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JP-7857214-B2 - Fluorine-containing polymer and method for producing the same

JP7857214B2JP 7857214 B2JP7857214 B2JP 7857214B2JP-7857214-B2

Inventors

  • 渡貫 俊

Assignees

  • ＡＧＣ株式会社

Dates

Publication Date
20260512
Application Date
20210202
Priority Date
20200214

Claims (8)

  1. In the presence of an ionic catalyst represented by the following formula (2), which consists of an anion and a countercation, and a compound having a substructure represented by the following formula (3), or, In the presence of at least one compound selected from the group consisting of the compound represented by the following formula (4) and the compound represented by the following formula (5), A method for producing a fluorine-containing polymer, comprising polymerizing a compound having at least two reactive carbon-carbon double bonds, The fluorine content of the compound having at least two reactive carbon-carbon double bonds is 20% by mass or more. A method for producing a fluorine-containing polymer, wherein the fluorine-containing polymer has a fluorine content of 50% by mass or more, a degree of unsaturation of 0.1 mEq/g or more, a glass transition temperature of -20°C or higher, and the relationship between the maximum value E * 1 of the complex modulus in the range of -50°C to (glass transition temperature -10°C) and the minimum value E * 2 of the complex modulus in the range of (glass transition temperature +10°C) to 250°C satisfies E * 2/E * 1 ≤ 0.01. In formula (2), A + represents a cation, alkali metal ion, or proton containing at least one element selected from the group consisting of nitrogen and phosphorus, and B- represents a monovalent anion containing at least one element selected from the group consisting of iodine, nitrogen, and sulfur. In formula (3), * represents a bond attached to an organic group. X1 and X2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or -CX3 X4 X5. X3 to X5 each independently represent a hydrogen atom, a fluorine atom, or a chlorine atom . In formula (4), Y1 represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms. Y2 and Y3 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. Y4 represents a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, a substituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amide group having 2 to 8 carbon atoms, an oxycarbonyl group, or a cyano group. In formula (5), Y5 and Y6 each independently represent an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms.
  2. The method for producing a fluorine-containing polymer according to claim 1, wherein the polydispersity of the fluorine-containing polymer is 2.0 or less.
  3. A method for producing a fluorine-containing polymer according to claim 1 or claim 2, wherein the weight-average molecular weight of the fluorine-containing polymer is 1,000 to 1,000,000.
  4. The fluorine-containing polymer is A polymer of the compound represented by the following formula (1), or a copolymer of the compound represented by the following formula (1) and a compound having a reactive carbon-carbon double bond and different from the compound represented by the aforementioned formula (1). A method for producing a fluorine-containing polymer according to any one of claims 1 to 3. In formula (1), Y7 represents a divalent organic group having at least one fluorine atom. R1 to R6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 5 carbon atoms. R1 and R3 , R4 and R5 , R2 and Y7 , and R6 and Y7 may each independently be linked to each other to form a cyclic structure.
  5. The method for producing a fluorine-containing polymer according to claim 4, wherein Y7 in formula (1) is a fluoroalkylene group having 1 to 60 carbon atoms, a fluoropolyether group having 1 to 60 carbon atoms, or a fluoroarylene group having 1 to 60 carbon atoms.
  6. A method for producing a fluorine-containing polymer according to claim 4 or claim 5, wherein the compound represented by formula (1) comprises at least one selected from the group consisting of divinylfluoroalkanes having 5 to 64 carbon atoms, divinylfluoropolyethers having 5 to 64 carbon atoms, and divinylfluoroarylenes having 5 to 64 carbon atoms .
  7. A method for producing a fluorine-containing polymer according to any one of claims 1 to 3 , wherein the compound having at least two reactive carbon-carbon double bonds includes a compound represented by the following formula (1). In formula (1), Y7 represents a divalent organic group having at least one fluorine atom. R1 to R6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 5 carbon atoms. R1 and R3 , R4 and R5 , R2 and Y7 , and R6 and Y7 may each independently be linked to each other to form a cyclic structure.
  8. A method for producing a fluorine-containing polymer according to claim 7 , comprising copolymerizing a compound represented by formula (1) with a compound having a reactive carbon-carbon double bond and being different from the compound represented by formula (1).

Description

This disclosure relates to fluorine-containing polymers and methods for producing the same. Radical polymerization reactions are widely used industrially because they offer excellent monomer versatility and can be easily carried out even in polar media such as water. When haloolefins, particularly fluoroolefins, are used as monomers, haloolefin polymers can be synthesized. Haloolefin polymers are useful as raw materials for low-reactivity carbon-carbon double bond solvents, low-reactivity solvents, heat transfer fluids, pharmaceutical and agricultural chemical intermediates, fire extinguishing agents, surfactants, surface treatment agents, low-friction sliding materials, mold release materials, resin molding additives, chemical-resistant greases, low refractive index materials, low dielectric constant materials, heat-resistant elastomers, thermoplastic elastomers, flame retardants, chemical-resistant ionomers, and photoresist materials. One known method for polymerizing haloolefins is the method described in Patent Document 1. Patent Document 1 describes a radical polymerization method for producing a haloolefin polymer or copolymer by radical polymerization of a specific haloolefin in the presence of a specific organic tellurium compound. This method is called TERP (organotellurium-mediated living radical polymerization). International Publication No. 2018/164147 The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and do not limit the present invention. In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. An aryl group is a monovalent group in aromatic compounds that corresponds to a residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms forming the aromatic ring. The term is used as a general term encompassing both homoaryl groups derived from carbocyclic compounds and heteroaryl groups derived from heterocyclic compounds. An arylene group is a divalent group that corresponds to a residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms in an aryl group. In this disclosure, the term "reactive carbon-carbon double bond" refers to a carbon-carbon double bond that can react in various ways as an olefin, and does not include aromatic double bonds. In this disclosure, the number of carbon atoms in a compound or its component means the number of carbon atoms in the substituent if the compound or component has substituents. In this disclosure, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid. (Meth)acrylate is a general term for acrylate and methacrylate. (Meth)acrylamide is a general term for acrylamide and methacrylamide. "Polymers" and "oligomers" are compounds formed by the polymerization of monomers. In other words, "polymers" and "oligomers" have multiple structural units. In this disclosure, unless otherwise specified, the phrase "polymerizing compound A" encompasses both cases of polymerizing compound A alone and cases of polymerizing compound A with other compounds. Similarly, the phrase "polymerizing compound A and compound B" encompasses both cases of polymerizing compound A and compound B alone, and cases of polymerizing compound A, compound B, and other compounds. Here, compound A and compound B represent any compounds described in this disclosure that have a reactive carbon-carbon double bond in their molecules. Furthermore, unless otherwise specified, the polymers described in this disclosure may be homopolymers of one compound or copolymers of two or more compounds. Fluorine-containing polymers The fluorine-containing polymer of this disclosure (hereinafter also simply referred to as the fluorine-containing polymer) has a fluorine content of 50% by mass or more, a degree of unsaturation of 0.1 mEq/g or more, a glass transition temperature (Tg) of -20°C or higher, and the relationship between the maximum value E * 1 of the complex modulus in the range of -50°C to (glass transition temperature -10°C) and the minimum value E * 2 of the complex