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WO2017010531A1 - Polymère contenant du fluor - Google Patents

Polymère contenant du fluor Download PDF

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Publication number
WO2017010531A1
WO2017010531A1 PCT/JP2016/070748 JP2016070748W WO2017010531A1 WO 2017010531 A1 WO2017010531 A1 WO 2017010531A1 JP 2016070748 W JP2016070748 W JP 2016070748W WO 2017010531 A1 WO2017010531 A1 WO 2017010531A1
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Prior art keywords
group
fluorine
atom
polymer
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2016/070748
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English (en)
Japanese (ja)
Inventor
優子 塩谷
將 神原
永井　隆文
足達　健二
柴沼　俊
泰宏 中野
專介 生越
大橋　理人
孝太郎 菊嶌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
University of Osaka NUC
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Daikin Industries Ltd
Osaka University NUC
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Priority to JP2017528717A priority Critical patent/JP6781434B2/ja
Publication of WO2017010531A1 publication Critical patent/WO2017010531A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
    • C07C63/74—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms

Definitions

  • the present invention relates to a fluoropolymer and a method for producing the same.
  • Fluoropolymers such as polytetrafluoroethylene (PTFE) have high chemical stability, high heat resistance, non-adhesiveness, low viscosity due to the small size of the fluorine element and its electronegativity. It has unique properties such as coefficient of friction and water / oil repellency.
  • PTFE polytetrafluoroethylene
  • a copolymer of PFA, tetrafluoroethylene (TFE) and ethylene which are copolymers of tetrafluoroethylene (TFE) and perfluoro (alkyl vinyl ether) (PAVE).
  • Copolymers such as polymers such as ETFE have been developed.
  • the required properties include, for example, properties such as affinity for water and organic solvents, cross-linking reactivity, and the like, which are properties opposite to the water and oil repellency inherently possessed by the fluoropolymer.
  • Non-Patent Document 1 describes a fluorine-containing copolymer used as a main raw material for weather-resistant paints. Specifically, in order to use a fluorine-containing polymer having high weather resistance as a paint, a hard coat material, etc., in order to have solubility in a solvent and crosslinking reactivity, hydrocarbon monomers such as vinyl ethers and vinyl esters are used. Copolymerized.
  • Patent Document 1 a radically polymerizable monomer is reacted in the presence of a sulfur compound with a fluorine-containing polymer having an iodine atom or a bromine atom at one or both ends and / or side chain ends of the main chain.
  • a method for producing a fluorine-containing block copolymer is described.
  • a polymer having higher thermal stability and higher chemical stability in combination with imparting desired characteristics to the fluoropolymer by introducing a monomer having the desired characteristics into the fluoropolymer can suppress long-term deterioration even when used in harsh environments and enables long-term use, so its technical significance is high, and there is room for further improvement in the above prior art .
  • the present inventors have conducted intensive research in view of the above-mentioned problems, and the fluoropolymer has a desired characteristic and high heat resistance by including a block having a specific structure at the end of the main chain in the molecule. It has been found that it exhibits high durability such as mechanical stability and high chemical stability.
  • the present invention has been completed based on the above findings. That is, the present invention relates to the following fluoropolymers.
  • Item 1 Formula (A):
  • R 1 , R 2 , R 3 and R 4 are the same or different for each expression and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an organic group.
  • ring B is the same or different for each expression and represents an aromatic ring group which may have one or more substituents.
  • Item 2. Formula (1):
  • (A) is as defined above, (B 1 ), (b 2 ) and (b 3 ) are the same or different and each represents (b), n represents an integer of 1 or more, m 1 , m 2 and m 3 are the same or different and each represents an integer of 0 or more, At least one of m 1 and m 2 represents an integer of 2 or more.
  • Item 2 The fluorine-containing polymer according to Item 1, represented by: Item 3.
  • Item 3 The fluorine-containing polymer according to Item 2, wherein m3 is 0 in the formula (1).
  • any of Items 1 to 3, wherein the ring B is a monocyclic aryl group which may have one or more substituents or a polycyclic aryl group which may have one or more substituents
  • the fluorine-containing polymer according to claim 1. Item 5.
  • Item 5. The fluorine-containing polymer according to any one of Items 1 to 4, wherein the ethylene monomer (A) is a perfluoroalkene.
  • Ring B is an aromatic ring group optionally having one or more substituents having at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom as a ring-constituting atom.
  • Item 6. The fluorine-containing polymer according to any one of Items 1 to 5.
  • Item 7. The fluorine-containing polymer according to any one of Items 1 to 6, wherein the ring B is an aromatic ring group having one nitrogen atom as a ring constituent atom and optionally having one or more substituents.
  • Ring B is an ester group, carboxyl group, cyano group, alkoxy group, phenyl group, hydroxyl group, -SiR (R is an alkyl group optionally having one or more substituents, one or more substituents
  • An aromatic ring having at least one group selected from the group consisting of an optionally substituted alkoxy group, an optionally substituted phenyl group or a hydroxyl group, and a halogen element Item 8.
  • a fluoropolymer having desired properties and high durability such as high thermal stability and high chemical stability is obtained.
  • the “ ⁇ -position” is represented by C * in the structure represented by R—CO—C * R 2 —CO—R or R—CO—C * R 2 —COH—R 2. Means the position.
  • substitution means replacement of a hydrogen atom or a fluorine atom in a molecule with another atom or group.
  • substituted means another atom or group that replaces one or more hydrogen atoms or fluorine atoms in the molecule.
  • hydrocarbon group means “alkyl group”, “alkenyl group”, “alkynyl group”, “cycloalkyl group”, “cycloalkenyl group”, “cycloalkadienyl”.
  • Group "and” aryl group ".
  • fluoro organic group means an organic group having at least one fluorine atom
  • perfluoro organic group means that all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms.
  • the perfluoro organic group may have a partial structure selected from the group consisting of ether oxygen and —SO 2 —.
  • perfluoro organic groups include perfluoroalkyl groups (eg, -CF 3 , -C 2 F 5 ), perfluoro (poly) ether groups (eg, C 3 F 7 -O-CF 3 ), and -CF 2 CF 2 SO 2 F.
  • the carbon number of the perfluoro organic group can be, for example, 1 to 10, 1 to 8, 1 to 6, or 1 to 4.
  • fluoro organic group includes “perfluoro organic group”.
  • acyl group includes “acryloyl group”, “alkanoyl group”, and “aroyl group”.
  • aromatic ring group includes “aryl group” and “heteroaryl group”.
  • heterocyclic group includes “non-aromatic heterocyclic group” and “heteroaryl group”.
  • examples of the “alkyl group” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. And a linear or branched alkyl group having 1 to 10 carbon atoms.
  • alkenyl group examples include vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4 And straight-chain or branched alkenyl groups having 2 to 10 carbon atoms, such as -penten-1-yl and 5-hexen-1-yl.
  • alkynyl group examples include ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, and 5-hexyne. Examples thereof include linear or branched alkynyl groups having 2 to 10 carbon atoms such as -1-yl.
  • examples of the “cycloalkyl group” include cyclopropyl, cyclobutyl, cyclopentyl, and cycloalkyl groups having 3 to 10 carbon atoms such as cyclohexyl and cycloheptyl.
  • examples of the “cycloalkenyl group” include cycloalkenyl groups having 3 to 10 carbon atoms such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and the like.
  • examples of the “cycloalkadienyl group” include cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, and cyclononadi.
  • examples thereof include cycloalkadienyl groups having 4 to 10 carbon atoms, such as enyl and cyclodecadienyl.
  • alkoxy group examples include straight-chain or methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, hexyloxy and the like. Examples include branched alkoxy groups having 1 to 10 carbon atoms.
  • alkanoyl group is a group represented by the formula: R—CO— (wherein R represents an alkyl group).
  • aryl group may be monocyclic, bicyclic, tricyclic, or tetracyclic.
  • aryl group may be an aryl group having 6 to 18 carbon atoms.
  • examples of the “aryl group” include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl.
  • examples of the “aralkyl group” include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4 -Phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl.
  • the “aroyl group” is a group represented by the formula: R—CO— (wherein R represents an aryl group).
  • non-aromatic heterocyclic group may be monocyclic, bicyclic, tricyclic, or tetracyclic.
  • non-aromatic heterocyclic group includes, for example, 1 to 4 ring atoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom in addition to a carbon atom. It is a non-aromatic heterocyclic group containing a hetero atom.
  • non-aromatic heterocyclic group can be saturated or unsaturated.
  • non-aromatic heterocyclic group examples include tetrahydrofuryl, oxazolidinyl, imidazolinyl (eg, 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (eg, 1-aziridinyl, 2-aziridinyl), azetidinyl (eg, 1-azetidinyl, 2-azetidinyl), pyrrolidinyl (eg, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl), piperidinyl (eg, 1-piperidinyl, 2-piperidinyl) , 3-piperidinyl), azepanyl (eg, 1-azepanyl, 2-azepanyl, 3-azepanyl, 4-azepanyl), azocanyl (eg, 1-azocanyl, 2-azepanyl, 2-azepany
  • a “heteroaryl group” means, for example, a monocyclic, bicyclic, or tricyclic, or tetracyclic, or pentacyclic, 5- to 18-membered heterocycle. It can be an aryl group.
  • heteroaryl group refers to, for example, 1 to 4 heteroatoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom in addition to a carbon atom as a ring-constituting atom. It is a heteroaryl group to be contained.
  • the “heteroaryl group” may have 3 to 17 carbon atoms, for example.
  • heteroaryl group includes “monocyclic heteroaryl group” and “aromatic fused heterocyclic group”.
  • examples of the “monocyclic heteroaryl group” include pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (eg, 2-furyl, 3 -Furyl), thienyl (eg, 2-thienyl, 3-thienyl), pyrazolyl (eg, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (eg, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl) , Isoxazolyl (eg, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (eg, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (eg, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl) ), Thiazolyl (eg, 3-isothiazo
  • examples of the “aromatic fused heterocyclic group” include isoindolyl (eg, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, Isoindolyl, 7-isoindolyl), indolyl (eg, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo [b] furanyl (eg, 2-indolyl) Benzo [b] furanyl, 3-benzo [b] furanyl, 4-benzo [b] furanyl, 5-benzo [b] furanyl, 6-benzo [b] furanyl, 7-benzo [b] furanyl), benzo [c ] Furanyl (eg, 2-ind
  • thioalkoxy group for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, pentylthio, hexylthio, etc.
  • thioalkoxy group for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, pentylthio, hexylthio, etc.
  • examples thereof include a branched thioalkoxy group having 1 to 10 carbon atoms.
  • Fluoropolymer of the present invention is Formula (A):
  • R 1 , R 2 , R 3 and R 4 are the same or different for each expression and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an organic group.
  • ring B is the same or different for each expression and represents an aromatic ring group which may have one or more substituents.
  • a fluorine-containing polymer comprising a block B composed of the continuous monomer units (b) at at least one of both ends of the main chain and the end of the side chain.
  • the fluoropolymer of the present invention is Formula (1):
  • (A) is as defined above, (B 1 ), (b 2 ) and (b 3 ) are the same or different and each represents (b) n represents an integer of 1 or more, m1, m2 and m3 are the same or different and each represents an integer of 0 or more, At least one of m1, m2 and m3 represents an integer of 2 or more.
  • each of the structures represented by (b 1 ) m 1 , (b 2 ) m 2 , (b 3 ) m 3 and ((a)-(b 3 ) m 3 ) n is a block. Is preferred.
  • the fluoropolymer represented by the formula (1) is a fluoropolymer having a graft chain.
  • the monomer unit (a) and the monomer unit (b) mean a monomer unit that can be formed from the monomer (A) and the monomer (B), respectively. It is not limited to what is formed from a body (A) and a monomer (B).
  • the fluoropolymer of the present invention is a block copolymer comprising a block A composed of a plurality of continuous monomer units (a) and a block B composed of a plurality of continuous monomer units (b).
  • the present specification further discloses a random copolymer containing the monomer unit (a) and the monomer unit (b).
  • the random copolymer containing the monomer unit (a) and the monomer unit (b) is prepared by a known production method using the monomer (A) and the monomer (B). Can be manufactured.
  • block A and the block B may be blocks in which the same monomer unit (a) and monomer unit (b) are continuous, respectively, or monomer units (a) that are not the same.
  • the monomer unit (b) may be a continuous block.
  • the content of the monomer unit (a) with respect to 100 mol% of all monomer units is 1 to 99 mol%, preferably 30 to 99 mol%, particularly preferably. Is from 50 to 99 mol%.
  • the content of the monomer unit (b) is from 1 to 99 mol%, preferably from 1 to 70 mol%, based on 100 mol% of all monomer units. Particularly preferred is 1 to 50 mol%.
  • the fluorine-containing polymer of the present invention may contain a constitutional unit other than the monomer unit (a) and the monomer unit (b) in the molecule. You may contain 10 mol% or less with respect to 100 mol% of units. From the viewpoint of efficiently imparting the structural uniformity of the fluoropolymer and the desired properties associated therewith, it is preferably 3 mol% or less, the monomer unit (a) and the monomer More preferably, it consists only of unit (b).
  • m1, m2 and m3 are the same or different and represent an integer of 0 or more, not particularly limited.
  • M1, m2 and m3 are the same or different and are preferably 5 or more and 10,000 or less, and particularly preferably 15 or more and 4000 or less.
  • n represents an integer of 0 or more, not particularly limited. Further, n is preferably 2 or more and 20000 or less, and particularly preferably 10 or more and 10,000 or less.
  • Examples of the fluoropolymer of the present invention represented by the above formula (1) include the following formula (2):
  • m1 and m2 are integers of 0 or more, one of which is 2 or more, n1 to n4 are integers of 0 or more, and their sum is 2 or more, a 1 represents -CH 2 CF 2- a 2 represents -CF 2 CF 2- a 3 represents -CF 2 C (CF 3 )- a 4 represents -CF 2 CF (OCF 3 )-
  • the structural units (b 1 ) and (b 2 ) in the formula ( 2 ) are the same or different, and the following formula (B-1):
  • ring B is the same or different for each expression, and each consists of a phenyl group, a naphthyl group, a quinolyl group, an isoquinolyl group, an indole group, or a pyridyl group, each of which may have one or more substituents.
  • the fluorine-containing polymer represented by the formula (2) is represented by the formula (2-1):
  • n1 and n4 are the same or different and represent an integer of 1 or more
  • m1 and m2 are the same or different and represent an integer of 0 or more
  • Either m1 or m2 represents an integer of 2 or more.
  • the fluoropolymer of the present invention may have a graft chain.
  • the formula (1-1) the formula (1-1):
  • n1, n2 and n5 are the same or different and represent an integer of 1 or more, m1 and m2 are the same or different and represent an integer of 0 or more, At least one of m1 and m2 represents an integer of 2 or more, m3 represents an integer of 2 or more.
  • formula (1-2) a structure represented by formula (1-2):
  • R f represents a perfluoroalkyl group having 1 to 3 carbon atoms
  • n1, n6 and n7 are the same or different and represent an integer of 1 or more
  • m1 and m2 are the same or different and represent an integer of 0 or more
  • At least one of m1 and m2 represents an integer of 2 or more
  • m3 represents an integer of 2 or more.
  • a fluorine-containing polymer having a structure represented by:
  • the graft chain when at least one of R 1 to R 4 in the formula (A) or at least one group of R 1 to R 4 is a chlorine atom, a bromine atom or an iodine atom,
  • the starting point may be an atom bonded with a chlorine atom, a bromine atom or an iodine atom.
  • the chlorine atom, bromine atom or iodine atom may remain bonded to at least a part of the atoms that can serve as the starting point.
  • the structure is preferably a block in which monomer units in parentheses to which m1, m2 and m3 are attached are continuous.
  • the partial structures denoted by n1, n2, n3, n4, n5, n6, and n7, respectively are monomer units in parentheses denoted by n1, n2, n3, n4, n5, n6, and n7, respectively. You may combine at random.
  • Ethylene monomer (A) The ethylene monomer (A) that gives the monomer unit (a) of the fluoropolymer of the present invention has the following formula (A):
  • R 1 , R 2 , R 3 and R 4 are the same or different for each expression and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an organic group.
  • R 1 , R 2 , R 3 and R 4 are each a fluorine atom, a chlorine atom, a trifluoromethyl group or a trifluoromethyl ether group. It is preferable that any two, three or all of them are fluorine atoms.
  • fluorine atoms When any three of them are fluorine atoms, the remaining one is a fluorine atom, chlorine atom, bromine atom, iodine atom, perfluoroalkyl group, -OR f group (R f is a C 1-5 carbon atom) Fluoroalkyl group) and the like are preferable.
  • the organic group is not particularly limited, and may be an alkyl group having 1 to 10 carbon atoms that may have one or more substituents, or 1 to carbon atoms that may have one or more substituents.
  • 10 alkoxy groups, a fluoroalkyl group having 1 to 10 carbon atoms which may have one or more substituents, the monomer unit (a), the monomer unit (b), block A, block B and a polymer containing the monomer units (a) and (b) are preferred.
  • the one or more substituents are not particularly limited, and are fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, carboxyl group, acyl group, alkoxy group, alkanoyl group, carbonyl group, thioalkoxy group, ester.
  • the terminal Is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a perfluoroalkyl group, an —OR f group (R f is a perfluoroalkyl group having 1 to 5 carbon atoms) or the like.
  • TFE t
  • Monomer (A) further includes monomers such as (1) fluoroolefin, (2) sulfonic acid-containing trifluorovir monomer, (3) ⁇ -fluoroolefin, and (4) cyano group-containing trifluorovinyl monomer. It may be.
  • each R independently represents a halogen atom or a perfluoroalkyl group having 1 to 10 carbon atoms
  • X 3 represents a halogen atom or a perfluoroalkyl group having 1 to 3 carbon atoms
  • b is an integer from 0 to 8
  • c is 0 or 1
  • d e and f are each independently an integer of 0 to 6 (where d + e + f> 0).
  • CF 2 CF-OCF 2 CF (CF 3 ) OCF 2 CF 2 -SO 2 H
  • CF 2 CF-OCF 2
  • CH 2 CF-CF 2 CF 2 CF 2 H
  • CH 2 CF-CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) -CO 2 Me
  • CH 2 CF-CF 2 OCF ( CF 3) CF 2 OCF (CF 3) -CH 2 OH , and the like.
  • CF 2 CF-O- (CF 2 CF (CF 3 ) O) m (CF 2 ) n -CN (A-5)
  • m is an integer of 0 to 5
  • n is an integer of 1 to 3.
  • CF 2 CF—OCF 2 CF (CF 3 ) OCF 2 CF 2 CN and the like can be mentioned.
  • TFE tetrafluoroethylene
  • CFE chlorotrifluoroethylene
  • HFP hexafluoropropylene
  • Fluorine-containing ethylene monomers such as perfluoro (alkyl vinyl ether) (PAVE) are preferred, and tetrafluoroethylene (TFE) is particularly preferred.
  • R 1 to R 4 in the formula (A) is a chlorine atom, bromine atom or iodine
  • An atom is preferred, and the graft chain can be extended starting from an atom to which the chlorine atom, bromine atom or iodine atom is bonded.
  • a chlorine atom and an iodine atom are preferred, and an iodine atom is more preferred.
  • iodotrifluoroethylene which easily forms a graft chain
  • CX 2 CX-R f -CH 2 RI (A-6) [Where: X represents a hydrogen atom, a fluorine atom or CH 3 ; R f represents a fluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, R represents a hydrogen atom or CH 3 .
  • CF 2 CFO (CF 2 CF (CF 3 )) m -O- (CF 2 ) n -Br (A-7) [Where m is an integer from 0 to 5, and n is an integer from 1 to 3. ] The monomer etc. which are represented by these are mentioned.
  • the monomer (A) a non-fluorinated monomer may be contained.
  • non-fluorine monomers include ethylene, vinyl chloride, vinylidene chloride, vinyl esters, vinyl lactones, vinyl amides, vinyl lactams, vinyl ethers, and the like.
  • the monomer (A) may be only a fluorinated monomer. preferable.
  • Fluorine-containing ethylene monomer (B) The fluorine-containing ethylene monomer (B) that gives the monomer unit (b) of the fluorine-containing polymer of the present invention has the following formula (B):
  • ring B is as defined above. ] It is represented by
  • the ring B is not particularly limited as long as it is an aromatic ring group which may have one or more substituents.
  • each of the rings B may be an aryl group or hetero ring which may have one or more substituents.
  • a phenyl group, a quinolyl group, an isoquinolyl group, a naphthyl group, an indole group, a pyridyl group, a chromenyl group, and a pyrrolyl group each of which may have one or more substituents , Furyl group, thienyl group, imidazole group, benzimidazole group, pyrazolyl group, oxazolyl group, thiazolyl group, pyrazyl group, anthracene ring, phenanthrene ring, pyrene ring, triphenylene ring, pentacene ring, chrysene ring, tetracene ring, picene ring, Examples include a pentaphen ring and a perylene ring. Of these, a phenyl group, a quinolyl group, a naphthyl group and the like, each of which may have one or more
  • the “one or more substituents” in the ring B are not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a carboxyl group, an optionally substituted hydrocarbon group, and a substituent. May have an aryl group, a perfluoro organic group, an acyl group, an alkoxy group, an alkanoyl group, a carbonyl group, a thioalkoxy group, an ester group, a cyano group, a silyl group, a siloxy group, a nitro group, and a substituent.
  • Examples thereof include a good amino group, an amide group optionally having a substituent, a sulfo group, a sulfonate group, a phosphate group, and a phosphate group.
  • it can select suitably according to the characteristic to give to a fluoropolymer.
  • hydrophilicity a hydroxyl group, a carboxyl group and the like are preferable.
  • lipophilicity affinity with an organic solvent
  • a hydrocarbon group, an alkoxy group, and an aryl group are preferable.
  • a cyano group, a halogen atom, a hydroxyl group, an amino group, an alkyl group or an alkoxy group having a nucleophilic functional group for example, hydroxyl group, amino group, etc.
  • a nucleophilic functional group for example, hydroxyl group, amino group, etc.
  • An alkyl group or an alkoxy group having a group for example, an epoxy group, an isocyanate group, an ester group, etc. is preferable.
  • the ring B can be an aromatic ring group having 2 or 3 or more substituents. Those substituents may be the same or different.
  • hydrophilicity or lipophilicity can be selected in accordance with the properties such as hydrophilicity or lipophilicity to be imparted to the material to which the fluorine-containing copolymer is applied.
  • An aromatic ring group having two or more groups to be expressed can be mentioned.
  • hydrophilicity when it is desired to impart hydrophilicity, it can be an aromatic ring group having two or more groups that exhibit hydrophilicity (for example, a hydroxy group, an amino group, a carboxyl group, etc.), and when it is desired to impart lipophilicity.
  • the ring B can be an aromatic ring group having a radical polymerizable group.
  • the substituent may be a trifluorovinyl group or another kind of radically polymerizable group.
  • Another type of radical polymerizable group is not particularly limited, and examples thereof include an organic group having an unsaturated bond, and more specifically, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, and the like.
  • these radical polymerizable groups may or may not react completely. These can be controlled by the production conditions and the type of radical polymerizable group selected.
  • the fluorine-containing polymer of the present invention can be a star polymer or a three-dimensional network polymer.
  • an unreacted radical polymerizable group remains, it can be reacted positively in another process depending on the purpose, for example, a crosslinking (curing) reaction in a molding process, a coating process, etc. Is possible.
  • the monomer (B) of the present invention is not particularly limited as long as it is a compound in which a trifluorovinyl group is bonded to an aromatic ring.
  • trifluorostyrene TMSt
  • 4-trifluorovinyl alkylbenzoate 4 -Trifluorovinylbenzoic acid
  • 4-hydroxytrifluorovinylbenzene 4-alkoxytrifluorovinylbenzene
  • 4-cyanotrifluorovinylbenzene 4-perfluoroalkyltrifluorovinylbenzene
  • 4-fluorotrifluorovinylbenzene 4 -Chlorotrifluorovinylbenzene
  • 4-bromotrifluorovinylbenzene 4-iodotrifluorovinylbenzene
  • 4-aminotrifluorovinylbenzene 4-acetamidotrifluorovinylbenzene
  • positional isomers of the compounds listed above may be used.
  • 3-trifluorovinylbenzoic acid may be used instead of 4-trifluorovinylbenzoic acid
  • trifluorovinyl-2-quinoline may be used.
  • trifluorovinyl-4-quinoline may be used.
  • the fluoropolymer of the present invention can be produced, for example, by the method described below or a method analogous thereto.
  • the fluoropolymer of the present invention comprises a group having a halogen atom or a thiocarbonyl group at at least one of both ends of the main chain containing the repeating monomer unit (a) and the terminal of the side chain, (1) One-electron reducing agent, known radical initiator, transition in polymer Za containing a repeating monomer unit (a) having a tellurium atom to which a group is bonded, with pH adjusted as necessary It can be produced by reacting the monomer (B) in the presence of one or more selected from the group consisting of a metal catalyst and an organic catalyst and / or (2) under light irradiation.
  • halogen atom an iodine atom, a bromine atom, a chlorine atom or the like is used, preferably an iodine atom or a bromine atom is used, and an iodine atom is particularly preferably used.
  • Z 1 and Z 2 are not particularly limited, and examples thereof include an alkyl group, an aryl group, and an alkylene glycol group, and these may be substituted.
  • Ar is preferably a phenyl group which may have a substituent, and more preferably a phenyl group.
  • the functional group in the tellurium atom having a functional group is not particularly limited, and examples thereof include an alkyl group and an aryl group.
  • a methyl group, a butyl group, a phenyl group, and the like are preferable, and a methyl group and a butyl group are more preferable.
  • Y 1 represents a monovalent or divalent metal ion (eg, Na) or an ammonium ion, n is an integer of 0-2.
  • a divalent iron salt and an amine compound e.g., polyamine.
  • polymerization initiators examples include Azo initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile).
  • metal species of the transition metal catalyst Cu, Ru, Fe, Ni, Ti, Co, Mn and the like are usually used, and Cu, Ru and Fe are preferable.
  • the above transition metal catalyst is preferably used in the presence of a ligand.
  • a low molecular compound having 2 to 6 nitrogen atoms is usually used, and one having 2 to 4 is preferable.
  • 2,2-bipyridyl (bipyridine) N, N ′, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, tris (2-pyridylmethyl) amine, tris [2- (Dimethylamino) ethyl] amine or the like is used.
  • organic catalyst quaternary ammonium salts, quaternary phosphonium salts, polycyclic compounds [eg, perylene] and the like are usually used.
  • quaternary ammonium salts quaternary phosphonium salts, polycyclic compounds [eg, perylene] and the like are usually used.
  • tetraalkylammonium iodide, tetraalkylphosphonium iodide and tributylmethylammonium iodide are preferably used, and tetrabutylammonium iodide and tributylmethylammonium iodide are particularly preferably used.
  • a temperature at which the reaction proceeds appropriately may be appropriately selected, and the temperature can be, for example, 0 to 120 ° C.
  • reaction time of the reaction a time sufficient for the reaction to proceed appropriately may be set as appropriate.
  • the time can be, for example, 0.5 to 50 hours.
  • the reaction may be performed in the presence of an inert gas (eg, helium gas, nitrogen gas, argon gas).
  • an inert gas eg, helium gas, nitrogen gas, argon gas.
  • the fluoropolymer of the present invention thus obtained can be purified by a conventional method such as reprecipitation and centrifugation using water, hexane or the like, if desired.
  • the fluoropolymer in which the monomer unit (a) is a monomer unit derived from tetrafluoroethylene is tetrafluoroethylene as the ethylene monomer (A)
  • the manufacturing method is, for example, In the presence of a polymerization initiator and in a solvent, a first polymerization reaction for polymerizing tetrafluoroethylene is reacted to obtain an active polytetrafluoroethylene polymerization intermediate, and active polytetrafluoro obtained in step A
  • the fluorine-containing ethylene monomer (B) is polymerized in the presence of an ethylene polymerization intermediate to obtain a fluorine-containing polymer in which the monomer unit (a) is a monomer unit derived from tetrafluoroethylene.
  • Stage B Can be a manufacturing method.
  • reaction conditions of stage A and the reaction conditions of stage B may be appropriately set according to, for example, the desired degree of polymerization of tetrafluoroethylene and the desired fluorine-containing ethylene monomer (B).
  • the following conditions can be employed.
  • the reaction of Step A can be suitably carried out in a pressure resistant reactor under pressure within a range of 0.1 MPaG to 2.0 MPaG with tetrafluoroethylene.
  • the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate. And diisopropyl peroxydicarbonate.
  • the polymerization initiator can be suitably used in an amount of 0.001 g to 5 g with respect to 100 g of tetrafluoroethylene, for example.
  • solvent examples include pentane, hexane, heptane, octane, isooctane, cyclohexane, benzene, toluene, xylene, petroleum ether, commercially available petroleum solvents (eg, EXXSOL D40 and ISOPER E [both trade names, ExxonMobil ), Tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, t-butyl acetate, isopropyl alcohol, propylene glycol methyl ether acetate, p-chlorobenzotrifluoride, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodi
  • the solvent can be one type or a combination of two or more types.
  • the solvent can be suitably used, for example, in an amount of 100 g to 500 kg with respect to 100 g of tetrafluoroethylene.
  • the reaction temperature of step A can preferably be in the range of ⁇ 50 to 150 ° C.
  • the reaction time for stage A can preferably be in the range of 0.1 to 48 hours.
  • the reaction of Step A can be suitably carried out with stirring. Stage A provides an active polytetrafluoroethylene polymerized intermediate.
  • Stage B is carried out after the reaction of stage A, i.e. in the presence of an active polytetrafluoroethylene polymerization intermediate.
  • tetrafluoroethylene remaining in the gas phase portion in the reaction vessel may be removed.
  • the fluorine-containing ethylene monomer (B) can be suitably used in an amount of 0.01 g to 100 g with respect to 100 g of tetrafluoroethylene.
  • the reaction temperature of stage B can preferably be in the range of ⁇ 50 to 100 ° C.
  • the reaction time for stage B can suitably be in the range of 0.1 to 48 hours.
  • the reaction of step B can be suitably carried out with stirring.
  • the fluoropolymer of the present invention thus obtained can be purified by a conventional method such as chloroform washing, if desired.
  • the fluoropolymer of the present invention can be obtained by performing the step B using a separately prepared polytetrafluoroethylene powder (generally, the active terminal remains as is generally known) without performing the step A. Can be obtained.
  • the said solvent may be used, superposition
  • Production Example 1 (Production of VdF / HFP copolymer elastomer having —CH 2 I at both ends of the main chain )
  • Pure water (1500 g) and 20 wt% aqueous solution of ammonium perfluorooctanoate (22 g) were supplied to the 3 L autoclave.
  • the inside of the system was replaced with an inert gas and the pressure was reduced.
  • the internal temperature was set to 80 ° C.
  • HFP was supplied until the internal pressure reached 0.73 MPa
  • VdF was supplied until the internal pressure reached 1.5 MPa.
  • VdF / HFP copolymer having —CH 2 I at both ends of the main chain was isolated and purified.
  • the number average molecular weight in terms of polystyrene as measured by GPC was 19,400.
  • Sodium dithionite (46.7 mg) and sodium hydrogen carbonate (8.40 mg) were added, and the inside of the system was sufficiently deaerated and replaced with an inert gas.
  • 4-trifluorovinylbenzoic acid (483 mg) was added, and the mixture was heated with stirring at 50 ° C. for 8 hours. Purification was performed by reprecipitation and centrifugation using water and hexane.
  • a TFE / PMVE copolymer (168 g) having —CF 2 I at one end of the main chain was isolated and purified from the obtained emulsion (1290 g).
  • the average molecular weight was 75000 from Mooney viscosity measurement.
  • the raw material polymer (tetrafluoroethylene and perfluoromethyl vinyl ether copolymer, 3.16 g) synthesized in Production Example 2 and a fluorinated solvent (ClCF 2 -CFCl-C 2 F 5 , 25.0 mL) are placed in a reaction vessel, and the raw material is added. Stir until the polymer is dissolved.
  • the reaction mixture was degassed and the inside of the vessel was purged with nitrogen, and then Azo initiator [2,2′-azobis (2,4-dimethylvaleronitrile)] (8.00 mg), trifluorostyrene (2.00 g) and toluene (2.0 mL) was added. Further, the inside of the container was sufficiently purged with nitrogen.
  • the mixture was heated and stirred at 50 ° C. for 8 hours. After reprecipitation using water and hexane for purification, the trifluorostyrene homopolymer was removed by washing thoroughly with chloroform and acetone to obtain the target block polymer. By 1 H NMR measurement, a broad peak was observed in the aromatic region, and the presence of a skeleton formed by polymerization of trifluorostyrene was confirmed. From the results of elemental analysis, it was found that the polymer contained 67.7 wt% of fluorine element and 10 mol% of skeleton derived from trifluorostyrene.
  • the raw material polymer (tetrafluoroethylene and perfluoromethyl vinyl ether copolymer, 1.48 g) synthesized in Production Example 2 and a fluorine-containing solvent (ClCF 2 -CFCl-C 2 F 5 , 12.0 mL) are placed in a reaction vessel, and the polymer Stir until dissolved.
  • the reaction mixture was degassed, and the inside of the vessel was purged with nitrogen.
  • Azo initiator [2,2′-azobis (2,4-dimethylvaleronitrile)] (5.50 mg)
  • styrene (1.00 g)
  • toluene 1.0 mL
  • the mixture was heated and stirred at 50 ° C. for 8 hours. After reprecipitation using water and hexane for purification, the trifluorostyrene homopolymer was removed by washing thoroughly with chloroform and acetone to obtain the target block polymer. By 1 H NMR measurement, a broad peak was observed in the aromatic region, and the presence of a skeleton formed by polymerization of trifluorostyrene was confirmed. From the results of elemental analysis, it was found that 60.3 wt% of fluorine element was contained, and that the polymer was a polymer containing 19 mol% of a styrene-derived skeleton.
  • Example 8 Heat resistance test of polymer
  • TG / DTA measurement was performed on the block polymers synthesized in Production Examples 1 and 2, Examples 1 and 7, and Comparative Examples 1 and 2, respectively, and a polytrifluorostyrene block was included in the main chain; and The thermal stability was evaluated for each case containing a polystyrene block.
  • the results of the TG / DTA measurement (decomposition start temperature) are shown in Tables 1 and 2 below. From the results shown in these tables, it was confirmed that a polymer having high heat resistance was obtained by utilizing a trifluorostyrene skeleton in which the main chain generated after polymerization becomes a perfluoroalkyl skeleton.
  • Example 9 Evaluation of lipophilicity of polymer
  • the contact angle measurement with respect to hexanedecane was performed on the polymers synthesized in Production Example 2 and Example 7 by the sample preparation method and the measurement method described later, respectively, and when the polytrifluorostyrene block was introduced into the main chain. Each case was evaluated for lipophilicity.
  • the contact angle measurement results (lipophilicity) are shown in Table 3 below. From the results shown in this table, it is confirmed that when a polytrifluorostyrene skeleton is introduced into the main chain after polymerization, it has a similar degree of heat resistance but higher lipophilicity than when it is not. It was done.
  • Sample preparation method A polymer solution was prepared by dissolving the polymer to be tested in ClCF 2 —CFCl—C 2 F 5 so as to have a concentration of 0.1 wt%. The polymer solution was dropped on a cover glass and air-dried in a fume hood, and then air-dried at 100 ° C. for 2 hours to prepare a polymer film. Measurement method: The contact angle after hexadecane (2 ⁇ L) was dropped onto the polymer film obtained by the sample preparation method and allowed to stand for 21 hours was measured.
  • Example 10 Blocking with unsubstituted trifluorostyrene [Fluorine-containing unit is PTFE]
  • PTFE Fluorine-containing unit
  • To the pressure-resistant reaction vessel 5 mL each of 1,3-bis (trifluoromethyl) benzene / HFE7300 mixed solvent was added. After sealing the container, the inside of the container was sufficiently replaced with an inert gas, and then a small amount of TFE was added to bring it into a slightly pressurized state. After raising the temperature to 70 ° C., TFE was added under pressure until TFE 0.7 MPaG was reached. Subsequently, tert-butyl peroxypivalate (0.14 g) was added and stirred with heating for 30 minutes.
  • Example 11 (grafting with unsubstituted trifluorostyrene)
  • the raw material polymer 250 mg
  • dimethyl sulfoxide (1.50 mL)
  • ClCF 2 -CFCl—C 2 F 5 (1.50 mL)
  • trifluorostyrene (3.00 g) prepared in Production Example 3 were added to the reaction vessel.
  • the inside of the reaction vessel was sufficiently purged with nitrogen.
  • sodium dithionite 49.6 mg was added, and the mixture was stirred with heating at 50 ° C. for 19 hours.
  • the resulting reaction mixture was purified by washing operations using various media to obtain the desired graft polymer (535 mg).
  • the obtained graft polymer was dispersed in deuterated chloroform, and 1H NMR and 19F NMR measurements were performed. A broad peak was observed in the aromatic region (8.4-5.0 ppm) on the 1H NMR chart, and a structure derived from the starting polymer was confirmed on the 19F NMR chart. From these, it was confirmed that trifluorostyrene was graft-polymerized. According to solid 19F NMR measurement, the ratio of the polytrifluorostyrene skeleton in the obtained polymer was 60 mol%.
  • Example 12 (grafting with unsubstituted trifluorostyrene)
  • the raw material polymer produced in Production Example 3 250 mg
  • dimethyl sulfoxide (0.150 mL)
  • ClCF 2 -CFCl—C 2 F 5 (2.85 mL)
  • 15-crown-5-ether 67 mg
  • Trifluorostyrene 3.00 g
  • sodium dithionite 49.6 mg
  • the resulting reaction mixture was purified by washing operations using various media to obtain the desired graft polymer (464 mg).
  • the obtained graft polymer was dispersed in deuterated chloroform, and 1H NMR and 19F NMR measurements were performed. A broad peak was observed in the aromatic region on the 1H NMR chart, and a structure derived from the starting polymer was confirmed on the 19F NMR chart. From these, it was confirmed that trifluorostyrene was graft-polymerized. Further, the results of elemental analysis revealed that 2.5% by weight of iodine element was contained, and in the graft polymer, 3.9 mol% of units having iodine atoms in the side chain remained. Solid 19F NMR measurement showed that the ratio of the polytrifluorostyrene skeleton in the obtained polymer was 46 mol%. Solid 19F NMR: ⁇ F ⁇ 79, ⁇ 108, ⁇ 119, ⁇ 171 ppm
  • Example 13 Heat resistance test of polymer
  • TG / DTA measurement was performed on each of the block polymers synthesized in Production Example 3 and Example 12, and the thermal stability was evaluated for the case where a polytrifluorostyrene block was included in the graft chain.
  • the results of the TG / DTA measurement (0.1% and 1% weight loss temperature) are shown in Table 4 below. From this result, by using a trifluorostyrene skeleton in which the main chain skeleton in the graft chain generated after polymerization becomes a perfluoroalkyl skeleton, a polymer having the same heat resistance as the perfluoropolymer used as a raw material can be obtained. It was confirmed that

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Abstract

La présente invention aborde le problème consistant à introduire un monomère présentant les caractéristiques souhaitées dans un polymère contenant du fluor, ce qui permet de conférer au polymère contenant du fluor lesdites caractéristiques souhaitées, et en outre, à fournir un polymère présentant une meilleure stabilité thermique et une meilleure stabilité chimique. Le problème est résolu par un polymère contenant du fluor contenant un motif monomère (a) dérivé d'au moins un monomère d'éthylène (A) possédant une structure spécifique, et un motif monomère (b) dérivé d'au moins un monomère d'éthylène contenant du fluor (B) possédant une structure spécifique, le bloc B formé des motifs monomères (b) en série étant fourni à au moins une extrémité terminale parmi les extrémités terminales des chaînes latérales et aux deux extrémités terminales de la chaîne principale.
PCT/JP2016/070748 2015-07-13 2016-07-13 Polymère contenant du fluor Ceased WO2017010531A1 (fr)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2000502625A (ja) * 1996-01-05 2000-03-07 バラード パワー システムズ インコーポレイティド α，β，β―トリフルオロスチレンをベースとする複合膜および置換α，β，β―トリフルオロスチレンをベースとする複合膜
JP2004529472A (ja) * 2001-05-15 2004-09-24 バラード パワー システムズ インコーポレイティド 改善されたイオン伝導性を有するイオン交換物質
JP2007536391A (ja) * 2004-05-07 2007-12-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ベースポリマーにグラフトされた安定なトリフルオロスチレン含有化合物

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JP2004529472A (ja) * 2001-05-15 2004-09-24 バラード パワー システムズ インコーポレイティド 改善されたイオン伝導性を有するイオン交換物質
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