Organopolysiloxane having tertiary amino group in molecular chain and method for producing same

Abstract

The purpose of the present invention is to provide an intermediate compound for providing a silicone macromonomer in which a (meth) acrylic group is introduced at a high ratio at both ends and a quaternary ammonium cation site is contained in the molecular chain. Specifically disclosed is an organopolysiloxane which is represented by general formula (1) and has a tertiary amino group in the molecular chain. (In general formula (1), each R independently represents a group selected from the group consisting of an alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms, and an aralkyl group having 7-10 carbon atoms, each R1 independently represents a group selected from the group consisting of an alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms, and an aralkyl group having 7-10 carbon atoms, and each R2 represents a group selected from the group consisting of an alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms, and an aralkyl group having 7-10 carbon atoms. Q1 and Q2 are each independently a hydrogen atom or a group represented by formula (2) (where at least one of Q1 and Q2 is a hydrogen atom, a is an integer of 1-400, and b is an integer of 1-50) (in formula (2), R1 is a group selected from the group consisting of an alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms, and an aralkyl group having 7-10 carbon atoms).

Description

Technical Field

[0001] This invention relates to organopolysiloxanes having tertiary amino groups in their molecular chains and methods for their manufacture. Background Technology

[0002] Silicone is widely used as a contact lens material due to its high oxygen permeability. However, silicone is hydrophobic, therefore, the introduction of hydrophilic groups has been studied to make the surface of contact lenses hydrophilic. Among these studies, the introduction of quaternary ammonium cation sites into the silicone chain has been reported (Patent Documents 1-4). In particular, Patent Document 1 describes a method for synthesizing a silicone macromonomer having polymerizable groups at both ends and quaternary ammonium cation sites in the molecular chain. Existing technical documents Patent documents

[0003] Patent Document 1: Japanese Patent Publication No. 2009-542855 Patent Document 2: Japanese Patent Publication No. 2009-533532 Patent Document 3: Japanese Patent Publication No. 2010-516873 Patent Document 4: Japanese Patent Publication No. 2009-521547 Summary of the Invention The problem the invention aims to solve

[0004] However, the manufacturing method described in Patent Document 1 presumably contains a certain amount of silicone without polymerizable groups as an impurity. Generally, it is not preferable to contain a large amount of compounds without polymerizable groups in silicone used as contact lens materials. Therefore, it is desirable to establish a method for manufacturing silicone macromonomers containing quaternary ammonium cation sites in the molecular chain that can introduce (meth)acrylate groups in a high proportion at both ends.

[0005] The purpose of this invention is to provide an organopolysiloxane, which is an intermediate compound for providing a silicone macromonomer with (meth)acrylic acid groups introduced in a high proportion at both ends and containing quaternary ammonium cation sites in the molecular chain. Solution for solving the problem

[0006] To achieve the aforementioned objectives, the inventors of this invention conducted intensive research and discovered a method for manufacturing a silicone macromonomer with quaternary ammonium cation sites in its molecular chain, incorporating (meth)acrylic acid groups in a high proportion at both ends. The inventors of this invention also synthesized a novel organopolysiloxane containing a tertiary amino group, which is used as an intermediate compound in this manufacturing method, thus completing this invention.

[0007] That is, the present invention provides an organopolysiloxane having a tertiary amino group in the molecular chain, represented by the following general formula (1). [Chemical Formula 1] (In general formula (1), R is a group independently selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms.) 1 The groups selected independently from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms, Q 1 and Q 2 Each of the atoms is a hydrogen atom or a group represented by the following formula (2), wherein Q is a hydrogen atom or a group represented by the following formula (2). 1 and Q 2 At least one of them is a hydrogen atom, where a is an integer from 1 to 400 and b is an integer from 1 to 50. [Chemical Formula 2] (In equation (2), R) 1 It is a group selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms.

[0008] Preferably, the organopolysiloxane also has the constituent elements shown in [1] or [2] below. [1] The organopolysiloxane, in the above general formula (1), Q 1 and Q 2 All are hydrogen atoms. [2] The organopolysiloxane, in the above general formula (1), Q 1 and Q 2 One of them is a hydrogen atom, Q 1 and Q 2 The other party is the group represented by the above formula (2).

[0009] The present invention also provides a method for manufacturing an organopolysiloxane having a tertiary amino group in its molecular chain, characterized in that the organopolysiloxane is represented by the following general formula (1): [Chemical Formula 3] (In general formula (1), R is a group independently selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms.) 1The groups selected independently from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms, Q 1 and Q 2 Each of the atoms is a hydrogen atom or a group represented by the following formula (2), wherein Q is a hydrogen atom or a group represented by the following formula (2). 1 and Q 2 At least one of them is a hydrogen atom, where a is an integer from 1 to 400 and b is an integer from 1 to 50. [Chemical Formula 4] (In equation (2), R) 1 It is a group selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. The manufacturing method comprises: reacting (A) an organohydrogen polysiloxane represented by the following general formula (3) with two ends containing hydrogenated silanes and (B) a tertiary amine having two allyl groups represented by the following general formula (4) in the presence of a platinum catalyst to obtain an organopolysiloxane represented by the above general formula (1). [Chemical Formula 5] (In general formula (3), R and a are as described above). [Chemical Formula 6] (In general formula (4), R) 1 (As mentioned above). The present invention also provides the manufacturing method thereof, wherein the organopolysiloxane represented by the above general formula (1) has an average of 1.5 to 2 terminal hydrogenated silanes in one molecule. Invention Effects

[0010] The tertiary amino-containing organopolysiloxane of the present invention is suitable as an intermediate compound for manufacturing silicone macromonomers having quaternary ammonium cation sites in the molecular chain and having (meth)acrylate groups introduced in a high proportion at both ends. Furthermore, the manufacturing method according to the present invention enables the efficient production of this tertiary amino-containing organopolysiloxane. Moreover, the tertiary amino-containing organopolysiloxane of the present invention is useful not only as the aforementioned silicone macromonomer but also as an intermediate readily derivatized to organopolysiloxanes having various reactive functional groups. Attached Figure Description

[0011] Figure 1 shows the organopolysiloxane with tertiary amino groups in the molecular chain synthesized in Example 1. 1 H-NMR spectrum. Detailed Implementation

[0012] The present invention will now be described in detail. [Organopolysiloxanes with tertiary amino groups in their molecular chains] The organopolysiloxanes having tertiary amino groups of the present invention are represented by the following general formula (1). [Chemical Formula 7] In the above general formula (1), R is a group independently selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. 1 The groups selected independently from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms, Q 1 and Q 2 Each is a hydrogen atom or a group represented by the following formula (2), where a is an integer from 1 to 400 and b is an integer from 1 to 50. [Chemical Formula 8] In equation (2) above, R 1 It is a group selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms.

[0013] In the above general formula (1), R is a group independently selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; etc. Examples of aryl groups having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl. Examples of aralkyl groups having 7 to 10 carbon atoms include phenylmethyl and phenylethyl. R is preferably methyl or phenyl, and more preferably methyl.

[0014] In the above general formulas (1) and (2), R 1 These are groups selected independently from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, and octyl alkyl groups; cyclopentyl and cyclohexyl alkyl groups are also examples. Examples of aryl groups having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl. Examples of aralkyl groups having 7 to 10 carbon atoms include phenylmethyl and phenylethyl. In the above general formulas (1) and (2), R 1 Preferably methyl and ethyl, more preferably methyl.

[0015] In the above general formula (1), Q 1 and Q 2 They are either hydrogen atoms or groups represented by the above formula (2) and are independent of each other.

[0016] In the above general formula (1), a is an integer from 1 to 400, preferably an integer from 1 to 100, and more preferably an integer from 5 to 50. b is an integer from 1 to 50, preferably an integer from 1 to 30, and more preferably an integer from 1 to 10.

[0017] [A method for manufacturing organopolysiloxanes containing tertiary amino groups in their molecular chains] The following details the method for manufacturing organopolysiloxanes with tertiary amino groups in the molecular chain, represented by the above general formula (1). The manufacturing method is characterized by comprising the step of reacting (A) an organohydropolysiloxane containing hydrosilyl groups at both ends, represented by the following general formula (3), with (B) a tertiary amine having two allyl groups, represented by the following general formula (4), in the presence of a platinum catalyst to obtain a compound represented by the above general formula (1). [Chemical Formula 9] [Chemical Formula 10]

[0018] In the above general formula (3), R is a group independently selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, and octyl alkyl groups; cyclopentyl and cyclohexyl cycloalkyl groups; etc. Examples of aryl groups having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl. Examples of aralkyl groups having 7 to 10 carbon atoms include phenylmethyl and phenylethyl.

[0019] In the above general formula (4), R 1 These are groups selected independently from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, and octyl alkyl groups; cyclopentyl and cyclohexyl alkyl groups; etc. Examples of aryl groups having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl. Examples of aralkyl groups having 7 to 10 carbon atoms include phenylmethyl and phenylethyl. 1 Preferably methyl and ethyl, more preferably methyl.

[0020] In the above general formula (3), a is an integer from 1 to 400, preferably an integer from 1 to 100, and more preferably an integer from 5 to 50.

[0021] In the manufacturing method of the present invention, the above-mentioned two-terminal hydrogen-modified organopolysiloxane is used in excess equivalent relative to the tertiary amine having two allyl groups. The molar ratio of b in the above general formula (1), which is the repeating number of the silicone chain and the tertiary amino group, is determined according to the molar ratio. The mixing ratio of the organopolysiloxane relative to the molar number of the tertiary amine is preferably 1.05 to 2 times.

[0022] As the catalyst used in the manufacturing method of the present invention, a known platinum catalyst can be used. In particular, a sodium chloroplatinate bicarbonate neutralizer-vinylsiloxane complex (Karstedt's Catalyst) is preferred. The amount of catalyst is not particularly limited, as long as a catalytic amount is achieved, but preferably, it is 10 to 1,000 ppm by weight relative to the two-terminated hydrogen-modified organopolysiloxane.

[0023] In the manufacturing method of the present invention, the reaction time, solvent, and other reaction conditions are not particularly limited. The reaction time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and most preferably 1 to 6 hours. The solvent is preferably an aromatic hydrocarbon solvent such as toluene or xylene.

[0024] The organopolysiloxane represented by the above general formula (1) contains a structure with a secondary amino group at the end represented by the above formula (2). This is because, in the manufacture of the organopolysiloxane represented by the above general formula (1), the tertiary amino group at the end of the organopolysiloxane, which has undergone internal rearrangement of the double bond due to a platinum catalyst, is hydrolyzed by post-treatment after the hydrosilylation reaction as shown in the following formula. [Chemical Formula 11]

[0025] That is, Q in the above general formula (1) 1 and Q 2 Each is a hydrogen atom or a group represented by the above formula (2) independently. The organopolysiloxane of general formula (1) obtained by reacting an organohydrogen polysiloxane containing hydrogenated silyl groups at both ends, represented by the above general formula (3) with a tertiary amine having two allyl groups, represented by the above general formula (4), is more preferably as shown below. [Chemical Formula 12] Among them, Q is preferred. 1 and Q 2 At least one of them is an organopolysiloxane bonded to hydrogen atoms, more preferably Q 1 and Q 2Both are organopolysiloxanes with silicon atoms bonded to hydrogen atoms. Q 1 and Q 2 Organopolysiloxanes, which contain hydrogen atoms on both ends, can introduce (meth)acrylic acid groups in a high proportion at both ends, making them more useful intermediates in providing silicone macromonomers containing quaternary ammonium cation sites in the molecular chain.

[0026] The above general formula (1) may also be a mixture of one or more compounds selected from the above organopolysiloxanes. More preferably, it may be an organopolysiloxane that has an average of 0 to 2, preferably 1 to 2, more preferably 1.5 to 2 hydrogen atoms bonded to silicon atoms in one molecule, and has an average of 0 to 2, preferably 0 to 1, more preferably 0.5 groups represented by the above formula (2) in one molecule. Example

[0027] The following examples illustrate the present invention in more detail, but the present invention is not limited to the following examples. In the following, 1 The H-NMR measurements were performed using an ULTRASHIELD 400 PLUS (manufactured by BRUKER).

[0028] [Example 1] Manufacturing of organopolysiloxanes with tertiary amino groups in the molecular chain, represented by the above general formula (1) In a three-necked flask equipped with a thermometer, a stirring device, and a reflux condenser, 50.0 g of the substance derived from the following formula (a) is added. [Chemical Formula 13] An organohydropolysiloxane with hydrogenated silanes at both ends, a toluene solution of 0.2 g of sodium bicarbonate chloroplatinate neutralized with vinylsiloxane complex (0.5 wt% platinum content), and 17 g of toluene were heated to 70 °C. 5.3 g of diallyl methylamine was added dropwise over 30 minutes, followed by heating and stirring at 75 °C for 2 hours. After the reaction was complete, the low-boiling fraction was removed at 100 °C for 1 hour under reduced pressure of 0.2 kPa. Then, 25 g of acetonitrile and 6.3 g of water were added, stirred, washed, and allowed to stand. The silicone layer was then separated. This separation and washing operation was repeated three times. The low-boiling fraction was removed at 85 °C for 1.5 hours under reduced pressure of 0.3 kPa, yielding 25 g of the organopolysiloxane represented by formula (b) below. [Chemical Formula 14] In formula (b), A is either a hydrogen atom bonded to a silicon atom or a group represented by formula (c) below. The organopolysiloxane is a mixture of two or more compounds different from A, having an average of 1.8 hydrogen atoms bonded to a silicon atom in one molecule and an average of 0.2 groups represented by formula (c) below in one molecule. [Chemical Formula 15]

[0029] The following describes the organopolysiloxane obtained in Example 1. 1 H-NMR spectrum. 1 H-NMR (400MHz, CDCl3): δ -0.23~0.20 (m, 264H), 0.33~0.50 (m, 12.4H), 1.32~1.48 (m, 12.4H), 2.01~2.51 (m, 21.4H), 4.58~4.68 (m, 1.8H)

[0030] According to the manufacturing method of the present invention, the above-mentioned organopolysiloxanes containing tertiary amino groups can be manufactured efficiently. The organopolysiloxanes containing tertiary amino groups of the present invention are suitable as intermediate compounds for manufacturing silicone macromonomers having quaternary ammonium cation sites in the molecular chain with (meth)acrylate groups introduced in a high proportion at both ends. Furthermore, the organopolysiloxanes containing tertiary amino groups of the present invention are useful not only as the above-mentioned silicone macromonomers, but also as intermediates readily derivatized to organopolysiloxanes having various reactive functional groups.

Claims

1. An organopolysiloxane having a tertiary amino group in its molecular chain, characterized in that, It can be represented by the following general formula (1): [Chemical Formula 1] (In general formula (1), R is a group independently selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms.) 1 The groups selected independently from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms, Q 1 and Q 2 Each of the atoms is a hydrogen atom or a group represented by the following formula (2), wherein Q is a hydrogen atom or a group represented by the following formula (2). 1 and Q 2 At least one of them is a hydrogen atom, where a is an integer from 1 to 400 and b is an integer from 1 to 50. [Chemical Formula 2] (In equation (2), R) 1 It is a group selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms.

2. The organopolysiloxane according to claim 1, wherein, In the above general formula (1), Q 1 and Q 2 All are hydrogen atoms.

3. The organopolysiloxane according to claim 1, wherein, In the above general formula (1), Q 1 and Q 2 One of them is a hydrogen atom, Q 1 and Q 2 The other party is the group represented by the above formula (2).

4. A method for manufacturing an organopolysiloxane having a tertiary amino group in its molecular chain, characterized in that, The organopolysiloxane is represented by the following general formula (1): [Chemical Formula 3] (In general formula (1), R is a group independently selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms.) 1 The groups selected independently from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms, Q 1 and Q 2 Each of the atoms is a hydrogen atom or a group represented by the following formula (2), wherein Q is a hydrogen atom or a group represented by the following formula (2). 1 and Q 2 At least one of them is a hydrogen atom, where a is an integer from 1 to 400 and b is an integer from 1 to 50. [Chemical Formula 4] (In equation (2), R) 1 It is a group selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. The manufacturing method comprises: reacting (A) an organohydrogen polysiloxane represented by the following general formula (3) with two ends containing hydrogenated silanes and (B) a tertiary amine having two allyl groups represented by the following general formula (4) in the presence of a platinum catalyst to obtain an organopolysiloxane represented by the above general formula (1). [Chemical Formula 5] (In equation (3), R and a are as described above). [Chemical Formula 6] (In equation (4), R) 1 (As mentioned above).

5. The manufacturing method according to claim 4, wherein, The organopolysiloxane represented by the above general formula (1) has an average of 1.5 to 2 terminal hydrogenated silanes in one molecule.

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