Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
• • 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
  • C08G77/06—Preparatory processes
• • 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
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups

Definitions

• the present invention relates to silane compound polymers.
• curable compositions have been variously improved according to their uses, and have been widely used industrially as raw materials for optical parts and moldings, adhesives, coating agents, and the like. Curable compositions are also attracting attention as compositions for optical element fixing materials such as adhesives for optical element fixing materials and sealing materials for optical element fixing materials.
• Optical devices include various lasers such as semiconductor lasers (LD), light emitting devices such as light emitting diodes (LED), light receiving devices, composite optical devices, optical integrated circuits, and the like.
• LD semiconductor lasers
• LED light emitting diodes
• Optical devices include various lasers such as semiconductor lasers (LD), light emitting devices such as light emitting diodes (LED), light receiving devices, composite optical devices, optical integrated circuits, and the like.
• LD semiconductor lasers
• LED light emitting devices
• LED light emitting diodes
• optical integrated circuits and the like.
• blue-light and white-light optical elements with shorter peak emission wavelengths have been developed and widely used.
• the brightness of such light-emitting elements having a short peak wavelength of light emission has been rapidly increased, and along with this, there is a tendency that the amount of heat generated by the optical elements is further increased.
• Patent Documents 1 to 3 propose compositions for optical element fixing materials containing polysilsesquioxane compounds as main components.
• Patent Document 4 describes hydrolysis and polycondensation of a mixture of a trifunctional silicon alkoxide, water, and an acid catalyst without using an organic solvent, and then removing the alcohol produced by the hydrolysis of the trifunctional silicon alkoxide.
• a method of making a polysilsesquioxane liquid comprising: In the examples of Patent Document 4, 3-mercaptopropyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, and phenyltrimethoxysilane were used as monomers to produce various polysilsesquioxane liquids. ing.
• Patent Document 5 describes a polysilsesquioxane liquid containing polysilsesquioxane having a specific repeating unit as a main component.
• a polysilsesquioxane liquid is produced using ethyltrimethoxysilane as a monomer.
• Patent Document 6 describes a condensation-reactive silicone composition containing polysilsesquioxane, etc., which is liquid at room temperature.
• liquid polysilsesquioxane is produced using methyltrimethoxysilane as a monomer.
• Patent Documents 4 to 6 describe silane compound polymers that are liquid at room temperature.
• methyltrialkoxysilane is used as a monomer, under the same reaction conditions as in Examples and Production Examples of Patent Documents 4 and 5, a silane compound polymer that is liquid at room temperature is produced. I found it hard to get.
• Patent Document 6 a silane compound polymer having repeating units derived from methyltrialkoxysilane and being liquid at room temperature can be obtained, but this silane compound polymer is thermosetting. Therefore, it was found that the silane compound polymer was not sufficiently cured unless a curing catalyst was added.
• the present invention has been made for the purpose of solving these problems, and has a repeating unit derived from methyltrialkoxysilane, is liquid at room temperature (25 ° C., the same applies hereinafter), and is thermosetting.
• An object of the present invention is to provide a silane compound polymer having properties.
• liquid at room temperature means fluid at 25°C.
• thermosetting refers to the property of curing only by heating without the presence of a curing catalyst.
• the present inventors have extensively studied silane compound polymers having repeating units derived from methyltrialkoxysilane. As a result, by adjusting the amount of alkoxy groups in the silane compound polymer, a silane compound polymer having repeating units derived from methyltrialkoxysilane, liquid at room temperature, and having thermosetting properties can be obtained. The present inventors have found that it can be obtained, and have completed the present invention.
• silane compound polymers [1] to [7] are provided.
• R 1 is an unsubstituted alkyl group having 2 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted carbon number It represents a group selected from the group consisting of 6 to 12 aryl groups.
• the amount of the repeating unit (1) contained in the silane compound polymer is 70 to 100 mol % with respect to the total amount of the repeating unit (1) and the repeating unit (2).
• the silane compound polymer has a T1 site represented by the following formula (3), a T2 site represented by the following formula (4), and a T3 site represented by the following formula (5), The silane compound polymer according to any one of [1] to [5], wherein the amount of T1 sites is 2.5 to 25 mol% with respect to the total amount of T1 sites, T2 sites and T3 sites.
• R 2 is an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted carbon number It represents a group selected from the group consisting of 6 to 12 aryl groups.
• X 1 to X 3 each independently represent a hydrogen atom or an alkyl group. A silicon atom is bonded to *.
• [7] The silane compound polymer according to [6], wherein the amount of T1 sites having an alkoxy group is 20 to 60 mol% of all T1 sites.
• a silane compound polymer that has a repeating unit derived from methyltrialkoxysilane, is liquid at room temperature, and has thermosetting properties.
• the silane compound polymer of the present invention is a silane compound polymer having the repeating unit (1) and having or not having the repeating unit (2), and satisfying the requirements 1 to 4. It is a coalescence.
• the silane compound polymer of the present invention has a repeating unit (1) represented by the following formula (1).
• Me represents a methyl group.
• the silane compound polymer of the present invention has or does not have a repeating unit (2) represented by the following formula (2).
• R 1 is an unsubstituted alkyl group having 2 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted represents a group selected from the group consisting of aryl groups having 6 to 12 carbon atoms having a group.
• the number of carbon atoms in the “unsubstituted alkyl group having 2 to 10 carbon atoms” represented by R 1 is preferably 2 to 6, more preferably 2 to 3.
• Examples of the "unsubstituted alkyl group having 2 to 10 carbon atoms” include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
• the number of carbon atoms in the “substituted alkyl group having 1 to 10 carbon atoms” represented by R 1 is preferably 1 to 6, more preferably 1 to 3.
• the number of carbon atoms means the number of carbon atoms in the portion (alkyl group portion) excluding the substituents. Therefore, when R 1 is a “substituted alkyl group having 1 to 10 carbon atoms”, the number of carbon atoms in R 1 may exceed 10 in some cases.
• Examples of the alkyl group of "substituted alkyl group having 1 to 10 carbon atoms” include methyl group and the same groups as those shown as "unsubstituted alkyl group having 2 to 10 carbon atoms".
• the number of substituent atoms in the "substituted alkyl group having 1 to 10 carbon atoms" is generally 1 to 30, preferably 1 to 20.
• substituents of the "substituted alkyl group having 1 to 10 carbon atoms” include halogen atoms such as fluorine, chlorine and bromine atoms; aryl groups such as phenyl; and the like.
• the number of carbon atoms in the “unsubstituted aryl group having 6 to 12 carbon atoms” represented by R 1 is preferably 6.
• Examples of the “unsubstituted aryl group having 6 to 12 carbon atoms” include phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
• the number of carbon atoms in the “substituted aryl group having 6 to 12 carbon atoms” represented by R 1 is preferably 6.
• the number of carbon atoms means the number of carbon atoms in the portion (aryl group portion) excluding the substituents. Therefore, when R 1 is a “substituted aryl group having 6 to 12 carbon atoms”, the number of carbon atoms in R 1 may exceed 12 in some cases.
• Examples of the aryl group of the "substituted aryl group having 6 to 12 carbon atoms” include the same aryl groups as the "unsubstituted aryl group having 6 to 12 carbon atoms".
• the number of substituent atoms (excluding the number of hydrogen atoms) of the "substituted aryl group having 6 to 12 carbon atoms" is usually 1-30, preferably 1-20.
• substituents of the "substituted aryl group having 6 to 12 carbon atoms" include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group and t-butyl.
• Alkyl groups such as group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and isooctyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy such as methoxy group and ethoxy group group; and the like.
• R 1 is preferably an unsubstituted alkyl group having 2 to 10 carbon atoms or an unsubstituted aryl group having 6 to 12 carbon atoms.
• the silane compound polymer of the present invention may have one type of R 1 or two or more types of R 1 . may be
• the silane compound polymer of the present invention satisfies Requirement 1 above. That is, in the silane compound polymer of the present invention, the amount of the repeating unit (1) is 70 to 100 mol%, preferably 80 to 100 mol%, based on the total amount of the repeating unit (1) and the repeating unit (2). mol %, more preferably 90 to 100 mol %, still more preferably 95 to 100 mol %. Conventionally, "a silane compound polymer having a repeating unit derived from methyltrialkoxysilane" tends to become solid at room temperature.
• the silane compound polymer of the present invention contains many repeating units (1) (that is, repeating units derived from methyltrialkoxysilane) and satisfies requirements 2 and 3 (that is, it is liquid at room temperature). and has thermosetting properties).
• a silane compound polymer satisfying requirements 1, 2, and 3 can be obtained by appropriately adjusting the amount of alkoxy groups in the silane compound polymer.
• the total amount of repeating units (1) and repeating units (2) in the silane compound polymer of the present invention is preferably 80 to 100 mol%, more preferably 85 to 100 mol%, still more preferably 85 to 100 mol% of all repeating units. 90 to 100 mol %.
• a silane compound polymer in which the total amount of repeating units (1) and (2) is 80 mol % or more of all repeating units tends to be liquid at room temperature and have thermosetting properties.
• the repeating unit other than the repeating unit (1) and the repeating unit (2) may be trimethylmethoxysilane or the like. Repeating units derived from monofunctional silane compounds, repeating units derived from bifunctional silane compounds such as dimethyldimethoxysilane, and repeating units derived from trifunctional silane compounds (excluding repeating unit (1) and repeating unit (2) ), and repeating units derived from tetrafunctional silane compounds such as tetramethoxysilane.
• the silane compound polymer of the present invention satisfies requirement 2 above. That is, the viscosity at 25° C. of the silane compound polymer of the present invention is 15,000 Pa ⁇ s or less, preferably 4,000 Pa ⁇ s or less, more preferably 2,000 Pa ⁇ s or less. Since the viscosity of the silane compound polymer of the present invention at 25° C. is 15,000 Pa ⁇ s or less, the silane compound polymer of the present invention has sufficient fluidity at room temperature. Therefore, the silane compound polymer of the present invention is suitable as a curable component of a curable composition containing no organic solvent. Although there is no particular lower limit for the viscosity at 25° C. of the silane compound polymer of the present invention, it is usually 0.3 Pa ⁇ s or more. Therefore, the silane compound polymer of the present invention preferably has a viscosity of 0.3 to 15,000 Pa ⁇ s at 25°C.
• viscosity at 25° C.” refers to the viscosity at a shear rate of 2.2 s ⁇ 1 using a cone plate with a cone radius (cone bottom radius) of 12.5 mm and a cone angle of 0.5 degrees. .
• the "viscosity at 25°C” refers to the viscosity at an angular frequency of 2.0 rad/s using a parallel plate with a radius of 12.5 mm.
• the silane compound polymer of the present invention satisfies requirement 3 above. That is, the silane compound polymer of the present invention can be sufficiently cured only by heating without the presence of a curing catalyst. Therefore, the silane compound polymer of the present invention is suitable as a curable component of a curable composition containing no curing catalyst.
• the time required for the stirring torque to reach 0.049 N/cm is preferably 1,500 seconds or less. More preferably, it is 1,000 seconds or less.
• a silane compound polymer whose stirring torque reaches 0.049 N/cm in 1,500 seconds or less is more suitable as a curable component of a curable composition having excellent thermosetting properties.
• the silane compound polymer of the present invention has a time of 100 to 1,500 seconds until the stirring torque reaches 0.049 N/cm when the thermosetting test described in the Examples is conducted. preferable.
• the silane compound polymer of the present invention satisfies requirement 4 above. That is, the silane compound polymer of the present invention has an alkoxy group.
• Requirement 4 it becomes easier to obtain a silane compound polymer that satisfies all of Requirement 1, Requirement 2, and Requirement 3. That is, even if the silane compound polymer contains many repeating units derived from methyltrialkoxysilane, it tends to become liquid at room temperature because it contains many alkoxy groups.
• a silane compound polymer having too many alkoxy groups tends to be inferior in thermosetting properties. Therefore, a silane compound polymer satisfying requirements 1, 2, and 3 can be obtained by appropriately adjusting the amount of alkoxy groups in the silane compound polymer.
• silane compound polymer (A) can be efficiently produced by hydrolyzing and polycondensing an alkoxysilane compound.
• silane compound polymer (A) those obtained by hydrolyzing and polycondensing an alkoxysilane compound may be referred to as "silane compound polymer (A)".
• the alkoxy group residual ratio of the silane compound polymer (A) is preferably 2.5 to 25%, more preferably 3.0 to 20%.
• the alkoxy group residual ratio of the silane compound polymer (A) represents the extent to which the alkoxy groups contained in the alkoxysilane compound used as the monomer remain in the silane compound polymer (A). be.
• a silane compound polymer (A) having an alkoxy group residual rate of 2.5% or more tends to be liquid at room temperature.
• a silane compound polymer (A) having an alkoxy group residual rate of 25% or less tends to have sufficient thermosetting properties.
• the alkoxy group residual rate can be calculated by measuring 1 H-NMR of the silane compound polymer (A). For example, when the silane compound polymer (A) is produced using methyltriethoxysilane, the 1 H-NMR of the silane compound polymer (A) is measured, and the ratio of the methyl group and the ethoxy group is the area ratio of the peak.
• the alkoxy group residual ratio of the silane compound polymer (A) can be calculated by obtaining based on the above.
• silane compound polymer of the present invention can be used in ketone solvents such as acetone; aromatic hydrocarbon solvents such as benzene; sulfur-containing solvents such as dimethylsulfoxide; ether solvents such as tetrahydrofuran; Since it is soluble in various organic solvents such as solvents; halogen-containing solvents such as chloroform; NMR at can be measured.
• ketone solvents such as acetone
• aromatic hydrocarbon solvents such as benzene
• sulfur-containing solvents such as dimethylsulfoxide
• ether solvents such as tetrahydrofuran
• repeating unit (1) and repeating unit (2) described above are represented by the following formula (6).
• R2 represents a methyl group or a group represented by R1 .
• O 1/2 indicates that an oxygen atom is shared with the adjacent repeating unit.
• the silane compound polymer of the present invention has three oxygen atoms bonded to a silicon atom, generally referred to as T sites, and other groups (groups represented by R 2 ) are combined to form a partial structure.
• T sites oxygen atoms bonded to a silicon atom
• other groups groups represented by R 2
• T site contained in the silane compound polymer of the present invention include the T1 site represented by the following formula (3), the T2 site represented by the following formula (4), and the T3 site represented by the following formula (5). .
• R 2 has the same meaning as above.
• X 1 to X 3 each independently represent a hydrogen atom or an alkyl group.
• the alkyl groups of X 1 to X 3 include methyl group, ethyl group, n-propyl group, isopropyl group and the like.
• * is bonded to a Si atom.
• the content ratio of the T1 site represented by the formula (3), the T2 site represented by the formula (4), and the T3 site represented by the formula (5) is determined according to a conventional method, as described in Patent Document 6. It can be determined by measuring 29 Si-NMR in a solution state of the silane compound polymer of the invention. As shown in formulas (3)-(5), the T3 site has three adjacent Si atoms, the T2 site has two adjacent Si atoms, while the T1 site has adjacent Si atoms. is only one. Therefore, the T1 site tends to constitute the terminal portion of the silane compound polymer and is an important site when interacting with other molecules.
• the state (liquid or solid) and thermosetting properties of a silane compound polymer are properties expressed as a result of interactions with other molecules. Therefore, the content of the T1 site and the ratio of the alkoxy group-containing T1 site to the entire T1 site are liquid at room temperature and have thermosetting properties, similar to the alkoxy group residual rate. It can be used as an index.
• the amount of the T1 site contained in the silane compound polymer of the present invention is preferably 2.5 to 25 mol%, more preferably 2.5 to 15 mol%, based on the total amount of the T1 site, T2 site and T3 site. .
• the ratio of alkoxy group-containing T1 sites to all T1 sites is preferably 20 to 60 mol %, more preferably 25 to 50%, of all T1 sites.
• the ratio of alkoxy group-containing T1 sites to all T1 sites can be calculated according to the method described in Examples.
• the weight average molecular weight (Mw) of the silane compound polymer of the present invention is preferably 500 to 20,000, more preferably 600 to 10,000, still more preferably 700 to 5,000.
• the molecular weight distribution (Mw/Mn) of the silane compound polymer of the present invention is not particularly limited, but is usually 1.00 to 10.00, preferably 1.10 to 6.00, more preferably 1.15 to 4.00. is.
• a silane compound polymer having a weight average molecular weight and a molecular weight distribution (Mw/Mn) within the above ranges is preferably used as a curable component of the curable composition.
• the mass average molecular weight (Mw) and number average molecular weight (Mn) can be obtained as standard polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, for example.
• the silane compound polymer of the present invention may be any of random copolymers, block copolymers, graft copolymers, alternating copolymers, and the like. However, random copolymers are preferable from the viewpoint of ease of production.
• the structure of the silane compound polymer of the present invention may be any one of a ladder type structure, a double decker type structure, a cage type structure, a partially cleaved cage type structure, a cyclic type structure and a random type structure.
• the method for producing the silane compound polymer of the present invention is not particularly limited.
• the method for producing the silane compound polymer of the present invention includes, for example, a step of hydrolytically polycondensing methyltrialkoxysilane in the presence of water and an acid catalyst (step PO), and polymerizing the silane compound obtained in step PO. Those having a step of purifying the union (step PU) are included.
• Step PO is a step of hydrolytic polycondensation of methyltrialkoxysilane in the presence of water and an acid catalyst.
• Methyltrialkoxysilane is used as an essential monomer.
• Methyltrialkoxysilane includes methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and the like.
• a trifunctional alkoxysilane compound other than methyltrialkoxysilane may be used as a monomer as long as a silane compound polymer satisfying Requirement 1 above can be obtained.
• Trifunctional alkoxysilane compounds other than methyltrialkoxysilane include trifunctional alkoxysilane compounds represented by the following formula (7).
• R 1 has the same meaning as above.
• OR represents an alkoxy group. OR's may be the same or different.
• the number of carbon atoms in the alkoxy group represented by OR is preferably 1-6, more preferably 1-3.
• the alkoxy group represented by OR includes a methoxy group, an ethoxy group, a propoxy group and the like.
• trifunctional alkoxysilane compound represented by formula (7) include ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n- Alkyltrialkoxysilane compounds such as propyltripropoxysilane; substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltripropoxysilane; aryltrialkoxysilane compounds such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane; substituted aryltrialkoxysilane compounds such as 4-methoxyphenyltrimeth
• the amount of methyltrialkoxysilane is generally 70 to 100 mol%, preferably 80 to 100 mol%, more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%, relative to the total amount of the trifunctional alkoxysilane compound. %.
• step PO in addition to the trifunctional alkoxysilane compound, a monofunctional alkoxysilane compound such as trimethylmethoxysilane, a bifunctional alkoxysilane compound such as dimethyldimethoxysilane, and a tetrafunctional alkoxysilane compound such as tetramethoxysilane are used as monomers.
• a monofunctional alkoxysilane compound such as trimethylmethoxysilane
• a bifunctional alkoxysilane compound such as dimethyldimethoxysilane
• a tetrafunctional alkoxysilane compound such as tetramethoxysilane
• the amount of the trifunctional alkoxysilane compound is preferably 80 to 100 mol %, more preferably 85 to 100 mol %, still more preferably 90 to 100 mol %, based on the total alkoxysilane compound.
• the amount of the trifunctional alkoxysilane compound is 80 mol % or more in the total alkoxysilane compound, it becomes easy to obtain a silane compound polymer that is liquid at room temperature and has thermosetting properties.
• the amount of water added into the reaction system in step PO is preferably an amount such that the molar ratio M of water and alkoxy groups derived from the following formula (F1) is 0.46 to 0.86, and is preferably 0.48 to 0. An amount of 0.80 is more preferred, and an amount of 0.50 to 0.70 is even more preferred.
• M H2O is the substance amount (number of moles) of water added to the reaction system
• M OR is the total number of alkoxy groups (total number of moles) in the alkoxysilane compound. For example, when 1 mol of water is added to 1 mol of methyltrialkoxysilane, the molar ratio M is 1/3 (0.33).
• Acid catalysts used in step (PO) include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid and nitric acid; organic acids such as acids; Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferred.
• the amount of the acid catalyst used is usually 0.05-10 mol %, preferably 0.1-5 mol %, relative to the total amount of the alkoxysilane compound.
• Process PO can be performed, for example, by putting an alkoxysilane compound, water, and an acid catalyst into a reaction vessel and stirring the resulting mixture.
• an organic solvent may be present in the reaction vessel.
• organic solvents include aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
• organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol and t-butyl alcohol; These solvents can be used singly or in combination of two or more.
• the organic solvent is preferably used in an amount of 0.05 to 3 times, more preferably 0.1 to 1.5 times the volume of the alkoxysilane compound.
• the reaction conditions of step PO are not particularly limited.
• the reaction temperature in step PO is generally 0 to 85°C, preferably 15 to 75°C.
• the reaction time in step PO is generally 30 minutes to 50 hours, preferably 1 to 24 hours.
• Process PO may be carried out under constant conditions from start to finish (that is, may have one step), or may have a plurality of steps with different reaction conditions. good too. Since a silane compound polymer having a desired molecular weight can be efficiently produced, the process PO consists of a step of hydrolyzing the alkoxysilane compound in the presence of water and an acid catalyst (step PO-I); Those that include a step of adjusting the molecular weight of the compound polymer (Step PO-II) are preferred.
• Step PO-I is a step of hydrolyzing the alkoxysilane compound in the presence of water and an acid catalyst.
• Step PO-I can be performed, for example, by placing an alkoxysilane compound, water, and an acid catalyst in a reaction vessel and stirring the resulting mixture.
• an organic solvent may be present in the reaction vessel. Examples of the organic solvent include those exemplified above as the organic solvent in step PO.
• the organic solvent is preferably used in an amount of 0.05 to 1, more preferably 0.1 to 0.5, by volume relative to the alkoxysilane compound.
• step PO-I The reaction conditions of step PO-I are not particularly limited.
• the reaction temperature in step PO-I is generally 0 to 50°C, preferably 15 to 35°C.
• the reaction time of step PO-I is usually 10 minutes to 2 hours, preferably 15 to 90 minutes.
• the water added for hydrolyzing the alkoxysilane compound is sufficiently consumed at the end of step PO-I.
• the amount of water consumed for example, when methyltriethoxysilane is used as a monomer, is measured by 1 H-NMR for the reaction product, and the amount of “Si—Me” and the amount of “Si—OEt” are can be inferred by comparing In step PO-I, not only the hydrolysis reaction of the alkoxysilane compound but also the polycondensation reaction may proceed.
• Step PO-II is a step of adjusting the molecular weight of the silane compound polymer. That is, step PO-II is a step of proceeding with the polycondensation reaction of the reaction product of step PO-I in order to produce a silane compound polymer having a desired molecular weight.
• step PO-II In order to adjust the molecular weight of the silane compound polymer, it is preferable to add a base to the reaction system when performing step PO-II, if necessary.
• a base By adding a relatively large amount of base, performing step PO-II at a relatively high temperature, or prolonging the reaction time of step PO-II, it is liquid at room temperature and has thermosetting properties.
• step PO-I by adjusting the amount of the acid catalyst and the reaction temperature to accelerate the hydrolysis reaction of the alkoxysilane compound, there is a tendency to obtain a silane compound polymer having a large molecular weight.
• step PO-II by adding a relatively small amount of base, performing step PO-II at a relatively low temperature, or shortening the reaction time of step PO-II, it is possible to obtain a liquid at room temperature and a thermosetting property. and have a relatively small molecular weight. Further, in step PO-I, by adjusting the amount of the acid catalyst and the reaction temperature to slightly suppress the hydrolysis reaction of the alkoxysilane compound, there is a tendency to obtain a silane compound polymer with a small molecular weight.
• the amount added is preferably 0.1 to 20 equivalents, more preferably 0.1 to 20 equivalents, relative to the acid catalyst used in step PO-I. 5 to 8 equivalents.
• Bases include aqueous ammonia; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline, 1,4-diazabicyclo [2.2.2]
• Organic bases such as octane and imidazole;
• Organic hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; Sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like metal alkoxides; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide;
• metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate;
• metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate;
• step PO-II The reaction conditions of step PO-II are not particularly limited.
• the reaction temperature in step PO-II is generally 20-85°C, preferably 24-70°C.
• the reaction time of step PO-II is generally 20 minutes to 48 hours, preferably 1 to 24 hours.
• Step PO-II allows the polycondensation reaction to proceed sufficiently in the same manner as the aging step, it is preferably carried out with stirring unlike the aging step. That is, in the aging step of leaving the mixture after the hydrolysis reaction to stand, a sufficient amount of water (3 equivalents of water with respect to the trifunctional silicon alkoxide) is added as in the example of Patent Document 4, and almost all This is considered to be a step suitable for the polycondensation reaction after substituting the alkoxy group of with a hydroxy group.
• the silane compound polymer of the present invention it is preferable to carry out under conditions in which the molar ratio M of water and alkoxy groups is in the range of 0.46 to 0.86.
• step PO-I Even when completely consumed, alkoxy groups remain in the reaction product of step PO-I.
• the reaction product of step PO-I contains a mixture of Si—OH and Si—OR, the polycondensation reaction of this reaction product is efficiently carried out to obtain a silane compound polymer having a desired molecular weight. In order to obtain, it is preferable to stir the inside of the reaction system.
• Step PO-II is preferably carried out in the presence of an organic solvent.
• the reaction system can be sufficiently stirred, and the polycondensation reaction of the reaction product of step PO-I can be sufficiently advanced. Further, since the polycondensation reaction of the reaction product in step PO-I can be carried out under diluted conditions, the molecular weight can be adjusted with good reproducibility.
• step PO-II examples include those exemplified above as the organic solvent in step PO. Therefore, when step PO-I is performed in the presence of an organic solvent, step PO-II can be performed using the organic solvent as it is. On the other hand, when step PO-I is performed in the absence of an organic solvent, step PO-II can be performed in the presence of an organic solvent by adding an organic solvent to the reaction mixture obtained in step PO-I. .
• an organic solvent is used in step PO-II, it is preferably 0.05 to 3 times, more preferably 0.1 to 1.5 times by volume the alkoxysilane compound used in step PO-I. of organic solvents are used.
• Step PO-II is preferably carried out in an open system.
• water and alcohol which are products in step PO, are easily released out of the reaction system, so that it is possible to avoid inhibition of the polycondensation reaction by water and alcohol. can.
• step PO-II is carried out in the presence of an organic solvent, excessive pressurization can be suppressed, so that the polycondensation reaction can proceed safely.
• An open system means a system in which a reaction system and its surrounding system are not completely shut off and molecules can move between them.
• Process PU is a process of purifying the obtained silane compound polymer. By performing the step PU, a highly pure silane compound polymer can be obtained. Such a silane compound polymer is more suitable as a curable component of a curable composition such as an optical element fixing material composition.
• Process PU includes a purification process by a solvent extraction method.
• purification steps by solvent extraction include those having the following steps.
• Step PU-I To the reaction mixture obtained in step PO, a water-immiscible organic solvent or water is added, if necessary, and the mixture is stirred and allowed to stand to separate into an organic phase and an aqueous phase.
• Step (Step PU-II) Step of separating the organic phase generated in Step PU-I, and washing the organic phase with water if necessary
• Step PU-III The organic phase separated in Step PU-II drying (step PU-IV) removing the solvent from the organic phase dried in step PU-III
• step PU-I if necessary, a solvent such as a water-immiscible organic solvent or water is added to the reaction mixture so that the reaction mixture obtained in step PO separates into an organic phase and an aqueous phase.
• a solvent such as a water-immiscible organic solvent or water is added to the reaction mixture so that the reaction mixture obtained in step PO separates into an organic phase and an aqueous phase.
• the amount of solvent to be added and the type of organic solvent are not particularly limited as long as the reaction mixture obtained in step PO separates into an organic phase and an aqueous phase.
• the silane compound polymer is usually contained in the organic phase. Therefore, in step PU-II, the organic phase produced in step PU-I is separated. After this, the organic phase may be washed with water according to conventional methods.
• step PU-III the organic phase is dried according to conventional methods such as adding magnesium sulfate.
• step PU-IV the solvent is removed from the organic phase. Removal of the solvent can be carried out according to a conventional method such as concentration treatment using an evaporator or vacuum drying treatment.
• Example 1 After charging 47.41 g (266 mmol) of methyltriethoxysilane into a 300 ml eggplant-shaped flask, 0.0693 g of 35% by mass hydrochloric acid (HCl: 0.665 mmol) was added to 9.576 g (531 mmol) of distilled water while stirring. , 0.250 mol % with respect to methyltriethoxysilane) was added, and the whole volume was stirred at 30° C. for 1 hour.
• HCl 35% by mass hydrochloric acid
• the system was heated to 70° C., 11.9 g of propyl acetate and 0.040 g of 28% aqueous ammonia solution (NH 3 : 0.658 mmol, 0.99 equivalent to HCl) were added thereto and stirred for 2 hours. After allowing the reaction solution to cool to room temperature (25° C.), 100 g of propyl acetate and 200 g of water were added to the solution for liquid separation, and the organic phase containing the reaction product was separated. Drying treatment was performed by adding magnesium sulfate to this organic phase. After removing the magnesium sulfate by filtration, the organic phase was concentrated by an evaporator, and then the obtained concentrate was vacuum-dried to obtain a silane compound polymer.
• aqueous ammonia solution NH 3 : 0.658 mmol, 0.99 equivalent to HCl
• Examples 2 to 4 Comparative Examples 1 to 3
• a silane compound polymer was obtained in the same manner as in Example 1, except that the conditions were changed to those shown in Table 1.
• thermosetting test The curing time was measured under the following conditions using an automatic curing time measuring device "Madoka” (manufactured by Cyber Co., Ltd.). A 0.20 mL sample was placed on a stainless steel plate heated to 170° C. and stirred. Since the stirring torque increases with time, the time (seconds) until reaching 0.049 N ⁇ cm was measured. Based on this time, the thermosetting property of the silane compound polymer was evaluated according to the following criteria. Since the silane compound polymers obtained in Comparative Examples 1 and 3 were solid, they were diluted with a mixed solvent [butyl diglycol acetate:tripropylene glycol monobutyl ether (4:6)] as a reference experiment.
• a mixed solvent butyl diglycol acetate:tripropylene glycol monobutyl ether (4:6)
• the amounts of the T1 site, the T2 site, and the T3 site were obtained based on the integrated values in the following ranges.
• the amounts of T1 site, T2 site, and T3 site were obtained based on the integrated values in the following ranges.
• T1 site -51.0 to -46.0 ppm
• T2 site -74.0 to -68.5 ppm
• T3 site -83.0 to -74.0 ppm
• Tables 1 and 2 show the following.
• the silane compound polymers obtained in Examples 1 to 4 contain repeating units derived from methyltrialkoxysilane, are liquid at room temperature, and have thermosetting properties.
• the silane compound polymers obtained in Comparative Examples 1 and 3 are solid at room temperature.
• the silane compound polymer obtained in Comparative Example 2 is liquid at room temperature, but is poor in thermosetting properties.

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