CN101955560A - Method for preparing chlorotrifluor ethylene homopolymer emulsion - Google Patents
Method for preparing chlorotrifluor ethylene homopolymer emulsion Download PDFInfo
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- CN101955560A CN101955560A CN2010101371176A CN201010137117A CN101955560A CN 101955560 A CN101955560 A CN 101955560A CN 2010101371176 A CN2010101371176 A CN 2010101371176A CN 201010137117 A CN201010137117 A CN 201010137117A CN 101955560 A CN101955560 A CN 101955560A
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Abstract
The invention relates to a method for preparing chlorotrifluor ethylene homopolymer emulsion, which comprises the following steps: taking the following components in percentage by mass: 10-50% of chlorotrifluor ethylene monomer, 0.5-5% of surfactant, 0.05-2% of initiator, 0.05-3% of buffering agent and 49.40-80% of deionized water, adding the components to an agitated reactor, adjusting the pH value to 4-10, and carrying out reaction for 4-24 hours under the condition of 10-100 DEG C in temperature, 0.3-2.0Mpa in pressure, 50-1000r.p.m in revolving speed of a blender to obtain the chlorotrifluor ethylene homopolymer emulsion. The method for preparing the chlorotrifluor ethylene homopolymer emulsion is simple in technology, safe and environmental friendly; and the chlorotrifluor ethylene homopolymer emulsion has the good stability under storage, dilution, centrifugation, high temperature, low temperature and under the condition of weak acid or alkalinity (the pH value is 4-14). Compared with the same type of polytetrafluoroethylene emulsion, the chlorotrifluor ethylene homopolymer emulsion of the invention has good film-forming property and good compactness after film-forming, can be widely applied to the fields of textile, leather, industrial filter cloth, batteries, electron and the like and meets the strict requirements of the fields in water resistance, anticorrosion, anti-gas and conductive performance.
Description
Technical field
The present invention relates to a kind of preparation method of trifluorochloroethylene homopolymerization emulsion.Belong to a kind of fluoro containing polymers polymkeric substance homopolymerization emulsion technical field of producing.
Background technology
Trifluorochloroethylene homopolymerization emulsion is a kind of derived product of voltalef.Daiflon is the fluorine-containing polymer that first business development is succeedd.Patent is the earliest delivered by German company, and inferior after Minnesota Mining and Manufacturing Company drops into commercial operation, commodity are called " kel-F ".Voltalef (PCTFE) belongs to first-generation fluorine superpolymer, and it is a kind of thermoplastic fluoropolymer, contains the chlorine atom in the macromolecular chain, and stronger polarity is arranged.
Although the research of international and domestic fluorine-containing polymer is many, mainly concentrating on tetrafluoroethylene, vinylidene and trifluorochloroethylene etc. is the research of basic monomer, and many industrialization that realized are arranged.Trifluorochloroethylene homopolymerization emulsion involved in the present invention is a kind of extremely pure fluoropolymer emulsions goods, and it has uvioresistant, performance such as heat-resisting, fire-retardant, and it is inorganic to the overwhelming majority, organic chemicals and organic solvent, and outstanding resistance to corrosion is arranged.The trifluorochloroethylene homopolymerization emulsion of the present invention's preparation is the voltalef emulsion dispersion system that contains complexed surfactant, and outward appearance is creamy white, show blue light, good fluidity, its goods have good thermostability, outstanding unreactiveness, characteristics such as excellent optical property and low-friction coefficient.Can be applicable to weaving, industrial filter cloth, battery, special dimensions such as electronics.The lubricated light of the coatingsurface of trifluorochloroethylene homopolymerization emulsion, and free of pinholes, fabricated product can be in ± 240 ℃ of temperature life-time service.
Voltalef can obtain by the monomeric body of trifluorochloroethylene, solution, suspension, the emulsion polymerization method that free radical causes, and also can be made by UV x radiation x initiated polymerization.For example: US2569524 openly reports the method for preparing voltalef with suspension polymerization; GB578168 discloses mass polymerization and has prepared voltalef; The patent of other synthetic voltalef also has US26563322, US2689242, US3671510, US4155953 etc., but above-mentioned patent does not all relate to the preparation method of trifluorochloroethylene homopolymerization emulsion.
Report introduction is arranged, and the letex polymerization of trifluorochloroethylene add ammonium sulfate, vat powder, bicarbonate of ammonia, and with formed carboxylic acid of voltalef oxidation and sodium hydroxide effect, formed sodium salt is made emulsifying agent with the distillation water as medium.After reaction finished, under vigorous stirring, the calcium chloride that adds capacity made the polymkeric substance flocculation.Product is through washing, drying, and yield is 12.5%, and this method monomer conversion is too low, does not have industrial value.
At present; the similar product emulsion of selling on the market is the emulsion of tetrafluoroethylene, but because the tetrafluoroethylene molecule is very symmetrical, does not wherein have the chlorine atom; so mobile extreme difference; and can not conduct electricity, as protective layer, tangible crackle and slit can occur with it; can not form fine and close film; influence the waterproof of coating, anticorrosion, the gas-tight performance.
Because the cause of technology and cost, present voltalef emulsion have all been introduced second, third even the 4th monomer, adopt emulsion method be poly-altogether to make, the emulsion of Xing Chenging just can not show the characteristic of voltalef fully like this.About the homopolymerization emulsion of trifluorochloroethylene, domestic also do not have to report more there is not the producer of large-scale production.
Summary of the invention
The object of the present invention is to provide a kind of technology simple, pollution-free, good product performance, the preparation method of the trifluorochloroethylene homopolymerization emulsion that productive rate is high.The trifluorochloroethylene homopolymerization emulsion for preparing with the present invention can overcome above-mentioned shortcoming, because contain a chlorine atom in its molecular structure, is not a complete symmetrical structure, so flowing property is good.As protective layer; trifluorochloroethylene homopolymerization emulsion can also form the good film of compactness; therefore can remedy the defective of ptfe emulsion, at weaving, industrial filter cloth, battery, special dimensions such as electronics have irreplaceable market to use wide potentiality and prospect.
In order to achieve the above object, the present invention is directed to the problems referred to above of present existence, start with, by adding the complexed surfactant of the tensio-active agent of preparation voluntarily from polymerization process, and, prepared the homopolymerization emulsion of the high trifluorochloroethylene of the productive rate of excellent property by improving polymerization technique.
Concrete technology is as follows:
Earlier measure the trifluorochloroethylene monomer: tensio-active agent: initiator: buffer reagent: deionized water=10%～50%: 0.5～5%: 0.05～2%: 0.05～3%: 49.40～80% according to following mass percent, then tensio-active agent, deionized water, initiator, buffer reagent, trifluorochloroethylene monomer are added in the reactor, regulating pH is 4～10, at 10 ℃～100 ℃, 0.3～2.0Mpa, the stirrer rotating speed is under 50～1000r.p.m condition, reaction 4～24h promptly gets trifluorochloroethylene homopolymerization emulsion.
Described tensio-active agent is that 20～100% fluorochemical surfactants and mass percent are that 0～80% non-fluorine surfactant is formed by mass percent, and wherein, non-fluorine surfactant is selected from fatty alcohol-polyoxyethylene ether or aliphatic acid polyethenoxy ether.Fatty alcohol-polyoxyethylene ether is that one or both arbitrary proportions in ethoxylated dodecyl alcohol and the polyoxyethylene octadecanol mix composition; Aliphatic acid polyethenoxy ether is that one or both arbitrary proportions in dodecylic acid Soxylat A 25-7 and the octadecanoic acid Soxylat A 25-7 mix composition.
Fluorochemical surfactant is selected from anionic or non-ionic type fluorochemical surfactant.The anionic fluorochemical surfactant is a kind of in perfluoro-pelargonic acid ammonium, perfluor oxygen in last of the ten Heavenly stems base benzene sulfonic acid sodium salt and the 15 fluorine capric acid ammoniums; The non-ionic type fluorochemical surfactant is synthetic voluntarily as follows:
Measure 1 part of quality polyoxyethylene glycol and 2～3 parts of quality tetrahydrofuran (THF)s earlier, then under nitrogen atmosphere, polyoxyethylene glycol is added in the there-necked flask, add tetrahydrofuran (THF) and triethylamine again, wherein the add-on of triethylamine equates with the mol ratio of polyoxyethylene glycol, open and stir, 55 ℃ of following constant temperature 1h slowly drip the commercially available CF that equates with the polyoxyethylene glycol mol ratio then
3(CF
2)
6(C
2H
4) COCl, after dropwising, continue to stir 2h, make it abundant reaction, remove and desolvate, 60 ℃ of vacuum-dryings obtain nonionic fluorochemical surfactant CF
3(CF
2)
6(C
2H
4) COO (CH
2CH
2O)
4-10H;
Described initiator is made up of an oxygenant and a reductive agent that molar weight equates; This initiator is a water miscible redox system.
Wherein, oxygenant is selected from water miscible Potassium Persulfate, and Sodium persulfate, ammonium peroxydisulfate, one or both in the alkaline earth salt are pressed arbitrary proportion and mixed composition; Reductive agent is selected from the solubility thiosulphate, sulfurous acid, and sulfoxylic acid, ammonium sulphite, S-WAT, potassium sulfite, one or both in the formaldehyde mix by arbitrary proportion.
Described buffer reagent is selected from yellow soda ash, sodium-acetate, Sodium phosphate dibasic, Trisodium Citrate, sodium benzoate, sodium tartrate, borax, Sodium Hydrogen Carbonate, the ammoniacal liquor one or both and mixes by arbitrary proportion.
The present invention has following advantage than prior art:
1. because the present invention has used a kind of tensio-active agent of being made up of fluorochemical surfactant and non-fluorine surfactant, compare as tensio-active agent with existing use perfluor carbochain, polymerization rate of the present invention is very fast, the trifluorochloroethylene monomer conversion is up to 58.3～92%, good product performance, technology is simple to operation.
2. the present invention adopts one or more synthetic tensio-active agents voluntarily, in the water-based system of buffer reagent is arranged, under a basic neutral environment, it is good not add any organic solvent synthetic trifluorochloroethylene homopolymerization product emulsion film forming, waterproof, anticorrosion, gas-tight, and do not contain any organic solvent, environmental protection.
3. trifluorochloroethylene homopolymerization emulsion of the present invention is a kind of fluorine-containing homopolymer emulsion of uniqueness, and it has uvioresistant, heat-resisting, fire-retardant performance, and it is inorganic to the overwhelming majority, organic chemicals and organic solvent have outstanding resistance to corrosion.
4. trifluorochloroethylene homopolymerization emulsion of the present invention is the voltalef aqueous dispersion liquid of stable existence in the composite emulsifying system, outward appearance is creamy white, show blue light, good fluidity, its goods have characteristics such as good storage, dilution, centrifugal, high temperature, low temperature and the stability under weak acid and alkaline condition (the pH value is 4～14), outstanding unreactiveness, excellent optical property and low-friction coefficient, can satisfy the particular requirement of special dimensions such as weaving, leather, industrial filter cloth, battery, electronics.
5. polymerization technique of the present invention is uncomplicated, and polymerization temperature can carry out in a relative wide scope with pressure, and polymerization time is short, and equipment is not had particular requirement, and suitability for industrialized production safety coefficient height is fit to suitability for industrialized production.
Embodiment
Below six embodiment further specify of the present invention, but the present invention is not limited only to these examples.
Embodiment 1
The preparation of nonionic fluorochemical surfactant.
Under nitrogen atmosphere, 200 gram exsiccant polyoxyethylene glycol are added in the there-necked flask, add 500 gram tetrahydrofuran (THF) and an amount of triethylamines again, an amount of triethylamine is meant that the add-on of triethylamine and the mol ratio of polyoxyethylene glycol are 1: 1.Open and stir, 55 ℃ of following constant temperature 1h slowly drip the CF that equates with the mol ratio of polyoxyethylene glycol then
3(CF
2)
6(C
2H
4) COCl.After dropwising, continue to stir 2h, make it abundant reaction.Remove and desolvate, product gets 720 gram nonionic fluorochemical surfactant CF through 60 ℃ of vacuum-dryings
3(CF
2)
6(C
2H
4) COO (CH
2CH
2O)
4-10H.
The preparation of trifluorochloroethylene homopolymerization emulsion
In 1500 gram deionized waters, add the initiator of forming by 8 gram Sodium Persulfates and 8 gram sodium bisulfites, 4 gram sodium carbonate buffer, the above-mentioned nonionic fluorochemical surfactant CF of 20 grams
3(CF
2)
6(C
2H
4) COO (CH
2CH
2O)
4-10H, mix, regulating pH is 10, pour in the autoclave of the good 2L of stopping property, with water circulating pump reactor is vacuumized, so that add 1000g trifluorochloroethylene monomer from the gas phase mouth, the unlatching reactor stirs, and initial reaction temperature is 10 ℃, control reactor stirrer rotating speed 500r.p.m, control reaction temperature is 10 ℃～20 ℃, reaction 20h finishes, and opens reactor, and obtaining milk shape emulsion from drain hole is trifluorochloroethylene homopolymerization emulsion, this trifluorochloroethylene homopolymerization emulsion appearance is the milky white liquid that has little blue light, good fluidity; Solid content is 35.5%; The median size of emulsion is at 86nm; Emulsion film water contact angle mean value is 110 °.With the unreacted trifluorochloroethylene MONOMER RECOVERY that is deposited in reactor bottom usefulness again, as calculated, the trifluorochloroethylene monomer conversion is 82%.Residual air in the reactor is recycled, in order to avoid influence environment.
Embodiment 2
Operation steps and equipment are with embodiment 1.As different from Example 1: the nonionic fluorochemical surfactant CF that adds 10 gram embodiment, 1 preparation
3(CF
2)
6(C
2H
4) COO (CH
2CH
2O)
4-10H and 5 grams, 15 fluorine capric acid ammoniums, control reaction temperature is 30 ℃.Last monomer conversion is 71%.
This trifluorochloroethylene homopolymerization emulsion appearance is the milky white liquid that has little blue light, good fluidity; Solid content is 32.2%; The median size of emulsion is at 98nm; Emulsion film water contact angle mean value is 105 °.
Embodiment 3
Operation steps and equipment are with embodiment 1.As different from Example 1: the nonionic fluorochemical surfactant CF that adds 3 gram embodiment, 1 preparation
3(CF
2)
6(C
2H
4) COO (CH
2CH
2O)
4-10H and 7 gram 15 fluorine capric acid ammoniums and 6g Potassium Persulphates, initial reaction temperature is controlled at 50 ℃.Last monomer conversion is 65.5%
This trifluorochloroethylene homopolymerization emulsion appearance that obtains is the milky white liquid that has little blue light, good fluidity; Solid content is 30.4%; The median size of emulsion is at 90nm; Emulsion film water contact angle mean value is 106 °.
Embodiment 4
Operation steps and equipment are with embodiment 1.As different from Example 1: add the 5g Sodium phosphate dibasic, 10 gram polyoxyethylene octadecanols, 2 grams, 15 fluorine capric acid ammoniums, initial reaction temperature is controlled at 70 ℃.Monomer conversion 58.3%.
The trifluorochloroethylene homopolymerization emulsion appearance that obtains has the milky white liquid of little blue light, good fluidity; Solid content is 28.0%; The median size of emulsion is at 102m; Emulsion film water contact angle mean value is 100 °.
Embodiment 5
Operation steps and equipment are with embodiment 1.As different from Example 1: add 10g persulfuric acid calcium, initial reaction temperature is controlled at 90 ℃.Monomer conversion is 79%
The trifluorochloroethylene homopolymerization emulsion appearance that obtains has the milky white liquid of little blue light, good fluidity; PH value 6.0; Solid content is 34.5%; The median size of emulsion is at 110nm; Emulsion film water contact angle mean value is 108 °.
Embodiment 6
With the 75kg deionized water, the nonionic fluorochemical surfactant that adds 400 gram Sodium Persulfates, 200 gram yellow soda ash and 1000 gram embodiment, 1 preparation, mix, regulating pH is 10, then they are joined the 100L autoclave, feed the nitrogen of 0.3Mpa～2.5Mpa, through the stopping property of 2～4 hours check reactors.Emptying nitrogen, with vacuum pump reactor is vacuumized, the trifluorochloroethylene monomer that adds 50kg then from the gas phase mouth of reactor, the unlatching reactor stirs, control reactor stirrer rotating speed 200r.p.m, control reaction temperature is 60 ℃, reaction 15h finishes, open reactor residual air retrieving arrangement, residual air in the reactor is reclaimed, obtaining milk shape emulsion from drain hole is the milky white liquid that outward appearance has little blue light, good fluidity, solid content is 38.0%, and the median size of emulsion is at 88nm, and emulsion film water contact angle mean value is 109 ° trifluorochloroethylene homopolymerization emulsion.Last monomer conversion is 92%.
Claims (1)
1. the preparation method of trifluorochloroethylene homopolymerization emulsion, it is characterized in that: measure the trifluorochloroethylene monomer according to following mass percent earlier: tensio-active agent: initiator: buffer reagent: deionized water=10～50%: 0.5～5%: 0.05～2%: 0.05～3%: 49.40～80%, then with tensio-active agent, deionized water, initiator, buffer reagent, the trifluorochloroethylene monomer is added in the reactor, regulating pH is 4～10, at 10 ℃～100 ℃, 0.3～2.0Mpa, the stirrer rotating speed is under 50～1000r.p.m condition, reaction 4～24h promptly gets trifluorochloroethylene homopolymerization emulsion;
Described tensio-active agent is that 20～100% fluorochemical surfactants and mass percent are that 0～80% non-fluorine surfactant is formed by mass percent;
Wherein, non-fluorine surfactant is fatty alcohol-polyoxyethylene ether or aliphatic acid polyethenoxy ether; Fatty alcohol-polyoxyethylene ether is that one or both arbitrary proportions in ethoxylated dodecyl alcohol and the polyoxyethylene octadecanol mix composition; Aliphatic acid polyethenoxy ether is that one or both arbitrary proportions in dodecylic acid Soxylat A 25-7 and the octadecanoic acid Soxylat A 25-7 mix composition;
Fluorochemical surfactant is selected from anionic fluorochemical surfactant or non-ionic type fluorochemical surfactant; The anionic fluorochemical surfactant is a kind of in perfluoro-pelargonic acid ammonium, perfluor oxygen in last of the ten Heavenly stems base benzene sulfonic acid sodium salt and the 15 fluorine capric acid ammoniums; The non-ionic type fluorochemical surfactant is synthetic voluntarily as follows: measure 1 part of quality polyoxyethylene glycol and 2～3 parts of quality tetrahydrofuran (THF)s earlier, then under nitrogen atmosphere, polyoxyethylene glycol is added in the there-necked flask, add tetrahydrofuran (THF) and triethylamine again, wherein the add-on of triethylamine equates with the mol ratio of polyoxyethylene glycol, open and stir, 55 ℃ of following constant temperature 1h slowly drip the commercially available CF that equates with the polyoxyethylene glycol mol ratio then
3(CF
2)
6(C
2H
4) COCl, drip, continue to stir 2h, make it abundant reaction, remove and desolvate, 60 ℃ of vacuum-dryings obtain nonionic fluorochemical surfactant CF
3(CF
2)
6(C
2H
4) COO (CH
2CH
2O)
4-10H;
Described initiator is made up of an oxygenant and a reductive agent that molar weight equates;
Wherein, oxygenant is selected from water miscible Potassium Persulfate, and Sodium persulfate, ammonium peroxydisulfate, one or both in the alkaline earth salt are pressed arbitrary proportion and mixed composition; Reductive agent is selected from the solubility thiosulphate, sulfurous acid, and sulfoxylic acid, ammonium sulphite, S-WAT, potassium sulfite, one or both in the formaldehyde mix by arbitrary proportion;
Described buffer reagent is selected from yellow soda ash, sodium-acetate, and Sodium phosphate dibasic, Trisodium Citrate, sodium benzoate, sodium tartrate, borax, Sodium Hydrogen Carbonate, one or both in the ammoniacal liquor mix by arbitrary proportion.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050639A (en) * | 2010-08-25 | 2011-05-11 | 潍坊绿城低碳建筑科技有限公司 | Inorganic seepage-proof agent of plate assembly type enclosing and filling system building |
| CN102153680A (en) * | 2011-02-25 | 2011-08-17 | 济南大学 | Phosphate surfactant and method for preparing trifluorochlor oethylene polymer |
| CN103467633A (en) * | 2013-09-29 | 2013-12-25 | 王文贵 | Chlorotrifluoroethylene homopolymerized emulsion used for filtering materials and production method |
| CN106188357A (en) * | 2016-07-05 | 2016-12-07 | 无锡华东锌盾科技有限公司 | A kind of water-based fluorocarbon resin emulsion and its preparation method and application |
| CN106715484A (en) * | 2014-09-04 | 2017-05-24 | 霍尼韦尔国际公司 | Methods for synthesizing stabilized polymers of chlorotrifluoroethylene and products manufactured using such polymers |
| CN113461991A (en) * | 2021-08-13 | 2021-10-01 | 四川大学 | Polychlorotrifluoroethylene film and preparation method and application thereof |
| CN117551369A (en) * | 2024-01-10 | 2024-02-13 | 德施普(辽宁)新材料技术有限公司 | Polychlorotrifluoroethylene-based paint and preparation method thereof |
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| TW334440B (en) * | 1995-06-24 | 1998-06-21 | Defence Dept Chung Shan Inst | Method for preparing solid chlorotrifluoroethylene homopolymer |
| CN101643523A (en) * | 2009-08-07 | 2010-02-10 | 常熟市新华化工有限公司 | Polychlorotrifluoroethylene resin preparation method |
-
2010
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Patent Citations (2)
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|---|---|---|---|---|
| TW334440B (en) * | 1995-06-24 | 1998-06-21 | Defence Dept Chung Shan Inst | Method for preparing solid chlorotrifluoroethylene homopolymer |
| CN101643523A (en) * | 2009-08-07 | 2010-02-10 | 常熟市新华化工有限公司 | Polychlorotrifluoroethylene resin preparation method |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050639A (en) * | 2010-08-25 | 2011-05-11 | 潍坊绿城低碳建筑科技有限公司 | Inorganic seepage-proof agent of plate assembly type enclosing and filling system building |
| CN102050639B (en) * | 2010-08-25 | 2011-12-21 | 潍坊绿城低碳建筑科技有限公司 | Seepage-proof agent of filling system for building |
| CN102153680A (en) * | 2011-02-25 | 2011-08-17 | 济南大学 | Phosphate surfactant and method for preparing trifluorochlor oethylene polymer |
| CN102153680B (en) * | 2011-02-25 | 2013-05-08 | 济南大学 | Phosphate surfactant and method for preparing trifluorochlor oethylene polymer |
| CN103467633A (en) * | 2013-09-29 | 2013-12-25 | 王文贵 | Chlorotrifluoroethylene homopolymerized emulsion used for filtering materials and production method |
| CN106715484A (en) * | 2014-09-04 | 2017-05-24 | 霍尼韦尔国际公司 | Methods for synthesizing stabilized polymers of chlorotrifluoroethylene and products manufactured using such polymers |
| CN106715484B (en) * | 2014-09-04 | 2019-03-26 | 霍尼韦尔国际公司 | Product for synthesizing the method for the stabilization of polymers of chlorotrifluoroethylene and being manufactured using this quasi polymer |
| CN106188357A (en) * | 2016-07-05 | 2016-12-07 | 无锡华东锌盾科技有限公司 | A kind of water-based fluorocarbon resin emulsion and its preparation method and application |
| CN113461991A (en) * | 2021-08-13 | 2021-10-01 | 四川大学 | Polychlorotrifluoroethylene film and preparation method and application thereof |
| CN117551369A (en) * | 2024-01-10 | 2024-02-13 | 德施普(辽宁)新材料技术有限公司 | Polychlorotrifluoroethylene-based paint and preparation method thereof |
| CN117551369B (en) * | 2024-01-10 | 2024-04-12 | 德施普(辽宁)新材料技术有限公司 | Polychlorotrifluoroethylene-based paint and preparation method thereof |
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