Pyrrolidone ring-containing organopolysiloxane and method for producing same

Abstract

PROBLEM TO BE SOLVED: In view of the above circumstances, the purpose of the present invention is to provide a pyrrolidone ring-containing organopolysiloxane that can be synthesized easily by a hydrosilylation reaction in the presence of a platinum catalyst, and to provide a method for producing the same. SOLUTION: An organopolysiloxane represented by formula (1) (in formula (1), R are independently groups selected from C1-10 alkyl groups, C6-10 aryl groups, and C7-10 aralkyl groups; 10 is a hydrogen atom or a methyl group; Y is a group represented by formula (2); m is an integer of 10-300; n is an integer of 1-150; and the bonding order of siloxane units bound by m and n may be block units or random, and n1 are independently integers of 1-10) (In formula (2), * represents a bonding site with a silicon atom of formula (1), and n2 is an integer of 1-12).

Description

Pyrrolidone ring-containing organopolysiloxane and method for producing same

[0001] The present invention relates to an organopolysiloxane having a pyrrolidone ring-containing group and a method for producing the same.

[0002] Organopolysiloxanes are widely used as contact lens materials due to their high oxygen permeability. However, because organopolysiloxanes are non-hydrophilic, attempts have been made to introduce various hydrophilic groups into them to impart hydrophilic properties.

[0003] Vinylpyrrolidone is one of the hydrophilic monomers commonly used in contact lens formulations. As examples of introducing a pyrrolidone ring into organo(poly)siloxanes, Patent Documents 1 and 2 describe organo(poly)siloxanes having one polymerizable group and a pyrrolidone ring-containing group. For example, Patent Document 1 describes an organo(poly)siloxane having a polymerizable group at one end of the molecular chain in which alkoxyethylpyrrolidone has been introduced at one end of the molecular chain. Patent Document 2 also describes an organo(poly)siloxane having a polymerizable group at one end of the molecular chain in which N-vinylpyrrolidone has been introduced at one end of the molecular chain.

[0004] Patent Document 3 describes a method for producing an organopolysiloxane having a polymerizable group at one or both ends and a pyrrolidone ring-containing group in a side chain, by subjecting a polymerizable group-containing organohydrogenpolysiloxane and N-vinylpyrrolidone or N-allylpyrrolidone to a hydrosilylation reaction in the presence of a rhodium catalyst. Patent Document 3 also describes that in the hydrosilylation reaction of an organohydrogenpolysiloxane with N-vinylpyrrolidone or N-allylpyrrolidone, a rhodium-containing catalyst has a favorable catalytic effect on the hydrosilylation reaction.

[0005] US Patent No. 5,959,117 JP 2019-026607 A JP 2013-139567 A

[0006] However, rhodium-containing catalysts are generally more expensive than platinum-based catalysts and have lower catalytic activity in hydrosilylation reactions. Therefore, platinum-based catalysts are preferred over rhodium-containing catalysts for hydrosilylation reactions. Therefore, there has been a demand for organopolysiloxanes that have polymerizable groups at both ends and pyrrolidone ring-containing groups in their side chains, which exhibit good reactivity in hydrosilylation reactions in the presence of platinum-based catalysts.

[0007] In view of the above circumstances, an object of the present invention is to provide a pyrrolidone ring-containing organopolysiloxane that can be easily synthesized by a hydrosilylation reaction in the presence of a platinum catalyst, and a method for producing the same.

[0008] As a result of extensive research conducted by the present inventors to solve the above-mentioned problems, they discovered that an organopolysiloxane having a pyrrolidone ring-containing group, as represented by the following formula (1), can be easily synthesized by a hydrosilylation reaction in the presence of a platinum group metal catalyst, particularly a platinum-based catalyst, thereby achieving the above-mentioned object, and thus completed the present invention.

[0009] That is, the present invention provides: [1] an organopolysiloxane represented by the following formula (1): (In 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; X is a hydrogen atom or a methyl group; Y is a group represented by the following formula (2); m is an integer of 10 to 300; n is an integer of 1 to 150; the bonding order of the siloxane units bracketed by m and n may form a block unit or may be random; and each n1 is independently an integer of 1 to 10.) (In formula (2), * represents a bond to the silicon atom in formula (1), and n2 is an integer of 1 to 12.)

[0010] The present invention further provides the organopolysiloxane, further having at least one of the following structures [2] to [4]: ​​[2] The organopolysiloxane, wherein in the formula (1), n1 is an integer of 2 to 6. [3] The organopolysiloxane, wherein in the formula (2), n2 is an integer of 1 to 8. [4] The organopolysiloxane, wherein in the formula (1), m is an integer of 50 to 120, and n is an integer of 1 to 20.

[0011] The present invention also provides [5] a method for producing an organopolysiloxane represented by the following formula (1): (In 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; X is a hydrogen atom or a methyl group; Y is a group represented by the following formula (2); m is an integer of 10 to 300; n is an integer of 1 to 150; the bonding order of the siloxane units bracketed by m and n may form a block unit or may be random; and each n1 is independently an integer of 1 to 10.) (In formula (2), * represents a bond to the silicon atom in formula (1), and n2 is an integer of 1 to 12.) (A) An organohydrogenpolysiloxane represented by the following formula (3): (In formula (3), R, X, m, n, and n1 are as defined above, and the bonding order of the siloxane units bounded by m and n may form a block unit or may be random), and (B) a pyrrolidone ring-containing compound having a double bond represented by the following formula (4): (wherein n2 is as defined above) in the presence of a platinum group metal catalyst to obtain the organopolysiloxane represented by formula (1).

[0012] The present invention further provides the above-mentioned production method, further having at least one of the following features [6] to [9]. [6] The above-mentioned production method, wherein the catalyst is a platinum-based catalyst. [7] The above-mentioned production method, wherein in the above formulas (1) and (3), n1 is an integer of 2 to 6. [8] The above-mentioned production method, wherein in the above formulas (2) and (4), n2 is an integer of 1 to 8. [9] The above-mentioned production method, wherein in the above formulas (1) and (3), m is an integer of 50 to 120, and n is an integer of 1 to 20. The present invention further provides a copolymer containing a repeating unit derived from the polymerization of the organopolysiloxane of any of the above [1] to [4] with another compound having a group polymerizable with the organopolysiloxane.

[0013] The present invention relates to a novel pyrrolidone ring-containing organopolysiloxane and provides a production method for easily introducing a pyrrolidone ring-containing group into an organohydrogenpolysiloxane.

[0014] The pyrrolidone ring-containing organopolysiloxane synthesized in Example 1 １ 1 is a H-NMR spectrum chart.

[0015] The present invention provides a pyrrolidone ring-containing organopolysiloxane represented by the following formula (1):

[0016] In the above formula (1), m is an integer of 10 to 300, preferably an integer of 50 to 120, and more preferably an integer of 60 to 100. n is an integer of 1 to 150, preferably an integer of 1 to 20, and more preferably an integer of 2 to 10. The bonding order of the siloxane units bracketed by m and n may form a block unit or may be random. n1 are each independently an integer of 1 to 10, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.

[0017] In the above formula (1), R 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 methyl, ethyl, propyl, butyl, and octyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, p-tolyl, and p-ethylphenyl. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and 2-phenylethyl. R is preferably a methyl group or a phenyl group, and more preferably a methyl group. Even more preferably, all of the R groups are methyl groups. X is a hydrogen atom or a methyl group.

[0018] In the above formula (1), Y is a group represented by the following formula (2). In the above formula (2), * indicates the bonding site with the silicon atom in the above formula (1), and n2 is an integer of 1 to 12, preferably an integer of 1 to 8, and more preferably an integer of 1 to 4.

[0019] Examples of organopolysiloxanes represented by formula (1) include compounds having the following structure: In the above formula, the bonding order of the siloxane units may be either to form a block unit or random.

[0020] [Method for Producing Pyrrolidone Ring-Containing Organopolysiloxane] The pyrrolidone ring-containing organopolysiloxane of the present invention represented by the above formula (1) can be obtained by reacting (A) an organohydrogenpolysiloxane represented by the following formula (3) with (B) a pyrrolidone ring-containing compound having a double bond represented by the following formula (4) in the presence of a platinum catalyst. In the above formula (3), R, X, m, n, and n1 are as defined above, and the bonding order of the siloxane units bounded by m and n may form block units or may be random. In the above formula (4), n2 is an integer of 1 to 12, preferably an integer of 1 to 8, and more preferably an integer of 1 to 4. The hydrosilylation reaction between a pyrrolidone ring-containing compound of formula (4) that does not have an oxyethylene structure (i.e., n2 = 0) and an organohydrogenpolysiloxane of formula (3) does not proceed well in the presence of a platinum catalyst, whereas the hydrosilylation reaction between a pyrrolidone ring-containing compound of formula (4) that has a structure in which n2 is an integer of 1 to 12 and an organohydrogenpolysiloxane of formula (3) proceeds well in the presence of a platinum group metal catalyst, particularly a platinum catalyst.

[0021] In the production method of the present invention, the ratio of the number of moles of the pyrrolidone ring-containing compound represented by formula (4) above to the total number of moles of hydrosilyl groups in the organopolysiloxane represented by formula (3) above is preferably 1.1 to 2.0 times, more preferably 1.2 to 1.8 times.

[0022] The platinum group metal catalyst may be any conventional platinum group metal catalyst containing a platinum group metal complex as a main component. A platinum group metal catalyst that does not contain rhodium is preferred. A platinum catalyst is more preferred, such as chloroplatinic acid, an alcohol solution or aldehyde solution of chloroplatinic acid, a complex of chloroplatinic acid and various olefins, a complex of chloroplatinic acid and a vinyl group-containing organosiloxane, or a complex of platinum and a vinyl group-containing organosiloxane. Of these, a complex of platinum and a vinyl group-containing organosiloxane is preferred, and a Karstedt catalyst, which is a complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, is particularly preferred. The amount of catalyst is not particularly limited as long as it is a catalytic amount, but it is preferably an amount that results in a platinum metal amount of 10 to 1,000 ppm, and more preferably an amount that results in a platinum metal amount of 30 to 100 ppm, relative to the mass of the organohydrogenpolysiloxane represented by formula (3) above.

[0023] In the production method of the present invention, the reaction conditions such as the reaction temperature, reaction time, and solvent used are not particularly limited. The reaction temperature is preferably 40°C or higher and 100°C or lower, and more preferably 70°C or higher and 100°C or lower. The reaction time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and most preferably 2 to 6 hours. The above reaction may be carried out without a solvent, but a solvent may also be used. The solvent is preferably an aromatic hydrocarbon solvent such as toluene or xylene.

[0024] The silicone of the present invention represented by the above formula (1) can be copolymerized with other monomers to produce a polymer. Examples of such other monomers include acrylic monomers such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol monoalkyl ether (meth)acrylate, trifluoroethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate; acrylic acid derivatives such as N,N-dimethylacrylamide, N,N-diethylacrylamide, N-acryloylmorpholine, and N-methyl(meth)acrylamide; other unsaturated aliphatic or aromatic compounds such as crotonic acid, cinnamic acid, and vinylbenzoic acid; and polymerizable group-containing silicone compounds. Acrylic monomers and acrylic acid derivatives are preferred. A polymer is obtained by polymerizing the silicone of the present invention with one or more of the above-mentioned other monomers.

[0025] In the production of a copolymer containing repeating units derived from the silicone of the present invention and other polymerizable monomers, the amount of the silicone of the present invention blended is preferably 1 to 70 parts by mass, more preferably 10 to 60 parts by mass, per 100 parts by mass of the total of the silicone of the present invention and the other polymerizable monomers. The silicone of the present invention can also be homopolymerized to form a polymer.

[0026] Copolymerization of the compound of the present invention with the other polymerizable monomers may be carried out by a conventionally known method. For example, known polymerization initiators such as thermal polymerization initiators and photopolymerization initiators may be used. Examples of such polymerization initiators include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total of the polymerization components.

[0027] Polymers containing repeating units derived from the compounds of the present invention have excellent surface wettability. Therefore, they are suitable for producing ophthalmic devices such as contact lenses (e.g., hydrophilic contact lenses, silicone hydrogels), intraocular lenses, and artificial corneas. The method for producing ophthalmic devices using the polymers is not particularly limited, and may follow conventional methods for producing ophthalmic devices. For example, cutting methods and molding methods can be used to mold the polymers into the shape of lenses such as contact lenses and intraocular lenses.

[0028] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0029] As described in the examples １ H-NMR was measured using an AVANCE-III 400 MHz (manufactured by BRUKER) using deuterated chloroform as a solvent and TMS (tetramethylsilane) as a standard substance. In the following formula, Me represents a methyl group.

[0030] Example 1 A separable flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 150 g of a methylhydrogenpolysiloxane represented by the following formula (a), 38.9 g of a pyrrolidone ring-containing organic compound represented by the following formula (b) (an amount such that the ratio of the number of moles of the pyrrolidone ring-containing organic compound to the total number of moles of hydrosilyl groups in the organopolysiloxane was 1.8), 3.0 g of a toluene solution of a chloroplatinic acid neutralized with sodium bicarbonate / vinylsiloxane complex (platinum content: 0.5 wt %), and 150 g of toluene, and the mixture was heated and stirred at 95°C for 6 hours. １ H-NMR confirmed that 100% of the hydrosilyl groups had reacted and disappeared. Next, the low-boiling fraction was removed under a reduced pressure of 0.5 kPa at 90°C for 1 hour. The crude product was then dissolved in 284 g of hexane. 251 g of isopropyl alcohol and 189 g of water were added to the solution, and after stirring, the mixture was allowed to stand, and the organopolysiloxane layer was separated and collected. This separation and washing procedure was repeated five times. The low-boiling fraction was removed under a reduced pressure of 0.4 kPa at 100°C for 2.5 hours, yielding 161 g (yield 94%) of an organopolysiloxane represented by the following formula (c):

[0031] The organopolysiloxane obtained in Example 1 is １ The H-NMR spectrum is shown. １ H-NMR (400MHz, CDCl ３ ):δ -0.16-0.25 (m, 540H), 0.40-0.51 (m, 12H), 0.51-0.60 (m, 4H), 1.49-1.62 (m, 12H), 1.62-1.73 (m, 4H), 1.92 (s, 6H), 1.93-2.01 (m, 12H), 2.34 (t, J=8.2Hz, 12H), 3.34 (t, J=6.8Hz, 12H), 3.38-3.55 (m, 36H), 4.08 (t, J=7.0Hz, 4H), 5.51 (s, 2H), 6.07 (s, 2H).

[0032] Comparative Example 1 The steps of Example 1 were repeated, with heating and stirring, except that 25.5 g of N-vinylpyrrolidone (an amount such that the ratio of the number of moles of N-vinylpyrrolidone to the total number of moles of hydrosilyl groups in the organopolysiloxane was 1.8) was used instead of the pyrrolidone ring-containing organic compound represented by the above formula (b). １ H-NMR confirmed that the hydrosilyl group had not reacted at all and that a pyrrolidone ring had not been introduced.

[0033] Comparative Example 2 The steps of Example 1 were repeated with heating and stirring, except that 28.8 g of N-allylpyrrolidone (an amount such that the ratio of the number of moles of N-allylpyrrolidone to the total number of moles of hydrosilyl groups in the organopolysiloxane was 1.8) was used instead of the pyrrolidone ring-containing organic compound represented by the above formula (b). １ H-NMR confirmed that the hydrosilyl group had not reacted at all and that a pyrrolidone ring had not been introduced.

[0034] As shown in Comparative Examples 1 and 2, in the presence of a chloroplatinic acid / sodium bicarbonate neutralized vinylsiloxane complex (Karlstedt catalyst) under the above conditions, N-vinylpyrrolidone and N-allylpyrrolidone did not react at all with the organohydrogenpolysiloxane represented by formula (a) above. On the other hand, in the production method of the present invention, the pyrrolidone ring-containing organic compound represented by formula (b) above and the organohydrogenpolysiloxane represented by formula (a) above exhibited good hydrosilylation reactivity under the same conditions as in Comparative Examples 1 and 2 and in the presence of the above platinum catalyst, and the target organopolysiloxane was obtained in high yield.

[0035] According to the production method of the present invention, pyrrolidone ring-containing groups can be easily introduced into organohydrogenpolysiloxanes in the presence of a platinum group metal catalyst, particularly in the presence of a platinum catalyst, to provide organopolysiloxanes having polymerizable groups at both ends and having pyrrolidone ring-containing groups in side chains at a lower cost and in a higher yield than conventional production methods.

[0036] The pyrrolidone ring-containing organopolysiloxane of the present invention can be copolymerized with other polymerizable monomers such as (meth)acrylic monomers to give polymers suitable for medical devices, including ophthalmic devices, etc. The compound of the present invention and the method for producing the compound are useful for producing ophthalmic devices, such as contact lens materials, intraocular lens materials, and artificial cornea materials.

Claims

1. An organopolysiloxane represented by the following formula (1): (In 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; X is a hydrogen atom or a methyl group; Y is a group represented by the following formula (2); m is an integer of 10 to 300; n is an integer of 1 to 150; the bonding order of the siloxane units bracketed by m and n may form a block unit or may be random; and each n1 is independently an integer of 1 to 10.) (In formula (2), * indicates the bonding site with the silicon atom in formula (1), and n2 is an integer of 1 to 12).

2. The organopolysiloxane of claim 1, wherein n1 in the formula (1) is an integer of 2 to 6.

3. The organopolysiloxane according to claim 1 or 2, wherein in the formula (2), n2 is an integer of 1 to 8.

4. The organopolysiloxane according to claim 1 or 2, wherein in the above formula (1), m is an integer of 50 to 120 and n is an integer of 1 to 20.

5. A method for producing an organopolysiloxane represented by the following formula (1): (In 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; X is a hydrogen atom or a methyl group; Y is a group represented by the following formula (2); m is an integer of 10 to 300; n is an integer of 1 to 150; the bonding order of the siloxane units bracketed by m and n may form a block unit or may be random; and each n1 is independently an integer of 1 to 10.) (In formula (2), * indicates the bonding site to the silicon atom in formula (1), and n2 is an integer of 1 to 12.) (A) An organohydrogenpolysiloxane represented by the following formula (3): (In formula (3), R, X, m, n, and n1 are as defined above, and the bonding order of the siloxane units bounded by m and n may form a block unit or may be random), and (B) a pyrrolidone ring-containing compound having a double bond represented by the following formula (4): (wherein n2 is as defined above) in the presence of a platinum group metal catalyst to obtain the organopolysiloxane represented by formula (1).

6. The method of claim 5, wherein the catalyst is a platinum-based catalyst.

7. The method of claim 5 or 6, wherein n1 is an integer of 2 to 6 in the above formulas (1) and (3).

8. The method of claim 5 or 6, wherein n2 is an integer of 1 to 8 in the above formulas (2) and (4).

9. The method of claim 5 or 6, wherein in the above formulas (1) and (3), m is an integer of 50 to 120, and n is an integer of 1 to 20.

10. A copolymer containing repeating units derived from the polymerization of the organopolysiloxane of claim 1 with another compound having a group polymerizable with said organopolysiloxane.

Images