004059 degradation Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000001804 emulsifying Effects 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- CSJWOWRPMBXQLD-UHFFFAOYSA-N 1,2,3,3,3-pentafluoro-1-(1,2,3,3,3-pentafluoroprop-1-enoxy)prop-1-ene Chemical compound FC(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)F CSJWOWRPMBXQLD-UHFFFAOYSA-N 0.000 description 2
- 210000000481 Breast Anatomy 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 238000005039 chemical industry Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011031 large scale production Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 125000005739 1,1,2,2-tetrafluoroethanediyl group Chemical group FC(F)([*:1])C(F)(F)[*:2] 0.000 description 1
- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- ZPDGEIZOHMBIST-UHFFFAOYSA-N 2-ethenoxy-1,1,1,2,3,3,3-heptafluoropropane Chemical class FC(F)(F)C(F)(C(F)(F)F)OC=C ZPDGEIZOHMBIST-UHFFFAOYSA-N 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N Ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910016861 F9SO3 Inorganic materials 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N Fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N Hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 230000036740 Metabolism Effects 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N Peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000010192 crystallographic characterization Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000994 depressed Effects 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CTISCMCFPOFTKK-UHFFFAOYSA-N ethene;trifluoro-$l^{3}-chlorane Chemical group C=C.FCl(F)F CTISCMCFPOFTKK-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000035786 metabolism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000002110 toxicologic Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
Abstract
The invention discloses a kind of method being applicable to prepare the fluoropolymer not containing perfluoro caprylic acid or perfluorooctane sulfonate, described preparation method includes: carried out aqueous emulsion polymerization by one or more fluorinated monomers, and when aqueous emulsion polymerization using poly-polyfluoroalkoxy ether acid as emulsifying agent, the fluoropolymer that the present invention prepares is free from perfluoro caprylic acid or perfluorooctane sulfonate, and described poly-polyfluoroalkoxy ether acid is the poly-polyfluoroalkoxy ether acid emulsifying agent of end group band halogen or hydrogen.Its technical scheme has related generally to the improvement in terms of three below: (1) selects poly-polyfluoroalkoxy ether acid and salt replacement PFOA/ PFOS thereof as fluorine-containing emulsifier, can be effectively applied to the aqueous emulsion polymerization of fluorinated monomer；(2) fluoropolymer prepared is without perfluoro caprylic acid or perfluorooctane sulfonate, meets environmental requirement；(3) meet cost accounting, do not increasing manufacturing facilities and the output per single reactor of equipment can be greatly improved in the case of personnel, simultaneously, moreover it is possible to improving the production target such as polymerization time, polymerization yield rate.
Description
Technical field
The present invention relates to the synthesis field of fluoropolymer, specifically, be that one is applicable to preparation without perfluoro caprylic acid
Or the method for the fluoropolymer of perfluorooctane sulfonate.
Background technology
Fluoropolymer is the general name of the alkanes polymer that part hydrogen atom is replaced by fluorine atoms, and is also that a class is more special
Different macromolecular material, can be carried out polyreaction under certain condition and form by one or more fluorochemical monomers, high in its structure
The fluorine carbon bond of bond energy and the fluorine atom shielding action to strand so that it is there is a series of excellent characteristic, such as: excellent is resistance to
Chemical corrosivity, dielectric properties, against weather, non-stick, excellent frictional behaviour etc., certainly, due to the performance of its excellence, contain
It is indispensable that fluoropolymer has become multiple fields such as modern science and technology, national defence, electric, chemical industry, medicine and mechanical industry
One of material.
In the polymerization process of fluoropolymer, it usually needs add a certain amount of fluorine-containing emulsifier, in the field, I
Know that perfluorooctane sulfonate (PFOS) or its salt can be but the most beautiful as far back as calendar year 2001 as the fluorine-containing emulsifier in polyreaction
Environmental Protection Administration of state (EPA) proposes disabling decree, to this end, 3M company have developed perfluoro butyl sulfonic acid (PFBS) C the most specially4F9SO3H
The fluorocarbon chain replacing PFOS, PFBS is short, without obvious persistency biological accumulation, can discharge body with human metabolism in the short time
Outward, and it mediates thing nonhazardous, and its commodity prove safeguard functions and environmentally friendly through a large amount of tests, by EPA and the world its
His environmental protection mechanism is ratified.But showing according to latest data, existing the most frequently used fluorine-containing emulsifier is perfluoro caprylic acid and salt thereof, with it
Reaching its maturity of market, its safety and environmental-protecting performance also suffered query, 2006, EPA promulgated restriction decree, and this decree is recognized
Generate the chemicals of PFOA for perfluorooctanoic acid (PFOA) and some decomposable asymmetric choice net due to stability of its height and to be difficult to degrade
Characteristic, it is most likely that the major diseases such as cause cancer, to this end, both at home and abroad Ge great manufacturing enterprise is just devoted to study a kind of new
Compound, to substitute this kind of fluorine-containing emulsifier with high stability feature, improves fluoropolymer and uses process in each field
In safety coefficient, particularly at medicine etc. with the industry field of direct body contact, its security performance is even more important.
Disclosed as having that fluorine-containing emulsifier in polymerization process uses: PFPE (CN101218264B), ring-type
Fluorochemical (CN102089335A), replacement perfluoro caprylic acid and the fluorine-containing emulsifier (CN101745338A) of its esters, formula
XCF2CF2(O)MCF2CF2OCF2The fluorine-containing emulsifier (CN101287766, CN101291987) that COOA represents, above-mentioned fluorine-containing emulsifying
Agent the most alternative PFOA/ PFOS is for the emulsion polymerization of fluorinated monomer, and the water-based emulsion of its fluoropolymer is the most not
Show fluorine-containing octanoic acid or its salt adverse effect.
From above-mentioned patent documentation disclosure we it will also be appreciated that existing disclosed fluorine-containing emulsifier all has
Effect, although solve the Toxicological Characterization of fluorine-containing emulsifier, but be all not directed to productivity and the granularity of fluoropolymer etc. and produce
Product feature, as a example by above-mentioned patent of invention CN101218264B, in this patent documentation, give polymerization time, particle mean size,
The particle specific gravity of SSG(fluoropolymer), the correction data of solids content, in addition to polymerization time, remainder data is all without obvious ripple
Dynamic, although it follows that the existing fluorine-containing emulsifier related to without perfluoro caprylic acid solve PFOA/ PFOS high stability and
The harm that human body may be caused by difficult degradation characteristic, but whole production efficiency is not made any substantial improvement, meanwhile,
The fluorine-containing emulsifier related to due to foregoing invention patent CN101218264B is PFPE, it is known that PFPE is
Being made up of the such ether chain of CF2 O CF 2, in its molecule, all of H atom is all substituted by F atom, raw from industry
For product, large-scale production can not be realized, it is necessary to adding institute's band halogen on end group in preparation process is not the list of F
Body, as chain-transferring agent, could realize industrialized production, and production technology is the most numerous and diverse, and based on existing market competition
Being growing more intense, we must find a kind of new fluorine-containing emulsifier, the use of the most alternative PFOA/ PFOS, also may be used meanwhile
From properties of product, it is thus achieved that economic benefit long-term, effective.
Summary of the invention
It is an object of the invention to provide a kind of being applicable to prepare without perfluoro caprylic acid or the fluoropolymer of perfluorooctane sulfonate
The method of thing, the method is to be carried out aqueous emulsion polymerization by one or more fluorinated monomers, and when aqueous emulsion polymerization with poly-polyfluoro
Alkoxyl ether acid does not contains perfluoro caprylic acid or perfluor as emulsifying agent, the fluoropolymer that fluorinated monomer is prepared by homopolymerization or copolymerization
Pungent sulfonic acid, meets environmental requirement, can be widely applied to the safety coefficient such as kitchen tools, medicine and requires in higher field.
The present invention is achieved through the following technical solutions: a kind of be applicable to preparation containing without perfluoro caprylic acid or perfluorooctane sulfonate
The method of fluoropolymer, described preparation method includes: carried out aqueous emulsion polymerization by one or more fluorinated monomers, and at water and milk
It is selected from following one or several using poly-polyfluoroalkoxy ether acid as emulsifying agent, described poly-polyfluoroalkoxy ether acid during liquid polymerization
The combination planted:
Meet the poly-polyfluoroalkoxy ether acid of lower formula I:
(I),
Meet the poly-polyfluoroalkoxy ether acid of lower formula II:
(II),
Meet the poly-polyfluoroalkoxy ether acid of lower formula III:
(III),
Wherein:
T:、、、、；
X:H, Cl, Br, I；
R:H, Cl, Br, I；
Y:SO3H and salt, COOH and salt thereof, CH2CH2COOH and salt, CH2CH2SO3H and salt thereof,
COOCH2CH2COOH and salt, COOCH2CH2SO3H and salt thereof,And salt；And salt；
The value of n is: 0～4
The value of m is: 1～20
The value of p is: 0～4
The value of q is: 0～1
The fluoropolymer that the present invention prepares is free from perfluoro caprylic acid or perfluorooctane sulfonate.
From the general structure of above-mentioned poly-polyfluoroalkoxy ether acid, poly-polyfluoroalkoxy ether acid and its esters are in the environment
Do not produce stable carbon 8, be not belonging to the carbon atom straight chain perfluorocarbon saturated hydrocarbons homologue more than 8 yet, simultaneously as the drawing of ehter bond
Enter, also make its degradation property increase, therefore, will not persistently be present in environment, it is difficult to form biology savings property, thus to human body
Damage.
Further, described poly-polyfluoroalkoxy ether acid is the poly-polyfluoroalkoxy ether acid breast of end group band halogen or hydrogen
Agent.
In the present invention, use poly-polyfluoroalkoxy ether acid emulsifying agent substitute in existing fluoropolymer manufacture use most
PFOA/ PFOS is effective, shows: the performance indications of described poly-polyfluoroalkoxy ether acid emulsifying agent include:
Acid number (in terms of NaOH): < 150 mg/g；
Cross oxygen value: < 1.5 g/100g；
Boiling point: < 260 DEG C；
Surface tension: < 40mN/m；
Critical micelle concentration (CMC): < 5%.
Optimizing, the performance indications of described poly-polyfluoroalkoxy ether acid emulsifying agent farther include:
Acid number (in terms of NaOH): < 100mg/g；
Cross oxygen value: < 0.5g/100g；
Boiling point: < 160 DEG C；
Surface tension: < 20mN/m；
Critical micelle concentration (CMC): < 1.5 %.
In the art, the selection of fluorinated monomer can include following several situation:
(I) dividing by physical state, described fluorinated monomer can be gaseous fluorinated monomer or liquid fluorinated monomers two class,
It can also be the combination of the fluorinated monomer of gaseous state and liquid；
(II) pressing structural formula to divide, one or more described fluorinated monomers include the fluorine-containing list of end group band halogen or hydrogen
Body, or, one or more described fluorinated monomers include perfluorinated monomer.
The fluorochemical monomer that the present invention relates to include tetrafluoroethene, CTFE, vinylidene, fluorothene, hexafluoropropene,
One or more in perfluoroisopropyl vinyl ethers, perfluoroalkyl vinyl ether, hexafluoroethylene.
The present invention uses aqueous emulsion polymerization, it follows that in this aqueous emulsion polymerization, fluorinated monomer and conduct are poly-
Outside the emulsifying agent of polyfluoroalkoxy ether acid, the most also should include water and initiator, the selection of initiator is relatively simple, mainly has two
Class: inorganic peroxide (such as persulfate etc.), organic peroxide (alkyl peroxide etc.).
For preferably realizing the polyreaction of fluoropolymer, the amount of poly-polyfluoroalkoxy ether acid is also limited by the present invention
Fixed, as follows: described aqueous emulsion polymerization refers to that poly-polyfluoroalkoxy ether acid is as emulsifying agent and this aqueous emulsion polymerization
The weight proportion of middle water is (0.1～20): 100.
The aqueous emulsion polymerization of indication of the present invention can be homopolymerization, is i.e. polymerized by a kind of fluorinated monomer, polymerization and
The fluoropolymer become is homopolymer, such as:
(1) fluorinated monomer described in is politef, in the aqueous emulsion using poly-polyfluoroalkoxy ether acid as emulsifying agent
Polymerization system is polymerized, wherein, in poly-polyfluoroalkoxy ether acid and aqueous emulsion polymerization the weight ratio of water be (0.1～
0.45): 100.
(2) fluorinated monomer described in is polytrifluorochloroethylene, at the water and milk using poly-polyfluoroalkoxy ether acid as emulsifying agent
Being polymerized in liquid polymerization system, wherein, poly-polyfluoroalkoxy ether acid is (0.4 with the weight ratio of water in aqueous emulsion polymerization
～0.75): 100.
Same, the aqueous emulsion polymerization of indication of the present invention can also be copolyreaction, i.e. different by two or more
Fluorinated monomer is polymerized, and the fluoropolymer being polymerized is copolymer, such as:
(1) fluorinated monomer described in is vinylidene and CTFE, using poly-polyfluoroalkoxy ether acid as emulsifying
The aqueous emulsion polymerization of agent is polymerized, wherein, poly-polyfluoroalkoxy ether acid and the weight of water in aqueous emulsion polymerization
Than being (0.5～0.9): 100.
(2) fluorinated monomer described in is vinylidene, tetrafluoroethene and hexafluoropropene, with poly-polyfluoroalkoxy ether acid and
Its salt is polymerized as in the aqueous emulsion polymerization of emulsifying agent, wherein, and poly-polyfluoroalkoxy ether acid and salt thereof and aqueous emulsion
In polymerization system, the weight ratio of water is (0.1～0.35): 100.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) present invention is using poly-polyfluoroalkoxy ether acid and salt thereof as the emulsifying in fluoropolymer aqueous emulsion polymerization
Agent, can effectively replace existing fluorine-containing emulsifier such as: PFOA/ PFOS etc., environmental friendliness, this poly-polyfluoroalkoxy ether acid and
Its salt will not produce stable carbon 8 in the environment, is also not belonging to the homologue of the carbon atom straight chain perfluorocarbon saturated hydrocarbons more than 8,
Simultaneously as the introducing of ehter bond, more make its degradation property increase, be difficult to be enriched with in the environment, be suitably widely popularized use.
(2) present invention is by poly-polyfluoroalkoxy ether acid and salt thereof as emulsifying agent, one or more fluorinated monomers enter
Row aqueous emulsion polymerization, prepared fluoropolymer does not contains perfluoro caprylic acid or perfluorooctane sulfonate, meets environmental requirement, there is not biology
Accumulative and other toxicity, can be widely applied in the field that the requirement of the safety coefficient such as kitchen tools, medicine is higher.
(3) solid of the fluorinated monomer aqueous emulsion in the present invention, produced with this kind of poly-polyfluoroalkoxy ether acid and salt thereof
Content is high (calculated by mass), is not increasing manufacturing facilities and equipment output per single reactor can be greatly improved, such as in the case of personnel:
With the solids content (calculated by mass) of fluorinated monomer aqueous emulsion prepared by this kind of poly-polyfluoroalkoxy ether acid and salt thereof, Ke Yida
To 35%～60%, it it is the solid of the fluorinated monomer aqueous emulsion typically using perfluoroalkyl acid and salt thereof to produce as surfactant
2～3 times of content.
(4) enforcement of the present invention applies also for using the aqueous emulsion polymerization of fluorinated monomer of tradition fluorinated emulsifying agent
Equipment, effectively raises the cost benefit of this polyreaction, great market value.
(5) in the present invention, needed for the fluorinated monomer aqueous emulsion with this kind of poly-polyfluoroalkoxy ether acid and salt production thereof
Production time is short, and the production capacity of process units can be greatly improved, and reduces production cost, such as: use perfluoroalkyl acid and
Salt produces Kynoar as emulsifying agent, and the one-pot reaction time is generally 8～10 hours, as used this kind of poly-polyfluoroalkoxy
Ether acid acid and salt thereof are as producing the surfactant of Kynoar, and its one-pot reaction time can foreshorten to 4～6 hours.
(6) in the present invention, nano level fluorinated monomer water and milk can be produced with this kind of poly-polyfluoroalkoxy ether acid and salt thereof
Liquid, emulsion is light blue transparence.
(7) fluorinated monomer of super high molecular weight in the present invention, can be produced with this kind of poly-polyfluoroalkoxy ether acid and salt thereof
Aqueous emulsion and sub-material, the relative number average molecular weight of general fluorinated monomer polymer is more than 10*106。
Detailed description of the invention
Below the goal of the invention of the present invention, technical scheme and beneficial effect are described in further detail.
It it is noted that described further below is all exemplary, it is intended to the required present invention is provided further
Bright, except as otherwise noted, all technology used herein and scientific terminology have the common skill with the technical field of the invention
The identical meanings that art personnel are generally understood that.
U.S. Environmental Protection Agency (EPA) (EPA) has revealed that PFOA/ PFOS and salt thereof have that degradability is poor, be prone to enrichment etc. in environment
Characteristic, all can cause toxic hazard to environment and human body, but due to its special performance, PFOA/ PFOS is often used for producing
Processing aid indispensable during high-effect fluoropolymer, these dynamical fluoropolymers are widely used the most
In the people's livelihood articles for use such as science and technology of aviation, transport, electron trade and kitchen tools, long-term use, it is most likely that cause cancer etc. are great
Disease.Existing published patent documentation CN101218264B, CN102089335A, CN101745338A, CN101287766,
CN101291987 has disclosed the harm of above-mentioned PFOA/ PFOS, and wishes to find one can substitute PFOA/ PFOS, and conduct
The fluorine-containing emulsifier that surfactant during aqueous emulsion polymerization uses, these fluorine-containing emulsifiers such as: PFPE, ring-type containing fluorination
Compound, replacement perfluoro caprylic acid and the fluorine-containing emulsifier of its esters, general formula X CF2CF2(O)MCF2CF2OCF2The fluorine-containing breast that COOA represents
Agent can be used to the aqueous emulsion polymerization of fluorinated monomer, also show the biology lower than PFOA/ PFOS and salt thereof
Accumulation and environmental degradability, but further, it is intended that find a kind of more efficient implementation, it may be assumed that can not only substitute
The fluorine-containing emulsifier that PFOA/ PFOS uses as surfactant during aqueous emulsion polymerization, simultaneously, moreover it is possible to raising polymerization time,
The production targets such as polymerization yield rate, thus meet cost-benefit accounting.It is applicable to preparation does not contains to this end, present invention is disclosed one
The method of the fluoropolymer of perfluoro caprylic acid or perfluorooctane sulfonate, its technical scheme has related generally to changing in terms of three below
Enter:
(1) selecting poly-polyfluoroalkoxy ether acid (and salt) replacement PFOA/ PFOS as fluorine-containing emulsifier, energy is effective
It is applied to the aqueous emulsion polymerization of fluorinated monomer；
(2) fluoropolymer prepared is without perfluoro caprylic acid or perfluorooctane sulfonate, meets environmental requirement；
(3) meet cost accounting, do not increase manufacturing facilities and personnel in the case of can be greatly improved equipment one-pot produce
Amount, simultaneously, moreover it is possible to improve the production target such as polymerization time, polymerization yield rate.
The following is and technical solution of the present invention is further described:
Fluoropolymer involved in the present invention is in poly-polyfluoroalkoxy ether acid conduct by one or more fluorinated monomers
Obtaining after liquid phase polymerization in the case of emulsifying agent, wherein, poly-polyfluoroalkoxy ether acid is selected from the following group of one or more
Close:
Meet the poly-polyfluoroalkoxy ether acid of lower formula I:
(I),
Meet the poly-polyfluoroalkoxy ether acid of lower formula II:
(II),
Meet the poly-polyfluoroalkoxy ether acid of lower formula III:
(III),
Wherein:
T:、、、、；
X:H, Cl, Br, I；
R:H, Cl, Br, I；
Y:SO3H and salt, COOH and salt thereof, CH2CH2COOH and salt, CH2CH2SO3H and salt thereof,
COOCH2CH2COOH and salt, COOCH2CH2SO3H and salt thereof,And salt；And salt；
The value of n is: 0～4
The value of m is: 1～20
The value of p is: 0～4
The value of q is: 0～1
From the general structure of above-mentioned poly-polyfluoroalkoxy ether acid, the poly-polyfluoroalkoxy ether acid that the present invention relates to is permissible
It is the poly-polyfluoroalkoxy ether acid emulsifying agent of end group band halogen or hydrogen, with vinylidene, oxygen, tetrafluoroethene and hexafluoropropene
Mixing by a certain percentage, under 500W ultra-vioket radiation, holding system temperature is at 65 DEG C, anti-by photooxidation free poly tone
Should, the poly-polyfluoroalkoxy ether acid of end group band hydrogen can be obtained.Structural formula is as follows:
Wherein, the value of n is: 0～4；The value of m is: 1～20；The value of p is: 0～4；The value of q is: 0～1.
The most such as: mix with certain proportion with bromotrifluoroethylene, oxygen, tetrafluoroethene and hexafluoropropene, in 500W ultraviolet
Under light irradiation, keep system temperature at 65 DEG C, reacted by photooxidation free poly tone, the poly-many of end group band bromine can be obtained
Fluoroalkyloxy ether acid emulsifying agent.Structural formula is as follows:
Wherein, the value of n is: 0～4；The value of m is: 1～20；The value of p is: 0～4；The value of q is: 0～1.
It is pointed out that in the structural formula of end group band halogen or the poly-polyfluoroalkoxy ether acid emulsifying agent of hydrogen, when
When on end group, the halogen of band is all F, i.e. PFPE, for commercial production, large-scale production can not be realized, it is necessary to
Adding institute's band halogen on end group in preparation process is not the monomer of F, as chain-transferring agent, could realize industrialized production, raw
Production. art is the most numerous and diverse, therefore, and the end group band halogen that the present invention relates to or the poly-polyfluoroalkoxy ether acid emulsifying agent of hydrogen
Do not include PFPE emulsifying agent.
When reality is applied, owing to above-mentioned poly-polyfluoroalkoxy ether acid and its esters will not produce stable carbon in the environment
8, also it is not belonging to the homologue of the carbon atom straight chain perfluorocarbon saturated hydrocarbons more than 8, simultaneously as the introducing of ehter bond, also makes it drop
Solution performance increase, therefore, the most poly-polyfluoroalkoxy ether acid as fluorine-containing emulsifier for fluorinated monomer aqueous emulsion polymerization and
During the fluoropolymer prepared, this fluoropolymer does not contains perfluoro caprylic acid or perfluorooctane sulfonate, will not persistently be present in environment,
Also it is difficult to form biological savings property, can be widely applied to the safety coefficient such as kitchen tools, medicine and require in higher people's livelihood articles for use, will not
Human body is damaged.
On this basis, the performance indications of the above-mentioned poly-polyfluoroalkoxy ether acid emulsifying agent enumerated are measured by we,
As shown in table 1:
Table 1
The liquid-phase polymerization that the present invention relates to is the preparation method of the fluoropolymer of a kind of routine, in the present invention,
This liquid phase polymerization refers to aqueous emulsion polymerization, the aqueous emulsion polymerization in its polymerization process mainly have fluorinated monomer, initiator,
Water, four elements of emulsifying agent, it is known that, we have found a kind of new fluorine-containing emulsifier (that is: poly-polyfluoroalkoxy
Ether acid emulsifying agent) substitute PFOA/ PFOS, and the fluoropolymer prepared is without perfluoro caprylic acid or perfluorooctane sulfonate, certainly,
To better implement the present invention, we also need the proportioning to fluorochemical monomer, initiator, poly-polyfluoroalkoxy ether acid emulsifying agent and water
Etc. selecting, indispensable.In invention, the selection of initiator mainly has two classes: inorganic peroxide is (such as persulfate
Deng), organic peroxide (alkyl peroxide etc.)；In the selection course of fluorinated monomer, it has been found that the choosing of fluorinated monomer
Select the following several situation that can include:
(1) by physical state divide, fluorinated monomer can be gaseous fluorinated monomer (such as: tetrafluoroethene, CTFE,
Vinylidene, hexafluoropropene etc.) or liquid fluorinated monomers (such as: perfluoropropylvinylether, perfluoro methyl vinyl ether etc.)
Two classes, it is also possible to be the combination of the fluorinated monomer of gaseous state and liquid (such as: tetrafluoroethene and the mixing of perfluoropropylvinylether
The mixture of thing, vinylidene and perfluoro methyl vinyl ether)；
(2) pressing structural formula to divide, fluorinated monomer can include the fluorochemical monomer of end group band halogen or hydrogen (such as: trifluoro chlorine
Ethylene, vinylidene etc.), it is also possible to include perfluorinated monomer (such as: tetrafluoroethene, perfluoropropylvinylether etc.).
From above-mentioned situation, the fluorinated monomer that the present invention relates to can be tetrafluoroethene, CTFE, hexafluoro third
Alkene, vinylidene, hexafluoropropylene oxide, perfluoroalkyl vinyl ether class, one or more in fluorothene etc., apply in reality
Time, the difference of the fluoropolymer owing to producing, corresponding, choose suitable fluorinated monomer and carry out homopolymerization or copolymerization also has accordingly
Standard, these are all by disclosed by prior art, but the present invention desirably finds out and is applicable to these homopolymerizations or copolyreaction
The proportioning of poly-polyfluoroalkoxy ether acid emulsifying agent and water so that under conditions of initiator exists, these homopolymerizations or copolymerization are anti-
Ying Junneng embodies the features such as polymerization time is fast, polymerization yield rate is high, and meanwhile, the fluoropolymer prepared is without perfluoro caprylic acid or complete
The pungent sulfonic acid of fluorine.To this end, the aqueous emulsion polymerization of fluorinated monomer is defined by the present invention, limit its poly-polyfluoroalkoxy used
Ether acid (using as emulsifying agent) is (0.1～20) with the weight proportion of water in this aqueous emulsion polymerization: 100, optimization, its
Weight proportion is (0.1～0.9): 100.
In actual production process, by prepared without perfluoro caprylic acid or the fluoropolymer of perfluorooctane sulfonate with conduct
The aqueous liquid dispersion of the aqueous solution of the salt of the poly-polyfluoroalkoxy ether acid of emulsifying agent, we are also referred to as dispersion.
First, it is known that this dispersion is also without perfluoro caprylic acid or perfluorooctane sulfonate, secondly, without perfluoro caprylic acid in this dispersion
Or the weight proportion of the fluoropolymer of perfluorooctane sulfonate and water should be (3～7): 10.In actual mechanical process, as emulsifying
The aqueous solution of the salt of the poly-polyfluoroalkoxy ether acid of agent is at the uniform velocity to drip poly-polyfluoroalkoxy ether acid in alkaline aqueous solution,
Dropping is while stirring and preparing, and rate of addition and mixing speed difference 0.1～10ml/s, 20～200rpm, preparation temperature is 25
～50 DEG C, the pH value of the aqueous solution of the salt of the poly-polyfluoroalkoxy ether acid prepared is 7～9, poly-polyfluoroalkoxy ether acid and water
Weight proportion is (0.1～20): 100, alkaline aqueous solution then can choose ammonia, sodium hydrate aqueous solution, potassium hydroxide aqueous solution,
The mixing of one or more in magnesium hydroxide aqueous solution, triethanolamine aqueous solution.
Enumerate the detailed description of the invention of the explanation present invention below with four exemplary embodiments, protection scope of the present invention is also
It is not limited to following example.
Embodiment 1:
Politef is produced through aqueous emulsion polymerization, in this aqueous emulsion polymerization by gaseous fluorinated monomer tetrafluoroethene
The addition bromo-poly-polyfluoroalkoxy ether acid of 1-, as fluorine-containing emulsifier, is embodied as step as follows:
A: the aqueous solution of the salt of the preparation bromo-poly-polyfluoroalkoxy carboxylic ether acid of 1-: add 700ml in 2000ml glass beaker
Deionized water and the ammonia of 100ml 25%, then by liquid glass droplet funnel the most at the uniform velocity dropping 200g in deionized water
The bromo-poly-polyfluoroalkanoic acids of 1-, is stirred while dropping, and mixing speed is 80 rpm, then, obtains poly-polyfluoro alcoxyl
Base ether acid ammonia spirit is standby, and wherein, the bromo-poly-polyfluoroalkoxy carboxylic ether acid ammonium of 1-is 20:100 with the weight proportion of water；
B: polymerization prepares: carry out replacing deoxygenation to polymerization autoclave with nitrogen, make this polymerization autoclave be evacuated to oxygen in still
Content≤25ppm；
C: polymerization process:
A: feed intake: in the 100L rustless steel polymerization autoclave have baffle plate add 55kg deionized water, 972g paraffin with
And the bromo-poly-polyfluoroalkoxy carboxylic ether acid ammonia spirit of 1-of 962.5g20%；
B: preparation initiator: 6.0g Ammonium persulfate. is dissolved in 1L warm water (about 75 DEG C), obtains the Ammonium persulfate. of 0.6%
Aqueous solution；
C: initiation reaction: pressurize polymerization autoclave with tetrafluoroethene, stirs and is warming up to 73 DEG C, stirring
Speed is 200rpm；Again with tetrafluoroethene, polymerization autoclave is boosted, until in polymeric kettle pressure reach 1.865Mpa,
When temperature is 73 DEG C, in polymeric kettle, add the initiator prepared in step b with dosing pump；
D: when the pressure of polymerization autoclave is down to 1.756MPa (generally in 5 minutes), again adds tetrafluoroethene, make
Pressure in polymerization autoclave is maintained at 1.865MPa, temperature is 73 DEG C, carries out polyreaction；
E: when tetrafluoroethene addition reaches 27kg, make polyreaction stop, the total response time is 160min.
After measured, the amount of the bromo-poly-polyfluoroalkoxy carboxylic ether acid ammonia of 1-used is 192.5g.
Comparative example 1:
Politef is produced through aqueous emulsion polymerization, in this aqueous emulsion polymerization by gaseous fluorinated monomer tetrafluoroethene
Addition perfluorooctanoic acid is as fluorine-containing emulsifier, and implementation step is same as in Example 1.
The aqueous dispersion of polytetrafluoroethyland that the method is obtained by we is measured, as follows: polymerization reaction time
For 330min, the amount of the perfluorooctanoic acid used is 275g.
Embodiment 2:
Produced polytrifluorochloroethylene by gaseous fluorinated monomer CTFE through aqueous emulsion polymerization, gather in this aqueous emulsion
In conjunction, the addition bromo-poly-polyfluoroalkoxy carboxylic ether acid of 1-is as fluorine-containing emulsifier, is embodied as step as follows:
A: the aqueous solution of the salt of the preparation bromo-poly-polyfluoroalkoxy carboxylic ether acid of 1-: add in 5000ml glass beaker
2800ml deionized water and the ammonia of 400ml 25%, then slowly at the uniform velocity dripped in deionized water by liquid glass droplet funnel
The bromo-poly-polyfluoroalkanoic acids of 1-of 800g, is stirred while dropping, and mixing speed is 80 rpm, then, is gathered many
Fluoroalkyloxy ether acid ammonia spirit is standby, and wherein, the bromo-poly-polyfluoroalkoxy carboxylic ether acid ammonia of 1-is 20 with the weight proportion of water:
100；
B: polymerization prepares: carry out replacing deoxygenation to polymerization autoclave with nitrogen, make this polymerization autoclave be evacuated to polymeric kettle
Interior oxygen content≤20ppm；
C: polymerization process:
A: feed intake: add 75kg deionized water, 160g sodium carbonate in the 100L rustless steel polymerization autoclave have baffle plate
And the bromo-poly-polyfluoroalkoxy carboxylic ether acid ammonia spirit of 1-of 962.5g 20%；
B: preparation initiator: 8.0g Ammonium persulfate. is dissolved in 1L warm water (about 75 DEG C), obtains the Ammonium persulfate. of 0.8%
Aqueous solution；
C: initiation reaction: pressurize polymerization autoclave with CTFE, stirs and is warming up to 50 DEG C, stir
Mixing speed is 500rpm；With CTFE, polymerization autoclave is boosted again, until pressure reaches in polymeric kettle
When 2.52Mpa, temperature are 50 DEG C, with dosing pump, in polymeric kettle, add the initiator prepared in step b；
D: in course of reaction, continues to add CTFE monomer in reactor, to keep reactor pressure to maintain
2.52Mpa, when CTFE addition reaches 35kg, makes polyreaction stop, and the total response time is 300min.
After measured, the amount of the bromo-poly-polyfluoroalkoxy carboxylic ether acid ammonia of 1-used is 487.5g.
Embodiment 3:
Vinylidene CTFE is produced through aqueous emulsion polymerization, in this aqueous emulsion by vinylidene, CTFE
In polymerization, the addition chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1-is as fluorine-containing emulsifier, is embodied as step as follows:
A: the aqueous solution of the salt of the preparation chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99 of 1-: add in 2000ml glass beaker
700ml deionized water and the ammonia of 100ml 25%, then slowly at the uniform velocity dripped in deionized water by liquid glass droplet funnel
The chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99 of 1-of 200g, is stirred while dropping, and mixing speed is 80 rpm, so
After, obtain poly-polyfluoroalkoxy ether acid aqueous ammonium, wherein, the chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1-and the weight of water
Proportioning is 20:100；
B: polymerization prepares: carry out replacing deoxygenation to polymerization autoclave with nitrogen, make this polymerization autoclave be evacuated to polymeric kettle
Interior oxygen content≤25ppm；
C: polymerization process:
A: feed intake: in the 100L rustless steel polymerization autoclave have baffle plate add 64kg deionized water, 800g paraffin with
And the aqueous solution of the chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1-of 2240g 20%；
B: preparation initiator: 32g Ammonium persulfate. is dissolved in 1L warm water (about 75 DEG C), obtains the Ammonium persulfate. water of 3.2%
Solution, then, adds the diethyl malonate of 80 grams in the ammonium persulfate aqueous solution of 3.2%, and the mixing obtaining compounding causes
Agent；
C: initiation reaction: use the vinylidene of 95mol% and the mix monomer of the CTFE of 5mol%, high pressure is gathered
Closing still to boost, stir and be warming up to 60 DEG C, mixing speed is 200rpm.Then with mix monomer, reactor is continued
The 2.5Mpa that is depressed into of continuing rising, maintenance autoclave temp is at 6060 DEG C, with dosing pump, by molten for the mixed initiator configured in step b
Liquid squeezes into reactor；
D: when the mix monomer addition of vinylidene, CTFE reaches 37Kg, make polyreaction stop, adding up to
Response time is 320min.
After measured, the amount of the chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1-used is 448g.
Embodiment 4:
Vinylidene hexafluoropropene tetrafluoro is produced through aqueous emulsion polymerization by vinylidene, hexafluoropropene, tetrafluoroethene
Ethylene, in this aqueous emulsion polymerization, the addition chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1-is as fluorine-containing emulsifier, specifically real
Execute step as follows:
A: the aqueous solution of the salt of the preparation chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99 of 1-: add in 5000ml glass beaker
2800ml deionized water and the ammonia of 400ml 25%, then slowly at the uniform velocity dripped in deionized water by liquid glass droplet funnel
The chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99 of 1-of 800g, is stirred while dropping, and mixing speed is 80 rpm, so
After, obtain poly-polyfluoroalkoxy ether acid aqueous ammonium, wherein, the chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1-and the weight of water
Proportioning is 20:100.
B: polymerization prepares: carry out replacing deoxygenation to polymerization autoclave with nitrogen, make this polymerization autoclave be evacuated to polymeric kettle
Interior oxygen content≤20ppm.
C: polymerization process:
A: feed intake: add 60kg deionized water, 80gPH regulator in the 100L rustless steel polymerization autoclave have baffle plate
The aqueous solution of the chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1-of (disodium hydrogen phosphate) and 750g 20%；
B: preparation initiator: 12.5g Ammonium persulfate. is dissolved in 1L warm water (about 75 DEG C), obtains the persulfuric acid of 1.25%
Aqueous ammonium；
The tetrafluoroethene mixing of the vinylidene of c: initiation reaction: 45mol%, the hexafluoropropene of 50mol% and 5mol% is single
Body, boosts to polymerization autoclave, stirs and is warming up to 120 DEG C, and mixing speed is 200rpm, then single with mixing
Reactor is continued to boost to 3.5Mpa by body, and maintenance autoclave temp is at 120 DEG C, with dosing pump, mixed by configured in step b
Close initiator solution and squeeze into reactor, start reaction；
D: when mix monomer inventory reaches 16.8Kg, keeping reaction temperature is 120 DEG C, and mixing speed 200rpm is used
Dosing pump, adds 10ml diethyl oxalate in autoclave；
E: when the mixing addition of vinylidene, hexafluoropropene and tetrafluoroethene reaches 24Kg, make polyreaction stop.
The total response time is 260min.
After measured, the amount of the chloro-poly-polyfluoroalkoxy ether-P-TOLUENE SULFO ACID 99's ammonium of 1-used is 448g.
In the industrial production, for obtaining by prepared without perfluoro caprylic acid or the fluoropolymer of perfluorooctane sulfonate with work
For the aqueous liquid dispersion of aqueous solution of salt of the poly-polyfluoroalkoxy ether acid of emulsifying agent, also can be in the following way:
As a example by separately below for the fluoropolymer prepared by above-described embodiment 1～4, had by embodiment 5～8
Body explanation.
Embodiment 5:
Carrying out the step of embodiment 1, after polyreaction stops, unreacted tetrafluoroethene in polymerization autoclave is being arranged
Enter recovery system, the aqueous polytetrafluoroethyldispersion emulsion obtained by cooling, and remove upper strata paraffin.
After measured, said method the solid component concentration of the aqueous polytetrafluoroethyldispersion emulsion prepared is about 49.09%, with
In aqueous emulsion polymerization, the weight ratio of water is 0.35:100.
Comparative example 2:
On the basis of comparative example 1, use the step of above-described embodiment 5, it is thus achieved that aqueous polytetrafluoroethyldispersion emulsion, through surveying
Fixed, the solid component concentration of this aqueous polytetrafluoroethyldispersion emulsion is about 32.6%, with the weight ratio of water in aqueous emulsion polymerization is
0.5:100.
Above-described embodiment 1, embodiment 5 and comparative example 1, comparative example 2 are added up, it is thus achieved that following data, such as table 2 institute
Show:
Table 2
Embodiment 6:
Carrying out the step of embodiment 2, after polyreaction stops, by CTFE unreacted in polymerization autoclave
Enter recovery system, the polytrifluorochloroethylene water-based emulsion obtained by cooling.
After measured, said method the solid component concentration of the aqueous polytetrafluoroethyldispersion emulsion prepared is about 43.38%, with
In aqueous emulsion polymerization, the weight ratio of water is 0.65:100.
Embodiment 7:
Carrying out the step of embodiment 3, after polyreaction stops, inclined by 95mol% unreacted in polymerization autoclave
The mix monomer of the CTFE of fluorothene and 5mol%, enters recovery system, the vinylidene trifluoro chlorine obtained by cooling
The water-based emulsion of ethylene copolymer, removes the paraffin on upper strata.
After measured, said method the solid constituent of the water-based emulsion of the vinylidene chlorotrifluoroethylene prepared
Concentration is about 46.88%, is 0.7:100 with the weight ratio of water in aqueous emulsion polymerization.
Embodiment 8:
Carrying out the step of embodiment 4, after polyreaction stops, by 45mol%'s unreacted in polymerization autoclave
The tetrafluoroethene mix monomer of vinylidene, the hexafluoropropene of 50mol% and 5mol% enters recovery system, inclined obtained by cooling
The water-based emulsion of fluorothene hexafluoropropene TFE copolymer.
After measured, said method the water-based emulsion of the vinylidene hexafluoropropene TFE copolymer prepared
Solid component concentration is about 37%, is 0.25:100 with the weight ratio of water in aqueous emulsion polymerization.
The method recorded according to JIS-K5663, we are to above-described embodiment 5～8 and the aqueous liquid dispersion that obtains of comparative example 2
The dispersion stabilization of (dispersion) is determined, it is thus achieved that following data, as shown in table 3:
Table 3
Wherein, the method for testing of mechanical stability is, is stirred by aqueous liquid dispersion 100g in 5000rpm even phase disperser
5min, measures its coagulation amount (unit: ppm) after placing 1d；The method of testing of high-temperature stability is, aqueous liquid dispersion is at 50 DEG C
After placing 60d, visually to determine whether precipitum.
In actual industrial production, above-mentioned four kinds of fluoropolymers (politef, the polytrifluorochloroethylene, partially related to
Fluorothene CTFE, vinylidene hexafluoropropene tetrafluoroethene) it is respectively provided with wide application prospect, such as: oil
The numerous areas such as chemical industry, electric, building coating or dipping, automobile decoration, appliance shell, medical science, quasiconductor, fiber cloth,
Now for patent documentation CN101218264B(documents 1), CN102089335A(documents 2), CN101745338A(pair
Than file 3), CN101287766(documents 4), CN101291987(documents 5) involved by fluorine-containing emulsifier, with reality
Execute as a example by example 1 and embodiment 5 are prepared the detailed description of the invention of politef and dispersion thereof, prepare politef respectively
And dispersion, its preparation time is as shown in table 4 with product index:
Table 4
According to above-mentioned data analysis, the present invention relates to by poly-polyfluoroalkoxy ether acid (the bromo-poly-polyfluoroalkoxy of 1-
Carboxylic ether acid ammonium) as emulsifying agent, during preparing fluoropolymer (politef) and aqueous liquid dispersion thereof, with contrast
File 1～5 compares, and all has a clear superiority on primary ion particle diameter, the solids content of aqueous liquid dispersion, percentage elongation,
The polymerization time of fluoropolymer, the particle specific gravity of SSG(fluoropolymer), to draw high the effect in terms of intensity the most ideal,
Suitably it is widely popularized use.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction, every depends on
Any simple modification of being made above example according to the technical spirit of the present invention, equivalent variations, each fall within the protection of the present invention
Within the scope of.
Claims (7)
1. one kind is applicable to preparation without perfluoro caprylic acid or the method for the fluoropolymer of perfluorooctane sulfonate, it is characterised in that: institute
The preparation method stated includes: carried out aqueous emulsion polymerization by one or more fluorinated monomers, and when aqueous emulsion polymerization with poly-polyfluoro
Alkoxyl ether acid is as emulsifying agent, and described poly-polyfluoroalkoxy ether acid is selected from the following combination of one or more:
Meet the poly-polyfluoroalkoxy ether acid of lower formula I:
(I),
Meet the poly-polyfluoroalkoxy ether acid of lower formula II:
(II),
Wherein:
T:、、、；
X:H, Br；
R:H, Br, I；
Y:SO3H and salt, COOH and salt thereof, CH2CH2COOH and salt, CH2CH2SO3H and salt thereof,
COOCH2CH2COOH and salt, COOCH2CH2SO3H and salt thereof,And salt；And salt；
The value of n is: 0～4；
The value of m is: 1～20；
The value of p is: 0～4；
The value of q is: 0～1；
Described prepared fluoropolymer is free from perfluoro caprylic acid or perfluorooctane sulfonate,
Described fluorinated monomer includes tetrafluoroethene, CTFE, vinylidene, fluorothene, hexafluoropropene, perfluoroalkyl second
One or more in alkene ether,
Described aqueous emulsion polymerization refers to that poly-polyfluoroalkoxy ether acid is as emulsifying agent and the weight of water in this aqueous emulsion polymerization
Amount proportioning is (0.1～20): 100,
Described poly-polyfluoroalkoxy ether acid is the poly-polyfluoroalkoxy ether acid emulsifying agent of end group band halogen or hydrogen.
A kind of preparation fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate of being applicable to the most according to claim 1
Method, it is characterised in that: the performance indications of described poly-polyfluoroalkoxy ether acid emulsifying agent include:
In terms of NaOH, acid number: < 150 mg/g；
Cross oxygen value: < 1.5 g/100g；
Boiling point: < 260 DEG C；
Surface tension: < 40mN/m；
Critical micelle concentration (CMC): < 5%.
A kind of preparation fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate of being applicable to the most according to claim 2
Method, it is characterised in that: the performance indications of described poly-polyfluoroalkoxy ether acid emulsifying agent include:
In terms of NaOH, acid number: < 100mg/g；
Cross oxygen value: < 0.5g/100g；
Boiling point: < 160 DEG C；
Surface tension: < 20mN/m；
Critical micelle concentration (CMC): < 1.5 %.
The preparation method of fluoropolymer the most according to claim 1, it is characterised in that: described fluorinated monomer is tetrafluoro
Ethylene, is being polymerized in the aqueous emulsion polymerization of emulsifying agent using poly-polyfluoroalkoxy ether acid, wherein, and poly-polyfluoro alcoxyl
Base ether acid is (0.1～0.45) with the weight ratio of water in aqueous emulsion polymerization: 100.
A kind of preparation fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate of being applicable to the most according to claim 1
Method, it is characterised in that: described fluorinated monomer is CTFE, at the water using poly-polyfluoroalkoxy ether acid as emulsifying agent
Being polymerized in emulsion polymerization systems, wherein, poly-polyfluoroalkoxy ether acid with the weight ratio of water in aqueous emulsion polymerization is
(0.4～0.75): 100.
A kind of preparation fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate of being applicable to the most according to claim 1
Method, it is characterised in that: described fluorinated monomer is vinylidene and CTFE, using poly-polyfluoroalkoxy ether acid as
The aqueous emulsion polymerization of emulsifying agent is polymerized, wherein, poly-polyfluoroalkoxy ether acid and water in aqueous emulsion polymerization
Weight ratio is (0.5～0.9): 100.
A kind of preparation fluoropolymer without perfluoro caprylic acid or perfluorooctane sulfonate of being applicable to the most according to claim 1
Method, it is characterised in that: described fluorinated monomer is vinylidene, tetrafluoroethene and hexafluoropropene, with poly-polyfluoroalkoxy
Ether acid is polymerized as in the aqueous emulsion polymerization of emulsifying agent, wherein, and poly-polyfluoroalkoxy ether acid and aqueous emulsion polymerization body
In system, the weight ratio of water is (0.1～0.35): 100.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410196792.4A CN103951772B (en) | 2014-05-09 | A kind of being applicable to is prepared without perfluoro caprylic acid or the method for the fluoropolymer of perfluorooctane sulfonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410196792.4A CN103951772B (en) | 2014-05-09 | A kind of being applicable to is prepared without perfluoro caprylic acid or the method for the fluoropolymer of perfluorooctane sulfonate |
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| CN103951772B true CN103951772B (en) | 2016-11-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504063A (en) * | 2011-10-31 | 2012-06-20 | 巨化集团公司 | Preparation method of fluorine-containing polymer |
| CN103936905A (en) * | 2014-05-09 | 2014-07-23 | 成都晨光博达橡塑有限公司 | Fluorine-containing polymer and preparation method thereof |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504063A (en) * | 2011-10-31 | 2012-06-20 | 巨化集团公司 | Preparation method of fluorine-containing polymer |
| CN103936905A (en) * | 2014-05-09 | 2014-07-23 | 成都晨光博达橡塑有限公司 | Fluorine-containing polymer and preparation method thereof |
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