Side-chain carbamate modified organosilicon macromonomer and copolymer thereof

Abstract

Provided is a silicone macromonomer having improved compatibility with a polymerizable hydrophilic monomer. A side-chain urethane-modified silicone macromonomer represented by formula (1). [Formula 1] # imgabs0 # (In formula (1), R is a C1-10 alkyl group or the like, X is a hydrogen atom or a methyl group, n1 is independently a number of 2-10, n2 is a number of 0-8, R1 is a group represented by formula (2) or (3), a is a number of 0-400, b is a number of 1-100, a + b is 1 < = a + b < = 500, and in formula (1), at least one group represented by formula (4) is present. ) [chemical formula 2]-CH2CH2-O-R2 (2) # imgabs1 # (In formula (2), R2 is a group represented by formula (4). In formula (3), R3 independently represents a hydrogen atom or a group represented by formula (4). ) [chemical formula 3] # imgabs2 # (In formula (4), R4 represents an alkyl group having 1-10 carbon atoms, or the like. )

Description

Technical Field

[0001] The invention relates to a side chain carbamate modified organic silicon macromonomer and a copolymer thereof. Background Art

[0002] Silicone is widely used as a contact lens material due to its high oxygen permeability. However, since silicone is non-hydrophilic, there have been reports of introducing hydrophilic groups to improve compatibility with polymerizable hydrophilic monomers.

[0003] As silicones (silicone macromers) with introduced hydrophilic groups, compounds with introduced hydroxyl groups have been disclosed (Patent Document 1). The introduction of hydroxyl groups improves the compatibility of silicone macromers with polymerizable hydrophilic monomers. However, in order to more freely incorporate polymerizable hydrophilic monomers into contact lens materials, further improvement of the compatibility of silicone macromers with polymerizable hydrophilic monomers is desired.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: U.S. Patent Application Publication No. 2017 / 0008990 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] Therefore, an object of the present invention is to provide a silicone macromonomer having improved compatibility with a polymerizable hydrophilic monomer.

[0009] Means for solving problems

[0010] The present inventors have conducted intensive studies to achieve the above-mentioned object and have found that adding a urethane moiety to the side chain of a silicone macromonomer improves compatibility with a polymerizable hydrophilic monomer, thereby completing the present invention.

[0011] That is, the present invention provides the following side-chain urethane-modified silicone macromonomer and copolymer thereof.

[0012] <1> A side chain urethane-modified silicone macromonomer represented by the following formula (1):

[0013] [Chemistry 1]

[0014]

[0015] (In 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, or an aralkyl group having 7 to 10 carbon atoms, X is independently a hydrogen atom or a methyl group, n1 is independently a number from 2 to 10, n2 is a number from 0 to 8, R 1 It is a group represented by the following formula (2) or formula (3), wherein a is a number from 0 to 400, and b is a number from 1 to 100, provided that a+b satisfies 1≤a+b≤500. The siloxane units enclosed by a and b may be connected in blocks or randomly.

[0016] [Chemistry 2]

[0017] -CH2CH2-OR 2 (2)

[0018]

[0019] (In formula (2), R 2 is a group represented by the following formula (4), wherein R 3 are independently a hydrogen atom or a group represented by the following formula (4), and in the above formula (1), there is at least one group represented by the following formula (4).

[0020] [Chemistry 3]

[0021]

[0022] (In formula (4), R 4 is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

[0023] <2> The side chain urethane-modified silicone macromonomer according to <1>, wherein in formula (4), R 4 It is a group selected from an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.

[0024] <3> A copolymer of the side chain urethane-modified silicone macromonomer according to <1> or <2> and a polymerizable hydrophilic monomer.

[0025] <4> The copolymer according to <3>, wherein the polymerizable hydrophilic monomer is at least one selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, acrylic acid, and methacrylic acid.

[0026] <5> A contact lens comprising the copolymer according to <3> or <4>.

[0027] Effects of the Invention

[0028] The side-chain carbamate-modified silicone macromer of the present invention has a carbamate moiety in its side chain, thereby improving its compatibility with polymerizable hydrophilic monomers. Therefore, the side-chain carbamate-modified silicone macromer of the present invention is suitable as a material for contact lenses, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The side chain carbamate modified silicone macromonomer obtained in Example 1 1 Graph of the H-NMR spectrum. DETAILED DESCRIPTION

[0030] Hereinafter, the present invention will be described in detail.

[0031] [Side-chain urethane-modified silicone macromonomer]

[0032] The side chain urethane-modified silicone macromonomer of the present invention is represented by the following formula (1).

[0033] [Chemistry 4]

[0034]

[0035] (In 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, or an aralkyl group having 7 to 10 carbon atoms, X is independently a hydrogen atom or a methyl group, n1 is independently a number from 2 to 10, n2 is a number from 0 to 8, R 1 It is a group represented by the following formula (2) or formula (3), wherein a is a number from 0 to 400, and b is a number from 1 to 100, wherein a+b satisfies 1≤a+b≤500. The siloxane units enclosed by a and b may be connected in blocks or randomly.

[0036] [Chemistry 5]

[0037] -CH2CH2-OR 2 (2)

[0038]

[0039] (In formula (2), R 2 is a group represented by the following formula (4), wherein R 3 are independently a hydrogen atom or a group represented by the following formula (4), and in the above formula (1), there is at least one group represented by the following formula (4).

[0040] [Chemistry 6]

[0041]

[0042] (In formula (4), R 4 is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

[0043] In the above 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, or 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, methylphenyl, and ethylphenyl. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and phenylethyl.

[0044] In the above formula (1), X is independently a hydrogen atom or a methyl group. n1 is independently 2 to 10, preferably 2 to 4, and n2 is 0 to 8, preferably 1 to 3. a is 0 to 400, preferably 5 to 100, and b is 1 to 100, preferably 1 to 20. However, a+b is 1 ≤ a+b ≤ 500, preferably 6 ≤ a+b ≤ 120. Furthermore, the bonding of the siloxane units enclosed by a and b may be random or block-like.

[0045] In the above formula (2), R 2 It is a group represented by the above formula (4).

[0046] In the above formula (3), R 3 Each of them is independently a hydrogen atom or a group represented by the above formula (4). In the above formula (1), there is at least one group represented by the above formula (4).

[0047] In the above formula (4), R 4is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, and octyl groups; and cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl groups. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and phenylethyl groups.

[0048] [Method for producing side-chain urethane-modified silicone macromonomer]

[0049] The method for producing a side chain urethane-modified silicone macromonomer of the present invention (hereinafter sometimes abbreviated as "the production method of the present invention") comprises a step of reacting an isocyanate represented by the following formula (5) with a side chain hydroxyl-modified silicone macromonomer represented by the following formula (6).

[0050] [Chemistry 7]

[0051]

[0052] (In formula (5), R 4 is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

[0053] [Chemistry 8]

[0054]

[0055] (In formula (6), 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, or an aralkyl group having 7 to 10 carbon atoms, X is independently a hydrogen atom or a methyl group, n1 is independently a number from 2 to 10, n2 is a number from 0 to 8, and R 5 It is a group represented by the following formula (7) or (8), wherein a is a number from 0 to 400, and b is a number from 1 to 100, provided that a+b satisfies 1≤a+b≤500. The siloxane units enclosed by a and b may be connected in blocks or randomly.

[0056] [Chemistry 9]

[0057] -CH2CH2-OH (7)

[0058]

[0059] In the above formula (5), R 4is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, and octyl groups; and cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl groups. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and phenylethyl groups.

[0060] In the above formula (6), 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, or 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, methylphenyl, and ethylphenyl. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and phenylethyl.

[0061] In the above formula (6), X is independently a hydrogen atom or a methyl group. n1 is independently 2 to 10, preferably 2 to 4, and n2 is independently 0 to 8, preferably 1 to 3. a is 0 to 400, preferably 5 to 100, and b is 1 to 100, preferably 1 to 20. However, a+b is 1 ≤ a+b ≤ 500, preferably 6 ≤ a+b ≤ 120. Furthermore, the bonding of the siloxane units enclosed by a and b may be block or random.

[0062] In the production method of the present invention, the molar ratio of the isocyanate represented by formula (5) to the hydroxyl group in formula (6) is preferably 0.1 to 2 times, more preferably 0.5 to 1 time.

[0063] As the catalyst used in the production method of the present invention, a known urethanization catalyst can be used. Examples of urethanization catalysts include tertiary amines such as triethylamine and 1,4-diazabicyclo[2.2.2]octane; and organometallic compounds such as iron(III) acetylacetonate, dibutyltin dilaurate, dioctyltin dilaurate, bismuth 2-ethylhexanoate, bismuth octoate, tetrabutyl orthotitanate, diisopropoxybis(acetylacetonate)titanium, tetrabutoxyzirconium, and zirconium tetraacetylacetonate. Of these, iron(III) acetylacetonate is preferred.

[0064] In the production method of the present invention, the amount of the catalyst is not particularly limited, but is preferably 10 to 1000 ppm relative to the weight of the hydroxyl-modified silicone macromonomer represented by formula (6).

[0065] In the production method of the present invention, the reaction temperature in the step of reacting the hydroxy-modified silicone macromonomer represented by formula (6) with the isocyanate represented by formula (5) in the presence of a urethanization catalyst is preferably 40°C or higher and 90°C or lower, and more preferably 50°C or higher and 70°C or lower.

[0066] In the production method of the present invention, reaction conditions such as reaction time and solvent are not particularly limited. The reaction time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and most preferably 2 to 6 hours. The solvent is preferably an aromatic hydrocarbon solvent such as toluene or xylene.

[0067] [Copolymer]

[0068] The side chain urethane-modified silicone macromonomer of the present invention has excellent compatibility with polymerizable hydrophilic monomers and therefore easily forms a copolymer.

[0069] Preferred examples of the polymerizable hydrophilic monomer include acrylamide monomers such as acrylamide, methacrylamide, N,N-dimethylacrylamide, and N,N-dimethylmethacrylamide; vinylamide monomers such as N-methyl-N-vinylacetamide; N-vinyl cyclic amide monomers such as N-vinylpyrrolidone and N-vinylcaprolactam; hydroxyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, N-hydroxyethylacrylamide, and N-hydroxyethylmethacrylamide; amino monomers such as N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminoethyl acrylate, and N,N-dimethylaminoethyl methacrylate; and carboxylic acid monomers such as acrylic acid and methacrylic acid.

[0070] The amount of the polymerizable hydrophilic monomer forming the copolymer is preferably 50 to 1000 parts by mass, more preferably 100 to 500 parts by mass, based on 100 parts by mass of the side chain urethane-modified silicone macromonomer.

[0071] Polymerization is carried out by heat or ultraviolet irradiation. These methods are well known in the art. Polymerization using ultraviolet irradiation is carried out by adding a photopolymerization initiator to a side-chain carbamate-modified silicone macromonomer and a polymerizable hydrophilic monomer, followed by ultraviolet irradiation. A representative photopolymerization initiator is 2-hydroxy-2-methyl-1-phenylpropanone (trade name: Omnirad-1173, manufactured by IGM Resins BV), but is not limited to this.

[0072] Example

[0073] The present invention will be described in more detail below with reference to the following examples, but modifications may be made without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited to the specific examples shown below.

[0074] Synthesis of Side-chain Carbamate-modified Silicone Macromonomer

[0075] [Example 1]

[0076] In a separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 100.0 g of a side chain hydroxy-modified silicone macromonomer represented by the following formula (a), 9.3 g of phenyl isocyanate (an amount such that the ratio of the number of moles of isocyanate to the total number of moles of hydroxyl groups in the side chain hydroxy-modified silicone macromonomer becomes 1.0), 0.0030 g of iron (III) acetylacetonate, 0.010 g of dibutylhydroxytoluene, 0.010 g of 4-methoxyphenol, and 30 g of toluene were placed, and heated and stirred at 60°C for 5 hours. After the reaction was completed, 1.5 g of KYOWAAD 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 1.5 hours. The solid was removed by pressure filtration. The low-boiling point fraction was removed at 75°C under a reduced pressure of 0.4 kPa for 2 hours to obtain 94.9 g of a side chain carbamate-modified silicone macromonomer represented by the following formula (b).

[0077] [Chemistry 10]

[0078]

[0079] The side chain urethane modified silicone macromonomer obtained in Example 1 is shown below. 1 H-NMR spectroscopy, and Figure 1 Shown in 1 Graph of the H-NMR spectrum.

[0080] 1 H-NMR (400MHz, CDCl3): δ-0.51~0.21 (m, 540H), 0.35~0.57 (m, 16H), 1.47~1.70 (m, 16H), 1.87 (s, 6H), 3.37 (t, J=7.1Hz, 1 2H), 3.59 (t, J=4.6Hz, 12H), 4.03 (t, J=7.0Hz, 4H), 4.24 (t, J=4.4Hz, 12H), 5.46 (s, 2H), 6.03 (s, 2H), 6.49~7.41 (m, 30H)

[0081] [Example 2]

[0082] Synthesis was performed in the same manner as in Example 1, except that 100.0 g of the side-chain hydroxyl-modified silicone macromonomer represented by the above formula (a), 9.8 g of cyclohexyl isocyanate (an amount such that the ratio of the number of moles of isocyanate to the total number of moles of hydroxyl groups in the side-chain hydroxyl-modified silicone macromonomer is 1.0), 0.0030 g of iron (III) acetylacetonate, 0.010 g of dibutylhydroxytoluene, 0.010 g of 4-methoxyphenol, and 30 g of toluene were used. 93.6 g of a side-chain urethane-modified silicone macromonomer represented by the following formula (c) was obtained.

[0083] [Chemistry 11]

[0084]

[0085] The side chain urethane modified silicone macromonomer obtained in Example 2 is shown below. 1 H-NMR spectrum.

[0086] 1 H-NMR (400MHz, CDCl3): δ-0.26~0.23 (m, 540H), 0.41~0.59 (m, 16H), 1.02~1.20 (m, 18H), 1.24~1.40 (m, 12H), 1.51~1.73 (m, 34H), 1.82~1.95 (m, 18H), 3.29~3.51 (m, 18H), 3.58 (t, J=4.5Hz, 12H), 4.08 (t, J=6.8Hz, 4H), 4.16 (t, J=3.8Hz, 12H), 4.63 (brs, 6H), 5.51 (s, 2H), 6.08 (s, 2H)

[0087] [Example 3]

[0088] Synthesis was performed in the same manner as in Example 1, except that 200.0 g of a side-chain hydroxyl-modified silicone macromonomer represented by the following formula (d), 18.2 g of phenyl isocyanate (an amount such that the ratio of the number of moles of isocyanate to the total number of moles of hydroxyl groups in the side-chain hydroxyl-modified silicone macromonomer is 0.5), 0.0060 g of iron (III) acetylacetonate, 0.020 g of dibutylhydroxytoluene, 0.020 g of 4-methoxyphenol, and 70 g of toluene were used. 189 g of a side-chain urethane-modified silicone macromonomer represented by the following formula (e) was obtained.

[0089] [Chemistry 12]

[0090]

[0091] (In the above formula (e), R 6 and R7 is a hydrogen atom or a group represented by the above formula (9), and has an average of 6 hydrogen atoms and 6 groups represented by the above formula (9) in one molecule.

[0092] The side chain urethane modified silicone macromonomer obtained in Example 3 is shown below. 1 H-NMR spectrum.

[0093] 1 H-NMR (400MHz, CDCl3): δ-0.39~0.24(m, 540H), 0.34~0.57(m, 16H), 1.45~1.71(m, 16H), 1.87(s, 6H), 3.25~3.50(m, 20H), 3.52~3.69 (m, 8H), 3.73~3.86 (m, 4H), 3.93~4.00 (m, 2H), 4.03 (t, J=7.0Hz, 4H), 4.07~4.41 (m, 8H), 5.47 (s, 2H), 6.03 (s, 2H), 6.61~7.43 (m, 30H)

[0094] [Example 4]

[0095] Synthesis was performed in the same manner as in Example 1, except that 200.0 g of the side-chain hydroxyl-modified silicone macromonomer represented by the above formula (d), 34.6 g of phenyl isocyanate (an amount such that the ratio of the number of moles of isocyanate to the total number of moles of hydroxyl groups in the side-chain hydroxyl-modified silicone macromonomer is 1.0), 0.0120 g of iron (III) acetylacetonate, 0.020 g of dibutylhydroxytoluene, 0.020 g of 4-methoxyphenol, and 100 g of toluene were used. 197 g of a side-chain carbamate-modified silicone macromonomer represented by the following formula (f) was obtained.

[0096] [Chemistry 13]

[0097]

[0098] The side chain urethane modified silicone macromonomer obtained in Example 4 is shown below. 1 H-NMR spectrum.

[0099] 1H-NMR (400MHz, CDCl3): δ-0.37~0.16(m, 540H), 0.34~0.54(m, 16H), 1.44~1.68(m, 16H), 1.87(s, 6H), 3.28~3.43(m , 12H), 3.53~3.63(m, 12H), 4.03(t, J=6.8Hz, 4H), 4.24~4.45(m, 12H), 5.46(s, 2H), 6.03(s, 2H), 6.58~7.43(m, 60H)

[0100] [Example 5]

[0101] Synthesis was performed in the same manner as in Example 1, except that 200.0 g of the side-chain hydroxyl-modified silicone macromonomer represented by the above formula (d), 19.1 g of cyclohexyl isocyanate (an amount such that the ratio of the number of moles of isocyanate to the total number of moles of hydroxyl groups in the side-chain hydroxyl-modified silicone macromonomer is 0.5), 0.0060 g of iron (III) acetylacetonate, 0.020 g of dibutylhydroxytoluene, 0.020 g of 4-methoxyphenol, and 70 g of toluene were used. 195 g of a side-chain urethane-modified silicone macromonomer represented by the following formula (g) was obtained.

[0102] [Chemistry 14]

[0103]

[0104] (In the above formula (g), R 8 and R 9 is a hydrogen atom or a group represented by the above formula (10), and has an average of 6 hydrogen atoms and 6 groups represented by the above formula (10) in one molecule.

[0105] The side chain urethane modified silicone macromonomer obtained in Example 5 is shown below. 1 H-NMR spectrum.

[0106] 1 H-NMR (400MHz, CDCl3): δ-0.37~0.27 (m, 540H), 0.36~0.60 (m, 16H), 0.97~1.21 (m, 18H), 1.21~1. 39(m, 12H), 1.47~1.78(m, 34H), 1.80~1.98(m, 18H), 3.21~4.29(m, 52H), 5.51(s, 2H), 6.07(s, 2H)

[0107] [Compatibility test]

[0108] [Test Examples 1 to 3]

[0109] A compatibility test was conducted on the side chain carbamate modified silicone macromonomers represented by the above formula (b), the above formula (e), and the above formula (f). A polymerizable hydrophilic monomer of the same weight was added to the silicone macromonomer to investigate compatibility. The polymerizable hydrophilic monomers used were dimethylacrylamide (DMAA), N-vinylpyrrolidone (NVP), and 2-hydroxyethyl methacrylate (HEMA). If the mixed solution became a transparent, uniform liquid, it was marked as "○." If it did not become a transparent, uniform liquid, it was marked as "×." The compatibility test was then conducted. The results are shown in Table 1.

[0110] [Comparative Test Examples 1 and 2]

[0111] The compatibility test was conducted in the same manner as in Test Examples 1 to 3 except that a side-chain hydroxyl-modified silicone macromonomer was used instead of the side-chain urethane-modified silicone macromonomer.

[0112] [Table 1]

[0113]

[0114] The side chain urethane-modified silicone macromonomer of the present invention exhibits higher compatibility with the polymerizable hydrophilic monomer than the side chain hydroxyl-modified silicone macromonomers of Comparative Test Examples 1 and 2.

[0115] Synthesis of copolymers

[0116] [Example 6]

[0117] 3 g of the side chain urethane modified silicone macromonomer represented by the above formula (b), 3 g of N-vinyl pyrrolidone (NVP), and 0.02 g of 2-hydroxy-2-methyl-1-phenylpropanone (trade name: Omnirad-1173, manufactured by IGM Resins BV) were mixed and stirred until a uniform solution was obtained. After standing to degas, the mixture was sealed in a mold. UV irradiation (wavelength 365 nm, irradiation dose 95000 mJ / cm) was performed using a metal halide lamp. 2 ), and cured at room temperature (20°C). The cured product is a transparent solid.

[0118] Industrial applicability

[0119] The silicone macromonomer of the present invention is highly compatible with polymerizable hydrophilic monomers and can be used as a material for contact lenses.

Claims

1. A side chain urethane-modified silicone macromonomer represented by the following formula (1): [Chemistry 1] In 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, or an aralkyl group having 7 to 10 carbon atoms, X is independently a hydrogen atom or a methyl group, n1 is independently a number from 2 to 10, n2 is a number from 0 to 8, and R 1 It is a group represented by the following formula (2) or formula (3), wherein a is a number from 0 to 400, and b is a number from 1 to 100, provided that a+b is 1≤a+b≤500. Furthermore, the bonding of the siloxane units enclosed by a and b may be block or random. [Chemistry 2] -CH2CH2-O-R 2 (2) In formula (2), R 2 is a group represented by the following formula (4), wherein R 3 are independently a hydrogen atom or a group represented by the following formula (4), in the above formula (1), there is at least one group represented by the following formula (4), [Chemistry 3] In formula (4), R 4 It is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

2. The side chain carbamate modified silicone macromonomer according to claim 1, wherein In formula (4), R 4 It is a group selected from an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.

3. The copolymer of the side chain urethane modified silicone macromonomer and a polymerizable hydrophilic monomer according to claim 1.

4. The copolymer according to claim 3, wherein The polymerizable hydrophilic monomer is one or more selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, acrylic acid and methacrylic acid.

5. Contact lens comprising the copolymer according to claim 3.

Images