JP2007031321A - Method for producing imide bonded with organosiloxane, triorganosilyl ester of amic acid bonded with organosiloxane, and method for manufacturing the same - Google Patents

Abstract

（Ａ¹はＣ１〜２０の二価有機基、Ａ²はＣ２〜４０の二価有機基。Ｓｘはケイ素数２〜２，０００のオルガノシロキサニル基を表す。αは該オルガノシロキサニル基の価数を表し、１〜１００の整数。）
【選択図】 なしAn object of the present invention is to provide a method for producing an imide bonded with an organosiloxane with high purity and high yield.
A triorganosilylamino group-containing organosiloxane and a dicarboxylic acid anhydride are reacted to obtain an amic acid triorganosilyl ester, which is then subjected to ring-closing imidization by detriorganosilanol reaction. 5) A process for producing an imide bonded with an organosiloxane.

(A ¹ is a C 1-20 divalent organic group, A ² is a C 2-40 divalent organic group, Sx is an organosiloxanyl group having ² to 2,000 silicon atoms, and α is the organosiloxanyl group. Represents the valence of the group and is an integer from 1 to 100.)
[Selection figure] None

Description

  INDUSTRIAL APPLICABILITY The present invention can be used for thermoplastic compositions for electronic materials, organic-inorganic hybrid materials, siloxane-modified resins, and the like, and a method for producing imides bonded with organosiloxanes, which are industrially useful compounds, and precursors The present invention relates to a triorganosilyl ester of amic acid bonded with an organosiloxane and a method for producing the same.

  Imides are thermally and chemically stable compounds and have a variety of applications in the field of materials science. Since aromatic imides are electron deficient, intramolecular charge transfer is observed in molecules combined with electron-rich compounds, and this property is used as a dye for organic EL (Non-patent Document 1: Chemistry of). Materials, 2003, 15: 1913-1917). In addition, photoexcitation of a molecule in which an aromatic imide having a relatively large conjugated system is linked to another dye causes efficient electron transfer and energy transfer in the molecule and in the associated body. (For example, Non-Patent Document 2: Journal of the American Chemical Society, 2004, 126, 10810-10811).

  In recent years, hybrid materials that combine the advantages of both organic and inorganic materials have been actively developed. Hybridization is achieved by combining various organic groups and organic polymers with siloxane, which is an inorganic skeleton. There are many examples. For example, JP-A-5-3218 (Patent Document 1) discloses a thermosetting composition obtained by using a linear siloxane having both ends sealed with maleimide and used as a semiconductor sealing material. It has been. In addition, it has been reported that when a nanocomposite of cage oligosiloxane and imide is prepared, high heat resistance is exhibited (Non-patent Document 3: Chemistry of Materials, 2003, Volume 15, pages 793-797). From such a viewpoint, there is a demand for a technique for freely bonding an imide to organosiloxanes having various structures.

  The simplest and classic method for synthesizing imides is to mix ammonia and primary amines with dicarboxylic acid anhydrides and react them. First, acid anhydrides are opened to form amic acid, and then heated. Causes dehydration cyclization and yields an imide in good yield (Scheme [A] below). In this method, only 1 mol of water is a by-product when 1 mol of imide is formed, and water generated simultaneously with imidation is removed by heating. Patent Document 1 and Non-Patent Document 3 also describe that an imide bonded with an organosiloxane is obtained by this method.

  However, in this method, for example, when an imide bonded with an organosiloxane is synthesized using an aliphatic amine bonded with a cyclic dimethylsiloxane as a reaction substrate, as shown in the following scheme [B], in the process of imidization reaction, It was found that disproportionation due to thermal breakage of the siloxane chain occurred, and by-products in which the siloxane portion was disproportionated were mixed in the imide formed. That is, with this imidization method, it is difficult to obtain an imide bonded with organosiloxane as a high-purity compound.

  Furthermore, some organosiloxanes having an aliphatic amino group gradually cause a disproportionation reaction even at room temperature, which may be inappropriate for use as an industrial raw material. Therefore, the above synthesis method is not optimal as a method for obtaining an imide having an organosiloxane bonded thereto.

  An imide bonded with an alkoxysilane, which is a silicon compound like siloxane, can be used as a silane coupling agent, and several methods for synthesizing it have been reported. The method of the above scheme [A] is described in US Pat. No. 3,755,354 (Patent Document 2), and JP-A-1-29385 (Patent Document 3) includes (1) aliphatic unsaturated bond. In US Pat. No. 4,271,744 (Patent Document 4), there is disclosed (2) a method in which an alkali metal salt of imide and a haloalkylalkoxysilane are reacted and condensed. Yes. In addition, US Pat. No. 6,191,286 (Patent Document 5) includes (3) a method of reacting a dicarboxylic acid anhydride and an alkoxysilane having an isocyanate group, and (4) heating bisamidosilane to imidosilane and aminosilane. A method of disproportionation and (5) a method of esterifying an amic acid obtained by reacting an amino group-containing silane and a dicarboxylic acid anhydride and imidizing it by heating are described. However, when these are applied to the synthesis of organosiloxane-bonded imides, it is difficult to remove the platinum compound used as a catalyst from the target compound in (1), and (2) uses a strongly basic reaction substrate. Siloxane disproportionation occurs. In (3), an organosiloxane having an isocyanate group must be prepared in advance, which increases the number of steps and reduces the overall yield. In (4), only one molecule of imide can be obtained from two molecules of amino group-containing organosiloxane, which is inferior in economic efficiency. In (5), a higher temperature is required for imidization than in the case where the amic acid is not esterified, and side reactions such as disproportionation of siloxane are promoted. Therefore, neither is a preferred method.

  A method for producing an imide bonded with an organosiloxane by hydrolyzing and condensing an imide bonded with an alkoxysilane obtained by the above known method is also conceivable. However, in this method, a mixture of various siloxanes is obtained, and it is difficult to obtain a desired siloxane having a defined structure and chain length.

  Patent Document 5 further describes (6) a method in which an amic acid obtained by reacting an amino group-containing silane and a dicarboxylic acid anhydride is silylated, and an amic acid silyl ester is heated to imidize. . In polyimide synthesis, it has been shown that the imidization reaction of polyamic acid trimethylsilyl ester can be performed at the same temperature as that of polyamic acid (Non-patent Document 4: Macromolecules, 1991, Vol. 24, 3475-3480), and organosiloxane is bonded. It may be an effective method for the synthesis of imides.

  Therefore, as shown in the following scheme [C], an imide synthesis reaction was performed using a cyclic dimethylsiloxane having a trimethylsilylated aliphatic amino group as a raw material. The intermediate amidic acid trimethylsilyl ester was obtained in quantitative yield, but in the subsequent imidation reaction, in addition to disproportionation of the cyclic siloxane, the formation of linear siloxane by ring opening was observed, and the trimethylsilylated product was observed. The disappointing result was obtained that the imide purity obtained was lower than when no raw material was used.

  As described above, various methods for synthesizing imides have been studied. However, they are not necessarily effective for synthesizing imides bonded with organosiloxanes that easily cause disproportionation reactions, and development of new imidization methods has been demanded.

JP-A-5-3218 US Pat. No. 3,755,354 JP-A-1-29385 US Pat. No. 4,271,741 US Pat. No. 6,191,286 Chemistry of Materials, 2003 Volume 15 pages 1913-1917. Journal of the American Chemical Society, 2004, 126, 10810-1081 Chemistry of Materials, 2003 Volume 15 pages 793-797. Macromolecules, 1991, 24, 3475-3480.

  The present invention has been made to meet the above-mentioned demand, and manufactures an imide bonded with an organosiloxane, which is an industrially useful compound, with high purity and high yield by suppressing the disproportionation reaction of the organosiloxane moiety. It is an object of the present invention to provide a method, a precursor thereof, and a production method.

  As a result of intensive studies to solve the above problems, the present inventors have made a novel method for producing an imide bonded with an organosiloxane, and a triorganosilyl ester of an amic acid bonded with an organosiloxane as a precursor and the production thereof. It came to know the method.

  That is, the present invention relates to a triorganosilylamino group-containing organosiloxane represented by the following general formula (2) in which a triorganosilyl group represented by the following general formula (1) is bonded to a nitrogen atom, and the following general formula: By reacting with the dicarboxylic acid anhydride represented by (3), the amidic acid triorganosilyl ester represented by the following general formula (4) is obtained, and then the deamidotrianol reaction is used to remove the amic acid triorganosilyl ester. Provided is a method for producing an imide bonded with an organosiloxane represented by the following general formula (5), characterized by ring-closing imidation of an organosilyl ester.

In the above formulas (1) to (5), R ¹ is a monovalent hydrocarbon group having 2 to 20 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, and A ¹ is A substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, and A ² represents a substituted or unsubstituted divalent organic group having 2 to 40 carbon atoms. Sx represents a monovalent or polyvalent organosiloxanyl group having a silicon number of 2 to 2,000. α represents the valence of the organosiloxanyl group and is an integer of 1 to 100.

  In the above general formulas (2), (4), and (5), the present invention is selected from a monovalent or polyvalent organosiloxanyl group in which Sx is a chain, cyclic, cage, or partially cleaved cage. A method for producing an imide bonded with the organosiloxane is provided.

  In the general formulas (2), (4), and (5), the present invention is a monovalent or polyvalent cyclic organosiloxanyl group represented by the following general formula (6): 7) and a monovalent or polyvalent chain organosiloxanyl group represented by (9), a monovalent or polyvalent cage organosiloxanyl group represented by the following general formula (11), and Provided is a method for producing an imide bonded with the above organosiloxane, which is selected from partially cleaved monovalent or polyvalent cage-like organosiloxanyl groups represented by the general formula (12).

（式（６）において、Ｒは互いに同一でも異なってもよく、フッ素原子で置換されていてもよい炭素数１〜２０の一価炭化水素基を表し、ａはオルガノシロキサニル基の価数を表し、１〜１０の整数、ｂは０〜１０の整数を表す。）

(In Formula (6), R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a fluorine atom, and a represents the valence of an organosiloxanyl group. Represents an integer of 1 to 10, and b represents an integer of 0 to 10.)

（式（７）において、Ｒは互いに同一でも異なってもよく、フッ素原子で置換されていてもよい炭素数１〜２０の一価炭化水素基を表し、Ｒ^xは炭素数１〜２０の置換又は非置換の一価炭化水素基あるいは下記一般式（８）で表されるトリオルガノシリルアミノ基で置換された有機基を表す。ｃは０〜１００の整数を表す。）

(In Formula (7), R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a fluorine atom, and R ^x is a substituted group having 1 to 20 carbon atoms. Or an unsubstituted monovalent hydrocarbon group or an organic group substituted with a triorganosilylamino group represented by the following general formula (8), c represents an integer of 0 to 100.)

（式（８）において、Ｒ¹、Ｒ²及びＡ¹は上記一般式（１）及び（２）で説明したものと同義の置換基を表す。）

(In the formula (8), R ¹ , R ² and A ¹ represent the same substituents as those described in the general formulas (1) and (2).)

（式（９）において、Ｒは互いに同一でも異なってもよく、フッ素原子で置換されていてもよい炭素数１〜２０の一価炭化水素基を表し、Ｒ^xは同一でも異なってもよく、炭素数１〜２０の置換又は非置換の一価炭化水素基あるいは上記一般式（８）で表されるトリオルガノシリルアミノ基で置換された有機基を表す。Ｒ^Sは炭素数１〜２０の一価炭化水素基あるいは下記一般式（１０）で表されるトリオルガノシロキシ基を表す。ｄはオルガノシロキサニル基の価数を表し、１〜１００の整数を、ｅは０〜１００の整数を表す。）

(In Formula (9), R may be the same or different from each other, represents a monovalent hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a fluorine atom, and R ^x may be the same or different; The substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or the organic group substituted with the triorganosilylamino group represented by the general formula (8) represents R ^S represents 1 to 20 carbon atoms. Represents a monovalent hydrocarbon group or a triorganosiloxy group represented by the following general formula (10), d represents the valence of the organosiloxanyl group, an integer of 1 to 100, and e is an integer of 0 to 100 Represents.)

（式（１１）において、Ｒは上記一般式（９）で定義したものと同義の置換基を表す。）

(In the formula (11), R represents a substituent having the same meaning as defined in the general formula (9).)

（式（１１）において、Ｒは互いに同一でも異なってもよく、フッ素原子で置換されていてもよい炭素数１〜２０の一価炭化水素基を表し、Ｒ^Sは炭素数１〜２０の一価炭化水素基あるいは上記一般式（１０）で表されるトリオルガノシロキシ基を表す。ｆ及びｈは０〜１０の整数、ｇはオルガノシロキサニル基の価数を表し、１〜２０の整数、ｉは０〜１９の整数を表す。但し、ｇとｉの和は６以上２０以下である。）

(In Formula (11), R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and R ^S represents one having 1 to 20 carbon atoms. Represents a valent hydrocarbon group or a triorganosiloxy group represented by the general formula (10), wherein f and h are integers of 0 to 10, g is an valence of an organosiloxanyl group, and is an integer of 1 to 20 I represents an integer of 0 to 19. However, the sum of g and i is 6 or more and 20 or less.)

（式（１２）において、Ｒは互いに同一でも異なってもよく、フッ素原子で置換されていてもよい炭素数１〜２０の一価炭化水素基を表す。Ｒ^S及びＲ^tはそれぞれ独立に炭素数１〜２０の一価炭化水素基あるいは上記一般式（１０）で表されるトリオルガノシロキシ基を表す。ｊ、ｌ及びｎは０〜１０の整数、ｋはオルガノシロキサニル基の価数を表し、１〜３の整数、ｍは０〜２の整数、ｏは２〜１６の整数を表す。但し、ｋとｍの和は３であり、ｍが２のとき、Ｒ^tは互いに結合して下記式（１３）

（式中、Ｒは互いに同一でも異なってもよく、フッ素原子で置換されていてもよい炭素数１〜２０の一価炭化水素基を表す。）
で表される基を形成してもよい。）

(In Formula (12), R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a fluorine atom. R ^S and R ^t are each independently carbon. Represents a monovalent hydrocarbon group of formula 1 to 20 or a triorganosiloxy group represented by the general formula (10), wherein j, l and n are integers of 0 to 10, and k is a valence of an organosiloxanyl group. , M is an integer from 0 to 2, and o is an integer from 2 to 16. However, the sum of k and m is 3, and when m is 2, R ^t are bonded to each other. The following formula (13)

(In the formula, R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom.)
You may form group represented by these. )

  In the present invention, the triorganosilyl group represented by the general formula (1) is a triethylsilyl group, a tert-butyldimethylsilyl group, a triisobutylsilyl group, a triisopropylsilyl group, or a texyldimethylsilyl group. A method for producing an imide bonded with the organosiloxane, selected from:

The present invention also provides a method for producing an imide bonded with the organosiloxane, wherein A ¹ in the general formula (2) is bonded with a nitrogen atom and sp ³ carbon.

  Furthermore, the present invention provides an amic acid triorganosilyl ester to which the organosiloxane represented by the general formula (4) is bonded.

  The present invention also includes a triorganosilylamino group-containing organosiloxane represented by the above general formula (2), wherein the triorganosilyl group represented by the above general formula (1) is bonded to a nitrogen atom, and the above general formula. There is provided a method for producing an amic acid triorganosilyl ester bonded with an organosiloxane represented by the above general formula (4), which comprises reacting with a dicarboxylic acid anhydride represented by (3).

  Furthermore, the present invention provides an organosiloxane represented by the above general formula (5), characterized in that the triorganosilyl ester of amic acid represented by the above general formula (4) is ring-closing imidized by a detriorganosilanol reaction. A method for producing an imide bonded with is provided.

  According to the present invention, an imide bonded with an organosiloxane can be produced with high purity and high yield. In the manufacturing method of this invention, since a chemically stable compound is used as a raw material, it is industrially preferable. Moreover, the disproportionation reaction of the organosiloxane portion can be suppressed by using a relatively bulky amic acid triorganosilyl ester as an intermediate.

  In the method for producing an imide bonded with an organosiloxane of the present invention, the starting material is the following general formula (2) in which one triorganosilyl group represented by the following general formula (1) is bonded to a nitrogen atom. ) -Containing triorganosilylamino group-containing organosiloxane. The triorganosilylamino group-containing organosiloxane represented by the following general formula (2) is a stable compound and can be stored for a long period of time without lowering the purity due to disproportionation of the siloxane.

In the general formula (1), R ¹ is a monovalent hydrocarbon group such as an alkyl group having 2 to 20 carbon atoms, an alkenyl group, an aryl group, or an aralkyl group, and R ² may be the same or different. Represents a monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. Specific examples of R ¹ include ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, cyclobutyl, pentyl, cyclopentyl, isopentyl. Group, tert-pentyl group, methylcyclopentyl group, hexyl group, cyclohexyl group, texyl group, methylcyclohexyl group, heptyl group, cycloheptyl group, norbornyl group, 2-ethylhexyl group, octyl group, isooctyl group, decyl group, dodecyl group A linear, branched or cyclic monovalent saturated hydrocarbon group such as tetradecyl group, hexadecyl group, octadecyl group, icosyl group, vinyl group, allyl group, propenyl group, 3-butenyl group, 2-butenyl group, Hexenyl group, cyclopentenyl group, cyclohexenyl group, -Monoborn unsaturated aliphatic hydrocarbon group such as norbornenyl group, octenyl group, decenyl group, ethynyl group, propynyl group, butynyl group, phenyl group, 4-tert-butylphenyl group, 2-tolyl group, 3-tolyl group 4-tolyl group, 2,6-dimethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,4, Monovalent aromatic hydrocarbon groups such as 6-trimethylphenyl group, naphthyl group, biphenylyl group, phenanthryl group, anthracenyl group, benzyl group, 1-phenylethyl group, 2-phenylethyl group, naphthylethyl group, etc. Is mentioned. Specific examples of R ² include a methyl group in addition to the specific examples of R ¹ .

  The triorganosilyl group represented by the general formula (1) is higher than the trimethylsilyl group, and specific examples thereof include ethyldimethylsilyl group, vinyldimethylsilyl group, ethynyldimethylsilyl group, diethylmethylsilyl group, n- Propyldimethylsilyl group, isopropyldimethylsilyl group, cyclopropyldimethylsilyl group, allyldimethylsilyl group, n-butyldimethylsilyl group, isobutyldimethylsilyl group, tert-butyldimethylsilyl group, cyclobutyldimethylsilyl group, 2-butyldimethyl Silyl group, triethylsilyl group, trivinylsilyl group, n-pentyldimethylsilyl group, cyclopentyldimethylsilyl group, methyldiisopropylsilyl group, isopropyldiethylsilyl group, n-hexyldimethylsilyl group, cyclohexyl Rudimethylsilyl group, cyclohexenyldimethylsilyl group, texyldimethylsilyl group, 1-methylcyclopentyldimethylsilyl group, phenyldimethylsilyl group, n-butyldiethylsilyl group, n-heptyldimethylsilyl group, cycloheptyldimethylsilyl group, 2-norbornyldimethylsilyl group, 5-norbornen-2-yldimethylsilyl group, 2-tolyldimethylsilyl group, 3-tolyldimethylsilyl group, 4-tolyldimethylsilyl group, benzyldimethylsilyl group, triisopropylsilyl group N-octyldimethylsilyl group, n-hexyldiethylsilyl group, decyldimethylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, dodecyldimethylsilyl group, tetradecyldimethylsilyl group, hexadecyldimethylsilyl group Group, octadecyl dimethyl silyl group, icosyl dimethyl silyl group. From the viewpoint of easy removal of triorganosilanol generated in the imidization reaction, the total number of carbon atoms of the substituents on the silicon atom is preferably 20 or less, more preferably 12 or less, and in particular, a triethylsilyl group, A tert-butyldimethylsilyl group, a triisobutylsilyl group, a triisopropylsilyl group, and a texyldimethylsilyl group are preferred.

In the above general formula (2), A ¹ represents a divalent organic group such as a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, an alkenylene group, an arylene group, or a group to which these are bonded. Include methylene, ethane-1,2-diyl, ethene-1,2-diyl, propane-1,3-diyl, propene-1,3-diyl, 2-methylpropane-1,3- Diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,2-cyclohexylene group 1,3-cyclohexylene group, 1,4-cyclohexylene group, 1,7-heptanediyl group, norbornane-2,5-diyl group, 1,8-octanediyl group, 1,10-decanediyl group, 1,12-dodecanediyl group, , 14-tetra-decane-diyl group, 1,16-hexadecane-diyl group, 1,18-octadecane-diyl group, 1,20- Ikosanjiiru group and the like.

  In the general formula (2), Sx represents a monovalent or polyvalent organosiloxanyl group having a silicon number of 2 to 2,000, preferably 2 to 200, more preferably 2 to 20. Sx is preferably a chain-like, cyclic, caged, or partially cleaved caged monovalent or polyvalent organosiloxanyl group. α represents the valence of the organosiloxanyl group, and is an integer of 1 to 100, particularly preferably 1 to 20.

  More preferably, Sx is a monovalent or polyvalent cyclic organosiloxanyl group represented by the following general formula (6), or a monovalent or polyvalent chain represented by the following general formulas (7) and (9). -Like organosiloxanyl group, monovalent or polyvalent cage-like organosiloxanyl group represented by the following general formula (11), and partially cleaved monovalent or polyvalent represented by the following general formula (12) Selected from among cage-like organosiloxanyl groups.

In the general formula (6), R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a fluorine atom, and a represents the valence of the organosiloxanyl group. In this case, since there are a bonds in Formula (6), α = a and an integer of 1 to 10. Moreover, b represents the integer of 0-10. Examples of the substituent represented by R include 3,3,3-trifluoropropyl group, nonafluorohexyl group, tridecafluorooctyl group, heptadecafluoro, in addition to the groups listed as specific examples of R ^2. Examples include decyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, pentafluorophenyl group and the like.

  Specific examples of the monovalent or polyvalent cyclic organosiloxanyl group represented by the general formula (6) include 1,3,3,5,5-pentamethylcyclotrisiloxane-1-yl group, 1 , 3,5-trimethylcyclopentasiloxane-1,3,5-triyl group, 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl group, 1,3,5, 5,7,7-hexamethylcyclotetrasiloxane-1,3-diyl group, 1,3,3,5,7,7-hexamethylcyclotetrasiloxane-1,5-diyl group, 1,3,5,5 7,7-pentamethylcyclotetrasiloxane-1,3,5-triyl group, 1,3,5,7-tetramethylcyclotetrasiloxane-1,3,5,7-tetrayl group, 1-methyl-3, 3,5,5,7,7-hexaethyltet Siloxane-1-yl group, 1-ethyl-3,3,5,5,7,7-hexamethylcyclotetrasiloxane-1-yl group, 1,3,5,7-tetramethyl-3,5,7 -Triethylcyclotetrasiloxane-1-yl group, 1,3,5,7-tetramethyl-3,5,7-trivinylcyclotetrasiloxane-1-yl group, 1,3,5,7-tetramethyl- 3,5,7-triphenylcyclotetrasiloxane-1-yl group, 1,3,5,7-tetramethyl-3,5,7-tris (3,3,3-trifluoropropyl) cyclotetrasiloxane Examples include 1-yl group, 1,3,3,5,5,7,7,9,9-nonamethylcyclopentasiloxane-1-yl group.

In the general formula (7), R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and is defined by the general formula (6) It is synonymous with. In this case, α = 1 since the number of bonds in equation (7) is one. R ^x represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or an organic group substituted with a triorganosilylamino group represented by the following general formula (8). Specific examples of the substituted or unsubstituted monovalent hydrocarbon group represented by R ^x include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a trifluoropropyl group, and 3-glycidyloxypropyl. Group, 3-methacryloyloxypropyl group, 3-acryloyloxypropyl group, 3-chloropropyl group, n-butyl group, isobutyl group, 2-butyl group, tert-butyl group, cyclobutyl group, pentyl group, cyclopentyl group, isopentyl Group, tert-pentyl group, methylcyclopentyl group, hexyl group, cyclohexyl group, texyl group, nonafluorohexyl group, methylcyclohexyl group, heptyl group, cycloheptyl group, norbornyl group, 2-ethylhexyl group, octyl group, isooctyl group, 5-norbornen-2-ylethylene Group, tridecafluorooctyl group, 3,4-epoxycyclohexylethyl group, decyl group, heptadecafluorodecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, vinyl group, allyl group, propenyl group, 3-butenyl group, 2-butenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, 5-norbornenyl group, cyclohexenylethyl group, octenyl group, decenyl group, ethynyl group, propynyl group, butynyl group, etc. Substituted aliphatic monovalent hydrocarbon group, phenyl group, 4-tert-butylphenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,6-dimethylphenyl group, 2,4-dimethylphenyl Group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 2,5-dimethyl Aryl groups such as ruphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, biphenylyl group, phenanthryl group, anthracenyl group, benzyl group, 1-phenylethyl group, 2-phenylethyl group, naphthylethyl group, aralkyl group And aromatic monovalent hydrocarbon groups such as the above and substituents represented by the following general formula (8). c represents an integer of 0 to 100, more preferably an integer of 0 to 10.

In the above general formula (8), R ¹ , R ² and A ¹ represent the same substituents as those described in the above general formulas (1) and (2). Specific examples of the substituent represented by the general formula (8) include N- (ethyldimethylsilyl) aminomethyl group, N- (vinyldimethylsilyl) aminomethyl group, N- (diethylmethylsilyl) aminomethyl group, N- (n-propyldimethylsilyl) aminomethyl group, N- (isopropyldimethylsilyl) aminomethyl group, N- (allyldimethylsilyl) aminomethyl group, N- (tert-butyldimethylsilyl) aminomethyl group, N- (2-butyldimethylsilyl) aminomethyl group, N- (triethylsilyl) aminomethyl group, N- (cyclopentyldimethylsilyl) aminomethyl group, N- (n-hexyldimethylsilyl) aminomethyl group, N- (cyclohexyldimethyl) Silyl) aminomethyl group, N- (texyldimethylsilyl) aminomethyl group, N (Phenyldimethylsilyl) aminomethyl group, N- (2-norbornyldimethylsilyl) aminomethyl group, N- (tolyldimethylsilyl) aminomethyl group, N- (benzyldimethylsilyl) aminomethyl group, N- (tri Isopropylsilyl) aminomethyl group, N- (n-octyldimethylsilyl) aminomethyl group, N-[(5-norbornen-2-ylethyl) dimethylsilyl] aminomethyl group, N- (decyldimethylsilyl) aminomethyl group, N- (tri-n-butylsilyl) aminomethyl group, N- (triisobutylsilyl) aminomethyl group, N- (octadecyldimethylsilyl) aminomethyl group,
N- (ethyldimethylsilyl) -3-aminopropyl group, N- (vinyldimethylsilyl) -3-aminopropyl group, N- (diethylmethylsilyl) -3-aminopropyl group, N- (n-propyldimethylsilyl) ) -3-aminopropyl group, N- (isopropyldimethylsilyl) -3-aminopropyl group, N- (allyldimethylsilyl) -3-aminopropyl group, N- (tert-butyldimethylsilyl) -3-aminopropyl Group, N- (2-butyldimethylsilyl) -3-aminopropyl group, N- (triethylsilyl) -3-aminopropyl group, N- (cyclopentyldimethylsilyl) -3-aminopropyl group, N- (n- Hexyldimethylsilyl) -3-aminopropyl group, N- (cyclohexyldimethylsilyl) -3-aminopropyl group N- (Texyldimethylsilyl) -3-aminopropyl group, N- (Phenyldimethylsilyl) -3-aminopropyl group, N- (2-norbornyldimethylsilyl) -3-aminopropyl group, N- ( Tolyldimethylsilyl) -3-aminopropyl group, N- (benzyldimethylsilyl) -3-aminopropyl group, N- (triisopropylsilyl) -3-aminopropyl group, N- (n-octyldimethylsilyl) -3 -Aminopropyl group, N- (phenethyldimethylsilyl) -3-aminopropyl group, N-[(5-norbornen-2-ylethyl) dimethylsilyl] -3-aminopropyl group, N- (decyldimethylsilyl) -3 -Aminopropyl group, N- (tri-n-butylsilyl) -3-aminopropyl group, N- (triisobutylsilyl) -3 Aminopropyl group, N- (naphthyldimethylsilyl) -3-aminopropyl group, N- (tert-butyldiphenylsilyl) -3-aminopropyl group, N- (triphenylsilyl) -3-aminopropyl group, N- (Octadecyldimethylsilyl) -3-aminopropyl group,
N- (ethyldimethylsilyl) -4-aminobutyl group, N- (vinyldimethylsilyl) -4-aminobutyl group, N- (diethylmethylsilyl) -4-aminobutyl group, N- (n-propyldimethylsilyl) ) -4-aminobutyl group, N- (isopropyldimethylsilyl) -4-aminobutyl group, N- (allyldimethylsilyl) -4-aminobutyl group, N- (tert-butyldimethylsilyl) -4-aminobutyl Group, N- (2-butyldimethylsilyl) -4-aminobutyl group, N- (triethylsilyl) -4-aminobutyl group, N- (cyclopentyldimethylsilyl) -4-aminobutyl group, N- (n- Hexyldimethylsilyl) -4-aminobutyl group, N- (cyclohexyldimethylsilyl) -4-aminobutyl group, N- (texyldimethyl) Ryl) -4-aminobutyl group, N- (phenyldimethylsilyl) -4-aminobutyl group, N- (2-norbornyldimethylsilyl) -4-aminobutyl group, N- (tolyldimethylsilyl) -4 -Aminobutyl group, N- (benzyldimethylsilyl) -4-aminobutyl group, N- (triisopropylsilyl) -4-aminobutyl group, N- (n-octyldimethylsilyl) -4-aminobutyl group, N -[(5-norbornen-2-ylethyl) dimethylsilyl] -4-aminobutyl group, N- (decyldimethylsilyl) -4-aminobutyl group, N- (tri-n-butylsilyl) -4-aminobutyl group N- (triisobutylsilyl) -4-aminobutyl group, N- (octadecyldimethylsilyl) -4-aminobutyl group,
N- (ethyldimethylsilyl) -3-amino-2-methylpropyl group, N- (vinyldimethylsilyl) -3-amino-2-methylpropyl group, N- (diethylmethylsilyl) -3-amino-2- Methylpropyl group, N- (n-propyldimethylsilyl) -3-amino-2-methylpropyl group, N- (isopropyldimethylsilyl) -3-amino-2-methylpropyl group, N- (allyldimethylsilyl)- 3-amino-2-methylpropyl group, N- (tert-butyldimethylsilyl) -3-amino-2-methylpropyl group, N- (2-butyldimethylsilyl) -3-amino-2-methylpropyl group, N- (triethylsilyl) -3-amino-2-methylpropyl group, N- (cyclopentyldimethylsilyl) -3-amino-2-methylpropyl N- (n-hexyldimethylsilyl) -3-amino-2-methylpropyl group, N- (cyclohexyldimethylsilyl) -3-amino-2-methylpropyl group, N- (texyldimethylsilyl) -3- Amino-2-methylpropyl group, N- (phenyldimethylsilyl) -3-amino-2-methylpropyl group, N- (2-norbornyldimethylsilyl) -3-amino-2-methylpropyl group, N- (Tolyldimethylsilyl) -3-amino-2-methylpropyl group, N- (benzyldimethylsilyl) -3-amino-2-methylpropyl group, N- (triisopropylsilyl) -3-amino-2-methylpropyl Group, N- (n-octyldimethylsilyl) -3-amino-2-methylpropyl group, N- (phenethyldimethylsilyl) -3-amino-2 Methylpropyl group, N-[(5-norbornen-2-ylethyl) dimethylsilyl] -3-amino-2-methylpropyl group, N- (decyldimethylsilyl) -3-amino-2-methylpropyl group, N- (Tri-n-butylsilyl) -3-amino-2-methylpropyl group, N- (triisobutylsilyl) -3-amino-2-methylpropyl group, N- (naphthyldimethylsilyl) -3-amino-2- Methylpropyl group, N- (octadecyldimethylsilyl) -3-amino-2-methylpropyl group,
N- (ethyldimethylsilyl) -4-aminophenyl group, N- (vinyldimethylsilyl) -4-aminophenyl group, N- (diethylmethylsilyl) -4-aminophenyl group, N- (n-propyldimethylsilyl) ) -4-aminophenyl group, N- (isopropyldimethylsilyl) -4-aminophenyl group, N- (allyldimethylsilyl) -4-aminophenyl group, N- (tert-butyldimethylsilyl) -4-aminophenyl Group, N- (2-butyldimethylsilyl) -4-aminophenyl group, N- (triethylsilyl) -4-aminophenyl group, N- (cyclopentyldimethylsilyl) -4-aminophenyl group, N- (n- Hexyldimethylsilyl) -4-aminophenyl group, N- (cyclohexyldimethylsilyl) -4-aminophenyl group N- (Texyldimethylsilyl) -4-aminophenyl group, N- (phenyldimethylsilyl) -4-aminophenyl group, N- (2-norbornyldimethylsilyl) -4-aminophenyl group, N- ( Tolyldimethylsilyl) -4-aminophenyl group, N- (benzyldimethylsilyl) -4-aminophenyl group, N- (triisopropylsilyl) -4-aminophenyl group, N- (n-octyldimethylsilyl) -4 -Aminophenyl group, N-[(5-norbornen-2-ylethyl) dimethylsilyl] -4-aminophenyl group, N- (decyldimethylsilyl) -4-aminophenyl group, N- (tri-n-butylsilyl) -4-aminophenyl group, N- (triisobutylsilyl) -4-aminophenyl group, N- (octadecyldimethylsilyl)- - aminophenyl group,
N- (ethyldimethylsilyl) -3-aminophenyl group, N- (vinyldimethylsilyl) -3-aminophenyl group, N- (diethylmethylsilyl) -3-aminophenyl group, N- (n-propyldimethylsilyl) ) -3-aminophenyl group, N- (isopropyldimethylsilyl) -3-aminophenyl group, N- (allyldimethylsilyl) -3-aminophenyl group, N- (tert-butyldimethylsilyl) -3-aminophenyl Group, N- (2-butyldimethylsilyl) -3-aminophenyl group, N- (triethylsilyl) -3-aminophenyl group, N- (cyclopentyldimethylsilyl) -3-aminophenyl group, N- (n- Hexyldimethylsilyl) -3-aminophenyl group, N- (cyclohexyldimethylsilyl) -3-aminophenyl group N- (Texyldimethylsilyl) -3-aminophenyl group, N- (Phenyldimethylsilyl) -3-aminophenyl group, N- (2-norbornyldimethylsilyl) -3-aminophenyl group, N- ( Tolyldimethylsilyl) -3-aminophenyl group, N- (benzyldimethylsilyl) -3-aminophenyl group, N- (triisopropylsilyl) -3-aminophenyl group, N- (n-octyldimethylsilyl) -3 -Aminophenyl group, N-[(5-norbornen-2-ylethyl) dimethylsilyl] -3-aminophenyl group, N- (decyldimethylsilyl) -3-aminophenyl group, N- (tri-n-butylsilyl) -3-aminophenyl group, N- (triisobutylsilyl) -3-aminophenyl group, N- (octadecyldimethylsilyl)- - aminophenyl group, and the like.

  Specific examples of the linear organosiloxanyl group represented by the general formula (7) include a pentamethyldisiloxanyl group, 3-vinyl-1,1,3,3-tetramethyldisiloxane-1 -Yl group, 3-methacryloyloxypropyl-1,1,3,3-tetramethyldisiloxane-1-yl group, 3-acryloyloxypropyl-1,1,3,3-tetramethyldisiloxane-1-yl Group, 3-glycidyloxypropyl-1,1,3,3-tetramethyldisiloxane-1-yl group, 3- (3,3,3-trifluoropropyl) -1,1,3,3-tetramethyl Disiloxane-1-yl group, 3-chloropropyl-1,1,3,3-tetramethyldisiloxane-1-yl group, 3- (3,4-epoxycyclohexylethyl) -tetramethyldisiloxane 1-yl group, 3- (5-norbornenyl) -1,1,3,3-tetramethyldisiloxane-1-yl group, 3- (5-norbornenylethyl) -1,1,3,3- Tetramethyldisiloxane-1-yl group, 3- [N- (triethylsilyl) -3-aminopropyl] -1,1,3,3-tetramethyldisiloxane-1-yl group, 3- [N- ( tert-Butyldimethylsilyl) -3-aminopropyl] -1,1,3,3-tetramethyldisiloxane-1-yl group, 3- [N- (Texyldimethylsilyl) -3-aminopropyl] -1 , 1,3,3-Tetramethyldisiloxane-1-yl group, 3- [N- (triisopropylsilyl) -3-aminopropyl] -1,1,3,3-tetramethyldisiloxane-1-yl The group 3- [N- (triisobuty Silyl) -3-aminopropyl] -1,1,3,3-tetramethyldisiloxane-1-yl group, 3- [N- (phenyldimethylsilyl) -3-aminopropyl] -1,1,3 3-tetramethyldisiloxane-1-yl group, 3- [N- (octyldimethylsilyl) -3-aminopropyl] -1,1,3,3-tetramethyldisiloxane-1-yl group, 3- [ N- (decyldimethylsilyl) -3-aminopropyl] -1,1,3,3-tetramethyldisiloxane-1-yl group, 3- [N- (octadecyldimethylsilyl) -3-aminopropyl] -1 , 1,3,3-tetramethyldisiloxane-1-yl group, 3- [N- (benzyldimethylsilyl) -3-aminopropyl] -1,1,3,3-tetramethyldisiloxane-1-yl Group, 3- [N -(Phenethyldimethylsilyl) -3-aminopropyl] -1,1,3,3-tetramethyldisiloxane-1-yl group, 3- [N- (naphthyldimethylsilyl) -3-aminopropyl] -1, 1,3,3-tetramethyldisiloxane-1-yl group, 1,1,3,3,5,5,5-heptamethyltrisiloxane-1-yl group, 1,1,3,3,5,5 5,7,7,7-nonamethyltetrasiloxane-1-yl group, 1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane-1-yl group Etc.

In the above general formula (9), R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and is defined by the general formula (6) It is synonymous with. R ^x may be the same or different and represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or an organic group substituted with a triorganosilylamino group represented by the above general formula (8). , Which is synonymous with that defined by the general formula (7). R ^S represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy group represented by the following general formula (10). Specific examples of the monovalent hydrocarbon group represented by R ^S are the same as the substituents exemplified as R ² . d represents the valency of the organosiloxanyl group. In this case, since the number of bonds in the formula (9) is d, α = d and an integer of 1 to 100, more preferably 1 to 10. Represents an integer. e represents an integer of 0 to 100, more preferably an integer of 0 to 10.

  Specific examples of the linear or branched organosiloxanyl group represented by the general formula (9) include 1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl. Group, 1,1,1,5,5,5-hexamethyl-3-trimethylsiloxytrisiloxane-3-yl group, 1,5-dihexyl-1,1,5,5-tetramethyl-3-hexyldimethylsiloxy Trisiloxane-3-yl group, 1,1,3,5,5-pentamethyl-1,5-divinyltrisiloxane-3-yl group, 1,1,3,5,5-pentamethyl-1,5-diphenyl Trisiloxane-3-yl group, 1,1,3,5,5-pentamethyl-1,5-bis (3-chloropropyl) trisiloxane-3-yl group, 1,1,3,5,5-pentamethyl -1,5-bis (3,3,3-to Fluoropropyl) trisiloxane-3-yl group, 1,1,3,5,5-pentamethyl-1,5-bis (5-norbornylethyl) trisiloxane-3-yl group, 1,1,3, 5,5-pentamethyl-1,5-bis (5-norbornenyl) trisiloxane-3-yl group, 1,1,1,3,5,5,7,7,7-octamethyltetrasiloxane-3-diyl Group, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane-3,5-diyl group, α, ω-bis (trimethylsiloxy) polydimethylsiloxanyl group and the like.

  In the general formula (10), R represents a substituent having the same meaning as that defined in the general formula (9). Specific examples of the triorganosiloxy group represented by the general formula (10) include trimethylsiloxy group, ethyldimethylsiloxy group, vinyldimethylsiloxy group, ethynyldimethylsiloxy group, diethylmethylsiloxy group, n-propyldimethylsiloxy group, 3,3,3-trifluoropropyldimethylsiloxy group, isopropyldimethylsiloxy group, cyclopropyldimethylsiloxy group, allyldimethylsiloxy group, n-butyldimethylsiloxy group, isobutyldimethylsiloxy group, tert-butyldimethylsiloxy group, cyclobutyl Dimethylsiloxy group, 2-butyldimethylsiloxy group, triethylsiloxy group, trivinylsiloxy group, n-pentyldimethylsiloxy group, cyclopentyldimethylsiloxy group, methyldiisopropylsiloxy group Isopropyldiethylsiloxy group, n-hexyldimethylsiloxy group, nonafluorohexyldimethylsiloxy group, cyclohexyldimethylsiloxy group, cyclohexenyldimethylsiloxy group, hexyldimethylsiloxy group, 1-methylcyclopentyldimethylsiloxy group, phenyldimethylsiloxy group, ( Pentafluorophenyl) dimethylsiloxy group, n-butyldiethylsiloxy group, n-heptyldimethylsiloxy group, cycloheptyldimethylsiloxy group, 2-norbornyldimethylsiloxy group, 5-norbornen-2-yldimethylsiloxy group, 2- Tolyldimethylsiloxy group, 3-tolyldimethylsiloxy group, 4-tolyldimethylsiloxy group, triisopropylsiloxy group, n-octyldimethylsiloxy group, tridecafluoro Octyldimethylsiloxy group, 5-norbornen-2-ylethyldimethylsiloxy group, n-hexyldiethylsiloxy group, decyldimethylsiloxy group, heptadecafluorodecyldimethylsiloxy group, tri-n-butylsiloxy group, triisobutylsiloxy group, Examples include dodecyldimethylsiloxy group, tetradecyldimethylsiloxy group, hexadecyldimethylsiloxy group, octadecyldimethylsiloxy group, icosyldimethylsiloxy group and the like.

In the said General formula (11), R is synonymous with what was defined by the said General formula (6). R ^S has the same meaning as defined in the general formula (9). f and h are integers of 0 to 10, preferably integers of 0 to 3. g represents the valence of the organosiloxanyl group. In this case, since there are g bonds in the formula (11), α = g, an integer of 1 to 20, and i is 0 to 19 Represents an integer. However, the sum of g and i is 6 to 20, preferably 6 to 14, more preferably 6, 8, 10, 12, or 14. Examples of the siloxane skeleton of the cage-shaped organosiloxanyl group represented by the general formula (11) include those having the following structure [D] (only silicon atoms and oxygen atoms are shown).

（但し、Ｒは上記の通り）
で表される基を形成してもよい。ｏは２〜１０の整数を表し、好ましくは２，４，６，８，１０のいずれかである。一般式（１２）で表される部分開裂したかご状オルガノシロキサンのシロキサン骨格として、例えば、下記構造［Ｅ］のものが挙げられる（ケイ素原子と酸素原子のみを示す）。 In the said General formula (12), R is synonymous with what was defined by the said General formula (6). R ^S has the same meaning as defined in the general formula (9), and R ^t represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy group represented by the general formula (10). Specific examples of the substituent represented by R ^t include the groups exemplified as R ^S. j, l and n are integers of 0 to 10, preferably an integer of 0 to 3. k represents the valence of the siloxanyl group, and in this case, the number of bonds in formula (12) is k. , Α = k, and an integer of 1 to 3. M represents an integer of 0 to 2, and the sum of k and m is 3. In this case, when m is 2, R ^t are bonded to each other and the following formula (13)

(However, R is as above)
You may form group represented by these. o represents an integer of 2 to 10, and is preferably any of 2, 4, 6, 8, and 10. Examples of the siloxane skeleton of the partially cleaved cage organosiloxane represented by the general formula (12) include those having the following structure [E] (only silicon atoms and oxygen atoms are shown).

  In the present invention, there is provided a silylamidic acid triorganosilyl ester bonded with an organosiloxane represented by the following general formula (4), which is a precursor of an imide bonded with an organosiloxane represented by the above general formula (5). . Furthermore, the triorganosilylamino group-containing organosiloxane represented by the above general formula (2) is reacted with the dicarboxylic acid anhydride represented by the following general formula (3), which is represented by the following general formula (4). A method for producing a triorganosilyl ester of amic acid to which an organosiloxane is bonded is provided.

In the above general formulas (3) and (4), A ¹ is a divalent organic group such as a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, an alkenylene group, an arylene group, a group to which these are bonded, and Sx is It represents a monovalent or polyvalent organosiloxanyl group having a silicon number of 2 to 2,000. α represents the valence of the organosiloxanyl group and has the same meaning as described above. R ¹ , R ² and Sx represent substituents having the same meanings as described in the general formulas (1) and (2).

In the above general formulas (3) and (4), A ² is a substituted or unsubstituted divalent alkylene group, alkenylene group or arylene group having 2 to 40 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. Represents an organic group such as a group to which these are bonded. Specific examples of A ² include 1,2-ethanediyl group, 1,2-ethenediyl group, 1,3-propanediyl group, 2,3-butanediyl group, 2-butene-2,3-diyl group, and 7-octene. -1,2-diyl group, cyclohexylene group, 1,2-phenylene group, 3,4,5,6-tetrahydrobenzene-1,2-diyl group, 4-chlorobenzene-1,2-diyl group, 5 -Norbornene-2,3-diyl group, 4,5,6,7-tetrahydronaphthalene-1,2-diyl group, naphthalene-1,8-diyl group, naphthalene-1,2-diyl group, naphthalene-2, 3-diyl group etc. are mentioned.

  Examples of the compound represented by the general formula (3) include succinic anhydride, 2-methylidene succinic anhydride, allyl succinic anhydride, 2-butenyl succinic anhydride, (2-methyl-2-propenyl). ) Succinic anhydride, octyl succinic anhydride, octenyl succinic anhydride, (2,7-octadienyl) succinic anhydride, dodecyl succinic anhydride, dodecenyl succinic anhydride, decyl succinic anhydride, decenyl succinic Acid anhydride, tetradecyl succinic anhydride, tetradecenyl succinic anhydride, hexadecyl succinic anhydride, hexadecenyl succinic anhydride, octadecyl succinic anhydride, octadecenyl succinic anhydride, maleic anhydride, 2-methylmaleic anhydride 2,3-dimethylmaleic anhydride, glutaric anhydride, 2,2-dimethylglucan Luric anhydride, 3,3-dimethylglutaric anhydride, 3-methylglutaric anhydride, 2,2,3,3,4,4-hexafluoropentanedioic anhydride, phthalic anhydride, 3-fluoro Phthalic anhydride, 4-fluorophthalic anhydride, 4-chlorophthalic anhydride, 4,5-dichlorophthalic anhydride, tetrachlorophthalic anhydride, 4-bromophthalic anhydride, tetrabromophthalic anhydride 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, 4-methylphthalic anhydride, 4-ethynylphthalic anhydride, 4-tert-butylphthalic anhydride, 4-phenylethynylphthalic anhydride, cyclohexane 1,2-dicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, cyclohexene-1,2-dicarboxylic anhydride, 4- Cyclohexene-1,2-dicarboxylic acid anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, 2,3-pyridine Dicarboxylic anhydride, 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, trimellitic anhydride chloride, trimellitic anhydride methyl ester, trimellitic anhydride trimethylsilyl ester , Trimellitic anhydride triethylsilyl ester, trimellitic anhydride tert-butyldimethylsilyl ester, trimellitic anhydride phenyldimethylsilyl ester, trimellitic anhydride texyldimethylsilyl ester, trimellitic anhydride triisopropyl ester, trimellitic anhydride Acid triisobutyl ester Ter, 5-norbornene-2,3-dicarboxylic anhydride, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride, 1,1-cyclopentanediacetic acid Anhydride, naphthalene-1,8-dicarboxylic acid anhydride, naphthalene-1,2-dicarboxylic acid anhydride, naphthalene-2,3-dicarboxylic acid anhydride, 4-bromonaphthalene-1,2-dicarboxylic acid anhydride, 2,2′-biphenyldicarboxylic acid anhydride and the like.

  The reaction of the triorganosilylamino group-containing organosiloxane represented by the general formula (2) and the dicarboxylic acid anhydride represented by the following general formula (3) is usually performed in the presence of a solvent. As a solvent that can be used, an aprotic solvent is preferable, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, ketones such as acetone, cyclopentanone, cyclohexanone, and methyl isobutyl ketone, N, N-dimethyl Amides such as acetamide, N, N-dimethylformamide, N-methylpyrrolidone, hydrocarbons such as hexane, isooctane, benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, acetonitrile, propio Nitriles such as nitrile and benzonitrile, sulfoxides such as dimethyl sulfoxide, and the like can be used. Two or more kinds of solvents can be mixed and used. Since the dicarboxylic acid anhydride which is a reaction substrate reacts with water to form a low-reactivity dicarboxylic acid, it is preferable to use a solvent with reduced water content in this reaction. The amount of the solvent used is arbitrary, but it is preferable to use an amount sufficient to dissolve the reaction substrate and the product.

  In this case, the proportion of the triorganosilylamino group-containing organosiloxane of the formula (2) and the dicarboxylic acid anhydride of the formula (3) is appropriately selected, but the latter 0.5 to 2 mol with respect to 1 mol of the former, In particular, the amount is preferably 0.8 to 1.2 mol.

  When the triorganosilylamino group-containing organosiloxane represented by the general formula (2) has two or more triorganosilylamino groups, the dicarboxylic acid anhydride represented by the general formula (3) to be reacted is used. It is possible to react all or part of the triorganosilylamino group by adjusting the equivalent amount.

  The reaction temperature of the triorganosilylamino group-containing organosiloxane represented by the general formula (2) and the dicarboxylic acid anhydride represented by the general formula (3) is 60 ° C. or lower, more preferably 0 to 40 ° C. Good to do. When the reaction temperature is high, the produced amic acid triorganosilyl ester is partially imidized and the purity is lowered. Moreover, when it cools too much, reaction progress will become slow.

  Examples of the amic acid triorganosilyl ester to which the organosiloxane represented by the general formula (4) thus produced is bonded include those exemplified in Tables 1 to 78.

  Here, examples of the amic acid triorganosilyl ester of the general formula (4) include those represented by the following general formulas (4) -1 to (4) -7.

（上記式中、Ｒ¹、Ｒ²、Ａ¹、Ａ²、Ｒ、ａ、ｂ、Ｒ^x、ｃ、Ｒ^S、ｄ、ｅ、ｆ、ｇ、ｈ、ｉ、ｊ、ｋ、ｌ、ｍ、ｎ、ｏ、Ｒ^tは上記定義の通りである。Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^e、Ｒ^fはそれぞれ上記Ｒと同様に定義される基である。）

(In the ^{formula, R 1, R 2, A} 1, A 2, R, a, b, R x, c, R S, d, e, f, g, h, i, j, k, l, m , N, o, and R ^t are as defined above, and R ^a , R ^b , R ^c , R ^d , R ^e , and R ^f are groups defined in the same manner as R above.)

  In the present invention, a method for producing an imide bonded with an organosiloxane represented by the following general formula (5) by ring-closing imidation of the amic acid triorganosilyl ester represented by the general formula (4) by detriorganosilanol reaction, preferably A triorganosilylamino group-containing organosiloxane represented by the above general formula (2) to which a triorganosilyl group represented by the above general formula (1) is bonded, and a dicarboxylic acid represented by the above general formula (3) By reacting with an acid anhydride, the amic acid triorganosilyl ester represented by the above general formula (4) is obtained, and then the amic acid triorganosilyl ester is ring-closed imidized by a detriorganosilanol reaction. Provides a method for producing an imide bonded with an organosiloxane represented by the following general formula (5) That.

In the above formula (5), R ¹ is a monovalent hydrocarbon group having 2 to 20 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be the same or different, and A ¹ is 1 to ¹ carbon atom. 20 substituted or unsubstituted divalent organic groups, A ² represents a substituted or unsubstituted divalent organic group having 2 to 40 carbon atoms. Sx represents a monovalent or polyvalent organosiloxanyl group having a silicon number of 2 to 2,000, and these groups have the same meanings as described in the general formulas (1) to (4). α represents the valence of the organosiloxanyl group and is an integer of 1 to 100.

  In the method for producing an imide bonded with an organosiloxane according to the present invention, the triorganosilyl ester represented by the general formula (4) is obtained by the production method according to the present invention, and then detriorganosilanol reaction is performed. The amic acid triorganosilyl ester is ring-closed imidized. The imidization by the detriorganosilanol reaction is preferably performed by heating the amic acid triorganosilyl ester represented by the general formula (4). The temperature of the imidization reaction is 40 ° C. or higher, preferably 100 to 300 ° C.

  The amidic acid triorganosilyl ester may be isolated, or may be imidized using the reaction mixture without isolation. A solvent may be used for the imidation reaction, and a solvent used for producing the amidic acid triorganosilyl ester can be used.

  The imidation reaction is preferably carried out under reduced pressure while distilling off the generated triorganosilanol, or under normal pressure while distilling off the triorganosilanol produced in an inert gas stream such as nitrogen or argon.

  Tables 1 to 78 are shown below. Here, in the following table, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, i-Pr is an isopropyl group, t-Bu is a tert-butyl group, i-Bu is an isobutyl group, and c-Pen is cyclopentyl. Group, Tx is texyl group, c-Hex is cyclohexyl group, Ph is phenyl group, Vi is vinyl group, TFP is 3,3,3-trifluoropropyl group, TMSO is trimethylsiloxy group, NFH is 3,3,4 , 4,5,5,6,6,6-nonafluorohexyl group, TDFO is 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl Group, HDFD represents 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl group.

Compounds in Tables 1-5:

Compounds in Tables 6-11:

Compounds in Tables 12-22:

Compounds in Tables 23-30:

Compounds in Tables 31-51:

Compounds in Tables 52-62:

Compounds in Tables 63-78:

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following examples, all reactions were performed in a nitrogen atmosphere. The GC measurement of the target product was performed as a 10% THF solution, and the purity was calculated by subtracting the solvent peak. For GPC measurement, THF eluent, TSKgelSuperHZ2000 (manufactured by Tosoh Corp.) × 3 was used, and a UV detector (wavelength 254 nm) was used. The purity was calculated by subtracting the peak due to the solvent.

    [Example 1] 1- [3- (tert-Butyldimethylsilylamino) propyl] -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane was used as a raw material. Synthesis of (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalimide (wherein Me represents a methyl group and t-Bu represents a tert-butyl group) To express.)

  (Amic acid silyl ester synthesis reaction) A 100 mL four-necked flask equipped with a Dimroth reflux condenser, a stirrer, a thermometer, and a dropping funnel was purged with nitrogen. 1.48 g (10 mmol) of phthalic anhydride was charged into the flask, and 24 g of dehydrated tetrahydrofuran (hereinafter abbreviated as THF) was added and dissolved. While stirring the solution at room temperature, 4.54 g (10 mmol) of 1- [3- (tert-butyldimethylsilylamino) propyl] -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane from a dropping funnel. ) Was added dropwise over 2.5 hours. After stirring for 1 hour at room temperature, the disappearance of the raw material was confirmed by GC analysis. A small amount of the reaction mixture was collected, concentrated, and analyzed by EI-MS to find N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalamide. It was found that acid tert-butyldimethylsilyl ester was formed as the main product.

The results of EI-MS analysis of N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalamic acid tert-butyldimethylsilyl ester are shown below. Show. m / z 601 (M ⁺ ), 586, 544, 454, 281, 130, 73

(Imidation reaction under normal pressure) The above reaction mixture was concentrated under reduced pressure to obtain 6.06 g of an orange oil. 180 mg of this oily substance was weighed into a glass vial, and the vial was put in an oven with the cap removed, and heated at 80 ° C. for 1 hour while nitrogen was bubbled, and further heated at 200 ° C. for 1 hour. Upon cooling, 137 mg of a yellow solid was obtained. From the analysis results of EI-MS and FT-IR, the target N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane- 1-yl) propyl] phthalimide. The GC purity was 99.5%, the GPC purity was 95.1%, and the yield was 98.1% based on phthalic anhydride. The EI-MS analysis results of N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalimide are shown below. m / z 469 (M ⁺ ), 454, 281, 130

  (Imidation reaction under reduced pressure) 113 mg of the above oily substance was weighed into a glass vial, and the vial was placed in an oven with the cap removed, and the temperature was gradually raised at 80 ° C. for 1 hour while reducing the pressure to 3.0 kPa. And heated at 130 ° C. for 2 hours. Upon cooling, 82 mg of a yellow solid was obtained. From the result of EI-MS analysis, the desired N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) was obtained. Propyl] phthalimide. The GC purity was 99.1%, the GPC purity was 96.5%, and the yield was 96.0% based on phthalic anhydride.

    [Example 2] N- [3- (1, 1- [3- (triethylsilylamino) propyl] -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane was used as a raw material. Synthesis of 3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalimide (In the following formula, Et represents an ethyl group.)

  (Amic acid silyl ester synthesis reaction) A 100 mL four-necked flask equipped with a Dimroth reflux condenser, a stirrer, a thermometer, and a dropping funnel was purged with nitrogen. 1.48 g (10 mmol) of phthalic anhydride was charged into the flask, and 24 g of dehydrated THF was added and dissolved. While stirring the solution at room temperature, 4.54 g (10 mmol) of 1- [3- (triethylsilylamino) propyl] -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane was added from the dropping funnel. Dropped in 5 hours. After stirring for 1 hour at room temperature, the disappearance of the raw material was confirmed by GC analysis (detector TCD, the same applies hereinafter). A small amount of the reaction mixture was collected, concentrated, and analyzed by EI-MS to find N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalamide. It was found that acid triethylsilyl ester was produced in quantitative yield.

The EI-MS analysis result of N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalamic acid triethylsilyl ester is shown below. m / z 601 (M ⁺ ), 572, 454, 281, 130

  (Imidation reaction under reduced pressure) The above reaction mixture was concentrated under reduced pressure to obtain 6.20 g of a pale yellow oil. Weigh 127 mg of this oil in a glass vial, put the vial in an oven with the cap removed, heat at 80 ° C. for 1 hour while reducing the pressure to 3.0 kPa, and heat at 130 ° C. for 1 hour. did. Upon cooling, 96 mg of a pale yellow solid was obtained. From the results of EI-MS analysis, the desired N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl] was obtained. ) Propyl] phthalimide. The GC purity was 96.9%, the GPC purity was 95.9%, and the yield was 99.8% based on phthalic anhydride.

    [Comparative Example 1] N- [3- (1,3,3, 1- (3-aminopropyl) -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane was used as a raw material. Synthesis of 5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalimide

(Amic acid synthesis reaction) A 100 mL four-necked flask equipped with a Dimroth reflux condenser, a stirrer, a thermometer, and a dropping funnel was replaced with nitrogen. 1.48 g (10 mmol) of phthalic anhydride was charged into the flask, and 20 g of dehydrated THF was added and dissolved. While stirring the solution at room temperature, 3.40 g (10 mmol) of 1- (3-aminopropyl) -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane was added from a dropping funnel in 1.5 hours. It was dripped. The reaction mixture was concentrated under reduced pressure to obtain 4.83 g of a white solid. When this solid was analyzed by MALDI-TOFMS (cobalt matrix), it was N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalamic acid. I understood it. The results of MALDI-TOFMS analysis are shown below. m / z 526 ([M + K] ⁺ ), 510 ([M + Na] ⁺ ), 281

  (Imidation reaction under normal pressure) Weigh 117 mg of the obtained solid into a glass vial, put the vial in the oven with the cap removed, and gradually raise the temperature at 80 ° C. for 1 hour while bubbling nitrogen. And heated at 200 ° C. for 1 hour. Upon cooling, 110 mg of a white solid was obtained. From the result of EI-MS analysis, the desired N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) was obtained. Propyl] phthalimide was found to be the main product. However, the GC purity was 95.3%, and N- [3- (1,3,3,5,5-pentamethylcyclotrisiloxane-1-yl) propyl] in which the siloxane was disproportionated by GC-MS analysis] It can be seen that phthalimide and N- [3- (1,3,3,5,5,7,7,9,9-nonamethylcyclopentasiloxane-1-yl) propyl] phthalimide are produced. Were 1.0% and 2.8%, respectively. The GPC purity was 87.8%, and a broad peak was detected on the high molecular weight side of the target product. The yield was 96.6% based on phthalic anhydride.

  (Imidation reaction under reduced pressure) 101 mg of the above solid was weighed into a glass vial, the cap was removed and the vial was placed in an oven, and the temperature was further gradually increased at 80 ° C. for 1 hour while reducing the pressure to 3.0 kPa. And heated at 130 ° C. for 1 hour. Upon cooling, 94 mg of a white solid was obtained. The GC purity of the desired N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalimide Was 95.2%. The disproportionation products N- [3- (1,3,3,5,5-pentamethylcyclotrisiloxane-1-yl) propyl] phthalimide and N- [3- (1,3,3,5) , 5,7,7,9,9-nonamethylcyclopentasiloxane-1-yl) propyl] phthalimide were 0.7% and 1.9%, respectively. The GPC purity was 93.4% and the yield was 94.5% based on phthalic anhydride.

    Comparative Example 2 1- [3- (Trimethylsilylamino) propyl] -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane was used as a raw material, and N- [3- (1,3 , 3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalimide

(Amic acid silyl ester synthesis reaction) A 100 mL four-necked flask equipped with a Dimroth reflux condenser, a stirrer, a thermometer, and a dropping funnel was purged with nitrogen. 1.48 g (10 mmol) of phthalic anhydride was charged into the flask, and 22 g of dehydrated THF was added and dissolved. While stirring the solution at room temperature, 2.12 g (10 mmol) of 1- [3- (trimethylsilylamino) propyl] -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane was added from a dropping funnel. It was dripped in 5 hours. The reaction mixture was concentrated under reduced pressure to obtain 5.43 g of a white solid. When this solid was analyzed by MALDI-TOFMS (cobalt matrix), N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalamic acid trimethylsilyl ester I found out that The results are shown below. m / z 598 ([M + K] ⁺ ), 281

  (Imidation reaction at normal pressure) 124 mg of the obtained solid was weighed into a glass vial, and the vial was placed in an oven with the cap removed, and the temperature was further gradually raised at 80 ° C. for 1 hour while nitrogen was bubbled. And heated at 200 ° C. for 1 hour. Upon cooling, 108 mg of a white solid was obtained. From the results of EI-MS analysis, the desired N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) was obtained. Propyl] phthalimide was found to be the main product. However, the GC purity is 90.9%, and the disproportionation products N- [3- (1,3,3,5,5-pentamethylcyclotrisiloxane-1-yl) propyl] phthalimide and N- The production amounts of [3- (1,3,3,5,5,7,7,9,9-nonamethylcyclopentasiloxane-1-yl) propyl] phthalimide were 0.9% and 1.5%, respectively. there were. Furthermore, it was found by GC-MS that a straight-chain siloxane with both ends capped with a trimethylsilyl group was produced, and the production amount was 6.0%. The GPC purity was 87.3%, and a broad peak was detected on the high molecular weight side of the target product.

  (Imidation reaction under reduced pressure) 119 mg of the above solid was weighed into a glass vial, and the vial was placed in an oven with the cap removed, and the temperature was further gradually raised at 80 ° C. for 1 hour while reducing the pressure to 3.0 kPa. And heated at 130 ° C. for 1 hour. Upon cooling, 100 mg of a white solid was obtained. The GC purity of the desired N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] phthalimide Was 92.4%. The disproportionation products N- [3- (1,3,3,5,5-pentamethylcyclotrisiloxane-1-yl) propyl] phthalimide and N- [3- (1,3,3,5) , 5,7,7,9,9-nonamethylcyclopentasiloxane-1-yl) propyl] phthalimide were 0.7% and 1.5%, respectively. In addition, 4.0% of linear siloxane was produced. The GPC purity was 89.6%, and a broad peak was detected on the high molecular weight side of the target product.

    [Example 3] 1,5-bis (3 using 1,5-bis [3- (triisopropylsilylamino) propyl] -1,1,3,3,5,5-hexamethyltrisiloxane as a raw material -Phthalimidopropyl) -1,1,3,3,5,5-hexamethyltrisiloxane synthesis (wherein i-Pr represents an isopropyl group)

  (Amic acid silyl ester synthesis reaction) A 100 mL four-necked flask equipped with a Dimroth reflux condenser, a stirrer, and a thermometer was purged with nitrogen. 296 mg (2.0 mmol) of phthalic anhydride was charged into the flask, and 8.38 g of dehydrated diethylene glycol dimethyl ether was added and dissolved. While the solution was stirred at room temperature, 635 mg (1.0 mmol) of 1,5-bis [3- (triisopropylsilylamino) propyl] -1,1,3,3,5,5-hexamethyltrisiloxane was added. After stirring for 3 hours at room temperature, it was confirmed by GC analysis that the raw material had disappeared. A small amount of the reaction mixture was collected, concentrated, and analyzed by MALDI-TOFMS. N, N′-bis [2- (triisopropylsiloxycarbonyl) benzoyl] -1,5-bis (aminopropyl) -1,1,3, It was found that 3,5,5-hexamethyltrisiloxane was produced in quantitative yield. The analysis results are shown below.

MALDI-TOFMS: m / z 970.5 (M + K ⁺ ), 954.4 (M + Na ⁺ ), 568.6;

  (Imidation reaction under normal pressure) 1.50 g of the above reaction mixture was concentrated under reduced pressure on a stainless steel petri dish, then placed in an oven, and heated at 240 ° C. for 0.5 hour while introducing nitrogen. Upon cooling, 88.8 mg of a yellow solid was obtained. From the results of EI-MS and FT-IR analysis, the desired 1,5-bis (3-phthalimidopropyl) -1,1,3,3,5,5- It was found to be hexamethyltrisiloxane. The GC purity was 94.6%, the GPC purity was 87.1%, and the yield was 94.6% based on phthalic anhydride. The analysis results are shown below.

EI-MS: m / z 567 ([M-Me] ⁺ ), 394, 246, 130

    [Comparative Example 3] 1,5-bis (3-phthalimidopropyl)-starting from 1,5-bis (3-aminopropyl) -1,1,3,3,5,5-hexamethyltrisiloxane Synthesis of 1,1,3,3,5,5-hexamethyltrisiloxane

  (Amic acid synthesis reaction) A 100 mL four-necked flask equipped with a Dimroth reflux condenser, a stirrer, and a thermometer was purged with nitrogen. 296 mg (2.0 mmol) of phthalic anhydride was charged into the flask, and 5.57 g of dehydrated diethylene glycol dimethyl ether was added and dissolved. While stirring the solution at room temperature, 323 mg (1.0 mmol) of 1,5-bis (3-aminopropyl) -1,1,3,3,5,5-hexamethyltrisiloxane was added. A white precipitate was formed, but when it was stirred at room temperature for 3 hours, it became a colorless solution, and it was confirmed by GC analysis that the raw material had disappeared. A small amount of the reaction mixture was collected, concentrated, and analyzed by MALDI-TOFMS. N, N′-bis (2-carboxybenzoyl) -1,5-bis (aminopropyl) -1,1,3,3,5,5 -It was found that hexamethyltrisiloxane was produced in quantitative yield. The analysis results are shown below.

MALDI-TOFMS: m / z 658.2 (M + K ⁺ ), 641.7 (M + Na ⁺ )

  (Imidation reaction at normal pressure) 1.20 g of the above reaction mixture was concentrated under reduced pressure on a stainless steel petri dish, then placed in an oven, and heated at 240 ° C. for 0.5 hours while ventilating with nitrogen. Upon cooling, 106 mg of a pale yellow oily substance was obtained. From the result of GC-MS analysis, the desired 1,5-bis (3-phthalimidopropyl) -1,1,3,3,5,5-hexamethyltrisiloxane was obtained. However, the GC purity was 75.9% and the GPC purity was 64.6%, and 1,3-bis (3-phthalimidopropyl) -1,1,3,3-as a by-product. Low purity because tetramethyldisiloxane and 1,7-bis (3-phthalimidopropyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane are produced in large quantities. . The yield was 93.8% based on phthalic anhydride.

    [Comparative Example 4] 1,5-bis (3-phthalimide using 1,5-bis [3- (trimethylsilylamino) propyl] -1,1,3,3,5,5-hexamethyltrisiloxane as a raw material Propyl) -1,1,3,3,5,5-hexamethyltrisiloxane (wherein Me represents a methyl group)

  (Amic acid synthesis reaction) A 100 mL four-necked flask equipped with a Dimroth reflux condenser, a stirrer, and a thermometer was purged with nitrogen. 296 mg (2.0 mmol) of phthalic anhydride was charged into the flask, and 6.87 g of dehydrated diethylene glycol dimethyl ether was added and dissolved. While stirring the solution at room temperature, 467 mg (1.0 mmol) of 1,5-bis [3- (trimethylsilylamino) propyl] -1,1,3,3,5,5-hexamethyltrisiloxane was added. When stirred at room temperature for 3 hours, a colorless solution was obtained, and the raw material disappeared, and N, N′-bis [(2-trimethylsiloxycarbonyl) benzoyl] -1,5-bis (aminopropyl) -1,1,3,3 5,5-Hexamethyltrisiloxane was produced in quantitative yield.

  (Imidation reaction at normal pressure) 1.40 g of the above reaction mixture was concentrated under reduced pressure on a stainless steel petri dish, then placed in an oven, and heated at 240 ° C. for 0.5 hours while ventilating nitrogen. Upon cooling, 94.2 mg of a pale yellow oily substance was obtained. From the result of analysis by GC-MS, the desired 1,5-bis (3-phthalimidopropyl) -1,1,3,3,5,5-hexamethyl was obtained. Although it was found that trisiloxane was produced, the GC purity was 78.0%, the GPC purity was 67.0%, and 1,3-bis (3-phthalimidopropyl) -1,1 as a by-product. , 3,3-tetramethyldisiloxane and 1,7-bis (3-phthalimidopropyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane are produced in large quantities. It was low purity. The yield was 88.1% based on phthalic anhydride.

Example 4 1- [3- (Triisopropylsilylamino) propyl] dimethylsiloxy-3,5,7,9,11,13,15-heptakis (trimethylsiloxy) pentacyclo [9.5.1.1 ^{3 , 9} . 1 ^5,15 . 1, ¹³ ] octasiloxane as a raw material, 1- (3-phthalimidopropyl) dimethylsiloxy-3,5,7,9,11,13,15-heptakis (trimethylsiloxy) pentacyclo [9.5.1. 1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] Synthesis of ^octasiloxane (wherein i-Pr represents an isopropyl group and Me represents a methyl group)

(Amic acid silyl ester synthesis reaction) A 50 mL four-necked flask equipped with a Dimroth reflux condenser, a stirrer, and a thermometer was purged with nitrogen. 1- [3- (Triisopropylsilylamino) propyl] dimethylsiloxy-3,5,7,9,11,13,15-heptakis (trimethylsiloxy) pentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13] was charged octasiloxane 266mg of (0.20 mmol) into a flask, and dissolved by adding dehydrated THF2.66G. When 29.6 mg (0.20 mmol) of phthalic anhydride was added and stirred for 24 hours at room temperature, it was confirmed by GC analysis that the raw material had disappeared. A small amount of the reaction mixture was collected, concentrated, and analyzed by MALDI-TOFMS. N- [2- (Triisopropylsiloxycarbonyl) benzoyl] -1- (3-aminopropyl) dimethylsiloxy-3,5,7,9,11 , 13,15-heptakis (trimethylsiloxy) pentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . It was found that [ ^1,7,13 ] octasiloxane was produced in quantitative yield. The analysis results are shown below.

MALDI-TOFMS: m / z 1500.1 (M + Na ⁺ ), 1461.7

(Imidation reaction under normal pressure) 0.50 g of the above reaction mixture was concentrated under reduced pressure on a stainless steel petri dish, then placed in an oven, and heated at 240 ° C. for 0.5 hours while ventilating with nitrogen. Upon cooling, 40.0 mg of a white solid was obtained. From the analysis results of MALDI-TOFMS and FT-IR, the desired 1- (3-phthalimidopropyl) dimethylsiloxy-3,5,7,9,11,13,15- Heptakis (trimethylsiloxy) pentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] found to be ^octasiloxane . The GC purity was 96.2%, the GPC purity was 92.8%, and the yield was 80.1% based on phthalic anhydride. The analysis results are shown below.

MALDI-TOFMS: m / z 1326.1 (M + Na +), 1287.0

Claims (8)

A triorganosilylamino group-containing organosiloxane represented by the following general formula (2) in which a triorganosilyl group represented by the following general formula (1) is bonded to a nitrogen atom, and the following general formula (3) By reacting with a dicarboxylic acid anhydride, an amic acid triorganosilyl ester represented by the following general formula (4) was obtained, and then the amidic acid triorganosilyl ester was removed by a detriorganosilanol reaction. The manufacturing method of the imide which the organosiloxane represented by the following general formula (5) couple | bonded characterized by making it combine.

(In the formula, R ¹ is a monovalent hydrocarbon group having 2 to 20 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, and A ¹ is a substitution having 1 to 20 carbon atoms. Or an unsubstituted divalent organic group, A ² represents a substituted or unsubstituted divalent organic group having 2 to 40 carbon atoms, and Sx is a monovalent or polyvalent organo group having 2 to 2,000 silicon atoms. Represents a siloxanyl group, α represents the valence of the organosiloxanyl group, and is an integer of 1 to 100.)   In the general formulas (2), (4), and (5), Sx is selected from a chain-like, cyclic, cage-like, or partially cleaved cage-like monovalent or polyvalent organosiloxanyl group. A method for producing an imide bonded with an organosiloxane as described in 1. In the general formulas (2), (4), and (5), Sx is a monovalent or polyvalent cyclic organosiloxanyl group represented by the following general formula (6), the following general formulas (7) and (9 ) Represented by a monovalent or polyvalent chain organosiloxanyl group, a monovalent or polyvalent caged organosiloxanyl group represented by the following general formula (11), and the following general formula (12) The method for producing an imide bonded with an organosiloxane according to claim 2, which is selected from partially cleaved monovalent or polyvalent cage-like organosiloxanyl groups represented by the formula:

(In the formula, Rs may be the same or different and each represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom; a represents the valence of an organosiloxanyl group; (The integer of 1-10, b represents the integer of 0-10.)

(In the formula, Rs may be the same or different and each represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and R ^x is a substituted or unsubstituted group having 1 to 20 carbon atoms. Represents a monovalent hydrocarbon group or an organic group substituted with a triorganosilylamino group represented by the following general formula (8), c represents an integer of 0 to 100.)

(In the formula, R ¹ , R ² and A ¹ represent substituents having the same meaning as described in the general formulas (1) and (2)).

(Wherein R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom; R ^x may be the same or different; Represents a substituted or unsubstituted monovalent hydrocarbon group of ˜20 or an organic group substituted with a triorganosilylamino group represented by the general formula (8), wherein R ^S is a monovalent carbon atom having 1 to 20 carbon atoms. It represents a hydrogen group or a triorganosiloxy group represented by the following general formula (10): d represents the valence of the organosiloxanyl group, an integer of 1 to 100, and e represents an integer of 0 to 100. )

(In the formula, R represents a substituent having the same meaning as defined in the general formula (9).)

(In the formula, R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and R ^S is a monovalent hydrocarbon having 1 to 20 carbon atoms. Or a triorganosiloxy group represented by the general formula (10), wherein f and h are integers of 0 to 10, g is a valence of an organosiloxanyl group, an integer of 1 to 20, and i is Represents an integer of 0 to 19. However, the sum of g and i is 6 or more and 20 or less.)

(In the formula, R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom. R ^S and R ^t each independently represents 1 to 1 carbon atoms. 20 represents a monovalent hydrocarbon group or a triorganosiloxy group represented by the above general formula (10), j, l and n are integers of 0 to 10, k represents a valence of an organosiloxanyl group, An integer of 1 to 3, m is an integer of 0 to 2, and o is an integer of 2 to 16. However, the sum of k and m is 3, and when m is 2, R ^t is bonded to each other and Formula (13)

(In the formula, R may be the same or different from each other, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a fluorine atom.)
You may form group represented by these. )   The triorganosilyl group represented by the general formula (1) is selected from a triethylsilyl group, a tert-butyldimethylsilyl group, a triisobutylsilyl group, a triisopropylsilyl group, and a texyldimethylsilyl group. The manufacturing method of the imide which the organosiloxane of any one of 1-3 is couple | bonded. The general formula (2) A ¹ in is attached at the nitrogen atom and sp ³ carbon, the production method of the imide bound organosiloxane according to any one of claims 1 to 4. An amic acid triorganosilyl ester to which an organosiloxane represented by the following general formula (4) is bonded.

(In the formula, R ¹ is a monovalent hydrocarbon group having 2 to 20 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, and A ¹ is a substitution having 1 to 20 carbon atoms. Or an unsubstituted divalent organic group, A ² represents a substituted or unsubstituted divalent organic group having 2 to 40 carbon atoms, and Sx is a monovalent or polyvalent organo group having 2 to 2,000 silicon atoms. Represents a siloxanyl group, α represents the valence of the organosiloxanyl group, and is an integer of 1 to 100.) A triorganosilylamino group-containing organosiloxane represented by the following general formula (2) in which a triorganosilyl group represented by the following general formula (1) is bonded to a nitrogen atom, and the following general formula (3) A method for producing an amic acid triorganosilyl ester bonded with an organosiloxane represented by the following general formula (4), wherein the dicarboxylic acid anhydride is reacted.

(In the formula, R ¹ is a monovalent hydrocarbon group having 2 to 20 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, and A ¹ is a substitution having 1 to 20 carbon atoms. Or an unsubstituted divalent organic group, A ² represents a substituted or unsubstituted divalent organic group having 2 to 40 carbon atoms, and Sx is a monovalent or polyvalent organo group having 2 to 2,000 silicon atoms. Represents a siloxanyl group, α represents the valence of the organosiloxanyl group, and is an integer of 1 to 100.) Production of an imide bonded with an organosiloxane represented by the following general formula (5), characterized in that the triorganosilyl ester of amic acid represented by the following general formula (4) is ring-closing imidized by a detriorganosilanol reaction Method.

(In the formula, R ¹ is a monovalent hydrocarbon group having 2 to 20 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, and A ¹ is a substitution having 1 to 20 carbon atoms. Or an unsubstituted divalent organic group, A ² represents a substituted or unsubstituted divalent organic group having 2 to 40 carbon atoms, and Sx is a monovalent or polyvalent organo group having 2 to 2,000 silicon atoms. Represents a siloxanyl group, α represents the valence of the organosiloxanyl group, and is an integer of 1 to 100.)