Fluoropolymer and method of making the same

Abstract

Provided is a novel polymer having a structure from 1,2-difluoroethylene and a method for producing the same. A fluorine-containing polymer characterized by having, as a part or all, a structural unit represented by the following general formula (1) and having a glass transition temperature of 100°C or higher.

Description

Technical Field

[0001] This invention relates to fluoropolymers and methods for manufacturing the same. Background Technology

[0002] Fluoropolymers are polymers used in a wide range of fields. Monomers used to manufacture these polymers include tetrafluoroethylene, vinylidene fluoride, and hexafluoropropylene.

[0003] A method for manufacturing 1,2-difluoroethylene is disclosed in Patent Document 1. Furthermore, Non-Patent Document 1 discloses the compound and polymers using the compound.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2019 / 216239

[0007] Non-patent literature

[0008] Non-patent literature 1: Poly (vinylene fluoride), Synthesis and Properties W.S. Durrell et al. Journal of Polymer Science: Part AVol. 3, pp. 2975-2982 (1965) Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The purpose of this invention is to provide a novel polymer having a structure derived from 1,2-difluoroethylene and a method for manufacturing the same.

[0011] Methods for solving problems

[0012] The present invention relates to a fluoropolymer, characterized in that it has structural units as part or all of the following general formula (1), and has a glass transition temperature of 100°C or higher.

[0013]

Chemistry 1

[0014]

[0015] The preferred weight-average molecular weight of the above-mentioned fluoropolymer is 5,000 to 5,000,000.

[0016] The present invention also relates to a fluoropolymer, characterized in that it has structural units represented by the following general formula (1) and structural units represented by the following general formula (2).

[0017]

Chemistry 2

[0018]

[0019]

Transformation 3

[0020]

[0021] (R1 is hydrogen, fluorine, a hydrocarbon group with 5 or fewer carbon atoms that is partially or completely fluorinated, or an OR5 group (R5 group is a hydrocarbon group with 5 or fewer carbon atoms that is partially or completely fluorinated. R2, R3, and R4 are each independently hydrogen or fluorine.)

[0022] The structural unit shown in the above general formula (2) is preferably at least one structural unit selected from the group of structural units shown in the following general formulas (3) to (8).

[0023]

Chemistry 4

[0024]

[0025] The preferred weight-average molecular weight of the above-mentioned fluoropolymer is 5,000 to 5,000,000.

[0026] The present invention also relates to a fluoropolymer, characterized in that it has structural units of the following general formula (1) as part or all of them, and is amorphous.

[0027]

Transformation 5

[0028]

[0029] The aforementioned amorphous fluoropolymer preferably has structural units represented by general formula (1) and structural units derived from hexafluoropropylene, and has a glass transition temperature of 35°C or higher.

[0030] The amorphous fluoropolymers described above preferably have a structural unit ratio of 70 mol% to 92 mol% as shown in general formula (1).

[0031] The aforementioned amorphous fluoropolymer preferably has structural units represented by general formula (1) and structural units from at least one unsaturated compound selected from the group consisting of 1225, 1234, 1243 and 1252 (all ASHRAE numbers, including isomers).

[0032] Furthermore, its glass transition temperature is above 35°C.

[0033] The structural units of the aforementioned amorphous fluoropolymers, preferably represented by general formula (1), are 0.1 mol% to 92 mol%.

[0034] The aforementioned amorphous fluoropolymer preferably has structural units shown in general formula (1) and general formula (20) below, and has a glass transition temperature of 35°C or higher.

[0035]

Transformation 6

[0036]

[0037] (R1 to R3 are selected from H and F, and Rf is a fluorinated alkyl group with 1 to 6 carbon atoms.)

[0038] The structural unit shown in the above general formula (20) is preferably at least one of the structural units shown in the following general formulas (7) to (9).

[0039]

Transformation 7

[0040]

[0041] The amorphous fluoropolymers described above preferably have a proportion of 70 mol% to 92 mol% of the structural units shown in general formula (1). The present invention also relates to a resin solution characterized in that it is prepared by dissolving the polymer described in any of the above claims in a common solvent.

[0042] The present invention also relates to a method for manufacturing the above-mentioned fluoropolymer, characterized in that it includes a step of polymerizing a monomer composition in which a monomer shown in the following general formula (10) is used as part or all of the monomer composition.

[0043]

Transformation 8

[0044]

[0045] The effects of the invention

[0046] The polymers of this invention have specific constituent units and can be either homopolymers or copolymers. Since they can also be easily copolymerized with other fluorinated monomers at a wide range of polymerization ratios, polymers with various physical properties can be obtained. The first polymer of this invention is a novel polymer with the advantages of a high glass transition temperature and solubility in common organic solvents. The second polymer of this invention is a novel polymer, a copolymer formed by copolymerizing 1,2-difluoroethylene with other monomers in any proportion. Such polymers can have various physical properties depending on their polymerization ratio. For example, resins with excellent chemical resistance and polymers soluble in common organic solvents can be obtained. The third polymer of this invention is a novel polymer with the advantages of being amorphous and soluble in common organic solvents. Detailed Implementation

[0047] The present invention is described in detail below. The present invention is a homopolymer or copolymer having the structure shown in the following general formula (1).

[0048]

Chemistry 9

[0049]

[0050] The structure shown in the above general formula (1) is constructed by using a structure having the following general formula (10).

[0051]

Chemistry 10

[0052]

[0053] The structure shown is obtained by polymerizing the compound as a monomer. The compound shown in general formula (10) is a known compound, but its use as a refrigerant has been mainly studied in the past, and its use as a polymerization monomer has been almost not studied.

[0054] Polymers having the structural units shown in the above general formula (1) can be made into resins with high Tg above 100°C. With this property, it is expected to be used for applications different from low Tg polymers such as polyvinylidene fluoride.

[0055] Furthermore, copolymers can be obtained with other monomers using conventional methods. Moreover, the copolymerization ratio can be easily changed. This method also allows it to be used as a copolymer component for adjusting various physical properties of the resin. For example, in the case of copolymerization with tetrafluoroethylene, 1,2-difluoroethylene, as a copolymer component, can be introduced in any proportion. This allows for appropriate adjustment of properties such as the resin's melting point and crystallinity.

[0056] It should be noted that the copolymers of the present invention generally exhibit excellent solubility in common solvents, but depending on the composition of the copolymer, they may sometimes become resins insoluble in common solvents. This is true, for example, when 1,2-difluoroethylene is copolymerized in tetrafluoroethylene, polyvinylidene fluoride, etc., at a low copolymerization ratio. While such polymers may not be soluble in common solvents, they can still adjust the properties of the resin without compromising the original chemical resistance and other properties inherent in polytetrafluoroethylene, polyvinylidene fluoride, etc.

[0057] Furthermore, the polymer of the present invention is soluble in common organic solvents such as acetone. Generally known fluoropolymers are not soluble in common organic solvents. However, the polymer of the present invention is soluble in common organic solvents, and therefore, from a cost and other perspectives, it can also be used in applications where the use of common organic solvents is required.

[0058] Furthermore, the polymers of the present invention, when copolymerized, can be formulated into amorphous polymers. These amorphous fluoropolymers exhibit excellent properties in terms of transparency, coatability, and adhesion, and are therefore particularly preferred for applications requiring such properties.

[0059] It should be noted that Non-Patent Document 1 disclosed a polymer obtained by using a monomer represented by the above general formula (10) or a monomer composition containing the above monomer as a raw material. However, Non-Patent Document 1 describes a polymer with a glass transition temperature of around 50°C. On the other hand, the inventors have discovered that by manufacturing a monomer of high purity and polymerizing it, the homopolymer of a compound having the structure represented by the above general formula (1) has a glass transition temperature of 100°C or higher. Since the glass transition temperature of the polymer described in Non-Patent Document 1 is around 50°C, it is clear that the same substance as the polymer of the present invention was not obtained, and it is significantly different from the polymer of the present invention.

[0060] In Non-Patent Document 1, it is impossible to obtain monomers with high purity. Therefore, it is impossible to obtain polymers similar to those of the present invention. According to the inventors' research, if the compound represented by general formula (10) is synthesized by the synthesis method in Non-Patent Document 1, various impurities such as vinylidene fluoride will be generated. Furthermore, in Non-Patent Document 1, since the purity of the precursor is 90%, components from impurities in this precursor will also be generated. In Non-Patent Document 1, there are records of removing impurities by capturing with dry ice (-78°C). However, this method cannot remove high-boiling-point compounds. As mentioned above, in Non-Patent Document 1, if we consider the records of polymers with a glass transition temperature of around 50°C, it is impossible to obtain monomers with high purity in Non-Patent Document 1. Therefore, polymers with a glass transition temperature of 100°C or higher are not disclosed.

[0061] As shown in the following synthesis example, the polymer with the monomer shown in the above general formula (10) as the main component will have a Tg of 86°C if it contains only 3.5% vinylidene fluoride. Even if the monomer prepared using existing methods uses a precursor with a purity of 90% or higher, byproducts such as VDF and 1122 will be generated at a rate of 35% or more. Therefore, it is preferable to use a monomer with high purity in order to produce polymer 1. Furthermore, in polymer 2, it is also preferable to use a monomer with high purity to stabilize the composition, and it is preferable to obtain a polymer with the specified physical properties in a stable manner.

[0062] Furthermore, when the fluoropolymer of the present invention is polymer 2 or polymer 3, if the purity of the monomer shown in the above general formula (10) is low, it is sometimes difficult to introduce the copolymer component into the resin. That is, sometimes the monomer is included in the polymer only in a low proportion of less than the amount added. In contrast, if a monomer with high purity is used, the copolymer component can be easily introduced into the resin, which is preferable from this point of view.

[0063] As described above, the fluoropolymer of the present invention can be amorphous. In this case, it is required that the copolymer components be introduced into the polymer in a specified ratio. To achieve this, it is also preferable to use monomers with high purity as raw materials.

[0064] In view of the above, in any of the polymers 1 to 3 described below, it is preferable to use a compound of general formula (10) with a purity of 99.5% by mass or more (more preferably 99.8% by mass or more, and most preferably 99.9% by mass or more) as a monomer to obtain the polymer.

[0065] The polymers of the present invention have the structural units shown in the above general formula (1), and more specifically, are the following three polymers.

[0066] (Polymer 1) has the structural unit shown in the above general formula (1) and has a glass transition temperature of 100°C or higher.

[0067] (Polymer 2) has the structural unit shown in the above general formula (1) and the structural unit shown in the following general formula (2).

[0068] (Polymer 3) has the structural unit shown in the above general formula (1) and is amorphous.

[0069] It should be noted that there are also polymers that satisfy multiple conditions of the above three polymers, and such polymers are also included in this invention.

[0070] For example, amorphous polymer 1, amorphous polymer 2, and polymer 2 with a glass transition temperature of 100°C or higher are also objects of this invention. They will be described in detail below.

[0071] (Polymer 1)

[0072] The polymer 1 of the present invention is a polymer having the structure shown in the above general formula (1) and having a glass transition temperature of 100°C or higher. That is, it refers to a polymer consisting only of the structure shown in the above general formula (1), or a copolymer having the structural units shown in the above general formula (1) and having a glass transition temperature of 100°C or higher.

[0073] It should be noted that, in this specification, the glass transition temperature is a value determined by DSC under the conditions shown in the examples.

[0074] The upper limit of the glass transition temperature is not particularly limited, but it is more preferably below 200°C, and even more preferably below 150°C.

[0075] The polymer 1 of the present invention can be obtained by polymerization of the monomers represented by the above general formula (10) or by polymerization of a monomer composition in which the monomers represented by the general formula (10) are necessary components.

[0076] It should be noted that the monomer shown in the above general formula (10) exists in both trans (E-form) and cis (Z-form) forms.

[0077]

Chemistry 11

[0078]

[0079] Therefore, the stereochemical configuration differs when only the trans form is used as a raw material, when only the cis form is used as a raw material, or when a mixture of them is used as a raw material. The polymer 1 of the present invention can be any one of them as long as its glass transition temperature is 100°C or higher. Alternatively, it can be a mixture of them in any proportion.

[0080] The polymer 1 of the present invention can be a polymer consisting solely of the structure shown in the above general formula (1), or it can be a copolymer incorporating other monomers. It should be noted that the type and amount of the copolymer used will affect the glass transition temperature, therefore its use needs to be determined with the glass transition temperature in mind.

[0081] It should be noted that the polymer 1, which is composed only of the structural units shown in the above general formula (1), varies slightly due to the presence ratio of cis and trans in the raw material monomers, but is within the range of 100℃ to 150℃.

[0082] The polymer 1 of the present invention can be a homopolymer, or a copolymer component can be used in the range where the glass transition temperature is 100°C or higher. It should be noted that when preparing a homopolymer, it is preferable to contain the structural unit shown in the above general formula (1) in a proportion of 99.5 mol% or more. The above structural unit is further preferably 99.8 mol% or more, and most preferably 99.9 mol% or more.

[0083] The polymer 1 of the present invention can also be a copolymer having structural units derived from the copolymer component, provided that its glass transition temperature is 100°C or higher. In the polymer 1 of the present invention, there are no particular limitations on the copolymer component that can be used. For example, the other monomers mentioned above are preferably selected from at least one of the group consisting of tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether), trifluorochloroethylene, trifluoroethylene, hexafluoroisobutylene, fluorinated vinyl, ethylene, propylene, and alkyl vinyl ethers.

[0084] The amount of copolymer component in polymer 1 of the present invention is not particularly limited, but is more preferably 99 mol% or less, further preferably 98 mol% or less, and most preferably 95 mol% or less.

[0085] The polymer 1 of the present invention preferably has an F / H ratio of 50% or more (molar ratio). If the F / H ratio is less than 50%, the thermal decomposition temperature decreases, and gas may be generated when molding the resin into films or tubes, which may make molding difficult. Furthermore, it is undesirable for the resin to become colored due to thermal decomposition. The lower limit of the F / H ratio is more preferably 50% or more, and even more preferably 55% or more. The upper limit of the F / H ratio is more preferably 95% (molar ratio), even more preferably 90%, and most preferably 80%.

[0086] The weight-average molecular weight of polymer 1 of the present invention is preferably 5,000 to 5,000,000. Being within this range is preferred from the perspective of heat resistance and molding processability. The upper limit is more preferably 3,000,000, and even more preferably 2,000,000. The lower limit is more preferably 8,000, and even more preferably 10,000. The weight-average molecular weight of the present invention is a value determined by gel permeation chromatography (GPC).

[0087] Polymer 1 of the present invention has the advantage of being soluble in common solvents. Known fluorinated polymers are difficult to dissolve in common solvents, and when used as resin solutions, they require dissolution in special solvents with particularly excellent dissolving power. Therefore, the use of expensive solvents can sometimes lead to increased costs. Polymer 1 of the present invention is particularly preferred from a cost perspective because it has good solubility in common solvents. Examples of common solvents capable of dissolving Polymer 1 of the present invention include acetone, methyl ethyl ketone, tetrahydrofuran, and N,N-dimethylformamide.

[0088] When the polymer 1 of the present invention is prepared into a resin solution dissolved in a common solvent, the resin concentration is preferably 1.0% to 10.0% by mass. The lower limit of the above resin concentration is more preferably 2.0% by mass, and even more preferably 2.5% by mass. The upper limit of the above resin concentration is more preferably 9.0% by mass, and even more preferably 8.0% by mass.

[0089] (Polymer 2)

[0090] In addition to the constituent unit shown in the general formula (1) above, the polymer 2 also has the structural unit shown in the general formula (2) below.

[0091]

Chemistry 12

[0092]

[0093] (R1 is hydrogen, fluorine, a hydrocarbon group with 5 or fewer carbon atoms that is partially or completely fluorinated, or an OR5 group (R5 group is a hydrocarbon group with 5 or fewer carbon atoms that is partially or completely fluorinated. R2, R3, and R4 are each independently hydrogen or fluorine.)

[0094] Examples of structural units represented by the general formula (2) above include structures of olefinic monomers from which at least one hydrogen atom can be fluorinated, structures of propylene monomers from which at least one hydrogen atom can be fluorinated, structures of butene monomers from which at least one hydrogen atom can be fluorinated, and structures of pentene monomers from which at least one hydrogen atom can be fluorinated. The fluoropolymers of the present invention may also utilize two or more copolymer structural units.

[0095] Examples of olefinic monomers that are at least one of the hydrogen atoms that can be replaced by fluorine include ethylene, vinylidene fluoride, tetrafluoroethylene, fluoroethylene, and 1,1,2-trifluoroethylene.

[0096] Examples of structural units for propeny monomers with at least one fluorine-substituted hydrogen atom include 1270, 1261, 1252, 1243, 1234, and 1225. Examples of structural units for buteny monomers with at least one fluorine-substituted hydrogen atom include 1390, 1381, 1372, 1363, 1354, 1345, 1336, 1327, and 1318. Examples of penteney monomers with at least one fluorine-substituted hydrogen atom include R600, R600a, nonafluoropentene, 1492, 1483, 1474, 1465, 1456, 1447, 1438, 1429, and perfluoropentene. It should be noted that these are all ASHRAE designations.

[0097] As structural units of at least one fluorine-substituted propylene monomer derived from a hydrogen atom, particularly preferred by ASHRAE designations are 1216 (hexafluoropropylene), 1225, 1234, 1243, and 1252. As such structural units, structural units represented by the following general formulas (11) to (16) are preferred.

[0098]

Chemistry 13

[0099]

[0100] (In the formula, Rf1 to Rf6 represent fluoromethyl groups having 1 to 3 fluorine atoms)

[0101] Specifically, examples of compounds providing the structure shown in the above general formula include 2,3,3,3-tetrafluoropropene (HFO-1234yf), (Z or E-)1,3,3,3-tetrafluoropropene (HFO-1234ze), (Z or E-)1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-)1,1,3,3,3-pentafluoropropene (HFO-1225zc), and (Z or E-)3,3,3-trifluoropropene (HFO-1243zf).

[0102] The structural unit shown in general formula (2) can also be

[0103]

Chemistry 14

[0104]

[0105] (R1 to R3 are selected from H and F, and Rf is a fluorinated alkyl group with 1 to 6 carbon atoms).

[0106] The structural unit shown in the above general formula (20) is a structural unit derived from a fluorinated vinyl ether compound. There are no particular limitations on the above fluorinated vinyl ether compound, and examples include perfluoromethyl vinyl ether (hereinafter general formula (7)), perfluoroethyl vinyl ether (hereinafter general formula (8)), and perfluoropropyl vinyl ether (hereinafter general formula (9)).

[0107]

Chemistry 15

[0108]

[0109] In the polymer (B) of the present invention, the structural unit shown in the above general formula (2) is particularly preferably the structural unit shown in the following general formulas (3) to (8).

[0110]

Chemistry 16

[0111]

[0112] The structure shown in general formula (3) is derived from a structural unit of tetrafluoroethylene, and the structure shown in general formula (4) is derived from a structural unit of vinylidene fluoride. Furthermore, the structure shown in general formula (5) is derived from a structural unit of perfluorovinyl methyl ether, and the structure shown in general formula (5) is derived from a structural unit of CH2=CFCF3. The structure shown in general formula (6) is derived from a structural unit of hexafluoropropylene. The structure shown in general formula (7) is derived from a structural unit of perfluoro(methyl vinyl ether). The structure shown in general formula (8) is derived from a structural unit of perfluoro(ethyl vinyl ether).

[0113] These are compounds known as fluorine-containing monomers. The polymer 2 of the present invention is a polymer in which the structure shown in general formula (1) is used as a copolymer component for general fluoropolymers such as polytetrafluoroethylene or polyvinylidene fluoride, which are used as polymers, or a substance modified with the structural unit shown in general formula (2) above for a polymer with the structure shown in general formula (1) as the main skeleton.

[0114] The glass transition temperature of these polymers 2 is not particularly limited and can be less than 100°C. The glass transition temperature of the polymers 2 is preferably -20°C to 99.9°C.

[0115] The polymer 2 of the present invention preferably contains structural units shown in general formula (1) and / or general formula (2) in a proportion of 1 mol% to 99 mol%. This range is preferred from the perspective of allowing arbitrary adjustment of crystallinity. The lower limit is more preferably 2 mol%, and even more preferably 5 mol%. The upper limit is more preferably 98 mol%, and even more preferably 95 mol%.

[0116] The polymer 2 of the present invention may further have structural units derived from copolymer components other than those shown in the above general formula (2). There are no particular limitations on such copolymer components; examples include trifluorochloroethylene and hexafluoroisobutylene.

[0117] There is no particular limitation on the amount of copolymer components other than the structural units shown in the above general formula (2), but it is more preferably 99 mol% or less, further preferably 98 mol% or less, and most preferably 95 mol% or less.

[0118] The polymer 2 of the present invention preferably has an F / H ratio of 50% or more (molar ratio). If the F / H ratio is less than 50%, the thermal decomposition temperature decreases, and gas may be generated when molding the resin into films or tubes, which may make molding difficult. Furthermore, it is undesirable for the resin to become colored due to thermal decomposition. The lower limit of the F / H ratio is more preferably 50% or more, and even more preferably 55% or more. The upper limit of the F / H ratio is more preferably 95% (molar ratio), even more preferably 90%, and most preferably 80%.

[0119] The weight-average molecular weight of polymer 2 of the present invention is preferably 5,000 to 5,000,000. Being within this range is preferred from the perspective of heat resistance and molding processability. The upper limit is more preferably 3,000,000, and even more preferably 2,000,000. The lower limit is more preferably 8,000, and even more preferably 10,000.

[0120] Polymer 2 of the present invention is soluble in a common solvent. As described above, polymers having structural units shown in general formula (1) are soluble in common solvents. Therefore, polymer 2, even when containing structural units shown in general formula (1) in a high proportion, is also soluble in a common solvent. This common solvent is not particularly limited, and examples include acetone, methyl ethyl ketone, tetrahydrofuran, methyl isobutyl ketone, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.

[0121] When the polymer 2 of the present invention is prepared into a resin solution dissolved in a common solvent, the resin concentration is preferably 1.0% to 10.0% by mass. The lower limit of the above resin concentration is more preferably 2.0% by mass, and even more preferably 2.5% by mass. The upper limit of the above resin concentration is more preferably 9.0% by mass, and even more preferably 8.0% by mass.

[0122] (Polymer 3)

[0123] Polymers having the structure shown in the above general formula (1) can also be made into amorphous polymers by adjusting their composition.

[0124] In this invention, "amorphous" means that the crystallinity calculated by X-ray crystallography based on the measurement method described in the examples is 0.5% or less. It should be noted that the measurement conditions here are those described in the following examples. More preferably, the crystallinity is 0%.

[0125] The amorphous fluoropolymer of the present invention preferably has a glass transition temperature of 35°C or higher. More preferably, it has a glass transition temperature of 40°C or higher, and even more preferably, it has a glass transition temperature of 50°C or higher.

[0126] The amorphous fluoropolymer of the present invention has the chemical structure shown in the above general formula (1) and the structure derived from the copolymer component. The crystallinity can be reduced by the type of structure derived from the copolymer component, the amount of its mixture, etc.

[0127] It should be noted that, as described above, polymer 3 can possess the properties of both polymer 1 and / or polymer 2. The specific compositions of amorphous fluoropolymers are illustrated below. It should be noted that polymer 3 only needs to meet the above conditions and is not limited to polymers (A) to (C) shown below.

[0128] (An amorphous fluoropolymer having structural units shown in general formula (1) and structural units derived from hexafluoropropylene, and a glass transition temperature of 35°C or higher)

[0129] An amorphous fluoropolymer can be produced using hexafluoropropylene as a copolymer component. In this case, the glass transition temperature is set to 35°C or higher. Hereinafter, this polymer will be referred to as polymer (A).

[0130] Polymer (A) possesses excellent properties as an amorphous fluoropolymer. Furthermore, in the various applications detailed below, a glass transition temperature of 35°C or higher is required, and this polymer exhibits excellent performance in meeting the requirements of such applications.

[0131] Polymer (A) preferably contains the structural unit shown in general formula (1) in a proportion of 86 mol% to 90 mol% relative to the total polymer amount. The lower limit is more preferably 87 mol%.

[0132] Polymer (A) preferably contains structural units derived from hexafluoropropylene in a proportion of 8.0 mol% to 30.0 mol% relative to the total polymer. The lower limit is preferably 10.0 mol%, and the upper limit is preferably 20.0 mol%.

[0133] Polymer (A) may also be a polymer having structural units (A) other than those derived from hexafluoropropylene, within the scope of not impairing the effects of the invention. The aforementioned other structural units (A) are preferably in a proportion of 90 mol% or less relative to the total polymer amount, or may be a polymer that does not contain the aforementioned other structural units (A) but consists only of structural units (A) derived from general formula (1) and structural units derived from hexafluoropropylene.

[0134] As for the other structural unit (A) mentioned above, there are no particular limitations, and any copolymerizable unsaturated polymerizable monomer can be used. For example, structures from compounds other than hexafluoropropylene, trifluorochloroethylene, ethylene, propylene, and alkyl vinyl ethers, etc., can be exemplified.

[0135] Polymer (A), as described above, has a glass transition temperature of 35°C or higher. Having such a glass transition temperature results in physical properties suitable for use in the various applications detailed below, and is therefore preferred.

[0136] (An amorphous fluoropolymer having structural units of the general formula (1) and structural units of at least unsaturated compounds selected from the group consisting of 1225, 1234, 1243 and 1252, and having a glass transition temperature of 35°C or higher)

[0137] Such amorphous fluoropolymers are denoted as polymer (B).

[0138] In polymer (B), “1225, 1234, 1243, 1252” refers to the structure indicated by ASHRAE number. Specifically, it is preferred to be at least one copolymer unit selected from the group consisting of monomer units having the structure shown by any of the following general formulas (11) to (16).

[0139]

Chemistry 17

[0140]

[0141] (In the formula, Rf1 to Rf6 represent fluoromethyl groups having 1 to 3 fluorine atoms)

[0142] Specifically, examples of compounds providing the structure shown in the above general formula include 2,3,3,3-tetrafluoropropene (HFO-1234yf), (Z or E-)1,3,3,3-tetrafluoropropene (HFO-1234ze), (Z or E-)1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-)1,1,3,3,3-pentafluoropropene (HFO-1225zc), and (Z or E-)3,3,3-trifluoropropene (HFO-1243zf).

[0143] The polymer (B) preferably contains the structural unit shown in general formula (1) in a proportion of 0.1 mol% to 90 mol% relative to the total polymer amount.

[0144] Polymer (B) preferably has structural units of at least one unsaturated compound selected from the group consisting of 1225, 1234, 1243 and 1252 in a proportion of 8.0 mol% to 99.9 mol% relative to the total polymer. The lower limit is preferably 10.0 mol%.

[0145] Polymer (B) may also be a polymer having structural units (B) other than those shown in general formula (1) and structural units from "1225, 1234, 1243, 1252" within the range that does not impair the effects of the invention. The aforementioned other structural units (B) are preferably in a proportion of 90 mol% or less relative to the total polymer amount, or may be a polymer that does not contain the aforementioned other structural units (A) but consists only of structural units shown in general formula (1) and structural units from "1225, 1234, 1243, 1252".

[0146] There are no particular limitations on the other structural unit (B) mentioned above, and any copolymerizable unsaturated polymerizable monomer can be used. For example, structures from compounds other than hexafluoropropylene, trifluorochloroethylene, ethylene, propylene, and alkyl vinyl ethers, etc., can be exemplified.

[0147] Polymer (B), as described above, has a glass transition temperature of 35°C or higher. Having such a glass transition temperature provides physical properties suitable for use in the various applications detailed below, and is therefore preferred.

[0148] (An amorphous fluoropolymer having the structural unit shown in general formula (1) and the structural unit shown in general formula (20) above, and having a glass transition temperature of 35°C or higher)

[0149] Such amorphous fluoropolymers are denoted as polymer (C).

[0150] The structural unit shown in general formula (20) is

[0151] [Chemistry 18]

[0152]

[0153] (R1 to R3 are selected from H and F, and Rf is a fluorinated alkyl group with 1 to 6 carbon atoms).

[0154] The structural unit shown in the above general formula (20) is a structural unit derived from a fluorinated vinyl ether compound. There are no particular limitations on the above fluorinated vinyl ether compound; examples include perfluoromethyl vinyl ether and perfluoropropyl vinyl ether.

[0155] There are no particular limitations on the structural units of the above-mentioned fluorinated vinyl ether compounds, but for example, at least one of the structural units shown in the following general formulas (7) to (9) is preferred.

[0156]

Chemistry 19

[0157]

[0158] The polymer (C) preferably contains the structural unit shown in general formula (1) in a proportion of 75 mol% to 90 mol% relative to the total polymer amount.

[0159] The polymer (C) preferably has the structural units shown in the above general formula (20) in a proportion of 8.0 mol% to 30.0 mol% relative to the total polymer. The lower limit is preferably 10.0 mol%, and the upper limit is preferably 25.0 mol%.

[0160] The polymer (C) may also be a polymer having structural units (C) other than those shown in general formula (1) and general formula (20) within the range that does not impair the effects of the invention. The aforementioned other structural units (C) are preferably in a proportion of 90 mol% or less relative to the total amount of polymer, and may also be a polymer that does not contain the aforementioned other structural units (A) but is composed only of the structural units shown in general formula (1) and general formula (20).

[0161] There are no particular limitations on the other structural unit (C) mentioned above, and any copolymerizable unsaturated polymerizable monomer can be used. For example, compounds other than those shown in general formula (20) among the compounds shown in general formula (2) above, trifluorochloroethylene, ethylene, propylene, and alkyl vinyl ethers, etc., can be exemplified.

[0162] The polymer (C) described above has a glass transition temperature of 35°C or higher. Having such a glass transition temperature provides suitable physical properties for use in the various applications detailed below, and is therefore preferred.

[0163] The polymer 3 of the present invention preferably has an F / H ratio of 50% or more (molar ratio). If the F / H ratio is less than 50%, the thermal decomposition temperature decreases, and gas may be generated when molding the resin into films or tubes, which may make molding difficult. Furthermore, it is undesirable for the resin to become colored due to thermal decomposition. The lower limit of the F / H ratio is more preferably 50% or more, and even more preferably 55% or more. The upper limit of the F / H ratio is more preferably 95% (molar ratio), even more preferably 90%, and most preferably 80%.

[0164] The weight-average molecular weight of the polymer 3 of the present invention is preferably 5,000 to 5,000,000. Being within this range is preferred from the perspective of heat resistance and processability. The upper limit is more preferably 3,000,000, and even more preferably 2,000,000. The lower limit is more preferably 8,000, and even more preferably 10,000.

[0165] The polymer 3 of the present invention is soluble in a common solvent. As described above, polymers having structural units shown in general formula (1) are soluble in common solvents. Therefore, polymer 3, even when containing structural units shown in general formula (1) in a high proportion, is also soluble in a common solvent. This common solvent is not particularly limited, and examples include acetone, methyl ethyl ketone, tetrahydrofuran, methyl isobutyl ketone, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.

[0166] When the polymer 3 of the present invention is prepared into a resin solution dissolved in a common solvent, the resin concentration is preferably 1.0% to 10.0% by mass. The lower limit of the above resin concentration is more preferably 2.0% by mass, and even more preferably 2.5% by mass. The upper limit of the above resin concentration is more preferably 9.0% by mass, and even more preferably 8.0% by mass.

[0167] (Aggregation Method)

[0168] The polymers 1 to 3 of the present invention can be produced by using the following general formula (10).

[0169]

Chemistry 20

[0170]

[0171] The monomers shown are obtained by polymerizing a monomer composition, either partially or entirely. The compound shown in the above general formula (10) is a known compound, and can be manufactured, for example, by the method described in Patent Document 1.

[0172] The compound represented by the above general formula (10) is preferably polymerized using a compound with a purity of 99.5% by mass or more. A purity of 99.8% by mass or more is more preferred, and a purity of 99.9% by mass or more is even more preferred. The method of manufacturing the compound represented by general formula (10) with a purity of 99.9% by mass or more is not particularly limited; methods such as preparative gas chromatography or multi-stage distillation can be cited.

[0173] In the polymer 1 described above, by using such a high purity monomer, a polymer with a high glass transition temperature of over 100°C is obtained. As mentioned above, such a polymer is a novel polymer.

[0174] The polymers 2 and 3 described above are also preferably obtained by using monomers (10) with a purity of 99.9% by mass or higher as raw materials. By using such monomers and by including unplanned constituent units, problems such as the inability to obtain the desired resin or the inability to obtain a stable resin with uniform properties can be prevented.

[0175] Furthermore, if a monomer of general formula (10) containing a large number of impurities is used, the copolymer component is difficult to enter the copolymer, thus resulting in the inability to obtain the desired resin. Specifically, for example, in the case of copolymerization with hexafluoropropylene, the hexafluoropropylene unit hardly enters the polymer in Non-Patent Document 1. However, according to experiments conducted by the inventors, if a monomer of high purity is used as a raw material, a copolymer of hexafluoropropylene and the monomer of general formula (10) can be obtained.

[0176] Thus, it can be seen that the copolymerization tendency differs when using high-purity monomers compared to using low-purity monomers. Consequently, polymers with novel compositions different from those in Non-Patent Document 1 can be obtained.

[0177] The manufacturing methods for polymers 1 to 3 are not particularly limited, and can be carried out by any conventional polymerization method such as solution polymerization, emulsion polymerization, or suspension polymerization. The solvents, emulsifiers, initiators, etc., used in these polymerizations are also not particularly limited, and generally known reagents can be used.

[0178] Post-polymerization processing can also be carried out by any conventional method. If necessary, the obtained polymer can be dissolved in a common solvent to prepare a resin solution.

[0179] The fluorinated resin of the present invention is suitable for use in optical materials, building materials, semiconductor-related materials, display-related materials, automotive materials, shipbuilding materials, aircraft materials, power generation-related materials, laminates, coating agents, and consumer goods.

[0180] Examples of such optical materials include optical components, spectacle lenses, optical lenses, optical units, DVD discs, photodiodes, anti-reflective materials, and microlens arrays.

[0181] Examples of building materials mentioned above include, for instance, membrane materials for shop windows, display cases, membrane structures (sports facilities, gardening facilities, atriums, etc.), roofing materials, ceiling materials, exterior wall materials, interior wall materials, and covering materials. Furthermore, beyond membrane materials for membrane structures, examples of outdoor-use materials include, for instance, soundproof walls, windbreaks, breakwaters, garage roofs, shopping mall and pedestrian street sidewalls, anti-glass scattering membranes, heat-resistant / water-resistant sheets, tent materials for tent warehouses, sunshade membrane materials, partial roofing materials for lighting, window materials that replace glass, glass replacements and other opening components, fireproof partition membrane materials, curtains, exterior wall reinforcement, waterproof membranes, smoke-proof membranes, flame-retardant transparent partitions, road reinforcement, interior decoration (lighting, walls, blinds, etc.), exterior decoration (curtains, signs, etc.), large-scale greenhouses, and membrane materials (roofing materials, ceiling materials, exterior wall materials, interior wall materials, etc.).

[0182] Examples of such electronic materials include printed circuit boards, ceramic wiring boards, electronic materials (printed circuit boards, wiring boards, insulating films, anti-stick films, etc.), thin film capacitors, electronic / electrical components, appliance casings, and precision mechanical parts.

[0183] Examples of semiconductor-related materials include protective films for semiconductor devices (such as interlayer insulating films, buffer coating films, passivation films, alpha ray shielding films, device sealing materials, interlayer insulating films for high-density mounting substrates, moisture-proof films for high-frequency devices (such as moisture-proof films for RF circuit devices, GaAs devices, InP devices, etc.), protective films (pellicle films), photolithography, and biochips.

[0184] Examples of materials related to displays include displays, touch panels, surface protective films for various displays (such as PDP, LCD, FED, OLED, and projection TVs), electrowetting surfaces, and image forming articles. Examples of automotive materials include roofs, vibration damping materials, and vehicle bodies.

[0185] Examples of materials related to power generation include solar cells, intermediates for electrolyte materials in solid polymer fuel cells, electrostatic induction conversion elements (such as vibratory generators, actuators, sensors, etc.), power generation devices, electrets used in electrostatic induction conversion elements such as microphones, surface materials for solar cell modules, mirror protection materials for solar power generation, surface materials for solar water heaters, and photovoltaic technology. Examples of laminates include films laminated with thermoplastic resins such as polyimide.

[0186] Examples of coating agents include waterproof coatings, anti-sticking agents, low-reflection coatings, anti-fouling coatings, non-adhesive coatings, waterproof and moisture-proof coatings, insulating films, chemical-resistant coatings, etching protective films, low-refractive-index films, anti-ink coatings, gas barrier films, patterned functional films, surface protective films for color filters used in displays, anti-fouling and anti-reflection films for solar cell cover glass, moisture-proof and anti-reflection coatings for deliquescent crystals or phosphate-based glasses, surface protection and anti-fouling coatings for phase-shifting masks and photomasks, hydrophobic coatings for photoresists used in immersion lithography, and release coatings for contact lithography masks. Release coatings for nanoimprint molds, passivation films for semiconductor components or integrated circuits, gas barrier films for silver electrodes of circuit boards or light-emitting elements such as LEDs, liquid crystal alignment films for liquid crystal display elements, lubricating coatings for magnetic recording media, gate insulating films, devices using the principle of electrowetting, electret films, chemical-resistant coatings for MEMS processes, antifouling coatings for medical devices, drug-resistant, antifouling, bio-resistant, and hydrophobic coatings for devices utilizing microfluidic technology, low-refractive materials for multilayer film coatings of optical filters, hydrophilic and hydrophobic patterned waterproof materials, patterned optical elements, etc.

[0187] Examples of such leisure and lifestyle products include fishing rods, rackets, golf clubs, and screens.

[0188] Example

[0189] The present invention will now be described in detail based on specific embodiments. In the following embodiments, unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass," respectively.

[0190] (The monomer shown in general formula (10))

[0191] The purity of the 1,2-difluoroethylene E monomer used in the following embodiments is 99.9% by mass or higher. It should be noted that, regarding purity, GC / MS confirmed the absence of impurity peaks, indicating a purity of 99.9% by mass. It should also be noted that the monomer was manufactured according to the embodiment of Patent Document 1, and separation was performed by preparative gas chromatography, thereby obtaining a high-purity monomer.

[0192] (Aggregation Method)

[0193] Polymers were polymerized according to the polymerization methods described in the following synthesis examples.

[0194] The obtained polymers were evaluated based on the following evaluation criteria.

[0195] (Acetone solubility)

[0196] Add 9g of acetone to 1g of the resin obtained from each synthesis example and stir using a stirrer. Dissolve the resin if no residue remains after 1 hour.

[0197] (Composition Analysis)

[0198] The composition of the copolymer was determined by solution NMR or fusion NMR.

[0199] Solution NMR Method

[0200] Measuring apparatus: VNMRS400 manufactured by Varian

[0201] Resonant frequency: 376.04 (Sfrq)

[0202] Pulse width: 30°

[0203] <Fused NMR Method>

[0204] Measuring apparatus: AVANCE300 manufactured by Bruker Japan

[0205] Resonant frequency: 282.40 [MHz]

[0206] Pulse width: 45°

[0207] (Molecular weight) Number average molecular weight (Mn), Weight average molecular weight (Mw)

[0208] Based on the results determined by the GPC method, the molecular weight is calculated using standard polystyrene as a benchmark. The determination is performed using the following methods, depending on the type of polymer.

[0209] GPC unit: TOSOH HLC-8020

[0210] Columns: 2 Shodex GPC806M, 1 each of GPC801 and 802

[0211] Development solvent: Tetrahydrofuran [THF]

[0212] Sample concentration: 0.1% by mass

[0213] Measurement temperature: 40℃

[0214] GPC units: TOSOH AS-8010, CO-8020 and SIMADZURID-10A

[0215] Columns: GMHHR-H 3

[0216] Development solvent: Dimethylformamide [DMF]

[0217] Sample concentration: 0.05% by mass

[0218] Measurement temperature: 40℃

[0219] (Differential Scanning Calorimetry (DSC))

[0220] A differential scanning calorimeter (Mettler Toredo, DSC822e) was used to obtain the DSC curve by heating 10 mg of sample at 10 °C / min. The temperature at which the extended line representing the second-order phase transition of the DSC curve intersects the tangent at the inflection point of the DSC curve is taken as the glass transition temperature.

[0221] (Crystallization)

[0222] The copolymer powder was compressed at 150°C to obtain a sheet-like molded product with a thickness of 0.2 mm.

[0223] The obtained sheet-like molded articles were measured using a fully automated multi-purpose X-ray diffractometer (manufactured by SmartLab: Rigaku Co., Ltd.) under the following conditions.

[0224] Measurement angle: 10°~30° (Light source: Cu / Kα, Wavelength: )

[0225] In addition, the peaks with a half-width of 2 or more between 17.0° and 18.5° are considered as amorphous parts, and the other peaks are considered as crystalline parts. After waveform separation of each peak, the crystallinity of each peak area is calculated using the following formula (1).

[0226] Crystallinity (%): Crystalline portion / (Crystalline portion + Amorphous portion) × 100 (1)

[0227] Polymer Synthesis Example 1

[0228] 1,330 g of deionized water and 0.67 g of methylcellulose were introduced into a 1.8 L autoclave, and the autoclave was then thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum. In the vacuum-sealed autoclave, 250 g of 1,2-difluoroethylene E-body was reacted with 1 ml of methanol and 2 g of di-n-propyl peroxide. The mixture was heated to 45 °C over 1.5 hours and maintained at 45 °C for 3 hours. Then, 4 g of di-n-propyl peroxide was introduced. The temperature was then maintained at 45 °C for 4 hours. The highest pressure reached during this period was 2.7 MPaG. Afterward, the pressure was released to atmospheric pressure, and the reaction product was washed with water and dried to obtain 198 g of fluoropolymer powder.

[0229] Its melting point is 196.3℃.

[0230] Polymer Synthesis Example 2

[0231] The 0.5-liter autoclave was thoroughly purged with nitrogen. Then, the autoclave was degassed under vacuum. 150g of HFE-347pc-f, 23g of 1,2-difluoroethylene E-body, and 4g of tetrafluoroethylene were introduced into the vacuum-sealed autoclave, and the autoclave was heated to 28°C. Next, 2.0g of a perfluorohexane solution (DHP-H) containing 8% by mass of di-(2,2,3,3,4,4,5,5,6,6,7,7-dodecylfluoroheptanoyl)peroxide was added to the autoclave to initiate polymerization. The initial polymerization pressure was 0.5 MPaG. To maintain the polymerization pressure, a mixed gas of 85 / 15 mol of 1,2-difluoroethylene E-body / tetrafluoroethylene was introduced. The temperature inside the autoclave was maintained at 28°C for 5 hours and 15 minutes, then the pressure was released back to atmospheric pressure. The reaction product was washed with water and dried to obtain 12.2g of fluoropolymer powder. The resulting resin contains 1,2-difluoroethylene E and tetrafluoroethylene in a molar ratio of 85.5 / 14.5. Its melting point is 210.0℃.

[0232] Polymer Synthesis Example 3

[0233] 915g of deionized water and 0.46g of methylcellulose were introduced into a 1.8L autoclave, and the autoclave was then thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 458g of perfluorooctane, 38g of 1,2-difluoroethylene E-body, and 38g of trifluoroethylene were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 34°C. Next, 3.0g of di-n-propyl peroxide and 1ml of methanol were added to the autoclave to initiate polymerization. The initial polymerization pressure was 1.1 MPaG. After maintaining the temperature of the autoclave at 35°C for 5 hours, the pressure was released to atmospheric pressure. The reaction product was washed with water and dried to obtain 9.6g of fluoropolymer powder. The obtained resin contained 1,2-difluoroethylene E-body and trifluoroethylene in a molar ratio of 64.4 / 35.6.

[0234] Its melting point is 205.6℃.

[0235] Polymer Synthesis Example 4

[0236] 915g of deionized water and 0.46g of methylcellulose were introduced into a 1.8L autoclave, and the autoclave was then thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 458g of perfluorooctane, 17g of 1,2-difluoroethylene E, and 66g of vinylidene fluoride were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 35°C. Next, 3.0g of di-n-propyl peroxide and 1ml of methanol were added to the autoclave to begin polymerization. The initial polymerization pressure was 1.5 MPaG. To maintain the polymerization pressure, a mixed gas of 43 / 57 mol of 1,2-difluoroethylene E and vinylidene fluoride was circulated, and the temperature inside the autoclave was maintained at 35°C for 18 hours. The pressure was then released back to atmospheric pressure, and the reaction product was washed with water and dried to obtain 39g of fluoropolymer powder.

[0237] The resulting resin contains 1,2-difluoroethylene E-body and vinylidene fluoride in a molar ratio of 42.9 / 57.1. Its melting point is 168.6℃.

[0238] Polymer Synthesis Example 5

[0239] 40 g of dichloropentafluoropropane (R-225) and 0.52 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 6.0 g of vinylidene fluoride (VdF) and 1.3 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 12.4 hours. The product was dried to obtain 1.20 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and VdF in a molar ratio of 42.9 / 57.1.

[0240] Its melting point is 163.6℃.

[0241] Polymer Synthesis Example 6

[0242] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature, purged with nitrogen, and then 3.0 g of VdF and 9.1 g of 1,2-difluoroethylene E-body were added. The autoclave was shaken at 25°C for 11.8 hours. The product was dried to obtain 1.81 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and VdF in a molar ratio of 96.5 / 3.5.

[0243] Its melting point is 205.9℃.

[0244] Polymer Synthesis Example 7

[0245] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 20.9 g of 2,3,3,3-tetrafluoropropylene (HFO-1234yf) and 3.8 g of 1,2-difluoroethylene E-polymer were added. The mixture was shaken at 25 °C for 13.2 hours. The product was dried to obtain 1.23 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-polymer and HFO-1234yf in a molar ratio of 16.3 / 83.7.

[0246] It has no melting point.

[0247] Polymer Synthesis Example 8

[0248] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 8.0 g of HFO-1234yf and 12.5 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 13.2 hours. The product was dried to obtain 0.93 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and HFO-1234yf in a molar ratio of 46.4 / 53.6.

[0249] It has no melting point.

[0250] Polymer Synthesis Example 9

[0251] The 0.5-liter autoclave was thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 150g of HFE-347pc-f, 23g of 1,2-difluoroethylene E-body, and 4g of tetrafluoroethylene were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 28°C. Next, 1.8g of DHP-H was added to the autoclave to begin polymerization. The initial polymerization pressure was 0.5 MPaG. To maintain the polymerization pressure, a mixed gas of 68 / 32 mol of 1,2-difluoroethylene E-body / tetrafluoroethylene was introduced. The temperature inside the autoclave was maintained at 28°C for 4 hours, after which the pressure was released back to atmospheric pressure. The reaction product was washed with water and dried to obtain 10.8g of fluoropolymer powder. The obtained resin contained 1,2-difluoroethylene E-body and tetrafluoroethylene in a molar ratio of 67.8 / 32.2. The melting point was 217.2°C.

[0252] Polymer Synthesis Example 10

[0253] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 15.0 g of trifluoromethyltrifluorovinyl ether (PMVE) and 1.3 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 13.2 hours. The product was dried to obtain 0.41 g of fluoropolymer. The resulting resin contained E-body and PMVE in a molar ratio of 29.8 / 70.2.

[0254] It has no melting point.

[0255] Polymer Synthesis Example 11

[0256] 40 g of R-225 and 0.42 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 6.0 g of PMVE and 10.2 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 13.2 hours. The product was dried to obtain 3.0 g of fluoropolymer. The resulting resin contained E-body and PMVE in a molar ratio of 95.3 / 4.5.

[0257] Its melting point is 173.3℃.

[0258] Polymer Synthesis Example 12

[0259] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 12.7 g of hexafluoropropylene (HFP) and 1.3 g of 1,2-difluoroethylene E were added, and the mixture was shaken at 25 °C for 13.0 hours. The product was dried to obtain 0.13 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E and HFP in a molar ratio of 84.1 / 15.9.

[0260] It has no melting point.

[0261] Polymer Synthesis Example 13

[0262] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 3.0 g of HFP and 5.2 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 13.0 hours. The product was dried to obtain 2.41 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and HFP in a molar ratio of 99.2 / 0.8.

[0263] Its melting point is 188.5℃.

[0264] Polymer Synthesis Example 14

[0265] Add 250 ml of pure water, 30 g of tert-butanol, and 0.025 g of polyacrylic acid to a 0.5 L stainless steel autoclave. Purge with nitrogen and apply slight pressure using 1,2-difluoroethylene E-body. While stirring at 1000 rpm, adjust the temperature to 80 °C and pressurize to 2.000 MPa using 1,2-difluoroethylene E-body. Then, pressurize with nitrogen to a mixture containing 0.077 g of ammonium persulfate dissolved in 3 ml of pure water. When the pressure drops to 1.99 MPa, introduce 1,2-difluoroethylene E-body to bring the pressure to 2.01 MPa, and repeat the above operation. After 2 hours and 16 minutes, add 20 g of 1,2-difluoroethylene E-body, then release the gas from the autoclave, cool, and recover 305 g of the dispersion.

[0266] The dispersion had a solids content of 6.6% by mass (polymer weight 20.1 g). The dispersion was dried to obtain 19 g of fluoropolymer. The melting point was 191.7 °C.

[0267] Polymer Synthesis Example 15

[0268] 600g of deionized water and 0.3g of methylcellulose were introduced into a 1.8L autoclave, and the autoclave was then thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 450g of hexafluoropropylene and 100g of 1,2-difluoroethylene E-body were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 35°C. Next, 6.0g of di-n-propyl peroxide was added to the autoclave to begin polymerization. The initial polymerization pressure was 1.5 MPaG. After maintaining the temperature at 35°C for 7 hours, the pressure was released to atmospheric pressure. The reaction product was washed with water and dried to obtain 17g of fluoropolymer powder. The obtained resin contained 1,2-difluoroethylene E-body and HFP in a molar ratio of 90.3 / 9.7.

[0269] It has no melting point.

[0270] Polymer Synthesis Example 16

[0271] 915g of deionized water and 0.458g of methylcellulose were introduced into a 1.8L autoclave, and the autoclave was then thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 458g of perfluorooctane, 7.5g of HFO-1234yf, and 80g of 1,2-difluoroethylene E-body were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 35°C. Next, 3.0g of di-n-propyl peroxide was added to the autoclave to begin polymerization. The initial polymerization pressure was 1.18 MPaG. To maintain the polymerization pressure, a mixed gas of 85 / 15 mol of 1,2-difluoroethylene E-body / HFO-1234yf was introduced, and the temperature inside the autoclave was maintained at 35°C for 16 hours. The pressure was then released back to atmospheric pressure, and the reaction product was washed with water and dried to obtain 78g of fluoropolymer powder. The resulting resin contains 1,2-difluoroethylene E-body and HFO-1234yf in a molar ratio of 84.3 / 15.7.

[0272] It has no melting point.

[0273] Polymer Synthesis Example 17

[0274] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 8.9 g of PMVE and 3.3 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 10.5 hours. The product was dried to obtain 0.33 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and PMVE in a molar ratio of 74.9 / 25.1.

[0275] It has no melting point.

[0276] Polymer Synthesis Example 18

[0277] 600g of deionized water and 0.3g of methylcellulose were introduced into a 1.8L autoclave, and the autoclave was then thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 150g of perfluorooctane, 100g of hexafluoropropylene, and 64g of 1,2-difluoroethylene E-body were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 35°C. Next, 1.5g of di-n-propyl peroxide was added to the autoclave to begin polymerization. The initial polymerization pressure was 1.16 MPaG. After maintaining the temperature at 35°C for 7 hours, the pressure was released back to atmospheric pressure. The reaction product was washed with water and dried to obtain 17g of fluoropolymer powder. The obtained resin contained 1,2-difluoroethylene E-body and HFP in a molar ratio of 94.9 / 5.1.

[0278] Its melting point is 151.2℃.

[0279] Polymer Synthesis Example 19

[0280] 915g of deionized water and 0.458g of methylcellulose were introduced into a 1.8L autoclave, and the autoclave was then fully purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 458g of perfluorooctane, 2g of HFO-1234yf, and 64g of 1,2-difluoroethylene E-body were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 35°C. Next, 3.0g of di-n-propyl peroxide was added to the autoclave to begin polymerization. The initial polymerization pressure was 0.96 MPaG. After maintaining the temperature at 35°C for 6 hours, the autoclave was depressurized and returned to atmospheric pressure. The reaction product was washed with water and dried to obtain 2.7g of fluoropolymer powder. The obtained resin contained 1,2-difluoroethylene E-body and HFO-1234yf in a molar ratio of 96.9 / 3.1.

[0281] Its melting point is 170.7℃.

[0282] Polymer Synthesis Example 20

[0283] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 9.7 g of PMVE and 2.6 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25°C for 5.5 hours. The product was dried to obtain 0.53 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and PMVE in a molar ratio of 73.1 / 26.9.

[0284] It has no melting point.

[0285] Polymer Synthesis Example 21

[0286] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 11.6 g of PMVE2 and 1.9 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25°C for 5.5 hours. The product was dried to obtain 0.69 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and PMVE in a molar ratio of 60.3 / 39.7.

[0287] It has no melting point.

[0288] Polymer Synthesis Example 22

[0289] 40 g of R-225 and 0.43 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 93.5 g of PMVE and 5.4 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25°C for 5.5 hours. The product was dried to obtain 0.65 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and PMVE in a molar ratio of 88.5 / 11.5.

[0290] It has no melting point.

[0291] Polymer Synthesis Example 23

[0292] The 0.5-liter autoclave was thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 150g of 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (HFE-347pc-f), 9.4g of 1,2-difluoroethylene E-body, and 15g of tetrafluoroethylene were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 28°C. Next, 1.5g of DHP-H was added to the autoclave to begin polymerization. The initial polymerization pressure was 0.5 MPaG. To maintain the polymerization pressure, a mixed gas of 54 / 46 mol of 1,2-difluoroethylene E-body / tetrafluoroethylene was introduced, and the temperature inside the autoclave was maintained at 28°C for 2 hours and 45 minutes. The pressure was then released back to atmospheric pressure, and the reaction product was washed with water and dried to obtain 10.7g of fluoropolymer powder. The resulting resin contains 1,2-difluoroethylene E and tetrafluoroethylene in a molar ratio of 53.9 / 46.1. Its melting point is 232.8℃.

[0293] Polymer Synthesis Example 24

[0294] The 0.5-liter autoclave was thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 150g of HFE-347pc-f, 6.8g of 1,2-difluoroethylene E-body, and 20g of tetrafluoroethylene were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 28°C. Next, 1.5g of DHP-H was added to the autoclave to begin polymerization. The initial polymerization pressure was 0.5 MPaG. To maintain the polymerization pressure, a mixed gas of 42 / 58 mol of 1,2-difluoroethylene E-body / tetrafluoroethylene was introduced, and the temperature inside the autoclave was maintained at 28°C for 1 hour and 50 minutes. The pressure was then released back to atmospheric pressure, and the reaction product was washed with water and dried to obtain 13.1g of fluoropolymer powder. The obtained resin contained 1,2-difluoroethylene E-body and tetrafluoroethylene in a molar ratio of 42.4 / 57.6. The melting point was 246.5°C.

[0295] Polymer Synthesis Example 25

[0296] 40 g of HFE-347pc-f and 0.86 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 4.9 g of VdF and 8.3 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25°C for 2 hours and 30 minutes using a shaker. The product was dried to obtain 2.0 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and VdF in a molar ratio of 92.4 / 7.6.

[0297] Its melting point is 203.5℃.

[0298] Polymer Synthesis Example 26

[0299] 40 g of HFE-347pc-f and 0.86 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 5.1 g of VdF and 7.8 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 1 hour and 54 minutes. The product was dried to obtain 1.2 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and VdF in a molar ratio of 85.7 / 14.3.

[0300] Its melting point is 201.4℃.

[0301] Polymer Synthesis Example 27

[0302] 40 g of HFE-347pc-f and 0.86 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 5.8 g of VdF and 7.2 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 2 hours and 35 minutes using a shaker. The product was dried to obtain 2.0 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and VdF in a molar ratio of 75.5 / 24.5.

[0303] Its melting point is 195.2℃.

[0304] Polymer Synthesis Example 28

[0305] 40 g of HFE-347pc-f and 0.86 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 12.2 g of VdF and 4.0 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 2 hours and 30 minutes using a shaker. The product was dried to obtain 2.4 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and VdF in a molar ratio of 53.3 / 46.7.

[0306] Its melting point is 182.5℃.

[0307] Polymer Synthesis Example 29

[0308] 40 g of HFE-347pc-f and 0.86 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 12.5 g of VdF and 1.1 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25°C for 2 hours and 35 minutes. The product was dried to obtain 2.2 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and VdF in a molar ratio of 29.2 / 70.8.

[0309] Its melting point is 163.6℃.

[0310] Polymer Synthesis Example 30

[0311] 40 g of HFE-347pc-f and 0.86 g of DHP-H were added to a 100 ml stainless steel (SUS) autoclave. The autoclave was cooled to dry ice temperature and purged with nitrogen. Then, 12.7 g of VdF and 0.6 g of 1,2-difluoroethylene E-body were added, and the mixture was shaken at 25 °C for 1 hour and 53 minutes. The product was dried to obtain 3.4 g of fluoropolymer. The resulting resin contained 1,2-difluoroethylene E-body and VdF in a molar ratio of 15.7 / 84.3.

[0312] Its melting point is 161.8℃.

[0313] Polymer Synthesis Example 31

[0314] The 0.5-liter autoclave was thoroughly purged with nitrogen under vacuum. Afterward, the autoclave was degassed under vacuum, and 150g of HFE-347pc-f, 2.1g of 1,2-difluoroethylene E-body, and 26g of tetrafluoroethylene were introduced into the vacuum-sealed autoclave. The autoclave was then heated to 28°C. Next, 1.0g of DHP-H was added to the autoclave to begin polymerization. The initial polymerization pressure was 0.60 MPaG. To maintain the polymerization pressure, a mixed gas of 1,2-difluoroethylene E-body / tetrafluoroethylene = 18 / 82 mol was introduced, and the temperature inside the autoclave was maintained at 28°C for 45 minutes. The pressure was then released back to atmospheric pressure, and the reaction product was washed with water and dried to obtain 11.3g of fluoropolymer powder. The obtained resin contained 1,2-difluoroethylene E-body and tetrafluoroethylene in a molar ratio of 19.0 / 81.0. The melting point was 288.8°C.

[0315] Table 1

[0316]

[0317] As shown in Table 1, the polymers of Synthetic Examples 1 to 29, which have the structural units shown in the general formula (1) above, are acetone-soluble. Furthermore, Synthetic Example 30 is also DMF-soluble. In addition, since a resin with a high Tg can be obtained by using a monomer with high purity (Synthetic Example 1), this is also preferable.

[0318] Furthermore, it is known that an amorphous resin can be obtained by using copolymer components in a specified proportion. Additionally, an amorphous resin with a glass transition temperature of 35°C or higher can also be suitably obtained.

[0319] Furthermore, as in Synthesis Example 31, when the copolymer with TFE has a low copolymerization ratio of 1,2-difluoroethylene, solubility in common solvents cannot be obtained, but this polymer exhibits excellent chemical resistance. Therefore, it is suitable for applications requiring chemical resistance.

[0320] Industrial applicability

[0321] The fluoropolymers of the present invention can be used in a variety of applications using fluoropolymers. In particular, they are suitable for applications where a common solvent is preferred.

Claims

1. A fluoropolymer, characterized in that, It has structural units represented by the following general formula (1) at a proportion of 99.5 mol% or more, and a glass transition temperature of 100°C or more. 【Chemistry 1】 。 2. The fluoropolymer as described in claim 1, wherein the weight-average molecular weight is 5,000 to 5,000,000.

3. A fluoropolymer, characterized in that, It has structural units shown in general formula (1) and general formula (2) below. 【Chemistry 2】 【Transformation 3】 R1 is hydrogen or an OR5 group, where the R5 group is a hydrocarbon group with 5 or fewer carbon atoms that is partially or completely fluorinated; R2, R3, and R4 are each independently hydrogen or fluorine. When R1 is hydrogen, the structural unit represented by general formula (2) is ethylene, vinylidene fluoride, or vinyl fluoride, and contains the structural unit represented by general formula (2) in a proportion of 5 mol% to 99 mol%. When R1 is OR5-based, the structural unit shown in general formula (2) is the same as the structural unit shown in general formula (8) or (9), containing the structural unit shown in general formula (2) in a proportion of 8.0 mol% to 25.0 mol%. 。 4. A fluoropolymer, characterized in that, It has structural units as shown in general formula (1) below, and has at least one structural unit selected from the group consisting of structural units shown in general formulas (4) and (6) below in a proportion of 5 mol% to 99 mol%, or has structural units shown in general formula (8) in a proportion of 8.0 mol% to 25.0 mol%. 【Chemistry 4】 【Transformation 5】 。 5. The fluoropolymer as described in claim 3 or 4, wherein the weight-average molecular weight is 5,000 to 5,000,000.

6. A fluoropolymer, characterized in that, Composed only of structural units shown in general formula (1) and structural units derived from tetrafluoroethylene, containing structural units derived from tetrafluoroethylene in a proportion of 14.5 mol% to 57.6 mol%, it is soluble in acetone with a resin solubility of 1.0 wt% to 10.0 wt%. 【Transformation 6】 。 7. A fluoropolymer, characterized in that, It has structural units represented by general formula (1) and structural units derived from hexafluoropropylene, the fluoropolymer being amorphous, and the proportion of structural units represented by general formula (1) being 70 mol% to 92 mol%, with structural units derived from hexafluoropropylene at a proportion of 8.0 mol% to 30.0 mol% relative to the total polymer. 【Transformation 7】 。 8. A fluoropolymer, characterized in that, It has structural units represented by general formula (1) and structural units of at least unsaturated compounds selected from the group consisting of 1225, 1234, 1243 and 1252, where 1225, 1234, 1243 and 1252 are ASHRAE designations. The structural units represented by general formula (1) are 0.1 mol% to 92 mol%, and have structural units of at least unsaturated compounds selected from the group consisting of 1225, 1234, 1243 and 1252 in a proportion of 8.0 mol% to 99.9 mol% relative to the total polymer. The fluoropolymer is amorphous and has a glass transition temperature of 35°C or higher. 【Transformation 8】 。 9. A fluoropolymer, characterized in that, It has structural units represented by general formula (1) and structural units represented by general formula (20) below, wherein the proportion of structural units represented by general formula (1) is 70 mol% to 92 mol%, and the proportion of structural units represented by general formula (20) is 8.0 mol% to 25.1 mol% relative to the total polymer. The fluoropolymer is amorphous and has a glass transition temperature of 35°C or higher. 【Chemistry 9】 【Chemistry 10】 R1 to R3 are selected from H and F, and Rf is a fluorinated alkyl group with 1 to 6 carbon atoms.

10. The fluoropolymer of claim 9, wherein, The structural unit shown in general formula (20) is at least one of the structural units shown in general formulas (7) to (9) below. 【Chemistry 11】 。 11. A resin solution, characterized in that, It is prepared by dissolving the polymer according to any one of claims 1 to 10 in a common solvent.

12. The method for manufacturing the fluoropolymer according to any one of claims 1 to 10, characterized in that, The process includes a step of polymerizing a monomer composition in which the monomers shown in the following general formula (10) are used as part or all of the monomer composition, wherein the compound shown in general formula (10) with a purity of 99.5% by mass or more is used as a raw material. 【Chemistry 12】 。

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