CN105111340A - Method for preparing fluorine-containing polymers - Google Patents
Method for preparing fluorine-containing polymers Download PDFInfo
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- CN105111340A CN105111340A CN201510553953.5A CN201510553953A CN105111340A CN 105111340 A CN105111340 A CN 105111340A CN 201510553953 A CN201510553953 A CN 201510553953A CN 105111340 A CN105111340 A CN 105111340A
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- fluorine
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- olefin monomers
- fluoropolymer
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Abstract
The invention discloses a method for preparing fluorine-containing polymers. The method comprises the following specific steps: adding a fluorine-containing phosphate monoester surfactant, deionized water and a pH buffer agent into a reaction kettle, and replacing air in the reaction kettle for three times by virtue of nitrogen; adding fluorine-containing olefin monomers and a free radical initiator into the reaction kettle, and stirring to generate emulsion polymerization; and purging remnant fluorine-containing olefin monomers by virtue of inert gas after the reaction, so as to obtain the fluorine-containing polymers. According to the method, the drawback that great harms are caused to human bodies and environment by a serious biological accumulation effect of an emulsifying agent which is used during existing preparation of the fluorine-containing polymers is solved.
Description
Technical field
The present invention relates to a kind of method preparing fluoropolymer, belong to chemical industry Polymer Synthesizing field.
Background technology
The development of China's fluoropolymer starts from the sixties, is mainly used in national defence.After the eighties, be widely used in the every field of national economy.Principal item comprises tetrafluoroethylene, polyvinylidene difluoride (PVDF), voltalef etc.At present, fluoropolymer plays irreplaceable effect in many pillar industries such as automotive industry, chemical industry, electronic apparatus.Flourish along with these industries, the demand of fluoropolymer can constantly increase.
The synthetic method of fluoropolymer is a lot, and the most frequently used is aqueous emulsion polymerization.In the process, Perfluorocaprylic Acid and salt thereof are absolutely necessary emulsifying agent.And such emulsifying agent stability is high, is difficult to degraded, easily causes environment to accumulate, there is carinogenicity and teratogenecity.From 2008, the production of European Union's restriction Perfluorocaprylic Acid and salts substances thereof and use.2015, the U.S. stopped producing such material completely.Therefore, in the urgent need to developing a kind of method preparing fluoropolymer newly, with the use of Perfluorocaprylic Acid and salts substances thereof in alternative production process.
Summary of the invention
The invention provides a kind of method preparing fluoropolymer, comprise the following steps:
1) fluorine-containing phosphate monoester tensio-active agent, deionized water, pH buffer reagent are added reactor, with air in nitrogen replacement still three times;
2) in reactor, add fluorinated olefin monomers and radical initiator, carry out emulsion polymerization under agitation;
3) by remaining fluorinated olefin monomers inert gas purge after reacting, fluoropolymer is obtained.
Further, the pH buffer reagent described in step 1) is sodium carbonate or sodium bicarbonate.
Further, step 2) described in fluorinated olefin monomers be any one in tetrafluoroethylene, vinylidene, trifluorochloroethylene.
Further, step 2) in radical initiator be water-soluble peroxide initiator or water soluble, redox initiator.
Further, radical initiator is ammonium persulphate, Potassium Persulphate, Sodium Persulfate one wherein or any two or more mixing, or by the one in above-mentioned persulphate or any two or more mixture and sodium bisulfite in molar ratio 1:1 mix.
Further, fluorine-containing phosphate monoester dosage of surfactant is 0.1 ~ 1% of fluorinated olefin monomers total amount by mass.
Further, step 2) in polymeric reaction temperature be 20 ~ 80 DEG C, the reaction times is 4 ~ 8h.
Further, the solid content in step 3) in gained fluoropolymer is 10 ~ 30% by weight.
Compared with prior art, the invention provides a kind of method preparing fluoropolymer of environmental protection, can avoid in process of production using Perfluorocaprylic Acid and salts substances thereof.Find in research, the phosphate monoester water soluble of organic hydroxy compounds, have excellent emulsifying property and dispersiveness, and toxicity is little, easily degrades.Be widely used as emulsifying agent, rust-preventive agent, static inhibitor and fabric finishing agent.Fluorine-containing phosphate monoester is especially remarkable to the emulsifying effectiveness of halogenated hydrocarbon material, meanwhile, compared with common phosphate monoester, has outstanding surfactivity.Fluorine-containing phosphate monoester is used as emulsifying agent synthesis fluoropolymer, Perfluorocaprylic Acid and its esters can be substituted.The present invention uses fluorine-containing phosphate monoester to substitute Perfluorocaprylic Acid and salts substances thereof first in fluoropolymer preparation, solves the environmental problem that in former building-up process, Perfluorocaprylic Acid and salts substances thereof cause.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
For the reactor of 1000mL, in the reactor cleaned, add fluorine-containing phosphate monoester tensio-active agent 0.9g, deionized water 180g, sodium carbonate 3g, fully dissolve.Continuous three times with air in nitrogen replacement still.Reactor is warming up to 40 DEG C.In reactor, continuous uniform adds tetrafluoroethylene 210g.Meanwhile, in reactor, add the initiator solution prepared in advance, start polyreaction.The compound method of this initiator solution is: 2.0g ammonium persulphate, 1.1g sodium bisulfite, the mixing of 200g deionized water are also fully dissolved and make.After all materials add, keep temperature of reaction kettle 40 DEG C, carry out polyreaction 4 hours, ensure that polyreaction is abundant.After question response still pressure no longer declines, continue insulation 40 DEG C and stir 30min.Stop stirring, reduce still temperature, residual gas in release still, and with nitrogen purging, obtain fluoropolymer emulsion.By analysis, the solid content in emulsion is 30%.
Embodiment 2
For the reactor of 1000mL, in the reactor cleaned, add fluorine-containing phosphate monoester tensio-active agent 0.07g, deionized water 180g, sodium bicarbonate 1g, fully dissolve.Continuous three times with air in nitrogen replacement still.Reactor is warming up to 20 DEG C.In reactor, continuous uniform adds tetrafluoroethylene 70g.Meanwhile, in reactor, add the initiator solution prepared in advance, start polyreaction.The compound method of this initiator solution is: 0.9g Potassium Persulphate, the mixing of 200g deionized water are also fully dissolved and make.After all materials add, keep temperature of reaction kettle 20 DEG C, carry out polyreaction 2 hours, ensure that polyreaction is abundant.After question response still pressure no longer declines, continue insulation 20 DEG C and stir 30min.Stop stirring, reduce still temperature, residual gas in release still, and with nitrogen purging, obtain fluoropolymer emulsion.By analysis, the solid content in emulsion is 10%.
Embodiment 3
For the reactor of 1000mL, in the reactor cleaned, add fluorine-containing phosphate monoester tensio-active agent 1.2g, deionized water 180g, sodium carbonate 1.7g, fully dissolve.Continuous three times with air in nitrogen replacement still.Reactor is warming up to 60 DEG C.In reactor, continuous uniform adds vinylidene 120g.Meanwhile, in reactor, add the initiator solution prepared in advance, start polyreaction.The compound method of this initiator solution is: 1.8g Sodium Persulfate, the mixing of 200g deionized water are also fully dissolved and make.After all materials add, keep temperature of reaction kettle 60 DEG C, carry out polyreaction 3 hours, ensure that polyreaction is abundant.After question response still pressure no longer declines, continue insulation 60 DEG C and stir 30min.Stop stirring, reduce still temperature, residual gas in release still, and with nitrogen purging, obtain fluoropolymer emulsion.By analysis, the solid content in emulsion is 18%.
Embodiment 4
For the reactor of 1000mL, in the reactor cleaned, add fluorine-containing phosphate monoester tensio-active agent 0.9g, deionized water 180g, sodium carbonate 2g, fully dissolve.Continuous three times with air in nitrogen replacement still.Reactor is warming up to 80 DEG C.In reactor, continuous uniform adds trifluorochloroethylene 140g.Meanwhile, in reactor, add the initiator solution prepared in advance, carry out polyreaction 3 hours, ensure that polyreaction is abundant.The compound method of this initiator solution is: 2g Sodium Persulfate, the mixing of 200g deionized water are also fully dissolved and make.After all materials add, keep temperature of reaction kettle 80 DEG C, ensure that polyreaction is fully carried out.After question response still pressure no longer declines, continue insulation 80 DEG C and stir 30min.Stop stirring, reduce still temperature, residual gas in release still, and with nitrogen purging, obtain fluoropolymer emulsion.By analysis, the solid content in emulsion is 23%.
Claims (8)
1. prepare a method for fluoropolymer, it is characterized in that: comprise the following steps:
1) fluorine-containing phosphate monoester tensio-active agent, deionized water, pH buffer reagent are added reactor, with air in nitrogen replacement still three times;
2) in reactor, add fluorinated olefin monomers and radical initiator, under agitation emulsion polymerization occurs;
3) by remaining fluorinated olefin monomers inert gas purge after reacting, fluoropolymer is obtained.
2. a kind of method preparing fluoropolymer according to claim 1, is characterized in that: the pH buffer reagent described in step 1) is sodium carbonate or sodium bicarbonate.
3. a kind of method preparing fluoropolymer according to claim 1, is characterized in that: step 2) described in fluorinated olefin monomers be any one in tetrafluoroethylene, vinylidene, trifluorochloroethylene.
4. a kind of method preparing fluoropolymer according to claim 1, is characterized in that: step 2) described in radical initiator be water-soluble peroxide initiator or water soluble, redox initiator.
5. a kind of method preparing fluoropolymer according to claim 1, it is characterized in that: step 2) described in radical initiator be ammonium persulphate, Potassium Persulphate, Sodium Persulfate one wherein or any two or more mixture, or by the one in above-mentioned persulphate or any two or more mixture and sodium bisulfite in molar ratio 1:1 mix.
6. a kind of method preparing fluoropolymer according to claim 1, is characterized in that: described fluorine-containing phosphate monoester dosage of surfactant is 0.1 ~ 1% of fluorinated olefin monomers total amount by mass.
7. a kind of method preparing fluoropolymer according to claim 1, is characterized in that: step 2) in polymeric reaction temperature be 20 ~ 80 DEG C, the reaction times is 4 ~ 8h.
8. a kind of method preparing fluoropolymer according to claim 7, is characterized in that: the solid content in step 3) in gained fluoropolymer is 10 ~ 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510553953.5A CN105111340A (en) | 2015-09-02 | 2015-09-02 | Method for preparing fluorine-containing polymers |
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| CN201510553953.5A CN105111340A (en) | 2015-09-02 | 2015-09-02 | Method for preparing fluorine-containing polymers |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461953A (en) * | 2021-06-16 | 2021-10-01 | 济南大学 | Preparation method of polychlorotrifluoroethylene resin |
| CN115746179A (en) * | 2022-11-08 | 2023-03-07 | 金华永和氟化工有限公司 | Fluorine-containing polymer and process for inhibiting self-polymerization in polymerization process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2559752A (en) * | 1951-03-06 | 1951-07-10 | Du Pont | Aqueous colloidal dispersions of polymers |
| CN101925619A (en) * | 2008-01-22 | 2010-12-22 | 杜邦特性弹性体有限责任公司 | Process for producing fluoropolymers |
| CN102153680A (en) * | 2011-02-25 | 2011-08-17 | 济南大学 | Phosphate surfactant and method for preparing trifluorochlor oethylene polymer |
-
2015
- 2015-09-02 CN CN201510553953.5A patent/CN105111340A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2559752A (en) * | 1951-03-06 | 1951-07-10 | Du Pont | Aqueous colloidal dispersions of polymers |
| CN101925619A (en) * | 2008-01-22 | 2010-12-22 | 杜邦特性弹性体有限责任公司 | Process for producing fluoropolymers |
| CN102153680A (en) * | 2011-02-25 | 2011-08-17 | 济南大学 | Phosphate surfactant and method for preparing trifluorochlor oethylene polymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461953A (en) * | 2021-06-16 | 2021-10-01 | 济南大学 | Preparation method of polychlorotrifluoroethylene resin |
| CN115746179A (en) * | 2022-11-08 | 2023-03-07 | 金华永和氟化工有限公司 | Fluorine-containing polymer and process for inhibiting self-polymerization in polymerization process thereof |
| CN115746179B (en) * | 2022-11-08 | 2024-02-13 | 金华永和氟化工有限公司 | Fluorine-containing polymer and process for inhibiting self-polymerization in polymerization process thereof |
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