CN101787091B - Fluoropolymer aqueous dispersion emulsion and preparation method thereof - Google Patents
Fluoropolymer aqueous dispersion emulsion and preparation method thereof Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 65
- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 62
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 62
- 239000006185 dispersion Substances 0.000 title abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000004945 emulsification Methods 0.000 title description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 62
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 39
- 239000011737 fluorine Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 22
- 150000001450 anions Chemical class 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 150000003254 radicals Chemical class 0.000 claims abstract description 5
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 claims description 46
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 37
- -1 polytetrafluoroethylene Polymers 0.000 claims description 35
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 23
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 20
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 18
- 125000000913 palmityl 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])C([H])([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 12
- 229920001577 copolymer Polymers 0.000 claims description 9
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 6
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 229920009638 Tetrafluoroethylene-Hexafluoropropylene-Vinylidenefluoride Copolymer Polymers 0.000 claims description 4
- 229920001774 Perfluoroether Polymers 0.000 claims description 3
- 125000002958 pentadecyl 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])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 3
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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 3
- 239000004094 surface-active agent Substances 0.000 abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 239000002608 ionic liquid Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 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 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of fluoropolymer aqueous dispersion emulsion, comprising the following steps: (1) surfactant which does not contain fluorine and has the following general formula is added into a reaction container which is vacuumized and is filled with water, wherein R1'and R2'can be same or different and are respectively methyl or ethyl; R1 and R2 can be same or different and are respectively selected from linear alkyl containing 8-20 carbon atoms; n is an integer from 1-6; Q is a counter balance anion; (2) a fluoropolymer monomer is added; (3) free radical initiator is added; and (4) monomers containing fluorine are polymerized to obtain fluoropolymer emulsion of which the solid content is 10-30 wt%. The invention also discloses fluoropolymer aqueous dispersion emulsion prepared by the method. The general formula is as follows: R1 (R1') (R2') N+ (CH2) nN+ (R1') (R2') R2 2Q-.
Description
Technical Field
The invention relates to a fluorine-containing aqueous polymer dispersion emulsion without a fluorine-containing surfactant, and also relates to a preparation method of the fluorine-containing aqueous polymer dispersion emulsion.
Background
The fluorine-containing polymer has the characteristics of good weather resistance, wide application temperature range, excellent dielectric property, non-adhesiveness, low friction and the like. These properties make fluoropolymers increasingly used in industrial, consumer and military applications.
Specific examples of the common fluorine-containing polymer include Polytetrafluoroethylene (PTFE), a copolymer of Tetrafluoroethylene (TFE) and Hexafluoropropylene (HFP), perfluoroalkoxy copolymer (PFA), ethylene-tetrafluoroethylene (ETFE) copolymer, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, polyvinylidene fluoride (PVDF), and the like.
The fluoropolymer may be prepared by suspension polymerization (see U.S. Pat. No. 3,855,191), emulsion polymerization (see U.S. Pat. No. 3,635,926), solution polymerization (see U.S. Pat. No. 3,642,742), gas phase polymerization (see U.S. Pat. No. 4,861,845) and the like. The most common polymerization methods currently used include suspension polymerization and emulsion polymerization.
A common method for preparing the fluorine-containing polymer by adopting the emulsion polymerization method comprises the steps of polymerizing fluorine-containing monomers in emulsion by using a fluorine-containing surfactant to form fluorine-containing polymer emulsion (wherein the content of the fluorine-containing polymer is 10-40 wt% generally), then removing the fluorine-containing surfactant which generally influences the performance of products, adding a certain amount of hydrocarbon surfactant to stabilize the polymer emulsion, and finally increasing the content of the fluorine-containing polymer of the obtained polymer emulsion to 50-70 wt% by concentration.
The reason for the common use of fluorosurfactants in the preparation of fluoropolymers by emulsion polymerization is because other common surfactants do not result in a stable polymer emulsion and emulsion breaking of the resulting product emulsion is often observed.
In addition, the fluoropolymer emulsion prepared by using the fluorine-containing surfactant needs a step of removing the fluorine-containing surfactant so as to prevent the fluorine-containing surfactant from influencing the environment and generating a biological continuous aggregation effect to influence the health of human bodies. Conventional methods for eliminating fluorosurfactants (e.g., ammonium perfluorooctanoate surfactant) from fluoropolymer emulsions include thermal concentration, ultrafiltration, and ion exchange.
For example, U.S. patent application No. 2005070633 discloses a method for removing fluorosurfactant from aqueous fluoropolymer emulsions by ion exchange, which specifically discloses adding an effective amount of nonionic surfactant to an aqueous fluoropolymer emulsion and mixing thoroughly to stabilize the aqueous emulsion, then contacting the resulting mixture with an anion exchange resin, and thoroughly contacting the aqueous fluoropolymer emulsion and anion exchange resin by agitation. The process of this us patent enables the amount of ammonium perfluorooctanoate in the aqueous fluoropolymer emulsion to be reduced to the desired level.
The existing method for preparing fluorine-containing polymer by emulsion polymerization has two defects:
(a) the need to use fluorosurfactants during the polymerization process, which are generally not environmentally friendly; and
(b) special steps are required to remove the fluorosurfactant so that it does not affect the properties of the final product, resulting in increased production costs.
For example, perfluorooctanoic acid (PFOA) or its salt is a synthetic chemical that is a necessary processing aid in the manufacture of high performance fluoropolymers. The prepared high-performance fluorine-containing polymer has special properties, and is widely applied to the fields of civil articles such as aviation science and technology, transportation, electronic industry, kitchen and the like, textile, paper, fire-fighting foam, paint, stone protection and the like. Although no established research results show that the perfluorooctanoic acid or the salt thereof can cause harm to human health, the perfluorooctanoic acid or the salt thereof has the characteristics of high stability and difficult degradation in the environment, and becomes a novel global persistent environmental pollutant at present. Therefore, in the preparation of such high performance fluoropolymers, it is desirable to avoid the use of perfluorooctanoic acid or its salt compounds as much as possible.
To overcome the above-mentioned deficiencies of the prior art, the art proposes a number of methods to replace or reduce the use of perfluorooctanoic acid or its salts in fluoropolymer emulsion polymerization.
For example, International patent application No. WO9717381 discloses a process for preparing homopolymers or copolymers of Chlorotrifluoroethylene (CTFE) which employs a redox initiator system to initiate the polymerization and which is supplemented with initiator several times during the polymerization and is therefore a surfactant-free aqueous emulsion polymerization. The method can well control the particle size and the distribution of polymer particles, and can prepare stable emulsion with solid content of up to 50% under the condition of no emulsifier. However, this method requires the addition of both reducing and oxidizing agents, which means that additional feeding routes and control devices are required, and the simultaneous feeding inevitably increases the risk of failure in the polymerization process.
US patent application US2004041878 develops a process for the preparation of emulsifier free fluoropolymers. The method also employs a redox system as an initiating system comprising one or more fluoroolefins capable of reducing an oxidizing metal ion and an oxidizing metal ion. The method adjusts the fluoropolymer molecular weight by adding a chain transfer agent and either an oxidizing agent or a reducing agent is added during the polymerization process instead of both, or oxidizing metal ions are added to initiate the polymerization and oxidizing metal ions are added during the polymerization process. However, this method has disadvantages in that the kind of the fluoroolefin in the initiating system is limited, and the fluoropolymer produced by this method is generally an amorphous or semi-crystalline fluoropolymer.
It is desirable to produce fluoropolymers without or substantially without low molecular weight fluorosurfactants, which are harmful to humans, thereby reducing the environmental burden and reducing manufacturing costs without the need for subsequent steps to remove the fluorosurfactants.
Accordingly, there remains a need in the art to develop a method for preparing aqueous fluoropolymer dispersion emulsions that does not require the use of fluorosurfactants, thereby eliminating the need for a subsequent fluorosurfactant removal step.
Disclosure of Invention
The object of the present invention is to provide a process for producing an aqueous dispersion emulsion of a fluorine-containing polymer, which does not require the use of a fluorine-containing surfactant.
Another object of the present invention is to provide an aqueous dispersion emulsion of a fluoropolymer obtained by the above-mentioned method of the present invention.
Accordingly, one aspect of the present invention is directed to a method for preparing an aqueous fluoropolymer emulsion comprising the steps of:
(1) adding a non-fluorosurfactant having the formula:
R1(R1’)(R2’)N+(CH2)nN+(R2’)(R1’)R2 2Q-
wherein,
R1and R2May be the same or different and are each selected from straight chain alkyl groups having from 8 to 20 carbon atoms;
R1' and R2' may be the same or different, and each is methyl or ethyl;
n is an integer of 1 to 6;
q is a counter anion;
(2) polymerizing the fluorine-containing monomer in the presence of an initiator to obtain a fluorine-containing polymer emulsion with a solid content of 10-30 wt%.
Another aspect of the present invention is directed to an aqueous fluoropolymer emulsion made by the above process comprising a fluoropolymer and a non-fluorosurfactant of the formula:
R1(R1’)(R2’)N+(CH2)nN+(R1’)(R2’)R2 2Q-
wherein,
R1and R2May be the same or different and are each selected from straight chain alkyl groups having from 8 to 20 carbon atoms;
R1' and R2' may be the same or different, and each is methyl or ethyl;
n is an integer of 1 to 6;
q is a counter anion.
Detailed Description
The preparation method of the fluorine-containing polymer aqueous emulsion comprises the step of polymerizing fluorine-containing monomer in the presence of non-fluorine-containing surfactant to obtain the fluorine-containing polymer aqueous emulsion with the solid content of 10-30 wt%.
The process for preparing the aqueous fluoropolymer emulsion of the present invention is identical to the conventional emulsion polymerization process for preparing fluoropolymer emulsions, except for the non-fluorinated surfactant.
In the present invention, the term "aqueous solvent" means a mixture of water in which water is the major amount and other water-soluble solvents. Non-limiting examples of such water-soluble solvents are, for example, C1-6Alkanols (e.g. methanol, ethanol, propanol, butanol, glycerol, etc.), C3-6Ketones (e.g. acetone, methyl ethyl ketone, etc.), C2-6Ethers (e.g., diethyl ether, methyl ethyl ether, etc.) or mixtures of two or more thereof.
In the present invention, the term "water-based amount" means that the amount of water in the aqueous solvent is more than 90% by weight, for example, 90 to 99.5% by weight, preferably 92 to 99% by weight, more preferably 95 to 98% by weight.
Non-limiting examples of fluoropolymers suitable for use in the process of the present invention include Polytetrafluoroethylene (PTFE), copolymers of Tetrafluoroethylene (TFE) and Hexafluoropropylene (HFP) (FEP or F46), copolymers of tetrafluoroethylene and perfluoroalkoxy vinyl ether (PFA), ethylene-tetrafluoroethylene (ETFE) copolymers, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymers, and polyvinylidene fluoride (PVDF), and the like.
The aqueous fluoropolymer emulsion obtained by the polymerization process of the present invention generally has a solid content of 10 to 30% by weight, preferably 15 to 25% by weight, the average particle size of the fluoropolymer particles in water is 10 to 400nm, preferably 50 to 250nm, and the aqueous emulsion contains more than 500ppm by weight, preferably 550 to 1000ppm, more preferably 600 to 800ppm, of non-fluorinated surfactant.
Non-fluorosurfactants suitable for use in the process of the present invention have the general formula:
R1(R1’)(R2’)N+(CH2)nN+(R1’)(R2’)R2 2Q-
wherein,
R1' andR2' may be the same or different, and each is methyl or ethyl;
R1and R2May be the same or different and are each selected from straight chain alkyl groups having from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms, more preferably from 12 to 16 carbon atoms; non-limiting examples thereof include, for example, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and the like.
In one embodiment of the invention, R is1And R2The groups are the same straight-chain alkyl groups and are selected from n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and the like.
In the non-fluorine-containing surfactant, n is an integer of 1 to 6, preferably 1 to 4, more preferably 2 to 3.
In the non-fluorine-containing surfactant, the group as the counter anion Q is not particularly limited, and it may be any suitable counter anion.
In the present specification, for convenience of description, the counter example Q in the compound of the above general formula is represented as a monovalent anion. However, one of ordinary skill in the art will appreciate that the counterion is not limited to a monovalent anion, and can be an anion of any valency (e.g., a divalent anion, a trivalent anion, etc.) or a mixture of anionic groups, so long as charge balance is achieved.
Non-limiting examples of such counter anions are, for example, halogens (e.g., fluorine, chlorine, bromine, iodine), sulfates, sulfites, nitrates, carboxylates, phosphates, sulfides, and the like, preferably monovalent counter anions such as halogens and nitrates, most preferably halogens.
The non-fluorine-containing surfactant has double hydrophobic long carbon chains and double hydrophilic configurations, so that the non-fluorine-containing surfactant has many unique properties compared with the traditional surfactant, and is very suitable to be used as a surfactant for replacing perfluorooctanoic acid or salts thereof in the polymerization reaction of fluorine-containing monomers.
Non-limiting examples of suitable non-fluorosurfactants are, for example:
C8H17(CH3)2N+-(CH2)3-N+(CH3)2C8H17·2Br-；
C8H17(CH3)(C2H5)N+-(CH2)3-N+(CH3)2C8H17·2Br-；
C8H17(CH3)2N+-(CH2)2-N+(CH3)2C10H21·2Cl-；
C12H25(CH3)2N+-(CH2)3-N+(CH3)2C12H25·2Br-；
C12H25(CH3)2N+-(CH2)4-N+(CH3)2C10H21·2F-；
C14H29(CH3)2N+-(CH2)3-N+(CH3)2C14H29·2Br-；
C14H29(CH3)2N+-(CH2)3-N+(C2H5)2C14H29·2Br-；
C16H33(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-；
C16H33(CH3)2N+-(CH2)3-N+(CH3)2C14H19·2Cl-；
C18H37(CH3)2N+-(CH2)2-N+(CH3)2C18H37·2Br-；
C16H33(CH3)2N+-(CH2)3-N+(CH3)2C10H21·2Br-；
C16H33(CH3)(C2H5)N+-(CH2)3-N+(CH3)(C2H5)C10H21·2Br-；
C8H17(CH3)2N+-(CH2)4-N+(CH3)2C16H33·2Br-；
C9H19(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2I-；
C12H25(CH3)2N+-(CH2)3-N+(CH3)2C14H29·2Br-(ii) a Or
C15H31(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-。
The initiator suitable for use in the process of the present invention is not particularly limited and may be any conventional free radical initiator known in the art. Suitable free radical initiators can be readily determined by one of ordinary skill in the art after reading this disclosure.
In one embodiment of the invention, the free radical initiator used is selected from persulfates, such as ammonium persulfate and the like.
The aqueous emulsion of the fluorine-containing polymer prepared by the method has the same or similar performance with the emulsion prepared by the ammonium perfluorooctanoate, and the emulsion breaking phenomenon is not found. As a result, the method of the invention does not need to use ammonium perfluorooctanoate surfactant, and greatly reduces the influence on the environment.
In addition, the method can be directly concentrated and applied without an additional subsequent step of removing the fluorine-containing surfactant, thereby reducing the manufacturing cost.
In a preferred embodiment of the present invention, a nonionic surfactant is added to the aqueous fluoropolymer emulsion obtained by polymerization to concentrate and separate the aqueous emulsion, and an ionic liquid type surfactant is added after the supernatant liquid is skimmed off to further stabilize the resulting concentrated aqueous fluoropolymer emulsion.
Suitable nonionic surfactants can be any conventional surfactant known in the art, such as Triton X100, GENAPOL X080, trideceth, and the like. The amount of the nonionic surfactant added is also not particularly limited and may be any conventional amount known in the art. For example, 3000-9000ppm (w/w), such as 5000ppm (w/w), 4000ppm (w/w), 8000ppm (w/w), etc.
Suitable ionic liquid type surfactants are also not particularly limited and may be any conventional ionic liquid type surfactants known in the art, such as C12minBr (see journal of chemistry 2009, 67, 11, page 1159-1165). Such ionic liquid type surfactants are also commercially available. Example (b)For example, it is available from Shanghai Sanai Rich Co., Ltd under the trade name IIS-031. The amount of the ionic liquid type surfactant added is also not particularly limited, and may be any effective amount to stabilize the fluoropolymer. For example, the content thereof in the aqueous fluoropolymer emulsion may be 100-400ppm (w/w), preferably 150-300ppm (w/w), etc.
Another aspect of the present invention relates to an aqueous fluoropolymer emulsion made by the above-described process of the present invention comprising a fluoropolymer and a non-fluorosurfactant of the formula:
R1(R1’)(R2’)N+(CH2)nN+(R1’)(R2’)R2 2Q-
wherein,
R1' and R2' may be the same or different, and each is methyl or ethyl;
R1and R2May be the same or different and are each selected from straight chain alkyl groups having from 8 to 20 carbon atoms;
n is an integer of 1 to 6;
q is a counter anion.
The groups and the number of repeating units in the above non-fluorosurfactant are as described above.
The aqueous fluoropolymer emulsion of the present invention generally has a solid content of 10 to 30% by weight, preferably 15 to 25% by weight, the fluoropolymer particles have an average particle size in water of 10 to 400nm, preferably 50 to 250nm, and the aqueous emulsion contains more than 500ppm by weight, preferably 550 to 1000ppm, more preferably 600 to 800ppm of the non-fluorosurfactant.
The invention will now be further illustrated with reference to the following examples, which are, however, intended to be illustrative only and not limiting.
Practice ofExample (b)
The test method comprises the following steps:
viscosity of the oil
The viscosity of the dispersion was measured using a Brookfield Rheometer DV-III at a temperature of 20 ℃.
Stability test
200g of the aqueous fluoropolymer dispersion were filtered through a 100 mesh standard sieve, added to a 400ml plastic beaker having a height of 10cm and a diameter of 8cm, stirred at a high speed of 8000rpm for 5 minutes, and the resulting precipitate was filtered through a 100 mesh standard sieve, dried and weighed.
Surface tension
Surface tension was measured by clean, flame treated platinum plates using a tensioner according to ASTM D1331.
Example 1
Charging C into a 100 liter reaction vessel containing 60 liters of water12H25(CH3)2N+-(CH2)3-N+(CH3)2C12H25·2Br-To a concentration of 500ppm (w/w), followed by the addition of 0.4g of ammonium persulfate. After vacuumizing, tetrafluoroethylene is introduced to make the pressure of the reaction vessel reach 2.0 MPa. Subsequent polymerization at 75 ℃ for 2 and a half hours gave an aqueous emulsion of PTFE having a solids content of 25% by weight. The total amount of tetrafluoroethylene monomer added was 15 kg. No precipitate formed by breaking the emulsion was found to be present in the aqueous PTFE emulsion.
To this dispersion was added 5000ppm of tridecylpolyoxyethylene ether, heated at 50 ℃ and allowed to stand at 55 ℃ for 10 hours, and the supernatant liquid was decanted to obtain a 60% by weight PTFE concentrated dispersion. The fluoropolymer dispersion had a viscosity of 30 mPas and a surface tension of 36mN/m, and 75% of PTFE solids coagulated after stirring at 8000rpm for 5 min.
To this fluoropolymer dispersion was added an ionic liquid type surfactant (IIS-031 available from Sanai Rich corporation, Shanghai) to a concentration of 200ppm (w/w as solids), and the mixture was stirred for 30 minutes, and then an appropriate amount of an aqueous NaCl solution was added to make the conductivity 700. mu.s/cm, and the mixture was stirred for 10 minutes, whereby the fluoropolymer dispersion was found to have a viscosity of 28 mPas and a surface tension of 29mN/m, and 10% of PTFE solid coagulated after stirring at 8000rpm for 5 minutes.
Example 2
Charging C into a 100 liter reaction vessel containing 60 liters of water16H33(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-To a concentration of 600ppm (w/w), followed by the addition of 0.4g of ammonium persulfate. And vacuumizing, introducing tetrafluoroethylene to enable the pressure of a reaction system to reach 2.0MPa, and polymerizing for 2 and half hours at the temperature of 75 ℃ to obtain a PTFE aqueous dispersion liquid with the solid content of 25 weight percent, wherein the total addition of the tetrafluoroethylene monomer is 15 kg. No precipitate formed by breaking the emulsion was found to be present in the aqueous PTFE emulsion.
To this dispersion was added 5000ppm of tridecylpolyoxyethylene ether, heated at 50 ℃ and allowed to stand at 55 ℃ for 10 hours, and the supernatant liquid was decanted to obtain a 70% by weight PTFE concentrated dispersion. To this fluoropolymer dispersion was added an ionic liquid type surfactant (IIS-031 available from Sanai Rich corporation, Shanghai) to a concentration of 200ppm (w/w as solids), and the mixture was stirred for 30 minutes, and then an appropriate amount of an aqueous NaCl solution was added to make the conductivity 700. mu.s/cm and stirred for 10 minutes, whereby the fluoropolymer dispersion had a viscosity of 28 mPas and a surface tension of 28mN/m, and 8% of PTFE solid coagulated after stirring at 8000rpm for 5 minutes.
Example 3
Charging C into a 100 liter reaction vessel containing 60 liters of water16H33(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-To a concentration of 1000ppm (w/w), followed by addition of 0.4g of ammonium persulfate. After vacuumizing, tetrafluoroethylene monomer is introduced to make the pressure of the reaction system reach 2.0 MPa. Polymerization was carried out at a temperature of 75 ℃ for 2 and a half hours to give an aqueous dispersion of PTFE having a solids content of 25% by weight, the final amount of tetrafluoroethylene added being 15 kg. No precipitate formed by breaking the emulsion was found to be present in the aqueous PTFE emulsion.
To this dispersion was added 5000ppm of tridecylpolyoxyethylene ether, heated at 50 ℃ and allowed to stand at 55 ℃ for 10 hours, and the supernatant liquid was decanted to obtain a 65% by weight concentrated dispersion of PTFE. To this fluoropolymer dispersion was added an ionic liquid (IIS-031, available from Sanai-Fuyunji Co., Ltd., Shanghai) to a concentration of 200ppm (w/w, in terms of solids), stirred for 30min, and an appropriate amount of an aqueous NaCl solution was added to give an electrical conductivity of 700. mu.s/cm, stirred for 10min, whereupon the fluoropolymer dispersion had a viscosity of 29 mPas and a surface tension of 28mN/m, and 8% of PTFE solid coagulated after 5min of high-speed stirring at 8000 rpm.
Comparative example 1
Ammonium perfluorooctanoate was added to a concentration of 1000ppm in a 100 liter reaction vessel containing 60 liters of water, followed by the addition of 0.4g of ammonium persulfate. After vacuumizing, tetrafluoroethylene monomer is introduced to make the pressure of the reaction system reach 2.0 MPa. Polymerization was carried out at a temperature of 75 ℃ for 2 and a half hours to obtain an aqueous dispersion of PTFE having a solids content of 25% by weight, and the final amount of tetrafluoroethylene monomer added was 15 kg. No precipitate formed by breaking the emulsion was found to be present in the aqueous PTFE emulsion.
To this dispersion was added 5000ppm of tridecylpolyoxyethylene ether, heated at 50 ℃ and allowed to stand at 55 ℃ for 10 hours, and the supernatant liquid was decanted to obtain a 60% by weight PTFE concentrated dispersion. The fluoropolymer dispersion had a viscosity of 30 mPas and a surface tension of 33mN/m, and 25% of PTFE solid coagulated after stirring at 8000rpm for 5 min.
Practice ofExample 4
Charging C into a 100 liter reaction vessel containing 60 liters of water16H33(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-To a concentration of 600ppm (w/w), followed by the addition of 0.4g of ammonium persulfate. After the reaction system was evacuated, a mixed gas of tetrafluoroethylene and hexafluoropropylene was introduced to make the pressure of the reaction system 3.0MPa, and polymerization was carried out at 95 ℃ for 2 and half hours to obtain an aqueous dispersion of fluorinated ethylene propylene having a solid content of 25% by weight, wherein the total amount of the tetrafluoroethylene monomer added was 15 kg and the total amount of the hexafluoropropylene monomer added was 4 kg. No precipitate formed by breaking was found in the aqueous perfluoroethylene-propylene emulsion.
To this dispersion was added 5000ppm of tridecylpolyoxyethylene ether, heated at 50 ℃ and allowed to stand at 55 ℃ for 10 hours, and the supernatant liquid was decanted to obtain a 40% by weight concentrated dispersion of polyperfluoroethylene propylene. To this fluoropolymer dispersion was added an ionic liquid type surfactant (IIS-031, available from Sanai-Rich corporation, Shanghai) to a concentration of 200ppm (w/w, as solids), stirred for 30min, and an appropriate amount of aqueous NaCl solution was added to make the conductivity 800. mu.s/cm, stirred for 10min, whereupon the fluoropolymer dispersion had a viscosity of 10 mPas and a surface tension of 27mN/m, and after 5min of high-speed stirring at 8000rpm, 0% of polyperfluoroethylene propylene solid coagulated.
As can be seen from the above test results, the use of the non-fluorosurfactant of the present invention in place of the fluorosurfactant (e.g., ammonium perfluorooctanoate surfactant) results in a fluoropolymer emulsion, and no demulsification of the resulting emulsion is observed.
Claims (17)
1. A method for preparing aqueous emulsion of fluorine-containing polymer comprises the following steps:
(1) adding a non-fluorosurfactant having the formula:
R1(R1’)(R2’)N+(CH2)nN+(R1’)(R2’)R22Q-
wherein,
R1and R2The same or different, and the same or different,each selected from linear alkyl groups having from 8 to 20 carbon atoms;
R1' and R2' same or different, each is methyl or ethyl;
n is an integer of 1 to 6;
q is a counter anion;
(2) polymerizing the fluorine-containing polymerized monomer in the presence of a free radical initiator to obtain a fluorine-containing polymer emulsion having a solid content of 10 to 30% by weight.
2. The method of claim 1, wherein said fluoropolymer is selected from the group consisting of polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, perfluoroalkoxy copolymers, ethylene-tetrafluoroethylene copolymers, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymers, and polyvinylidene fluoride;
the non-fluorosurfactant is present at a concentration greater than 500ppm by weight.
3. The method of claim 2 wherein the non-fluorosurfactant is present at a concentration of 550-1000ppm by weight.
4. The method of claim 3 wherein the non-fluorosurfactant is present at a concentration of 600-800ppm by weight.
5. The method of claim 1 or 2, wherein R is1And R2Identical or different, each being selected from linear alkyl groups having from 10 to 18 carbon atoms.
6. The method of claim 1 or 2, wherein R is1And R2Identical or different, each being selected from linear alkyl groups having from 12 to 16 carbon atoms.
7. The method of claim 1 or 2, wherein R is1And R2The same or different, each being selected from the group consisting of n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl.
8. The method of claim 1 or 2, wherein n is an integer from 1 to 4.
9. A method according to claim 1 or 2, characterized in that n is an integer from 2 to 3.
10. The method of claim 1 or 2, wherein the non-fluorosurfactant is selected from the group consisting of:
C8H17(CH3)2N+-(CH2)3-N+(CH3)2C8H17·2Br-；
C8H17(CH3)(C2H5)N+-(CH2)3-N+(CH3)2C8H17·2Br-；
C8H17(CH3)2N+-(CH2)2-N+(CH3)2C10H21·2Cl-；
C12H25(CH3)2N+-(CH2)3-N+(CH3)2C12H25·2Br-；
C12H25(CH3)2N+-(CH2)4-N+(CH3)2C10H21·2F-；
C14H29(CH3)2N+-(CH2)3-N+(CH3)2C14H29·2Br-；
C14H29(CH3)2N+-(CH2)3-N+(C2H5)2C14H29·2Br -；C16H33(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-；
C16H33(CH3)2N+-(CH2)3-N+(CH3)2C14H19·2Cl-；
C16H33(CH3)(C2H5)N+-(CH2)3-N+(CH3)(C2H5)C10H21·2Br-；
C18H37(CH3)2N+-(CH2)2-N+(CH3)2C18H37·2Br-；
C16H33(CH3)2N+-(CH2)3-N+(CH3)2C10H21·2Br-；
C8H17(CH3)2N+-(CH2)4-N+(CH3)2C16H33·2Br-；
C9H19(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2I-；
C12H25(CH3)2N+-(CH2)3-N+(CH3)2C14H29·2Br-(ii) a Or
C15H31(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-。
11. A fluoropolymer emulsion comprising a fluoropolymer and a non-fluorosurfactant of the formula:
R1(R1’)(R2’)N+(CH2)nN+(R1’)(R2’)R22Q-
wherein,
R1' and R2' same or different, each is methyl or ethyl;
R1and R2Identical or different, each selected from linear alkyl groups having from 8 to 20 carbon atoms;
n is an integer of 1 to 6;
q is a counter anion.
12. The fluoropolymer emulsion of claim 11 wherein said fluoropolymer is selected from the group consisting of polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and perfluoroalkylvinylether, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, and polyvinylidene fluoride;
the non-fluorosurfactant is present at a concentration greater than 500ppm by weight.
13. The fluoropolymer emulsion of claim 12 wherein the concentration of non-fluorosurfactant is 550-1000ppm by weight.
14. The fluoropolymer emulsion of claim 13 wherein the concentration of non-fluorosurfactant is 600-800ppm by weight.
15. Fluoropolymer emulsion according to claim 11 or 12 wherein R is1And R2Identical or different, each being selected from the group consisting of n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl; and n is an integer of 1-4.
16. The fluoropolymer emulsion of claim 15 wherein n is an integer from 2 to 3.
17. Fluoropolymer emulsion according to claim 11 or 12 wherein said non-fluorosurfactant is selected from the group consisting of:
C8H17(CH3)2N+-(CH2)3-N+(CH3)2C8H17·2Br-；
C8H17(CH3)(C2H5)N+-(CH2)3-N+(CH3)2C8H17·2Br-；
C8H17(CH3)2N+-(CH2)2-N+(CH3)2C10H21·2Cl-；
C12H25(CH3)2N+-(CH2)3-N+(CH3)2C12H25·2Br-；
C12H25(CH3)2N+-(CH2)4-N+(CH3)2C10H21·2F-；
C14H29(CH3)2N+-(CH2)3-N+(CH3)2C14H29·2Br-；
C14H29(CH3)2N+-(CH2)3-N+(C2H5)2C14H29·2Br-；
C16H33(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-；
C16H33(CH3)2N+-(CH2)3-N+(CH3)2C14H19·2Cl-；
C16H33(CH3)(C2H5)N+-(CH2)3-N+(CH3)(C2H5)C10H21·2Br-；
C18H37(CH3)2N+-(CH2)2-N+(CH3)2C18H37·2Br-；
C16H33(CH3)2N+-(CH2)3-N+(CH3)2C10H21·2Br-；
C8H17(CH3)2N+-(CH2)4-N+(CH3)2C16H33·2Br-；
C9H19(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2I-；
C12H25(CH3)2N+-(CH2)3-N+(CH3)2C14H29·2Br-(ii) a Or
C15H31(CH3)2N+-(CH2)3-N+(CH3)2C16H33·2Br-。
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| CN102344519B (en) * | 2011-07-13 | 2013-04-10 | 山东东岳高分子材料有限公司 | Production method of modified polytetrafluoroethylene dispersion resin suitable for processing capillary tubes |
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