WO2020246301A1 - フルオロポリエーテル基含有ポリマー及びその製造方法 - Google Patents
フルオロポリエーテル基含有ポリマー及びその製造方法 Download PDFInfo
- Publication number
- WO2020246301A1 WO2020246301A1 PCT/JP2020/020636 JP2020020636W WO2020246301A1 WO 2020246301 A1 WO2020246301 A1 WO 2020246301A1 JP 2020020636 W JP2020020636 W JP 2020020636W WO 2020246301 A1 WO2020246301 A1 WO 2020246301A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- containing polymer
- fluoropolyether
- formula
- fluoropolyether group
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
- C08G65/3233—Molecular halogen
- C08G65/3236—Fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
Definitions
- the present invention relates to a fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluorooxyalkylene group-containing polymer residue in the molecule), and more specifically, a coating film having excellent water and oil repellency and abrasion resistance.
- the present invention relates to a fluoropolyether group-containing polymer forming the above, and a method for producing the polymer.
- a fluoropolyether group-containing compound has water- and oil-repellent properties, chemical resistance, lubricity, mold release property, antifouling property, etc. because its surface free energy is very small. Utilizing its properties, it is industrially widely used as water and oil repellent antifouling agents for paper and fibers, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, protective films, etc. ing. However, its properties mean that it is non-adhesive and non-adhesive to other base materials at the same time, and although it can be applied to the surface of the base material, it is difficult to adhere the coating film. ..
- a silane coupling agent is well known as a substance that binds an organic compound to the surface of a base material such as glass or cloth, and is widely used as a coating agent on the surface of various base materials.
- the silane coupling agent has 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 causes a self-condensation reaction due to moisture in the air or the like to form a film.
- the film becomes a durable and strong film by chemically and physically bonding the hydrolyzable silyl group to the surface of glass, metal, or the like.
- Patent Document 1 Patent No. 6451279.
- Patent Document 1 as an intermediate of the fluoropolyether group-containing polymer, for example, the following 3rd grade alcohol is used.
- the intermediate is a polymer having both a reactive olefin moiety and a hydroxyl group, but since the hydroxyl group is tertiary, the reactivity is poor and the hydroxyl group cannot be effectively used.
- the present inventor has made an organometallic reagent having ⁇ hydrogen in a fluoropolyether group-containing polymer having a carbonyl group at the end, specifically, an aliphatic unsaturated double at the end.
- Rf is a monovalent or divalent fluoropolyether group-containing polymer residue
- X is an independently divalent organic group
- ⁇ is 1 or 2.
- the present invention provides the following fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluorooxyalkylene group-containing polymer residue in the molecule) and a method for producing the same.
- the following general formula (1) (In the formula, Rf is a monovalent or divalent fluoropolyether group-containing polymer residue, X is an independently divalent organic group, and ⁇ is 1 or 2.) Fluoropolyether group-containing polymer represented by.
- Rf is a monovalent or divalent fluoropolyether group-containing polymer residue
- X is an independently divalent organic group
- ⁇ is 1 or 2.
- Fluoropolyether group-containing polymer represented by [2] The fluoropolyether group-containing polymer according to [1], wherein ⁇ of the formula (1) is 1, and Rf is a group represented by the following general formula (2).
- A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having 3 -CF groups at the end and -CF 2 H groups at the end or -CH 2 F groups at the end, and Rf H is 1. It is a fluorooxyalkylene group containing more than one hydrogen atom, d is an integer of 1 to 3 independently for each unit, and p, q, r, s, t, u, and v are 0 to 200, respectively.
- X is an alkylene group having 2 to 12 carbon atoms or an alkylene group containing an arylene group having 8 to 16 carbon atoms. Group-containing polymer.
- the fluoropolyether group-containing polymer of the present invention is represented by the following general formula (1), and preferably has a number average molecular weight of 1,000 to 50,000 in terms of polystyrene. It is a containing polymer.
- Rf is a monovalent or divalent fluoropolyether group-containing polymer residue
- X is an independently divalent organic group
- ⁇ is 1 or 2.
- the fluoropolyether group-containing polymer of the present invention has a monovalent fluoropolyether group or a divalent fluoropolyether group-containing polymer residue (that is, a monovalent or divalent fluoropolyether group-containing polymer residue).
- a monovalent fluoropolyether group or a divalent fluoropolyether group-containing polymer residue that is, a monovalent or divalent fluoropolyether group-containing polymer residue.
- Rf is a monovalent or divalent fluoropolyether group-containing polymer residue
- ⁇ is 1 (that is, Rf 1 is a monovalent fluorooxyalkylene group-containing polymer residue).
- A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having 3 -CF groups at the end and -CF 2 H groups at the end or -CH 2 F groups at the end, and Rf H is 1. It is a fluorooxyalkylene group containing more than one hydrogen atom, d is an integer of 1 to 3 independently for each unit, and p, q, r, s, t, u, and v are 0 to 200, respectively.
- each of these units may be linear or branched, and parentheses with p, q, r, s, t, u, v.
- Each repeating unit shown in may be randomly combined.
- A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having 3 -CF groups at the end and -CF 2 H groups at the end or -CH 2 F groups at the end, which is preferable.
- Rf H is a fluorooxyalkylene group containing one or more hydrogen atoms, for example, CF 2 O unit, C 2 F 4 O unit, C 3 F 6 O unit, In one or more combinations of each perfluorooxyalkylene repeating unit such as C 4 F 8 O unit, C 5 F 10 O unit, C 6 F 12 O unit, one of the fluorine atoms in each repeating unit. Examples thereof include those in which one or two are replaced with hydrogen atoms.
- d is an integer of 1 to 3 independently for each unit, and is preferably 1.
- p, q, r, s, t, u, and v are integers of 0 to 200, respectively, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, and r is an integer of 0 to 100.
- s is an integer of 0 to 100
- t is an integer of 0 to 100
- u an integer of 0 to 100
- v is an integer of 0 to 100
- p + q + r + s + t + u + v 3 to 200, preferably 10 to 105, more preferably.
- each unit may be linear or branched.
- each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly combined.
- the monovalent fluoropolyether group represented by the formula (2) include the following.
- the sum of r', s', and v'is 3 to 200, and each repeating unit shown in parentheses with p', q', r', and s' may be randomly combined.
- (C 2 F 4 OC 4 F 8 O) indicates a structure in which (C 2 F 4 O) units and (C 4 F 8 O) units are alternately repeated.)
- divalent fluoropolyether group represented by the formula (3) include the following.
- p', q', r', and s' are integers of 1 to 200, respectively, and the sum of p', q', r', and s', respectively, is 3 to 200.
- r 1 , r. 2 is an integer from 1 to 198, and the sum of r 1 + r 2 is from 2 to 199.
- each repeating unit shown in parentheses with p', q', r', s' is random. May be combined.
- Examples of such X include the following groups.
- the number average molecular weight of the fluoropolyether group-containing polymer represented by the above formula (1) is preferably 1,000 to 50,000, more preferably 1,500 to 10,000, still more preferably 2,500. It is in the range of ⁇ 8,000. If the number average molecular weight is less than 1,000, the water and oil repellency and antifouling properties that are the characteristics of the perfluoroalkylene ether structure may not be sufficiently exhibited, and if it exceeds 50,000, the concentration of the terminal functional group becomes small. Too much, the reactivity and adhesion with the base material may decrease.
- the number average molecular weight referred to in the present invention refers to a number average molecular weight using polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following conditions.
- fluoropolyether group-containing polymer represented by the above formula (1) examples include those shown below.
- p', q', r', v', w', r 1 , r 2 are the same as above, and the total of each p', q', v'is 3 to 200. The sum of r 1 + r 2 is 2 to 199. Further, each repeating unit shown in parentheses with p'and q'may be randomly combined.
- C 2 F 4 OC 4) F 8 O indicates a structure in which (C 2 F 4 O) units and (C 4 F 8 O) units are alternately repeated.
- Y is a desorbable monovalent group, for example, hydrogen atom, halogen atom, hydroxyl group, alkoxy group, amino group, alkylamino group, thiol group, alkylthio group, acyl group and the like. Can be mentioned.
- Examples of such Y include the following groups.
- fluoropolyether group-containing polymer represented by the above formula (4) include those shown below.
- p', q', r', v', w', r 1 , r 2 are the same as above, and the total of each p', q', v'is 3 to 200. The sum of r 1 + r 2 is 2 to 199. Further, each repeating unit shown in parentheses with p'and q'may be randomly combined.
- C 2 F 4 OC 4) F 8 O indicates a structure in which (C 2 F 4 O) units and (C 4 F 8 O) units are alternately repeated.
- organometallic reagent having ⁇ -hydrogen specifically, a hydrogen having an aliphatic unsaturated double bond (olefin moiety) at the terminal and ⁇ -hydrogen (that is, hydrogen bonded to the carbon atom at the ⁇ -position of the metal atom).
- organometallic reagent having ⁇ -hydrogen for example, the following can be used.
- the amount of the organometallic reagent having ⁇ -hydrogen used is 2 to 1 equivalent with respect to 1 equivalent of the reactive end group (desorbable monovalent group) of the fluoropolyether group-containing polymer represented by the above formula (4). It is preferable to use 5 equivalents, more preferably 2.5 to 3.5 equivalents, and even more preferably about 3 equivalents.
- a reagent other than the above reagent may be added to the method for producing the fluoropolyether group-containing polymer represented by the above formula (1) as long as the object of the present invention is not impaired.
- 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 reaction compound is a fluorine compound.
- Fluorine-based solvents include 1,3-bistrifluoromethylbenzene, trifluoromethylbenzene, perfluorosolvents sold by AGC (Asahiclean AC2000, Asahiclean AC6000), and HFE-based solvents sold by 3M.
- Solvents (NOVEC 7100: C 4 F 9 OCH 3 , NOVEC 7200: C 4 F 9 OC 2 H 5 , NOVEC 7300: C 2 F 5- CF (OCH 3 ) -CF (CF 3 ) 2, etc.), also sold by 3M Examples thereof include perfluorosolvents (PF5080, PF5070, PF5060, etc.).
- the fluorine-based solvent may be used alone or in combination. Further, as the solvent, an organic solvent can be used in addition to the above-mentioned fluorine-based solvent.
- ether solvents such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used.
- THF tetrahydrofuran
- monoethylene glycol dimethyl ether diethylene glycol dimethyl ether
- diethylene glycol dimethyl ether triethylene glycol dimethyl ether
- tetraethylene glycol dimethyl ether tetraethylene glycol dimethyl ether
- dioxane dioxane
- the amount of the solvent used is 10 to 600 parts by mass, preferably 50 to 400 parts by mass, and more preferably 200 to 350 parts by mass with respect to 100 parts by mass of the fluoropolyether group-containing polymer represented by the above formula (4). Can be used.
- a fluoropolyether group-containing polymer represented by (AGC) is mixed with a Grignard reagent as a nucleophile (organic metal reagent having ⁇ hydrogen), for example, Asahiclean AC6000 (manufactured by AGC) as a solvent, and THF is mixed at 0 to 80 ° C. It is aged at 45 to 70 ° C., more preferably about 50 ° C. for 1 to 12 hours, preferably 5 to 7 hours.
- the fluoropolyether group-containing polymer represented by the above formula (1) of the present invention has two types of structures having different reactivity, that is, an olefin moiety easily converted into a functional group and a highly reactive secondary hydroxyl group. Therefore, various functional groups can be introduced by selecting the reaction conditions.
- the functional group that can be introduced include a hydrolyzable silyl group (for example, an alkoxysilyl group), an alkyl group, a phenyl group, a vinyl group, an allyl group, an acyl group, a carboxyl group, an ester group, and an amide group.
- Examples thereof include a hydroxyl group, an amino group, a thiol group, a polyether group, a silyl group, a siloxane group, a thioester group, a phosphoric acid ester group and a phosphoric acid group.
- the fluoropolyether group-containing polymer of the present invention can be used as, for example, a surface treatment agent, such as a base material or an article, for example, a car navigation system, a mobile phone, a smartphone, a digital camera, a digital video camera, a PDA, or a portable audio system.
- a surface treatment agent such as a base material or an article
- a car navigation system a mobile phone, a smartphone, a digital camera, a digital video camera, a PDA, or a portable audio system.
- Players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastrocameras, copying machines, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection It can be suitably used for surface treatment of optical articles such as films.
- the number average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC).
- Example 1 150 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 7.5 ⁇ 10-2 mol) was placed in a reaction vessel, and the mixture was stirred. Then, the following formula (A) (A) A mixed solution of 100 g (2.5 ⁇ 10 ⁇ 2 mol) of the compound represented by ( 2 ), 200 g of Asahiclean AC6000, and 100 g of PF5060 was added dropwise to the reaction vessel, and then heated at 50 ° C. for 6 hours. After completion of heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The underlying fluorine compound layer was recovered by a liquid separation operation and then washed with acetone.
- a mixed solution of 100 g (2.5 ⁇ 10 ⁇ 2 mol) of the compound represented by ( 2 ), 200 g of Asahiclean AC6000, and 100 g of PF5060 was added dropwise to the reaction vessel, and then heated at 50 ° C
- Example 2 10.2 ml of 3-butenyl magnesium bromide (0.5 M THF solution: 5.1 ⁇ 10 -3 mol) was placed in a reaction vessel, and the mixture was stirred. Then, the following formula (C) (C) A mixed solution of 10 g (1.7 ⁇ 10 -3 mol) of the compound represented by (1.7 ⁇ 10 -3 mol), 20 g of Asahiclean AC6000, and 10 g of PF5060 was added dropwise to the reaction vessel, and then heated at 50 ° C. for 6 hours. After completion of heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise.
- C A mixed solution of 10 g (1.7 ⁇ 10 -3 mol) of the compound represented by (1.7 ⁇ 10 -3 mol), 20 g of Asahiclean AC6000, and 10 g of PF5060 was added dropwise to the reaction vessel, and then heated at 50 ° C. for 6 hours. After completion of heating, the mixture was cooled
- Example 5 14.4 ml of 5-hexenylmagnesium bromide (0.5 M THF solution: 7.2 ⁇ 10 -3 mol) was placed in a reaction vessel, and the mixture was stirred. Then, the following formula (I) (I) A mixed solution of 10 g (2.4 ⁇ 10 -3 mol) of the compound represented by (2), 20 g of Asahiclean AC6000, and 10 g of PF5060 was added dropwise to the reaction vessel, and then heated at 50 ° C. for 6 hours. After completion of heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The underlying fluorine compound layer was recovered by a liquid separation operation and then washed with acetone.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Included in the technical scope.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Description
で表され、好適にはポリスチレン換算での数平均分子量が1,000~50,000である、官能基変換容易なオレフィン部位と反応性の高い2級水酸基を併せ持つフルオロポリエーテル基含有ポリマーを製造できることを見出し、本発明をなすに至った。
〔1〕
下記一般式(1)
で表され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)で表される基である〔1〕記載のフルオロポリエーテル基含有ポリマー。
〔3〕
前記式(1)のαが2であり、Rfが下記一般式(3)で表される基である〔1〕記載のフルオロポリエーテル基含有ポリマー。
〔4〕
前記式(1)において、Xが、炭素数2~12のアルキレン基、又は炭素数8~16のアリーレン基を含む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〕
ポリスチレン換算での数平均分子量が1,000~50,000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)
で表されるフルオロポリエーテル基含有ポリマーとβ水素を有する有機金属試薬とを反応させることを特徴とする〔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。
〔7〕
β水素を有する有機金属試薬が、グリニャール試薬である〔6〕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。
〔8〕
グリニャール試薬が、下記式から選ばれる化合物である〔7〕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。
また、p、q、r、s、t、u、vはそれぞれ0~200の整数、好ましくは、pは5~100の整数、qは5~100の整数、rは0~100の整数、sは0~100の整数、tは0~100の整数、uは0~100の整数、vは0~100の整数であり、p+q+r+s+t+u+v=3~200、好ましくは10~105であり、より好ましくはp+qは10~105、特に15~65の整数であり、r=s=t=u=v=0である。p+q+r+s+t+u+vが上記上限値より小さければ密着性や硬化性が良好であり、上記下限値より大きければフルオロポリエーテル基の特徴を十分に発揮することができるので好ましい。
展開溶媒:ハイドロクロロフルオロカーボン(HCFC)-225
流量:1mL/min.
検出器:蒸発光散乱検出器
カラム:東ソー社製 TSKgel Multipore HXL-M
7.8mmφ×30cm 2本使用
カラム温度:35℃
試料注入量:20μL(濃度0.3質量%のHCFC-225溶液)
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とβ水素を有する有機金属試薬とを反応させる方法が好ましい。
また、溶剤としては、上記フッ素系溶剤以外に有機溶剤を用いることができる。有機溶剤として、テトラヒドロフラン(THF)、モノエチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、ジオキサンなどのエーテル系溶剤を用いることができる。有機溶剤は単独で使用してもフッ素系溶剤と混合して使用してもよい。
で表されるフルオロポリエーテル基含有ポリマーと、求核剤(β水素を有する有機金属試薬)としてグリニャール試薬、溶剤として例えばアサヒクリンAC6000(AGC社製)、THFを混合し、0~80℃、好ましくは45~70℃、より好ましくは約50℃で、1~12時間、好ましくは5~7時間熟成する。
続いて、反応を停止し、分液操作により水層とフッ素溶剤層を分離する。得られたフッ素溶剤層を更に有機溶剤で洗浄し、溶剤を留去することで、上記式(1)で表されるフルオロポリエーテル基含有ポリマーが得られる。
ここで、導入することができる官能基としては、加水分解性シリル基(例えばアルコキシシリル基等)、アルキル基、フェニル基、ビニル基、アリル基、アシル基、カルボキシル基、エステル基、アミド基、ヒドロキシル基、アミノ基、チオール基、ポリエーテル基、シリル基、シロキサン基、チオエステル基、リン酸エステル基、リン酸基などが挙げられる。
反応容器に、3-ブテニルマグネシウムブロミド150ml(0.5M THF溶液:7.5×10-2mol)を入れ、撹拌した。続いて、下記式(A)
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(B)
で表されるフルオロポリエーテル基含有ポリマー95g(数平均分子量;約3,900)を得た。
δ1.4-1.7(C-CH 2 CH2CH=CH2)2H
δ1.9-2.2(C-CH 2 CH2CH=CH2,-CF2-CH(OH)-CH2-)3H
δ3.6-3.8(-CF2-CH(OH)-CH2-)1H
δ4.8-4.9(-CH2CH=CH 2 )2H
δ5.5-5.6(-CH2CH=CH2)1H
反応容器に、3-ブテニルマグネシウムブロミド10.2ml(0.5M THF溶液:5.1×10-3mol)を入れ、撹拌した。続いて、下記式(C)
で表される化合物10g(1.7×10-3mol)、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(D)
で表されるフルオロポリエーテル基含有ポリマー9g(数平均分子量;約5,700)を得た。
δ1.4-1.7(C-CH 2 CH2CH=CH2)2H
δ1.9-2.2(C-CH 2 CH2CH=CH2,-CF2-CH(OH)-CH2-)3H
δ3.6-3.8(-CF2-CH(OH)-CH2-)1H
δ4.8-4.9(-CH2CH=CH 2 )2H
δ5.5-5.6(-CH2CH=CH2)1H
反応容器に、3-ブテニルマグネシウムブロミド28.8ml(0.5M THF溶液:1.4×10-2mol)を入れ、撹拌した。続いて、下記式(E)
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(F)
で表されるフルオロポリエーテル基含有ポリマー9.4g(数平均分子量;約4,200)を得た。
δ1.4-1.7(C-CH 2 CH2CH=CH2)4H
δ1.9-2.2(C-CH 2 CH2CH=CH2,-CF2-CH(OH)-CH2-)6H
δ3.6-3.8(-CF2-CH(OH)-CH2-)2H
δ4.8-4.9(-CH2CH=CH 2 )4H
δ5.5-5.6(-CH2CH=CH2)2H
反応容器に、3-ブテニルマグネシウムブロミド14.4ml(0.5M THF溶液:7.2×10-3mol)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8.9g(数平均分子量;約4,100)を得た。
δ1.4-1.7(C-CH 2 CH2CH=CH2)2H
δ1.9-2.2(C-CH2CH 2 CH=CH2,-CF2-CH(OH)-CH2-)3H
δ3.6-3.8(-CF2-CH(OH)-CH2-)1H
δ4.8-4.9(-CH2CH=CH 2 )2H
δ5.5-5.6(-CH2CH=CH2)1H
反応容器に、5-ヘキセニルマグネシウムブロミド14.4ml(0.5M THF溶液:7.2×10-3mol)を入れ、撹拌した。続いて、下記式(I)
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(J)
で表されるフルオロポリエーテル基含有ポリマー8.2g(数平均分子量;約4,200)を得た。
δ1.3-1.8(C-CH 2 CH 2 CH 2 CH2CH=CH2)6H
δ1.9-2.1(C-CH2CH2CH2CH 2 CH=CH2)2H
δ3.3-3.5(-CF2-CH(OH)-CH2-)1H
δ3.6-3.8(-CF2-CH(OH)-CH2-)1H
δ4.7-4.9(-CH2CH=CH 2 )2H
δ5.5-5.7(-CH2CH=CH2)1H
Claims (8)
- 前記式(1)のαが1であり、Rfが下記一般式(2)で表される基である請求項1記載のフルオロポリエーテル基含有ポリマー。
- 前記式(1)において、Xが、炭素数2~12のアルキレン基、又は炭素数8~16のアリーレン基を含むアルキレン基である請求項1~3のいずれか1項に記載のフルオロポリエーテル基含有ポリマー。
- ポリスチレン換算での数平均分子量が1,000~50,000である請求項1~4のいずれか1項に記載のフルオロポリエーテル基含有ポリマー。
- β水素を有する有機金属試薬が、グリニャール試薬である請求項6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。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/616,299 US20220306803A1 (en) | 2019-06-06 | 2020-05-26 | Fluoropolyether group-containing polymer and production method therefor |
EP20818692.4A EP3981823A4 (en) | 2019-06-06 | 2020-05-26 | FLUOROPOLYETHER GROUP-CONTAINING POLYMER AND PROCESS FOR ITS PREPARATION |
CN202080040602.3A CN113906082A (zh) | 2019-06-06 | 2020-05-26 | 含有氟聚醚基的聚合物及其制造方法 |
KR1020217042805A KR20220019104A (ko) | 2019-06-06 | 2020-05-26 | 플루오로폴리에테르기 함유 폴리머 및 그 제조 방법 |
JP2021524775A JP7156523B2 (ja) | 2019-06-06 | 2020-05-26 | フルオロポリエーテル基含有ポリマー及びその製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-105865 | 2019-06-06 | ||
JP2019105865 | 2019-06-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020246301A1 true WO2020246301A1 (ja) | 2020-12-10 |
Family
ID=73652880
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/020636 WO2020246301A1 (ja) | 2019-06-06 | 2020-05-26 | フルオロポリエーテル基含有ポリマー及びその製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20220306803A1 (ja) |
EP (1) | EP3981823A4 (ja) |
JP (1) | JP7156523B2 (ja) |
KR (1) | KR20220019104A (ja) |
CN (1) | CN113906082A (ja) |
TW (1) | TW202112894A (ja) |
WO (1) | WO2020246301A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024075471A1 (ja) * | 2022-10-07 | 2024-04-11 | 信越化学工業株式会社 | フルオロポリエーテル基含有アクリル化合物、活性エネルギー線硬化性組成物、該硬化性組成物の硬化被膜、並びに物品 |
WO2024075458A1 (ja) * | 2022-10-05 | 2024-04-11 | 信越化学工業株式会社 | フルオロポリエーテル基含有ポリマー |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0151279B2 (ja) | 1981-06-03 | 1989-11-02 | Matsushita Electric Ind Co Ltd | |
WO2019039226A1 (ja) * | 2017-08-22 | 2019-02-28 | Agc株式会社 | 含フッ素エーテル化合物、含フッ素エーテル組成物、コーティング液、物品およびその製造方法 |
WO2019049753A1 (ja) * | 2017-09-05 | 2019-03-14 | Agc株式会社 | 含フッ素エーテル化合物、組成物および物品 |
JP2019044158A (ja) * | 2017-08-31 | 2019-03-22 | Agc株式会社 | 含フッ素エーテル化合物、含フッ素エーテル組成物、コーティング液、物品およびその製造方法 |
WO2020111009A1 (ja) * | 2018-11-28 | 2020-06-04 | Agc株式会社 | 含フッ素化合物、含フッ素化合物含有組成物、コーティング液、物品及びその製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6119656B2 (ja) * | 2014-03-31 | 2017-04-26 | 信越化学工業株式会社 | フルオロポリエーテル基含有ポリマー |
JP6358193B2 (ja) * | 2015-08-26 | 2018-07-18 | 信越化学工業株式会社 | 含フッ素硬化性組成物及びゴム物品 |
-
2020
- 2020-05-26 WO PCT/JP2020/020636 patent/WO2020246301A1/ja active Application Filing
- 2020-05-26 JP JP2021524775A patent/JP7156523B2/ja active Active
- 2020-05-26 CN CN202080040602.3A patent/CN113906082A/zh active Pending
- 2020-05-26 KR KR1020217042805A patent/KR20220019104A/ko unknown
- 2020-05-26 EP EP20818692.4A patent/EP3981823A4/en active Pending
- 2020-05-26 US US17/616,299 patent/US20220306803A1/en active Pending
- 2020-06-04 TW TW109118742A patent/TW202112894A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0151279B2 (ja) | 1981-06-03 | 1989-11-02 | Matsushita Electric Ind Co Ltd | |
WO2019039226A1 (ja) * | 2017-08-22 | 2019-02-28 | Agc株式会社 | 含フッ素エーテル化合物、含フッ素エーテル組成物、コーティング液、物品およびその製造方法 |
JP2019044158A (ja) * | 2017-08-31 | 2019-03-22 | Agc株式会社 | 含フッ素エーテル化合物、含フッ素エーテル組成物、コーティング液、物品およびその製造方法 |
WO2019049753A1 (ja) * | 2017-09-05 | 2019-03-14 | Agc株式会社 | 含フッ素エーテル化合物、組成物および物品 |
WO2020111009A1 (ja) * | 2018-11-28 | 2020-06-04 | Agc株式会社 | 含フッ素化合物、含フッ素化合物含有組成物、コーティング液、物品及びその製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024075458A1 (ja) * | 2022-10-05 | 2024-04-11 | 信越化学工業株式会社 | フルオロポリエーテル基含有ポリマー |
WO2024075471A1 (ja) * | 2022-10-07 | 2024-04-11 | 信越化学工業株式会社 | フルオロポリエーテル基含有アクリル化合物、活性エネルギー線硬化性組成物、該硬化性組成物の硬化被膜、並びに物品 |
Also Published As
Publication number | Publication date |
---|---|
TW202112894A (zh) | 2021-04-01 |
JPWO2020246301A1 (ja) | 2020-12-10 |
CN113906082A (zh) | 2022-01-07 |
US20220306803A1 (en) | 2022-09-29 |
KR20220019104A (ko) | 2022-02-15 |
EP3981823A4 (en) | 2022-12-28 |
JP7156523B2 (ja) | 2022-10-19 |
EP3981823A1 (en) | 2022-04-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI373480B (en) | Per-fluoro polyether compound, antifouling coating composition and film containing same | |
JP5235026B2 (ja) | フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品 | |
JP6828744B2 (ja) | フルオロポリエーテル基含有ポリマー、表面処理剤及び物品 | |
US10696848B2 (en) | Fluorinated ether compound, coating liquid, article and novel compounds | |
JP4873666B2 (ja) | パーフルオロポリエーテル基を有するアクリレート化合物 | |
TWI439489B (zh) | 含有氟氧伸烷基聚合物組成物及含有該組成物的表面處理劑及以該表面處理劑處理的物品 | |
JP7070587B2 (ja) | フルオロポリエーテル基含有ポリマー、表面処理剤及び物品 | |
JP7276464B2 (ja) | フルオロポリエーテル基含有ポリマー、表面処理剤及び物品 | |
US20100029889A1 (en) | Perfluoroether moiety-containing polymer and a surface treating agent comprising the same | |
KR102084270B1 (ko) | 플루오로옥시알킬렌기 함유 중합체 변성 실란 및 상기 실란을 포함하는 표면 처리제, 및 상기 표면 처리제로 표면 처리된 물품 | |
JP6680350B2 (ja) | フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品 | |
KR20120120012A (ko) | 플루오로옥시알킬렌기 함유 폴리머 조성물 및 상기 조성물을 포함하는 표면처리제 및 상기 표면처리제로 표면 처리된 물품 | |
JP6891952B2 (ja) | 含フッ素コーティング剤組成物及び該組成物を含有する表面処理剤並びに物品 | |
JP2015196723A (ja) | フルオロポリエーテル基含有ポリマー | |
JP7318735B2 (ja) | フルオロポリエーテル基含有ポリマー、表面処理剤及び物品 | |
JP6777212B1 (ja) | パーフルオロポリエーテル基を有するシロキサンアクリレート | |
WO2021210420A1 (ja) | フルオロポリエーテル基含有ポリマー及び/又はその部分(加水分解)縮合物を含む表面処理剤及び物品 | |
JP7156523B2 (ja) | フルオロポリエーテル基含有ポリマー及びその製造方法 | |
JP6544570B2 (ja) | 表面改質剤、コーティング組成物及び物品 | |
TW201739787A (zh) | 含有氟聚醚基之聚合物改質矽烷、表面處理劑及物品 | |
JP4759952B2 (ja) | 含フッ素エーテルおよびその用途 | |
JP6488890B2 (ja) | フルオロオキシアルキレン基含有ポリマー変性ホスホン酸誘導体、該誘導体を含む表面処理剤、該表面処理剤で処理された物品及び光学物品 | |
JP6888545B2 (ja) | 表面処理剤、物品及び表面処理方法 | |
CN117222689A (zh) | 含有氟聚醚基的聚合物、表面处理剂和物品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20818692 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021524775 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20217042805 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2020818692 Country of ref document: EP |