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WO2015046551A1 - Polymère contenant un cycle borazine, composition correspondante, borazine réticulée et matériau électronique utilisant ledit polymère contenant un cycle borazine ou une borazine réticulée - Google Patents

Polymère contenant un cycle borazine, composition correspondante, borazine réticulée et matériau électronique utilisant ledit polymère contenant un cycle borazine ou une borazine réticulée Download PDF

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WO2015046551A1
WO2015046551A1 PCT/JP2014/075982 JP2014075982W WO2015046551A1 WO 2015046551 A1 WO2015046551 A1 WO 2015046551A1 JP 2014075982 W JP2014075982 W JP 2014075982W WO 2015046551 A1 WO2015046551 A1 WO 2015046551A1
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borazine
carbon atoms
containing polymer
ring
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PCT/JP2014/075982
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昌己 大村
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新日鉄住金化学株式会社
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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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences

Definitions

  • the present invention relates to a novel borazine ring-containing polymer, a borazine composition, a borazine crosslinked product, and an electronic material using them.
  • a borazine ring-containing polymer can be cross-linked alone or reacted with various cross-linking agents to provide heat resistance, transparency, dielectric properties, thermal conductivity, gas barrier properties, hardness, chemical resistance, weather resistance, insulation , Low refraction, hydrolysis resistance, sublimation resistance and processability, can be given to various applications such as laminates, interlayer insulation films, sealing materials and other electronic materials, paints, adhesives, etc. Can be used.
  • a borazine ring-containing polymer (also referred to as a borazine polymer) is excellent in heat resistance, transparency, dielectric properties, thermal conductivity, gas barrier properties, hardness, chemical resistance, weather resistance and charge transport properties, high heat resistant material, low It is expected as a dielectric material, a high heat dissipation material and a low refractive material.
  • Patent Document 1 compounds having an unsubstituted and halogeno group
  • Patent Documents 2 and 3 aminoborazine
  • Patent Document 4 polyaminoborazine
  • Patent Document 5 alkylborazine
  • Borazine siloxane polymer Patent Document 6
  • Various compounds such as a compound having a polycyclic aromatic group Patent Document 7) have been studied.
  • the unsubstituted compound and the compound having a halogeno group are easily hydrolyzed.
  • the compounds having aminoborazine, alkylborazine, and polycyclic aromatics have improved hydrolyzability, but are difficult to handle because they are sublimable and have low solvent solubility.
  • the borazine-siloxane polymer has improved handleability, but has insufficient solvent solubility, has defects in processability such as film forming property, and has insufficient heat stability. Furthermore, since it is difficult to separate the metal polymerization catalyst, the transparency is also low.
  • the conventional borazine compounds have problems in stability such as hydrolysis resistance or handleability, processability such as film forming property, and thermal stability.
  • a borazine ring-containing polymer obtained by reacting a borazine compound with siloxane imide and a crosslinked product of the borazine ring-containing polymer and a crosslinking agent are excellent. I found it.
  • this invention is a borazine ring containing polymer characterized by including the repeating unit structure represented by following General formula (1).
  • a 1 to A 3 each independently represents a hydrogen atom or a monovalent substituent.
  • Z 1 and Z 2 are each independently an atomic group composed of a hydrocarbon having 2 to 12 carbon atoms and may have a ring structure forming a condensed ring.
  • Y represents an atomic group containing a linear, cyclic or cage-type siloxane bond containing two or more silicon atoms in the main chain, and each silicon atom constituting the siloxane bond independently represents a hydrogen atom or a monovalent group.
  • Examples of the monovalent substituent bonded to the silicon atom include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituent W (the substituent W is an alkyl group having 1 to 12 carbon atoms, carbon A phenyl group which may be substituted with an alkoxy group or a hydroxy group having 1 to 12), or a naphthyl group which may be substituted with a substituent W, more preferably an alkyl group having 1 to 6 carbon atoms. is there.
  • a terminal group can be bonded to at least one B- in the general formula (1).
  • the terminal group includes an alkyl group having 1 to 12 carbon atoms, a carbon number of 7 to 30 aralkyl groups, aryl groups having 6 to 30 carbon atoms, alkylamino groups having 1 to 30 carbon atoms, alkoxyamino group-containing alkylamino groups having 2 to 30 carbon atoms, aralkylamino groups having 7 to 30 carbon atoms, carbon numbers 6-30 arylamino groups, C1-C12 alkoxy groups, C7-C30 aralkyloxy groups, C6-C30 aryloxy groups, C2-C30 ester groups, hydroxyl groups, ethenyls Groups, ethynyl groups, acryloyl groups, isocyanate groups, or imide groups.
  • the terminal group includes a secondary amino group having 2 to 30 carbon atoms.
  • the present invention also includes a borazine polymer composition containing the borazine ring-containing polymer and a crosslinking agent, and a borazine crosslinked product obtained by crosslinking the borazine polymer composition. It is. Furthermore, the present invention is an electronic material comprising the above borazine ring-containing polymer or an electronic material comprising the above borazine crosslinked body.
  • the borazine ring-containing polymer of the present invention is a polymer having a structure in which a borazine ring and an atomic group having a siloxane bond are bonded via an imide bond, and has heat resistance, flexibility, thermal decomposition stability, and solvent solubility. Further, a material excellent in processability such as transparency, low refractive index property, sublimation resistance and film forming property can be provided. Furthermore, this borazine ring-containing polymer can be cross-linked alone or reacted with various cross-linking agents to provide heat resistance, transparency, dielectric properties, thermal conductivity, gas barrier properties, hardness, chemical resistance, and weather resistance. In addition, a material excellent in insulation, low refractive index and hydrolysis resistance can be provided.
  • borazine ring-containing polymer or crosslinked product can be easily separated from the metal polymerization catalyst, and thus has high transparency and excellent weather resistance. Therefore, it can be used for various uses such as electronic materials such as laminates, interlayer insulating films, and sealing materials, paints, and adhesives.
  • the borazine ring-containing polymer of the present invention has a structural unit represented by the general formula (1).
  • a 1 to A 3 each independently represents a hydrogen atom or a monovalent substituent.
  • the substituent is not particularly limited, and examples thereof include alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 30 carbon atoms, and carbon atoms having 7 carbon atoms.
  • Preferred examples include an aralkyl group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group, a hydroxyl group, a carboxyl group, and a vinyl group.
  • the alkyl group may have a linear structure, a branched structure, or a cyclic structure. When these substituents have a carbon atom, the carbon number is preferably in the range of 1 to 10.
  • a 1 to A 3 are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an amino group, and more preferably a carbon atom.
  • a monovalent substituent may be further bonded to these monovalent substituents, preferably an alkyl group or a phenyl group, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • Z 1 and Z 2 are each independently an atomic group composed of a hydrocarbon having 2 to 12 carbon atoms, and together with an adjacent imide group form a ring structure.
  • the ring structure containing the imide group in the general formula (1) is a hydrocarbon group that becomes a 5-membered cyclic nitrogen-containing ring.
  • the ring containing the imide group may be condensed with another ring structure.
  • Another preferred ring structure is a benzene ring, a cyclohexene ring, a norbornene ring, or a methylnorbornene ring.
  • Y represents an atomic group containing two or more silicon atoms in the main chain and containing a linear, cyclic or cage-type siloxane bond, and each silicon atom constituting the siloxane bond is independently a hydrogen atom or a monovalent group.
  • the substituents of The description of the monovalent substituent is the same as the description of R 1 to R 10 described later.
  • Examples of atomic groups containing preferred siloxane bonds are shown below.
  • An example of an atomic group containing a linear siloxane bond is represented by the following general formula (2).
  • An example of an atomic group containing a cyclic siloxane bond is represented by the following general formula (3).
  • An example of an atomic group containing a cage-type siloxane bond is a silsesquioxane, that is, a network-type polymer or polyhedral cluster having a structure of (X—SiO 1.5 ) n obtained by hydrolyzing a trifunctional silane.
  • a silsesquioxane that is, a network-type polymer or polyhedral cluster having a structure of (X—SiO 1.5 ) n obtained by hydrolyzing a trifunctional silane.
  • R 1 to R 10 are each independently a hydrogen atom or a monovalent substituent.
  • R 1 to R 10 are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a naphthyl group, and the phenyl group or naphthyl group is a substituent W May be substituted.
  • W represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group.
  • n represents 1 or an integer of 2 or more. Preferably, it is 3 to 17 because the balance between toughness, heat resistance and compatibility with other resins is excellent. More preferably, it is 3-7.
  • m and p each independently represent an integer of 1 or 2 or more. Preferably, it is 1 to 4 because the balance between toughness, heat resistance and compatibility with other resins is excellent. More preferably, it is 1-2.
  • R 1 to R 10 are alkyl groups having 1 to 12 carbon atoms, they may be any of chain, branched and cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl- n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl -N-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-
  • R 1 to R 10 are alkoxy groups having 1 to 12 carbon atoms, specific examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, and s-butoxy group.
  • the number of carbon atoms is more preferably 1 to 6, and more preferably 1 to 3 carbon atoms.
  • the structure of the alkyl moiety may be any of a chain, a branch, and a ring.
  • R 1 to R 10 are a phenyl group or a substituted phenyl group
  • specific examples include a phenyl group, an o-hydroxyphenyl group, an m-hydroxyphenyl group, a p-hydroxyphenyl group, an o-methoxyphenyl group
  • Examples include m-methoxyphenyl group, p-methoxyphenyl group, o-tolyl group, m-tolyl group, p-tolyl group and the like.
  • R 1 to R 10 are naphthyl groups or naphthyl groups
  • specific examples include ⁇ -naphthyl groups, ⁇ -naphthyl groups, and the like.
  • the borazine ring-containing polymer (a-3) of the present invention includes, as an example, B, B ′, B ′′ -trichloroborazine (a-1) and an imide-modified siloxane compound (a-2) at both ends.
  • the degree of polymerization of the borazine ring-containing polymer can be controlled by the charge ratio of (a-1) and (a-2) and the reaction conditions (temperature, solvent, time).
  • the degree of polymerization is such that at least one molecule of each of (a-1) and (a-2) has reacted, and is preferably a number in terms of polystyrene in view of excellent solvent solubility and film formability.
  • the average molecular weight (Mn) is preferably 500,000 or less, more preferably 100,000 or less, and further preferably 2000 to 20000. Further, from the viewpoint of thermal stability and ease of formation of a borazine crosslinked product, borazine is used. ring It is preferable that both ends of the containing polymer are borazine rings.
  • the borazine ring in the unit structure constituting the borazine ring-containing polymer of the present invention has three Bs, which can participate in the polymerization, but some B do not participate in the polymerization and have end groups. Can have. And since it has three B, a part may form a crosslinked structure, However, As for the polymer, crosslinking
  • crosslinking does not fully advance like the borazine crosslinked body of this invention.
  • the borazine ring-containing polymer of the present invention desirably has solvent solubility in at least one organic solvent such as THF and toluene, thereby determining a preferable degree of polymerization and degree of crosslinking. In the case of crosslinking, not only the N—B bond but also a bond group may be interposed between N and B.
  • the terminal of the polymer becomes a borazine ring, so that it can be bonded to B as a terminal group described later.
  • one of three Bs of the borazine ring other than the terminal may remain without being involved in the polymerization, and the terminal group can be bonded thereto.
  • the terminal of the polymer becomes a secondary amino group derived from an imide group.
  • the borazine ring-containing polymer of the present invention includes, for example, as shown in the following reaction formula (4), B, B ′, B ′′ -trichloroborazine (a-1) and both-end imide-modified siloxane compound (a-2)
  • This B, B ′, B ′′ -trichloroborazine (a-1) is produced by a condensation reaction of boron trichloride and an amino compound.
  • This B, B ′, B ′′ -trichloroborazine (a-1) is produced by a condensation reaction of boron trichloride and an amino compound.
  • the B, B ′, B ′′ -trichloroborazine (a-1) thus obtained is reacted with both terminal imide-modified siloxane compounds (a-2). This reaction is divided into two steps.
  • the borazine ring-containing polymer (a-3) can be obtained.
  • n 0 or an integer of 1 or more.
  • reaction formula (4) the reaction can be carried out using boron trifluoride, boron tribromide or boron triiodide instead of boron trichloride.
  • B, B ′, B ′′ -trichloroborazine B, B ′, B ′′ -trifluoroborazine, B, B ′, B ′′ -tribromoborazine or B, B ′, B ′′ -tri Iodoborazine is obtained.
  • a borazine ring-containing polymer (a-3) can also be produced by imidizing these.
  • boron trichloride is used because it is easy to handle in solution and waste gas (unreacted boron chloride and hydrogen chloride) generated during the reaction can be easily treated outside the system.
  • B, B ′, B ′′ -trichloroborazine used is preferable.
  • B, B ′, B ′′ -trichloroborazine will be described as a representative.
  • the both-end imide group-modified siloxane compound (a-2) can be prepared by hydrosilylating a siloxane having a hydrosilyl group at both ends and an imide compound having an unsaturated bond with a platinum catalyst.
  • the imide group include maleimide, citraconic acid imide, itaconic acid imide, phthalic acid imide, nadic acid imide, nadic acid imide, methyl nadic acid imide, cis-4-cyclohexene-1,2-dicarboxylic acid imide, cis-1
  • Examples include 2-cyclohexanedicarboxylic imide and allyl nadic imide.
  • the imide-modified siloxane compound (a-2) may be used alone or as a mixture of two or more. From the viewpoint of solubility and control of the crosslinking reaction, one kind is used. It is preferable to use only.
  • another imide compound other than (a-2) may be mixed and reacted.
  • imide compounds include maleimide, citraconic imide, itaconic imide, phthalic imide, nadic imide, methyl nadic imide, cis-4-cyclohexene-1,2-dicarboxylic imide, cis-1 , 2-cyclohexanedicarboxylic acid imide, monoimide compounds such as allyl nadic acid imide, and the like.
  • the molecular weight of the borazine ring-containing polymer can be adjusted by mixing and reacting these monoimide compounds.
  • the larger the mixing amount of the monoimide compound the smaller the molecular weight of the borazine ring-containing polymer.
  • it may be a diimide compound obtained by imidizing a dicarboxylic acid anhydride such as pyromellitic acid diimide, or a polyfunctional imide compound having two or more imide groups.
  • the imide compound preferably has a polymerizable unsaturated bond, and examples of the unsaturated imide compound include maleimide and imide compounds having a norbornene structure.
  • maleimide, nadic imide and the like can be mentioned.
  • halogen atoms of at least one terminal borazine ring remaining without reacting are substituted with an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and a carbon number.
  • 6-30 aryl groups C1-C30 alkylamino groups, C2-C30 alkoxysilyl group-containing alkylamino groups, C7-C30 aralkylamino groups, C6-C30 arylamino groups
  • an alkylamino group having 1 to 30 carbon atoms an alkoxyamino group-containing alkylamino group having 2 to 30 carbon atoms, and an aralkyl having 7 to 30 carbon atoms.
  • An amino group, an arylamino group having 6 to 30 carbon atoms, an ethenyl group, an ethynyl group, an acryloyl group, an isocyanate group, and an imide group are preferable, and an imide group is more preferable.
  • ester group having 2 to 12 carbon atoms that is, the RO (C ⁇ O) — group
  • examples of the ester group having 2 to 12 carbon atoms, that is, the RO (C ⁇ O) — group include a methoxycarbonyl group, an ethoxycarbonyl group, etc., and an alkyl group having 1 to 12 carbon atoms and an aralkyl group having 7 to 30 carbon atoms.
  • An arylamino group having 6 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an alkylamino group containing an alkoxysilyl group having 2 to 30 carbon atoms, an aralkylamino group having 7 to 30 carbon atoms, and an alkyl group having 6 to 30 carbon atoms Examples of the arylamino group, the alkoxy group having 1 to 12 carbon atoms, the aralkyloxy group having 7 to 30 carbon atoms, and the aryloxy group having 6 to 30 carbon atoms are the same as those described above for R 1 to R 10 .
  • These groups can be introduced by substituting a halogen atom on the borazine ring with a compound that provides a corresponding substituent, for example, at least one boron that forms a borazine ring by reacting with addition of maleimide.
  • a borazine ring-containing polymer in which the terminal group bonded to the atom is a maleimide group is obtained.
  • the solvent used in the reaction of B, B ′, B ′′ -trichloroborazine and the imide compound is not particularly limited as long as it does not react with the raw material, but is a hydrocarbon solvent such as hexane, toluene, heptane, benzene, xylene and the like.
  • a chlorine-containing solvent such as dichloromethane, chloroform or carbon tetrachloride, an ether solvent such as tetrahydrofuran or diethyl ether, etc., preferably toluene or chlorobenzene, and a dehydrated solvent is recommended.
  • These solvents may be used alone or in appropriate combination of two or more, and the reactor is preferably replaced with an inert gas dried in advance.
  • the reaction is performed by heating and dissolving B, B ′, B ′′ -trichloroborazine in a solvent, and then adding an imide compound. After the addition, the mixture is refluxed at the boiling point of the solvent. Therefore, it is necessary to treat waste gas such as a trap in pure water outside the system.
  • the reaction temperature varies depending on the solvent and the like, but is usually 0 to 200 ° C, more preferably 100 to 150 ° C. If the reaction temperature is too high, it becomes difficult to control the reaction, and if it is too low, the reaction rate becomes slow, which is not preferable.
  • the reaction time varies depending on the raw materials and solvent, but is usually 3 to 24 hours. Preferably, it is 3 to 10 hours.
  • reprecipitation is preferably performed using the difference in solubility.
  • borazine ring-containing polymer of the present invention examples include the following repeating structures. However, it is not necessarily limited to these.
  • the borazine ring-containing polymer of the present invention can be made into a composition by a known reaction such as thermal reaction or photoreaction alone or in the presence of a crosslinking agent, and this can be made into a borazine crosslinked product.
  • the crosslinking method include thermosetting and photocuring.
  • the crosslinked borazine crosslinked is a polymer in which borazine ring-containing polymers are polymerized without using a crosslinking agent other than the borazine ring-containing polymer.
  • crosslinked the borazine composition is what a borazine ring containing polymer superposed
  • the borazine ring-containing polymers react with each other, so that the number average molecular weight of the borazine crosslinked product is twice or more that of the borazine ring-containing polymer.
  • borazine ring-containing polymer and the borazine crosslinked product can be dispersed in a polymer matrix.
  • the borazine composition of this invention contains the said borazine ring containing polymer and arbitrary crosslinking agents.
  • the crosslinking agent is a compound having an active group that reacts with A 1 to A 3 , R 1 to R 10 or the terminal group in the borazine ring-containing polymer.
  • the cross-linking agent known ones can be used. For example, amino group, imide group, phenolic hydroxyl group, cyanate group, ethenyl group, ethynyl group, thiol group, carboxyl group, phenolic hydroxyl group, vinyl ether group (hereinafter, It is also a compound having an “active group”).
  • the end group of the borazine ring-containing polymer is a carbon-carbon unsaturated group such as an ethynyl group or an ethenyl group. It is particularly useful when it is a bond.
  • the active group is a cyanate group, an ethenyl group, an ethynyl group, or a vinyl ether group, it is particularly useful when the terminal group of the borazine ring-containing polymer is an amino group.
  • the active group is an ethenyl group or an ethynyl group
  • the A 1 to A 3 , R 1 to R 10 or the terminal group of the borazine ring-containing polymer is a hydrogen atom.
  • a bifunctional or higher functional group is preferred because the molecular weight of the borazine crosslinked product tends to increase.
  • the borazine composition may contain a crosslinking accelerator such as triphenylphosphine, 2-ethyl-4methylimidazole, zinc octylate.
  • a crosslinking accelerator such as triphenylphosphine, 2-ethyl-4methylimidazole, zinc octylate.
  • borazine crosslinked body of this invention An example of the manufacturing method of the borazine crosslinked body of this invention is demonstrated below. However, it is not necessarily limited to these.
  • the borazine ring-containing polymer (b-21) having maleimide forms a composition with bisphenol A (c-1), which is a bifunctional phenolic hydroxyl group, it is thermally cured at 150 to 250 ° C.
  • a borazine crosslinked product (d-1) is obtained by the reaction of the following formula. At this time, triphenylphosphine may be added as an accelerator.
  • the borazine crosslinked product thus obtained is preferable because it is more excellent in stability such as hydrolysis resistance, heat resistance, and toughness than the borazine polymer.
  • the borazine ring-containing polymer thus obtained and its cross-linked product have a siloxane imide group, and therefore, compared to conventional borazine compounds, stability such as hydrolysis resistance, handleability, and film-forming properties. It is excellent in workability such as heat resistance and flame resistance, and can be used for various applications such as electronic materials such as laminates, interlayer insulating films and sealing materials, paints and adhesives. In addition, low dielectric constant and high thermal conductivity can be expected as in the case of conventional borazine compounds.
  • Example 1 Synthesis of borazine ring-containing polymer having nadic imide siloxane chain
  • 100 g of dehydrated toluene was added and cooled to 0 ° C. while replacing with nitrogen.
  • the mixture was stirred while maintaining 0 ° C., and 100 mL of boron trichloride (1.0 M toluene solution) was slowly added with a syringe and dissolved.
  • 9.31 g of dehydrated aniline was dripped very slowly with a syringe over about 3 hours. After dropping, the temperature was gradually raised to 110 ° C., and the mixture was heated to reflux for 20 hours under a nitrogen stream.
  • reaction solution was recrystallized from toluene and purified by sublimation to obtain B, B ′, B ′′ -trichloro-N, N ′, N ′′ -triphenylborazine (a-3) as white solid crystals. Prepared. The yield was 16.0 g and the yield was 90%.
  • nadic acid imide was further added and reacted for 5 hours, and cooled to room temperature.
  • the precipitate was filtered, washed with dehydrated toluene, and vacuum dried to obtain a borazine ring-containing heavy body (b-7) having a white solid nadic imide siloxane chain.
  • the end group of borazine B is also nadic imide.
  • the yield was 7.2 g, and the yield was 74.1%.
  • the product was identified by IR measurement and elemental analysis, and a borazine ring-containing polymer having a nadic imide siloxane chain was confirmed.
  • Example 2 Synthesis of borazine ring-containing polymer having maleimide siloxane chain
  • 100 g of dehydrated chlorobenzene was added and cooled to 0 ° C. while replacing with nitrogen.
  • a-4 After adding 5.00 g of B, B ′, B ′′ -trichloro-N, N ′, N ′′ -triphenylborazine (a-4) and 7.58 g of maleimide siloxane ( réelle-7) at both ends, the temperature is increased to 130 °
  • the mixture was stirred while gradually raising the temperature.
  • the mixture was heated to reflux for 20 hours under a nitrogen stream.
  • Example 3 (Synthesis of a borazine ring-containing polymer having a long maleimide siloxane chain)
  • Example 4 (Synthesis of a borazine ring-containing polymer having a cyclic maleimide siloxane chain)
  • the end group of borazine B is also maleimide. Yield 64.7%.
  • the product was identified by 1 H-NMR, IR measurement, and elemental analysis, and a borazine ring-containing polymer having a maleimide siloxane chain was confirmed.
  • Example 5 (Synthesis of borazine ring-containing polymer having cis-4-cyclohexene-1,2-dicarboxylic acid imide siloxane chain) A borazine ring having a pale yellow transparent solid maleimide siloxane chain in the same manner as in Example 2 except that 8.9 g of cis-4-cyclohexene-1,2-dicarboxylic imide was used as the maleimide siloxane at both ends. 9.5 g of the containing polymer (b-13) was obtained. The end group of borazine B is also maleimide. Yield 69.1%.
  • Comparative Example 1 As a comparative example, the above B, B ′, B ′′ -trichloro-N, N ′, N ′′ -triphenylborazine (a-4) was used.
  • the borazine ring-containing polymers obtained in the above examples and comparative examples were subjected to solubility determination and hydrolysis resistance evaluation. Moreover, the heat resistance of the crosslinked body obtained by thermosetting these borazine ring containing polymers was measured.
  • solubility 50 mg of the above borazine polymer was added to 1 g of a solvent (THF and toluene), and after sufficiently stirring at room temperature, insoluble matter was confirmed. When visually inspected, the case where there was an insoluble matter was indicated as x, and the case where there was no insoluble matter was indicated as ⁇ . However, even if there was an insoluble matter at room temperature, the temperature was raised to 50 ° C. and the dissolution could be confirmed as ⁇ .
  • the hydrolysis resistance was evaluated by adding 50 mg of the above borazine polymer to 1 g of methanol (methanol) containing 10 mg of pure water, stirring sufficiently at room temperature, and then adding aniline which is an amine compound as a hydrolysis component.
  • the case where the amine compound was detected by 1 H-NMR analysis was marked as x.
  • the heat resistance evaluation was performed under the conditions of a temperature increase rate of 10 ° C./min under a nitrogen stream of 200 mL / min using a differential thermothermal gravimetric simultaneous measurement device (device name: TG / DTA7300 manufactured by SII Nano Technology).
  • a 10% weight loss temperature (T d 10 ) and a weight loss (residual carbon ratio) at 900 ° C. were measured. The results obtained from these measurements are shown in Table 1.
  • Example 6 The solubility determination, hydrolysis resistance evaluation, and heat resistance evaluation of a crosslinked product obtained by crosslinking a borazine ring polymer and a crosslinking agent were performed. 8.0 g of borazine ring-containing polymer (b-1) having a maleimide siloxane chain prepared in Example 2, 2.0 g of bisphenol A (BPA) as a phenol compound, and 0.10 g of triphenylphosphine as a curing accelerator were blended. Thus, a borazine polymer resin composition was obtained. This borazine polymer composition was molded at 175 ° C., post-cured at 250 ° C. for 5 hours, and subjected to various physical property measurements. The measurement method was the same as for the borazine ring polymer, and the results obtained are shown in Table 2.
  • BPA bisphenol A
  • the borazine ring-containing polymer of the present invention gives a material excellent in processability such as heat resistance, flexibility, thermal decomposition stability, solvent solubility, transparency, low refractive index property, sublimation resistance and film formability. be able to. Furthermore, this crosslinked product of borazine ring-containing polymer has heat resistance, transparency, dielectric properties, thermal conductivity, gas barrier properties, hardness, chemical resistance, weather resistance, insulation properties, low refractive properties, and hydrolysis resistance. Excellent material can be given. Furthermore, since the separation of the metal polymerization catalyst is easy, it has high transparency and excellent weather resistance, and can be used for various applications such as electronic materials such as laminates, interlayer insulating films, and sealing materials, paints, and adhesives.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Sealing Material Composition (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention concerne : un polymère contenant un cycle borazine qui a non seulement une excellente stabilité et une excellente aptitude au traitement mais également d'excellentes caractéristiques en termes de résistance à la chaleur, transparence, propriétés diélectriques, conductivité thermique, propriétés de barrière aux gaz, dureté, résistance chimique, résistance aux intempéries, propriétés isolantes et faible biréfringence. Ledit polymère est approprié pour un matériau électronique tel qu'un stratifié, un film isolant intercouche, un matériau d'étanchéité ou analogue. L'invention concerne également un produit réticulé de ce polymère contenant un cycle borazine. L'invention conerne également un polymère contenant un cycle borazine qui est obtenu par réaction de B, B ', B''-trichloroborazine et d'un composé de siloxane à terminaison imide, dont les deux extrémités sont modifiées avec un cycle contenant de l'azote qui contient un groupe imide ; et un produit réticulé qui est obtenu par réticulation de ce polymère contenant un cycle borazine.
PCT/JP2014/075982 2013-09-30 2014-09-30 Polymère contenant un cycle borazine, composition correspondante, borazine réticulée et matériau électronique utilisant ledit polymère contenant un cycle borazine ou une borazine réticulée WO2015046551A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6487A (en) * 1987-02-13 1989-01-05 Ultrasyst Defense & Space Inc Preceramic polymer of boron nitride
JPH07324135A (ja) * 1994-05-31 1995-12-12 Tonen Corp ポリボロシラザンの製造方法
JP2002317049A (ja) * 2001-04-18 2002-10-31 Nippon Shokubai Co Ltd ホウ素含有ポリマー組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6487A (en) * 1987-02-13 1989-01-05 Ultrasyst Defense & Space Inc Preceramic polymer of boron nitride
JPH07324135A (ja) * 1994-05-31 1995-12-12 Tonen Corp ポリボロシラザンの製造方法
JP2002317049A (ja) * 2001-04-18 2002-10-31 Nippon Shokubai Co Ltd ホウ素含有ポリマー組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
K. J. L. PACIOREK ET AL.: "Boron Nitride Preceramic Polymer Studies", CERAM. ENG. SCI. PROC., vol. 9, no. 7-8, 1988, pages 993 - 999 *

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