JP2010047699A - Organic silicon polymer and its preparation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel polymer having the excellent heat resistance, weather resistance and operativity. <P>SOLUTION: The organic silicon polymer obtained from an adamantane polyol, and a hydrosilane compound such as a 1,4-bis(phenyl silyl) benzene is represented by formula (1), [wherein R<SP>1</SP>and R<SP>2</SP>, which may be same or different, each represent a hydrogen atom, a hydroxy group, a 1C-5C alkyl group, a 1C-5C alkoxy group, a phenyl group, a fluorine atom, or a chlorine atom, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>, which may be same or different, each represent a hydrogen atom, a hydroxy group, a 1C-12C alkyl group, a 1C-12C alkoxy group, a 6C-15C aryl group, a thienyl group, a furyl group, a chlorine atom, or a group represented by formula (2), äwherein R<SP>1</SP>and R<SP>2</SP>, which are same as in the formula (1), and B represents a hydrogen atom, or a silicon atom in another repeating unit shown in the formula (1)}, and A represents a 6C-20C arylene group]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel organosilicon polymer excellent in heat resistance and having an adamantane skeleton in the main chain, and a method for producing the organosilicon polymer.

  Silicone resin is an excellent material used in various fields such as sealing agents such as light emitting diodes (LEDs), coating agents such as hard coats for spectacle lenses, and plastic substrates. In these applications, in recent years, a material having higher heat resistance has been required while maintaining transparency, and particularly in the near ultraviolet and white LED encapsulants, high heat and 400 nm or less due to high output. Materials that can withstand ultraviolet light degradation are desired. Up to now, epoxy resin has been used as a sealant material for LEDs, but no epoxy resin that can withstand the high heat and ultraviolet light degradation of 400 nm or less has been developed. Silicone resin is an alternative to epoxy resin. The use of is being considered. The silicon resin used for this purpose is a polymer having a silicon-oxygen bond and is known to be a relatively flexible resin. For example, poly (dimethylsiloxane) is known as the silicon resin (see Non-Patent Document 1). This poly (dimethylsiloxane) has a number average molecular weight of about 100,000 to 270,000, and can be applied to various applications.

  However, the poly (dimethylsiloxane) has a 10% thermal weight loss temperature of about 350 ° C. regardless of the number average molecular weight of about 100,000, and despite its very large molecular weight, the poly (dimethylsiloxane) has a relatively low temperature. There was room for improvement in terms of disassembly. This is considered to be due to the fact that the main chain (silicon-oxygen bond) is flexible.

  On the other hand, since adamantane derivatives have excellent heat resistance and transparency, they can be expected to be applied to highly functional materials such as heat resistant polymers and electronic materials such as semiconductor resists. As a polymer having such adamantane in the main chain skeleton, for example, a polymer in which adamantanes are linked to each other is known (for example, see Non-Patent Document 2). Although the polymer exhibits a relatively high thermogravimetric decrease temperature, it is extremely hard because the main chain is rigid, has low solubility in organic solvents, and is considered to have limited use, and there is room for improvement. was there.

  Therefore, the present inventors, in the case of an organosilicon polymer having both a silicon-oxygen bond and an adamantane skeleton in the main chain, provide heat resistance, weather resistance and resistance by a rigid adamantane skeleton and a relatively flexible silicon-oxygen bond. A polymer excellent in operability was expected to be obtained, and such a polymer was synthesized (see Non-Patent Document 3). The inventors filed an application for this polymer, that is, an alternating polymer having an O—Si—O bond and an adamantane unit in the main chain (Japanese Patent Application No. 2007-052673). This polymer, when not crosslinked, has a number average molecular weight of about 10,000, a 10% thermal weight loss temperature in a nitrogen atmosphere is 506 ° C., and has excellent heat resistance.

European Polymer Journal, 1978, Volume 14, pages 875-884. Macromolecules, 2004, 37, 7069-7071 Proceedings of the 87th Annual Meeting of the Chemical Society of Japan CD-ROM, published on March 12, 2007, lecture number 3R3-25

  In order to further utilize the organosilicon polymer having the above bond, the present inventors have examined a polymer having excellent heat resistance even when the molecular weight is lower than that of the polymer. Even if it has a lower molecular weight, if it has heat resistance equivalent to that of the above polymer, the solubility in organic solvents is also improved, so the use is considered to be further expanded.

  Accordingly, an object of the present invention is to provide an organosilicon polymer having an adamantane skeleton, which is expected to be excellent in heat resistance, weather resistance, and operability. The object is to provide an organosilicon polymer exhibiting equivalent heat resistance.

  Based on the above idea, the present inventors have conducted further studies on the production of a novel organosilicon polymer in which a rigid adamantane skeleton and a relatively flexible silicon-oxygen bond are introduced into the main chain. As a result, it is possible to obtain an organosilicon polymer having a desired structure by reacting an adamantane polyol compound and a specific hydrosilane compound, and the obtained organosilicon polymer has high heat resistance and is sealed for LED. Found that there is a possibility that it can be used in applications requiring various heat resistances including an agent, and in particular, it has been found that even if it has a lower molecular weight than a conventional organosilicon polymer, it has equivalent heat resistance, The present invention has been completed.

  That is, the first present invention is an organosilicon polymer having a structure in which one or two or more repeating units represented by the following formula (1) are linked by 2 to 1,000.

[In formula, R < ¹ > and R < ² > may be the same or different, respectively, a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, a C1-C5 alkoxy group, a phenyl group, a fluorine atom, Or R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different, and each is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Group, aryl group having 6 to 15 carbon atoms, thienyl group, furyl group, chlorine atom, or the following formula (2)

{In formula, R < ¹ > and R < ² > are synonymous with said Formula (1) respectively, B shows the silicon atom in the other repeating unit shown by a hydrogen atom or Formula (1). }
And A is an arylene group having 6 to 20 carbon atoms. ]
Moreover, 2nd this invention is the organosilicon polymer which has a structure which 1-type or 2 or more types of repeating units shown by following formula (2) connected 2-1000.

^{{Wherein, R 1, R 2, R} 3, R 4, R 5, and ^{R 6, R 1, R 2, R} 3 in each of the formulas ^{(1), R 4, R} 5, and the ^{R 6} It is synonymous. }
The third aspect of the present invention is a dehydrogenation cup comprising one or more adamantane polyol compounds represented by the following formula (4) and one or more hydrosilane compounds represented by the following formula (5). A method for producing an organosilicon polymer represented by the formula (1) or the formula (3), wherein dehydrogenation coupling is performed in the presence of a ring catalyst.

{Wherein, ^{R 1,} and ^{R 2} have the same meanings as ^{R 1,} and ^{R 2} in each of the formulas (1). }

^{{Wherein, R 3, R 4, R 5} , R 6, and A have the same meanings as ^{R 3, R 4, R 5} , R 6, and A in each of the formulas (1). }
Furthermore, a fourth aspect of the present invention is a manufacturing method characterized by using the following formula (6) as a hydrosilane compound in the above-described manufacturing method.

^{{Wherein, R 3, R 4, R} 5, and ^{R 6, R} 3 in each of the formulas ^{(1), R 4, R} 5, and ^{R 6} as synonymous. }

  The organosilicon polymer of the present invention has excellent characteristics resulting from having an adamantane skeleton, for example, excellent characteristics such as high heat resistance, and since the adamantane skeleton is not directly linked in the main chain, it has flexibility. Have. It is also possible to control various physical properties of the polymer obtained by selecting the type of adamantane polyol compound and the hydrosilane compound to be dehydrogenated. And even if the organosilicon polymer of this invention is a low molecular weight, it shows the heat resistance equivalent to the conventional polymer. This indicates that the solubility in an organic solvent is improved, and the use of the organosilicon polymer is expanded. From this, it is clear that if the molecular weights are comparable, they exhibit higher heat resistance than conventional polymers.

  The organosilicon polymer obtained by the method of the present invention is stable when synthesized by dehydrogenation coupling using a hydrosilane compound having a plurality of silicon atoms such as 1,4-bis (phenylsilyl) benzene. In such a state, a polymer having a hydrosilyl group can be obtained. Therefore, a variety of polymers can be synthesized by using the organosilicon polymer having a hydrosilyl group obtained by the above-described method, and further by dehydrogenation coupling.

  As described above, the organosilicon polymer of the present invention is excellent in heat resistance, and is useful as various industrial polymer materials such as LED sealing agents, or raw materials thereof.

  The organosilicon polymer of the present invention is a novel organosilicon polymer having an adamantane skeleton, and can be produced using a corresponding adamantane polyol compound as a raw material.

Hereinafter, the reaction product (monomer) used in the organosilicon polymer of the present invention and the production method thereof, reaction conditions, reaction procedures, products and the like will be described in detail.
(Organosilicon polymer)
The organosilicon polymer of the present invention has a structure in which one or two or more repeating units each represented by the following formula (1) are connected in an amount of 2 to 1,000.

R ¹ and R ² in the above formula (1) may be the same or different and are each a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, or fluorine. An atom or a chlorine atom.

  Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Among these, a methyl group and an ethyl group are preferable in consideration of productivity of the organosilicon polymer.

  Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. Among these, a methoxy group and an ethoxy group are preferable in consideration of productivity of the obtained organosilicon polymer.

Moreover, R < ³ >, R < ⁴ >, R < ⁵ > and R < ⁶ > in the said Formula (1) may be the same or different, respectively, a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group, and C1-C12 An alkoxy group, an aryl group having 6 to 15 carbon atoms, a thienyl group, a furyl group, a chlorine atom, or the following formula (2)

{In formula, R < ¹ > and R < ² > are synonymous with said Formula (1) respectively, B shows the silicon atom in the other repeating unit shown by a hydrogen atom or Formula (1). }
It is group shown by these. Among these groups, when at least one group of R ³ , R ⁴ , R ⁵ , and R ⁶ is a hydrogen atom, the obtained organosilicon polymer can be used as it is, and further, dehydration can be performed. By elementary coupling, it is possible to obtain a polymer into which various hydrosilane compounds are introduced according to the purpose.

  Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Among these, considering the productivity of the obtained organosilicon polymer, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, and a hexyl group are particularly preferable.

  Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, A dodecyloxy group is mentioned. Among these, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, and hexyloxy group are preferable because of the advantage that the obtained organosilicon polymer has high reactivity, and methoxy group, ethoxy group, propoxy group is particularly preferable. Groups are preferred.

  The aryl group having 6 to 15 carbon atoms may have a substituent, and examples of the aryl group include a phenyl group, a tolyl group, a chlorophenyl group, a naphthyl group, and a methoxyphenyl group. Among these, a phenyl group is particularly preferable because an organosilicon polymer can be obtained with a high yield.

  Further, the group represented by the formula (2) refers to a group in which a hydrogen atom of at least one hydroxyl group of an adamantane polyol compound is eliminated and a remaining oxygen atom is bonded to silicon. In consideration of the reaction, this group is preferably a group derived from the adamantane polyol compound of the formula (4), which is the monomer described above. Here, when a part of the repeating unit of the organosilicon polymer in which B in the formula (2) is a hydrogen atom is exemplified, a structure represented by the following formula (7) is exemplified.

^{{Wherein, R 1, R 2, R} 3, R 4, R 5, and ^{R 6, R 1, R 2, R} 3 in each of the formulas ^{(1), R 4, R} 5, and the ^{R 6} It is synonymous. }
The organosilicon polymer when B represents a silicon atom in another repeating unit represented by the formula (1) is a polymer having a branched structure or a crosslinked structure, and a part of the repeating unit. Is exemplified by a structure represented by the following formula (8).

^{{Wherein, R 1, R 2, R} 3, R 4, R 5, and ^{R 6, R 1, R 2, R} 3 in each of the formulas ^{(1), R 4, R} 5, and the ^{R 6} It is synonymous. }
These polymers include, in particular, an adamantane polyol compound of the formula (4) and a hydrosilane in which at least one of R ^{3 to} R ⁶ is a hydrogen atom among the hydrosilane compounds represented by the formula (5) or (6). When the compound is dehydrogenated, it can be obtained by blending the adamantane polyol compound at a ratio of 1 mol or more with respect to 1 mol of the hydrosilane compound.

  A in the formula (1) is an arylene group having 6 to 20 carbon atoms. Specific examples of the arylene group include the following.

  Each bar line bonded to an arylene group represents a bond. Among these groups, a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group are preferable, and a 1,4-phenylene group is particularly preferable from the viewpoint of the usefulness of the obtained organosilicon polymer. preferable.

  The organosilicon polymer when A in the formula (1) is a 1,4-phenylene group is represented by the following formula (3).

{Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ^{6 in} Formula (1), respectively. It is synonymous. }
Among the polymers composed of the repeating unit represented by the formula (3), an organosilicon polymer in which at least one of R ³ , R ⁴ , R ⁵ , and R ⁶ has a hydrogen atom can be used as it is. In addition, the organosilicon polymer can be further dehydrogenated and can be a polymer into which various hydrosilane compounds are introduced according to the purpose.

The organosilicon polymer of the present invention is formed by linking repeating units represented by the formula (1) (structures in parentheses), and the repeating unit contained in the organosilicon polymer consists of only one type of repeating unit. It may be a homopolymer (homopolymer) or a copolymer (copolymer) composed of a plurality of different types of repeating units. Here, different types of repeating units mean that the combinations of R ^{1 to} R ⁶ are different, each represented by the formula (1). In addition, when the organosilicon polymer of the present invention is a copolymer (copolymer), the plurality of types of repeating units are arranged in a block shape even if the random copolymer is a plurality of types of repeating units arranged at random. A block copolymer may be used. Furthermore, the organosilicon polymer of the present invention is not limited to a straight chain and may have a branched structure or a crosslinked structure. The organosilicon polymer having a branched structure or a cross-linked structure means that when at least one group of R ^{3 to} R ⁶ is a hydrogen atom, the R ^{3 to} R ⁶ portion may also be dehydrogenated, It is shown as a polymer having a repeating unit represented by the formula (7) or (8).

  In the present invention, specific examples of the repeating unit represented by the formula (1) or (3) include the following.

  The organosilicon polymer of the present invention is formed by connecting 2 to 1000 repeating units represented by the formula (1) (hereinafter, this repeating unit may be simply referred to as “n”). From the viewpoint of the usefulness of the obtained polymer, n is preferably 2 to 800, more preferably 3 to 600, still more preferably 3 to 100, and most preferably 3 to 70. In general, a repeating unit having about 2 to 20 linked units and a molecular weight of about several thousand is sometimes referred to as an oligomer. However, in the present invention, the oligomer is also treated as a polymer.

In the present invention, the repeating unit “n” is a value determined by the following method. That is, the adamantane polyol compound represented by the formula (4) described in detail below, the type and blending ratio of the hydrosilane compound represented by the formula (5) or (6), and ¹ H-NMR of the obtained organosilicon polymer From the spectrum and IR spectrum, first, the compound constituting the repeating unit is confirmed. Next, “n” is obtained by dividing the weight average molecular weight (Mw) of the organosilicon polymer determined by gel permeation chromatography (molecular weight standard sample: polystyrene) by the molecular weight of the compound constituting the repeating unit. In addition, since the terminal of an organosilicon polymer does not have big influence on molecular weight as shown below, in this invention, the molecule | numerator of a terminal shall be calculated | required and "n" shall be calculated | required.

  Further, the weight average molecular weight (Mw) of the organosilicon polymer of the present invention may be appropriately adjusted according to the type of adamantane polyol compound and hydrosilane compound used, the intended use, etc., and the above “n” is in the above range. Is not particularly limited as long as the range satisfies the above. The specific weight average molecular weight (Mw) is 500 to 1,000,000, preferably 500 to 500,000, more preferably 700 to 400,000, more preferably 750 to 70000, most preferably measured by gel permeation chromatography using polystyrene as a standard sample. Preferably it is 750-50000.

In the present invention, the terminal of the organosilicon polymer is usually a “—Si (R ³ ) (R ⁴ ) H” group and a “—OH” group. Various groups can be introduced into these terminal groups by utilizing the reactivity of the groups. For example, when the terminal of the organosilicon polymer is a “—Si (R ³ ) (R ⁴ ) H” group, a glycidyloxypropyl group, 3,4-epoxycyclohexylethyl is introduced. Group, vinyl group, trichlorosilylpropyl group, triethoxysilylpropyl group and the like. Moreover, when the terminal of the organosilicon polymer is an “—OH” group, an allyl group, a glycidyl group, an acryloyl group, a methacryloyl group, and the like can be given.

(Method for producing organosilicon polymer)
The organosilicon polymer of the present invention can be suitably produced by the method shown below. It can be obtained by polymerizing a polymerizable composition containing an adamantane polyol compound represented by the following formula (4), a hydrosilane compound represented by the following formula (5), and a dehydrogenation coupling catalyst. That is, an adamantane polyol compound represented by the following formula (4) and a hydrosilane compound represented by the following formula (5) can be suitably produced by dehydrogenation coupling in the presence of a dehydrogenation coupling catalyst. it can.

{Wherein, ^{R 1,} and ^{R 2} have the same meanings as ^{R 1,} and ^{R 2} in each of the formulas (1). }

^{{Wherein, R 3, R 4, R 5} , R 6, and A have the same meanings as ^{R 3, R 4, R 5} , R 6, and A in each of the formulas (1). }
Specific examples of the adamantane polyol compound represented by the formula (4) include 1,3-adamantanediol, 5-methyl-1,3-adamantanediol, 5-ethyl-1,3-adamantanediol, 5, 7-dimethyl-1,3-adamantanediol, 5,7-diethyl-1,3-adamantanediol, 5-fluoro-1,3-adamantanediol, 5-chloro-1,3-adamantanediol, 5,7- Difluoro-1,3-adamantanediol, 1,3,5-adamantanetriol, 7-methyl-1,3,5-adamantanetriol, 7-ethyl-1,3,5-adamantanetriol, 7-fluoro-1, Examples include 3,5-adamantanetriol, 1,3,5,7-adamantanetetraol, and the like. Among these, 1,3-adamantanediol, 5,7-dimethyl-1,3-adamantanediol, and 1,3,5-adamantanetriol are preferable from the viewpoint of the usefulness of the obtained organosilicon polymer. In addition, you may use these adamantane polyol compounds in mixture of 2 or more types.

In the hydrosilane compound represented by the formula (5), R ³ and R ⁵ are the same group in consideration of the productivity of the obtained organosilicon polymer and the availability of the hydrosilane compound of the formula (5). R ⁴ and R ⁶ are preferably the same group. Specific examples of the hydrosilane compound represented by the formula (5) include 1,4-disilylbenzene, 1,4-bis (phenylsilyl) benzene, 1,4-bis (methylsilyl) benzene, 1,4. -Bis (ethylsilyl) benzene, 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diethylsilyl) benzene, 1,4-bis (hexylsilyl) benzene, 1,4-bis (dihexylsilyl) benzene 1,4-bis (chlorosilyl) benzene, 1,4-bis (dichlorosilyl) benzene, 1,3-disilylbenzene, 1,3-bis (phenylsilyl) benzene, 1,3-bis (methylsilyl) benzene 1,3-bis (ethylsilyl) benzene, 1,3-bis (dimethylsilyl) benzene, 1,3-bis (diethylsilyl) benzene, , 3-bis (hexylsilyl) benzene, 1,3-bis (dihexylsilyl) benzene, 1,3-bis (chlorosilyl) benzene, 1,3-bis (dichlorosilyl) benzene, 1,2-disilylbenzene, 1,2-bis (phenylsilyl) benzene, 1,2-bis (methylsilyl) benzene, 1,2-bis (ethylsilyl) benzene, 1,2-bis (dimethylsilyl) benzene, 1,2-bis (diethylsilyl) ) Benzene, 1,2-bis (hexylsilyl) benzene, 1,2-bis (dihexylsilyl) benzene, 1,2-bis (chlorosilyl) benzene, 1,2-bis (dichlorosilyl) benzene, 1,4- Disilylnaphthalene, 1,4-bis (phenylsilyl) naphthalene, 1,4-bis (methylsilyl) naphthalene, 1,4-bis ( Tilsilyl) naphthalene, 1,4-bis (dimethylsilyl) naphthalene, 1,4-bis (diethylsilyl) naphthalene, 1,4-bis (hexylsilyl) naphthalene, 1,4-bis (dihexylsilyl) naphthalene, 1, Examples thereof include 4-bis (chlorosilyl) naphthalene and 1,4-bis (dichlorosilyl) naphthalene.

  Among these, it is preferable to use a hydrosilane compound represented by the following formula (6) from the viewpoint of the usefulness of the obtained organosilicon polymer.

^{{Wherein, R 3, R 4, R} 5, and ^{R 6, R} 3 in each of the formulas ^{(1), R 4, R} 5, and ^{R 6} as synonymous. }
Specific examples of the hydrosilane compound represented by the formula (6) include 1,4-disilylbenzene, 1,4-bis (phenylsilyl) benzene, 1,4-bis (methylsilyl) benzene, 1,4. -Bis (ethylsilyl) benzene, 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diethylsilyl) benzene, 1,4-bis (hexylsilyl) benzene, 1,4-bis (dihexylsilyl) benzene 1,4-bis (chlorosilyl) benzene and 1,4-bis (dichlorosilyl) benzene.

  Among these, those having two or more hydrogen atoms on the silicon atom are preferable because the resulting polymer can be further polymerized. Specifically, 1,4-disilylbenzene, 1,4-bis (phenylsilyl) benzene, 1,4-bis (methylsilyl) benzene, 1,4-bis (ethylsilyl) benzene, 1,4-bis (Hexylsilyl) benzene can be mentioned, and among these, 1,4-disilylbenzene and 1,4-bis (phenylsilyl) benzene can be particularly preferable.

  In the present invention, if the amount of the hydrosilane compound used is too small, the yield of the resulting organosilicon polymer is reduced, and if it is too large, the post-treatment process becomes complicated. It is preferable to use 1.5 mol, particularly 0.4 to 1.25 mol. In addition, when using what has a 3 or more hydroxyl group (adamantane triol and / or adamantane tetraol) as an adamantane polyol compound, in order to obtain the organosilicon polymer of this invention which does not have a crosslinked structure, the usage-amount of a hydrosilane compound Is preferably used in an amount of 0.2 to 1.5 mol, particularly 0.4 to 1.25 mol, per mol of the adamantane polyol compound. Conversely, when the adamantane polyol compound used includes an adamantane triol compound, 0.4 to 5.0 mol, particularly 0.8 to 3.0 mol, of the hydrosilane compound is used with respect to 1 mol of all adamantane polyols used. Thus, the organosilicon polymer of the present invention having a branched structure (for example, the polymer represented by the formula (7) or (8)) can be obtained. When the adamantane polyol compound used includes an adamantane tetraol compound, 0.8 to 7.0 mol, particularly 1.2 to 5.0 mol of hydrosilane compound is used with respect to 1 mol of all adamantane polyols used. Thus, the organosilicon polymer of the present invention having a crosslinked structure (for example, the polymer represented by the formula (8)) can be obtained.

  In the present invention, as the dehydrogenation coupling catalyst, a known compound used as a catalyst can be used without limitation when dehydrogenating an alcohol and hydrosilane, but from the good efficiency of siloxylation reaction, Rhodium-based catalysts, platinum-based catalysts, and palladium-based catalysts can be preferably used. Among these, it is preferable to use chlorotris (triphenylphosphine) rhodium (I), dichloropalladium (II), hexachloroplatinic (IV) acid hexahydrate or the like because of its availability. If the amount of the dehydrogenation coupling catalyst is too small, the dehydrogenation coupling reaction does not proceed sufficiently. If the amount is too large, the resulting organosilicon polymer is colored, so 1 mol of the adamantane polyol compound to be used. On the other hand, it is preferable to use 0.00025 to 0.50 mol, particularly 0.0005 mol to 0.20 mol, particularly 0.001 mol to 0.10 mol. Although described in detail below, the molecular weight of the resulting organosilicon polymer can also be controlled by adjusting the amount of the dehydrogenation coupling catalyst used within the above range.

  The dehydrogenative coupling of the adamantane polyol compound can be performed without a solvent or in the presence of a solvent. However, if the adamantane polyol compound and the hydrosilane compound do not form a homogeneous solution, the dehydrogenation coupling may be performed in the presence of an organic solvent. preferable. The organic solvent used at this time is preferably an organic solvent that does not inhibit the dehydrogenation coupling reaction. Specific examples include aromatic hydrocarbons such as benzene, toluene, xylene; diethyl ether, diisopropyl ether, di-n- Examples include ethers such as butyl ether, tetrahydrofuran, cyclopentyl methyl ether, and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and sulfoxides such as dimethyl sulfoxide. Among these, it is particularly preferable to use toluene, tetrahydrofuran, N, N-dimethylformamide, or N, N-dimethylacetamide from the viewpoint of good operability and good dissolution of raw materials. Although the usage-amount of an organic solvent is not restrict | limited in particular, It is preferable that it is 1 to 200 mass times with respect to the adamantane polyol compound used from the ease of operativity, and 2 to 100 mass times is obtained.

  In the present invention, the dehydrogenation coupling reaction is preferably performed by mixing each reaction reagent in an organic solvent as described above. The reaction temperature is not particularly limited, but a sufficient conversion can be usually obtained at 0 to 200 ° C, particularly preferably 50 to 180 ° C. The reaction time is not particularly limited, but a sufficient conversion can be usually obtained in 1 to 200 hours, particularly preferably 5 to 100 hours. The reaction temperature can be adjusted while arbitrarily adjusting the reaction rate, for example, by gradually increasing the temperature according to the properties of the adamantane polyol compound and the hydrosilane compound to be used.

  In the present invention, the molecular weight of the resulting organosilicon polymer can be controlled by the amount and type of organic solvent used, and also depends on the reaction temperature, the amount of dehydrogenation coupling catalyst used, and the reaction time. Can be controlled. An example is shown below.

  In the present invention, when an organosilicon polymer is prepared in an organic solvent, the organosilicon polymer of the present invention tends to have a lower solubility in an organic solvent as the molecular weight increases, as with a general organic polymer. When the amount of solvent used is small, a relatively low molecular weight organosilicon polymer is obtained, and when the amount of solvent used is large, a higher molecular weight organosilicon polymer is obtained. Also, depending on the type of organosilicon polymer, a relatively low molecular weight organosilicon polymer can be obtained by performing a dehydrogenation coupling reaction using an organic solvent having a low solubility of the desired organosilicon polymer. When a dehydrogenation coupling reaction is carried out using an organic solvent having a high solubility of the organosilicon polymer, a higher molecular weight organosilicon polymer is obtained. Therefore, when the organosilicon polymer is adjusted in an organic solvent, the molecular weight can be controlled to some extent depending on the amount and type of the organic solvent used, although it varies depending on the target organosilicon polymer.

  The higher the reaction temperature of the dehydrogenation coupling is within the above temperature range, the higher the molecular weight organosilicon polymer is obtained. Therefore, the molecular weight can be controlled to some extent by the difference in the reaction temperature. Furthermore, since the progress of the dehydrogenation coupling reaction is slow when the amount of the dehydrogenation coupling catalyst used is small, the molecular weight can be controlled to some extent by the amount of the dehydrogenation coupling catalyst used. In addition, if the reaction time is short, the dehydrogenation coupling reaction may not proceed sufficiently. Therefore, the molecular weight can be controlled to some extent due to the difference in the reaction time. That is, the molecular weight of the target organosilicon polymer can be controlled to some extent by the type and amount of the organic solvent used, the reaction temperature, the amount of dehydrogenation coupling catalyst, and the reaction time.

  In addition, the reaction can be stopped by adding a monohydrosilane compound such as trimethylsilane or a monoalkene compound such as allyl alcohol into the reaction system, and an organosilicon polymer having an arbitrary molecular weight can be obtained. It is.

In the present invention, when a functional group is introduced at the end of the organosilicon polymer obtained by the above method, when the end of the organosilicon polymer is a “—Si (R ³ ) (R ⁴ ) H” group, 3 -By hydrosilylation with unsaturated bond-containing compounds such as glycidyloxy-1-propene, 3,4-epoxycyclohexylethylene, acetylene, 3-trichlorosilyl-1-propene, and 3-triethoxysilyl-1-propene Functional groups can be introduced. Moreover, when the terminal of the organosilicon polymer is -OH group, leaving groups such as allyl chloride, allyl bromide, epichlorohydrin, acrylic acid chloride, acrylic acid anhydride, methacrylic acid chloride, methacrylic acid anhydride, etc. Each functional group can be introduced by reacting the contained compound under basic conditions. The difference in the terminal of the organosilicon polymer may be determined by the blending ratio of the adamantane polyol compound represented by the formula (3) and the hydroxysilane compound represented by the formula (4) or the formula (5). it can.

  The method for separating and purifying the organosilicon polymer of the present invention is not particularly limited and varies depending on the target organosilicon polymer. For example, when it is prepared in an organic solvent, the catalyst used is filtered and reprecipitated. It can be purified by this method. It is possible to obtain a plate-like resin by carrying out the reaction in an arbitrary mold without using an organic solvent, in which case there is no need for purification.

  Further, by using the obtained silicon-containing adamantane polymer as a raw material and dehydrogenative coupling with a new hydrosilane compound, it is also possible to obtain a polymer having a higher molecular weight.

(Use of organosilicon polymer)
When using the organosilicon polymer of the present invention, if necessary, a filler, a coupling agent, a flame retardant, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, and an antistatic agent. Various additives such as additives, dyes, pigments, and fragrances and stabilizers can be mixed and used.

  Since the organosilicon polymer of the present invention contains a silicon-oxygen bond and an adamantane skeleton in the main chain, it has excellent heat resistance and has a relatively soft silicon-oxygen bond that is not cross-linked. Have sex. For this reason, it also has the advantage that the operativity at the time of using the organosilicon polymer of this invention is good. Furthermore, since it has an aryl group in the molecular chain, it exhibits excellent heat resistance even with a low molecular weight product.

  In addition, it has a feature that it has an adamantane unit with high fat solubility and a relatively flexible silicon-oxygen bond, and is highly soluble in organic solvents. Furthermore, as described above, since even a low molecular weight product exhibits excellent heat resistance, there is an advantage that the solubility in an organic solvent is higher than that of conventional resins. Moreover, even when dissolved in air or an organic solvent, it can exist stably without causing gelation.

  The organosilicon polymer of the present invention can be suitably used for various plastic substrate raw materials, coating agent raw materials, adhesive raw materials, sealant raw materials and the like, taking advantage of the above characteristics.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1
A 30 ml two-necked flask equipped with a Dimroth condenser and a spin bar was purged with nitrogen, then 5 ml of N, N-dimethylformamide, 0.08 g (0.44 mmol) of 1,3-adamantanediol, 1,4-bis (phenylsilyl) 0.13 g (0.44 mmol) of benzene was added. After stirring at room temperature for a while, 3.6 mg (0.02 mmol) of dichloropalladium (II) was added, and the mixture was stirred at 100 ° C. for 24 hours. After completion of the reaction, ethanol and water were added to precipitate a solid. The precipitated solid was reprecipitated with tetrahydrofuran (THF) -hexane to obtain 0.051 g of a light gray polymer.

As a result of measuring proton nuclear magnetic resonance ( ¹ H-NMR) spectrum and infrared absorption (IR) spectrum of the obtained light gray solid, the structure of the target polymer mainly contains a repeating unit of the following formula (9). The structure was confirmed. The measurement results are shown below.

¹ H-NMR spectrum (in CDCl ₃ ): δ 1.25 to 1.53 (m, 28H, adamantane ring H), δ 7.50-7.74 (br m, 14H, phenyl group H)
IR spectrum (KBr method): 1067, 1127 cm ⁻¹ (Si—O stretching vibration)
The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight dispersion (Mw / Mn; weight average molecular weight divided by number average molecular weight) of the polymer obtained by gel permeation chromatography (GPC) are polystyrene. As a result of conversion, Mw was 15680, Mn was 5600, and Mw / Mn was 2.8. From this result, n in the formula (9) was determined, and n = 25. Further, under a nitrogen stream, the results of measurement of 5% thermogravimetric decrease temperature (Td ₅ ) and 10% thermogravimetric decrease temperature (Td ₁₀ ) by thermogravimetric analysis showed that Td ₅ was 327 ° C. and Td ₁₀ was 441 ° C. there were. Despite its low molecular weight, it showed a high thermogravimetric loss temperature.

  In GPC, Shodex KF806 (manufactured by Showa Denko KK) and KF804 (manufactured by Showa Denko KK) were connected in series as the column, and the temperature was 45 ° C., and tetrahydrofuran was used as the developing solvent. Detection was performed with ultraviolet light at 241 nm. Molecular weight analysis was performed using polystyrene standard samples. The following examples and comparative examples were similarly analyzed.

Example 2
In Example 1, by concentrating the ether layer remaining after separating the precipitated polymer, a low molecular weight polymer was precipitated, and this was reprecipitated with THF-hexane to obtain a solid containing the low molecular weight polymer. 0.036 g was obtained.

As a result of measuring ¹ H-NMR spectrum and IR spectrum of the obtained polymer, a spectrum almost the same as that of Example 1 was obtained, and it was confirmed that the structure of the target polymer was the above formula (9).

As a result of calculating Mw, Mn, and Mw / Mn of the obtained polymer by polystyrene conversion by GPC, Mw was 11840, Mn was 3200, and Mw / Mn was 3.7. From this result, n in the formula (9) was determined, and n = 19. In a nitrogen stream, as a result of thermogravimetric analysis measurement, Td ₅ is 236 ° C., _{Td 10} was 441 ° C.. Despite its low molecular weight, it showed a high thermogravimetric loss temperature.

Example 3
A 30 ml two-necked flask equipped with a Dimroth condenser and a spin bar was purged with nitrogen, and then 15 ml of toluene, 0.13 g (0.8 mmol) of 1,3-adamantanediol, 0.23 g of 1,4-bis (phenylsilyl) benzene ( 0.8 mmol) was added. After stirring at room temperature for a while, 5.3 mg (0.03 mmol) of dichloropalladium (II) was added, and the mixture was stirred at 100 ° C. for 72 hours. After completion of the reaction, ethanol and water were added to precipitate a solid. The precipitated solid was reprecipitated with THF-hexane to obtain 0.05 g of a light gray polymer.

As a result of measuring ¹ H-NMR spectrum and IR spectrum of the obtained light gray solid, it was confirmed that the structure of the target polymer was a structure mainly containing a repeating unit of the following formula (10). The measurement results are shown below.

¹ H-NMR spectrum (in CDCl ₃ ): δ 1.38-2.24 (m, 12H, adamantane ring H), δ 5.25-5.52 (br s, 2H, SiH), δ 7.30-7 .54 (br m, 14H, phenyl group H)
IR spectrum (KBr method): 1150, 1130 cm ⁻¹ (Si—O stretching vibration)
As a result of calculating Mw, Mn, and Mw / Mn of the obtained polymer by polystyrene conversion by GPC, Mw was 21460, Mn was 5800, and Mw / Mn was 3.7. From this result, n in the formula (10) was obtained, and n = 47. As a result of thermogravimetric analysis measurement under a nitrogen stream, Td ₅ was 434 ° C. and Td ₁₀ was 515 ° C. Despite its low molecular weight, it showed a high thermogravimetric loss temperature.

Example 4
In Example 3, by concentrating the ether layer remaining after separating the precipitated polymer, a low molecular weight polymer was precipitated, and this was reprecipitated with THF-hexane to obtain a solid 0 consisting of a low molecular weight polymer. 0.068 g was obtained.

As a result of measuring ¹ H-NMR spectrum and IR spectrum of the obtained white solid, a spectrum almost the same as that of Example 3 was obtained, and the structure of the target polymer was a structure having the skeleton of the formula (10). It was confirmed.

As a result of calculating Mw, Mn, and Mw / Mn of the obtained polymer by polystyrene conversion by GPC, Mw was 4290, Mn was 3300, and Mw / Mn was 1.3. From this result, n in the formula (10) was determined, and n = 9. In a nitrogen stream, as a result of thermogravimetric analysis measurement, Td ₅ is 320 ° C., _{Td 10} was 361 ° C.. Despite its low molecular weight, it showed a high thermogravimetric loss temperature.

Example 5
A 30 ml two-necked flask equipped with a Dimroth condenser and a spin bar was purged with nitrogen, and then N, N-dimethylformamide 15 ml, 1,3-adamantanediol 0.054 g (3.0 mmol), 1,4-bis (phenylsilyl) 0.42 g (3.0 mmol) of benzene was added. After stirring for a while at room temperature, 21.9 mg (0.12 mmol) of dichloropalladium (II) was added, followed by stirring at 140 ° C. for 48 hours. After completion of the reaction, the solid formed in the container was washed with hexane and filtered to obtain 0.58 g of a light gray solid.

As a result of measuring ¹ H-NMR spectrum and IR spectrum of the obtained light gray solid, it was confirmed that the structure of the target polymer was a structure mainly containing a repeating unit of the following formula (11). The measurement results are shown below.

¹ H-NMR spectrum (in CDCl ₃ ): δ 1.64-2.34 (br m, 42 H, adamantane ring H), δ 7.23-7.83 (br m, 4 H, phenyl group H)
IR spectrum (KBr method): 1065, 1130 cm ⁻¹ (Si—O stretching vibration)
As a result of calculating Mw, Mn, and Mw / Mn of the obtained polymer by polystyrene conversion by GPC, Mw was 3720, Mn was 3100, and Mw / Mn was 1.2. From this result, n in the formula (11) was obtained, and n = 6. Further, as a result of thermogravimetric analysis measurement under a nitrogen stream, Td ₅ was 279 ° C. and Td ₁₀ was 387 ° C. Despite its low molecular weight, it showed a high thermogravimetric loss temperature.

Comparative Example 1
A 30 ml two-necked flask equipped with a Dimroth condenser and a spin bar was purged with nitrogen, and then 15 ml of toluene, 0.532 g (4.59 mmol) of 1,4-cyclohexanediol and 0.410 g (3.79 mmol) of phenylsilane were added. After stirring at room temperature for a while, 20.1 mg (0.113 mmol) of dichloropalladium (II) was added, and the mixture was stirred at 140 ° C. for 24 hours. After completion of the reaction, the catalyst was filtered, dried under reduced pressure, and then hydrolyzed to obtain 0.598 g of the target polymer as a white solid.

As a result of measuring ¹ H-NMR spectrum and IR spectrum of the obtained white solid, it was confirmed that the structure of the target polymer was the structure of the following formula (12). The measurement results are shown below.

¹ H-NMR spectrum (in CDCl ₃ ): δ 1.6-2.2, 3.8-4.2 (m, 10H, H of cyclohexane ring), δ 6.8-7.8 (m, 5H, phenyl Group H)
IR spectrum (NaCl method): 1049, 1134 cm ⁻¹ (Si—O stretching vibration), 3387 cm ⁻¹ (O—H stretching vibration)
In order to carry out the GPC measurement of the target product, when dissolved in tetrahydrofuran, a white insoluble matter was precipitated, and the molecular weight could not be measured. Probably, it is thought that it gelled in tetrahydrofuran, and it seems that it became the ultra high molecular weight substance.

In addition, as a result of thermogravimetric analysis measurement under a nitrogen stream, Td ₅ was 297 ° C. and Td ₁₀ was 380 ° C.

Comparative Example 2
A 30 ml two-necked flask equipped with a Dimroth condenser and a spin bar was purged with nitrogen, and then 15 ml of toluene, 0.368 g (4.84 mmol) of 1,2-propanediol and 0.523 g (4.83 mmol) of phenylsilane were added. After stirring at room temperature for a while, 25.7 mg (0.145 mmol) of dichloropalladium (II) was added, and the mixture was stirred at 140 ° C. for 24 hours. After completion of the reaction, the catalyst was filtered, dried under reduced pressure, and then hydrolyzed to obtain 0.671 g of the target polymer as a white solid.

As a result of measuring ¹ H-NMR spectrum and IR spectrum of the obtained white solid, it was confirmed that the structure of the target polymer was the structure of the following formula (13). The measurement results are shown below.

¹ H-NMR spectrum (in CDCl ₃ ): δ 1.18 (d, 3H, —CH ₃ , J = 3.1 Hz), δ 3.3-3.8 (m, 2H, —CH ₂ —), δ ₃ . 8-4.0 (m, 1H, CH), δ 6.8-7.8 (m, 5H, H of phenyl group)
IR spectrum (NaCl method): 1041 cm ⁻¹ (Si—O stretching vibration), 3341 cm ⁻¹ (O—H stretching vibration)
In order to carry out the GPC measurement of the target product, when dissolved in tetrahydrofuran, a white insoluble matter was precipitated, and the molecular weight could not be measured. Probably, it is thought that it gelled in tetrahydrofuran, and it seems that it became the ultra high molecular weight substance.

In addition, as a result of thermogravimetric analysis measurement under a nitrogen stream, Td ₅ was 265 ° C. and Td ₁₀ was 321 ° C.

Reference Example 1 (organosilicon polymer of Non-Patent Document 3)
A 30 ml two-necked flask equipped with a Dimroth condenser and a spin bar was purged with nitrogen, and then N, N-dimethylformamide 15 ml, 1,3-adamantanediol 0.577 g (3.43 mmol), phenylsilane 0.377 g (3.48 mmol) ) Was added. After stirring at room temperature for a while, 22.8 mg (0.129 mmol, 3.8 mol% of 1,3-adamantanediol as a raw material) of dichloropalladium (II) was added, followed by stirring at 140 ° C. for 24 hours. After completion of the reaction, ether and water were added to precipitate a solid. By reprecipitating this solid with THF-hexane, 0.160 g of a high molecular weight polymer was obtained as a white solid.

As a result of measuring proton nuclear magnetic resonance ( ¹ H-NMR) spectrum and infrared absorption (IR) spectrum of the obtained white solid, it was confirmed that the structure of the target polymer was the structure of the following formula (14). It was. The measurement results are shown below.

¹ H-NMR spectrum (in CDCl ₃ ): δ 0.49 (s, 1H, H of Si—OH), δ 0.75-2.46 (m, 14H, H of adamantane ring), δ 7.29-7. 61 (m, 5H, phenyl group H)
IR spectrum (NaBr method): 1060, 1140 cm ⁻¹ (Si—O stretching vibration), 3414 cm ⁻¹ (O—H stretching vibration)
As a result of calculating Mw, Mn, and Mw / Mn of the obtained polymer by polystyrene conversion by GPC, Mw was 39500, Mn was 10140, and Mw / Mn was 3.6. From this result, n in the formula (4) was obtained, and n = 137. In addition, as a result of measurement of 5% thermogravimetric decrease temperature (Td ₅ ) and 10% thermogravimetric decrease temperature (Td ₁₀ ) by thermogravimetric analysis under a nitrogen stream, Td ₅ was 410 ° C. and Td ₁₀ was 506 ° C. there were.

  As described above, the organosilicon polymer of the present invention shown in the examples has a number average molecular weight of 1/30 to 1/1 compared with, for example, poly (dimethylsiloxane) described in Non-Patent Document 1. Despite being about 17, the 10% thermal weight loss temperature under a nitrogen atmosphere exceeds 350 ° C., indicating that the polymer is excellent in heat resistance while being a low molecular weight product. Furthermore, when compared with the organosilicon polymer of Reference Example 1, the organosilicon polymer of the present invention (Example 3), which has a relatively similar structure, has about 1/3 repeating unit “n” (Reference Example 1 n = 137, Example 3 Although n = 47), almost the same heat resistance results are shown, indicating that the polymer is excellent in heat resistance.

Claims (4)

An organosilicon polymer having a structure in which one or two or more repeating units represented by the following formula (1) are linked by 2 to 1,000.

[In formula, R < ¹ > and R < ² > may be the same or different, respectively, a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, a C1-C5 alkoxy group, a phenyl group, a fluorine atom, Or R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different, and each is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Group, an aryl group having 6 to 15 carbon atoms, a thienyl group, a furyl group, a chlorine atom, or the following formula (2),

{In formula, R < ¹ > and R < ² > are respectively synonymous with the said Formula (1), B shows the silicon atom in the other repeating unit shown by the hydrogen atom or the said Formula (1). }
And A is an arylene group having 6 to 20 carbon atoms. ] The organosilicon polymer according to claim 1, wherein the organosilicon polymer has a structure in which 2 to 1000 repeating units represented by the following formula (3) are connected.

^{{Wherein, R 1, R 2, R} 3, R 4, R 5, and ^{R 6, R 1, R 2, R} 3 in each of the formulas ^{(1), R 4, R} 5, and the ^{R 6} It is synonymous. } One or more adamantane polyol compounds represented by the following formula (4) and one or more hydrosilane compounds represented by the following formula (5) are dehydrated in the presence of a dehydrogenation coupling catalyst. 3. The process for producing an organosilicon polymer according to claim 1 or 2, wherein the element is subjected to elementary coupling.

{Wherein, ^{R 1,} and ^{R 2} have the same meanings as ^{R 1,} and ^{R 2} in each of the formulas (1). }

^{{Wherein, R 3, R 4, R 5} , R 6, and A have the same meanings as ^{R 3, R 4, R 5} , R 6, and A in each of the formulas (1). } The method for producing an organosilicon polymer according to claim 3, wherein a hydrosilane compound represented by the following formula (6) is used as the hydrosilane compound.

^{{Wherein, R 3, R 4, R} 5, and ^{R 6, R} 3 in each of the formulas ^{(1), R 4, R} 5, and ^{R 6} as synonymous. }