Organopolysiloxane having a tertiary amino group in its molecular chain and method for producing 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 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 1-10 alkyl group, a 6-10 aryl group, and a 7-10 aralkyl group, Q1 and Q2 are each mutually independently a group including a polyethylene glycol unit or a specific amino group, 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 its 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, because silicone is hydrophobic, the introduction of hydrophilic groups is being considered to make the contact lens surface hydrophilic. Among these, the introduction of quaternary ammonium cation moieties into silicone chains has been reported (Patent Documents 1-4). 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 [Overview of the project] [Problems that the invention aims to solve]

[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. Generally, it is undesirable for silicone used as a contact lens material to contain a large amount of compounds without polymerizable groups. Therefore, there is a need to establish a method for producing a silicone macromer containing a quaternary ammonium cation moiety in the molecular chain, which can introduce (meth)acrylic groups at both ends in a high proportion.

[0005] An object of the present invention is to provide an organopolysiloxane which is an intermediate compound for providing a silicone macromer having a quaternary ammonium cation site in a molecular chain thereof, in which (meth)acrylic groups are introduced at a high ratio at both terminals. [Means for Solving the Problem]

[0006] As a result of intensive studies to achieve the above object, the present inventor has found a production method for synthesizing a silicone macromer having a quaternary ammonium cation site in a molecular chain thereof in which (meth)acrylic groups are introduced at a high ratio at both terminals. The present inventor has synthesized a novel tertiary amino group-containing organopolysiloxane to be used as an intermediate compound in said production method, and has accomplished the present invention.

[0007] That is, the present invention provides an organopolysiloxane having a tertiary amino group in a molecular chain thereof, represented by the following general formula (1). [Chemical Formula] (In general formula (1), each 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, and R 1 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, and Q 1 and Q 2 are each independently a group represented by the following formula (2) or the following formula (3), a is an integer of 1 to 400, and b is an integer of 1 to 50) [Chemical Formula] (In formula (2), n1 is an integer of 2 to 10, and n2 is an integer of 0 to 10) [Chemical Formula] (In formula (3), R 1is 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 has the constitutional requirements shown in the following [1], [2] or [3]. [1] In the above general formula (1), Q 1 and Q 2 are both groups represented by the above formula (2), the organopolysiloxane. [2] In the above general formula (1), Q 1 and Q 2 one of which is a group represented by the above formula (2), and Q 1 and Q 2 the other of which is a group represented by the above formula (3), the organopolysiloxane. [3] In the above general formula (1), Q 1 and Q 2 are both groups represented by the above formula (3), the organopolysiloxane.

[0009] The present invention further provides a method for producing an organopolysiloxane having a tertiary amino group in a molecular chain, represented by the following general formula (1),

Chemical Formula

Chemical Formula

[0010] The present invention further provides a method for producing an organopolysiloxane having a tertiary amino group in its molecular chain, represented by the above general formula (1), further comprising the step of reacting an organohydrogenpolysiloxane containing hydrosilyl groups at both ends with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain an organopolysiloxane represented by the above general formula (4). The present invention further provides a method for producing an organopolysiloxane represented by the above general formula (1) having an average of 0.5 to 2 groups represented by the above formula (2) in one molecule. [Effects of the Invention]

[0011] 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 moiety in a molecular chain with a high proportion of (meth)acrylic groups introduced at both ends. Furthermore, the production method of the present invention allows for the efficient production of the tertiary amino group-containing organopolysiloxane. Moreover, 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 is easily derived to organopolysiloxanes having various reactive functional groups. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 is the 1H-NMR spectral chart of the organopolysiloxane having a tertiary amino group in the molecular chain synthesized in Example 1. [Modes for carrying out the invention]

[0013] The present invention will be described in detail below. [Organopolysiloxanes containing tertiary amino groups in their molecular chains] 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 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. 1 These are groups 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, Q 1 and Q 2These are mutually independent bases represented by the following formula (2) or formula (3), where a is an integer from 1 to 400 and b is an integer from 1 to 50. [ka] In equation (2) above, n1 is an integer between 2 and 10, and n2 is an integer between 0 and 10. [ka] In the above equation (3), R 1 This group is 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.

[0014] In the above general formula (1), R is independently selected from C1-C10 alkyl groups, C6-C10 aryl groups, and C7-C10 aralkyl groups. Examples of C1-C10 alkyl groups include methyl, ethyl, propyl, butyl, and octyl groups; and cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Examples of C6-C10 aryl groups include phenyl, methylphenyl, and ethylphenyl groups. Examples of C7-C10 aralkyl groups include phenylmethyl and phenylethyl groups. R is preferably a methyl group and a phenyl group, and more preferably a methyl group.

[0015] In the above general formulas (1) and (3), R 1 R is a group independently selected from C1-C10 alkyl groups, C6-C10 aryl groups, and C7-C10 aralkyl groups. Examples of C1-C10 alkyl groups include methyl, ethyl, propyl, butyl, and octyl groups; and cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Examples of C6-C10 aryl groups include phenyl, methylphenyl, and ethylphenyl groups. Examples of C7-C10 aralkyl groups include phenylmethyl and phenylethyl groups. In the above general formulas (1) and (3), R 1The group is preferably a methyl group and an ethyl group, and more preferably a methyl group.

[0016] In the above general formula (1), Q 1 and Q 2 These are groups that are independently represented by formula (2) or formula (3) above.

[0017] In the above general formula (1), a is an integer between 1 and 400, preferably between 1 and 100, and more preferably between 5 and 50. b is an integer between 1 and 50, preferably between 1 and 30, and more preferably between 1 and 10.

[0018] In the above formula (2), n1 is an integer between 2 and 10, preferably between 2 and 4, and n2 is an integer between 0 and 10, preferably between 1 and 6.

[0019] [Method for producing organopolysiloxanes having tertiary amino groups in the molecular chain] A method for producing an organopolysiloxane having a tertiary amino group in the molecular chain represented by the general formula (1) above will be described in detail below. The manufacturing method is characterized by comprising the step of reacting (A) an organopolysiloxane having a tertiary amino group in a molecular chain represented by the following general formula (4) and (B) a (poly)ethylene glycol monoalkenyl ether represented by the following general formula (6) in the presence of a platinum catalyst to obtain the compound represented by the above general formula (1). [ka] [ka]

[0020] In the above general formula (4), Q 3 These are independently hydrogen atoms or groups represented by the following formulas (3) or (5), and there is at least one Q in one molecule. 3 That is a hydrogen atom. [ka] [ka]

[0021] In the above general formula (4), R is independently selected from C1-C10 alkyl groups, C6-C10 aryl groups, and C7-C10 aralkyl groups. Examples of C1-C10 alkyl groups include methyl, ethyl, propyl, butyl, and octyl groups; and cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Examples of C6-C10 aryl groups include phenyl, methylphenyl, and ethylphenyl groups. Examples of C7-C10 aralkyl groups include phenylmethyl and phenylethyl groups. R is preferably a methyl group and a phenyl group, and more preferably a methyl group.

[0022] In the above general formulas (4), (3), and (5), R 1 R is a group independently selected from C1-C10 alkyl groups, C6-C10 aryl groups, and C7-C10 aralkyl groups. Examples of C1-C10 alkyl groups include methyl, ethyl, propyl, butyl, and octyl groups; and cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Examples of C6-C10 aryl groups include phenyl, methylphenyl, and ethylphenyl groups. Examples of C7-C10 aralkyl groups include phenylmethyl and phenylethyl groups. In the above general formulas (4), (3), and (5), R 1 The group is preferably a methyl group and an ethyl group, and more preferably a methyl group.

[0023] In the above general formula (4), a is an integer between 1 and 400, preferably between 1 and 100, and more preferably between 5 and 50. b is an integer between 1 and 50, preferably between 1 and 30, and more preferably between 1 and 10.

[0024] In the above general formula (6), n3 is an integer between 0 and 8, preferably between 0 and 2. n4 is an integer between 0 and 10, preferably between 1 and 6.

[0025] The organopolysiloxane represented by the above general formula (4) preferably has the following structure. [ka] The hydrosilyl group of the above organopolysiloxane reacts with the (poly)ethylene glycol monoalkenyl ether represented by the above general formula (6) to give the above organopolysiloxane of general formula (1) having the structure represented by formula (2) at its terminal end.

[0026] As described above, the organopolysiloxane of the present invention includes a structure having a secondary amino group represented by formula (3) at its terminus. This is because, in the production of the organohydrogenpolysiloxane represented by the general formula (4) above, the terminus having a tertiary amino group, whose double bond has undergone internal rearrangement by a platinum catalyst, is hydrolyzed during post-treatment after the hydrosilylation reaction as shown in the following formula, to give a structure having a secondary amino group represented by formula (3) at its terminus. [ka] Therefore, the organopolysiloxane represented by the general formula (4) above may be a compound having the following structure, and may be a mixture of a compound having a group represented by formula (5) above at one end and a compound having a group represented by formula (3) above at one end. [ka]

[0027] The organopolysiloxane represented by the above general formula (4) may be a mixture of one or more compounds selected from the above organopolysiloxanes. Preferably, the organopolysiloxane has an average of 0 to 2 hydrogen atoms, more preferably 1 to 2, and even more preferably 1.5 to 2 hydrogen atoms bonded to silicon atoms in one molecule.

[0028] The organopolysiloxane represented by the above general formula (1) is preferably Q 1 and Q 2 Compounds where both are groups represented by the above formula (2), Q 1 and Q 2 Compounds in which both are groups represented by the above formula (3), and Q 1 and Q 2 The compound may be one of which is a group represented by formula (2) and the other is a group represented by formula (3), or it may be a mixture of two or more compounds selected from these. More preferably, the organopolysiloxane may have an average of 0 to 2 groups represented by formula (2) per molecule, preferably 0.5 to 2, more preferably 1 to 2, and even more preferably 1.5 to 2, and an average of 0 to 2 groups represented by formula (3) per molecule, preferably 0 to 1.5, more preferably 0 to 1, and even more preferably 0 to 0.5.

[0029] In the production method of the present invention, (poly)ethylene glycol monoalkenyl ether is used in excess of the organopolysiloxane. The blending ratio of (poly)ethylene glycol monoalkenyl ether is preferably 1.05 to 1.4 times the number of moles of terminal hydrosilyl groups contained in the organopolysiloxane.

[0030] The (poly)ethylene glycol monoalkenyl ether used in the manufacturing method of the present invention may be a commercially available product. Examples include allyl glycol, diethylene glycol monoallyl ether, and polyethylene glycol allyl ether (product names: Uniox PKA-5001 (average molecular weight: 200), Uniox PKA-5002 (average molecular weight: 400), Uniox PKA-5003 (average molecular weight: 450), Uniox PKA-5004 (average molecular weight: 750), Uniox PKA-5005 (average molecular weight: 1,500), all manufactured by NOF Corporation).

[0031] Any known platinum catalyst can be used as the catalyst in the manufacturing method of the present invention. In particular, a sodium bicarbonate chlorplatinate-vinylsiloxane complex (Karstedt's Catalyst) is more preferred. The amount of catalyst is not particularly limited and any catalytic amount is acceptable, but preferably it is 10 to 1,000 ppm relative to the mass of the organohydrogenpolysiloxane containing hydrosilyl groups at both ends.

[0032] In the manufacturing 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.

[0033] The method for producing the organopolysiloxane represented by the above general formula (4) is not particularly limited, but for example, it can be obtained by reacting an organohydrogenpolysiloxane containing hydrosilyl groups at both ends with a tertiary amine having two allyl groups in the presence of a platinum catalyst. In this production method, the reaction conditions such as reaction time and the solvent used are not particularly limited and can be set as appropriate.

[0034] Preferably, the above-mentioned organohydrogenpolysiloxane containing hydrosilyl groups at both ends and a tertiary amine having two allyl groups are reacted in excess of the hydrosilyl groups in the presence of a platinum catalyst to obtain the organopolysiloxane represented by the above general formula (4) as an intermediate. Then, the (poly)ethylene glycol monoalkenyl ether represented by the above general formula (6) is added to the reaction system and reacted to produce the organopolysiloxane represented by the above general formula (1). The above-mentioned organohydrogenpolysiloxane containing hydrosilyl groups at both ends is used in excess of the tertiary amine having two allyl groups. The molar ratio determines b in the above general formula (1), which is the number of repeating units of the silicone chain and the tertiary amino group-containing site. The blending ratio of the organopolysiloxane is preferably 1.05 to 2 times the number of moles of the tertiary amine.

[0035] In the method for producing the organopolysiloxane represented by the above general formula (1), the intermediate product (4) may be isolated in the first step before proceeding to the next step, or the process may proceed to the next step without isolating the intermediate product (4) after the reaction in the first step, either without treatment or by simply removing the solvent and unreacted raw materials. As a method for obtaining the organopolysiloxane represented by the above general formula (1) without isolating the intermediate product (4), for example, an organohydrogenpolysiloxane containing hydrosilyl groups at both ends and a tertiary amine having two allyl groups may be reacted in the presence of a platinum catalyst to confirm that no tertiary amine raw materials remain. Then, (poly)ethylene glycol allyl ether and a platinum catalyst may be added to the reaction solution and heated and stirred. After the reaction is complete, the low-boiling fraction may be removed and the mixture may be washed to obtain the organopolysiloxane having a tertiary amino group in the molecular chain represented by the above general formula (1). [Examples]

[0036] 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 1H-NMR measurements were performed using an ULTRASHIELD400 PLUS (BRUKER).

[0037] [Synthesis Example 1] A three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser contains the following formula [ka] 50.0 g of organohydrogenpolysiloxane containing hydrosilyl groups at both ends, represented by the formula shown, 0.2 g of a toluene solution of sodium bicarbonate chlorplatinate neutralized 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 complete, the low-boiling fraction was removed under reduced pressure of 0.2 kPa at 100°C for 1 hour. Subsequently, 25 g of acetonitrile and 6.3 g of water were added, stirred, washed, and allowed to stand to separate the silicone layer. This liquid-liquid separation and washing procedure was repeated three times. The low-boiling fraction was removed under reduced pressure of 0.3 kPa at 85°C for 1.5 hours to obtain 24 g of organopolysiloxane represented by the formula shown below (a). [ka] In formula (a), A is a hydrogen atom bonded to a silicon atom or a group represented by the following formula, independently of each other. The organopolysiloxane is a mixture of two or more compounds in which A is different, and has an average of 1.8 hydrogen atoms bonded to silicon atoms and an average of 0.2 groups represented by the following formula (b) per molecule. [ka]

[0038] [Example 1] Production of organopolysiloxanes having tertiary amino groups in the molecular chain, represented by the above general formula (1) In a three-necked flask equipped with a thermometer, stirrer, and reflux condenser, 250.0 g of organopolysiloxane represented by formula (a) obtained in Synthesis Example 1, 1.0 g of toluene solution of sodium bicarbonate chlorplatinate-vinylsiloxane complex (platinum content 0.5 wt%), and 83 g of toluene were charged and heated to 70°C. 24.3 g of allyl glycol and 0.5 g of toluene solution of sodium bicarbonate chlorplatinate-vinylsiloxane complex (platinum content 0.5 wt%) were added, and the mixture was heated and stirred at 75°C for 1.5 hours. After the reaction was complete, the low-boiling fraction was removed under reduced pressure of 0.3 kPa at 90°C for 1 hour. Subsequently, 125 g of acetonitrile and 31 g of water were added, stirred, washed, and allowed to stand to separate the silicone layer. This liquid-liquid separation and washing procedure was repeated three times. The low-boiling fraction was removed under reduced pressure of 0.9 kPa at 100°C for 1.5 hours, yielding 247 g of organopolysiloxane represented by the following formula (c). [ka] In the above formula (c), Q 1 These are groups that are independently represented by the following formula (d) or the above formula (b). The organopolysiloxane is Q 1 A mixture of two or more different compounds, having an average of 1.8 groups represented by formula (d) and an average of 0.2 groups represented by formula (b) per molecule. [ka]

[0039] The above organopolysiloxane 1 The H-NMR spectrum is shown. 1 H-NMR(400MHz, CDCl3):δ -0.14~0.22(m,264H),0.41~0.56(m,16H),1.37~1.66(m,16H),2.06~2.58(m,21 .4H),3.42(t,J=7.0Hz,3.6H),3.51(t,J=4.6Hz,3.6H),3.70(t,J=4.4Hz,3.6H)

[0040] The manufacturing method of the present invention allows for the efficient production of tertiary amino group-containing organopolysiloxanes. The tertiary amino group-containing organopolysiloxane of the present invention is suitable as an intermediate compound for producing silicone macromers having a quaternary ammonium cation moiety in the molecular chain, with a high proportion of (meth)acrylic groups introduced 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 is easily derived to organopolysiloxanes having various reactive functional groups.

Claims

1. 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 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 These are groups 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, Q １ and Q ２ (These are mutually independent bases represented by the following formula (2) or formula (3), where a is an integer from 1 to 400 and b is an integer from 1 to 50.) 【Chemistry 2】 (In equation (2), n1 is an integer between 2 and 10, and n2 is an integer between 0 and 10.) 【Transformation 3】 (In formula (3), R １ (The group is 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. In the above general formula (1), Q １ and Q ２ The organopolysiloxane according to claim 1, wherein both are groups represented by the above formula (2).

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

4. In the above general formula (1), Q １ and Q ２ The organopolysiloxane according to claim 1, wherein both are groups represented by the above formula (3).

5. A method for producing an organopolysiloxane having a tertiary amino group in the molecular chain, represented by the following general formula (1): 【Chemistry 4】 (In general formula (1), R is 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, R １ These are groups 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, Q １ and Q ２ (These are mutually independent bases represented by the following formula (2) or formula (3), where a is an integer from 1 to 400 and b is an integer from 1 to 50.) 【Transformation 5】 (In equation (2), n1 is an integer between 2 and 10, and n2 is an integer between 0 and 10.) 【Transformation 6】 (In formula (3), R １ (This group is 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 is characterized by comprising the step of reacting (A) an organopolysiloxane represented by the following general formula (4) having a tertiary amino group in its molecular chain and (B) a (poly)ethylene glycol monoalkenyl ether represented by the following general formula (6) in the presence of a platinum catalyst to obtain an organopolysiloxane represented by the above general formula (1) having a tertiary amino group in its molecular chain. 【Transformation 7】 (In general formula (4), R, R １ a and b are as described above, Q ３ These are, independently of each other, a hydrogen atom or a group represented by the following formula (3) or (5), and there is at least one Q in one molecule. ３ (This is a hydrogen atom.) 【Transformation 8】 【Chemistry 9】 (In equations (5) and (3), R １ (As stated above) 【Chemistry 10】 (In general formula (6), n3 is an integer from 0 to 8, and n4 is an integer from 0 to 10).

6. A method for producing an organopolysiloxane having a tertiary amino group in its molecular chain, according to claim 5, further comprising the step of reacting an organohydrogenpolysiloxane containing hydrosilyl groups at both ends with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain an organopolysiloxane represented by the above general formula (4).

7. The method for producing an organopolysiloxane represented by the above general formula (1) has an average of 0.5 to 2 groups represented by the above formula (2) in one molecule, according to claim 5 or 6.

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