CN101787091B - Fluoropolymer aqueous dispersion emulsion and preparation method thereof - Google Patents

Fluoropolymer aqueous dispersion emulsion and preparation method thereof Download PDF

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Publication number
CN101787091B
CN101787091B CN2010100228946A CN201010022894A CN101787091B CN 101787091 B CN101787091 B CN 101787091B CN 2010100228946 A CN2010100228946 A CN 2010100228946A CN 201010022894 A CN201010022894 A CN 201010022894A CN 101787091 B CN101787091 B CN 101787091B
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fluoropolymer
emulsion
fluorochemical surfactant
tetrafluoroethylene
positive
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CN101787091A (en
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纪云
粟小理
乐勇坚
俞子豪
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Shanghai Huayi sanaifu New Material Co., Ltd
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Shanghai 3F New Materials Co Ltd
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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

A kind of fluoropolymer aqueous dispersion emulsion and preparation method thereof
Technical field
The present invention relates to a kind of fluoropolymer aqueous dispersion emulsion that does not contain fluorochemical surfactant, also relate to the preparation method of this fluoropolymer aqueous dispersion emulsion.
Background technology
Fluoropolymer has good weatherability, and the use temperature scope is wide, dielectric properties are excellent, characteristic such as viscosity, low frictional properties not.These characteristics make fluoropolymer obtain increasingly extensive application in industrial circle, daily field, military domain.
The object lesson of common fluoropolymer comprises multipolymer, perfluoroalkyl alkoxy copolymer (PFA), ethylene-tetrafluoroethylene (ETFE) multipolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers and the polyvinylidene difluoride (PVDF) (PVDF) etc. of polytetrafluoroethylene (PTFE), tetrafluoroethylene (TFE) and R 1216 (HFP).
The preparation fluoropolymer can adopt suspension polymerization (referring to U.S. Pat 3,855,191), emulsion polymerization is (referring to U.S. Pat 3,635,926), solution polymerization process (referring to U.S. Pat 3,642,742), gaseous polymerization are (referring to U.S. Pat 4, method such as 861,845).The most frequently used polymerization process comprises suspension polymerization and emulsion polymerization at present.
The method that common employing emulsion polymerization prepares fluoropolymer comprises use fluorochemical surfactant polymerization fluorochemical monomer in emulsion; form fluoropolymer emulsion (wherein the content of fluoropolymer is generally 10%-40 weight %); remove the fluorochemical surfactant that can influence product performance usually then; add a certain amount of hc-surfactant with the stabilization of polymer emulsion, be increased to 50～70 weight % by the fluoropolymer content that concentrates the polymer emulsion that to obtain at last.
Usually the reason of using fluorochemical surfactant during by the emulsion polymerization prepared fluoropolymer is because other common tensio-active agent can not obtain the stable polymer emulsion, observes the product emulsion generation demulsifying phenomenon that obtains usually.
In addition, the fluoropolymer emulsion that uses fluorochemical surfactant to make needs a step of removing fluorochemical surfactant, in order to avoid this fluorochemical surfactant exerts an influence to environment and produces the biological crowding effect that continues, influences HUMAN HEALTH.The method of fluorochemical surfactant in traditional elimination fluoropolymer emulsion (for example Perfluorocaprylic Acid ammonium surfactant) has hot method of enrichment, ultrafiltration process and ion exchange method.
For example, U.S. Patent application US 2005070633 discloses a kind of method of eliminating fluorochemical surfactant in the fluoropolymer aqueous dispersion emulsion with ion exchange method, it specifically discloses nonionic surface active agent and the thorough mixing that adds significant quantity in fluoropolymer aqueous dispersion emulsion, make water-based emulsion stable, the mixture that obtains is contacted with anionite-exchange resin, fluoropolymer aqueous dispersion emulsion is fully contacted with anionite-exchange resin by stirring.This United States Patent (USP) method can make the amount of the ammonium perfluorocaprylate in the fluoropolymer aqueous dispersion emulsion be reduced to the level that requires.
The existing method for preparing fluoropolymer with emulsion polymerization has two big shortcomings:
(a) need to use fluorochemical surfactant in the polymerization process process, common this fluorochemical surfactant is not to be eco-friendly; With
(b) need special step to remove fluorochemical surfactant in order to avoid it influences the performance of the finished product, the result has improved production cost.
For example, Perfluorocaprylic Acid (PFOA) or its salt are a kind of chemical of synthetic, are to make processing aid necessary in the high-performance fluorine-containing polymer process.The high-performance fluorine-containing polymer property that makes is special, is widely used in people's livelihood articles for use and fields such as textiles, stationery, fire-fighting foams, coating and stone material protection such as science and technology of aviation, transportation, electron trade, kitchen.Though the achievement in research that not have at present to determine shows that Perfluorocaprylic Acid or its salt can work the mischief to human health, the characteristics that Perfluorocaprylic Acid or its salt is highly stable, be difficult to degrade in environment become novel global persistence environmental pollutant now.Therefore, in this type of high performance fluorine polymer manufacture process, hope can avoid using Perfluorocaprylic Acid or its esters compound as far as possible.
For overcoming the above-mentioned defective of prior art, this area has proposed many methods and has substituted or reduce Perfluorocaprylic Acid or the application of its salt in the fluoropolymer emulsion polymerization.
For example, application number is that the international application for patent of WO9717381 discloses the homopolymer of a kind of preparation trifluorochloroethylene (CTFE) or the method for multipolymer, it adopts redox initiation system to come initiated polymerization, and in polymerization process, repeatedly add initiator, so it is a kind of aqueous emulsion polymerization of surfactant-free.This method is controlling polymers grain diameter size and distributing well, and this is external not to have can to make under the situation of emulsifying agent solid content up to 50% stable emulsion.But this method requires to add simultaneously reductive agent and oxygenant, and this just means that needs increase extra reinforced route and control device, and the reinforced simultaneously risk of failing in the polymerization process that inevitably increased.
U.S. Patent application US2004041878 develops a kind of preparation method of fluoropolymer of emulsifier-free.This method also adopts redox system to make initiator system, wherein comprises the Fluorine containing olefine and the oxidative metal ion of one or more energy oxygen reduction voltinism metal ions.This method all adds by adding chain-transfer agent and adjust the fluoropolymer molecular weight and add a kind of in oxygenant or the reductive agent rather than two kinds again in polymerization process, perhaps adds the oxidative metal ion initiated polymerization and add oxidative metal ion in polymerization process.But the shortcoming of this method is that the kind of Fluorine containing olefine limits to some extent in the initiator system, and the fluoropolymer of this method preparation generally is non-crystalline state or hypocrystalline fluoropolymer.
The present lower molecular weight fluorochemical surfactant that the preparation method of ideal fluoropolymer preferably need not or substantially need not be harmful, thus can reduce environmental pressure and need not the follow-up step of removing fluorochemical surfactant and reduce manufacturing cost.
Therefore, this area still needs to develop a kind of preparation method of fluoropolymer aqueous dispersion emulsion, and it does not need to use fluorochemical surfactant, thereby has eliminated the step of removing fluorochemical surfactant subsequently.
Summary of the invention
Goal of the invention of the present invention provides a kind of preparation method of fluoropolymer aqueous dispersion emulsion, and it does not need to use fluorochemical surfactant.
Another object of the present invention provides a kind of fluoropolymer aqueous dispersion emulsion that makes with aforesaid method of the present invention.
Therefore, one aspect of the present invention relates to a kind of preparation method of fluoropolymer aqueous dispersion emulsion, and it comprises the steps:
(1) in the reaction vessel that water or aqueous solvent are housed, add non-fluorochemical surfactant with following general formula:
R 1(R 1’)(R 2’)N +(CH 2) nN +(R 2’)(R 1’)R 2?2Q -
Wherein,
R 1And R 2Can be identical or different, be selected from straight chained alkyl separately with 8-20 carbon atom;
R 1' and R 2' can be identical or different, respectively do for oneself methyl or ethyl;
N is the integer of 1-6;
Q is a counter anion;
(2) polymerization fluorochemical monomer in the presence of initiator obtains the fluoropolymer emulsion that solid content is 10-30 weight %.
Another aspect of the present invention relates to a kind of fluoropolymer aqueous dispersion emulsion that makes with aforesaid method, and it comprises the non-fluorochemical surfactant of fluoropolymer and following general formula:
R 1(R 1’)(R 2’)N +(CH 2) nN +(R 1’)(R 2’)R 2?2Q -
Wherein,
R 1And R 2Can be identical or different, be selected from straight chained alkyl separately with 8-20 carbon atom;
R 1' and R 2' can be identical or different, respectively do for oneself methyl or ethyl;
N is the integer of 1-6;
Q is a counter anion.
Embodiment
The preparation method of fluoropolymer aqueous dispersion emulsion of the present invention is included in polymerization fluorochemical monomer under the existence of non-fluorochemical surfactant, and obtaining solid content is the step of the fluoropolymer aqueous dispersion emulsion of 10-30 weight %.
Except described non-fluorine surfactant, it is identical that the preparation method of fluoropolymer aqueous dispersion emulsion of the present invention and traditional being used to prepare the emulsion polymerisation process of fluoropolymer emulsion.
In the present invention, term " aqueous solvent " is meant that water accounts for the water of main amount and the mixture that other water-soluble solvent forms.The indefiniteness example of described water-soluble solvent has, for example C 1-6Alkanol (as methyl alcohol, ethanol, propyl alcohol, butanols, glycerol etc.), C 3-6Ketone (for example acetone, methylethylketone etc.), C 2-6Two or more mixture of ether (for example ether, methyl ethyl ether etc.) or its.
In the present invention, term " water accounts for main amount " is meant that the amount of water in the aqueous solvent surpasses 90 weight %, for example 90-99.5 weight %, better 92-99 weight %, better 95-98 weight %.
The indefiniteness example that is applicable to the fluoropolymer of the inventive method comprises multipolymer (FEP or F46), tetrafluoroethylene and perfluorinated alkoxy vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene (ETFE) multipolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers and the polyvinylidene difluoride (PVDF) (PVDF) etc. of polytetrafluoroethylene (PTFE), tetrafluoroethylene (TFE) and R 1216 (HFP).
The solid content of the fluoropolymer aqueous dispersion emulsion that makes with polymerization process of the present invention is generally 10-30 weight %, be preferably 15-25 weight %, the mean particle size of described fluoropolymer particles in water is 10-400nm, be preferably 50-250nm, and contain in the above-mentioned water-based emulsion greater than 500ppm (weight), be preferably 550-1000ppm, more preferably the non-fluorochemical surfactant of 600-800ppm.
The non-fluorochemical surfactant that is applicable to the inventive method has following general formula:
R 1(R 1’)(R 2’)N +(CH 2) nN +(R 1’)(R 2’)R 2?2Q -
Wherein,
R 1' and R 2' can be identical or different, respectively do for oneself methyl or ethyl;
R 1And R 2Can be identical or different, be selected from separately and have 8-20 carbon atom, better 10-18 carbon atom, the better straight chained alkyl of 12-16 carbon atom; Its indefiniteness example has, for example n-octyl, n-nonyl, positive decyl, positive ten dicarbonyls, positive 14 carbon backs, positive 16 carbon backs, positive 18 carbon backs etc.
In an example of the present invention, described R 1And R 2Group is identical straight chained alkyl, is selected from positive ten dicarbonyls, positive 14 carbon backs, positive 16 carbon backs, positive 18 carbon backs etc.
In described non-fluorochemical surfactant, n is 1-6, is preferably 1-4, more preferably the integer of 2-3.
In described non-fluorochemical surfactant, without particular limitation as the group of counter anion Q, it can be any suitable counter anion.
In this manual, for convenient statement, the example Q that contends with in the above-mentioned general formula compound is expressed as univalent anion.But, those having ordinary skill in the art will appreciate that these counter ion are not limited to univalent anion, it can be the negatively charged ion (for example two valency negatively charged ion, trivalent negatively charged ion etc.) of any valence state or the mixture of anionic group, as long as can reach charge balance.
The indefiniteness example of described counter anion has, and for example halogen (as fluorine, chlorine, bromine, iodine), sulfate radical, inferior sulfate radical, nitrate radical, carboxylate radical, phosphate radical, sulfonium ion etc. better are monovalence counter anion such as halogen and nitrate radical, preferably halogen.
Described non-fluorochemical surfactant is because of its distinctive two hydrophobic long carbochains and double-hydrophilic configuration, therefore comparing it with conventional surfactant presents many particular performances, is suitable as very much the polyreaction that tensio-active agent replacement Perfluorocaprylic Acid or its salt are used for fluorochemical monomer.
The indefiniteness example of suitable non-fluorochemical surfactant has, for example:
C 8H 17(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 8H 17·2Br -；
C 8H 17(CH 3)(C 2H 5)N +-(CH 2) 3-N +(CH 3) 2C 8H 17·2Br -；
C 8H 17(CH 3) 2N +-(CH 2) 2-N +(CH 3) 2C 10H 21·2Cl -；
C 12H 25(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 12H 25·2Br -；
C 12H 25(CH 3) 2N +-(CH 2) 4-N +(CH 3) 2C 10H 21·2F -；
C 14H 29(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 29·2Br -；
C 14H 29(CH 3) 2N +-(CH 2) 3-N +(C 2H 5) 2C 14H 29·2Br -；
C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2Br -；
C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 19·2Cl -；
C 18H 37(CH 3) 2N +-(CH 2) 2-N +(CH 3) 2C 18H 37·2Br -；
C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 10H 21·2Br -；
C 16H 33(CH 3)(C 2H 5)N +-(CH 2) 3-N +(CH 3)(C 2H 5)C 10H 21·2Br -；
C 8H 17(CH 3) 2N +-(CH 2) 4-N +(CH 3) 2C 16H 33·2Br -；
C 9H 19(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2I -；
C 12H 25(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 292Br -Perhaps
C 15H 31(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2Br -。
Suitable initiator with the inventive method is without particular limitation, can be any conventional free radical initiator known in the art.After having read content disclosed by the invention, those of ordinary skill in the art can easily determine suitable radical initiator.
In an example of the present invention, the radical initiator of use is selected from persulphate, for example ammonium persulphate etc.
The fluoropolymer aqueous dispersion emulsion that makes with the inventive method has identical or similar performance with the emulsion that makes with ammonium perfluorocaprylate, does not find to exist demulsifying phenomenon.The inventive method need not to use the Perfluorocaprylic Acid ammonium surfactant as a result, has greatly alleviated the influence to environment.
In addition, the step that the inventive method need not extra follow-up removal fluorochemical surfactant just can directly concentrate application, thereby has reduced manufacturing cost.
In a better example of the present invention, in the fluoropolymer aqueous dispersion emulsion that polymerization obtains, add nonionogenic tenside, so that make this water-based emulsion concentrate layering, after skimming supernatant liquor, add the further stable spissated fluoropolymer aqueous dispersion emulsion that obtains of ion liquid type tensio-active agent.
Suitable nonionogenic tenside can be any conventional surfactants known in the art, for example Triton X 100, GENAPOL X080, tridecyl polyoxyethylene groups ether etc.The add-on of described nonionogenic tenside is also without particular limitation, can be the content of any routine known in the art.For example, 3000-9000ppm (w/w) is as 5000ppm (w/w), 4000ppm (w/w), 8000ppm (w/w) etc.
Suitable ion liquid type tensio-active agent is also without particular limitation, can be the ion liquid type tensio-active agent of any routine known in the art, for example C 12MinBr (seeing " chemical journal " 2009 67 volumes o. 11th 1159-1165 page or leaf).This ion liquid type surfactivity also is commercially available.For example, the trade(brand)name that it can IIS-031 is available from Shanghai three Ai Fu limited-liability company.The add-on of described ion liquid type tensio-active agent is also without particular limitation, can be the significant quantity of any stabilize fluoropolymer.For example its content can be 100-400ppm (w/w) in fluoropolymer aqueous dispersion emulsion, is preferably 150-300ppm (w/w) etc.
Another aspect of the present invention relates to the fluoropolymer aqueous dispersion emulsion that makes with aforesaid method of the present invention, and it comprises the non-fluorochemical surfactant of fluoropolymer and following general formula:
R 1(R 1’)(R 2’)N +(CH 2) nN +(R 1’)(R 2’)R 2?2Q -
Wherein,
R 1' and R 2' can be identical or different, respectively do for oneself methyl or ethyl;
R 1And R 2Can be identical or different, be selected from straight chained alkyl separately with 8-20 carbon atom;
N is the integer of 1-6;
Q is a counter anion.
Each group in the above-mentioned non-fluorochemical surfactant and the quantity of repeating unit are all as previously described.
The solid content of fluoropolymer aqueous dispersion emulsion of the present invention is generally 10-30 weight %, be preferably 15-25 weight %, the mean particle size of described fluoropolymer particles in water is 10-400nm, be preferably 50-250nm, and contain in the above-mentioned water-based emulsion greater than 500ppm (weight), be preferably 550-1000ppm, more preferably the described non-fluorochemical surfactant of 600-800ppm.
Further specify the present invention below with reference to embodiment, yet the intention of described embodiment only is explanation and does not lie in restriction the present invention.
Embodiment
Test method:
Viscosity
Use Brookfield Rheometer DV-III, 20 ℃ of viscosity of measuring dispersion down of temperature.
Stability test
The 200g fluoropolymer dispersion in water filters with 100 mesh standard sieves, joins high 10cm, in the 400ml plastic beaker of diameter 8cm, at 8000rpm high-speed stirring 5min, the precipitation that generates is filtered by 100 mesh standard sieves, and dry, weigh.
Surface tension
According to ASTM D1331, use tightening pulley, by platinum plate surface tension cleaning, flame treating.
Embodiment 1
In 100 liters of reaction vessels that 60 premium on currency are housed, add C 12H 25(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 12H 252Br -Make it concentration and reach 500ppm (w/w), add the ammonium persulphate of 0.4g subsequently.Vacuumize the back and feed tetrafluoroethylene, make the pressure of reaction vessel reach 2.0MPa.75 ℃ temperature polymerization 2 and a half hours, obtain the PTFE water-based emulsion of solid content 25 weight % subsequently.Total add-on of tetrafluoroethylene monomer is 15 kilograms.Do not find the throw out that this PTFE water-based emulsion exists breakdown of emulsion to form.
In this dispersion liquid, add 5000ppm tridecyl polyoxyethylene groups ether, 50 ℃ of heating, and in 55 ℃ static 10 hours, the supernatant liquid that inclines, the PTFE that obtains 60 weight % concentrates dispersion liquid.This fluoropolymer dispersions viscosity is 30mPas, and surface tension is 36mN/m, and 75% PTFE solid cohesion is arranged behind 8000rpm high-speed stirring 5min.
In this fluoropolymer dispersions, add ion liquid type tensio-active agent (IIS-031, available from Shanghai three Ai Fu limited-liability company), making its concentration is 200ppm (w/w is in solid), stirs 30min, add an amount of NaCl aqueous solution, making specific conductivity is 700 μ s/cm, stirs 10min, and recording fluoropolymer dispersions viscosity is 28mPas, surface tension is 29mN/m, and 10% PTFE solid cohesion is arranged behind 8000rpm high-speed stirring 5min.
Embodiment 2
In 100 liters of reaction vessels that 60 premium on currency are housed, add C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 332Br -Make its concentration reach 600ppm (w/w), add the ammonium persulphate of 0.4g subsequently.Vacuumize back feeding tetrafluoroethylene and make the pressure of reaction system reach 2.0MPa, polymerization is 2 and a half hours under 75 ℃ temperature, obtains the PTFE aqueous liquid dispersion of solid content 25 weight %, and total add-on of tetrafluoroethylene monomer is 15 kilograms.Do not find the throw out that this PTFE water-based emulsion exists breakdown of emulsion to form.
In this dispersion liquid, add 5000ppm tridecyl polyoxyethylene groups ether, 50 ℃ of heating, and in 55 ℃ static 10 hours, the supernatant liquid that inclines, the PTFE that obtains 70 weight % concentrates dispersion liquid.In this fluoropolymer dispersions, add ion liquid type tensio-active agent (IIS-031, available from Shanghai three Ai Fu limited-liability company), making its concentration is 200ppm (w/w is in solid), stirs 30min, add an amount of NaCl aqueous solution, making specific conductivity is 700 μ s/cm, stirs 10min, and this moment, fluoropolymer dispersion viscosity was 28mPas, surface tension is 28mN/m, and 8% PTFE solid cohesion is arranged behind 8000rpm high-speed stirring 5min.
Embodiment 3
In 100 liters of reaction vessels that 60 premium on currency are housed, add C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 332Br -, make it concentration 1000ppm (w/w), add the ammonium persulphate of 0.4g subsequently.Vacuumizing back feeding tetrafluoroethylene monomer makes the pressure of reaction system reach 2.0MPa.Polymerization is 2 and a half hours under 75 ℃ temperature, obtains the PTFE aqueous liquid dispersion of solid content 25 weight %, and final tetrafluoroethylene add-on is 15 kilograms.Do not find the throw out that this PTFE water-based emulsion exists breakdown of emulsion to form.
In this dispersion liquid, add 5000ppm tridecyl polyoxyethylene groups ether, 50 ℃ of heating, and in 55 ℃ static 10 hours, the supernatant liquid that inclines, the PTFE that obtains 65 weight % concentrates dispersion liquid.In this fluoropolymer dispersions, add ionic liquid (IIS-031, available from Shanghai three Ai Fu limited-liability company), making its concentration is 200ppm (w/w is in solid), stirs 30min, add an amount of NaCl aqueous solution, making specific conductivity is 700 μ s/cm, stirs 10min, and this moment, fluoropolymer dispersion viscosity was 29mPas, surface tension is 28mN/m, and 8% PTFE solid cohesion is arranged behind 8000rpm high-speed stirring 5min.
Comparative Examples 1
In 100 liters of reaction vessels that 60 premium on currency are housed, add ammonium perfluorocaprylate, make it concentration and reach 1000ppm, add the ammonium persulphate of 0.4g subsequently.Vacuumizing the back feeds the pressure that tetrafluoroethylene monomer makes it reaction system and reaches 2.0MPa.75 ℃ temperature polymerizations 2 and a half hours, obtain the PTFE aqueous liquid dispersion of solid content 25 weight %, the add-on of final tetrafluoroethylene monomer is 15 kilograms.Do not find the throw out that this PTFE water-based emulsion exists breakdown of emulsion to form.
In this dispersion liquid, add 5000ppm tridecyl polyoxyethylene groups ether, 50 ℃ of heating, and in 55 ℃ static 10 hours, the supernatant liquid that inclines, the PTFE that obtains 60 weight % concentrates dispersion liquid.This fluoropolymer dispersions viscosity is 30mPas, and surface tension is 33mN/m, and 25% PTFE solid cohesion is arranged behind 8000rpm high-speed stirring 5min.
Embodiment 4
In 100 liters of reaction vessels that 60 premium on currency are housed, add C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 332Br -Make its concentration reach 600ppm (w/w), add the ammonium persulphate of 0.4g subsequently.The mixed gas that vacuumizes back feeding tetrafluoroethylene and R 1216 makes the pressure of reaction system reach 3.0MPa, polymerization is 2 and a half hours under 95 ℃ temperature, obtain the perfluoroethylene-propylene aqueous liquid dispersion of solid content 25 weight %, total add-on of tetrafluoroethylene monomer is 15 kilograms, and total add-on of R 1216 is 4kg.Do not find the throw out that this perfluoroethylene-propylene water-based emulsion exists breakdown of emulsion to form.
In this dispersion liquid, add 5000ppm tridecyl polyoxyethylene groups ether, 50 ℃ of heating, and in 55 ℃ static 10 hours, the supernatant liquid that inclines, the perfluoroethylene-propylene that obtains 40 weight % concentrates dispersion liquid.In this fluoropolymer dispersions, add ion liquid type tensio-active agent (IIS-031, available from Shanghai three Ai Fu limited-liability company), making its concentration is 200ppm (w/w is in solid), stirs 30min, add an amount of NaCl aqueous solution, making specific conductivity is 800 μ s/cm, stirs 10min, and this moment, fluoropolymer dispersion viscosity was 10mPas, surface tension is 27mN/m, and 0% perfluoroethylene-propylene solid cohesion is arranged behind 8000rpm high-speed stirring 5min.
By top test-results as seen, replace fluorochemical surfactant (for example Perfluorocaprylic Acid ammonium surfactant) can obtain fluoropolymer emulsion, do not find that there is demulsifying phenomenon in the emulsion that obtains with the non-fluorochemical surfactant of the present invention.

Claims (17)

1. the preparation method of a fluoropolymer aqueous dispersion emulsion, it comprises the steps:
(1) in the reaction vessel that water or aqueous solvent are housed, add non-fluorochemical surfactant with following general formula:
R 1(R 1’)(R 2’)N +(CH 2) nN +(R 1’)(R 2’)R 22Q -
Wherein,
R 1And R 2Identical or different, be selected from straight chained alkyl separately with 8-20 carbon atom;
R 1' and R 2' identical or different, respectively do for oneself methyl or ethyl;
N is the integer of 1-6;
Q is a counter anion;
(2) polymerization fluoropolymer monomer in the presence of radical initiator obtains the fluoropolymer emulsion that solid content is 10-30 weight %.
2. the method for claim 1 is characterized in that described fluoropolymer is selected from the multipolymer of tetrafluoroethylene, tetrafluoroethylene and R 1216, perfluoroalkyl alkoxy copolymer, ethylene-tetrafluoroethylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers and polyvinylidene difluoride (PVDF);
By weight, the concentration of described non-fluorochemical surfactant is greater than 500ppm.
3. method as claimed in claim 2 is characterized in that, by weight, the concentration of described non-fluorochemical surfactant is 550-1000ppm.
4. method as claimed in claim 3 is characterized in that, by weight, the concentration of described non-fluorochemical surfactant is 600-800ppm.
5. method as claimed in claim 1 or 2 is characterized in that R 1And R 2Identical or different, be selected from straight chained alkyl separately with 10-18 carbon atom.
6. method as claimed in claim 1 or 2 is characterized in that R 1And R 2Identical or different, be selected from straight chained alkyl separately with 12-16 carbon atom.
7. method as claimed in claim 1 or 2 is characterized in that R 1And R 2Identical or different, be selected from n-octyl, n-nonyl, positive decyl, positive ten dicarbonyls, positive 14 carbon backs, positive 16 carbon backs and positive 18 carbon backs separately.
8. method as claimed in claim 1 or 2 is characterized in that n is the integer of 1-4.
9. method as claimed in claim 1 or 2 is characterized in that n is the integer of 2-3.
10. method as claimed in claim 1 or 2 is characterized in that described non-fluorochemical surfactant is selected from:
C 8H 17(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 8H 17·2Br -；
C 8H 17(CH 3)(C 2H 5)N +-(CH 2) 3-N +(CH 3) 2C 8H 17·2Br -；
C 8H 17(CH 3) 2N +-(CH 2) 2-N +(CH 3) 2C 10H 21·2Cl -；
C 12H 25(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 12H 25·2Br -；
C 12H 25(CH 3) 2N +-(CH 2) 4-N +(CH 3) 2C 10H 21·2F -；
C 14H 29(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 29·2Br -；
C 14H 29(CH 3) 2N +-(CH 2) 3-N +(C 2H 5) 2C 14H 29·2Br? -；C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2Br -；
C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 19·2Cl -；
C 16H 33(CH 3)(C 2H 5)N +-(CH 2) 3-N +(CH 3)(C 2H 5)C 10H 21·2Br -；
C 18H 37(CH 3) 2N +-(CH 2) 2-N +(CH 3) 2C 18H 37·2Br -；
C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 10H 21·2Br -；
C 8H 17(CH 3) 2N +-(CH 2) 4-N +(CH 3) 2C 16H 33·2Br -；
C 9H 19(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2I -；
C 12H 25(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 292Br -Perhaps
C 15H 31(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2Br -。
11. a fluoropolymer emulsion, it comprises the non-fluorochemical surfactant of fluoropolymer and following general formula:
R 1(R 1’)(R 2’)N +(CH 2) nN +(R 1’)(R 2’)R 22Q -
Wherein,
R 1' and R 2' identical or different, respectively do for oneself methyl or ethyl;
R 1And R 2Identical or different, be selected from straight chained alkyl separately with 8-20 carbon atom;
N is the integer of 1-6;
Q is a counter anion.
12. fluoropolymer emulsion as claimed in claim 11 is characterized in that described fluoropolymer is selected from multipolymer, ethylene-tetrafluoroethylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers and the polyvinylidene difluoride (PVDF) of the multipolymer of tetrafluoroethylene, tetrafluoroethylene and R 1216, tetrafluoroethylene and perfluorinated alkoxy vinyl ether;
By weight, the concentration of described non-fluorochemical surfactant is greater than 500ppm.
13. fluoropolymer emulsion as claimed in claim 12 is characterized in that, by weight, the concentration of described non-fluorochemical surfactant is 550-1000ppm.
14. fluoropolymer emulsion as claimed in claim 13 is characterized in that, by weight, the concentration of described non-fluorochemical surfactant is 600-800ppm.
15., it is characterized in that R as claim 11 or 12 described fluoropolymer emulsions 1And R 2Identical or different, be selected from n-octyl, n-nonyl, positive decyl, positive ten dicarbonyls, positive 14 carbon backs, positive 16 carbon backs and positive 18 carbon backs separately; Described n is the integer of 1-4.
16. fluoropolymer emulsion as claimed in claim 15 is characterized in that described n is the integer of 2-3.
17., it is characterized in that described non-fluorochemical surfactant is selected from as claim 11 or 12 described fluoropolymer emulsions:
C 8H 17(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 8H 17·2Br -；
C 8H 17(CH 3)(C 2H 5)N +-(CH 2) 3-N +(CH 3) 2C 8H 17·2Br -；
C 8H 17(CH 3) 2N +-(CH 2) 2-N +(CH 3) 2C 10H 21·2Cl -；
C 12H 25(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 12H 25·2Br -；
C 12H 25(CH 3) 2N +-(CH 2) 4-N +(CH 3) 2C 10H 21·2F -；
C 14H 29(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 29·2Br -；
C 14H 29(CH 3) 2N +-(CH 2) 3-N +(C 2H 5) 2C 14H 29·2Br -；
C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2Br -；
C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 19·2Cl -；
C 16H 33(CH 3)(C 2H 5)N +-(CH 2) 3-N +(CH 3)(C 2H 5)C 10H 21·2Br -；
C 18H 37(CH 3) 2N +-(CH 2) 2-N +(CH 3) 2C 18H 37·2Br -；
C 16H 33(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 10H 21·2Br -；
C 8H 17(CH 3) 2N +-(CH 2) 4-N +(CH 3) 2C 16H 33·2Br -；
C 9H 19(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2I -；
C 12H 25(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 14H 292Br -Perhaps
C 15H 31(CH 3) 2N +-(CH 2) 3-N +(CH 3) 2C 16H 33·2Br -。
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