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EP-4741442-A1 - DOUBLE-TERMINAL (METH)ACRYLIC-MODIFIED SILICONE MACROMER HAVING TERTIARY AMINO GROUP OR QUATERNARY AMMONIUM CATION SITE IN MOLECULAR CHAIN, AND METHOD FOR PRODUCING SAME

EP4741442A1EP 4741442 A1EP4741442 A1EP 4741442A1EP-4741442-A1

Abstract

[Object] One of the purposes of the present invention is to provide a silicone macromer having a (meth)acrylic group in a high percentage at double-terminals and having a quaternary ammonium cation site in a molecular chain. [Solution] The present invention provides a double-terminal (meth)acrylic-modified silicone macromer having a tertiary amino group in a molecular chain represented by the following general formula (1): The present invention further provides a double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in a molecular chain represented by the following general formula (4): In general formulas (1) and (4), 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 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 2 is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; X is, independently of each other, a hydrogen atom or a methyl group; Q is a divalent organic group; "a" is, independently of each other, an integer of 1 to 400; "b" is an integer of 1 to 50; "n1" is, independently of each other, an integer of 2 to 10; and Y is a chlorine atom, a bromine atom, or an iodine atom.

Inventors

  • WATANABE, TAKUMA

Assignees

  • SHIN-ETSU CHEMICAL CO., LTD.

Dates

Publication Date
20260513
Application Date
20240702

Claims (18)

  1. A double-terminal (meth)acrylic-modified silicone macromer having a tertiary amino group in a molecular chain, represented by the following general formula (1): wherein, 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 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; X is, independently of each other, a hydrogen atom or a methyl group; Q is a divalent organic group; "a" is, independently of each other, an integer of 1 to 400; "b" is an integer of 1 to 50; and "n1" is, independently of each other, an integer of 2 to 10.
  2. The double-terminal (meth)acrylic-modified silicone macromer having a tertiary amino group in the molecular chain according to claim 1, wherein Q in said general formula (1) is, independently of each other, a group represented by the following formula (2) or the following formula (3): wherein, in formula (2), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, "n2" is an integer of 2 to 10, and "n3" is an integer of 0 to 10; wherein, in formula (3), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, and 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.
  3. A double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in a molecular chain, represented by the following general formula (4): wherein, in general formula (4), 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 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 2 is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; X is, independently of each other, a hydrogen atom or a methyl group; Q is a divalent organic group; "a" is, independently of each other, an integer of 1 to 400; "b" is an integer of 1 to 50; "n1" is, independently of each other, an integer of 2 to 10; and Y is a chlorine atom, a bromine atom, or an iodine atom.
  4. The double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in the molecular chain according to claim 3, wherein Q in said general formula (4) is, independently of each other, a group represented by the following formula (2) or (3): wherein, in formula (2), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, "n2" is an integer of 2 to 10, and "n3" is an integer of 0 to 10; wherein, in formula (3), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, and 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.
  5. A method for producing a double-terminal (meth)acrylic-modified silicone macromer having a tertiary amine in a molecular chain, represented by the following general formula (1): wherein, 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 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; X is, independently of each other, a hydrogen atom or a methyl group; Q is a divalent organic group; "a" is, independently of each other, an integer of 1 to 400; "b" is an integer of 1 to 50; and "n1" is, independently of each other, an integer of 2 to 10, wherein the method comprises a step of subjecting an organopolysiloxane (A) having a tertiary amino group in a molecular chain represented by the following general formula (7) to a reaction with an isocyanate (B) having a (meth)acrylic group represented by the following general formula (10) to obtain the double-terminal (meth)acrylic-modified silicone macromer represented by said general formula (1): wherein, in formula (7), R, R 1 , a, and b are as defined above, and Q 1 is a group represented by the following formula (8) or (9): wherein, in formula (8), "n2" is an integer of 2 to 10, and "n3" is an integer of 0 to 10; wherein, in formula (9), R 1 is as defined above; wherein, in general formula (10), X and "n1" are as defined above.
  6. The method for producing the double-terminal (meth)acrylic-modified silicone macromer having a tertiary amine in the molecular chain according to claim 5, wherein Q in said general formula (1) is, independently of each other, a group represented by the following formula (2) or the following formula (3): wherein, in formula (2), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, and "n2" and "n3" are as defined above; wherein, in formula (3), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, and R 1 is as defined above.
  7. The method for producing the double-terminal (meth)acrylic-modified silicone macromer having a tertiary amine in the molecular chain according to claim 5, further comprising a step of subjecting an organopolysiloxane having a hydrosilyl group at least at one terminal and having a tertiary amino group in a molecular chain to a reaction with a (poly)ethylene glycol allyl ether in the presence of a platinum catalyst to obtain the organopolysiloxane (A) having a tertiary amino group in the molecular chain represented by said general formula (7).
  8. The method for producing the double-terminal (meth)acrylic-modified silicone macromer having a tertiary amine in the molecular chain according to claim 7, further comprising a step of reacting a double-terminal hydrosilyl group-modified organohydrogen polysiloxane with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain the organopolysiloxane having a hydrosilyl group at a terminal and having a tertiary amino group in the molecular chain.
  9. A method for producing a double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in a molecular chain, represented by the following general formula (4): wherein, in general formula (4), 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 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 2 is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; X is, independently of each other, a hydrogen atom or a methyl group; Q is a divalent organic group; "a" is, independently of each other, an integer of 1 to 400; "b" is an integer of 1 to 50; "n1" is, independently of each other, an integer of 2 to 10; and Y is a chlorine atom, a bromine atom, or an iodine atom, wherein the method comprises a step of subjecting a double-terminal (meth)acrylic-modified silicone macromer (a) having a tertiary amino group in a molecular chain represented by the following general formula (1) to a reaction with a halogenated hydrocarbon (b) represented by the following formula (14) to obtain the double-terminal (meth)acrylic-modified silicone macromer represented by said general formula (4): wherein, in general formula (1), R, R 1 , X, Q, "a", "b", and "n1" are as defined above; wherein, in formula (14), R 2 is as defined above, and Y is a chlorine atom, a bromine atom, or an iodine atom.
  10. The method for producing the double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in the molecular chain according to claim 9, wherein Q in said general formulas (1) and (4) is a group represented by the following formula (2) or the following formula (3): wherein, in formula (2), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, "n2" is, independently of each other, an integer of 2 to 10, and "n3" is, independently of each other, an integer of 0 to 10; wherein, in formula (3), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, and R 1 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.
  11. The method for producing the double-terminal (meth)acrylic-modified silicone macromer according to claim 10, further comprising a step of subjecting an organopolysiloxane having a hydroxy group or a secondary amino group at a terminal and having a tertiary amino group in a molecular chain to a reaction with an isocyanate having a (meth)acrylic group to obtain the double-terminal (meth)acrylic-modified silicone macromer (a) represented by said general formula (1).
  12. The method for producing the double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in the molecular chain according to claim 11, wherein the organopolysiloxane having a hydroxy group or a secondary amino group at a terminal and having a tertiary amino group in the molecular chain is represented by the following general formula (7): wherein, in general formula (7), R, R 1 , "a", and "b" are as defined above, and Q 1 is, independently of each other, a group represented by the following formula (8) or (9): wherein, in formula (8), "n2" and "n3" are as defined above; wherein, in formula (9), R 1 is as defined above.
  13. The method for producing the double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in the molecular chain according to claim 12, further comprising a step of subjecting an organopolysiloxane having a hydrosilyl group at least at one terminal and having a tertiary amino group in a molecular chain to a reaction with a (poly)ethylene glycol allyl ether in the presence of a platinum catalyst to obtain the organopolysiloxane having a tertiary amino group in the molecular chain represented by general formula (7).
  14. The method for producing the double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in the molecular chain according to claim 13, further comprising a step of reacting a double-terminal hydrosilyl group-modified organohydrogen polysiloxane with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain the organopolysiloxane having a hydrosilyl group at a terminal and having a tertiary amino group in the molecular chain.
  15. A copolymer of the double-terminal (meth)acrylic-modified silicone macromer having a tertiary amino group in the molecular chain according to claim 1 and a polymerizable monomer having a group that polymerizes with the (meth)acrylic-modified silicone macromer.
  16. A copolymer of the double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in the molecular chain according to claim 3 and a polymerizable monomer having a group that polymerizes with the (meth)acrylic-modified silicone macromer.
  17. A silicone hydrogel comprising the copolymer according to claim 15 or 16.
  18. An ophthalmic lens comprising the silicone hydrogel according to claim 17.

Description

TECHNICAL FIELD The present invention relates to a double-terminal (meth)acrylic-modified silicone macromer having a tertiary amino group or a quaternary ammonium cation site in a molecular chain, and a method for producing the same. BACKGROUND ART 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 is being considered to make the contact lens surface hydrophilic. Among such considerations, the introduction of quaternary ammonium cation sites in silicone chains has been reported (Patent Literature 1 to 4). Among such reports, Patent Literature 1 describes a method for synthesizing a silicone macromer having a polymerizable group at double-terminals and having a quaternary ammonium cation site in a molecular chain. PRIOR LITERATURE PATENT LITERATURE Patent Literature 1: JP National Phase Laid-Open No. 2009-542855Patent Literature 2: JP National Phase Laid-Open No. 2009-533532Patent Literature 3: JP National Phase Laid-Open No. 2010-516873Patent Literature 4: JP National Phase Laid-Open No. 2009-521547 SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION However, it is inferred that in a production method according to Patent Literature 1, a certain amount of silicone without polymerizable groups is contained as an impurity. It is unfavorable for silicone that is typically used as a contact lens material to contain a large amount of compounds without polymerizable groups. It is therefore desirable to establish a method for producing a silicone macromer having a quaternary ammonium cation site in a molecular chain, in which a (meth)acrylic group is introduced in a high percentage at double-terminals. One of the purposes of the present invention is to provide a silicone macromer having a (meth)acrylic group in a high percentage at double-terminals and having a quaternary ammonium cation site in a molecular chain. MEANS FOR SOLVING THE PROBLEMS As a result of diligent research to achieve the aforementioned purpose, the inventor found that subjecting an organopolysiloxane having a hydroxy group or a secondary amino group at double-terminals and having a tertiary amino group in a molecular chain to a reaction with an isocyanate having a (meth)acrylic group, followed by quaternization into a quaternary ammonium salt to give a silicone macromer having a (meth)acrylic group in a high percentage at double-terminals and having a quaternary ammonium cation site in a molecular chain, thereby completing the present invention. That is, the present invention provides a double-terminal (meth)acrylic-modified silicone macromer having a tertiary amino group in a molecular chain represented by the following general formula (1): wherein, 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: R1 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; X is, independently of each other, a hydrogen atom or a methyl group; Q is a divalent organic group; "a" is, independently of each other, an integer of 1 to 400; "b" is an integer of 1 to 50; and "n1" is, independently of each other, an integer of 2 to 10. Preferably, the double-terminal (meth)acrylic-modified silicone macromer further comprises the constituent feature of the following item [1]. [1] The double-terminal (meth)acrylic-modified silicone macromer having a tertiary amino group in the molecular chain, wherein Q in said general formula (1) is, independently of each other, a group represented by the following formula (2) or the following formula (3): wherein, in formula (2), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, "n2" is an integer of 2 to 10, and "n3" is an integer of 0 to 10; wherein, in formula (3), the site marked with ** bonds to the silicon atom, the site marked with * bonds to the carbonyl group, and R1 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 present invention further provides a double-terminal (meth)acrylic-modified silicone macromer having a quaternary ammonium cation site in a molecular chain represented by the following general formula (4): wherein, in general formula (4), 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; R1 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; R2 i