Organopolysiloxane having tertiary amino group in molecular chain, and production method of the same

Abstract

To provide an organopolysiloxane which is an intermediate compound for providing a silicone macromer introduced with (meth)acrylic groups to both terminals in a high rate, and including a quaternary ammonium cation part in a molecular chain.SOLUTION: There is provided an organopolysiloxane having a tertiary amino group in a molecular chain, which is expressed by the following general formula (1). In the general formula (1), R is mutually independently a group selected from the group consisting of a 1-10C alkyl group, a 6-10C aryl group, and a 7-10C aralkyl group, R1 is mutually independently a group selected from the group consisting of a 1-10C alkyl group, a 6-10C aryl group, and a 7-10C aralkyl group, Q1 and Q2 are each mutually independently a group including a hydrogen atom or a specific amino group provided that 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.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an organopolysiloxane having a tertiary amino group in the molecular chain and a method for producing the same. [Background technology]

[0002] Silicone is widely used as a contact lens material due to its high oxygen permeability. However, since silicone is hydrophobic, the introduction of hydrophilic groups has been studied to hydrophilize the contact lens surface. Among them, the introduction of quaternary ammonium cation moieties into silicone chains has been reported (Patent Documents 1 to 4). In particular, Patent Document 1 describes a method for synthesizing a silicone macromer having polymerizable groups at both ends and a quaternary ammonium cation moiety in the molecular chain. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2009-542855 [Patent Document 2] Special Publication No. 2009-533532 [Patent Document 3] Special Publication No. 2010-516873 [Patent Document 4] Special Publication No. 2009-521547 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it is presumed that the manufacturing method described in Patent Document 1 contains a certain amount of silicone without polymerizable groups as an impurity. It is generally not preferable for silicones used as contact lens materials to contain a large amount of compounds without polymerizable groups. Therefore, it is desirable to establish a manufacturing method for silicone macromers that contain quaternary ammonium cation moieties in the molecular chain and that can introduce a high proportion of (meth)acrylic groups to both ends.

[0005] An object of the present invention is to provide an organopolysiloxane that is an intermediate compound for providing a silicone macromer having a high proportion of (meth)acrylic groups at both ends and containing a quaternary ammonium cation moiety in the molecular chain. [Means for solving the problem]

[0006] As a result of intensive research conducted by the inventors in order to achieve the above object, they discovered a method for synthesizing a silicone macromer having a quaternary ammonium cation moiety in the molecular chain and having a high proportion of (meth)acrylic groups introduced at both ends. The inventors then synthesized a novel tertiary amino group-containing organopolysiloxane to be used as an intermediate compound in the manufacturing method, thereby completing the present 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). [ka] (In the general formula (1), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R 1 are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; Q 1 and Q 2 are each independently a hydrogen atom or a group represented by the following formula (2), provided that Q 1 and Q 2 at least one of the groups is a hydrogen atom, a is an integer of 1 to 400, and b is an integer of 1 to 50. [ka] (In formula (2), R 1 is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms).

[0008] Preferably, the organopolysiloxane further satisfies the following constituent requirement [1] or [2]. [1] In the above general formula (1), Q 1 and Q 2 and [2] In the above general formula (1), Q 1 and Q 2 is a hydrogen atom, and Q 1 and Q 2 the other of which is a group represented by the above formula (2).

[0009] The present invention further provides a method for producing an organopolysiloxane having a tertiary amino group in the molecular chain, represented by the following general formula (1): [ka] (In the general formula (1), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R 1 are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; Q 1 and Q 2 are each independently a hydrogen atom or a group represented by the following formula (2), provided that Q 1 and Q 2 at least one of the groups is a hydrogen atom, a is an integer of 1 to 400, and b is an integer of 1 to 50. [ka] (In formula (2), R 1 are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. The present invention provides a method for producing an organopolysiloxane represented by the general formula (1), comprising the step of reacting (A) an organohydrogenpolysiloxane having 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 an organopolysiloxane represented by the general formula (1). [ka] (In the general formula (3), R and a are as defined above.) [ka] (In general formula (4), R 1 is as above) The present invention further provides the above-mentioned production method, wherein the organopolysiloxane represented by the above general formula (1) has an average of 1.5 to 2 terminal hydrosilyl groups per molecule. Effect of the Invention

[0010] The tertiary amino group-containing organopolysiloxane of the present invention is suitable as an intermediate compound for producing a silicone macromer having a quaternary ammonium cation site in the molecular chain with a high proportion of (meth)acrylic groups introduced at both ends. In addition, the production method of the present invention can efficiently produce the tertiary amino group-containing organopolysiloxane. Furthermore, the tertiary amino group-containing organopolysiloxane of the present invention is useful not only as the above silicone macromer, but also as an intermediate that can be easily derived into organopolysiloxanes having various reactive functional groups. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a 1H-NMR spectrum chart of the organopolysiloxane having a tertiary amino group in the molecular chain, synthesized in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be described in detail below. [Organopolysiloxane with tertiary amino groups in the molecular chain] The organopolysiloxane having a tertiary amino group of the present invention is represented by the following general formula (1). [ka] In the above general formula (1), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R 1 are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; Q 1 and Q 2 are each independently a hydrogen atom or a group represented by the following formula (2), a is an integer of 1 to 400, and b is an integer of 1 to 50. [ka] In the above formula (2), R 1 is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

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

[0014] In the above general formula (1) and formula (2), R 1are each independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, and an ethylphenyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group and a phenylethyl group. In the above general formula (1) and formula (2), R 1 is preferably a methyl group or an ethyl group, more preferably a methyl group.

[0015] In the above general formula (1), Q 1 and Q 2 are each independently a hydrogen atom or a group represented by the above formula (2).

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

[0017] [Method for producing organopolysiloxane having tertiary amino groups in the molecular chain] The method for producing the organopolysiloxane having tertiary amino groups in the molecular chain represented by the above general formula (1) is described in detail below. The production method is characterized by comprising the step of reacting (A) an organohydrogenpolysiloxane 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). [ka] [ka]

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

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

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

[0021] In the production method of the present invention, the above-mentioned organopolysiloxane modified with hydrogen at both ends is used in an excess equivalent amount relative to the tertiary amine having two allyl groups. The molar ratio determines b in the above general formula (1), which is the number of repetitions of the silicone chain and the tertiary amino group-containing portion. The blending ratio of the organopolysiloxane is preferably 1.05 to 2 times the number of moles of the tertiary amine.

[0022] The catalyst used in the production method of the present invention may be a known platinum catalyst. In particular, a chloroplatinic acid neutralized with sodium bicarbonate·vinylsiloxane complex (Karstedt's Catalyst) is preferred. The amount of catalyst is not particularly limited as long as it is a catalytic amount, but is preferably 10 to 1,000 ppm based on the weight of the organopolysiloxane modified with hydrogen at both ends.

[0023] In the production method of the present invention, the reaction conditions such as the reaction time and the solvent used 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 having a secondary amino terminal at its terminal, represented by the above formula (2). This is because, in the production of the organopolysiloxane represented by the above general formula (1), the tertiary amino terminal, which is the result of internal rearrangement of the double bond by a platinum catalyst present at the terminal of the organopolysiloxane, is hydrolyzed by post-treatment after the hydrosilylation reaction, as shown in the following formula. [ka]

[0025] That is, Q in the above general formula (1) 1 and Q 2 are each independently a hydrogen atom or a group represented by the above formula (2). The organopolysiloxane of general formula (1) obtained by reacting an organohydrogenpolysiloxane containing hydrosilyl groups at both ends represented by the above formula (3) with a tertiary amine having two allyl groups represented by the above formula (4) is more preferably as shown below. [ka] Among them, Q 1 and Q 2At least one of Q is a silicon-bonded hydrogen atom. 1 and Q 2 and Q are preferably both silicon-bonded hydrogen atoms. 1 and Q 2 In organopolysiloxanes in which both are hydrogen atoms, it is possible to introduce a high proportion of (meth)acrylic groups to both ends, making them more useful intermediates for providing silicone macromers that contain quaternary ammonium cation moieties in the molecular chain.

[0026] The above general formula (1) may be one or a mixture of two or more compounds selected from the above organopolysiloxanes. More preferred is an organopolysiloxane having an average of 0 to 2, preferably 1 to 2, more preferably 1.5 to 2 hydrogen atoms bonded to silicon atoms per molecule, and an average of 0 to 2, preferably 0 to 1, more preferably 0 to 0.5 groups represented by the above formula (2) per molecule. EXAMPLES

[0027] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the following 1 H-NMR measurements were performed using an ULTRASHIELD400 PLUS (BRUKER).

[0028] [Example 1] Production of organopolysiloxane having tertiary amino groups in the molecular chain represented by the above general formula (1) In a three-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, add the following compound (a): [ka] 50.0 g of organohydrogenpolysiloxane containing hydrosilyl groups at both ends represented by the formula (I), 0.2 g of a toluene solution of chloroplatinic acid neutralized with sodium bicarbonate and vinylsiloxane complex (platinum content 0.5 wt%), and 17 g of toluene were charged and heated to 70°C. 5.3 g of diallylmethylamine was added dropwise over 30 minutes, and the mixture was heated and stirred at 75°C for 2 hours. After the reaction was completed, low boiling point fractions were removed at 100°C for 1 hour under a reduced pressure of 0.2 kPa. Next, 25 g of acetonitrile and 6.3 g of water were added, stirred, washed, and then allowed to stand to separate the silicone layer. This separation and washing operation was repeated three times. Low boiling point fractions were removed at 85°C for 1.5 hours under a reduced pressure of 0.3 kPa, and 24 g of organopolysiloxane represented by the formula (b) was obtained. [ka] In formula (b), each A is independently a hydrogen atom bonded to a silicon atom or a group represented by the following formula (c): The organopolysiloxane is a mixture of two or more compounds with different As, and has an average of 1.8 hydrogen atoms bonded to silicon atoms per molecule and an average of 0.2 groups represented by the following formula (c) per molecule. [ka]

[0029] The organopolysiloxane obtained in Example 1 is 1 The H-NMR spectrum is shown. 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 production method of the present invention, the above-mentioned tertiary amino group-containing organopolysiloxane can be efficiently produced. The tertiary amino group-containing organopolysiloxane of the present invention is suitable as an intermediate compound for producing a silicone macromer having a quaternary ammonium cation site in the molecular chain in which (meth)acrylic groups are introduced at a high rate at both ends. Furthermore, the tertiary amino group-containing organopolysiloxane of the present invention is useful not only as the above-mentioned silicone macromer, but also as an intermediate that can be easily derived into organopolysiloxanes having various reactive functional groups.

Claims

1. An organopolysiloxane having a tertiary amino group in the molecular chain, represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; Q １ and Q. ２ are each independently a hydrogen atom or a group represented by the following formula (2), １ and Q. ２ At least one of the groups is a hydrogen atom, a is an integer from 1 to 400, and b is an integer from 1 to 50. 【Chemistry 2】 (In formula (2), R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms).

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

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

4. A method for producing an organopolysiloxane having a tertiary amino group in the molecular chain, represented by the following general formula (1), comprising the steps of: 【Chemistry 3】 (In general formula (1), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; Q １ and Q. ２ are each independently a hydrogen atom or a group represented by the following formula (2), １ and Q. ２ At least one of the groups is a hydrogen atom, a is an integer from 1 to 400, and b is an integer from 1 to 50. 【Chemistry 4】 (In formula (2), R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. The above-mentioned production method includes a step of reacting (A) an organohydrogenpolysiloxane having 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 an organopolysiloxane represented by the above general formula (1). 【Chemistry 5】 (In formula (3), R and a are as defined above.) 【Chemistry 6】 (In formula (4), R １ is as above).

5. 5. The method according to claim 4, wherein the organopolysiloxane represented by the general formula (1) has an average of 1.5 to 2 terminal hydrosilyl groups per molecule.

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