A method suitable for preparing fluoropolymers free of perfluorooctanoic acid or perfluorooctanoic acid

A technology of perfluorooctanoic acid and perfluorooctanoic acid, which is applied in the field of fluoropolymer synthesis, can solve the problem of no substantial improvement in production efficiency, no involvement of fluoropolymer yield and particle size, and no way to achieve large-scale production Production and other issues, to achieve the effect of being suitable for widespread use, not easy to enrich, and improving the output of a single kettle

Active Publication Date: 2016-11-30
成都晨光博达新材料股份有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] From the content disclosed in the above patent documents, we can also know that the existing disclosed fluorine-containing emulsifiers are all effective. Although the toxicological characteristics of fluorine-containing emulsifiers have been solved, none of them involve the production Product characteristics such as rate and particle size, taking the above-mentioned invention patent CN101218264B as an example, in this patent document, the comparison data of polymerization time, average particle size, SSG (particle specific gravity of fluoropolymer) and solid content are given, except polymerization time In addition, the rest of the data did not fluctuate significantly. It can be seen that although the existing fluorinated emulsifiers that do not contain PFOA have solved the possible harm to the human body caused by the high stability and refractory properties of PFOA / PFOS, they have no effect on the entire production process. The efficiency has not been substantially improved. At the same time, since the fluorine-containing emulsifier involved in the above invention patent CN101218264B is perfluoropolyether, we know that perfluoropolyether is composed of -CF2-O-CF 2 - such ether chains Composition, all the H atoms in the molecule are replaced by F atoms. From the perspective of industrial production, there is no way to achieve large-scale production. It is necessary to add a monomer whose terminal halogen is not F in the preparation process. As a chain transfer agent, industrial production can only be realized, and the production process is relatively complicated. Based on the increasingly fierce competition in the existing market, we must find a new fluorine-containing emulsifier, which can not only replace the use of PFOA / PFOS, but also Based on product performance, long-term and effective economic benefits can be obtained

Method used

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  • A method suitable for preparing fluoropolymers free of perfluorooctanoic acid or perfluorooctanoic acid
  • A method suitable for preparing fluoropolymers free of perfluorooctanoic acid or perfluorooctanoic acid
  • A method suitable for preparing fluoropolymers free of perfluorooctanoic acid or perfluorooctanoic acid

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preparation example Construction

[0092] The liquid-phase polymerization involved in the present invention is a conventional preparation method of fluorine-containing polymers. In the present invention, the liquid-phase polymerization refers to aqueous emulsion polymerization, and the aqueous emulsion polymerization system in the polymerization process mainly includes fluorinated monomers Body, initiator, water, emulsifier four basic components, known, we found a new fluorine-containing emulsifier (ie: polyfluoroalkoxy ether acid emulsifier) ​​to replace PFOA / PFOS, And the fluorine-containing polymer that makes does not contain perfluorooctanoic acid or perfluorooctanoic acid, certainly, for realizing the present invention better, we also need to fluorine-containing monomer, initiator, polyfluoroalkoxy ether acid emulsifier It is indispensable to choose the ratio of water and water. In the invention, there are mainly two types of initiators: inorganic peroxides (such as persulfates, etc.), organic peroxides (a...

Embodiment 1

[0099] Polytetrafluoroethylene is prepared from the gaseous fluorinated monomer-tetrafluoroethylene through aqueous emulsion polymerization, and 1-bromo-polyfluoroalkoxyether acid is added to the aqueous emulsion polymerization as a fluorine-containing emulsifier. The specific implementation steps as follows:

[0100] A: Prepare the aqueous solution of the salt of 1-bromo-polyfluoroalkoxycarboxy ether acid: add 700ml of deionized water and 100ml of 25% ammonia water to a 2000ml glass beaker, and then pour it into the deionized water slowly and uniformly through the glass dropping funnel Add dropwise the 1-bromo-polyfluoroalkyl carboxylic acid of 200g, stir while dripping, the stirring speed is 80 rpm, then, obtain polyfluoroalkoxy ether acid ammonium aqueous solution for subsequent use, wherein, 1-bromo -The weight ratio of ammonium polyfluoroalkoxy carboxy etherate to water is 20:100;

[0101] B: Polymerization preparation: Replace the high-pressure polymerization kettle wit...

Embodiment 2

[0113] Polychlorotrifluoroethylene is prepared from gaseous fluorinated monomer—chlorotrifluoroethylene through aqueous emulsion polymerization, and 1-bromo-polyfluoroalkoxy carboxylether acid is added in the aqueous emulsion polymerization as a fluorine-containing emulsifier. The specific implementation steps are as follows:

[0114] A: Prepare the aqueous solution of the salt of 1-bromo-polyfluoroalkoxycarboxy ether acid: add 2800ml of deionized water and 400ml of 25% ammonia water in a 5000ml glass beaker, and then slowly and uniformly pour into the deionized water through the glass dropping funnel Add dropwise the 1-bromo-polyfluoroalkyl carboxylic acid of 800g, stir while dripping, the stirring speed is 80 rpm, then, obtain polyfluoroalkoxy ether acid ammonium aqueous solution for subsequent use, wherein, 1-bromo - The weight ratio of poly(polyfluoroalkoxy carboxy ether ammonium acid) to water is 20:100;

[0115] B: Polymerization preparation: replace the high-pressure p...

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Abstract

The invention discloses a method suitable for preparing a fluorine-containing polymer without perfluorooctanoic acid or perfluorooctane sulfonic acid. The preparation method comprises: performing aqueous emulsion polymerization with one or more fluorinated monomers; During aqueous emulsion polymerization, polyfluoroalkoxy ether acid is used as emulsifier, the fluorine-containing polymer prepared by the present invention is free of perfluorooctanoic acid or perfluorooctane sulfonic acid, and the polyfluoroalkoxy ether acid is terminal Polyfluoroalkoxy ether acid emulsifier based on halogen or hydrogen. Its technical scheme mainly involves the following three improvements: (1) Selecting polyfluoroalkoxy ether acid and its salt to replace PFOA / PFOS as fluorine-containing emulsifier, which can be effectively applied to the aqueous emulsion of fluorinated monomers Polymerization reaction; (2) the prepared fluoropolymer does not contain perfluorooctanoic acid or perfluorooctane sulfonic acid, which meets environmental requirements; (3) conforms to cost accounting, and can greatly increase the unit cost of equipment without increasing production equipment and personnel. At the same time, it can also improve production indicators such as polymerization time and polymerization yield.

Description

technical field [0001] The invention relates to the field of synthesis of fluorine-containing polymers, in particular, it is a method suitable for preparing fluorine-containing polymers not containing perfluorooctanoic acid or perfluorooctylsulfonic acid. Background technique [0002] Fluoropolymer is a general term for alkane polymers in which some hydrogen atoms are replaced by fluorine atoms. It is also a special kind of polymer material, which can be polymerized by one or more fluorine-containing monomers under certain conditions. The fluorine-carbon bond with high bond energy in its structure and the shielding effect of fluorine atoms on the molecular chain make it have a series of excellent characteristics, such as: excellent chemical corrosion resistance, dielectric properties, weather resistance, non-stickiness, excellent Friction properties, etc. Of course, due to its excellent performance, fluoropolymers have become one of the indispensable materials in many fields...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F114/26C08F114/24C08F214/22C08F214/28C08F2/26
Inventor 刘皓陆盛麟张林周家发郎宏波
Owner 成都晨光博达新材料股份有限公司
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