阅读说明：本技术 含氟芳香族聚合物及其制造方法 (Fluorine-containing aromatic polymer and process for producing the same ) 是由 足达健二 生越专介 于 2019-08-28 设计创作，主要内容包括：本发明所要解决的技术问题在于,提供一种含氟芳香族聚合物及其制造方法等。前述技术问题可通过具有下述式(1)所示的单体单元的聚合物等得到解决(式(1)中,R～1在每次出现时独立地为卤素原子、NR～(11)R～(12)(R～(11)和R～(12)各自独立地为氢原子或有机基团。)、或有机基团；n1为0～4的范围内的整数；可存在于邻位的2个R～1可与相邻的苯环的2个碳原子一起形成环,该环可具有有机基团作为取代基；L～1是单键、氧原子、硫原子、-L～(11)-O-、-O-L～(12)-O-、-L～(13)-S-、或-S-L～(14)-S-(L～(11)～L～(14)各自独立地为可具有1个以上取代基的亚烷基。)。)。(The present invention has been made to solve the above problems, and an object of the present invention is to provide a fluorine-containing aromatic polymer and a method for producing the same. The above-mentioned problems can be solved by a polymer having a monomer unit represented by the following formula (1) (in the formula (1), R is 1 Independently at each occurrence is a halogen atom, NR 11 R 12 (R 11 And R 12 Each independently a hydrogen atom or an organic group. ) Or an organic group; n1 is an integer in the range of 0-4; 2R which may be present in ortho position 1 May form a ring, which may have an organic group as a substituent, together with 2 carbon atoms of the adjacent benzene ring; l is 1 Is a single bond, an oxygen atom, a sulfur atom, -L 11 ‑O‑、‑O‑L 12 ‑O‑、‑L 13 -S-, or-S-L 14 ‑S‑(L 11 ～L 14 Each independently is an alkylene group which may have 1 or more substituents. ). ).)

1. A polymer having a monomer unit represented by the following formula (1):

in the formula (1), the reaction mixture is,

R¹independently at each occurrence is a halogen atom, NR¹¹R¹²Or an organic group, wherein R¹¹And R¹²Each independently a hydrogen atom or an organic group,

n1 is an integer in the range of 0 to 4,

with or without 2R in ortho position¹(ii) a With 2R in ortho position¹In the case of (2), R¹Form a ring or no ring together with 2 carbon atoms of the adjacent benzene ring; in the case of forming a ring, the ring may or may not have an organic group as a substituent,

L¹is a single bond, an oxygen atom, a sulfur atom, -L¹¹-O-、-O-L¹²-O-、-L¹³-S-, or-S-L¹⁴-S-, wherein L¹¹～L¹⁴Each independently is an alkylene group with or without 1 or more substituents.

2. The polymer of claim 1, wherein L is¹Is a single bond, an oxygen atom, -L¹¹-O-, or-O-L¹²-O-。

3. The polymer of claim 1 or 2, wherein n1 is 0, 1, or 2.

4. The polymer according to any one of claims 1 to 3, which further has a monomer unit represented by the following formula (2):

in the formula (2), the reaction mixture is,

R²independently at each occurrence is a halogen atom, NR²¹R²²Or an organic group, wherein R²¹And R²²Each independently a hydrogen atom or an organic group,

n2 is an integer in the range of 0 to 4,

with or without 2R in ortho position²(ii) a With 2R in ortho position²In the case of (2), R²Form a ring or no ring together with 2 carbon atoms of the adjacent benzene ring; in the case of forming a ring, the ring may or may not have an organic group as a substituent,

L²is a single bond, an oxygen atom, a sulfur atom, -L²¹-O-、-O-L²²-O-、-L²³-S-, or-S-L²⁴-S-, wherein L²¹～L²⁴Each independently is an alkylene group with or without 1 or more substituents.

5. The polymer of claim 4, wherein L²Is a single bond, an oxygen atom, -L²¹-O-、or-O-L²²-O-。

6. A polymer having a monomer unit represented by the following formula (1'):

in the formula (1'), in the presence of a catalyst,

b is a heteroarylene group with or without 1 or more substituents,

L⁴is a single bond, an oxygen atom, a sulfur atom, -L⁴¹-O-、-O-L⁴²-O-、-L⁴³-S-, or-S-L⁴⁴-S-, wherein L⁴¹～L⁴⁴Each independently is an alkylene group with or without 1 or more substituents.

7. The polymer according to claim 6, wherein B is furan-diyl, oxazole-diyl, isoxazole-diyl, oxadiazole-diyl, thiophene-diyl, thiazole-diyl, isothiazole-diyl, thiadiazole-diyl, pyrrole-diyl, pyrazole-diyl, imidazole-diyl, triazole-diyl, pyridine-diyl, pyridazine-diyl, pyrimidine-diyl, pyrazine-diyl, triazine-diyl, or tetrazine-diyl, and the above groups may or may not have 1 or more substituents.

8. The polymer of claim 6 or 7, wherein L⁴Is a single bond, an oxygen atom, -L⁴¹-O-, or-O-L⁴²-O-。

9. A method for producing a polymer having a monomer unit represented by the following formula (3):

in the formula (3), the reaction mixture is,

a is an arylene group with or without 1 or more substituents or a heteroarylene group with or without 1 or more substituents,

L³is a single bond, an oxygen atom, a sulfur atom, -L³¹-O-、-O-L³²-O-、-L³³-S-, or-S-L³⁴-S-, wherein L³¹～L³⁴Each independently is an alkylene group with or without 1 or more substituents,

the method includes the step of polymerizing a monomer including a compound represented by the following formula (4), and a ligand selected from the group consisting of a phosphine and a compound having a pyridine ring:

in the formula (4), X¹Is a halogen atom selected from chlorine atom, bromine atom and iodine atom, M is a metal selected from copper, zinc, nickel, iron, cobalt and tin, A and L³The same meaning as described above.

10. The method according to claim 9, wherein a is phenylene, furan-diyl, oxazole-diyl, isoxazol-diyl, oxadiazole-diyl, thiophene-diyl, thiazole-diyl, isothiazol-diyl, thiadiazole-diyl, pyrrole-diyl, pyrazole-diyl, imidazole-diyl, triazole-diyl, pyridine-diyl, pyridazine-diyl, pyrimidine-diyl, pyrazine-diyl, triazine-diyl, or tetrazine-diyl, and the above groups may or may not have 1 or more substituents.

11. The method of claim 9 or 10, wherein L³Is a single bond, an oxygen atom, -L³¹-O-, or-O-L³²-O-。

12. The process of any one of claims 9 to 11, wherein the polymerization is carried out in the presence of a solvent.

13. The process according to any one of claims 9 to 12, wherein the polymerization is carried out in the range of 50 to 150 ℃.

14. A film comprising the polymer of any one of claims 1 to 8.

Technical Field

The present invention relates to a novel fluorine-containing aromatic polymer and a method for producing the same.

Background

Poly (p-xylylene) is extremely excellent in electrical insulation, chemical resistance, heat resistance, cold resistance, gas barrier property, and the like, and is used for various coatings (for example, a coating for medical equipment, an electronic coating, an LED coating, a coating for automobile parts, a coating for defense, or a coating for aerospace industry machines).

Parylene is manufactured by vacuum evaporation. Specifically, the following formula:

[ solution 1]

The solid dimer (referred to as "dimeric paraxylene" or "[ 2,2] paracyclophane") is heated in a vacuum environment to obtain a gaseous dimer, and radicals generated by thermal decomposition of the gaseous dimer are attached to the surface of an adherend and polymerized to obtain a parylene (for example, patent document 1 and non-patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 9-59406

Non-patent document

Non-patent document 1: hicks, Craig; duffy, bredan; hargaden, Grainne C., Organic Chemistry Frontiers (2014),1(6),716-

Disclosure of Invention

Technical problem to be solved by the invention

The method for producing parylene by vacuum deposition has a problem of high equipment investment and running cost because a large vacuum deposition apparatus is required. Further, this production method has a problem that only the counterpiece can be synthesized due to the limitation of raw materials.

The present invention aims to provide a novel fluorine-containing aromatic polymer and a method for producing the same.

Means for solving the problems

The present invention includes the following aspects.

Item 1.

A polymer having a monomer unit represented by the following formula (1),

[ solution 2]

[ in the formula,

R¹independently at each occurrence is a halogen atom, NR¹¹R¹²(R¹¹And R¹²Each independently a hydrogen atom or an organic group), or an organic group,

n1 is an integer in the range of 0 to 4,

2R which may be present in ortho position¹May form a ring, which may have an organic group as a substituent, together with 2 carbon atoms of the adjacent benzene ring;

L¹is a single bond, an oxygen atom, a sulfur atom, -L¹¹-O-、-O-L¹²-O-、-L¹³-S-, or-S-L¹⁴-S-(L¹¹～L¹⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

Item 2.

The polymer of item 1, wherein L¹Is a single bond, an oxygen atom, -L¹¹-O-, or-O-L¹²-O-。

Item 3.

The polymer according to item 1 or 2, wherein n1 is 0, 1 or 2.

Item 4.

The polymer according to any one of items 1 to 3, further comprising a monomer unit represented by the following formula (2),

[ solution 3]

[ in the formula,

R²independently at each occurrence is a halogen atom, NR²¹R²²(R²¹And R²²Each independently a hydrogen atom or an organic group. ) Or an organic group;

n2 is an integer in the range of 0-4;

2R which may be present in ortho position²May form a ring, which may have an organic group as a substituent, together with 2 carbon atoms of the adjacent benzene ring;

L²is a single bond, an oxygen atom, a sulfur atom, -L²¹-O-、-O-L²²-O-、-L²³-S-, or-S-L²⁴-S-(L²¹～L²⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

Item 5.

The polymer of item 4, wherein L²Is a single bond, an oxygen atom, -L²¹-O-, or-O-L²²-O-。

Item 6.

A polymer having a monomer unit represented by the following formula (1'),

[ solution 4]

[ in the formula,

b is a heteroarylene group which may have 1 or more substituents,

L⁴is a single bond, oxygenAtom, sulfur atom, -L⁴¹-O-、-O-L⁴²-O-、-L⁴³-S-, or-S-L⁴⁴-S-(L⁴¹～L⁴⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

Item 7.

The polymer according to item 6, wherein B is furan-diyl, oxazole-diyl, isoxazol-diyl, oxadiazole-diyl, thiophene-diyl, thiazole-diyl, isothiazol-diyl, thiadiazole-diyl, pyrrole-diyl, pyrazole-diyl, imidazole-diyl, triazole-diyl, pyridine-diyl, pyridazine-diyl, pyrimidine-diyl, pyrazine-diyl, triazine-diyl, or tetrazine-diyl, which may have 1 or more substituents.

Item 8.

The polymer of item 6 or 7, wherein L⁴Is a single bond, an oxygen atom, -L⁴¹-O-, or-O-L⁴²-O-。

Item 9.

A method for producing a polymer having a monomer unit represented by the following formula (3),

[ solution 5]

[ in the formula,

a is an arylene group which may have 1 or more substituents or a heteroarylene group which may have 1 or more substituents,

L³is a single bond, an oxygen atom, a sulfur atom, -L³¹-O-、-O-L³²-O-、-L³³-S-, or-S-L³⁴-S-(L³¹～L³⁴Each independently is an alkylene group which may have 1 or more substituents. ).]

The method includes the step of polymerizing monomers comprising: a compound represented by the following formula (4), and a ligand selected from the group consisting of a phosphine and a compound having a pyridine ring,

[ solution 6]

(in the formula, X¹Is a halogen atom selected from chlorine atom, bromine atom and iodine atom, M is a metal selected from copper, zinc, nickel, iron, cobalt and tin, A and L³The same meaning as described above).

Item 10.

The method of item 9, wherein a is phenylene, furan-diyl, oxazole-diyl, isoxazol-diyl, oxadiazole-diyl, thiophene-diyl, thiazole-diyl, isothiazol-diyl, thiadiazole-diyl, pyrrole-diyl, pyrazole-diyl, imidazole-diyl, triazole-diyl, pyridine-diyl, pyridazine-diyl, pyrimidine-diyl, pyrazine-diyl, triazine-diyl, or tetrazine-diyl, which may have 1 or more substituents.

Item 11.

The method of item 9 or 10, wherein L³Is a single bond, an oxygen atom, -L³¹-O-, or-O-L³²-O-。

Item 12.

The method of any of claims 9-11, wherein the polymerizing is carried out in the presence of a solvent.

Item 13.

The method according to any one of items 9 to 12, wherein the polymerization is carried out in a range of 50 to 150 ℃.

Item 14.

A film comprising the polymer according to any one of items 1 to 8.

Effects of the invention

The present invention provides a novel fluorine-containing aromatic polymer and a method for producing the same. More specifically, the present invention provides a polymer having a monomer unit represented by formula (1), which cannot be produced by a conventional vacuum deposition method, and a method for producing the same.

Detailed Description

The foregoing summary of the invention does not describe each disclosed embodiment or every implementation of the invention.

The following description of the invention more particularly exemplifies example embodiments.

The multiple locations of the present invention are provided for guidance by way of illustration, and the illustration can be used in various combinations.

In each case, the illustrated groups serve as non-exclusive and representative groups.

All publications, patents and patent applications cited in this specification are herein incorporated by reference as if fully set forth.

Term(s) for

The meaning of a symbol and an abbreviation used in the present specification can be understood in the context of the present specification without specific description, as a meaning generally used in the art to which the present invention pertains.

In the present specification, the term "comprising" includes the meaning of the term "consisting essentially of …" and the term "consisting of …".

The steps, treatments, or operations described in the present specification can be performed at room temperature without any particular limitation.

In the present specification, room temperature may mean a temperature in the range of 10 to 40 ℃.

In this specification, the symbol "C_n-m"(here, n and m are each a number) represents that the number of carbon atoms is n or more and m or less, as is generally understood by those skilled in the art.

In the present specification, unless otherwise specified, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the present specification, the "organic group" refers to a group formed by removing 1 hydrogen atom from an organic compound.

Examples of the "organic group" include

An alkyl group which may have 1 or more substituents,

An alkenyl group which may have 1 or more substituents,

Alkynyl which may have 1 or more substituents,

Cycloalkyl which may have 1 or more substituents,

Cycloalkenyl which may have 1 or more substituents,

Cycloalkadienyl which may have 1 or more substituents,

An aryl group which may have 1 or more substituents,

Aralkyl which may have 1 or more substituents,

Non-aromatic heterocyclic group which may have 1 or more substituents

A heteroaryl group which may have 1 or more substituents,

A cyano group,

Aldehyde group,

RO-、

RS-、

RCO-、

RSO₂-、

ROCO-, and

ROSO₂-

(in these formulae, R is independently

An alkyl group which may have 1 or more substituents,

An alkenyl group which may have 1 or more substituents,

Alkynyl which may have 1 or more substituents,

Cycloalkyl which may have 1 or more substituents,

Cycloalkenyl which may have 1 or more substituents,

Cycloalkadienyl which may have 1 or more substituents,

An aryl group which may have 1 or more substituents,

Aralkyl which may have 1 or more substituents,

A non-aromatic heterocyclic group which may have 1 or more substituents, or

Heteroaryl groups which may have more than 1 substituent).

Examples of the "substituent" include a halogen atom, a cyano group, an amino group, an alkoxy group, and an alkylthio group. The 2 or more substituents may be the same or different from each other.

In the present specification, the "alkyl group" is not particularly limited, and examples thereof include straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), a pentyl group (for example, n-pentyl group, isopentyl group, neopentyl group), and a hexyl group.

In the present specification, unless otherwise stated, examples of the "alkoxy group" include straight-chain or branched-chain alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy (n-propoxy, isopropoxy), butoxy (n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), pentyloxy, and hexyloxy.

In the present specification, unless otherwise stated, the "alkylthio group" includes straight-chain or branched-chain alkylthio groups having 1 to 10 carbon atoms such as a methylthio group, an ethylthio group, a propylthio group (n-propylthio group, isopropylthio group), a butylthio group (n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group), a pentylthio group, and a hexylthio group.

In the present specification, unless otherwise stated, examples of the "alkenyl group" include linear or branched alkenyl groups having 2 to 10 carbon atoms such as a vinyl group, a 1-propen-1-yl group, a 2-propen-1-yl group, an isopropenyl group, a 2-buten-1-yl group, a 4-penten-1-yl group, and a 5-hexen-1-yl group.

In the present specification, unless otherwise stated, examples of the "alkynyl" group include straight-chain or branched alkynyl groups having 2 to 10 carbon atoms such as an ethynyl group, a 1-propyn-1-yl group, a 2-propyn-1-yl group, a 4-pentyn-1-yl group, and a 5-hexyn-1-yl group.

In the present specification, unless otherwise specified, examples of the "cycloalkyl group" include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups.

In the present specification, unless otherwise specified, examples of the "cycloalkenyl group" include cycloalkenyl groups having 3 to 10 carbon atoms such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

In the present specification, unless otherwise stated, examples of the "cycloalkadienyl group" include cycloalkadienyl groups having 4 to 10 carbon atoms such as a cyclobutadienyl group, a cyclopentadienyl group, a cyclohexadienyl group, a cycloheptadienyl group, a cyclooctadienyl group, a cyclononadienyl group, and a cyclodecadienyl group.

In the present specification, unless otherwise specified, "aryl" may be of a monocyclic type, bicyclic type, tricyclic type, or tetracyclic type.

In the present specification, unless otherwise specified, the "aryl group" may be an aryl group having 6 to 18 carbon atoms.

In the present specification, unless otherwise specified, examples of the "aryl group" include phenyl, 1-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups.

In the present specification, "arylene" refers to a group formed by removing 1 hydrogen atom from the aforementioned "aryl".

In the present specification, unless otherwise stated, examples of the "arylene group" include 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, 4' -biphenylene, 1, 2-naphthylene, 1, 3-naphthylene, and 1, 4-naphthylene.

In the present specification, unless otherwise stated, examples of the "aralkyl group" include, for example, benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 2-biphenylmethyl, 3-biphenylmethyl, and 4-biphenylmethyl.

In the present specification, the term "non-aromatic heterocyclic group" refers to a group formed by removing 1 hydrogen atom from a non-aromatic heterocyclic ring.

In the present specification, unless otherwise specified, "non-aromatic heterocyclic group" may be a monocyclic type, bicyclic type, tricyclic type, or tetracyclic type.

In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be saturated or unsaturated.

In the present specification, unless otherwise stated, the "non-aromatic heterocyclic group" may be, for example, a 5 to 18-membered non-aromatic heterocyclic group.

In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" may be, for example, a non-aromatic heterocyclic group containing 1 to 4 hetero atoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom as ring-constituting atoms in addition to a carbon atom.

In the present specification, unless otherwise stated, examples of the "non-aromatic heterocyclic group" include tetrahydrofuranyl group, oxazolidinyl group, imidazolinyl group (e.g., 1-imidazolinyl group, 2-imidazolinyl group, 4-imidazolinyl group), aziridinyl group (e.g., 1-aziridinyl group, 2-aziridinyl group), pyrrolidinyl group (e.g., 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group), piperidinyl group (e.g., 1-piperidinyl group, 2-piperidinyl group, 3-piperidinyl group), azepanyl group (e.g., 1-azepanyl group, 2-azepanyl group, 3-azepanyl group, 4-azepanyl group), azocinyl group (e.g., 1-azepanyl group, 2-azepanyl group, 3-azepanyl group, 4-azepanyl group), 2-azacyclooctyl, 3-azacyclooctyl, 4-azacyclooctyl), piperazinyl (e.g.: 1, 4-piperazin-1-yl, 1, 4-piperazin-2-yl), diazacycloheptyltrienyl (for example: 1, 4-diazepatrien-1-yl, 1, 4-diazepatrien-2-yl, 1, 4-diazepatrien-5-yl, 1, 4-diazepatrien-6-yl), diazacyclo-octane-yl (for example: 1, 4-diazacyclooctan-1-yl, 1, 4-diazacyclooctan-2-yl, 1, 4-diazacyclooctan-5-yl, 1, 4-diazacyclooctan-6-yl, 1, 5-diazacyclooctan-1-yl, 1, 5-diazacyclooctan-2-yl, 1, 5-diazacyclooctan-3-yl), tetrahydropyranyl (for example: tetrahydrofuran-4-yl), morpholinyl (e.g.: 4-morpholinyl), thiomorpholinyl (e.g.: 4-thiomorpholinyl), 2-oxazolidinyl, dihydrofuranyl, dihydropyranyl, and dihydroquinolinyl, and the like.

In the present specification, unless otherwise specified, "heteroaryl" may be a monocyclic type, bicyclic type, tricyclic type, or tetracyclic type.

In the present specification, unless otherwise stated, "heteroaryl" may be, for example, a 5-to 18-membered heteroaryl.

In the present specification, unless otherwise specified, "heteroaryl" may be, for example, a heteroaryl group containing 1 to 4 heteroatoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom as ring-constituting atoms in addition to a carbon atom.

In the present specification, unless otherwise specified, "heteroaryl" includes "monocyclic heteroaryl" and "aromatic condensed heterocyclic group".

In the present specification, unless otherwise stated, examples of the "monocyclic heteroaryl" may include pyrrolyl (e.g., 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (e.g., 2-furyl, 3-furyl), thienyl (e.g., 2-thienyl, 3-thienyl), pyrazolyl (e.g., 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (e.g., 1-imidazolyl, 2-imidazolyl, 4-imidazolyl), isoxazolyl (e.g., 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (e.g., 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (e.g., 3-isothiazolyl, 3-oxazolyl, etc.), 4-isothiazolyl, 5-isothiazolyl), thiazolyl (e.g.: 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (e.g.: 1,2, 3-triazol-3-yl, 1,2, 4-triazol-4-yl), oxadiazolyl (for example: 1,2, 4-oxadiazol-3-yl, 1,2, 4-oxadiazol-5-yl), thiadiazolyl (for example: 1,2, 4-thiadiazol-3-yl, 1,2, 4-5-yl), tetrazolyl, pyridyl (e.g.: 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g.: 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (for example: 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), and pyrazinyl, and the like.

In the present specification, unless otherwise stated, examples of the "aromatic fused heterocyclic group" include isoindolyl groups (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl), indolyl groups (e.g., 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo [ b ] furyl groups (e.g., 2-benzo [ b ] furyl, 3-benzo [ b ] furyl, 4-benzo [ b ] furyl, 5-benzo [ b ] furyl, 6-benzo [ b ] furyl, 7-benzo [ b ] furyl) and the like, Benzo [ c ] furyl (e.g., 1-benzo [ c ] furyl, 4-benzo [ c ] furyl, 5-benzo [ c ] furyl), benzo [ b ] thienyl (e.g., 2-benzo [ b ] thienyl, 3-benzo [ b ] thienyl, 4-benzo [ b ] thienyl, 5-benzo [ b ] thienyl, 6-benzo [ b ] thienyl, 7-benzo [ b ] thienyl), benzo [ c ] thienyl (e.g., 1-benzo [ c ] thienyl, 4-benzo [ c ] thienyl, 5-benzo [ c ] thienyl), indazolyl (e.g., 1-indazolyl, 2-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (e.g., 1-benzimidazolyl, 5-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (e.g., 1-benzimidazolyl, 1-indazolyl, 5-indazolyl, etc, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl), 1, 2-benzisoxazolyl (e.g., 1, 2-benzisoxazol-3-yl, 1, 2-benzisoxazol-4-yl, 1, 2-benzisoxazol-5-yl, 1, 2-benzisoxazol-6-yl, 1, 2-benzisoxazol-7-yl), benzoxazolyl (e.g., 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1, 2-benzisothiazolyl (e.g., 1, 2-benzisothiazol-3-yl, 1, 2-benzisothiazol-4-yl, 1, 2-Benzisothiazol-5-yl, 1, 2-Benzisothiazol-6-yl, 1, 2-Benzisothiazol-7-yl), a benzothiazolyl group (e.g., 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), an isoquinolinyl group (e.g., 1-isoquinolinyl, 3-isoquinolinyl, 4-isoquinolinyl, 5-isoquinolinyl), a quinolyl group (e.g., 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 8-quinolyl), a cinnolinyl group (e.g., 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl), phthalazinyl (e.g., 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (e.g., 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), quinoxalinyl (e.g., 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl, 8-quinoxalinyl), pyrazolo [1,5-a ] pyridinyl (e.g., pyrazolo [1,5-a ] pyridin-2-yl, pyrazolo [1,5-a ] pyridin-3-yl, pyrazolo [1,5-a ] pyridin-4-yl, pyrazolo [1,5-a ] pyridin-5-yl, pyrazolo [1,5-a ] pyridin-6-yl, pyrazolo [1,5-a ] pyridin-7-yl), imidazo [1,2-a ] pyridinyl (e.g., imidazo [1,2-a ] pyridin-2-yl, imidazo [1,2-a ] pyridin-3-yl, imidazo [1,2-a ] pyridin-5-yl, imidazo [1,2-a ] pyridin-6-yl, imidazo [1,2-a ] pyridin-7-yl, and imidazo [1,2-a ] pyridin-8-yl), and the like.

In the present specification, "heteroarylene group" refers to a group formed by removing 1 hydrogen atom from the aforementioned "heteroaryl group".

In the present specification, unless otherwise stated, examples of the "heteroarylene group" include furan-diyl (e.g., furan-2, 5-diyl), oxazole-diyl (e.g., oxazole-2, 5-diyl), isoxazole-diyl (e.g., isoxazole-3, 5-diyl), oxadiazole (e.g., furazan-3, 4-diyl), thiophene-diyl (e.g., thiophene-2, 5-diyl), thiazole-diyl (e.g., thiazole-2, 5-diyl), isothiazole-diyl (e.g., isothiazole-3, 5-diyl), thiadiazole-diyl (e.g., 1,2, 5-thiadiazole-3, 4-diyl), pyrrole-diyl (e.g., pyrrole-2, 5-diyl), pyrazole-diyl (for example: pyrazole-3, 5-diyl), imidazole-diyl (for example: imidazole-2, 5-diyl), triazole-diyl (for example: 1,2, 3-triazole-4, 5-diyl), pyridine-diyl (for example: pyridine-1, 4-diyl, pyridine-2, 3-diyl, pyridine-2, 4-diyl, pyridine-2, 5-diyl, pyridine-2, 6-diyl), pyridazine-diyl (for example: pyridazin-4, 5-diyl), pyrimidin-diyl (for example: pyrimidine-2, 5-diyl), pyrazine-diyl (e.g.: pyrazine-2, 6-diyl), triazine-diyl (e.g.: 1,3, 5-triazine-2, 6-diyl), tetrazine-diyl (for example: 1,2,4, 5-tetrazin-3, 6-diyl), indole-diyl, benzimidazole-diyl, benzofuran-diyl, benzothiophene-diyl, quinoline-diyl, isoquinoline-diyl, quinazoline-diyl, phthalazin-diyl, and the like.

A polymer having a monomer unit represented by the formula (1)

The polymer according to one embodiment of the present invention is a polymer having a monomer unit represented by the following formula (1):

[ solution 7]

[ in the formula,

R¹independently at each occurrence is a halogen atom, NR¹¹R¹²(R¹¹And R¹²Each independently a hydrogen atom or an organic group), or an organic group,

n1 is an integer in the range of 0 to 4,

may be present in ortho position2R¹May form a ring, which may have an organic group as a substituent, together with 2 carbon atoms of the adjacent benzene ring,

L¹is a single bond, an oxygen atom, a sulfur atom, -L¹¹-O-、-O-L¹²-O-、-L¹³-S-, or-S-L¹⁴-S-(L¹¹～L¹⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

Note that-L¹¹-O-and-L¹³Each of-S-is preferably bonded to the benzene ring at the left end and CF at the right end₂And (4) a base.

R¹Preferred is a halogen atom, an amino group which may have 1 or 2 alkyl groups as substituents, or an alkyl group which may have 1 or more halogen atoms as substituents. The number of substitution of the halogen atom in the alkyl group is appropriately selected depending on the number of hydrogen atoms in the alkyl group, and is, for example, an integer in the range of 0 to 9. The alkyl group having a halogen atom as a substituent (i.e., a halogenated alkyl group) may be, for example, an alkyl group in which all hydrogen atoms of the alkyl group are replaced with fluorine atoms (i.e., a perfluoroalkyl group).

R¹Further preferably a halogen atom, an amino group, C_1-10Alkyl, mono C_1-10Alkylamino, di-C_1-10Alkylamino, or halogeno C_1-10Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6An alkyl group.

In addition, in R¹In the case of an alkyl group or the like, the polymer having a monomer unit represented by the formula (1) is excellent in solubility in a solvent, and therefore, can be used as a coating composition or an impregnating composition containing the polymer and a solvent.

At R¹In the case of a halogen atom, R¹The unit represented by the formula (1) can be further linked by reacting with a compound represented by the formula (4) described later. That is, the polymer may be, for example, a three-dimensional polymer having a unit represented by the following formula:

[ solution 8]

(in the formula, L¹The same meaning as described above).

n1 is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.

L¹¹～L¹⁴Each is preferably C_1-6Alkylene, more preferably C_1-4An alkylene group.

L¹Preferably a single bond, an oxygen atom, -L¹¹-O-, or-O-L¹²-O-。

At 2R's present in ortho position¹In the case of forming a ring together with 2 carbon atoms of the adjacent benzene ring, the monomer unit represented by formula (1) is, for example, a unit represented by the following formula (1A) or (1B):

[ solution 9]

[ in the formula,

Z^1Aand Z^1BEach of which forms, together with the adjacent benzene ring, a fused ring, R of which is a substituent^1AAnd R^1BEach independently at each occurrence is a halogen atom, NR^11AR^12A(R^11AAnd R^12AEach independently a hydrogen atom or an organic group), or an organic group,

n1A and n1B are each an integer in the range of 0 to 4,

L^1Aand L^1BEach is a single bond, an oxygen atom, a sulfur atom, -L^11A-O-、-O-L^12A-O-、-L^13A-S-, or-S-L^14A-S-(L^11A～L^14AEach independently is an alkylene group which may have 1 or more substituents. ).]。

In the formula (1A), Z is contained^1ASpecific examples of the condensed ring with the benzene ring adjacent thereto include aromatic condensed rings, and examples thereof include naphthalene, indole, benzimidazole, benzofuran, benzothiophene, quinoline, isoquinoline, and quinolineOxazoline, phthalazine, benzotriazole.

R^1APreferably a halogen atom, an amino group, an alkyl group, a monoalkylamino group, a dialkylamino group, or a haloalkyl group, and more preferably a halogen atom, an amino group, or C_1-10Alkyl, mono C_1-10Alkylamino, di-C_1-10Alkylamino, or halogeno C_1-10Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6An alkyl group.

n1A is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.

L^11A～L^14AEach is preferably C_1-6Alkylene, more preferably C_1-4An alkylene group.

L^1APreferably a single bond, an oxygen atom, -L^11A-O-, or-O-L^12A-O-。

Z in the formula (1B)^1BN1B and L^1BFor example with Z in formula (1A)^1AN1A and L^1ALikewise, the preferred embodiments are also the same.

In the polymer having a monomer unit represented by the formula (1), the number of the monomer unit represented by the formula (1) is not particularly limited, and is, for example, in the range of 5 to 500000, preferably 10 to 100000, and more preferably 15 to 50000. The structures of the monomer units may be the same or different from each other.

The polymer having the monomer unit represented by formula (1) may be a homopolymer or a copolymer.

The copolymer may be a copolymer having 2 or more monomer units represented by formula (1), or may be a copolymer having, for example, a monomer unit in which n1 is 0 in formula (1) and a monomer unit in which n1 is 1 in formula (1).

The polymer having a monomer unit represented by the formula (1) may further have a monomer unit represented by the following formula (2):

[ solution 10]

[ in the formula,

R²independently at each occurrence is a halogen atom, NR²¹R²²(R²¹And R²²Each independently a hydrogen atom or an organic group. ) Or an organic group, or a salt thereof,

n2 is an integer in the range of 0 to 4,

2R which may be present in ortho position²May form a ring, which may have an organic group as a substituent, together with 2 carbon atoms of the adjacent benzene ring,

L²is a single bond, an oxygen atom, a sulfur atom, -L²¹-O-、-O-L²²-O-、-L²³-S-, or-S-L²⁴-S-(L²¹～L²⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

Note that-L²¹-O-and-L²³Each of-S-is preferably bonded to the benzene ring at the left end and to CF at the right end₂And (4) a base.

R²Preferably a halogen atom, an amino group, an alkyl group, a monoalkylamino group, a dialkylamino group, or a haloalkyl group, and more preferably a halogen atom, an amino group, or C_1-10Alkyl, mono C_1-10Alkylamino, di-C_1-10Alkylamino, or halogeno C_1-10Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6An alkyl group.

n2 is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.

L²¹～L²⁴Each is preferably C_1-6Alkylene, more preferably C_1-4An alkylene group.

L²Preferably a single bond, an oxygen atom, -L²¹-O-, or-O-L²²-O-。

At 2R's present in ortho position²In the case of forming a ring together with 2 carbon atoms of the adjacent benzene ring, the unit represented by formula (2) is, for example, a unit represented by the following formula (2A):

[ solution 11]

[ in the formula,

Z^2Ar as a substituent of a fused ring forming the fused ring together with an adjacent benzene ring^2AIndependently at each occurrence is a halogen atom, NR^21AR^22A(R^21AAnd R^22AEach independently a hydrogen atom or an organic group. ) Or an organic group, or a salt thereof,

n2A is an integer in the range of 0 to 4,

L^2Ais a single bond, an oxygen atom, a sulfur atom, -L^21A-O-、-O-L^22A-O-、-L^23A-S-, or-S-L^24A-S-(L^21A～L^24AEach independently is an alkylene group which may have 1 or more substituents. ).]。

Comprising Z^2ASpecific examples of the fused ring to the benzene ring adjacent thereto include aromatic fused rings, and examples thereof include naphthalene, indole, benzimidazole, benzofuran, benzothiophene, quinoline, isoquinoline, quinazoline, phthalazine, and benzotriazole.

R^2APreferably a halogen atom, an amino group, an alkyl group, a monoalkylamino group, a dialkylamino group, or a haloalkyl group, and more preferably a halogen atom, an amino group, or C_1-10Alkyl, mono C_1-10Alkylamino, di-C_1-10Alkylamino, or halogeno C_1-10Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6An alkyl group.

n2A is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.

L^21A～L^24AEach is preferably C_1-6Alkylene, more preferably C_1-4An alkylene group.

L^2APreferably a single bond, an oxygen atom, -L^21A-O-, or-O-L^22A-O-。

In the polymer having a monomer unit represented by the formula (1), the number of the monomer unit represented by the formula (2) is not particularly limited, and is, for example, in the range of 5 to 500000, more preferably 10 to 100000, and further preferably 15 to 50000. The structures of the monomer units may be the same or different from each other.

The molar ratio of the monomer unit represented by formula (1) to the monomer unit represented by formula (2) is not particularly limited, and is, for example, 10: 90-90: 10, more preferably 20: 80-80: 20, more preferably 30: 70-70: 30, or more.

A polymer having a monomer unit represented by the formula (1

Another embodiment of the polymer of the present invention is a polymer having a monomer unit represented by the following formula (1'):

[ solution 12]

[ in the formula,

b is a heteroarylene group which may have 1 or more substituents,

L⁴is a single bond, an oxygen atom, a sulfur atom, -L⁴¹-O-、-O-L⁴²-O-、-L⁴³-S-, or-S-L⁴⁴-S-(L⁴¹～L⁴⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

Note that-L⁴¹-O-and-L⁴³S-is each preferably bonded to B at the left end and CF at the right end₂And (4) a base.

B is preferably a 5-to 10-membered heteroarylene group which may have 1 or more substituents, more preferably a furan-diyl group, oxazole-diyl group, isoxazol-diyl group, oxadiazole-diyl group, thiophene-diyl group, thiazole-diyl group, isothiazol-diyl group, thiadiazole-diyl group, pyrrole-diyl group, pyrazole-diyl group, imidazole-diyl group, triazole-diyl group, pyridine-diyl group, pyridazine-diyl group, pyrimidine-diyl group, pyrazine-diyl group, triazine-diyl group or tetrazine-diyl group which may have 1 or more substituents.

The substituent is preferably a halogen atom, an amino group which may have 1 or 2 organic groups as a substituent, or an organic group, more preferably a halogen atom, an amino group, an alkyl group, a monoalkyl group, or a haloalkyl group, and still more preferably a halogen atom, an amino group, or C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-4Alkyl, mono C_1-4Alkylamino, di-C_1-4Alkylamino, or perfluoro C_1-2An alkyl group. When the substituent is a halogen atom, the substituent may be reacted with a compound represented by formula (4) described later to further link a unit represented by formula (1'), or the like.

L⁴¹～L⁴⁴Each is preferably C_1-6Alkylene, more preferably C_1-4An alkylene group.

L⁴Preferably a single bond, an oxygen atom, -L⁴¹-O-, or-O-L⁴²-O-。

The polymer having the monomer unit represented by formula (1') may be a homopolymer or a copolymer.

The copolymer may have 2 or more monomer units represented by formula (1'), or may be, for example, a copolymer of a monomer unit in which B in formula (1') is a heteroarylene group having no substituent, and a monomer unit in which B in formula (1') is a heteroarylene group having 1 or more substituents.

The polymer having the monomer unit represented by formula (1') may further have at least one selected from the monomer unit represented by formula (1) and the monomer unit represented by formula (2).

The form of the polymer having the monomer unit represented by the formula (1) or (1)' may be, for example, linear or branched (e.g., star-shaped or comb-shaped).

The copolymer having a monomer unit represented by the formula (1) or (1)' (for example, a copolymer having a monomer unit represented by the formula (1) and a monomer unit represented by the formula (2)) may be, for example, a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer.

In contrast to the conventional polyparaxylylene having a peak in the range of 300 to 350 ℃ in Differential Scanning Calorimetry (DSC), a polymer having a monomer unit represented by the formula (1) or (1)' more preferably has no peak in the entire range of 300 to 350 ℃ in DSC. Such low crystallinity provides good processability.

The polymer having the monomer unit represented by the formula (1) or (1)' may have a temperature in the range of 510 to 530 ℃ when it shows a 5% mass loss in a thermal mass measurement at a temperature rise rate of 10 ℃/min, for example.

The glass transition temperature (Tg) of the polymer having the monomer unit represented by the formula (1) or (1)' is not particularly limited, and may be, for example, in the range of 500 to 550 ℃.

Method for producing polymer having monomer unit represented by formula (3)

A method for producing a polymer according to one embodiment of the present invention is a method for producing a polymer having a monomer unit represented by the following formula (3):

[ solution 13]

[ in the formula,

a is an arylene group which may have 1 or more substituents, or a heteroarylene group which may have 1 or more substituents,

L³is a single bond, an oxygen atom, a sulfur atom, -L³¹-O-、-O-L³²-O-、-L³³-S-, or-S-L³⁴-S-(L³¹～L³⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

Note that-L³¹-O-and-L³³S-is each preferably bonded to A at the left end and to CF at the right end₂And (4) a base.

The method includes the step of polymerizing a monomer including a compound represented by the following formula (4), and a ligand selected from the group consisting of a phosphine and a compound having a pyridine ring:

[ solution 14]

(in the formula, X¹Is a halogen atom selected from chlorine atom, bromine atom and iodine atom, M is a metal selected from copper, zinc, nickel, iron, cobalt and tin, A and L³The same meaning as described above. ).

In the formulae (3) and (4), A is preferably C which may have 1 or more substituents_6-10An arylene group, or a 5-to 10-membered heteroarylene group which may have 1 or more substituents.

A is more preferably phenylene, furan-diyl, oxazole-diyl, isoxazol-diyl, oxadiazole-diyl, thiophene-diyl, thiazole-diyl, isothiazol-diyl, thiadiazole-diyl, pyrrole-diyl, pyrazole-diyl, imidazole-diyl, triazole-diyl, pyridine-diyl, pyridazine-diyl, pyrimidine-diyl, pyrazine-diyl, triazine-diyl or tetrazine-diyl which may have 1 or more substituents.

A is also preferably a phenylene group which may have 1 or more substituents, and is also preferably a 1, 3-phenylene group which may have 1 or more substituents, or a 1, 4-phenylene group which may have 1 or more substituents.

The substituent is preferably a halogen atom, an amino group, an alkyl group, a monoalkylamino group, a dialkylamino group, or a halogenated alkyl group, and more preferably a halogen atom, an amino group, or C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-4Alkyl, mono C_1-4Alkylamino, di-C_1-4Alkylamino, or perfluoro C_1-2An alkyl group.

L³¹～L³⁴Each is preferably C_1-6Alkylene, more preferably C_1-4An alkylene group.

In formulae (3) and (4), L³Preferably a single bond, an oxygen atom, -L³¹-O-, or-O-L³²-O-。

In the formula (4), M usually forms a coordinate bond with the aforementioned ligand. M is preferably copper, and more preferably copper (I).

Examples of the "compound having a pyridine ring" as the ligand include phenanthroline (e.g., 1, 10-phenanthroline), 2' -bipyridine, pyridine, picoline, and lutidine (e.g., 2, 6-lutidine).

The "phosphine" as the ligand is preferably a trialkylphosphine or triarylphosphine. Specific examples of the trialkylphosphines include tricyclohexylphosphine, triisopropylphosphine, tri-tert-butylphosphine, tri-tert-hexylphosphine, triamantylphosphine, tricyclopentylphosphine, di-tert-butylmethylphosphine, and tris (bicyclo [2,2] tris (tert-butylphosphine))]Tri (C) s such as octyl) phosphine, trinonolphosphine and the like_3-20Alkyl) phosphines.

Specific examples of triarylphosphines include tris (monocyclic aryl) phosphine such as triphenylphosphine, tris (mesityl) phosphine, and tris (o-tolyl) phosphine. Among them, triphenylphosphine, tricyclohexylphosphine, and tri-t-butylphosphine are preferable.

The aforementioned ligands are preferably bidentate ligands.

As a preferred example thereof, 1, 10-phenanthroline may be mentioned.

The number of ligands coordinated to the monomer depends on the oxidation number of the metal M, the number of coordination atoms of the ligand, and the like, and is more preferably 1 to 3.

The aforementioned monomers are obtained by known methods, including, for example: an organoboron compound which is a boric acid having a moiety represented by the following formula (5) or an ester thereof or a salt thereof:

[ solution 15]

(X¹A and L³The same meanings as described above), and

a metal compound which is a hydroxide, halide, alkoxide, aryloxide, thioalkoxide or thioaryloxide of the metal M,

A ligand selected from the group consisting of phosphines and compounds having a pyridine ring, and

tetrafluoroethylene

A step of reaction.

This method may be, for example, the method described in WO 2015/050236.

The aforementioned monomers may be isolated or purified by a conventional method, or may be used for polymerization without isolation or purification.

The polymerization of the aforementioned monomers is preferably carried out in the presence of a solvent.

Examples of the solvent include hydrocarbons (for example, aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene), ethers (for example, chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), ketones (for example, chain ketones such as acetone, cyclic ketones such as cyclohexanone), and 2 or more kinds thereof may be mixed and used, but the solvent is not limited thereto. The solvent is preferably an ether solvent, and more preferably a cyclic ether solvent.

The polymerization of the aforementioned monomers can be carried out by, for example, heating. The polymerization temperature of the monomer is not particularly limited as long as the polymerization can be carried out, and is, for example, in the range of 20 to 200 ℃ and preferably 50 to 150 ℃.

The polymerization time of the monomer is not particularly limited, but is, for example, in the range of 0.5 to 60 hours, preferably 2 to 24 hours.

The polymer obtained by polymerizing the aforementioned monomer can be washed, dried or purified by a usual method. The washing solvent is not particularly limited, and examples thereof include water, concentrated nitric acid, hydrocarbons (e.g., hexane), alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methyl ethyl ketone), and combinations of 2 or more thereof. In one embodiment, as washing solvent, preferably at least concentrated nitric acid is used.

A polymer having a monomer unit represented by the formula (6)

The polymer according to another embodiment of the present invention is a polymer having a monomer unit represented by the following formula (6):

[ solution 16]

[ in the formula,

G¹and G²Each independently an arylene group which may have 1 or more substituents, or a heteroarylene group which may have 1 or more substituents,

L⁵is a single bond, an oxygen atom, a sulfur atom, -L⁵¹-O-、-O-L⁵²-O-、-L⁵³-S-, or-S-L⁵⁴-S-(L⁵¹～L⁵⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

Note that-L⁵¹-O-and-L⁵³Each of-S-is preferably bonded to G at the left end¹Right end bonded to CF₂And (4) a base.

In the formula (6), G¹And G²Each is preferably C which may have 1 or more substituents_6-10An arylene group, or a 5-to 10-membered heteroarylene group which may have 1 or more substituents.

G¹And G²Each is more preferably a phenylene group, furan-diyl group, oxazole-diyl group, isoxazol-diyl group, oxadiazole-diyl group, thiophene-diyl group, thiazole-diyl group, isothiazol-diyl group, thiadiazole-diyl group, pyrrole-diyl group, pyrazole-diyl group, imidazole-diyl group, triazole-diyl group, pyridine-diyl group, pyridazine-diyl group, pyrimidine-diyl group, pyrazine-diyl group, triazine-diyl group, or tetrazine-diyl group which may have 1 or more substituents.

G¹And G²Each is also preferably a phenylene group which may have 1 or more substituents, and is also preferably a 1, 3-phenylene group which may have 1 or more substituents, or a 1, 4-phenylene group which may have 1 or more substituents.

The substituent is preferably a halogen atom, an amino group, an alkyl group, a monoalkylamino group, a dialkylamino group, or a halogenated alkyl group, and more preferably a halogen atom, an amino group, or C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-4Alkyl, mono C_1-4Alkylamino, di-C_1-4Alkylamino, or perfluoro C_1-2An alkyl group. When the substituent is a halogen atom, the substituent may be further substituted with a halogen atomA unit represented by the connection formula (6), and the like.

L⁵¹～L⁵⁴Each is preferably C_1-6Alkylene, more preferably C_1-4An alkylene group.

L⁵Preferably a single bond, an oxygen atom, -L⁵¹-O-, or-O-L⁵²-O-。

The monomer unit represented by the formula (6) is more preferably a monomer unit represented by the following formula (7):

[ solution 17]

[ in the formula,

R³and R⁴Each independently at each occurrence is a halogen atom, NR³¹R³²(R³¹And R³²Each independently a hydrogen atom or an organic group. ) Or an organic group, or a salt thereof,

n3 and n4 are each independently an integer in the range of 0 to 4,

2R which may be present in ortho position³Or R⁴May form a ring, which may have an organic group as a substituent, together with 2 carbon atoms of the adjacent benzene ring,

L⁶is a single bond, an oxygen atom, a sulfur atom, -L⁶¹-O-、-O-L⁶²-O-、-L⁶³-S-, or-S-L⁶⁴-S-(L⁶¹～L⁶⁴Each independently is an alkylene group which may have 1 or more substituents. ).]。

R³And R⁴Each is preferably a halogen atom, an amino group, an alkyl group, a monoalkylamino group, a dialkylamino group, or a halogenated alkyl group, and more preferably a halogen atom, an amino group, or C_1-10Alkyl, mono C_1-10Alkylamino, di-C_1-10Alkylamino, or halogeno C_1-10Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6An alkyl group.

Each of n3 and n4 is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.

L⁶¹～L⁶⁴Each is preferably C_1-6Alkylene, more preferably C_1-4An alkylene group.

L⁶Preferably a single bond, an oxygen atom, -L⁶¹-O-, or-O-L⁶²-O-。

At 2R's present in ortho position³Or R⁴When a ring is formed together with 2 carbon atoms of an adjacent benzene ring, specific examples of the ring include an aromatic condensed ring, and examples thereof include naphthalene, indole, benzimidazole, benzofuran, benzothiophene, quinoline, isoquinoline, quinazoline, phthalazine, and benzotriazole.

The ring may have 1 or more substituents. The substituent is preferably a halogen atom, an amino group, an alkyl group, a monoalkylamino group, a dialkylamino group, or a halogenated alkyl group, and more preferably a halogen atom, an amino group, or C_1-6Alkyl, mono C_1-6Alkylamino, di-C_1-6Alkylamino, or halogeno C_1-6Alkyl, particularly preferably fluorine atom, chlorine atom, amino group, C_1-4Alkyl, mono C_1-4Alkylamino, di-C_1-4Alkylamino, or perfluoro C_1-2An alkyl group.

In the repeating unit of 2 or more of the monomer units represented by formula (6), the right end of 1 unit may be bonded to either the left end or the right end of the other unit. That is, the polymer having a monomer unit represented by formula (6) may have a unit represented by the following formula (6A) or (6B):

[ solution 18]

(in the formula, G¹、G²And L⁵The same meaning as described above),

the unit represented by the formula (6A) and the unit represented by the formula (6B) may be both present.

The polymer having the monomer unit represented by formula (6) may be a homopolymer or a copolymer.

The copolymer may have 2 or more kinds of monomer units represented by formula (6).

The form of the polymer having the monomer unit represented by the formula (6) may be, for example, linear or branched (e.g., star-shaped or comb-shaped).

The form of the copolymer having the monomer unit represented by formula (6) may be, for example, a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer.

The polymer having a monomer unit represented by the formula (6) more preferably has no peak in the DSC over the entire range of 300 to 350 ℃. Such low crystallinity provides good processability.

The temperature at which the polymer having the monomer unit represented by formula (6) exhibits a 5% mass reduction in a thermal mass measurement at a temperature increase rate of 10 ℃/min may be in the range of 510 to 530 ℃.

The glass transition temperature (Tg) of the polymer having the monomer unit represented by formula (6) is not particularly limited, and may be, for example, in the range of 500 to 550 ℃.

Method for producing polymer having monomer unit represented by formula (6)

A method for producing a polymer according to an embodiment of the present invention includes: a step of subjecting a monomer represented by the following formula (8) to coupling polymerization:

[ solution 19]

(in the formula, X²And X³Each independently being a halogen atom, G¹、G²And L⁵The same meaning as described above).

In the formula (8), X²And X³Each is preferably a fluorine atom, a chlorine atom, or a bromine atom.

The monomer represented by formula (8) can be produced, for example, by a method comprising the steps of:

a compound represented by the following formula (9):

[ solution 20]

(wherein M' is a metal selected from the group consisting of copper, zinc, nickel, iron, cobalt and tin, G¹、L⁵And X²The same meanings as described above), and

a compound represented by the following formula (10):

[ solution 21]

(in the formula, X⁴Is a halogen atom, G²And X³The same meaning as described above. )

The reaction takes place.

In the formula (9), M' may be the same metal as M in the formula (4), and preferred metals are also the same. M' usually forms a coordinate bond with a ligand in the same manner as M.

In the formula (10), X⁴Preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. As X³And X⁴The combination of (1) is preferably a combination of a bromine atom and an iodine atom.

The lower limit of the amount of the compound represented by formula (9) may be, for example, 0.5 mol, 0.8 mol, or 1 mol with respect to 1 mol of the compound represented by formula (10).

The upper limit of the amount of the compound represented by formula (9) may be, for example, 5 moles, 3 moles, 2 moles, or 1.5 moles with respect to 1 mole of the compound represented by formula (10).

The amount of the compound represented by the formula (9) may be, for example, in the range of 0.5 to 1.5 moles relative to 1 mole of the compound represented by the formula (10).

The aforementioned reaction is preferably carried out in the presence of a solvent.

Examples of the solvent include hydrocarbons (for example, aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene), ethers (for example, linear ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), ketones (for example, linear ketones such as acetone, cyclic ketones such as cyclohexanone), and 2 or more kinds thereof may be mixed and used, but not limited thereto. The solvent is preferably an ether solvent, and more preferably a cyclic ether solvent.

The aforementioned reaction can be carried out by heating, for example. The reaction is not particularly limited as long as the reaction can proceed, and is, for example, 20 to 200 ℃ and more preferably 50 to 150 ℃.

The reaction time is not particularly limited, and is, for example, in the range of 0.5 to 60 hours, and more preferably 2 to 24 hours.

The coupling polymerization is preferably carried out in the presence of a transition metal catalyst, preferably in the presence of at least one selected from the group consisting of a nickel catalyst, a palladium catalyst and a cobalt catalyst.

Examples of the nickel catalyst include 0-valent nickel complexes; a 0-valent nickel complex produced in the reaction from a II-valent nickel complex; or a complex obtained by mixing them with at least 1 compound (ligand) selected from ketones, diketones, phosphines, diamines, bipyridines, cyclodienes and phenanthrolines.

The ketone is not particularly limited, and examples thereof include dibenzylideneacetone.

The diketone is not particularly limited, and examples thereof include beta diketones such as acetylacetone, 1-phenyl-1, 3-butanedione, 1, 3-diphenylpropanedione, and hexafluoroacetylacetone.

The phosphine is not particularly limited, and examples thereof include the phosphines exemplified in the step of polymerizing the monomer containing the compound represented by the formula (4).

The diamine is not particularly limited, and tetramethylethylenediamine, 1, 2-diphenylethylenediamine, and the like can be mentioned.

The bipyridine is not particularly limited, and examples thereof include 2,2' -bipyridyl, 4' -dimethyl-2, 2' -bipyridine, 5' -dimethyl-2, 2' -bipyridine, 6' -dimethyl-2, 2' -bipyridine, 4' -di-tert-butyl-2, 2' -bipyridine, 4' -dimethoxy-2, 2' -bipyridine, 2' -biquinoline, and α, α ', α ″ -terpyridine.

The cyclic diene is not particularly limited, and examples thereof include cyclopentadiene, cyclooctadiene, cyclodecadiene, and the like.

The phenanthroline is not particularly limited and may be, for example, examples thereof include 1, 10-phenanthroline, 2-methyl-1, 10-phenanthroline, 3-methyl-1, 10-phenanthroline, 5-methyl-1, 10-phenanthroline, 2, 9-dimethyl-1, 10-phenanthroline, 2, 9-diphenyl-1, 10-phenanthroline, 4, 7-dimethyl-1, 10-phenanthroline, 5, 6-dimethyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, and 3,4,7, 8-tetramethyl-1, 10-phenanthroline.

The 0-valent nickel complex is not particularly limited, and examples thereof include Ni (cod)₂、Ni(cdd)₂(cdd is cyclodeca-1, 5-diene), Ni (cdt)₂(cdt is cyclodecan-1, 5, 9-triene), Ni (vch)₂(vch is 4-vinylcyclohexene), Ni (CO)₄、(PCy₃)₂Ni-N≡N-Ni(PCy₃)₂、Ni(PPh₃)₄And the like.

Examples of the nickel (II) -valent nickel complex include nickel chloride, nickel bromide, nickel acetate, nickel (II) bis (acetylacetonate), and a complex in which a phosphine ligand such as triphenylphosphine is coordinated to these. These nickel complexes having a valence of II are reduced by a reducing substance (phosphine, zinc, an organic metal reagent, etc.) coexisting in the reaction, for example, to produce a nickel complex having a valence of 0.

The 0-valent nickel complex or the 0-valent nickel complex produced by reduction of the II-valent nickel complex may be converted into a 0-valent nickel complex which participates in the reaction by reacting with a ligand added as necessary during the reaction. It should be noted that it is not necessarily certain that these ligands have several coordinates to the 0-valent nickel complex in the reaction.

Examples of the palladium catalyst include, for example, 0-valent palladium complexes; a 0-valent palladium complex produced from a I-valent or II-valent palladium complex in a reaction; or a complex obtained by mixing them with at least 1 compound (ligand) selected from ketones, diketones, phosphines, diamines, bipyridines, cyclodienes and phenanthrolines. The ketones, diketones, phosphines, diamines, bipyridines, cycloalkadienes, and phenanthrolines can be the same as those exemplified for the nickel catalyst.

The 0-valent palladium complex is not particularly limited, and examples thereof include

Pd₂(dba)₃(dba is dibenzylideneacetone),

Pd₂(dba)₃-CHCl₃、Pd(dba)₂、

Pd(cod)₂(cod is cycloocta-1, 5-diene),

Pd(dppe)₂(dppe is 1, 2-bis (diphenylphosphino) ethane),

Pd(PCy₃)₂(Cy is cyclohexyl),

Pd(Pt-Bu₃)₂(t-Bu is a tert-butyl group),

Pd(PPh₃)₄(Ph is phenyl), and

tris { tris [3, 5-bis (trifluoromethyl) phenyl ] phosphine } palladium (0), and the like.

Examples of the palladium complex having a valence of I include di- μ -chlorobis (tri-tert-butylphosphino) dipalladium (I), di- μ -bromobis (tri-tert-butylphosphino) dipalladium (I), di- μ -iodobis (tri-tert-butylphosphino) dipalladium (I), di- μ -chlorobis { tris (1-adamantyl) phosphine } dipalladium (I), di- μ -bromobis { tris (1-adamantyl) phosphine } dipalladium (I), and di- μ -iodobis { tris (1-adamantyl) phosphine } dipalladium (I).

Examples of the II-valent palladium complex include

Palladium chloride, palladium bromide, palladium acetate, bis (acetylacetonato) palladium (II), dichloro (. eta.) compound⁴-1, 5-cyclooctadiene) palladium (II), dibromo (. eta.)⁴-1, 5-cyclooctadiene) palladium (II), bis (acetonitrile) dichloropalladium (II), bis (benzonitrile) dichloropalladium (II), and bis- μ -chlorobis { (η -allyl) palladium } (II);

and the number of the first and second groups,

and complexes in which phosphine ligands such as triphenylphosphine are coordinated to these groups.

The nickel complex, the palladium complex, and the like are often used in the reaction by forming a uniform solution with a reaction substrate using the ligand as described above, but they can be used in the form of a heterogeneous catalyst by dispersing or supporting them in a polymer such as polystyrene or polyethylene. Such a heterogeneous catalyst has an advantage in a process of recovering the catalyst and the like. Specific examples of the catalyst structure include a structure in which a metal atom is fixed by a phosphine polymer or the like obtained by introducing a phosphine into a crosslinked Polystyrene (PS) chain, as shown in the following chemical formula. In addition to these, polymeric phosphines described in the following documents may be used:

1) kanbara et al, Macromolecules, 2000, Vol.33, p.657

2) Yamamoto et al, J.Polym.Sci., 2002, Vol.40, p.2637

3) Japanese laid-open patent publication No. H06-32763

4) Japanese patent laid-open publication No. 2005-281454

5) Japanese patent laid-open publication No. 2009-527352.

[ solution 22]

(wherein PS represents polystyrene and Ph represents phenyl).

Examples of the cobalt catalyst include (Cl) Co (PPh)₃)₃、(C₅H₅)₂Co(PPh₃)₂(C₅H₅Is cyclopentadienyl), (C)₅H₅)₂Co(cod)₂And a complex in which a phosphine ligand such as triphenylphosphine is coordinated to tris (acetylacetonate) cobalt (III) or cobalt (II) chloride.

The ligand/catalyst molar ratio may be, for example, in the range of 0.5 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 2.

The catalyst may be used alone in 1 kind, or may be used in combination of 2 or more kinds. In one embodiment, the catalyst is preferably a nickel catalyst.

The upper limit of the amount of the catalyst may be preferably 1.2 mol, more preferably 1.1 mol, and still more preferably 1 mol, based on 1 mol of the monomer.

The lower limit of the amount of the catalyst may be preferably 0.01 mol, more preferably 0.005 mol, and still more preferably 0.001 mol, based on 1 mol of the monomer.

The amount of the catalyst may be preferably in the range of 0.001 to 1.2 mol, more preferably 0.005 to 1.1 mol, and still more preferably 0.01 to 1 mol, based on 1 mol of the monomer.

The coupling polymerization is preferably carried out in the presence of a solvent.

Examples of such solvents include:

aromatic hydrocarbons such as benzene, toluene, and xylene;

ethers such as cyclopentyl methyl ether, tetrahydrofuran, bis (2-methoxyethyl) ether, and 1, 2-bis (2-methoxyethoxy) ethane;

nitriles such as acetonitrile and propionitrile;

ketones such as acetone, methyl ethyl ketone, and isobutyl methyl ketone;

dialkyl sulfoxides such as dimethyl sulfoxide; and

n, N-dimethylformamide, N-dimethylacetamide, and hexaalkylphosphoric triamides [ for example: hexamethylphosphoric acid amide ], and the like.

The solvent can be used alone in 1, or can be combined with 2 or more.

The temperature and time of the coupling polymerization are not particularly limited as long as the coupling can be carried out.

The temperature may be, for example, in the range of 10 to 150 ℃, and preferably, in the range of 15 to 100 ℃.

The time may be, for example, in the range of 0.5 to 30 hours, and preferably in the range of 1 to 24 hours.

The polymer having the unit represented by the formula (1), (1)', (3), or (6) can be used, for example, at a high temperature (e.g., 450 ℃ or lower). In addition, the polymer is excellent in ultraviolet resistance and can be used for a long time under severe conditions. The polymer has low friction coefficient and dielectric constant, and is excellent in gap permeability.

Specific examples of the use of the polymer having a unit represented by the formula (1), (1)', (3), or (6) include coatings. Examples of the coating layer include a coating layer for medical equipment (for example, a stent, a cardiac support device, an electrosurgical tool, a cochlear implant, an intraocular implant, a mandrel, a molding die, a catheter, an elastomer seal, a needle, an epidural probe, a medical electronic device), an electronic coating layer (for example, a printed circuit board, a component, a sensor, a MEMS (micro-electro-mechanical system), a capacitor, a wafer, a ferrite core, a display, a metal part), an LED coating layer (for example, a display, an electro-optical bulletin board, a traffic sign, an aircraft lamp, a traffic signal, a score board, a lamp for a ship, a refrigerator for civil use, a lamp for a vehicle, outdoor lighting), a coating layer for an automobile part (for example, a tire pressure sensor, a tire pressure monitoring system, a fuel cell technology, a gasket, a seal), a coating layer for protection or for an aerospace industry machine (for example, a MEMS, a, Sensors, circuit card assemblies, motor parts, power supplies, back plates, elastomeric parts).

Further, the polymer having the unit represented by the formula (1), (1)', (3), or (6) can also be used as, for example, a sealing material, a diaphragm, or an insulating film (e.g., a semiconductor interlayer insulating film).

Film

A film according to one embodiment of the present invention contains a polymer having a unit represented by formula (1), (1)', (3), or (6).

In the film, the content of the polymer having the unit represented by the formula (1), (1)', (3), or (6) is not particularly limited, and is, for example, in the range of 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more.

The film may contain an additive in addition to the polymer having the unit represented by the formula (1), (1)', (3), or (6). Examples of the additive include a colorant, a plasticizer, an antioxidant, an ultraviolet absorber, a filler, a flame retardant, an antistatic agent, an antibacterial agent, and a combination of 2 or more of these.

The thickness of the film is an arithmetic average of the respective thicknesses measured at 10 points on the film selected to exclude a specific purpose.

The lower limit of the thickness of the film may be, for example, 0.2 μm, 2 μm, or 10 μm.

The upper limit of the thickness of the film may be, for example, 200 μm, 150 μm, or 100 μm.

The thickness of the film may be, for example, in the range of 0.2 to 200 μm, 2 to 150 μm, or 10 to 100 μm.

The film has not only the physical properties of a polymer containing a unit represented by the formula (1), (1)', (3) or (6), but also excellent transparency, for example.

The method for producing the film includes: for example, a step of applying a predetermined pressure to a polymer having a monomer unit represented by the formula (1), (1)', (3), or (6).

Examples

Hereinafter, one embodiment of the present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.

The notation in the examples is used to indicate the following meaning.^t

^tBu: tert-butyl radical

Ph: phenylene radical

phen: phenanthroline

TFE: tetrafluoroethylene

bpy: bipyridine

COD: 1, 5-cyclooctadiene

[ examples 1 to 1]p-PhCF₂CF₂Synthesis of homopolymers

1.p-BrPhCF₂CF₂Synthesis of Cu (phen)

[ solution 23]

In a glove box, the mixture was prepared by mixing 5, 5-dimethyl-2- (4-bromophenyl) -1,3, 2-dioxaborolane (dioxabornane) (592mg, 2.2mmol), CuO^tBu (267mg, 2.0mmol) and 1, 10-phenanthroline (phen: 360mg, 2.0mmol) were mixed in 20mL of THF solvent and stirred at room temperature for 30 minutes to prepare p-BrPhCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 15 hours. After degassing the unreacted TFE, concentration and washing with hexane gave a brown solid complex compound: p-BrPhCF₂CF₂Cu(phen)(880.47mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：6.71(br,Ar),6.95(br,Ar),7.24(br,phen),7.36(br,phen),7.91(br,phen),8.68(br,phen).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-107.9(br,2F),-106.5(br,2F)

2.p-PhCF₂CF₂Synthesis of homopolymers

[ solution 24]

(wherein m1 is an integer of 2 or more).

In a glove box, p-BrPhCF₂CF₂A THF solution (0.3mL) of Cu (phen) (15mg, 0.03mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. The product was washed with methanol, acetone and water in this order and dried under vacuum to give a white solid polymer: p-PhCF₂CF₂Homopolymer (2.9 mg).

Tg：519℃

IR peak: 1202cm^-1,1146cm^-1,637cm^-1

Solid body¹H NMR(700MHz,neat,rt,δ/ppm)：0.071(br),0.80(br),1.20(br),6.75(br)

Solid body¹⁹F NMR(700MHz,neat,rt,δ/ppm)：-122.56(br)

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. Thus suggesting p-PhCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310-330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

Examples 1 to 2]p-PhCF₂CF₂Synthesis of homopolymers

The same procedures as in example 1-1 were carried out except that in 2. of example 1-1, the product was washed with methanol, acetone, concentrated nitric acid and acetone in this order to give p-PhCF₂CF₂A homopolymer.

[ example 2-1]m-PhCF₂CF₂Synthesis of homopolymers

1.m-BrPhCF₂CF₂Synthesis of Cu (phen)

[ solution 25]

In a glove box, the mixture was prepared by mixing 5, 5-dimethyl-2- (3-bromophenyl) -1,3, 2-dioxaborolan (592mg, 2.2mmol), CuO^tBu (267mg, 2.0mmol) and 1, 10-phenanthroline (phen: 360mg, 2.0mmol) were mixed in 20mL of THF solvent and stirred at room temperature for 30 minutes to prepare m-BrPhCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 15 hours. After degassing the unreacted TFE, concentration and washing with hexane gave a brown solid complex compound: m-BrPhCF₂CF₂Cu(phen)(750.40mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：6.77(br,phen),6.87(t,Ar),6.96(br,Ar),7.00(br,phen),7.29(br,phen),8.04(d,Ar),8.50(br,Ar),8.70(br,phen).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-108.9(br,2F),-108.7(br,2F)

2.m-PhCF₂CF₂Synthesis of homopolymers

[ solution 26]

(wherein m2 is an integer of 2 or more).

In a glove box, m-BrPhCF₂CF₂Cu (phen) (15mg, 0.03mmol) in THF (0.3mL) was added to a 50mL autoclave at 100 deg.CThe mixture was stirred with heating for 24 hours. The product was washed with methanol, acetone and water in this order and dried under vacuum to give a white solid polymer: m-PhCF₂CF₂Homopolymer (18.7 mg).

Tg：518℃

IR peak: 1210cm^-1，1150cm^-1，640cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), no peak is observed in the vicinity of 310 to 330 ℃. From this, m-PhCF was found₂CF₂Homopolymers do not have melting points. Thus, m-PhCF₂CF₂The homopolymer has good processability.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min by thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

[ examples 2 to 2]m-PhCF₂CF₂Synthesis of homopolymers

In 2. of example 2-1, the same operation as in example 2-1 was carried out except that the product was washed with methanol, acetone, concentrated nitric acid and acetone in this order to obtain m-PhCF₂CF₂A homopolymer.

[ example 3]m-PhCF₂CF₂/p-PhCF₂CF₂Synthesis of copolymer

[ solution 27]

(wherein m3 and m4 are the same or different and are each an integer of 1 or more).

In a glove box, m-BrPhCF₂CF₂Cu (phen) (7.5mg, 0.015mmol) and p-BrPhCF₂CF₂A THF solution (0.3mL) of Cu (phen) (7.5mg, 0.015mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. Washing the product with methanol, acetone and water and vacuum drying to obtainPolymer to white solid: m-PhCF₂CF₂/p-PhCF₂CF₂Copolymer (3.47 mg).

IR peak: 1209cm^-1，1151cm^-1，641cm^-1

[ example 4-1]p-PhOCF₂CF₂Synthesis of homopolymers

1.p-BrPhOCF₂CF₂Synthesis of Cu (phen)

[ solution 28]

In a glove box, p-BrPhOCu (phen) was prepared by mixing 4-bromophenol (103.8mg, 0.60mmol), CuMes (91mg, 0.50mmol), and 1, 10-phenanthroline (phen: 108mg, 0.60mmol) in 10mL of THF solvent and stirring at room temperature for 30 minutes. The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 15 hours. After degassing unreacted TFE, THF was added and insoluble solids were removed by filtration, and the filtrate was concentrated and washed with hexane to give a brown solid complex compound: p-BrPhOCF₂CF₂Cu(phen)(125.19mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：6.70(2H),6.95(4H),7.24(4H),8.57(2H)

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-88.7(br,2F),-111.4(br,2F)

¹³C NMR(400MHz,THF,rt,δ/ppm)：115.07,121.79(Ar),123.43,124.93,127.24,129.9(Ar),135.73,141.95,148.08,149.06.

2.p-PhOCF₂CF₂Synthesis of homopolymers

[ solution 29]

(wherein m5 is an integer of 2 or more).

In the glove box, the glove box is provided with a plurality of grooves,p-BrPhOCF₂CF₂A THF solution (0.3mL) of Cu (phen) (15.47mg, 0.03mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. The product was washed with methanol, acetone and water in this order and dried under vacuum to give a white solid polymer: p-PhOCF₂CF₂Homopolymer (3.27 mg).

IR peak: 1205cm^-1，1146cm^-1，639cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. This suggests p-PhOCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310-330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

[ examples 4 and 2]p-PhOCF₂CF₂Synthesis of homopolymers

In 1. of example 4-1, TFE was pressurized to 3.5atm, heated at 40 ℃ for 24 hours, unreacted TFE was degassed, and then concentrated and ether-washed; and in 2 of example 4-1, the product was washed with methanol, acetone, concentrated nitric acid and acetone in this order. In the same manner as in example 4-1 except for the above-mentioned operation, p-PhOCF was obtained₂CF₂A homopolymer.

EXAMPLE 5 production of film

For the m-PhCF obtained in example 2₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

[ example 6]m-PhOCF₂CF₂Synthesis of homopolymers

1.m-BrPhOCF₂CF₂Synthesis of Cu (phen)

[ solution 30]

In a glove box, m-BrPhOCu (phen) was prepared by mixing 3-bromophenol (103.8mg, 0.60mmol), CuMes (91mg, 0.50mmol), and 1, 10-phenanthroline (phen: 108mg, 0.60mmol) in 10mL of THF solvent and stirring at room temperature for 30 minutes. The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. After degassing the unreacted TFE, concentration and ether washing gave a brown solid complex compound: m-BrPhOCF₂CF₂Cu(phen)(168.95mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：6.54(br,Ar),6.80(br,Ar),7.06(br,phen),7.37(br,phen),7.79(br,phen),8.48(br,phen).

¹⁹F NMR(400MHz,C₆D₆Rt, δ/ppm): -88.7(br,2F), -111.3(br,2F) (ion: -90.0(br,2F), -116.7(br,2F))

2.m-PhOCF₂CF₂Synthesis of homopolymers

[ solution 31]

(wherein m6 is an integer of 2 or more).

In a glove box, m-BrPhOCF₂CF₂A THF solution (0.3mL) of Cu (phen) (15.47mg, 0.03mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: m-PhOCF₂CF₂Homopolymer (5.39 mg).

IR peak: 1211cm^-1，1153cm^-1，643cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. This suggests that m-PhOCF₂CF₂Homopolymers inHas a melting point or undergoes a phase transition at a temperature of about 310 to 330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 7 production of film

For m-PhOCF obtained in example 6₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

[ example 8]p(2-CH₃)C₆H₄OCF₂CF₂Synthesis of homopolymers

1.4-Br,2-CH₃C₆H₄OCF₂CF₂Synthesis of Cu (phen)

[ solution 32]

In a glove box, 4-Br,2-CH was prepared by mixing 4-bromo-2-methylphenol (112.00mg, 0.60mmol), CuMes (91mg, 0.50mmol), and 1, 10-phenanthroline (phen: 108mg, 0.60mmol) in 10mL of THF solvent, and stirring at room temperature for 30 minutes₃C₆H₄OCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. After degassing the unreacted TFE, concentration and ether washing gave a brown solid complex compound: 4-Br,2-CH₃C₆H₄OCF₂CF₂Cu(phen)(208.0mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：6.69-7.35(br,Ar),8.56(br,Ar).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-88.6(br,2F),-111.7(br,2F)

¹³C NMR(400MHz,THF,rt,δ/ppm)：15.71(Me),116.99,123.71,125.30,126.82,128.92,129.16,133.10,134.09,137.55,143.82,149.19,149.88

2.p(2-CH₃)C₆H₄OCF₂CF₂Synthesis of homopolymers

[ solution 33]

(wherein m7 is an integer of 2 or more).

In a glove box, 4-Br,2-CH₃C₆H₄OCF₂CF₂A THF solution (0.3mL) of Cu (phen) (15.89mg, 0.03mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: p (2-CH)₃)C₆H₄OCF₂CF₂Homopolymer (5.08 mg).

IR peak: 1210cm^-1，1150cm^-1，636cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. Thus suggesting p (2-CH)₃)C₆H₄OCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310-330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 9 production of film

For p (2-CH) obtained in example 8₃)C₆H₄OCF₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

[ example 10]p(3-CH₃)C₆H₄OCF₂CF₂Synthesis of homopolymers

1.4-Br,3-CH₃C₆H₄OCF₂CF₂Synthesis of Cu (phen)

[ chemical 34]

In a glove box, 4-Br,3-CH was prepared by mixing 4-bromo-3-methylphenol (112.00, 0.60mmol), CuMes (91mg, 0.50mmol), and 1, 10-phenanthroline (phen: 108mg, 0.60mmol) in 10mL of THF solvent, and stirring at room temperature for 30 minutes₃C₆H₄OCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. After degassing the unreacted TFE, concentration and ether washing gave a brown solid complex compound: 4-Br,3-CH₃C₆H₄OCF₂CF₂Cu(phen)(232.6mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：6.69-7.43(br,Ar),8.56(br,Ar).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-87.8(br,2F),-110.9(br,2F)

¹³C NMR(400MHz,THF,rt,δ/ppm)：21.66,119.21,121.12,124.26,126.79,129.11,132.16,137.56,138.15,143.81,149.97,150.96

2.p(3-CH₃)C₆H₄OCF₂CF₂Synthesis of homopolymers

[ solution 35]

(wherein m8 is an integer of 2 or more).

In a glove box, 4-Br,3-CH₃C₆H₄OCF₂CF₂A THF solution (0.3mL) of Cu (phen) (15.89mg, 0.03mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. Sequentially using methanol, acetone,The product was washed with concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: p (3-CH)₃)C₆H₄OCF₂CF₂Homopolymer (3.50 mg).

IR peak: 1210cm^-1，1150cm^-1，637cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. Thus suggesting p (3-CH)₃)C₆H₄OCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310 to 330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 11 production of film

For p (3-CH) obtained in example 10₃)C₆H₄OCF₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

[ example 12]p(2-NH₂)PhOCF₂CF₂Synthesis of homopolymers

1.4-Br,2-NH₂PhOCF₂CF₂Synthesis of Cu (phen)

[ solution 36]

In a glove box, 4-Br,2-NH was prepared by mixing 4-bromo, 2-aminophenol (56mg, 0.30mmol), CuMes (55mg, 0.30mmol), and 1, 10-phenanthroline (phen: 54mg, 0.3mmol) in 10mL of THF solvent, and stirring at room temperature for 30 minutes₂PhOCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. Degassing unreacted TFE, concentrating, and washing with ether to obtain a brown solid complexCompound (a): 4-Br,2-NH₂PhOCF₂CF₂Cu(phen)(109.8mg)。

¹H NMR(400MHz,THF-d₈,rt,δ/ppm)：4.70,6.37,6.59,6.91,7.95,8.14,8.68,9.01

¹⁹F NMR(400MHz,THF-d₈,rt,δ/ppm)：-92.0(br,2F),-141.4(br,2F)

2.p(2-NH₂)PhOCF₂CF₂Synthesis of homopolymers

[ solution 37]

(wherein m9 is an integer of 2 or more).

In a glove box, 4-Br,2-NH is added₂PhOCF₂CF₂A THF solution (0.3mL) of Cu (phen) (15.9mg, 0.03mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: p (2-NH)₂)PhOCF₂CF₂Homopolymer (13.2 mg).

IR peak: 1205cm^-1，1151cm^-1，640cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. Thus suggesting p (2-NH)₂)PhOCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310-330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 13 production of film

For p (2-NH) obtained in example 12₂)PhOCF₂CF₂Powder of homopolymer, mortarPressure was applied to obtain a transparent film.

[ example 14]p(2-Cl)PhOCF₂CF₂Synthesis of homopolymers

1.4-Br,2-ClPhOCF₂CF₂Synthesis of Cu (phen)

[ solution 38]

In a glove box, 4-Br,2-ClPhOCu (phen) was prepared by mixing 4-bromophenol (103.8mg, 0.60mmol), CuMes (91mg, 0.50mmol), and 1, 10-phenanthroline (phen: 108mg, 0.60mmol) in 10mL of THF solvent, and stirring at room temperature for 30 minutes. The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. After degassing the unreacted TFE, concentration and ether washing gave a brown solid complex compound: 4-Br,2-ClPhOCF₂CF₂Cu(phen)(298.2mg)。

¹H NMR(400MHz,THF-d₈,rt,δ/ppm)：7.26,7.45,7.62,7.95,8.14,8.68,9.04

¹⁹F NMR(400MHz,THF-d₈,rt,δ/ppm)：-92.8(br,2F),-114.9(br,2F)

2.p(2-Cl)PhOCF₂CF₂Synthesis of homopolymers

[ solution 39]

(wherein m10 is an integer of 2 or more).

In a glove box, 4-Br,2-ClPhOCF₂CF₂A THF solution (0.3mL) of Cu (phen) (16.5mg, 0.03mmol) was added to a 50mL autoclave and stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: p (2-Cl) PhOCF₂CF₂Homopolymer (8.7 mg).

IR peak: 1207cm^-1，1151cm^-1，640cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. This suggests that p (2-Cl) PhOCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310-330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 15 production of film

For the p (2-Cl) PhOCF obtained in example 14₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

[ example 16]p-(3-C₅H₁₁)PhOCF₂CF₂Synthesis of homopolymers

1.4-Br,3-C₅H₁₁PhOCF₂CF₂Synthesis of Cu (phen)

[ solution 40]

In a glove box, 4-Br,3-C is added₅H₁₁PhOH (243mg, 1.0mmol), CuMes (182mg, 1.0mmol), and 1, 10-phenanthroline (phen: 180mg, 1.0mmol) were mixed in 10mL of THF solvent, and stirred at room temperature for 30 minutes to prepare 4-Br,3-C₅H₁₁PhOCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. After degassing the unreacted TFE, concentration and ether washing gave a brown solid complex compound: 4-Br,3-C₅H₁₁PhOCF₂CF₂Cu(phen)(310.05mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：6.71(br,Ar),8.86(br,Ar),7.24(br,phen),7.36(br,phen),7.91(br,phen),8.68(br,phen).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-95.6(br,2F),-110.8(br,2F)

2.p-(3-C₅H₁₁)PhOCF₂CF₂Synthesis of homopolymers

[ solution 41]

(wherein m11 is an integer of 2 or more).

In a glove box, 4-Br,3-C₅H₁₁PhOCF₂CF₂A THF solution (0.3mL) of Cu (phen) (17.6mg, 0.03mmol) was added to a 50mL autoclave and stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: p- (3-C)₅H₁₁)PhOCF₂CF₂Homopolymer (2.05 mg).

IR peak: 1210cm^-1，1150cm^-1，636cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. This suggests that p- (3-C)₅H₁₁)PhOCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310 to 330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 17 production of film

For p- (3-C) obtained in example 16₅H₁₁)PhOCF₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

EXAMPLE 18]p-PhCH₂OCF₂CF₂Synthesis of homopolymers

1.p-BrPhCH₂OCF₂CF₂Synthesis of Cu (phen)

[ solution 42]

p-BrPhCH was prepared by mixing 4-bromobenzyl alcohol (111.6mg, 0.60mmol), CuMes (91mg, 0.50mmol), and 1, 10-phenanthroline (phen: 108mg, 0.60mmol) in 10mL of THF solvent, and stirring at room temperature for 30 minutes₂OCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. After degassing the unreacted TFE, concentration and ether washing gave a brown solid complex compound: p-BrPhCH₂OCF₂CF₂Cu(phen)(182.14mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm):4.97(s,CH2),6.71(br,Ar),7.00(br,Ar),7.13(br,phen),7.28(br,phen),7.46(br,phen),8.52(br,phen).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm):-109.7(br,2F),-92.7(br,2F)

2.p-PhCH₂OCF₂CF₂Synthesis of homopolymers

[ solution 43]

(wherein m12 is an integer of 2 or more).

In a glove box, p-BrPhCH₂OCF₂CF₂A THF solution (0.3mL) of Cu (phen) (15.8mg, 0.03mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone and water and dried under vacuum to give a white solid polymer: p-PhCH₂OCF₂CF₂Homopolymer (5.00 mg).

FT-IR(ATR)：ν_CF(cm^-1)：1202,1147.ν_CH(cm^-1)：637.

EXAMPLE 19 production of film

For the p-PhCH obtained in example 18₂OCF₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

[ example 20]

2-(4-BrPh)C₂H₄OCF₂CF₂Synthesis of Cu (phen)

[ solution 44]

In a glove box, 2- (4-BrPh) CH was prepared by mixing 2- (4-bromophenyl) ethylene alcohol (6.0mg, 0.03mmol), CuMes (5.5mg, 0.03mmol), and 1, 10-phenanthroline (phen: 5.4mg, 0.03mmol) in 10mL of THF solvent, and stirring at room temperature for 30 minutes₂CH₂OCu (phen). The complex compound was obtained as a brown solid by transferring the solution to a pressure-resistant vessel and pressurizing TFE to 3.5atm, and heating at 40 ℃ for 24 hours: 2- (4-BrPh) CH₂CH₂OCF₂CF₂Cu (phen) (crude,¹⁹f NMR yield 61%).

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：2.16(4H),6.72(2H),6.74(2H),6.80(2H),7.00(4H),7.07(2H),7.40(2H).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-93.4(br,2F),-110.0(br,2F)

[ example 21]pPhC₃H₆OCF₂CF₂Synthesis of homopolymers

1.2-(4-BrPh)C₃H₆OCF₂CF₂Synthesis of Cu (phen)

[ solution 45]

In a glove box, 4-bromobenzene is put inPhenol (103.8mg, 0.60mmol), CuMes (91mg, 0.50mmol), and 1, 10-phenanthroline (phen: 108mg, 0.60mmol) were mixed in 10mL of THF solvent, and stirred at room temperature for 30 minutes to prepare 2- (4-BrPh) C₃H₆OCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. After degassing the unreacted TFE, concentration and ether washing gave a brown solid complex compound: 2- (4-BrPh) C₃H₆OCF₂CF₂Cu(phen)(125.19mg)。

¹H NMR(400MHz,THF,rt,δ/ppm)：1.88(2H),2.65(2H),3.88(2H),7.06(2H),7.29(2H),7.91(2H),8.70(2H),8.62(2H),9.03(2H).

¹⁹F NMR(400MHz,THF,rt,δ/ppm)：-95.2(br,2F),-111.7(br,2F)

2.pPhC₃H₆OCF₂CF₂Synthesis of homopolymers

[ solution 46]

(wherein m13 is an integer of 2 or more).

In a glove box, 2- (4-BrPh) C₃H₆OCF₂CF₂A THF solution (0.3mL) of Cu (phen) (16.7mg, 0.03mmol) was added to a 50mL autoclave and stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: pPhC₃H₆OCF₂CF₂Homopolymer (6.81 mg).

IR peak: 1198cm^-1，1144cm^-1，636cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. This suggested that pPhC₃H₆OCF₂CF₂The homopolymer has a melting point or a generating phase at a temperature of about 310 to 330 DEG CAnd (6) changing.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 22 production of film

For pPhC obtained in example 21₃H₆OCF₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

[ example 23]m(3-Br)PhOCF₂CF₂Synthesis of homopolymers

1.Br₂PhOCF₂CF₂Synthesis of Cu (phen)

[ solution 47]

In a glove box, Br was prepared by mixing 3, 5-dibromophenol (150.0mg, 0.60mmol), CuMes (91mg, 0.50mmol), and 1, 10-phenanthroline (phen: 108mg, 0.60mmol) in 10mL of THF solvent, and stirring at room temperature for 30 minutes₂PhOCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. After degassing the unreacted TFE, concentration and ether washing gave a brown solid complex compound: br₂PhOCF₂CF₂Cu(phen)(221.22mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：6.71(br,Ar),6.95(br,Ar),7.24(br,phen),7.36(br,phen),7.91(br,phen),8.68(br,phen).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-89.5(br,2F),-116.3(br,2F)

2. Having m (3-Br) PhOCF₂CF₂Synthesis of polymers of the units

[ solution 48]

(wherein m14 is an integer of 2 or more).

In a glove box, by mixing p-BrPhOCF₂CF₂A THF solution (0.3mL) of Cu (phen) (17.8mg, 0.03mmol) was added to a 50mL autoclave and stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: m (3-Br) PhOCF₂CF₂Homopolymer (2.47 mg).

IR peak: 1210cm^-1，1150cm^-1，636cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. This suggests that m (3-Br) PhOCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310-330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 24 production of film

For the PhOCF with m (3-Br) obtained in example 23₂CF₂The powder of the polymer of the unit was pressed with a mortar to obtain a transparent film.

[ example 25]

p-PhOCF₂CF₂Synthesis of homopolymers

[ solution 49]

(in the formula, m5 has the same meaning as described above).

In a glove box, 4-BrPhOK (21.1mg, 0.10mmol), CuBr (14.3mg, 0.10mmol), and 1, 10-phenanthroline (phen: 18.0mg, 0.10mmol) were mixed in 100uL of DMF solvent inStirring at room temperature for 30 minutes produced 4-BrPhOCu (phen). The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 2.0atm and heated at 100 ℃ for 24 hours. After degassing the unreacted TFE, the product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: p-PhOCF₂CF₂Homopolymer (19.2 mg).

IR peak: 1205cm^-1，1146cm^-1，639cm^-1

When the temperature is measured at a temperature range of 100 to 430 ℃ at a temperature rise rate of 10 ℃/min by using a differential scanning calorimeter (product name EXstar6000, manufactured by Seiko Instruments Inc.), a peak is observed in the vicinity of 310 to 330 ℃. This suggests p-PhOCF₂CF₂The homopolymer has a melting point or a phase transition at a temperature of about 310-330 ℃.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.

EXAMPLE 26 production of film

For the p-PhOCF obtained in example 25₂CF₂Powder of homopolymer, and pressure was applied using a mortar to obtain a transparent film.

[ example 27]5- (3-Bromopyridinyl) OCF₂CF₂Synthesis of Cu (phen) homopolymer

1.5- (3-Bromopyridinyl) OCF₂CF₂Synthesis of Cu (phen)

[ solution 50]

In a glove box, 5- (3-bromopyridyl) ocu (phen) was prepared by mixing 3-bromo, 5-hydroxypyridine (174mg, 1.0mmol), CuMes (182mg, 1.0mmol), and 1, 10-phenanthroline (phen: 180mg, 1.0mmol) in 10mL of THF solvent and stirring at room temperature for 30 minutes. The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 40 ℃ for 24 hours. Make the reaction not reactTFE degassing, concentration and ether washing to give the complex compound as a brown solid: 3-Br,5- (3-bromopyridyl) OCF₂CF₂Cu(phen)(180.39mg)。

¹H NMR(400MHz,THF,rt,δ/ppm)：7.80(1H),7.97(2H),8.12(2H),8.41(1H),8.60(1H),8.67(2H),9.08(2H).

¹⁹F NMR (400MHz, THF, rt,. delta./ppm): neutral form-92.57 (br,2F), -119.73(br,2F) ion form-89.74 (br,2F), -115.91(br,2F)

2.5- (3-Bromopyridinyl) OCF₂CF₂Synthesis of Cu (phen) homopolymer

[ solution 51]

(wherein m15 is an integer of 2 or more).

In a glove box, 5- (3-bromopyridyl) OCF₂CF₂A THF solution (0.3mL) of Cu (phen) (15.5mg, 0.03mmol) was added to a 50mL autoclave, and the mixture was stirred at 100 ℃ for 24 hours. The product was washed sequentially with methanol, acetone, concentrated nitric acid and acetone and dried under vacuum to give a white solid polymer: p-PhOCF₂CF₂Homopolymer (3.16 mg).

IR peak: 1209cm^-1，1151cm^-1，642cm^-1

[ example 28]

Imidazolyl CF₂CF₂Synthesis of Cu (phen) homopolymer

[ solution 52]

(wherein m16 is an integer of 2 or more).

In a glove box, the imidazolyl Cu (phen) was prepared by mixing 4-bromoimidazole (44.0mg, 0.30mmol), CuMes (55mg, 0.30mmol), and 1, 10-phenanthroline (phen: 100mg, 0.30mmol) in 5mL of DMF solvent and stirring at room temperature for 30 minutes.The solution was transferred to a pressure-resistant vessel and TFE was pressurized to 3.5atm and heated at 80 ℃ for 24 hours. After degassing unreacted TFE, concentration was performed, and it was again dissolved in DMF and filtered. And then washed with methanol, acetone and dried under vacuum to obtain a white solid polymer: imidazolyl CF₂CF₂Homopolymer (75.7 mg).

IR peak: 1209cm^-1，1153cm^-1，642cm^-1

[ example 29]p-C₆H₄CF₂CF₂C₆H₄Synthesis of homopolymers

1.p-BrC₆H₄CF₂CF₂C₆H₄Synthesis of Br

[ Hua 53]

In a glove box, p-BrC is put in₆H₄CF₂CF₂Cu (phen) (249mg, 0.50mmol), 1-bromo-4-iodobenzene (141mg, 0.50mmol) were mixed in 10mL of THF solvent and stirred at 60 ℃ for 3 hours. After the reaction was complete, concentration and purification by recrystallization gave a white solid: p-BrC₆H₄CF₂CF₂C₆H₄Br(225mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：7.58(d,4H),7.33(d,4H)

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-114.5(s,4F)

2.p-C₆H₄CF₂CF₂C₆H₄Synthesis of homopolymers

[ solution 54]

(wherein m17 is an integer of 2 or more).

In glove boxp-BrC₆H₄CF₂CF₂C₆H₄Br(12.3mg，0.03mmol)、Ni(cod)₂A DMF solution (0.03mL) (9.9mg,0.036mmol), bpy (5.64mg, 0.036mmol) and COD (3.7. mu.L, 0.03mmol) was added to a 50mL autoclave and stirred at 60 ℃ for 16 hours. The product was washed sequentially with methanol, acetone and water and dried under vacuum to give a white solid polymer: p-PhCF₂CF₂Homopolymer (4.99 mg).

Example 30]Having p-C₆H₄OCF₂CF₂C₆H₄Synthesis of polymers of the units

1.p-BrC₆H₄OCF₂CF₂C₆H₄Synthesis of Br

[ solution 55]

In a glove box, p-BrPhOCF₂CF₂Cu (phen) (258mg, 0.50mmol), 1-bromo-4-iodobenzene (141mg, 0.50mmol) were mixed in 10mL of THF solvent and stirred at 60 ℃ for 3 hours. After the reaction was completed, the reaction mixture was concentrated and purified by silica gel column chromatography to obtain an oily transparent liquid: p-BrC₆H₄OCF₂CF₂C₆H₄Br(172.48mg)。

¹H NMR(400MHz,C₆D₆,rt,δ/ppm)：7.64(d,2H),7.53(d,2H),7.45(d,2H),7.22(d,2H).

¹⁹F NMR(400MHz,C₆D₆,rt,δ/ppm)：-117.3(t,2F),-90.5(t,2F)

2.p-C₆H₄OCF₂CF₂C₆H₄Synthesis of homopolymers

[ solution 56]

(wherein m18 and m19 are the same or different and are each an integer of 1 or more).

In a glove box, p-BrC is put in₆H₄OCF₂CF₂C₆H₄Br(12.8mg，0.03mmol)、Ni(cod)₂A DMF solution (0.03mL) (9.9mg,0.036mmol), bpy (5.64mg, 0.036mmol) and COD (3.7. mu.L, 0.03mmol) was added to a 50mL autoclave and stirred at 60 ℃ for 16 hours. The product was washed sequentially with methanol, acetone and water and dried under vacuum to give a white solid polymer: p-PhOCF₂CF₂Homopolymer (5.74 mg).

FT-IR(ATR)：ν_CF(cm^-1)：1207,1151.ν_CH(cm^-1)：638.

When the measurement was carried out at a temperature range of 100 ℃ to 700 ℃ at a temperature rise rate of 10 ℃/min using thermogravimetry (manufactured by Hitachi High-Tech Sci. Corp., product name STA7200RV), a weight loss of 5% was observed in the vicinity of 520 ℃.