WO2024247807A1 - Fluoropolyether group–containing polymer and production method for same - Google Patents

Abstract

A fluoropolyether group–containing polymer that is represented by general formula (1) (in which Rf is a monovalent or divalent fluoropolyether group, Z is independently a trivalent or tetravalent organic group, X is independently a single bond or a divalent organic group, α is 1 or 2, and β is 2 or 3, provided that the hydroxyl groups in the formula are secondary hydroxyl groups) and has a number average molecular weight of 1,000–50,000 in terms of polystyrene has both secondary hydroxyl groups (hydroxyl groups bonded to a secondary carbon atom), which are more reactive than tertiary hydroxyl groups (hydroxyl groups bonded to a tertiary carbon atom), and 2 or 3 (2–6 per molecule) olefin portions (terminal olefins indicated by CH₂=CH-), which are easily converted to a functional group, at the end of the molecular chain thereof and can therefore be modified to have a variety of terminal groups (functional groups).

Description

Fluoropolyether group-containing polymer and method for producing same

The present invention relates to a fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluoropolyether group in the molecule), and more particularly to a novel fluoropolyether group-containing polymer having at the molecular chain end two or three (2 to 6 in the molecule) olefin moieties (i.e., terminal olefins represented by CH ₂ ═CH-) that can be easily converted to functional groups, and a secondary hydroxyl group (i.e., a hydroxyl group bonded to a secondary carbon atom) that is more reactive than a tertiary hydroxyl group (i.e., a hydroxyl group bonded to a tertiary carbon atom), and a method for producing the same.

In recent years, the use of touch panels for screens, including mobile phone displays, has accelerated. However, touch panels have exposed screens and are often in direct contact with fingers or cheeks, which makes them susceptible to dirt such as sebum. As a result, there is an increasing demand every year for technology that makes it difficult for fingerprints to appear on the surface of displays to improve appearance and visibility, and technology that makes it easy to remove dirt, and there is a need to develop materials that can meet these demands. In particular, since the surface of touch panel displays is prone to fingerprints, there is a demand for the provision of a water- and oil-repellent layer. However, while conventional water- and oil-repellent layers are highly water- and oil-repellent and easy to wipe off, there is a problem in that their anti-fouling performance deteriorates during use.

Generally, fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, and stain resistance. Taking advantage of these properties, they are widely used industrially as water and oil repellent and stain resistant agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, and more. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and although they can be applied to the surface of a substrate, it has been difficult to make the coating adhere to it.

On the other hand, silane coupling agents are well known as agents that bond organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for the surfaces of various substrates. Silane coupling agents have an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. The coating becomes a strong and durable coating as the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

Therefore, a composition has been disclosed that uses a fluoropolyether group-containing polymer in which a hydrolyzable silyl group has been introduced into a fluoropolyether group-containing compound, and that can form a coating on the substrate surface that is easily adhered to the substrate surface and has water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, etc. (Patent Document 1: Japanese Patent No. 6451279).

の３級アルコールを用いている。該中間体は反応性オレフィン部位と水酸基を併せ持つポリマーであるが、水酸基が３級である（即ち、３級の炭素原子に結合した水酸基である）ため、反応性に乏しく、水酸基を有効利用できていなかった。 In Patent Document 1, as an intermediate for a fluoropolyether group-containing polymer, for example, a compound represented by the following formula (1) is described.

The intermediate is a polymer having both a reactive olefin moiety and a hydroxyl group, but since the hydroxyl group is tertiary (i.e., a hydroxyl group bonded to a tertiary carbon atom), it has poor reactivity and the hydroxyl group cannot be effectively utilized.

Patent No. 6451279

The present invention has been made in consideration of the above circumstances, and aims to provide a novel fluoropolyether group-containing polymer that has two or three (2 to 6 in the molecule) olefin moieties at the ends of the molecular chain that can be easily converted to functional groups (i.e., terminal olefins represented by _CH2 =CH-), and secondary hydroxyl groups (i.e., hydroxyl groups bonded to secondary carbon atoms) that are more reactive than tertiary hydroxyl groups (i.e., hydroxyl groups bonded to tertiary carbon atoms), and a method for producing the same.

（式中、Ｒｆは１価又は２価のフルオロポリエーテル基であり、Ｙは脱離可能な一価の基であり、αは１又は２である。）
で表されるカルボニル基を末端に有するフルオロポリエーテル基含有ポリマーに、オレフィン部位を２～６個有し、かつβ水素を有する有機金属試薬を作用させることで、下記一般式（１）

（式中、Ｒｆは上記と同じであり、Ｚは独立に３価又は４価の有機基であり、Ｘは独立に単結合又は２価の有機基であり、αは１又は２であり、βは２又は３である。但し、式中の水酸基は２級水酸基である。）
で表され、ポリスチレン換算での数平均分子量が１，０００～５０，０００であるフルオロポリエーテル基含有ポリマーを合成できることを見出し、本発明をなすに至った。 As a result of intensive research to achieve the above object, the present inventors have discovered a fluoropolyether group-containing polymer having two or three (2 to 6 in a molecule) olefin moieties at the molecular chain terminals that can be easily converted to functional groups (i.e., terminal olefins represented by CH ₂ ═CH—) and secondary hydroxyl groups (i.e., hydroxyl groups bonded to secondary carbon atoms) that are more reactive than tertiary hydroxyl groups (i.e., hydroxyl groups bonded to tertiary carbon atoms), represented by the following general formula (4):

(In the formula, Rf is a monovalent or divalent fluoropolyether group, Y is a removable monovalent group, and α is 1 or 2.)
The fluoropolyether group-containing polymer having a terminal carbonyl group represented by the following general formula (1) is reacted with an organometallic reagent having 2 to 6 olefin moieties and β-hydrogen to obtain a fluoropolyether group-containing polymer having a terminal carbonyl group represented by the following general formula (1):

(In the formula, Rf is the same as above, Z is independently a trivalent or tetravalent organic group, X is independently a single bond or a divalent organic group, α is 1 or 2, and β is 2 or 3. However, the hydroxyl group in the formula is a secondary hydroxyl group.)
The present invention has been made based on the discovery that it is possible to synthesize a fluoropolyether group-containing polymer having a number average molecular weight of 1,000 to 50,000 in terms of polystyrene.

（式中、Ｒｆは１価又は２価のフルオロポリエーテル基であり、Ｚは独立に３価又は４価の有機基であり、Ｘは独立に単結合又は２価の有機基であり、αは１又は２であり、βは２又は３である。但し、式中の水酸基は２級水酸基である。）
で表され、ポリスチレン換算での数平均分子量が１，０００～５０，０００であるフルオロポリエーテル基含有ポリマー。
［２］
　前記式（１）のαが１であり、Ｒｆが下記一般式（２）で表される１価のフルオロポリエーテル基である［１］に記載のフルオロポリエーテル基含有ポリマー。

（式中、Ａはフッ素原子、水素原子、又は末端が－ＣＦ₃基、－ＣＦ₂Ｈ基もしくは－ＣＨ₂Ｆ基である１価のフッ素含有基であり、ｐ、ｑ、ｒ、ｓはそれぞれ０～２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３～２００であり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは単位毎に独立して１～３の整数であり、該単位は直鎖状であっても分岐状であってもよい。）
［３］
　前記式（１）のαが２であり、Ｒｆが下記一般式（３）で表される２価のフルオロポリエーテル基である［１］に記載のフルオロポリエーテル基含有ポリマー。

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０～２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３～２００であり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは単位毎に独立して１～３の整数であり、該単位は直鎖状であっても分岐状であってもよい。）
［４］
　前記式（１）において、Ｘが、単結合、炭素数２～１２のアルキレン基、又は炭素数６～８のアリーレン基を含む炭素数２～１０のアルキレン基である［１］～［３］のいずれかに記載のフルオロポリエーテル基含有ポリマー。
［５］
　前記式（１）において、Ｚが、炭素数２～１２の３価又は４価の直鎖状脂肪族飽和炭化水素基、又は炭素数８～１６の芳香環を含む直鎖状の３価又は４価の脂肪族飽和炭化水素基である［１］～［４］のいずれかに記載のフルオロポリエーテル基含有ポリマー。
［６］
　下記一般式（４）

（式中、Ｒｆは１価又は２価のフルオロポリエーテル基であり、Ｙは脱離可能な一価の基であり、αは１又は２である。）
で表されるフルオロポリエーテル基含有ポリマーと、オレフィン部位を２～６個有し、かつβ水素を有する有機金属試薬とを反応させる工程を含む［１］～［５］のいずれかに記載のフルオロポリエーテル基含有ポリマーの製造方法。 Accordingly, the present invention provides the following fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluoropolyether group in the molecule) and a method for producing the same.
[1]
The following general formula (1)

(In the formula, Rf is a monovalent or divalent fluoropolyether group, Z is independently a trivalent or tetravalent organic group, X is independently a single bond or a divalent organic group, α is 1 or 2, and β is 2 or 3. However, the hydroxyl group in the formula is a secondary hydroxyl group.)
and having a number average molecular weight in terms of polystyrene of 1,000 to 50,000.
[2]
The fluoropolyether group-containing polymer according to [1], wherein α in the formula (1) is 1 and Rf is a monovalent fluoropolyether group represented by the following general formula (2):

(In the formula, A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a _-CF3 group, a _-CF2H group, or a _-CH2F group; p, q, r, and s are each an integer of 0 to 200, and p+q+r+s=3 to 200; each repeating unit may be linear or branched, and each repeating unit may be bonded randomly; and d is independently an integer of 1 to 3 for each unit, and the unit may be linear or branched.)
[3]
The fluoropolyether group-containing polymer according to [1], wherein α in the formula (1) is 2, and Rf is a divalent fluoropolyether group represented by the following general formula (3):

(In the formula, p, q, r, and s each represent an integer of 0 to 200, and p+q+r+s=3 to 200; each repeating unit may be linear or branched; each repeating unit may be randomly bonded to another repeating unit; and d is independently an integer of 1 to 3 for each unit, and each unit may be linear or branched.)
[4]
In the formula (1), X is a single bond, an alkylene group having 2 to 12 carbon atoms, or an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms [1] to [3]. The fluoropolyether group-containing polymer according to any one of the above.
[5]
In the formula (1), Z is a trivalent or tetravalent linear aliphatic saturated hydrocarbon group having 2 to 12 carbon atoms, or a linear trivalent or tetravalent aliphatic saturated hydrocarbon group containing an aromatic ring having 8 to 16 carbon atoms. [1] to [4] The fluoropolyether group-containing polymer according to any one of the above.
[6]
The following general formula (4)

(In the formula, Rf is a monovalent or divalent fluoropolyether group, Y is a removable monovalent group, and α is 1 or 2.)
The method for producing a fluoropolyether group-containing polymer according to any one of [1] to [5], comprising reacting a fluoropolyether group-containing polymer represented by the formula: with an organometallic reagent having 2 to 6 olefin moieties and β-hydrogen.

The fluoropolyether group-containing polymer of the present invention has two or three (2 to 6 in the molecule) olefin moieties (terminal olefins represented by CH ₂ ═CH-) at the molecular chain end that are easily converted to functional groups, and secondary hydroxyl groups (i.e., hydroxyl groups bonded to secondary carbon atoms) that are more reactive than tertiary hydroxyl groups (i.e., hydroxyl groups bonded to tertiary carbon atoms), and thus can be modified to various terminal groups (functional groups), and compounds useful for forming coatings with excellent water and oil repellency and abrasion resistance can be easily obtained. In addition, the fluoropolyether group-containing polymer of the present invention can be a polymer excellent in various durability properties such as chemical resistance and weather resistance, because the linking structure between the fluoropolyether group of the main chain and the olefin moiety at the molecular chain end (excluding the secondary hydroxyl group moiety; HO-CH=) is preferably a trivalent or tetravalent aliphatic saturated hydrocarbon group that may contain an aromatic ring such as a benzene ring.

（式中、Ｒｆは１価又は２価のフルオロポリエーテル基であり、Ｚは独立に３価又は４価の有機基であり、Ｘは独立に単結合又は２価の有機基であり、αは１又は２であり、βは２又は３である。但し、式中の水酸基は２級水酸基である。） The fluoropolyether group-containing polymer of the present invention is represented by the following general formula (1) and has a number average molecular weight of 1,000 to 50,000 in terms of polystyrene.

(In the formula, Rf is a monovalent or divalent fluoropolyether group, Z is independently a trivalent or tetravalent organic group, X is independently a single bond or a divalent organic group, α is 1 or 2, and β is 2 or 3. However, the hydroxyl group in the formula is a secondary hydroxyl group.)

The number average molecular weight of the fluoropolyether group-containing polymer represented by the above formula (1) is 1,000 to 50,000, and preferably in the range of 1,500 to 10,000. If the number average molecular weight is less than 1,000, the water and oil repellency and stain resistance, which are characteristics of the fluoropolyether group, may not be fully exhibited, and if it exceeds 50,000, the concentration of the terminal functional groups may become too small, resulting in reduced reactivity and adhesion with the substrate. The number average molecular weight referred to in this invention refers to the number average molecular weight measured by gel permeation chromatography (GPC) under the following conditions, using polystyrene as the standard substance.

[Measurement conditions]
Developing solvent: Hydrochlorofluorocarbon (HCFC)-225
Flow rate: 1mL/min.
Detector: Evaporative light scattering detector Column: Tosoh Corporation TSKgel Multipore HXL-M
7.8 mmφ×30 cm 2 columns used Column temperature: 35°C
Sample injection volume: 20 μL (HCFC-225 solution with a concentration of 0.3% by mass)

In the above formula (1), Rf is a monovalent or divalent fluoropolyether group. When α is 1, it is a monovalent fluoropolyether group (fluorooxyalkyl group), and when α is 2, it is a divalent fluoropolyether group (fluorooxyalkylene group).

（式中、Ａはフッ素原子、水素原子、又は末端が－ＣＦ₃基、－ＣＦ₂Ｈ基もしくは－ＣＨ₂Ｆ基である１価のフッ素含有基であり、ｐ、ｑ、ｒ、ｓはそれぞれ０～２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３～２００であり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは単位毎に独立して１～３の整数であり、該単位は直鎖状であっても分岐状であってもよい。） In the above formula (1), when α is 1, the monovalent fluoropolyether group represented by Rf is preferably a monovalent fluoropolyether group represented by the following general formula (2).

(In the formula, A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a _-CF3 group, a _-CF2H group, or a _-CH2F group; p, q, r, and s are each an integer of 0 to 200, and p+q+r+s=3 to 200; each repeating unit may be linear or branched, and each repeating unit may be bonded randomly; and d is independently an integer of 1 to 3 for each unit, and the unit may be linear or branched.)

In the above formula ( ₂ ), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal _-CF3 group, _-CF2H group, or _-CH2F group. Examples of the monovalent fluorine-containing group having _a terminal _-CF3 group, _-CF2H group, or -CH2F group include _{CF3- , CF3CF2- , CF3CF2CF2- , CF3CF2CF2CF2- , CF2HCF2CF2-} , _{CH2FCF2CF2- ,} and the like, and is preferably a fluorine _atom , a _{-CF3 group ,} a _{-CF2CF3 group} , or _{a -CF2CF2CF3 group} , and more _preferably a fluorine atom.

In the above formula (2), p, q, r, and s are each an integer of 0 to 200, preferably p is an integer of 0 to 100, q is an integer of 0 to 100, r is an integer of 0 to 100, and s is an integer of 0 to 100, and p+q+r+s=3 to 200, preferably 10 to 100, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other. If p+q+r+s is smaller than the upper limit, adhesion and curability are good, and if it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable.
d is independently an integer of 1 to 3, preferably 1 or 2, for each unit, and the unit may be linear or branched.

（式中、ｐ’、ｑ’、ｒ’、ｓ’はそれぞれ１以上の整数であり、各式におけるｐ’、ｑ’、ｒ’、ｓ’の合計は３～２００、好ましくは１０～１００である。また、ｐ’、ｑ’、ｒ’、ｓ’が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Specific examples of such monovalent fluoropolyether groups include the following.

(In the formulae, p', q', r', and s' are each an integer of 1 or more, and the total of p', q', r', and s' in each formula is 3 to 200, preferably 10 to 100. In addition, each repeating unit shown in parentheses with p', q', r', and s' may be bonded randomly.)

（式中、ｐ、ｑ、ｒ、ｓ、ｐ＋ｑ＋ｒ＋ｓは上記と同じであり、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｄは上記と同じであり、該単位は直鎖状であっても分岐状であってもよい。） In the above formula (1), when α is 2, the divalent fluoropolyether group represented by Rf is preferably a divalent fluoropolyether group represented by the following general formula (3).

(In the formula, p, q, r, s, and p+q+r+s are the same as above, each repeating unit may be linear or branched, each repeating unit may be randomly bonded to another repeating unit, d is the same as above, and the unit may be linear or branched.)

（式中、ｐ’、ｑ’、ｒ’、ｓ’、ｑ１’、ｒ１’、ｒ２’はそれぞれ１以上の整数であり、各式におけるｐ’、ｑ’、ｒ’、ｓ’、ｑ１’、ｒ１’、ｒ２’の合計は３～２００、好ましくは１０～１００である。また、ｐ’、ｑ’、ｒ’、ｓ’が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Specific examples of such divalent fluoropolyether groups include the following.

(In the formulae, p', q', r', s', q1', r1', and r2' are each an integer of 1 or more, and the total of p', q', r', s', q1', r1', and r2' in each formula is 3 to 200, preferably 10 to 100. In addition, each repeating unit shown in parentheses with p', q', r', and s' may be bonded randomly.)

In the above formula (1), Z is independently a trivalent or tetravalent organic group (particularly a hydrocarbon group), preferably a trivalent or tetravalent linear aliphatic saturated hydrocarbon group having 2 to 12 carbon atoms, or a linear trivalent or tetravalent aliphatic saturated hydrocarbon group containing an aromatic ring having 8 to 16 carbon atoms (particularly a divalent to tetravalent benzene ring), and more preferably a trivalent linear aliphatic saturated hydrocarbon group having 2 or 3 carbon atoms.

Examples of Z include the following groups: In the following structure, it is preferable that the bond on the left side is bonded to a carbon atom, and the other bond is bonded to X.

In the above formula (1), X is independently a single bond or a divalent organic group (particularly a hydrocarbon group), preferably a single bond, an alkylene group having 1 to 12 carbon atoms, or an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (e.g., an alkylene/arylene group having 8 to 16 carbon atoms), and more preferably a methylene group, an ethylene group, or a propylene group.

Examples of such X include the following groups: In the following structure, it is preferable that the left bond is bonded to Z, and the right bond is bonded to a carbon atom.

（式中、ｐ’、ｑ’、ｒ’、ｓ’、ｒ１’、ｒ２’はそれぞれ１以上の整数であり、各式におけるｐ’、ｑ’、ｒ’、ｓ’の合計は３～２００、好ましくは１０～１００であり、ｒ１’、ｒ２’の合計は２～１９９、好ましくは９～９９である。また、ｐ’、ｑ’、ｒ’、ｓ’が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Examples of the fluoropolyether group-containing polymer represented by formula (1) and having a number average molecular weight of 1,000 to 50,000 in terms of polystyrene include those shown below.

(In the formulae, p', q', r', s', r1', and r2' each represent an integer of 1 or more, the sum of p', q', r', and s' in each formula is 3 to 200, preferably 10 to 100, and the sum of r1' and r2' is 2 to 199, preferably 9 to 99. In addition, each repeating unit shown in parentheses with p', q', r', and s' may be bonded randomly.)

（式中、Ｒｆ、αは上記と同じであり、Ｙは脱離可能な一価の基である。）
で表されるフルオロポリエーテル基含有ポリマーと、オレフィン部位を２～６個、好ましくは２個又は３個有し、かつβ水素（即ち、金属原子に対してβ位に位置する炭素原子に結合した水素原子）を有する有機金属試薬とを反応させる工程を含むことが好ましい。 The method for producing the fluoropolyether group-containing polymer represented by the above formula (1) includes the steps of:

(In the formula, Rf and α are the same as above, and Y is a removable monovalent group.)
It is preferable that the method includes a step of reacting a fluoropolyether group-containing polymer represented by the formula (I) with an organometallic reagent having 2 to 6, preferably 2 or 3, olefin moieties and having β hydrogen (i.e., a hydrogen atom bonded to a carbon atom located at the β position relative to a metal atom).

In the above formula (4), Y is a removable monovalent group, such as a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a thiol group, an alkylthio group, or an acyloxy group.

Examples of such Y include the following groups.

（式中、ｐ’、ｑ’、ｒ’、ｓ’、ｒ１’、ｒ２’はそれぞれ１以上の整数であり、各式におけるｐ’、ｑ’、ｒ’、ｓ’の合計は３～２００、好ましくは１０～１００であり、ｒ１’、ｒ２’の合計は２～１９９、好ましくは９～９９である。また、ｐ’、ｑ’、ｒ’、ｓ’が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Examples of the fluoropolyether group-containing polymer represented by the above formula (4) include those shown below.

(In the formulae, p', q', r', s', r1', and r2' each represent an integer of 1 or more, the sum of p', q', r', and s' in each formula is 3 to 200, preferably 10 to 100, and the sum of r1' and r2' is 2 to 199, preferably 9 to 99. In addition, each repeating unit shown in parentheses with p', q', r', and s' may be bonded randomly.)

Examples of organometallic reagents having 2 to 6, preferably 2 or 3, olefin moieties and β-hydrogen (a hydrogen atom bonded to a carbon atom located in the β-position relative to a metal atom) include organolithium reagents, Grignard reagents, organozinc reagents, organoboron reagents, and organotin reagents, and it is particularly preferable to use Grignard reagents and organozinc reagents from the viewpoint of ease of handling.

As the organometallic reagent, for example, the following can be used:

The amount of the organometallic reagent having 2 to 6 olefin moieties and β-hydrogen is preferably 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and even more preferably 2.8 to 3.2 equivalents per equivalent of the reactive terminal group of the fluoropolyether group-containing polymer represented by the above formula (4).

In addition, a solvent can be used in the method for producing the fluoropolyether group-containing polymer represented by the above formula (1). The solvent used at this time is not particularly limited, but it is preferable to use a fluorine-based solvent because the fluoropolyether group-containing polymer represented by the formula (1) and the formula (4) is a fluorine compound. Examples of fluorine-based solvents include 1,3-bistrifluoromethylbenzene, trifluoromethylbenzene, perfluoro-based solvents sold by AGC (ASAHIKLIN AC2000, ASAHIKLIN AC6000), HFE-based solvents sold by 3M (NOVEC7100: _C4F9OCH3 , NOVEC7200: _C4F9OC2H5 , NOVEC7300: _C2F5 -CF( _{OCH3 ) -CF} ( _CF3 ) _{2 ,} etc.), and perfluoro-based solvents also sold by 3M (PF5080, _PF5070 , PF5060, etc.). The fluorine- _based solvents may be used _alone or in combination.

In the method for producing the fluoropolyether group-containing polymer represented by the above formula (1), an organic solvent can be used in addition to a fluorine-based solvent. As the organic solvent, an ether-based solvent such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or dioxane can be used. These organic solvents may be used alone or mixed with a fluorine-based solvent.

The amount of the solvent used is 10 to 600 parts by mass, preferably 50 to 400 parts by mass, and more preferably 150 to 300 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer represented by the above formula (4).

In the method for producing the fluoropolyether group-containing polymer represented by the above formula (1), a catalyst may be added in addition to the above components.

In the method for producing the fluoropolyether group-containing polymer represented by formula (1) above, the reaction conditions for the fluoropolyether group-containing polymer represented by formula (4) and an organometallic reagent having 2 to 6 olefin moieties and β-hydrogen are preferably 0 to 80°C, preferably 50 to 70°C, and aging for 1 to 6 hours, preferably 3 to 6 hours.

Then, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by a separation operation. The resulting fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain the fluoropolyether group-containing polymer represented by the above formula (1).

The fluoropolyether group-containing polymer of the present invention has a monovalent fluoropolyether group or a divalent fluoropolyether group (i.e., a monovalent or divalent fluoropolyether group), and has 2 to 6 olefin moieties (terminal olefins with a vinyl structure represented by CH ₂ ═CH-) that can be easily converted to functional groups, and one or two secondary hydroxyl groups (i.e., hydroxyl groups bonded to secondary carbon atoms) that are more reactive than tertiary hydroxyl groups (i.e., hydroxyl groups bonded to tertiary carbon atoms), and can be modified to various terminal groups (functional groups).
Examples of the terminal group (functional group) to which the olefin moiety is modified include hydrolyzable silyl groups such as halogenated silyl groups such as alkoxysilyl groups and chlorosilyl groups, aminosilyl groups, (poly)silazane structures, hydroxyl groups, amino groups, thiol groups, epoxy groups, carbonyl groups, etc. Examples of the terminal group (functional group) to which the secondary hydroxyl group is modified include ester groups, ether groups, siloxy groups, urethane groups, etc.

The fluoropolyether group-containing polymer of the present invention can be suitably used for applications such as surface treatment agents, surface modifiers, hard coat additives, and elastomer materials.

The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples. In the following examples, the number average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC). Room temperature is 23°C.

で表されるグリニャール試薬９４ｍｌ（０．８Ｍ　ＴＨＦ溶液：７．５×１０^-2ｍｏｌ）を入れ、撹拌した。続いて、下記式（Ｂ）

で表される化合物１００ｇ（２．５×１０^-2ｍｏｌ）、アサヒクリンＡＣ６０００　２００ｇ、ＰＦ５０６０　１００ｇの混合液を反応容器内に滴下した後、５０℃で６時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。分液操作により、下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｃ）

で表されるフルオロポリエーテル基含有ポリマー９７ｇ（数平均分子量約３，９００）を得た。 [Example 1]
In a reaction vessel, the following formula (A)

94 ml (0.8 M THF solution: 7.5 × 10 ^-2 mol) of a Grignard reagent represented by the following formula (B) was added and stirred.

A mixture of 100 g (2.5×10 ⁻² mol) of a compound represented by the formula (I), 200 g of Asahiklin AC6000, and 100 g of PF5060 was dropped into a reaction vessel, and then heated at 50° C. for 6 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation, and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the formula (C):

Thus, 97 g of a fluoropolyether group-containing polymer represented by the formula (number average molecular weight: about 3,900) was obtained.

で表されるグリニャール試薬２１ｍｌ（０．５Ｍ　ＴＨＦ溶液：１．１×１０^-2ｍｏｌ）を入れ、撹拌した。続いて、下記式（Ｅ）

で表される化合物２０ｇ（３．５×１０^-3ｍｏｌ）、アサヒクリンＡＣ６０００　４０ｇ、ＰＦ５０６０　２０ｇの混合液を反応容器内に滴下した後、５０℃で６時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。分液操作により、下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｆ）

で表されるフルオロポリエーテル基含有ポリマー９．２ｇ（数平均分子量約６，１００）を得た。 [Example 2]
In a reaction vessel, the following formula (D)

Then, 21 ml (0.5 M THF solution: 1.1×10 ⁻² mol) of a Grignard reagent represented by the following formula (E) was added and stirred.

A mixture of 20 g (3.5×10 ⁻³ mol) of a compound represented by the formula (F), 40 g of Asahiklin AC6000, and 20 g of PF5060 was dropped into a reaction vessel, and then heated at 50° C. for 6 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation, and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the formula (F)

Thus, 9.2 g of a fluoropolyether group-containing polymer represented by the formula (number average molecular weight: about 6,100) was obtained.

で表されるグリニャール試薬１８ｍｌ（０．８Ｍ　ＴＨＦ溶液：１．４×１０^-2ｍｏｌ）を入れ、撹拌した。続いて、下記式（Ｇ）

で表される化合物１０ｇ（２．４×１０^-3ｍｏｌ）、アサヒクリンＡＣ６０００　２０ｇ、ＰＦ５０６０　１０ｇの混合液を反応容器内に滴下した後、５０℃で６時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。分液操作により、下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｈ）

で表されるフルオロポリエーテル基含有ポリマー９．６ｇ（数平均分子量約４，６００）を得た。 [Example 3]
In a reaction vessel, the following formula (A)

Then, 18 ml (0.8 M THF solution: 1.4 × 10 ^-2 mol) of a Grignard reagent represented by the following formula (G) was added and stirred.

A mixture of 10 g (2.4×10 ⁻³ mol) of a compound represented by the formula (II), 20 g of Asahiklin AC6000, and 10 g of PF5060 was dropped into a reaction vessel, and then heated at 50° C. for 6 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation, and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the formula (H):

Thus, 9.6 g of a fluoropolyether group-containing polymer represented by the formula (number average molecular weight: about 4,600) was obtained.

で表されるグリニャール試薬１４ｍｌ（０．５Ｍ　ＴＨＦ溶液：７．２×１０^-3ｍｏｌ）を入れ、撹拌した。続いて、下記式（Ｊ）

で表される化合物１０ｇ（２．４×１０^-3ｍｏｌ）、アサヒクリンＡＣ６０００　２０ｇ、ＰＦ５０６０　１０ｇの混合液を反応容器内に滴下した後、５０℃で６時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。分液操作により、下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｋ）

で表されるフルオロポリエーテル基含有ポリマー８．５ｇ（数平均分子量４，３００）を得た。 [Example 4]
In a reaction vessel, the following formula (I)

Then, 14 ml (0.5 M THF solution: 7.2×10 ⁻³ mol) of a Grignard reagent represented by the following formula (J) was added and stirred.

A mixture of 10 g (2.4×10 ⁻³ mol) of a compound represented by the formula (I), 20 g of Asahiklin AC6000, and 10 g of PF5060 was dropped into a reaction vessel, and then heated at 50° C. for 6 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation, and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the formula (K):

Thus, 8.5 g of a fluoropolyether group-containing polymer represented by the formula (number average molecular weight: 4,300) was obtained.

で表されるグリニャール試薬２５ｍｌ（０．８Ｍ　ＴＨＦ溶液：２．０×１０^-2ｍｏｌ）を入れ、撹拌した。続いて、下記式（Ｌ）

で表される化合物２０ｇ（３．４×１０^-3ｍｏｌ）、アサヒクリンＡＣ６０００　２０ｇ、ＰＦ５０６０　１０ｇの混合液を反応容器内に滴下した後、５０℃で６時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。分液操作により、下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｍ）

で表されるフルオロポリエーテル基含有ポリマー１９ｇ（数平均分子量６，０００）を得た。 [Example 5]
In a reaction vessel, the following formula (A)

25 ml (0.8 M THF solution: 2.0 × 10 ^-2 mol) of a Grignard reagent represented by the following formula (L) was added and stirred.

A mixture of 20 g (3.4×10 ⁻³ mol) of a compound represented by the formula (I), 20 g of Asahiklin AC6000, and 10 g of PF5060 was dropped into a reaction vessel, and then heated at 50° C. for 6 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation, and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the formula (M):

Thus, 19 g of a fluoropolyether group-containing polymer represented by the formula (number average molecular weight: 6,000) was obtained.

で表されるグリニャール試薬１４ｍｌ（０．５Ｍ　ＴＨＦ溶液：７．２×１０^-3ｍｏｌ）を入れ、撹拌した。続いて、下記式（О）

で表される化合物１０ｇ（２．４×１０^-3ｍｏｌ）、アサヒクリンＡＣ６０００　２０ｇ、ＰＦ５０６０　１０ｇの混合液を反応容器内に滴下した後、５０℃で６時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。分液操作により、下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｐ）

で表されるフルオロポリエーテル基含有ポリマー７．９ｇ（数平均分子量４，３００）を得た。 [Example 6]
In a reaction vessel, the following formula (N)

Then, 14 ml (0.5 M THF solution: 7.2×10 ⁻³ mol) of a Grignard reagent represented by the following formula (O) was added and stirred.

A mixture of 10 g (2.4×10 ⁻³ mol) of a compound represented by the formula (II), 20 g of Asahiklin AC6000, and 10 g of PF5060 was dropped into a reaction vessel, and then heated at 50° C. for 6 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation, and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the formula (P):

Thus, 7.9 g of a fluoropolyether group-containing polymer represented by the formula (number average molecular weight: 4,300) was obtained.

で表されるグリニャール試薬１５ｍｌ（０．５Ｍ　ＴＨＦ溶液：７．５×１０^-3ｍｏｌ）を入れ、撹拌した。続いて、下記式（Ｒ）

で表される化合物１０ｇ（２．５×１０^-3ｍｏｌ）、アサヒクリンＡＣ６０００　２０ｇ、ＰＦ５０６０　１０ｇの混合液を反応容器内に滴下した後、５０℃で６時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。分液操作により、下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｓ）

で表されるフルオロポリエーテル基含有ポリマー９．１ｇ（数平均分子量４，１５０）を得た。 [Example 7]
In a reaction vessel, the following formula (Q)

Then, 15 ml (0.5 M THF solution: 7.5×10 ⁻³ mol) of a Grignard reagent represented by the following formula (R) was added and stirred.

A mixture of 10 g (2.5×10 ⁻³ mol) of a compound represented by the formula (II), 20 g of Asahiklin AC6000, and 10 g of PF5060 was dropped into a reaction vessel, and then heated at 50° C. for 6 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation, and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the formula (S):

Thus, 9.1 g of a fluoropolyether group-containing polymer represented by the formula (number average molecular weight: 4,150) was obtained.

In this way, it was possible to introduce two or three olefin moieties (2 to 6 per molecule) that are easily converted to functional groups at the molecular chain end of the fluoropolyether group-containing polymer, as well as highly reactive secondary hydroxyl groups (1 or 2 per molecule). The fluoropolyether group-containing polymer of the present invention has two types of structures with different reactivities, namely, the olefin moiety and the hydroxyl group, and various functional groups can be introduced by selecting the reaction conditions.

The present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and provides similar effects is included in the technical scope of the present invention.

Claims (6)

The following general formula (1)

(In the formula, Rf is a monovalent or divalent fluoropolyether group, Z is independently a trivalent or tetravalent organic group, X is independently a single bond or a divalent organic group, α is 1 or 2, and β is 2 or 3. However, the hydroxyl group in the formula is a secondary hydroxyl group.)
and having a number average molecular weight in terms of polystyrene of 1,000 to 50,000. 2. The fluoropolyether group-containing polymer according to claim 1, wherein α in the formula (1) is 1, and Rf is a monovalent fluoropolyether group represented by the following general formula (2):

(In the formula, A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a _-CF3 group, a _-CF2H group, or a _-CH2F group; p, q, r, and s are each an integer of 0 to 200, and p+q+r+s=3 to 200; each repeating unit may be linear or branched, and each repeating unit may be bonded randomly; and d is independently an integer of 1 to 3 for each unit, and the unit may be linear or branched.) 2. The fluoropolyether group-containing polymer according to claim 1, wherein α in the formula (1) is 2, and Rf is a divalent fluoropolyether group represented by the following general formula (3):

(In the formula, p, q, r, and s each represent an integer of 0 to 200, and p+q+r+s=3 to 200; each repeating unit may be linear or branched; each repeating unit may be randomly bonded to another repeating unit; and d is independently an integer of 1 to 3 for each unit, and each unit may be linear or branched.) The fluoropolyether group-containing polymer according to claim 1, wherein in the formula (1), X is a single bond, an alkylene group having 2 to 12 carbon atoms, or an alkylene group having 2 to 10 carbon atoms and including an arylene group having 6 to 8 carbon atoms. The fluoropolyether group-containing polymer according to claim 1, wherein in formula (1), Z is a trivalent or tetravalent linear aliphatic saturated hydrocarbon group having 2 to 12 carbon atoms, or a trivalent or tetravalent linear aliphatic saturated hydrocarbon group containing an aromatic ring having 8 to 16 carbon atoms. The following general formula (4)

(In the formula, Rf is a monovalent or divalent fluoropolyether group, Y is a removable monovalent group, and α is 1 or 2.)
The method for producing the fluoropolyether group-containing polymer according to any one of claims 1 to 5, comprising reacting the fluoropolyether group-containing polymer represented by the formula (1) with an organometallic reagent having 2 to 6 olefin moieties and β-hydrogen.