CN101745338B - Method for preparing fluorine-containing polymer without containing perfluorocaprylic acid - Google Patents
Method for preparing fluorine-containing polymer without containing perfluorocaprylic acid Download PDFInfo
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- CN101745338B CN101745338B CN200810238288.0A CN200810238288A CN101745338B CN 101745338 B CN101745338 B CN 101745338B CN 200810238288 A CN200810238288 A CN 200810238288A CN 101745338 B CN101745338 B CN 101745338B
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- fluorine
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- tetrafluoroethene
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Abstract
The invention belongs to the field of fluorine-containing polymer preparation, and provides a fluorine-containing emulsifying agent for replacing perfluorocaprylic acid and salt thereof. A2O3SCF2 (CF2OCF (CF3))n-1COOA, CF3CF2 (CF2OCF (CF3))n-1COOA, H3COOCF2 (CF2OCF (CF3))n-1COOA, in the formula, n is 1 to 4, and A is hydrogen atom, alkali metal or NH4. The invention also provides a method for preparing fluorine-containing polymer without containing perfluorocaprylic acid by using the fluorine-containing emulsifying agent. The fluorine-containing emulsifying agent of the invention has better emulsifying and dispersing effects, and the quality of an obtained product is in accordance with that of a reaction product in presence of PFOA.
Description
Technical field
The invention belongs to fluoropolymer preparation field, particularly relate to one not containing the preparation method of the fluorine resin of perfluoro caprylic acid (PFOA).
Background technology
The hydrogen partial of fluorine-containing surfactant (fluorine containing surfactant) mainly in hydrocarbon chain hydrophobic grouping or be all the surfactant that fluorine atom instead of, also can be described as fluorocarbon surfactant (fluorocarbonsurfactant), fluorinated surfactant (fluorinated surfactant).The hydrophilic group part of fluorine-containing surfactant is the same with the hydrophilic group of common hc-surfactant, its classification is also identical with hc-surfactant, when it is water-soluble, all title non-ion fluorin carbon surface active agents that can not ionize, what can ionize is referred to as ionic fluorocarbon surfactant, and the latter can divide seed anionic, cationic and both sexes fluorocarbon surfactant by the raw figured stone ionic type of hydrophilic group again.
Fluorine-containing surfactant (Fluorinated Surfactants) is the one that surface-active is the highest in surfactant up to now, and " three is high " (high surface, high heat-resistant stability, high chemical stability) " two hate " (fluorine-containing alkyl water and oil repellence) is the performance of its uniqueness.Fluorine-containing surfactant is widely used as emulsifying agent (polymerization process), wetting agent, anti-fouling agent, spreading agent, antiplastering aid, foaming agent etc.
The polymerization methods of fluorine monomer is by traditional classification, and have dispersin polymerization, suspend and get conjunction, polymerisation in solution, emulsion polymerisation, emulsion polymerisation is a kind of comparatively ripe industrialized producing technology, and the production of more than 50% fluoropolymer adopts this process route.But Fluorine containing olefine emulsion polymerization technique, has harsher requirement to emulsifying agent, its hydrophobic end must all or part ofly be saturated hydrocarbons that is fluorine-containing or fluorine-containing, chlorine, otherwise polymerisation is difficult to carry out.
The application of fluorine-containing surfactant in fluoropolymer manufactures is long-standing, and its Main Function is the polymerization stability, the structure primary particle state and reactor cleannes that ensure fluoropolymer, is the necessary assistant of suitability for industrialized production fluoropolymer.
In the past few decades, PFOA, PFOS are surfactants with the most use during fluoropolymer manufactures.Experimental data and theory show, take into account activity and the solubility in media as well of surfactant, carbon number in surfactant carbon chain is usually between 6 ~ 10, and it is best with the performance of the surfactant of straight chain type 8 carbon atoms, with perfluoro caprylic acid compounds (Perfluorooctanoic Acid, be abbreviated as PFOA), perfluor sulfonyl compound (Perfluorooctane Sulfonate, be abbreviated as PFOS) its representative substances just, important function has been played in the manufacturing of fluoropolymer, its cost performance as emulsifying agent is undoubtedly in the first place of numerous surfactant always.
But since the later stage in last century, all analyze PFOA or PFOS that detected trace in the animal body of scientist on blood of human body, the Antarctic Continent, tested simultaneously and also find that the half-life of this kind of material in nature is very long, potential risks are existed to organism.Scientist by finding after guinea pig is done experiment with it simultaneously, and PFOA has caused a series of tumor disease in animals.Therefore the expert of Environmental Protection Agency thinks, does not get rid of the possibility of PFOA to human carcinogen.Especially several years ago about propagation and the reply tentative programme of not glutinous pot-Teflon event, people are allowed to create doubt and worry to these high performance materials.
Research shows, PFOA is also one of organic pollution of the most difficult degradation found in the world at present, has the possibility of persistence bioaccumulation Long-distance Migrating, can cause negative effect to human health and living environment; Thus, PFOA has listed the alternative material of persistence organic pollutant (POPs) in.On November 11st, 2004, " Convention of Stockholm about persistence organic pollutant " that be intended to the anthropogenic discharge reducing and eliminate lasting pollutant (POPs) formally comes into force to China.In January, 2006, the U.S. environment protection Room requires 2010, and the fluororesin Fluorine-Contained Oil-Water-Proofing production firm PFOA consumption of the U.S. cuts down by 2010 5%; Within 2015, do not re-use PFOA.On December 27th, 2006, European Parliament and council of ministers combine issue " instruction about restriction PFOS is sold and used " (2006/122/EC point out: perfluoro caprylic acid and salt (PFOA) is under a cloud the harmfulness similar haply to PFOS.On June 1st, 2007, EU REACH Legislation comes into force, and its object is exactly that the producing and selling of standard chemical product in the measure of regulation, carry out under condition, otherwise must just forbid that it uses.Under the advocating of Environmental Protection Agency, the production discharge capacity of PFOA95% is agreed to reduce before 2010 at the latest by 8 u s companys comprising Du Pont, also guarantees that this compound does not appear in the consumer products of 95% simultaneously.By 2015, in all products, all PFOA will be prohibitted the use.
Therefore, developing the green substitute of PFOA is also very urgent task.
After calendar year 2001, U.S. EPA proposed forbidding PFOS effect, 3M company, in the not full of life and energy PFOS Related product of statement in 2002, researches and develops perfluoro butyl sulfonic acid (PFBS, Perfluorobutane sulfonate) C4F9SO3H simultaneously and replaces PFOS.The fluorocarbon chain of PFBS is short, and without obvious persistence biological accumulation, the short time excretes with human metabolism, and it mediates thing nonhazardous.The new Scotchguard Protectors commodity matter of being produced by PFBS through a large amount of test, safeguard function and environmentally friendly, and through U.S. EPA and the approval of other environmental protection mechanism of the world.
When E.I.Du Pont Company utilizes telomerisation to produce perfluoroalkyl monomeric, mainly C6 base product, does not have C8 base composition, so not containing PFOS/PFOA.Do not have PFOS in these C6 telomers, its toxicity is also little than C8.So substitute PFOS/PFOA with C6 telomer, Daikin and Dow corning put out jointly the product of C6 (PFHS, Perfluorohexane Sulfonate).But it is the mixture that carbochain is different that telomerization method is prepared in the end product of all-fluoroalkyl compound, and its carbochain is issued wider, how to control reaction condition and guarantees cessation reaction in required carbon chain range, be difficult to accomplish.
Also once someone used low carbon chain fluorine surfactant (C1-C2), the shortcoming of highly significant is had: i.e. non-telogenic performance in fluoropolymer synthesis, there is the transfer of low carbon chain during polymeric chain is increased, thus create unwanted low-molecular weight polymer, affect the quality of product.
There is expert in the recovery of fluorinated surfactant as these research and development, so occur various with the patent (US3882153 of the content reducing C8 class surfactant, cycling and reutilization, US4282162), use the fixed or free-standing resin (WO200/35971 of nonionic, non-fluorinated surfactants and anion exchange, US20030220442, US20040143052, WO2000/051988, US6861466, US20050189299, US20060148973) fluorine surfactant is reclaimed.But above-mentioned cycling and reutilization technology also exists shortcoming: the problem being first treatment effeciency, and fixed bed anion exchange process can support fluorine surfactant effectively, after process, the concentration of C8 can lower than 5PPM.But can not well concentrate for bulky polymer dispersion liquid or latex, so just have little time process at all.Fluoridize body for each and must be equipped with special anion exchange bed, this is difficult to effectively be avoided when guaranteeing recovery and bed scrubber polluting.And exchange column is often open, and can not avoid the gel of anion exchange bed.Moreover, for the large polymeric dispersions of some particle and flocculation liquid easily in exchange resin anion (R.A.) grain broken and lose.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide the fluorine-containing emulsifier of a kind of alternative perfluoro caprylic acid and its esters, provide a kind of not containing the formula of the fluoropolymer of PFOS/PFOS, namely the fluorine-containing surfactant of one or more non-PFOA/PFOS is selected to be applied to the polymerization technique of fluorine-containing latex, thus make in produced product completely not containing PFOA/PFOS class material, this key is wherein that such surfactant will have enough emulsion dispersion effects, is also non-PFOA class material simultaneously.
The active surface activating agent of this inventor to alternative PFOA is studied, about surfactant selected to pay special attention to following some: the material 1, in such material and system does not all react; 2, after such material mixes with material various in system, surface-active and dispersiveness remain unchanged; 3, under system reaction temperature and pressure, such material does not decompose; 4, price is quite or lower, and the material easily obtained.Surfactant of the present invention meets some conditional request above-mentioned completely, particularly from critical micelle concentration and capillary measurement result, compared with original surfactant, better can reach dispersion effect.
The invention provides the fluorine-containing emulsifier of a kind of alternative perfluoro caprylic acid and its esters, its structure is as follows: A
2o
3sCF
2(CF
2oCF (CF
3))
n-1cOOA, CF
3cF
2(CF
2oCF (CF
3))
n-1cOOA, H
3cOOCF
2(CF
2oCF (CF
3))
n-1cOOA, n=1 ~ 4 in formula, A is hydrogen atom, alkali metal or NH
4.
The present invention is based on fluorine-containing emulsifier, and have selected the fluorine-containing emulsifier of above three compounds perfluoro caprylic acid and its esters as an alternative, its carbon number is between 2 ~ 12.Under above three kinds of surfactants exist, carry out emulsion polymerisation, alternative PFOA carries out emulsion polymerisation, can reach better emulsification and dispersion effect, and it is consistent or better that products obtained therefrom quality and PFOA exist lower product quality of reacting.
As fluorine-containing emulsifier used in the present invention, select different n values, its surface-active shown is different, and general n value is higher, and its dispersion effect is better, and consumption is also fewer, otherwise n value is less, and its dispersion effect is poorer, and consumption is also more.
Preferably, n=3-4
Preferably, the concentration of surfactant solution is 0.1-10%, percentage by weight; Preferred, the concentration of surfactant solution is 0.5-5%, percentage by weight.
The present invention also provides a kind of not containing the preparation method of the fluoropolymer of perfluoro caprylic acid, it is characterized in that, use above-mentioned fluorine-containing emulsifier, adopt emulsion polymerisation process, in polymeric kettle, add water, then add fluorine-containing emulsifier and auxiliary agent, pass into polymerization single polymerization monomer, at temperature 10-200 DEG C, under pressure 0-6.0MPa, under the effect of initator, initiator amount is the 0.1%-10% of monomer gross mass; Monomer generation homopolymerization or copolymerization, utilize physics or chemical coagulation method to carry out condensing and wash, dewater, and obtains not containing the fluoropolymer of perfluoro caprylic acid.
Preferred, the concentration of surfactant solution is 0.5-5%, percentage by weight.
Described polymerization single polymerization monomer is selected from: one or more in ethene, tetrafluoroethene (TFE), hexafluoropropene (HFP), vinylidene (VDF), CTFE (CTFE), perfluor positive propylene and ethylene base ether (PPVE), perfluoroethylvinyl ether (PEVE), perfluoro methyl vinyl ether (PMVE) and/or perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride (PSVE).Namely polymerization comprises the homopolymerization of monomer self, also the copolymerization of two or more monomer is comprised, as the homopolymerization of tetrafluoroethene, the homopolymerization of vinylidene, the homopolymerization of CTFE, the copolymerization of tetrafluoroethene and hexafluoropropene, the copolymerization of vinylidene and CTFE, the copolymerization of vinylidene and hexafluoropropene, the copolymerization of tetrafluoroethene and ethene, vinylidene, the copolymerization of tetrafluoroethene and hexafluoropropene, tetrafluoroethene and perfluor positive propylene and ethylene base ether (PPVE) (or perfluor 3, 6-dioxa-4-methyl-7-octene sulfonyl fluoride (PSVEO, or perfluoroethylvinyl ether (PEVE), or perfluoro methyl vinyl ether (PMVE)) copolymerization etc.
Described initator is selected from: isopropyl benzene hydroperoxide, t-butylcumylperoxide, benzoyl peroxide, ammonium persulfate or potassium peroxydisulfate.
From this inventive method, the surfactant used is compared with PFOA, purity is higher, effective content can reach more than 95% (amylose content of PFOA is generally more than 73%), critical micelle concentration is lower, have better emulsification and dispersion effect, it is consistent to there is lower product quality of reacting in products obtained therefrom quality and PFOA.
Compared with prior art, excellent results of the present invention is: employ with H first
2o
3sCF
2(CF
2oCF (CF
3))
n-1cOOA, CF
3cF
2(CF
2oCF (CF
3))
n-1cOOA, H
3cOOCF
2(CF
2oCF (CF
3))
n-1cOOA, with n=1 ~ 4 in above formula, A is hydrogen atom, alkali metal or NH
4) structure is that emulsifying agent replaces perfluoro caprylic acid and its esters emulsifying agent to produce the method for fluorubber, thus obtained fluorubber is not containing PFOA and its esters.It is that dispersant is polymerized to obtain the physical and mechanical properties of fluorubber that the physical and mechanical properties of this polymer is enough to reach with PFOA.In addition, the successful Application of this material amount matter, efficiently avoid the harm that PFOA may cause environment and health, is significant.
Detailed description of the invention
Below by more concrete being described this invention of example.
Embodiment 1: for the polymeric kettle of 10L, adds 7.2kg deionized water, 72g emulsifying agent K in the polymeric kettle cleaned
2o
3sCF
2(CF
2oCF (CF
3))
3the initator isopropyl benzene hydroperoxide solution of COOK and 22g and other auxiliary agent; Find time, deoxygenation, be qualified to oxygen content≤30ppm; Then boost to polymerization kettle temperature raising with VDF monomer, after the still temperature of still to be polymerized, still pressure reach technological requirement, start polymerisation, temperature 150 DEG C, it is 3.0% molecular weight regulator carbon tetrachloride 350ml that rear measuring pump at the uniform velocity squeezes into mass concentration.In polymerization process, keep still temperature still pressure constant, after reaching certain reacting dose, stop reacting.Cohesion, washing, oven dry, pulverize, finally obtain PVDF product.
Embodiment 2: change emulsifying agent is CF
3cF
2(CF
2oCF (CF
3))
3cOOK, other operate similarly to Example 1.
Comparative example one: change emulsifying agent is Perfluorooctanoic acid potassium salt, and other carrying out similarly to Example 1 operate.
PVDF performance comparison under table 1 different emulsifiers
| Project | Molecular weight (Mw) | Heat decomposition temperature (DEG C) | Melt index (g/10min) | Fusing point (DEG C) | Weatherability 6000h |
| Embodiment 1 | 51.7 | 432 | 1.2 | 161 | Unchanged |
| Embodiment 2 | 53.2 | 433 | 1.2 | 161 | Unchanged |
| Comparative example one | 52.5 | 431 | 1.2 | 160 | Unchanged |
Embodiment 3
2500g deionized water is added, 25g (NH in 5 liters of reactors
4)
2o
3sCF
2(CF
2oCF (CF
3))
2cOONH
4, reactor is found time, guarantees that oxygen content is not more than 30ppm.Be that 20: 80 tetrafluoroethene and hexafluoropropene mix monomer boost to polymeric kettle with mass ratio, when pressure be 2.5MPa temperature reach 85 DEG C time, squeeze into the initiator potassium persulfate 20ml that concentration is 10%, and continuing to pass into mass ratio, to be that 80: 20 tetrafluoroethene mix with hexafluoropropene single, makes reacting kettle inner pressure maintain 2.5MPa.After this time pressure and temperature reaction is maintained, when reaction stops reaction after a certain amount of.Emulsion obtains FEP finished product after cohesion, sintering, granulation.
Embodiment 4
Change emulsifying agent is H
3cOOCF
2(CF
2oCF (CF
3))
2cOONH
4, other operate similarly to Example 3.Comparative example two: change emulsifying agent is Perfluorooctanoic acid potassium salt, and other carrying out similarly to Example 1 operate.
FEP performance comparison under table 3 different emulsifiers
| Project | Melt index (g/10min) | Fusing point (DEG C) | Heat decomposition temperature (DEG C) | Hot strength (Mpa) | Elongation at break (%) |
| Practical example one | 1.2 | 166.0 | 441.5 | 34.5 | 336 |
| Practical example two | 1.2 | 165.9 | 442.7 | 34.2 | 340 |
| Comparative example two | 1.3 | 166.3 | 441.1 | 34.3 | 337 |
Embodiment 5:
For the polymeric kettle of 10L, in the polymeric kettle cleaned, add 7.2kg deionized water, 85g (NH
4)
2o
3sCF
2(CF
2oCF (CF
3))
n-1cOONH
4other corresponding reagent and additive in polymerization of fluorine-containing emulsifier; Find time, deoxygenation, be qualified to oxygen content≤30ppm; Then to polymerization kettle temperature raising boosting, after the still temperature base still pressure of still to be polymerized reaches technological requirement, the benzoyl peroxide solution of concentration 10% is squeezed into measuring pump, beginning polymerisation.Temperature 75 DEG C, in polymerization process, keeps still temperature still pressure constant, and adds initator at any time according to polymerisation situation, after reaching certain reacting dose, stops reacting.Cohesion, washing, oven dry, finally open and be smelt sheet and test.
Embodiment 6: change fluorine-containing emulsifier is CF
3cF
2(CF
2oCF (CF
3))
n-1cOONH
4other carrying out similarly to Example 1 operate.
Comparative example three: change emulsifying agent is perfluorooctanoic acid, and other operate similarly to Example 5.
Embodiment 5, embodiment 6 are compared with comparative example one, comparative example two, and result is that the curability of product vulcanizate and physical property thereof are basically identical even better, and the physical and mechanical properties of above-mentioned each routine polymerization product is shown in table 1.
FKM performance comparison under table 4 different emulsifiers
| Experiment number | Mooney viscosity ML 1+10 121℃ | Hot strength MPa | Elongation at break % | MH | TC90 min |
| Embodiment 5 | 53 | 15.9 | 208 | 2.2301 | 2:30 |
| Embodiment 6 | 52 | 15.5 | 201 | 2.2418 | 2:46 |
| Comparative example three | 53 | 15.2 | 203 | 2.2115 | 2:57 |
Note: MH---peak torque, TC90---cure time
Claims (1)
1., not containing a preparation method for the fluoropolymer of perfluoro caprylic acid, it is characterized in that, use the fluorine-containing emulsifier of following structure, CF
3cF
2(CF
2oCF (CF
3))
n-1cOOA, in formula, n=3-4, A are hydrogen atom or alkali metal;
Adopt emulsion polymerisation process, in polymeric kettle, add water, then add fluorine-containing emulsifier and auxiliary agent, pass into polymerization single polymerization monomer, at temperature 10-200 DEG C, under pressure 0-6.0MPa, under the effect of initator, initiator amount is the 0.1%-10% of monomer gross mass; Monomer generation homopolymerization or copolymerization, utilize physics or chemical coagulation method to carry out condensing and wash, dewater, and obtains not containing the fluoropolymer of perfluoro caprylic acid;
The concentration of fluorine-containing emulsifier solution is 0.1-10%, percentage by weight; Described initator is selected from: isopropyl benzene hydroperoxide, t-butylcumylperoxide, benzoyl peroxide, ammonium persulfate or potassium peroxydisulfate.
2. as claimed in claim 1 not containing the preparation method of the fluoropolymer of perfluoro caprylic acid, it is characterized in that, the concentration of fluorine-containing emulsifier solution is 0.5-5%, percentage by weight.
3. as claimed in claim 1 not containing the preparation method of the fluoropolymer of perfluoro caprylic acid, it is characterized in that, described polymerization single polymerization monomer is selected from: one or more in ethene, tetrafluoroethene, hexafluoropropene, vinylidene, CTFE, perfluor positive propylene and ethylene base ether, perfluoroethylvinyl ether, perfluoro methyl vinyl ether and/or perfluor 3,6-dioxa-4-methyl-7-octene sulfonyl fluoride.
4. as claimed in claim 1 not containing the preparation method of the fluoropolymer of perfluoro caprylic acid, it is characterized in that, polymerization comprises the homopolymerization of tetrafluoroethene, the homopolymerization of vinylidene, the homopolymerization of CTFE, the copolymerization of tetrafluoroethene and hexafluoropropene, the copolymerization of vinylidene and CTFE, the copolymerization of vinylidene and hexafluoropropene, the copolymerization of tetrafluoroethene and ethene, vinylidene, the copolymerization of tetrafluoroethene and hexafluoropropene, and/or tetrafluoroethene and perfluor positive propylene and ethylene base ether or perfluor 3, 6-dioxa-4-methyl-7-octene sulfonyl fluoride, or perfluoroethylvinyl ether, or the copolymerization of perfluoro methyl vinyl ether.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307600A (en) * | 1998-07-07 | 2001-08-08 | 大金工业株式会社 | Process for producing fluoropolymer |
| CN101186669A (en) * | 2007-11-20 | 2008-05-28 | 山东东岳神舟新材料有限公司 | Method for preparing microemulsion of fluorinated ethylene propylene powder |
| CN101274969A (en) * | 2007-11-20 | 2008-10-01 | 山东东岳神舟新材料有限公司 | Microemulsion polymerization method for fluoropolymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307600A (en) * | 1998-07-07 | 2001-08-08 | 大金工业株式会社 | Process for producing fluoropolymer |
| CN101186669A (en) * | 2007-11-20 | 2008-05-28 | 山东东岳神舟新材料有限公司 | Method for preparing microemulsion of fluorinated ethylene propylene powder |
| CN101274969A (en) * | 2007-11-20 | 2008-10-01 | 山东东岳神舟新材料有限公司 | Microemulsion polymerization method for fluoropolymer |
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