WO2022025237A1 - Dérivé d'oxyde de diarylphosphine - Google Patents

Dérivé d'oxyde de diarylphosphine Download PDF

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WO2022025237A1
WO2022025237A1 PCT/JP2021/028295 JP2021028295W WO2022025237A1 WO 2022025237 A1 WO2022025237 A1 WO 2022025237A1 JP 2021028295 W JP2021028295 W JP 2021028295W WO 2022025237 A1 WO2022025237 A1 WO 2022025237A1
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group
substituted
salt
unsubstituted
compound
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由佳 美濃
広幸 篠原
優斗 北村
直倫 西村
博良 藤野
英市 伊川
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片山化学工業株式会社
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Priority to JP2022539596A priority Critical patent/JPWO2022025237A1/ja
Priority to CN202180059755.7A priority patent/CN116157409A/zh
Publication of WO2022025237A1 publication Critical patent/WO2022025237A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • 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
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present disclosure relates to diarylphosphine oxide derivatives.
  • Phosphorus compounds are used in various applications due to their properties. It is meaningful to provide a novel phosphorus-containing compound.
  • the present disclosure provides a method for synthesizing a diarylphosphine oxide derivative, which has been considered to be particularly difficult in the past.
  • R 1 and R 2 are aryl groups that are different or identical and each independently has a substituent.
  • Ra is a group having an unsaturated double bond, a group having an epoxy group, a group containing a hydroxy group, or a group containing a phosphorus.
  • Phosphine oxide compound or salt thereof is a group having an unsaturated double bond, a group having an epoxy group, a group containing a hydroxy group, or a group containing a phosphorus.
  • Phosphine oxide compound or salt thereof (Item 2) The phosphine oxide compound or a salt thereof according to item 1, wherein the aryl groups in R 1 and R 2 each independently have one, two or three substituents.
  • Item 3 Item 2.
  • Item 4 Item 2.
  • IItem 5) Item 2.
  • Item 6 Item 6.
  • Item 10 Item 4.
  • the phosphine oxide compound or a salt thereof according to the section. (Item 13) Ra is
  • R 3 and R 4 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • n is 1 or 2
  • each R 3 may be the same or different, and each R 4 may be the same or different.
  • R5 is a hydrogen, or substituted or unsubstituted alkyl group
  • R 6 , R 7 , R 8 and R 9 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • n 1 and n 2 are 1 to 3 independently of each other.
  • each R 6 may be the same or different
  • each R 7 may be the same or different.
  • each R 8 may be the same or different, and each R 9 may be the same or different.
  • Item 14 Item 6.
  • the phosphine oxide compound has the following general formula (I).
  • R 1 , R 2 are as described in item 1
  • R 3 , R 4 , n and R 5 are as described in item 13, the compound or salt thereof according to item 13. ..
  • (Item 16) The phosphine oxide compound or a salt thereof according to item 15, wherein the aryl groups in R 1 and R 2 each independently have one, two or three substituents.
  • (Item 17) The phosphine oxide compound or a salt thereof according to item 16, wherein the substituent on the aryl group in R 1 and R 2 is a substituted or unsubstituted alkyl.
  • the phosphine oxide compound has the following general formula (II).
  • R 1 , R 2 are as described in item 1, and R 6 , R 7 , R 8 , R 9 , n 1 , and n 2 are as described in item 13. 13.
  • Item 19 Item 6.
  • Item 20 Item 19.
  • the phosphine oxide compound has the following general formula (III).
  • R 1 and R 2 are the compounds according to item 13 or salts thereof, as described in item 1.
  • the phosphine oxide compound has the following general formula (IV).
  • R 1 and R 2 are the compounds according to item 1 or salts thereof, as described in item 1.
  • R 10 , R 11 , R 12 and R 13 are independently hydrogen, halogen groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or Unsubstituted heterocyclic group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted thioalkoxy group, substituted or unsubstituted alkoxycarbonyl group.
  • n 3 , n 4 and n 5 are 0 to 3, respectively.
  • Item 24 The compound or salt thereof.
  • the aryl groups in R 1 and R 2 each independently have three substituents, n 3 and n 4 are 0, n 5 is 1-3, and Ar is unsubstituted.
  • the compound or salt thereof. (Item 30)
  • the phosphine oxide compound has the following general formula (IVa).
  • R 10 and R 11 are independently hydrogen, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted heterocyclic group, substituted, respectively.
  • an unsubstituted or unsubstituted aryl group a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted thioalkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkylcarbonyl.
  • Selected from the group consisting of groups and substituted or unsubstituted aminocarbonyl groups Item 24.
  • the compound or salt thereof The phosphine oxide compound or a salt thereof according to item 30, wherein the aryl groups in R 1 and R 2 each have three independent substituents.
  • R 1 and R 2 are independently substituted or unsubstituted aryl groups, respectively.
  • R 3 and R 4 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • n is 1 or 2
  • each R 3 may be the same or different, and each R 4 may be the same or different.
  • R5 is a homopolymer or copolymer comprising hydrogen or a substituted or unsubstituted alkyl group as a constituent. (Item 34) 33.
  • copolymer according to item 33 which is a copolymer with (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid halide, (meth) acrylic acid salt, styrene or acrylonitrile.
  • (Item 35) The following general formula (VI)
  • R 1 and R 2 are independently substituted or unsubstituted aryl groups, respectively.
  • R 6 , R 7 , R 8 and R 9 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • n 1 and n 2 are independently 1 or 2, respectively.
  • each R 6 may be the same or different, and each R 7 may be the same or different.
  • each R 8 may be the same or different, and each R 9 may be the same or different) as a constituent component.
  • the copolymer according to item 35 which is a copolymer with an epoxy compound.
  • (Item 37) Additives comprising the compound or salt according to any one of items 1-32 or the homopolymer or copolymer according to any one of items 33-36.
  • (Item 38) An anti-fog agent comprising the compound or salt according to any one of items 1 to 32, or the homopolymer or copolymer according to any one of items 33 to 36.
  • (Item 39) A flame retardant comprising the compound or salt according to any one of items 1 to 32, or the homopolymer or copolymer according to any one of items 33 to 36.
  • (Item 43) A surface modifier comprising the compound or salt according to any one of items 1-32 or the homopolymer or copolymer according to any one of items 33-36.
  • (Item 44) A phosphorus-imparting agent comprising the compound or salt according to any one of items 1 to 32, or the homopolymer or copolymer according to any one of items 33 to 36.
  • (Item 45) The compound or salt according to any one of items 1 to 32 in an electric / electronic-related part, an OA-related part, an automobile part, a train part, an aircraft part, a fiber, a sheet, a film, or an acrylic glass.
  • Use of the compound or salt according to any one of 32, or the homopolymer or copolymer according to any one of items 33-36. (Item 46)
  • the compound or salt according to any one of items 1 to 32, or the homopolymer or copolymer according to any one of items 33 to 36 can be used for electrical / electronic related parts, OA related parts, and automobile parts.
  • a method comprising the step of applying the compound or salt, or the homopolymer or copolymer, to an object in need thereof.
  • the present disclosure provides a novel compound that is a diarylphosphine oxide derivative.
  • Materials using this novel compound have low water absorption and can be used for various purposes.
  • the fluctuation of the aryl group is suppressed by introducing a substituent such as a methyl group which causes steric hindrance into the aryl group, the loss is reduced, and the dielectric constant (Dk) and the dielectric tangent (Df) are reduced. ) Is lower, and a highly insulating resin can be obtained.
  • FIG. 1 shows the results of GC-MS of the product of Example 1.
  • FIG. 2 shows the results of GC-MS of the product of Example 2.
  • substitution means replacing a specific hydrogen atom of an organic compound with another atom or atomic group.
  • substituted refers to an atom or functional group in which another substance is substituted in the chemical structure.
  • substitutions are made by replacing one or more hydrogen atoms in an organic compound or substituent with another atom or group of atoms, or as a double or triple bond. That means. It is also possible to remove one hydrogen atom and replace it with a monovalent substituent, or combine it with a single bond to form a double bond, and remove two hydrogen atoms into a divalent substituent. It can be substituted or combined with a single bond to form a triple bond.
  • C1, C2 ,,, and Cn represent the number of carbon atoms (where n represents an arbitrary positive integer). Therefore, C1 is used to represent a substituent with one carbon atom.
  • alkyl refers to a monovalent group produced by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, or propane, and is generally represented by C n H 2n + 1- . (Here, n is a positive integer).
  • alkane an aliphatic hydrocarbon
  • propane propane
  • C n H 2n + 1- a positive integer
  • the alkyl can be straight or branched.
  • substituted alkyl refers to an alkyl in which H of the alkyl is substituted with the substituents defined above.
  • C1 to C2 alkyl C1 to C3 alkyl, C1 to C4 alkyl, C1 to C5 alkyl, C1 to C6 alkyl, C1 to C7 alkyl, C1 to C8 alkyl, C1 to C9 alkyl, and C1 to C10 alkyl.
  • C1 to C11 alkyl or C1 to C20 alkyl C1 to C2 substituted alkyl, C1 to C3 substituted alkyl, C1 to C4 substituted alkyl, C1 to C5 substituted alkyl, C1 to C6 substituted alkyl, C1 to C7 substituted alkyl, C1 to C8 It can be substituted alkyl, C1-C9 substituted alkyl, C1-C10 substituted alkyl, C1-C11 substituted alkyl or C1-C20 substituted alkyl.
  • C1 to C10 alkyl means a linear or branched alkyl having 1 to 10 carbon atoms, and is methyl (CH 3- ), ethyl (C 2 H 5- ), n-propyl.
  • (CH 3 CH 2 CH 2- ) isopropyl ((CH 3 ) 2 CH-), n-butyl (CH 3 CH 2 CH 2 CH 2- ), n-pentyl (CH 3 CH 2 CH 2 CH 2 CH 2 ) -), N-hexyl (CH 3 CH 2 CH 2 CH 2 CH 2 CH 2- ), n-heptyl (CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2- ), n-octyl (CH 3 CH) 2 CH 2 CH 2 CH 2 CH 2 CH 2- ), n-nonyl (CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2- ), n-decyl (CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2- ), n-decyl (CH 3 CH 2 CH
  • cycloalkyl group refers to an alkyl having a cyclic structure. Specific examples include C3 to C4 cycloalkyl, C3 to C5 cycloalkyl, C3 to C6 cycloalkyl, C3 to C7 cycloalkyl, C3 to C8 cycloalkyl, C3 to C9 cycloalkyl, C3 to C10 cycloalkyl, and C3 to C11.
  • cyclopropyl, cyclohexyl and the like are exemplified as cycloalkyl.
  • the "substituted cycloalkyl group” means a hydrogen-substituted cycloalkyl group.
  • alkoxy group refers to a monovalent group generated by the loss of the hydrogen atom of the hydroxy group of alcohols, and is generally represented by Cn H 2n + 1 O- (where n is 1 or more). Is an integer of).
  • substituted alkoxy group refers to an alkoxy in which H of alkoxy is substituted by the substituent defined above. Specific examples include C1 to C2 alkoxy, C1 to C3 alkoxy, C1 to C4 alkoxy, C1 to C5 alkoxy, C1 to C6 alkoxy, C1 to C7 alkoxy, C1 to C8 alkoxy, C1 to C9 alkoxy, and C1 to C10 alkoxy.
  • C1 to C10 alkoxy means linear or branched alkoxy containing 1 to 10 carbon atoms, and methoxy (CH 3 O-), ethoxy (C 2 H 5 O-), and the like. Examples thereof include n-propoxy (CH 3 CH 2 CH 2 O-).
  • heterocyclic group refers to a group having a cyclic structure that also contains carbon and a heteroatom.
  • the heteroatom is selected from the group consisting of O, S and N, and may be the same or different, and may contain one or two or more.
  • Heterocyclic groups can be aromatic or non-aromatic and can be monocyclic or polycyclic.
  • the heterocyclic group may be substituted.
  • substituted heterocyclic group means a heterocyclic group in which hydrogen is substituted.
  • aryl group refers to a group formed by the detachment of one hydrogen atom bonded to the ring of an aromatic hydrocarbon. Phenyl group (C 6 H 5- ) from benzene, tolyl group (CH 3 C 6 H 4- ) from toluene, xylyl group ((CH 3 ) 2 C 6 H 3- ) from xylene, naphthyl from naphthalene. The group (C 10 H 8- ) is induced. The number of carbon atoms may be 6 to 12.
  • Aryl groups include monocyclic (phenyl group), dicyclic (naphthyl group) and tricyclic (anthrasenyl group and the like).
  • heteroaryl group refers to a group in which one or more carbon atoms constituting the ring of an aromatic hydrocarbon are substituted with a heteroatom. Examples include, but are not limited to, pyridine, pyrrole, thiophene, furan, imidazole, oxazole, thiazole, indol, quinoline, isoquinoline, quinoxalin, pyrazine, benzimidazole.
  • aryloxy group refers to a monovalent group generated by the loss of a hydrogen atom of a hydroxy group of an aryl group substituted with a hydroxy group, and is not limited to, for example, C. Examples thereof include 6 H 5 O-, CH 3 C 6 H 4 O-, (CH 3 ) 2 C 6 H 3 O-, and C 10 H 8 O-.
  • the "thioalkoxy group” is a group in which the oxygen atom of the "alkoxy group” is replaced with a sulfur atom, and is generally represented by -SR (where R is an alkyl group).
  • alkoxycarbonyl group refers to a group represented by -C (O) OR (where R is an alkyl group).
  • R is an alkyl group.
  • substituted alkoxycarbonyl group means a hydrogen-substituted alkoxycarbonyl group.
  • halogen (group) refers to elements such as chlorine (Cl), bromine (Br), and iodine (I) that belong to Group 17 of the Periodic Table (referred to as Group 17 in the recent definition). Refers to the monovalent group of.
  • alkylcarbonyl group refers to a monovalent group formed by removing OH from a carboxylic acid.
  • Representative examples of the alkylcarbonyl group include acetyl (CH 3 CO-), C 2 H 5 CO- and the like.
  • the number of carbon atoms in the alkyl moiety may be 1 to 6 or the like.
  • the "substituted alkylcarbonyl group” is one in which the hydrogen of the acyl is substituted with the substituents defined above.
  • aminocarbonyl group is a group in which hydrogen of ammonia or amine is substituted with an acid group (acyl group).
  • substituted aminocarbonyl group refers to a group in which hydrogen on nitrogen is substituted.
  • the aminocarbonyl group is also referred to as an amide.
  • allylen group refers to a group formed by the detachment of two hydrogen atoms bonded to the ring of an aromatic hydrocarbon.
  • Phenylene group (-C 6 H 4- ) from benzene, methyl phenylene group (-CH 3 C 6 H 3- ) from toluene, dimethylphenylene group (-(CH 3 ) 2 C 6 H 3- ) from xylene.
  • a naphthylene group (-C 10 H 7- ) is derived from naphthalene. The number of carbon atoms may be 6 to 12.
  • heteroarylene group refers to a group in which one or more carbon atoms constituting the ring of an aromatic hydrocarbon are substituted with a heteroatom and have two bonding points. Examples include, but are not limited to, pyridinediyl, pyrrol diyl, thiophene diyl, frangyl, imidazole diyl, oxazole diyl, thiazole diyl, indole diyl, quinoline diyl, isoquinoline diyl, quinoxaline diyl, pyrazine diyl, benzimidazole diyl. ..
  • group having an unsaturated double bond is a group containing a carbon-carbon double bond such as an alkene, a carbon-only group such as ethylene or propylene, and a carboxylate such as acrylic or methacryl. Examples include groups including groups.
  • group having an epoxy group means a group having oxacyclopropane (oxylan), which is a 3-membered ring ether, in its structural formula.
  • epoxy compound refers to a compound containing an epoxy group. It may include groups such as those listed in “Groups with Epoxy Groups”.
  • group containing a hydroxy group means any group containing a hydroxy group as a functional group. It also contains groups including OH groups in aromatics such as phenol. Examples thereof include a hydroxyphenyl group, a dihydroxyphenyl group and a trihydroxyphenyl group.
  • the "phosphorus-containing group” includes any group containing phosphorus.
  • Phosphorus may be phosphine oxide, phosphindioxy (hypophosphoric acid), phosphintrioxide (phosphoric acid), phosphintetraoxide (phosphoric acid).
  • linker refers to a group that connects two or more groups.
  • the linker can be a non-reactive group in the application in which it is used.
  • polymer is also referred to as a polymer, and is a substance consisting of one or several kinds of atoms or atomic groups as a constituent unit, which are repeatedly linked to each other, and the constituents of the molecule. It is a substance in which the number of repetitions of a unit is very large, and a certain physical property of the substance does not change by increasing or decreasing one or several constituent units.
  • Polymers can include homopolymers and copolymers.
  • the term "monomer” is also referred to as a monomer, and refers to a compound that can be a constituent unit of the basic structure of a polymer by a polymerization reaction. In some cases, one type of monomer forms multiple types of structural units.
  • the monomers of the present disclosure can also be bonded to other substances via radical polymerization.
  • homomopolymer is also referred to as a homopolymer, and refers to a polymer obtained by polymerization using a single monomer.
  • the term "copolymer” is also referred to as a copolymer, and refers to a polymer obtained by polymerization using a plurality of monomers.
  • the monomer may be formed by copolymerization with a monomer different from the monomer of the present disclosure.
  • Monomers different from the monomers of the present disclosure include (meth) acrylic acid, (meth) acrylic acid esters (eg, (meth) methyl acrylate), (meth) acrylic acid halides, (meth) acrylates, styrene or Acrylonitrile and the like can be mentioned.
  • polymerization refers to a reaction in which a high molecular weight compound (polymer) is produced from a low molecular weight compound (monomer).
  • (meth) acrylic acid refers to acrylic acid and / or methacrylic acid.
  • acid halide is also referred to as an acid halide and refers to a compound in which the OH group contained in the carboxyl group of a carboxylic acid is replaced with a halogen.
  • halogen there are four types: acid fluoride, acid chloride, acid bromide, and acid iodide.
  • base refers to the definition of Bronsted-Lowry and refers to a substance that receives protons.
  • Examples of the “base” include salts of weak acids and alkali metals. Alkali carbonate metals (eg, K 2 CO 3 ) can be mentioned.
  • alkali metal means lithium, sodium, potassium, rubidium, cesium and francium.
  • (meth) acrylic acid means acrylic acid, methacrylic acid, or both.
  • the "additive” means a substance added to an arbitrary substance.
  • anti-fog agent refers to a substance that maintains the transparency of a certain material (for example, polyacrylic acid), and the retention of transparency is typically due to making the surface of the substance more hydrophobic. ..
  • phosphorus-imparting agent refers to a substance that imparts a phosphorus component to a certain substance, and is typically achieved by binding a group containing phosphorus to a certain substance.
  • the phosphorus-imparting agent having a (meth) acrylic group can bind a group containing a phosphorus to a compound having a radically polymerizable group by radical polymerization.
  • Phosphorin-imparting agents are used in the manufacture of, for example, fertilizers, pesticides, pharmaceuticals, pesticides, explosives, electronic materials, catalysts, flame retardants, metal surface treatment agents, detergents, antifreezes, surfactants, defoamers, and lubricants. Can be used.
  • the "radical polymerizable group” means an arbitrary group polymerized by a radical reaction. Typical examples include, but are not limited to, a group having an unsaturated double bond at the end of the substituent. Examples of such radically polymerizable groups include, but are not limited to, allyl, substituted allyl, styrene, substituted styrene, acrylic, substituted acrylic, methacrylic, substituted methacrylic and the like.
  • the compounds of the present disclosure include salts.
  • alkali metals lithium, sodium or potassium, etc.
  • alkaline earth metals calcium, etc.
  • magnesium transition metals
  • zinc transition metals
  • ammonium salts with organic bases and amino acids, or inorganic acids (hydrochloride, sulfuric acid, etc.).
  • the compounds of the present disclosure are not limited to specific isomers, but all possible isomers (keto-enol isomer, imine-enamine isomer, diastereoisomer, optical isomer, rotational isomer, etc.). And isomers are included.
  • One or more hydrogen, carbon or other atoms of the compounds of the present disclosure may be substituted with isotopes of hydrogen, carbon or other atoms.
  • the compounds of the present disclosure include all radioactive labels of the compounds of the present disclosure. Examples of isotopes that can be incorporated into the compounds of the present disclosure are 2 H, 3 H, 11 C, 13 C, 14 C, 15 N, 18 O, 17 O, 31 P, 32 P, 35 S, 18 respectively. Includes hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, iodine and chlorine, such as F, 123 I and 36 Cl.
  • R 1 R 2 A phosphine oxide compound or a salt thereof, which is indicated by During the ceremony R 1 and R 2 are aryl groups that are different or identical and each independently has a substituent.
  • Ra is a group having an unsaturated double bond, a group having an epoxy group, a group containing a hydroxy group, or a group containing a phosphorus.
  • a phosphine oxide compound or a salt thereof is provided.
  • the products of various compounds derived from the diarylphosphine oxide derivatives having a substituent on the aryl group of the present disclosure have an electrical loss as compared with the case of a phosphine oxide of an aryl group having no corresponding substituent. It can be a product having a small amount of (dielectric tangent, Df), a lower dielectric constant (Dk), and a lower dielectric tangent (Df), and a high insulating property.
  • Df dielectric tangent
  • Dk dielectric constant
  • Df dielectric tangent
  • Insulation can be high.
  • the aryl groups in R 1 and R 2 each independently have one, two or three substituents. By adjusting the number of substituents, a product with desirable electrical properties can be obtained.
  • each of the aryl groups in R 1 and R 2 has one substituent.
  • the aryl groups in R 1 and R 2 each have two substituents.
  • the aryl groups in R 1 and R 2 each have three substituents.
  • the introduction of polar groups allows the conductivity to be adjusted and the desired product can be prepared.
  • R 1 and R 2 the substituents are independently -C1 to C4 alkyl groups, respectively.
  • the aryl group having the substituent is a monocyclic, bicyclic or tricyclic ring having the substituent.
  • the size of the ring of the aryl group can adjust the dielectric loss tangent (Df) to prepare the desired product.
  • the aryl group having the substituent is a phenyl group having the substituent.
  • R 1 and R 2 are identical to each other.
  • Ra is a group having an unsaturated double bond at the end, a group having an epoxy group at the end, an aryl group having two or more hydroxys, or a group containing a phosphine oxide. By adjusting Ra , it can be used for various purposes.
  • Ra is N-(2-aminoethyl)-2-aminoethyl
  • R 3 and R 4 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • n is 1 or 2
  • each R 3 may be the same or different, and each R 4 may be the same or different.
  • R5 is a hydrogen, or substituted or unsubstituted alkyl group
  • R 6 , R 7 , R 8 and R 9 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • n 1 and n 2 are 1 to 3 independently of each other.
  • each R 6 may be the same or different
  • each R 7 may be the same or different.
  • each R 8 may be the same or different, and each R 9 may be the same or different.
  • * Indicates a coupling point.
  • Ra is an acryloyloxymethyl group, a methacryloyloxymethyl group, an epoxymethyloxypropyl group or a 2,5-dihydroxyphenyl group.
  • the phosphine oxide compound is the following general formula (I).
  • the phosphine oxide compound is the following general formula (II).
  • R 1 , R 2 are as described above, and R 6 , R 7 , R 8 , R 9 , n 1 , and n 2 are as described above.
  • the phosphine oxide compound is the following general formula (III).
  • R 1 and R 2 are as described above.
  • the above compound can be kneaded with respect to the resin.
  • the linker can be a non-reactive group in the intended use. By adjusting the linker, phosphine oxide compounds having various properties can be obtained.
  • the linker -(C (R 10 ) (R 11 )) n3- (Ar) n5- (C (R 12 ) (R 13 )) n4- And R 10 , R 11 , R 12 and R 13 are independently hydrogen, halogen groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or Unsubstituted heterocyclic group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted thioalkoxy group, substituted or unsubstituted alkoxycarbonyl group.
  • n 3 , n 4 and n 5 are 0 to 3 independently of each other.
  • the linker
  • the phosphine oxide compound is the following general formula (IVa).
  • R 10 and R 11 are independently hydrogen, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted heterocyclic group, substituted, respectively.
  • an unsubstituted or unsubstituted aryl group a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted thioalkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkylcarbonyl. It is selected from the group consisting of groups and substituted or unsubstituted aminocarbonyl groups.
  • the present disclosure is based on the following general formula (V).
  • R 1 and R 2 are independently substituted or unsubstituted aryl groups, respectively.
  • R 3 and R 4 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • n is 1 or 2
  • each R 3 may be the same or different, and each R 4 may be the same or different.
  • R5 is a homopolymer or copolymer comprising hydrogen or a substituted or unsubstituted alkyl group as a constituent.
  • it is a copolymer with (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid halide, (meth) acrylic acid salt, styrene or acrylonitrile.
  • R 1 and R 2 are independently substituted or unsubstituted aryl groups, respectively.
  • R 6 , R 7 , R 8 and R 9 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • n 1 and n 2 are independently 1 or 2, respectively.
  • each R 6 may be the same or different, and each R 7 may be the same or different.
  • each R 8 may be the same or different, and each R 9 may be the same or different) as a constituent component.
  • it is a copolymer with an epoxy compound.
  • Various epoxy compounds can be modified by the phosphine oxides of the present disclosure.
  • additives are provided that include the above compounds or salts, or homopolymers or copolymers.
  • an anti-fog agent comprising the above compounds or salts, or homopolymers or copolymers is provided.
  • a flame retardant comprising the above compounds or salts, or homopolymers or copolymers is provided.
  • electrical / electronic parts OA-related parts, automobile parts, train parts, aircraft parts or fibers containing the above compounds or salts, or homopolymers or copolymers are provided.
  • a sheet, film, or acrylic glass comprising the above compounds or salts, or homopolymers or copolymers is provided.
  • a polymerization additive comprising the above compounds or salts, or homopolymers or copolymers is provided.
  • a surface modifier comprising the above compounds or salts, or homopolymers or copolymers is provided.
  • a phosphorus-imparting agent comprising the above compounds or salts, or homopolymers or copolymers is provided.
  • additives, anti-fog agents, flame retardants, electrical / electronic parts, OA-related parts, automobile parts, train parts, aircraft parts, fibers, sheets, films, acrylic glass, polymerization addition The use of the compounds or salts of the present disclosure, or homopolymers or copolymers of the present disclosure, in agents, surface modifiers or phosphorus-imparting agents is provided. These uses are for the compounds or salts of the present disclosure, or homopolymers or copolymers of the present disclosure, with additives, antifog agents, flame retardants, electrical / electronic parts, OA parts, automotive parts, trains. It also includes being used to satisfy many applications such as two or more or three or more of parts, aircraft parts, fibers, sheets, films, acrylic glasses, polymerization additives, surface modifiers or phosphorus-imparting agents at the same time. do.
  • the present disclosure relates the compounds or salts of the present disclosure, or homopolymers or copolymers of the present disclosure, to electrical / electronic parts, OA related parts, automotive parts, train parts, aircraft parts, A method used in fibers, sheets, films or acrylic glasses, or as an additive, antifog, flame retardant, polymerization additive, surface modifier or phosphorus-imparting agent, wherein the method is the compound or Provided are methods comprising applying a salt, or homopolymer or copolymer thereof, to an object in need thereof.
  • the method of the present disclosure comprises a compound or salt of the present disclosure, or a homopolymer or copolymer of the present disclosure, with an object (eg, as a main component, a polyester resin, an aromatic polyester resin, a polyurethane resin, etc.).
  • an object eg, as a main component, a polyester resin, an aromatic polyester resin, a polyurethane resin, etc.
  • the methods of the present disclosure combine the compounds or salts of the present disclosure, or homopolymers or copolymers of the present disclosure, with an object (eg, a material intended to be anti-fog, eg, a poly (meth) acrylic resin. , Polycarbonate resin, polyester resin, polystyrene resin), and if necessary, complete the product.
  • an object eg, a material intended to be anti-fog, eg, a poly (meth) acrylic resin. , Polycarbonate resin, polyester resin, polystyrene resin
  • the methods of the present disclosure make a compound or salt of the present disclosure, or a homopolymer or copolymer of the present disclosure, an object (eg, a material intended to be flame retardant, eg, a polyester resin).
  • an object eg, a material intended to be flame retardant, eg, a polyester resin.
  • the methods of the present disclosure are compounds or salts of the present disclosure, or homopolymers or copolymers of the present disclosure, subject to objects (eg, electrical / electronic parts, OA parts, automotive parts, etc.
  • Train parts, aircraft parts for example, as main components, polyester resin, aromatic polyester resin, polyurethane resin, polyvinyl chloride resin, polyamide resin, polyimide resin, polycarbonate resin, ABS resin, AS resin, BT resin, polyethylene resin , Polypropylene resin, polystyrene resin, poly (meth) acrylic resin, polyacetal resin, polyvinyl acetate resin, epoxy resin, phenol resin, melamine resin, benzoxazine resin), and if necessary, products Includes the process of completing.
  • the methods of the present disclosure are compounds or salts of the present disclosure, or homopolymers or copolymers of the present disclosure, subject to an object (eg, a fiber, sheet, film, eg, a polyester resin as the main component, aroma.
  • an object eg, a fiber, sheet, film, eg, a polyester resin as the main component, aroma.
  • the methods of the present disclosure add a compound or salt of the present disclosure, or a homopolymer or copolymer of the present disclosure, to an object (eg, acrylic glass, eg, a poly (meth) acrylic resin).
  • an object eg, acrylic glass, eg, a poly (meth) acrylic resin.
  • it includes the step of applying and, if necessary, the step of completing the product.
  • the methods of the present disclosure use a compound or salt of the present disclosure, or a homopolymer or copolymer of the present disclosure, as a polymerization additive, surface modifier or phosphorus-imparting agent as an object (eg, polymerization, Materials intended for surface modification or phosphorus addition, such as polyester resin, aromatic polyester resin, polyurethane resin, polyvinyl chloride resin, polyamide resin, polyimide resin, polycarbonate resin, ABS resin, AS resin, BT resin, polyethylene resin.
  • a polymerization additive e.g, polymerization, Materials intended for surface modification or phosphorus addition, such as polyester resin, aromatic polyester resin, polyurethane resin, polyvinyl chloride resin, polyamide resin, polyimide resin, polycarbonate resin, ABS resin, AS resin, BT resin, polyethylene resin.
  • Polypropylene resin, Polystyrene resin, Poly (meth) acrylic resin, Polyacetal resin, Polyacetic acid vinyl resin, Epoxy resin, Phenolic resin, Melamine resin, Benzoxazine resin Includes the process of completing.
  • the polymer of the present disclosure when it is a copolymer, it may be a copolymer copolymerized with a radically polymerizable monomer.
  • a radically polymerizable monomer examples include, but are not limited to, styrene and acrylic acid esters (for example, alkyl acrylate such as methyl acrylate and ethyl acrylate, alkyl styrene such as methyl styrene and ethyl styrene).
  • radical polymerization monomer examples include styrene, 2-methoxystyrene, 3-methoxystyrene, and 4-methoxystyrene as such radical polymerization monomers.
  • the present disclosure provides a method for producing a monomer. Examples of the manufacturing method and the following are given, but the present invention is not limited thereto.
  • R 1 and R 2 are independently aryls
  • R 3 and R 4 are independently hydrogen or substituted or unsubstituted alkyl groups, respectively.
  • This reaction can be carried out by heating diarylphosphine oxide with an aldehyde or ketone in a solvent.
  • aldehydes examples include formaldehyde (methanal), acetaldehyde (etanal), propionaldehyde (propanal), butanal, pentanal, hexanal, heptanal, octanal, nonanal, and decanal.
  • Paraformaldehyde can be used as the formaldehyde.
  • Examples of the ketone that can be used in this reaction include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, and methyl amyl ketone.
  • solvent used in this reaction examples include methanol, ethanol, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, dioxane, toluene, xylene, dimethylformamide, dimethylacetamide and the like.
  • Examples of the solvent used in this reaction include ethyl acetate, butyl acetate, diethyl ether, tetrahydrofuran, dioxane, dichloromethane, dimethylformamide, dimethylacetamide and the like.
  • Acrylic acid chloride, methacrylic acid chloride and the like can be used.
  • Examples of the base that can be used include potassium carbonate, sodium carbonate, sodium hydrogen carbonate, cesium carbonate, trimethylamine, triethylamine and the like.
  • a phosphorus-containing (meth) acrylic acid ester derivative can also be obtained by reacting the above intermediate compound with (meth) acrylic acid in a solvent.
  • solvent used in this reaction examples include chloroform, dichloromethane, 1,2-dichloroethane (EDC), diethyl ether, THF, dioxane and the like.
  • Acrylic acid, methacrylic acid and the like can be used.
  • R 1 and R 2 are independently aryls, and R 3 is hydrogen or a substituted or unsubstituted alkyl group.
  • a phosphorus-containing (meth) acrylic acid ester derivative can also be obtained by reacting the above intermediate compound with (meth) acrylic acid in a solvent.
  • solvent used in this reaction examples include chloroform, dichloromethane, 1,2-dichloroethane (EDC), diethyl ether, THF, dioxane and the like.
  • Acrylic acid, methacrylic acid and the like can be used.
  • a diarylphosphine oxide derivative containing a group having an epoxy group can be produced by mixing diarylphosphine oxide and a compound having an epoxy group having an unsaturated double bond in a solvent, adding a radical initiator and heating.
  • the radical initiator can be the same as the method for producing the polymer.
  • the polymerization initiator include azoisobutyronitrile (AIBN), azobisdimethylvaleronitrile (ADVN), azobismethylbutyronitrile (AMBN) and the like as azo compound-based thermal polymerization initiators, and organic peroxides.
  • the physical thermal polymerization initiator include dibenzoyl peroxide (BPO), t-butyl hydroperoxide (TBHP), cumene hydroperoxide, di-t-butyl hydroperoxide and the like.
  • reaction solvent examples include methanol, ethanol, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, dioxane, toluene, xylene, dimethylformamide, dimethylacetamide, ethyl acetate, butyl acetate and the like.
  • diarylphosphine oxide derivative containing dihydroxy-substituted aryl group (Synthesis of diarylphosphine oxide derivative containing dihydroxy-substituted aryl group)
  • the diarylphosphine oxide derivative containing a dihydroxy-substituted aryl group can be produced by dissolving diarylphosphine oxide in a solvent, dropping the benzoquinone derivative dissolved in the solvent, and heating and aging.
  • R x and R y can be arbitrary substituents or together to form a ring, respectively).
  • the reaction solvent include methanol, ethanol, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, dioxane, toluene, xylene, dimethylformamide, dimethylacetamide, ethyl acetate, butyl acetate and the like.
  • Usable bases include alkali metals (lithium, sodium, potassium), alkyl metals (alkyl lithium, alkyl sodium, alkyl potassium), alkoxy alkali metals (lithium alkoxide, sodium alkoxide, potassium alkoxide), alkali metal hydroxides (alkali metal hydroxides). Examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide) and alkali metal hydrides (lithium hydride, sodium hydride, potassium hydride) and the like.
  • reaction solvent examples include methanol, ethanol, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, dioxane, toluene, xylene, dimethylformamide, dimethylacetamide, ethyl acetate, butyl acetate and the like.
  • dihalo compound examples include dichloroethane, dibromoethane, diiodoethane, ⁇ , ⁇ '-dichloro-paraxylene, ⁇ , ⁇ '-dibromo-paraxylene, and ⁇ , ⁇ '-diiodo-paraxylene.
  • the polymers of the present disclosure can be obtained by polymerizing the compounds of the present disclosure.
  • the polymerization may be homopolymerization or copolymerization.
  • Polymerization of compounds having an acrylic group or a methacrylic group can be carried out by radical polymerization.
  • the polymerization initiator include azoisobutyronitrile (AIBN), azobisdimethylvaleronitrile (ADVN), azobismethylbutyronitrile (AMBN) and the like as azo compound-based thermal polymerization initiators, and organic peroxides.
  • Examples of the physical thermal polymerization initiator include dibenzoyl peroxide (BPO), t-butyl hydroperoxide (TBHP), cumene hydroperoxide, di-t-butyl hydroperoxide and the like.
  • BPO dibenzoyl peroxide
  • TBHP t-butyl hydroperoxide
  • cumene hydroperoxide di-t-butyl hydroperoxide
  • Polymerization of a compound having an epoxy group can be carried out by anionic polymerization or cationic polymerization.
  • anion polymerization initiator examples include various alkyl metal compounds (for example, methyl lithium, n-butyllithium, t-butyllithium, methylmagnesium chloride, methylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide), and various alkoxy metal compounds (eg, methyllithium chloride, butylmagnesium bromide).
  • alkyl metal compounds for example, methyl lithium, n-butyllithium, t-butyllithium, methylmagnesium chloride, methylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide
  • alkoxy metal compounds eg, methyllithium chloride, butylmagnesium bromide
  • aryl metal compounds eg, phenyllithium, phenylsodium, phenylmagnesium chloride, phenylmagnesium bromide
  • various amine-based curing agents eg, diethylenetetramine, tri.
  • Aliper amines such as ethylenete
  • thiol-based curing agents for example, 1,4-butanedithiol, 1,6-hexanedithiol
  • Various blended acids eg, sulfuric acid, perchloric acid, trifluoromethanesulfonic acid
  • Lewis acids eg, aluminum trichloride, boron trifluoride, titanium tetrachloride, tin tetrachloride
  • heat a cationic polymerization initiator
  • a sulfonium salt for example, (2-ethoxy-1-methyl-2-oxoethyl) methyl-2-naphthalenylsulfonium hexafluoroantimonate, 4- (methoxycarbonyloxy) phenylbenzylmethylsulfonium hexafluoro) Antimonate, 4-acetoxyphenyldimethylsulfonium hexa
  • a polymer containing the following derived from an acrylate compound as a constituent component can be produced.
  • the present disclosure also provides copolymers of acrylate compounds with methyl acrylate, methyl methacrylate, styrene and acrylonitrile.
  • a polymer containing the following derived from a compound having an epoxy group as a constituent component can be produced.
  • the present disclosure also provides a copolymer with an epoxy compound.
  • the present disclosure provides additives comprising the compounds of the present disclosure or salts thereof, or homopolymers or copolymers of the present disclosure.
  • Uses of the additive include any of those described herein.
  • the present disclosure provides articles comprising the above-mentioned compounds of the present disclosure or salts thereof, or homopolymers or copolymers of the present disclosure.
  • Such articles include anti-fog agents, flame retardants, electrical / electronic parts, OA-related parts, automotive parts, train parts, aircraft parts or fibers, sheets, films, or acrylic glass, polymerization additions. Examples include agents and surface modifiers.
  • the homopolymers or copolymers of the present disclosure have low water absorption and are useful as anti-fog agents.
  • the compounds of the present disclosure or salts thereof can also be used as anti-fog agents.
  • the compound of the present disclosure or a salt thereof is a solid (preferably a powder), it is easy to handle and can be easily used in an appropriate amount. It can be less wasteful than if it were a liquid.
  • the compounds of the present disclosure or salts thereof, or homopolymers or copolymers of the present disclosure contain phosphorus and may be useful as flame retardants.
  • the compound of the present disclosure or a salt thereof is a solid (preferably a powder), it is easy to handle and can be easily used in an appropriate amount. It can be less wasteful than if it were a liquid.
  • the homopolymers or copolymers of the present disclosure are flame-retardant and are useful in electrical / electronic related parts, OA related parts, automobile parts, train parts, aircraft parts, fibers and the like.
  • the homopolymers or copolymers of the present disclosure are easy to mold and have transparency, so that they can be used as sheets, films, or acrylic glasses.
  • the compound of the present disclosure or a salt thereof can be polymerized, and the properties of the polymer produced as a polymerization additive can be changed.
  • the compound of the present disclosure or a salt thereof is a solid (preferably a powder), it is easy to handle and can be easily used in an appropriate amount. It can be less wasteful than if it were a liquid.
  • the compound of the present disclosure or a salt thereof can be bonded to the surface of an object and can change the surface properties as a surface modifier.
  • the compound of the present disclosure or a salt thereof is a solid (preferably a powder), it is easy to handle and can be easily used in an appropriate amount. It can be less wasteful than if it were a liquid.
  • the present disclosure provides a phosphorus-imparting agent comprising the above-mentioned compound of the present disclosure or a salt thereof.
  • the phosphorus-imparting agents of the present disclosure include fertilizers, pesticides, pharmaceuticals, pesticides, explosives, electronic materials, catalysts, flame retardants, metal surface treatment agents, detergents, antifreeze liquids, surfactants, defoamers, and lubricants. Can be used in.
  • the compound of the present disclosure or a salt thereof is a solid (preferably a powder), it is easy to handle and can be easily used in an appropriate amount. It can be less wasteful than if it were a liquid.
  • the compound of the present disclosure or a salt thereof contains a (meth) acrylic acid moiety that can be easily subjected to radical polymerization, and phosphorus can be easily imparted to other substances.
  • the target to which phosphorus is applied may be any one to which radicals generated in the (meth) acrylic acid moiety can react.
  • the compound of the present disclosure or a salt thereof has an effect of lowering the water absorption rate and is also useful for producing a compound having low water absorption.
  • the compound of the present disclosure or a salt thereof is a solid (preferably a powder), it is easy to handle and can be easily used in an appropriate amount. It can be less wasteful than if it were a liquid.
  • the present disclosure provides a surface treatment method using the above-mentioned compound of the present disclosure or a salt thereof.
  • This surface treatment method can reduce the water absorption of the surface.
  • the method may include the step of polymerizing the compound or salt represented by the general formula (I) on the surface.
  • the surface can be resin or glass.
  • the compound of the present disclosure or a salt thereof is a solid (preferably a powder), it is easy to handle and can be easily used in an appropriate amount. It can be less wasteful than if it were a liquid.
  • AN Acrylonitrile
  • GC-MS Gas chromatograph mass spectrometer
  • MA Methyl acrylate Mes: 2,4,6-trimethylphenyl MMA: Methyl methacrylate
  • NMR Nuclear magnetic resonance
  • PMA Methyl polyacrylate
  • Ph phenyl rt: Room temperature ( For example, 15 ° C to 25 ° C)
  • St Styrene
  • THF Tetrahydrofuran
  • the permittivity was measured using Toyo Technica's permittivity measurement system WKR6510P at a measurement frequency of 1 MHz and a measurement temperature of 25 ° C.
  • Example 7 20.0 g of the light brown solid obtained in Example 2 was weighed in a 200 mL separable flask, 4 times the weight of 2-butanone was added, and the mixture was stirred well. After degassing and replacing with nitrogen, the temperature was increased to 40 ° C. After adding 0.20 g of benzoyl peroxide, the temperature inside the reaction vessel was raised to 80 ° C., and the reaction was carried out for 20 hours. After completion of the reaction, the reaction solution was added dropwise to hexane to precipitate the produced polymer. The precipitated polymer was washed with ion-exchanged water and dried in a vacuum dryer to obtain 14.5 g of white powder. The weight average molecular weight and the dielectric constant of the obtained polymer were measured.
  • Comparative Example 1 20.0 g of Comparative Compound 1 was weighed in a 200 mL separable flask, 4 times the weight of 2-butanone was added, and the mixture was well stirred. After degassing and replacing with nitrogen, the temperature was increased to 40 ° C. After adding 0.22 g of benzoyl peroxide, the temperature inside the reaction vessel was raised to 80 ° C., and the reaction was carried out for 20 hours. After completion of the reaction, the reaction solution was added dropwise to hexane to precipitate the produced polymer. The precipitated polymer was washed with ion-exchanged water and dried in a vacuum dryer to obtain 16.3 g of white powder. The weight average molecular weight and the dielectric constant of the obtained polymer were measured.
  • the polymer made of the compound of the present invention having a substituent on the aryl group has a significantly lower dielectric constant (Dk) and dielectric tangent (Df) than the polymer made of the compound of Comparative Example 1 having no substituent on the aryl group. Has been shown to have.
  • the novel phosphorus compound can be used in various applications. For example, it is used in anti-fog agents, flame retardants, electrical / electronic parts, OA-related parts, automobile parts, train parts, aircraft parts or fibers, sheets, films, acrylic glass, polymerization additives, etc. obtain. It can also be used as a phosphorus-imparting agent.

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Abstract

La présente invention concerne un nouveau composé de phosphore, en particulier un composé d'oxyde de phosphine représenté par la formule générale Ra-P(=O)R1R2 ou un sel du composé d'oxyde de phosphine. Dans la formule, R1 et R2 sont identiques ou différents et représentent chacun indépendamment un groupe aryle substitué, et Ra est un groupe ayant une double liaison insaturée, un groupe époxydé, un groupe hydroxylé ou un groupe contenant un phosphore. Les groupes aryle de R1 et R2 ont chacun un à trois substituants.
PCT/JP2021/028295 2020-07-31 2021-07-30 Dérivé d'oxyde de diarylphosphine WO2022025237A1 (fr)

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TW202210497A (zh) 2022-03-16
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