Silicon compound and method for producing same
阅读说明：本技术 硅化合物及其制造方法 (Silicon compound and method for producing same ) 是由 田中彻 川守崇司 海野雅史 于 2018-05-16 设计创作，主要内容包括：本发明为具有下述通式(I)所示的结构单元的硅化合物。通式(I)中,m表示1～30的整数,n表示使得重均分子量为5,000～1,000,000的数字,R<Sup>1</Sup>～R<Sup>4</Sup>各自独立地表示碳数为1～8的烷基或碳数为6～14的芳基,R<Sup>5</Sup>及R<Sup>6</Sup>各自独立地表示碳数为1～8的烷基或碳数为6～14的芳基,R<Sup>7</Sup>～R<Sup>10</Sup>各自独立地表示碳数为1～8的烷基或碳数为6～14的芳基,n个结构单元中,m、R<Sup>1</Sup>～R<Sup>10</Sup>的组合可以全部相同,也可以一部分或全部不同。<Image he="176" wi="700" file="DDA0002280295200000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention is a silicon compound having a structural unit represented by the following general formula (I). In the general formula (I), m represents an integer of 1-30, n represents a number for making the weight average molecular weight 5,000-1,000,000, R 1 ～R 4 Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R 5 And R 6 Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R 7 ～R 10 Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and m and R are represented by n structural units 1 ～R 10 In combination with (1)They may be all the same or may be partially or entirely different.)
1. A silicon compound having a structural unit represented by the following general formula (I),
[ chemical formula No. 1]
In the general formula (I),
m represents an integer of 1 to 30,
n represents a number such that the weight average molecular weight is 5,000 to 1,000,000,
R1～R4each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R5and R6Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R7～R10each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
m, R in n structural units1～R10All of the combinations of (A) and (B) may be the same or may be partially or completely different.
2. A method for producing a silicon compound having a structural unit represented by the following general formula (I), which comprises a step of producing the compound using a compound represented by the following general formula (II),
[ chemical formula No. 2]
In the general formula (I),
m represents an integer of 1 to 30,
n represents a number such that the weight average molecular weight is 5,000 to 1,000,000,
R1～R4each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R5and R6Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R7～R10each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
m, R in n structural units1～R10All of the combinations of (A) and (B) may be the same or partially or totally different;
[ chemical formula No. 3]
In the general formula (II),
R1～R4each independently represents an alkyl group having 1 to 8 carbon atoms orAn aryl group having 6 to 14 carbon atoms,
R5and R6Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
3. The method for producing a silicon compound according to claim 2, comprising a step of producing the compound represented by the following general formula (III),
[ chemical formula No. 4]
In the general formula (III),
m represents an integer of 1 to 30,
R7～R10each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
Technical Field
One embodiment of the present invention relates to a silicon compound and a method for producing the same.
Background
As a compound obtained by hydrolyzing and condensing an organosilicon compound having 3 hydrolyzable groups, (RSiO)1.5)nThe silsesquioxanes are shown. Since it has a chemical structure which can be also called an intermediate between silicone resin and glass and is excellent in heat resistance, transparency, weather resistance and the like, it has attracted attention as an optical, semiconductor or electronic material, and many studies have been reported.
As the silsesquioxane, a random structure without a specific structure, a double layer (double decker) structure, a ladder structure, or a cage structure, which can define a structure, is known. Although any structure has excellent characteristics, a ladder type or a cage type, which can specify a structure, is excellent from the viewpoint of precise material design and characteristic expression.
However, these silsesquioxanes have a strong cohesive property, and cause phase separation when mixed for modifying a conventional resin, and thus desired characteristics may not be obtained. Therefore, a method of introducing silsesquioxane into the main chain of a polymer to suppress aggregation has been developed. For example,
Disclosure of Invention
Technical problem to be solved by the invention
According to one embodiment of the present invention, it is an object to provide a polymer having a ladder-type silsesquioxane introduced into a main chain, which has a silicon number as small as 6, is low in cost, and has excellent heat resistance, as compared with a conventional silsesquioxane having a polyhedral structure.
Means for solving the problems
Specific means for achieving the above object are as follows.
[1] A silicon compound having a structural unit represented by the following general formula (I).
[ chemical formula No. 1]
[ in the general formula (I), m represents an integer of 1-30, n represents a number for making the weight average molecular weight 5,000-1,000,000, R1～R4Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R5And R6Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R7～R10Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and m and R are represented by n structural units1～R10All of the combinations of (A) and (B) may be the same or may be partially or completely different.]
[2] A method for producing a silicon compound having a structural unit represented by the following general formula (I), which comprises a step of producing the compound using a compound represented by the following general formula (II).
[ chemical formula No. 2]
[ in the general formula (I), m represents an integer of 1-30, n represents a number such that the weight average molecular weight is 5A number of 000 to 1,000,000, R1～R4Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R5And R6Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R7～R10Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and m and R are represented by n structural units1～R10All of the combinations of (A) and (B) may be the same or may be partially or completely different.]
[ chemical formula No. 3]
[ in the general formula (II), R1～R4Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R5And R6Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.]
[3] The method for producing a silicon compound according to [2], which comprises a step of producing the compound by using a compound represented by the following general formula (III).
[ chemical formula No. 4]
[ in the general formula (III), m represents an integer of 1 to 30, R7～R10Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.]
Effects of the invention
According to one embodiment of the present invention, a polymer having a ladder-type silsesquioxane introduced into a main chain, which is low in cost and excellent in heat resistance, can be provided.
Drawings
FIG. 1 shows 3 geometrical isomers of a compound represented by the general formula (Z)1H NMR spectrum.
FIG. 2 shows 3 geometrical isomers of the compound represented by the general formula (Z)13C NMR spectrum.
FIG. 3 shows 3 geometrical isomers of a compound represented by the general formula (Z)13C NMR spectrum enlargement.
FIG. 4 shows 3 geometrical isomers of the compound represented by the general formula (Z)29Si NMR spectrum.
Detailed Description
An embodiment of the present invention will be described below, but the present invention is not limited to the following example.
"silicon compound"
One embodiment of the silicon compound is characterized by having a structural unit represented by the following general formula (I).
[ chemical formula No. 5]
In the general formula (I), m represents an integer of 1-30, n represents a number for making the weight average molecular weight 5,000-1,000,000, R1～R4Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R5And R6Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R7～R10Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and m and R are represented by n structural units1～R10All of the combinations of (A) and (B) may be the same or may be partially or completely different.
In the general formula (I), R1、R2、R3And R4Each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
R1～R4The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and may have a linear chain or a branched chain, or may be acyclic or cyclic.
R1～R4The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 8 carbon atoms. Within this carbon number range, the aryl group may further have an alkane having a straight chain or a branched chain bonded to at least 1 carbon atom forming a carbocyclic ringAnd (4) a base.
As R1～R4Examples of the alkyl group include methyl, ethyl, isobutyl, cyclohexyl, isooctyl, phenyl, and alkyl-substituted phenyl, and the alkyl group is preferably an unsubstituted or substituted phenyl group having 6 to 8 carbon atoms.
In the general formula (I), R5And R6Each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
R5And R6The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and may have a linear chain or a branched chain, or may be acyclic or cyclic.
R5And R6The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 8 carbon atoms. Within this carbon number range, the aryl group may also have a linear or branched alkyl group bonded to at least 1 carbon atom forming a carbocyclic ring.
As R5And R6Examples of the alkyl group include methyl, ethyl, isobutyl, cyclohexyl, isooctyl, phenyl, and alkyl-substituted phenyl, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms or an unsubstituted or substituted phenyl group having 6 to 8 carbon atoms.
In the general formula (I), R7、R8、R9And R10Each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
R7～R10The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and may have a linear chain or a branched chain, or may be acyclic or cyclic.
R7～R10The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 8 carbon atoms. Within this carbon number range, the aryl group may also have a linear or branched alkyl group bonded to at least 1 carbon atom forming a carbocyclic ring.
As R7～R10Examples thereof include, independently of one another, methyl, ethyl, isobutyl, cyclohexyl, isooctyl, phenyl, alkyl-substituted phenyl and the like, preferably an alkyl group having 1 to 4 carbon atoms,Unsubstituted or substituted phenyl having 6 to 8 carbon atoms.
n is preferably a number such that the weight average molecular weight is 5,000 to 1,000,000.
When n is small and the weight average molecular weight is less than 5,000, the temperature is reduced by 5% thermogravimetry, and it is difficult to obtain heat resistance exceeding 400 ℃. When the weight average molecular weight exceeds 1,000,000, the compatibility is lowered, and it is difficult to use the composition as a raw material of the composition. From the viewpoint of heat resistance and compatibility, n is more preferably a number such that the weight average molecular weight is 3,000 to 500,000, and still more preferably a number such that the weight average molecular weight is 4,000 to 100,000.
m is preferably an integer of 1 to 30.
The siloxane backbone linking the ladder silsesquioxanes acts as a soft segment and moves vigorously at high temperatures. On the other hand, ladder-type silsesquioxanes have strong cohesive properties, and a cohesive force acts between molecules or within molecules. Therefore, it is considered that the polymer of one embodiment has improved heat resistance by allowing the polymer main chain in which the ladder-type silsesquioxane is linked by the soft segment to move in a specific molecular chain at high temperature. However, when m exceeds 30, the influence of the ladder-type silsesquioxane on the siloxane main chain becomes small, and therefore the effect of heat resistance is remarkably reduced. The specific molecular chain movement for improving heat resistance is more preferably 1 to 25 m, and still more preferably 1 to 20 m.
R between the structural units in the n structural units of the general formula (I)1～R10All of combinations of (2) and (m) may be the same, or some or all of them may be different.
Process for producing silicon compound "
An example of a method for producing a silicon compound having a structural unit represented by the general formula (I) will be described below. The silicon compound having a structural unit represented by the general formula (I) is not limited to the compound produced by the following production method.
The method for producing a silicon compound having a structural unit represented by the general formula (I) preferably includes a step of producing the compound using a compound represented by the following general formula (II). Further, it is preferable to include a step of producing the compound represented by the following general formula (III). More preferably, the method comprises a step of reacting the compound represented by the general formula (II) with the compound represented by the general formula (III).
[ chemical formula No. 6]
In the general formula (II), R1～R4Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, R5And R6Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
In the general formula (II), R1～R4Each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
R1～R4The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and may have a linear chain or a branched chain, or may be acyclic or cyclic.
R1～R4The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 8 carbon atoms. Within this carbon number range, the aryl group may also have a linear or branched alkyl group bonded to at least 1 carbon atom forming a carbocyclic ring.
As R1～R4Examples of the alkyl group include methyl, ethyl, isobutyl, cyclohexyl, isooctyl, phenyl, and alkyl-substituted phenyl, and the alkyl group is preferably an unsubstituted or substituted phenyl group having 6 to 8 carbon atoms.
In the general formula (II), R5And R6Each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
R5And R6The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and may have a linear chain or a branched chain, or may be acyclic or cyclic.
R5And R6The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 8 carbon atoms. Within this carbon number range, the aryl group may further haveSo that an alkyl group having a straight chain or a branched chain is bonded to at least 1 carbon atom forming the carbocyclic ring.
As R5And R6Examples of the alkyl group include methyl, ethyl, isobutyl, cyclohexyl, isooctyl, phenyl, and alkyl-substituted phenyl, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms or an unsubstituted or substituted phenyl group having 6 to 8 carbon atoms.
In the method for producing a silicon compound having a structural unit represented by the general formula (I), the compound represented by the general formula (II) may be obtained from the above-mentioned R1～R6At least 1 compound or 2 or more compounds are used in combination.
[ chemical formula No. 7]
In the general formula (III), m represents an integer of 1 to 30, R7～R10Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
In the general formula (III), R7～R10Each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.
R7～R10The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and may have a linear chain or a branched chain, or may be acyclic or cyclic.
R7～R10The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 8 carbon atoms. Within this carbon number range, the aryl group may also have a linear or branched alkyl group bonded to at least 1 carbon atom forming a carbocyclic ring.
As R7～R10Examples of the alkyl group include methyl, ethyl, isobutyl, cyclohexyl, isooctyl, phenyl, and alkyl-substituted phenyl, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms or an unsubstituted or alkyl-substituted phenyl group having 6 to 8 carbon atoms.
m is preferably an integer of 1 to 30. In order to exert a specific molecular chain motion for improving heat resistance, m is more preferably 1 to 25, and m is further preferably 1 to 20.
In the method for producing a silicon compound having a structural unit represented by the general formula (I), the compound represented by the general formula (III) may be obtained from the above-mentioned R7～R10And m is used in combination with at least 1 or 2 or more compounds.
When a silicon compound having a structural unit represented by the general formula (I) is produced using at least one of the compound represented by the general formula (II) and the compound represented by the general formula (III), the reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and specific examples thereof include toluene, ethylbenzene, xylene, hexane, heptane, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl acetate, and isobutyl acetate.
When a silicon compound having a structural unit represented by the general formula (I) is produced using at least one of the compound represented by the general formula (II) and the compound represented by the general formula (III), a platinum-based catalyst is preferably used. Examples of the platinum-based catalyst include chloroplatinic acid, catalysts of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalyst), platinum-divinyltetramethylsiloxane complexes (Karstedt catalyst), platinum-cyclovinylmethylsiloxane complexes, platinum-octanal complexes, and Pt [ P (C) which is a platinum-phosphine complex6H5)3]4、PtCl[P(C6H5)3]3、Pt[P(C4H9)3]4Pt [ P (OC) as platinum-phosphite complex6H5)3]4、Pt(OC4H9)3]4And dicarbonyldichloroplatinum.
The compounds of the general formula (II) have geometric isomers. Specifically, there are a case where the vinyl groups are located at positions facing inward, a case where the vinyl groups are located at positions facing outward, and a case where one of the vinyl groups is located at a position facing inward and the remaining vinyl groups are located at a position facing outward. For example, R in the formula (II)1～R4Is phenyl (C)6H5)、R5、R6Is methyl (CH)3) In this case, the following 3 geometric isomers are considered. In the method for producing a silicon compound having a structural unit represented by the general formula (I), the compound represented by the general formula (II) may be used alone or in combination of 2 or 3 kinds of these isomers.
[ chemical formula No. 8]
"Process for producing Compound represented by the general formula (II)"
An example of the method for producing the compound represented by the general formula (II) will be described below. The compound represented by the general formula (II) is not limited to the compound produced by the following production method.
In the production of the compound represented by the general formula (II), for example, at least one of the compound represented by the following general formula (IV) and the compound represented by the following general formula (V) can be used.
[ chemical formula No. 9]
In the general formula (IV), R1～R4Each independently represents an alkyl group or an aryl group.
In the general formula (V), R1～R4Each independently represents an alkyl group or an aryl group, X represents a 1-valent metal element, and 4X's may be the same or partially or completely different.
In the general formula (IV) and the general formula (V), R1～R4Is as R in the compound of formula (II)1～R4The introduced group is as described in the above general formula (II) in detail.
In the general formula (V), X represents a 1-valent metal element, preferably a metal element selected from Li, Na and Ka, and 4X's may be the same or partially or completely different.
In the compound represented by the general formula (V), the OX groups are preferably oriented in the same direction with respect to the siloxane ring, as described in Angewandt Chemie International Edition, (2016), (55, 9336) to 9339, for example. The OH groups of the compounds of the formula (IV) are likewise preferably in the same direction. This is for producing the compound represented by the general formula (II) by allowing a silicon compound represented by the following general formula (VI) to act on these compounds.
[ chemical formula No. 10]
In the general formula (VI), R5And R6Each independently represents an alkyl group or an aryl group.
In the general formula (VI), R5And R6Is as R in the compound of formula (II)5And R6The introduced group is as described in the above general formula (II) in detail.
At least 1 of the compound represented by the general formula (IV) and the compound represented by the general formula (V) is reacted with the compound represented by the general formula (VI) preferably in the presence of a base such as triethylamine in a solvent. The solvent to be used is not particularly limited, and specific examples thereof include toluene, ethylbenzene, xylene, hexane, heptane, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl acetate, and isobutyl acetate.
The compound represented by the general formula (IV) and the compound represented by the general formula (V) can be obtained by hydrolyzing and condensing an organic silane compound having 3 hydrolyzable groups.
For example, the compound represented by the general formula (V) can be obtained by reacting an organosilane compound having 3 hydrolyzable groups with a base represented by x (oh). Here, X represents a 1-valent metal element. Further, the compound represented by the general formula (VI) can be obtained by reacting the compound represented by the general formula (V) with an acid such as hydrochloric acid.
As an example, the compound represented by the general formula (V) can be produced using a compound represented by the following general formula (VII).
[ chemical formula No. 11]
In the general formula (VII), R1～R4Each independently represents an alkyl or aryl group, R11Represents an alkyl group.
In the general formula (VII), R1～R4As R in formula (V)1～R4And is introduced further as R in the compound represented by the general formula (II)1～R4The introduced group is as described in the above general formula (II) in detail.
In the general formula (VII), R11Preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl and isobutyl.
When producing the compound represented by the general formula (V) from the compound represented by the general formula (VII), a base may be used in order to accelerate the reaction. The base is not particularly limited, and a basic compound represented by x (oh) can be used, and specific examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like.
The compound represented by the general formula (V) is preferably obtained by reacting a compound represented by the general formula (VII) in a solvent in the presence of water and a base. The solvent to be used is not particularly limited, and specific examples thereof include toluene, ethylbenzene, xylene, hexane, heptane, 2-propanol, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl acetate, and isobutyl acetate.
The compound represented by the general formula (IV) is preferably obtained by reacting a compound represented by the general formula (V) in a solvent in the presence of water and an acid. The compound represented by the general formula (IV) is easily dissolved in a solvent, and the solvent used is not particularly limited, and specific examples thereof include toluene, ethylbenzene, xylene, hexane, heptane, 2-propanol, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl acetate, and isobutyl acetate.