Classifications

• • 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
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
• • 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
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • 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
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present disclosure relates to silicon-containing monomers and mixtures containing them, polysiloxanes containing siloxane bonds, and methods for producing them.
• Polymer compounds containing siloxane bonds utilize their high heat resistance and transparency, and are used as coating materials for liquid crystal displays and organic EL displays, coating materials for image sensors, and semiconductor fields. It is used as a sealing material in. It is also used as a hard mask material for multilayer resists because it has high oxygen plasma resistance.
• polysiloxane As a photosensitive material capable of patterning and forming, it is required to be soluble in an alkaline aqueous solution such as an alkaline developer.
• a silanol group in the polysiloxane or to introduce an acidic group into the polysiloxane.
• an acidic group include a phenol group, a carboxyl group, a fluorocarbinol group and the like.
• Patent Document 1 discloses a polysiloxane having a silanol group as a soluble group in an alkaline developer.
• Patent Document 2 discloses a polysiloxane having a phenol group
• Patent Document 3 discloses a polysiloxane having a carboxyl group
• Patent Document 4 discloses a hexafluoroisopropanol group (2-hydroxy-1,1). , 1, 3, 3, 3-Fluoroisopropyl groups [-C (CF 3 ) 2 OH] are disclosed.
• These polysiloxanes are photosensitive such as having a photoacid generator or a quinonediazide group. It is used as a positive resist composition in combination with a compound.
• the polysiloxane comprising the above has good transparency, heat resistance, and acid resistance, and the pattern structure based on the polysiloxane is promising as a permanent structure in various devices.
• Japanese Unexamined Patent Publication No. 2012-242600 Japanese Unexamined Patent Publication No. 4-130324 Japanese Unexamined Patent Publication No. 2005-330488 JP-A-2015-129908 Japanese Unexamined Patent Publication No. 2014-156461
• the present inventors include a silicon-containing monomer that is liquid at room temperature (23 ° C.) or a silicon-containing monomer thereof as a raw material thereof so as to facilitate the production of an industrial scale of a polysiloxane having a hexafluoroisopropanol group.
• One of the purposes is to provide a mixture.
• Another object of the present invention is to provide a method for producing the above mixture.
• Another object of the present invention is to provide a polysiloxane obtained by polymerizing the above mixture and a method for producing the polysiloxane.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms.
• R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms independently of each other, and all or part of the hydrogen atoms in the alkyl groups are fluorine atoms.
• N is an integer of 1 to 5
• p is an integer of 0 to 1
• q is an integer of 0 to 1
• r is an integer of 0 to 1
• s is an integer of 0 to 1.
• p + q + r + s 3.
• the mixture containing the silicon-containing monomer according to the embodiment of the present invention contains at least one silicon-containing monomer represented by the formula (I) (1) and the silicon-containing monomer represented by the formula (II) (2-1). It contains at least one selected from the group consisting of a monomer and a silicon-containing monomer represented by the formula (2-2).
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms.
• R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms independently of each other, and all or part of the hydrogen atoms in the alkyl groups are fluorine atoms.
• N is an integer of 1 to 5
• p is an integer of 0 to 1
• q is an integer of 0 to 1
• r is an integer of 0 to 1
• s is an integer of 0 to 1.
• p + q + r + s 3.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• a method for producing a mixture containing a silicon-containing monomer comprises a silicon compound represented by the formula (3) and at least one of (III) methanol and ethanol, and is represented by the formula (4). React with mixed alcohols, including at least one of the represented alcohols. Thereby, (I) at least one kind of silicon-containing monomer (1) and (II) at least one selected from the group consisting of silicon-containing monomer (2-1) and silicon-containing monomer (2-2) are included.
• a method of producing a mixture comprises a silicon compound represented by the formula (3) and at least one of (III) methanol and ethanol, and is represented by the formula (4). React with mixed alcohols, including at least one of the represented alcohols.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where X is a halogen atom, n is an integer of 1 to 5, and p is an integer of 0 to 1.
• R 6 is a linear alkyl group having 3 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, and all or a part of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be replaced.
• R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms independently of each other, and all or part of the hydrogen atoms in the alkyl groups are fluorine atoms.
• N is an integer of 1 to 5
• p is an integer of 0 to 1
• q is an integer of 0 to 1
• r is an integer of 0 to 1
• s is an integer of 0 to 1.
• p + q + r + s 3.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• the silicon compound represented by the formula (3) is reacted with a mixture of methanol and ethanol.
• a mixture comprising a silicon-containing monomer is produced, comprising at least one selected from.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where X is a halogen atom, n is an integer of 1 to 5, and p is an integer of 0 to 1.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be replaced.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• the polysiloxane according to the embodiment of the present invention contains at least one kind of silicon-containing monomer represented by the formula (1), a silicon-containing monomer represented by the formula (2-1), and a formula (2-2). It comprises polymerizing a mixture comprising at least one selected from the group consisting of the represented silicon-containing monomers.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms.
• R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms independently of each other, and all or part of the hydrogen atoms in the alkyl groups are fluorine atoms.
• N is an integer of 1 to 5
• p is an integer of 0 to 1
• q is an integer of 0 to 1
• r is an integer of 0 to 1
• s is an integer of 0 to 1.
• p + q + r + s 3.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• the method for producing a polysiloxane according to an embodiment of the present invention includes at least one kind of silicon-containing monomer represented by the formula (1), a silicon-containing monomer represented by the formula (2-1), and a formula (2-). It is a method for producing a polysiloxane in which a mixture is polymerized, which comprises at least one selected from the group consisting of the silicon-containing monomers represented by 2).
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms.
• R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms independently of each other, and all or part of the hydrogen atoms in the alkyl groups are fluorine atoms.
• N is an integer of 1 to 5
• p is an integer of 0 to 1
• q is an integer of 0 to 1
• r is an integer of 0 to 1
• s is an integer of 0 to 1.
• p + q + r + s 3.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• a silicon-containing monomer or a mixture containing the same which is a liquid at room temperature (23 ° C.) is provided. Also provided is a method of producing the above mixture. Further, a polysiloxane obtained by polymerizing the above mixture and a method for producing the polysiloxane are provided.
• the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent.
• the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• cyclic alkyl group includes not only a monocyclic structure but also a polycyclic structure. The same applies to the "cycloalkyl group”.
• organic group in the present specification means an atomic group obtained by removing one or more hydrogen atoms from an organic compound.
• the “monovalent organic group” represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
• hexafluoroisopropanol group represented by -C (CF 3 ) 2 OH may be referred to as "HFIP group”.
• Silicon-containing monomer (1) First, the silicon-containing monomer (1) according to the embodiment of the present invention will be described. In the following, the silicon-containing monomer represented by the formula (1) will be referred to as a silicon-containing monomer (1).
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be replaced.
• R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms independently of each other, and all or part of the hydrogen atoms in the alkyl groups are fluorine atoms.
• N is an integer of 1 to 5
• p is an integer of 0 to 1
• q is an integer of 0 to 1
• r is an integer of 0 to 1
• s is an integer of 0 to 1.
• p + q + r + s 3.
• the silicon-containing monomer (1) having these structures is preferable because it remains liquid regardless of whether it is stored at room temperature or refrigerated.
• the silicon-containing monomer (1) having these structures is preferable because it remains liquid regardless of whether it is stored at room temperature or refrigerated.
• the silicon-containing monomer (1) according to the embodiment of the present invention can be left as a liquid regardless of whether it is stored at room temperature or refrigerated. This makes it easy to handle even when used on an industrial scale.
• the mixture containing the silicon-containing monomer is represented by (I) at least one of the silicon-containing monomers (1), (II) the silicon-containing monomer represented by the formula (2-1), and the formula (2-2). Includes at least one selected from the group consisting of silicon-containing monomers.
• the silicon-containing monomer represented by the formula (2-1) is referred to as a silicon-containing monomer (2-1)
• the silicon-containing monomer represented by the formula (2-2) is referred to as a silicon-containing monomer (2-2). It is described as.
• the silicon-containing monomer (1) is described in ⁇ 1. As described in Silicon-containing monomer (1)>.
• the silicon-containing monomer (2-1) is as follows.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• the silicon-containing monomer (2-2) is as follows.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• the following group ( 1HFIP ) in the formula (1), the formula (2-1), and the formula (2-2) may be any of the groups represented by the following formulas (1A) to (1D). preferable. Further, it is preferable that p is 0 in the formula (1). (In the equation, wavy lines indicate that the intersecting line segments are bonds.)
• the simple substance of these silicon-containing monomers and the mixture consisting of only these silicon-containing monomers can be stored at room temperature (23 ° C.) or refrigerated (4 ° C.). Also becomes solid.
• the mixture containing the contained monomer it can be made into a liquid even when stored at room temperature (23 ° C.).
• by selecting an appropriate mixing ratio as described later it can be made into a liquid even when stored in a refrigerator (4 ° C.). That is, at least selected from the group consisting of (II) silicon-containing monomer (2-1) and silicon-containing monomer (2-2), which have been solid at room temperature or refrigerated and may be difficult to use on an industrial scale.
• a liquid By mixing the silicon-containing monomer according to one embodiment of the present invention into a mixture, a liquid can be obtained at room temperature or in a refrigerator. Due to the effect that the silicon-containing monomer according to the embodiment of the present invention can be liquefied including the solid component (II), it can be liquefied at room temperature or refrigerated in a wider range of compositions.
• the ratio of the component (I) and the component (II) satisfies the following relationship in terms of mass ratio.
• the mixture containing the silicon-containing monomer can be made into a liquid at room temperature.
• the ratio of the component (I) and the component (II) satisfies the following relationship in terms of mass ratio.
• (I) component / ⁇ (I) component + (II) component ⁇ ⁇ 0.17 By satisfying the above relationship in terms of the ratio of the component (I) and the component (II) in terms of mass ratio, the mixture containing the silicon-containing monomer can be made into a liquid both at room temperature and in refrigeration.
• the mixture containing a silicon-containing monomer according to an embodiment of the present invention contains at least one of a silicon compound represented by the formula (3), methanol and ethanol, and at least one alcohol represented by the formula (4). It is obtained by reacting with a mixed alcohol containing.
• the silicon compound represented by the formula (3) will be referred to as a silicon compound (3).
• the alcohol represented by the formula (4) is referred to as alcohol (4).
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where X is a halogen atom, n is an integer of 1 to 5, and p is an integer of 0 to 1.
• the alcohol (4) is selected depending on the mixture containing the silicon-containing monomer of interest.
• the alcohol (4) specifically, 1-propanol, 2-propanol, 1-butanol, 2-butanol (isobutyl alcohol), 2-methyl-2-butanol, 1-pentanol, 3-methyl-1- Butanol (isoamyl alcohol), 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 2-pentanol, 3-methyl-2-butanol, 3-pentanol, 2-methyl-2-butanol, 3-Fluoropropanol, 3,3-difluoropropanol, 3,3,3-trifluoropropanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,3-pentafluoropropanol, 1, 1,1,3,
• the water content of the mixed alcohol is preferably 5 wt% or less, more preferably 1 wt% or less.
• reaction condition The reaction method for producing the mixture according to the embodiment of the present invention is not particularly limited. Typical examples include a method in which a mixed alcohol is dropped and reacted with the silicon compound (3), and a method in which the silicon compound (3) is dropped and reacted with the mixed alcohol.
• the amount of mixed alcohol used is not particularly limited. From the viewpoint of efficient progress of the reaction, 1 molar equivalent or more and 10 molar equivalents or less are preferable, and 1 molar equivalent or more and 3 molar equivalents or less are more preferable with respect to the Si—X bond contained in the silicon compound (3).
• the addition time of the mixed alcohol or the silicon compound (3) is not particularly limited.
• the addition time is preferably, for example, 10 minutes or more and 24 hours or less, and more preferably 30 minutes or more and 6 hours or less.
• the optimum temperature of the reaction during dropping varies depending on the reaction conditions, but specifically, it is preferably 0 ° C. or higher and 70 ° C. or lower.
• the reaction can be completed by aging while continuing stirring after the dropping is completed.
• the aging time is not particularly limited, and is preferably 30 minutes or more and 6 hours or less from the viewpoint of sufficiently advancing the desired reaction.
• the reaction temperature during aging is the same as that at the time of dropping or higher than that at the time of dropping. Specifically, the reaction temperature during aging is preferably 10 ° C. or higher and 80 ° C. or lower.
• the reactivity between the mixed alcohol and the silicon compound (3) is high, and the halogenosilyl group is rapidly converted to the alkoxysilyl group.
• the hydrogen halide generated during the reaction is removed. It is preferable to do so.
• As a method for removing hydrogen halide it is produced by adding known hydrogen halide trapping agents such as amine compounds, orthoesters, sodium alkoxides, epoxy compounds and olefins, as well as heating, degassing, vacuum heating or bubbling dry nitrogen. There is a method of removing the hydrogen halide gas to the outside of the system. These methods may be performed alone or in combination of two or more.
• Examples of the hydrogen halide scavenger include ortho ester and sodium alkoxide.
• Examples of the orthoester include trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, trimethyl orthoacetate, triethyl orthoformate, trimethyl orthopropionic acid, and trimethyl orthobenzoate. Since it is easily available, trimethyl orthoformate or triethyl orthoformate is preferable.
• Examples of the sodium alkoxide include sodium methoxide and sodium ethoxide.
• the reaction solution of the mixed alcohol and the silicon compound (3) may be diluted with a solvent.
• the solvent used is not particularly limited as long as it does not react with the mixed alcohol used and the silicon compound (3), and pentane, hexane, heptane, octane, toluene, xylene, tetrahydrofuran, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-. Dimethoxyethane, 1,4-dioxane and the like can be used. These solvents may be used alone or in combination.
• the mixture containing the silicon-containing monomer produced by the above-mentioned method includes (I) at least one of the silicon-containing monomers (1), (II) the silicon-containing monomer (2-1), and the silicon-containing monomer (2-2). Includes at least one selected from the group consisting of.
• the silicon-containing monomer (1) remains liquid regardless of whether it is stored at room temperature or refrigerated.
• both the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2) remain solid regardless of whether they are stored at room temperature or refrigerated.
• the mixture containing the silicon-containing monomer according to the embodiment of the present invention can also be obtained by reacting the silicon compound (3) with a mixture of methanol and ethanol.
• the mixture containing the silicon-containing monomer contains at least one silicon-containing monomer represented by the formula (I-1) (5), (II) the silicon-containing monomer (2-1), and the silicon-containing monomer (2).
• the silicon-containing monomer represented by the formula (5) will be referred to as a silicon-containing monomer (5).
• the silicon-containing monomer (5) is as follows.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom.
• the following group ( 1HFIP ) in the formula (3), the formula (2-1), and the formula (2-2) may be any of the groups represented by the following formulas (1A) to (1D). preferable. Further, it is preferable that p is 0 in the formula (1). (In the equation, wavy lines indicate that the intersecting line segments are bonds.)
• the ratio of the component (I-1) and the component (II) satisfies the following relationship in terms of mass ratio.
• the obtained mixture containing the silicon-containing monomer can be made into a liquid at room temperature.
• the ratio of the component (I-1) and the component (II) satisfies the following relationship in terms of mass ratio.
• the resulting mixture containing the silicon-containing monomer can be made into a liquid at room temperature or in a refrigerator. ..
• the silicon-containing monomer (5) having these structures is preferable because it remains liquid regardless of whether it is stored at room temperature or refrigerated. On the other hand, both the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2) remain solid regardless of whether they are stored at room temperature or refrigerated.
• the silicon-containing monomer (5) By mixing the silicon-containing monomer (5) according to the embodiment of the present invention with at least one selected from the group consisting of the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2), at room temperature. It can remain liquid even when stored. Furthermore, by selecting an appropriate mixing ratio, it can remain liquid even when stored in a refrigerator. This makes it easy to handle the mixture containing the silicon-containing monomer even when it is used on an industrial scale.
• the polysiloxane is represented by at least one kind of silicon-containing monomer represented by the formula (I) (1), the silicon-containing monomer represented by the formula (II) (2-1), and the formula (2-2). It is obtained by polymerizing (hydrolyzing and polycondensing reaction) a mixture containing a silicon-containing monomer containing at least one selected from the group consisting of silicon-containing monomers.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.
• the following group ( 1HFIP ) in the formula (1), the formula (2-1), and the formula (2-2) may be any of the groups represented by the following formulas (1A) to (1D). preferable. Further, it is preferable that p is 0 in the formula (1). (In the equation, wavy lines indicate that the intersecting line segments are bonds.)
• the ratio of the component (I) to the component (II) satisfies the following relationship in terms of mass ratio.
• the ratio of the component (I) and the component (II) satisfies the above relationship in terms of mass ratio, the mixture containing the silicon-containing monomer can be made into a liquid at room temperature. Therefore, it is easy to handle the mixture on an industrial scale during the production of polysiloxane.
• the ratio of the component (I) and the component (II) satisfies the following relationship in terms of mass ratio.
• (I) component / ⁇ (I) component + (II) component ⁇ ⁇ 0.17 By satisfying the above relationship in terms of the ratio of the component (I) and the component (II) in terms of mass ratio, the mixture containing the silicon-containing monomer can be made into a liquid both at room temperature and in refrigeration. Therefore, it is easier to handle the mixture on an industrial scale during the production of polysiloxane.
• the present hydrolysis polycondensation reaction can be carried out by a general method in the hydrolysis and condensation reaction of hydrolyzable silane. Specifically, at least one of (I) a silicon-containing monomer (1) and at least one selected from the group consisting of (II) a silicon-containing monomer (2-1) and a silicon-containing monomer (2-2). , Containing, after collecting the mixture containing the silicon-containing monomer in the reaction vessel, water for hydrolysis, if necessary, a catalyst for advancing the polycondensation reaction, and the reaction solvent are added into the reactor and stirred. Then, if necessary, heating is carried out to allow the hydrolysis and polycondensation reaction to proceed, whereby a polysiloxane (solution) is obtained.
• a "polysiloxane solution” is obtained in which polysiloxane is miscible with the above water by hydrolysis without adding a special reaction solvent to obtain a uniform solution state.
• the details are unknown, it is derived from the above-mentioned silicon-containing monomer (1) and at least one selected from the group consisting of the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2) by hydrolysis.
• the silanol group of the polysiloxane contributes to the mixing with the above water, and the by-produced solvent component (for example, when alkoxysilane is used, the corresponding alcohol is by-produced) is the polysiloxane and the above-mentioned water. It is thought that it contributes to mixing. Further, the same solvent as the reaction solvent described later may be further added to the polysiloxane (solution) obtained by performing the above hydrolysis polycondensation.
• the catalyst for advancing the polycondensation reaction is not particularly limited, and examples thereof include an acid catalyst and a base catalyst.
• Acid catalysts include hydrochloric acid, nitrate, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, tosylic acid, formic acid, maleic acid and malonic acid.
• a polyvalent carboxylic acid such as succinic acid, or an anhydride of these acids can be exemplified.
• triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, or sodium carbonate can be used. It can be exemplified.
• reaction solvent In the hydrolysis and polycondensation reaction, it is not always necessary to use a reaction solvent, and a raw material compound, water and a catalyst can be mixed and hydrolyzed and polycondensed.
• the reaction solvent when used, the type thereof is not particularly limited. Among them, a polar solvent is preferable, and an alcohol solvent is more preferable, because of its solubility in a raw material compound, water, and a catalyst.
• the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol.
• a step of adjusting the pH of the polysiloxane solution by extraction, washing with water or the like may be carried out, if necessary, or a step of adjusting the concentration of the polysiloxane solution by solvent distillation, concentration, dilution or the like. May be carried out.
• the silicon compound represented by the following chemical formula is referred to as HFA-Ph-CS.
• the silicon compound obtained in this example was identified by the method shown below.
• GPC Global Permeation Chromatography
• GC Gas Chromatography
• Example 1 While performing N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was heated to an internal temperature of 50 ° C., and the mixed alcohol (12.1 g, 309.9 mmol, 3.9 eq.), (The breakdown of the mixed alcohol is EtOH (7.14 g, 154.9 mmol, 1.9 eq.) And MeOH (4.96 g, 154.9 mmol, 1.9 eq.) Were slowly added dropwise (maintaining an internal temperature of 45 to 55 ° C.). After the dropping of the mixed alcohol was completed, the mixture was stirred at an internal temperature of 50 ° C.
• Example 2 While performing N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was heated to an internal temperature of 50 ° C., and the mixed alcohol (15.4 g, 309.9 mmol, 3.9 eq.), (The breakdown of the mixed alcohol is EtOH (11.4 g, 247.9 mmol, 3.1 eq.), MeOH (0.5 g, 15.5 mmol, 0.2 eq.), 1-propanol (0.9 g, 15.5 mmol, 0.2 eq.), Isobutanol (1.2 g, 15.5 mmol, 0.2 eq.) And isoamyl alcohol (1.4 g, 15.5 mmol, 0.2 eq.) Were slowly added dropwise (maintaining an internal temperature of 45 to 55 ° C.).
• the mixture was stirred at an internal temperature of 50 ° C. for 30 minutes, and the HCl gas and the unreacted alcohol were distilled off by an evaporator (bath 40 ° C., 10 hPa, 1 hr). At this time, the yield was 32 g. Then, simple distillation was carried out to obtain 27.5 g of the mixture.
• the mixture had a silicon-containing monomer V having a structure shown in Table 2 of 5.2%, a silicon-containing monomer VI of 43.1%, and a silicon-containing monomer. VII was 10.8%, silicon-containing monomer VIII was 12.9%, and silicon-containing monomer IX was 13.8%, which were the main components of the mixture.
• both were liquid.
• Example 3 While performing N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was heated to an internal temperature of 50 ° C., and the mixed alcohol (12.1 g, 309.9 mmol, 3.9 eq.), (The breakdown of the mixed alcohol is MeOH (7.94 g, 247.9 mmol, 3.1 eq.), EtOH (0.71 g, 15.5 mmol, 0.2 eq.), 1-propanol (0.9 g, 15.5 mmol, 0.2 eq.), Isobutanol (1.2 g, 15.5 mmol, 0.2 eq.) And isoamyl alcohol (1.4 g, 15.5 mmol, 0.2 eq.) Were slowly added dropwise (maintaining an internal temperature of 45 to 55 ° C.).
• the mixture was stirred at an internal temperature of 50 ° C. for 30 minutes, and the HCl gas and the unreacted alcohol were distilled off by an evaporator (bath 40 ° C., 10 hPa, 1 hr). At this time, the yield was 29 g. Then, simple distillation was carried out to obtain 25.8 g of the mixture.
• the mixture contained 39.4% of silicon-containing monomer X, 10.9% of silicon-containing monomer XI, and silicon-containing monomer having the structures shown in Table 3.
• Example 4 As a result of mixing 1 g of the ethyl form of Comparative Example 1 and 1 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 5 As a result of mixing 0.75 g of the ethyl compound of Comparative Example 1 and 0.25 g of the propyl compound of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 6 As a result of mixing 0.80 g of the ethyl compound of Comparative Example 1 and 0.20 g of the propyl compound of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 7 As a result of mixing 0.85 g of the ethyl compound of Comparative Example 1 and 0.15 g of the propyl compound of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, they remained liquid at room temperature and became solid when refrigerated.
• Example 8 As a result of mixing 1 g of the ethyl compound of Comparative Example 1 and 1 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 9 As a result of mixing 0.75 g of the ethyl compound of Comparative Example 1 and 0.25 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 10 As a result of mixing 0.8 g of the ethyl compound of Comparative Example 1 and 0.2 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 11 As a result of mixing 0.85 g of the ethyl compound of Comparative Example 1 and 0.15 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, they remained liquid at room temperature and became solid when refrigerated.
• Example 12 As a result of mixing 1 g of the ethyl form of Comparative Example 1 and 1 g of the isoamyl form of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 13 As a result of mixing 0.75 g of the ethyl compound of Comparative Example 1 and 0.25 g of the isoamyl acetate of Synthetic Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 14 As a result of mixing 0.8 g of the ethyl compound of Comparative Example 1 and 0.2 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 15 As a result of mixing 0.85 g of the ethyl compound of Comparative Example 1 and 0.15 g of the isoamyl acetate of Synthetic Example 3 and storing them at room temperature and refrigeration for 1 week, they remained liquid at room temperature and became solid in refrigeration.
• Example 16 As a result of mixing 1 g of the methyl form of Comparative Example 2 and 1 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 17 As a result of mixing 0.75 g of the methyl form of Comparative Example 2 and 0.25 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 18 As a result of mixing 0.80 g of the methyl form of Comparative Example 2 and 0.20 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 19 As a result of mixing 0.85 g of the methyl form of Comparative Example 2 and 0.15 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, they remained liquid at room temperature and became solid when refrigerated.
• Example 20 As a result of mixing 1 g of the methyl compound of Comparative Example 2 and 1 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 21 As a result of mixing 0.75 g of the methyl compound of Comparative Example 2 and 0.25 g of the isobutyl compound of Synthetic Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 22 As a result of mixing 0.8 g of the methyl compound of Comparative Example 2 and 0.2 g of the isobutyl compound of Synthetic Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 23 As a result of mixing 0.85 g of the methyl compound of Comparative Example 2 and 0.15 g of the isobutyl compound of Synthetic Example 2 and storing them at room temperature and refrigerating for 1 week, they remained liquid at room temperature and became solid when refrigerated.
• Example 24 As a result of mixing 1 g of the methyl compound of Comparative Example 2 and 1 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 25 As a result of mixing 0.75 g of the methyl compound of Comparative Example 2 and 0.25 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 26 As a result of mixing 0.8 g of the methyl compound of Comparative Example 2 and 0.2 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.
• Example 27 As a result of mixing 0.85 g of the methyl compound of Comparative Example 2 and 0.15 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigeration for 1 week, they remained liquid at room temperature and became solid in refrigeration.
• Example 28 As a result of mixing 0.25 g of the ethyl form of Comparative Example 1, 0.25 g of the methyl form of Comparative Example 2 and 0.5 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, they were all liquid. rice field.
• Example 1-P At room temperature (23 ° C.), the silicon-containing monomer mixture (5.0 g, 10.2 mmol) obtained in Example 1, pure water (0.68 g, 37.5 mmol), acetic acid (0.02 g, 0.36 mmol). was mixed. Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added and mixed very easily. Then, the mixture was stirred at 100 ° C. under full reflux for 1 hr. The obtained reaction solution was returned to room temperature, and the weight average molecular weight (Mw) was measured by GPC and found to be 1740.
• Mw weight average molecular weight
• Example 2-P Silicon-containing monomer mixture (5.0 g, 10.2 mmol), pure water (0.68 g, 37.5 mmol), acetic acid (0.02 g, 0.36 mmol) obtained in Example 2 at room temperature (23 ° C.). Was mixed. Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added and mixed very easily. Then, the mixture was stirred at 100 ° C. under full reflux for 1 hr. The obtained reaction solution was returned to room temperature, and the weight average molecular weight (Mw) was measured by GPC. As a result, it was 1690.
• Mw weight average molecular weight
• Example 3-P Silicon-containing monomer mixture (5.0 g, 10.2 mmol), pure water (0.68 g, 37.5 mmol), acetic acid (0.02 g, 0.36 mmol) obtained in Example 3 at room temperature (23 ° C.). Was mixed. Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added and mixed very easily. Then, the mixture was stirred at 100 ° C. under full reflux for 1 hr. The obtained reaction solution was returned to room temperature, and the weight average molecular weight (Mw) was measured by GPC. As a result, it was 2060.
• Mw weight average molecular weight
• Example 4-P At room temperature (23 ° C.), the silicon-containing monomer mixture (5.0 g, 10.2 mmol) obtained in Example 1 was dissolved in 2-butanol (2.5 g) and then pure water (0.68 g, 37). .5 mmol) and acetic acid (0.02 g, 0.36 mmol). Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added, mixed and dissolved very easily. Then, the mixture was stirred at 100 ° C. under total reflux for 24 hours. The obtained reaction solution was returned to room temperature, and the weight average molecular weight (Mw) was measured by GPC and found to be 1080.
• Mw weight average molecular weight
• Example 3-P was the most excellent, followed by Example 1-P and Example 2-P.
• the detailed mechanism of this tendency is not clear, but it is because the hydrolysis and polycondensation reaction rates increase as the carbon number of the alkoxide moiety and the proportion of structures with less steric hindrance in the silicon-containing monomer mixture are shorter. Conceivable. It was also found that the hydrolysis and polycondensation reaction rates could be controlled using a reaction solvent as in Example 4-P.
• Example 2-coP At room temperature (23 ° C.), the silicon-containing monomer mixture (5.0 g, 10.2 mmol) obtained in Example 2, triethoxyphenylsilane (22.9 g, 95.2 mmol), KBM-303 (manufactured by Shinetsu Silicone Co., Ltd.). , 2.9 g, 11.9 mmol), pure water (6.8 g, 374.8 mmol), and acetic acid (0.21 g, 3.57 mmol) were mixed. Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added and mixed very easily. Then, the mixture was stirred at 40 ° C. for 1 hr, 70 ° C.
• the silicon-containing monomer and its mixture of the present invention are useful as a synthetic raw material for a polymer resin, a polymer modifier, a surface treatment agent for an inorganic compound, various coupling agents, and an intermediate raw material for organic synthesis.
• the polysiloxane of the present invention and the film obtained from the polysiloxane are soluble in an alkaline developing solution, have patterning performance, and are excellent in heat resistance and transparency.
• a protective film for semiconductors, a flattening material, and a microlens It can be used as a material, an insulating protective film for a touch panel, a liquid crystal display TFT flattening material, a core or clad forming material for an optical waveguide, a resist for an electron beam, a multilayer resist intermediate film, an underlayer film, an antireflection film and the like.
• fine particles such as polytetrafluoroethylene, silica, titanium oxide, zirconium oxide, and magnesium fluoride are used in an arbitrary ratio for the purpose of adjusting the refractive index. Can be mixed and used in.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Silicon Polymers (AREA)
• Macromonomer-Based Addition Polymer (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=81755856

Family Applications (1)

Country Status (5)

Citations (3)

Family Cites Families (7)

• 2021
  • 2021-11-09 KR KR1020237020148A patent/KR20230110761A/ko not_active Withdrawn
  • 2021-11-09 JP JP2022565201A patent/JPWO2022113724A1/ja not_active Withdrawn
  • 2021-11-09 CN CN202180078224.2A patent/CN116457363A/zh active Pending
  • 2021-11-09 WO PCT/JP2021/041158 patent/WO2022113724A1/ja not_active Ceased
  • 2021-11-24 TW TW110143696A patent/TW202227461A/zh unknown

Patent Citations (3)

Also Published As

Similar Documents

Legal Events