JP6618897B2 - Novel polymer and production method thereof - Google Patents

Description

  The present invention relates to a novel polymer and a method for producing the same.

  Conventionally, polymers obtained by polymerizing monomers having an unsaturated bond such as styrene, vinyl acetate, (meth) acrylate and the like have been widely used in various fields. In particular, since poly (meth) acrylate has excellent transparency and a high refractive index, it is used for optical members such as lenses, films, optical fibers, and semiconductor encapsulating materials (Patent Document 1).

  However, although poly (meth) acrylate is excellent in transparency and refractive index, it has a problem of poor heat resistance because of its low glass transition temperature (Tg).

  On the other hand, a polyimide resin is commercially available as a polymer having excellent heat resistance, and is known as a resin that can be used for a long time even at a high temperature of 250 ° C. or higher.

  However, since polyimide is a thermosetting resin and does not have thermoplasticity, injection molding or extrusion molding is difficult, the shape of the molded product is limited, and it is very expensive. Therefore, an inexpensive heat-resistant polymer excellent in heat resistance is desired.

  JP 2004-143109 A

  An object of the present invention is to provide a novel polymer having excellent heat resistance and exhibiting thermoplasticity.

  As a result of intensive studies in view of the above problems, the present inventor conducted a polymerization reaction using an oxazolidinone derivative derived from an amino acid, alanine, as a raw material monomer. As a result, a novel compound having a high glass transition temperature (Tg) It was found that an excellent polymer can be obtained. Moreover, it discovered that it could convert into the polyfunctional polymer which has an amino group and a carboxyl group on the same carbon by hydrolyzing the obtained polymer. As a result of further research based on this knowledge, the present inventor has completed the present invention.

That is, the present invention provides a novel oxazolidinone polymer and a production method thereof.
Item 1.
General formula (2):

(Wherein R ¹ represents a hydrogen atom or an organic group.
R ² and R ³ are the same or different and are a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hetero which may have a substituent. Represents an aryl group, or R ² and R ³ may combine with each other to form a ring with adjacent carbon atoms;
R ⁴ represents a hydrogen atom or a halogen atom. )
The polymer containing the structural unit represented by these.
Item 2.
Group represented by R ¹ is an alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, heteroarylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, heteroaryloxy group, an alkoxycarbonylalkyl group Item 2. The polymer according to Item 1, wherein the polymer is an aryloxycarbonylalkyl group, or a heteroaryloxycarbonylalkyl group (these groups optionally have a substituent).
Item 3.
Item 3. The polymer according to Item 1 or 2, further comprising a structural unit derived from a polymerizable monomer other than the structural unit represented by the general formula (2).
Item 4.
The polymer according to any one of Items 1 to 3,
General formula (1):

(Wherein, R ⁴ represents a hydrogen atom or a halogen atom. Wavy line, the double bond stereochemistry E-form, Z form, or .R ¹ ~ indicating that it is a mixture of E-form and Z-form R ³ is the same as described above), and a polymer obtained by copolymerizing a monomer represented by the above and another polymerizable monomer.
Item 5.
Item 3. The method for producing a polymer according to Item 1 or 2,
General formula (1):

(Wherein, R ⁴ represents a hydrogen atom or a halogen atom. Wavy line, the double bond stereochemistry E-form, Z form, or .R ¹ ~ indicating that it is a mixture of E-form and Z-form R ³ is the same as above.)
A production method comprising a step of polymerizing a monomer represented by:
Item 6.
Item 5. The method for producing a polymer according to Item 3 or 4, wherein
General formula (1):

(Wherein, R ⁴ represents a hydrogen atom or a halogen atom. Wavy line, the double bond stereochemistry E-form, Z form, or .R ¹ ~ indicating that it is a mixture of E-form and Z-form R ³ is the same as above.)
A production method comprising a step of copolymerizing a monomer represented by the above and another polymerizable monomer.
Item 7.
General formula (5):

(Wherein R ¹ represents a hydrogen atom or an organic group.
R ⁴ represents a hydrogen atom or a halogen atom.
Y represents a hydrogen atom or a counter cation. )
A process for producing a polymer comprising a structural unit represented by
A manufacturing method provided with the process of hydrolyzing the polymer of claim | item 1.
Item 8.
General formula (1a):

(Wherein R ^1a represents a hydrogen atom or an organic group.
R ^2a and R ^3a are the same or different and are a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hetero which may have a substituent. Represents an aryl group, or R ² and R ³ may combine with each other to form a ring with adjacent carbon atoms;
R ^4a represents a hydrogen atom or a halogen atom.
The wavy line indicates that the stereochemistry of the double bond is E-form, Z-form, or a mixture of E-form and Z-form. However, the compounds represented by the following formulas (a) to (e) are excluded. )
A compound represented by

Item 9.
Item 5. A resin composition for an optical material using the polymer according to any one of Items 1 to 4.
Item 10.
Item 5. A molded body using the polymer according to any one of Items 1 to 4.
Item 11.
Item 5. An optical material using the polymer according to any one of Items 1 to 4.
Item 12.
Item 5. A lens using the polymer according to any one of Items 1 to 4.

  ADVANTAGE OF THE INVENTION According to this invention, the polymer which has the novel oxazolidinone structure which shows the outstanding heat resistance, transparency, refractive index, and thermoplasticity, and its manufacturing method can be provided.

  Moreover, the polyfunctional polymer which has a hydrophilic amino group and a carboxyl group on the same carbon can be manufactured by hydrolyzing the polymer which has an oxazolidinone structure of this invention. Such a polyfunctional polymer has excellent water absorbability and can be used for applications such as a polymer absorbent.

1 is a ¹ H-NMR chart of the monomer obtained in Production Example 1. FIG. FIG. 2 is an IR chart of the monomer obtained in Production Example 1. FIG. 3 is a ¹ H-NMR chart of the monomer obtained in Production Example 3. FIG. 4 is an IR chart of the monomer obtained in Production Example 3. FIG. 5 is an IR chart of the polymer obtained in Example 16. FIG. 6 is a photograph of a water-containing gel obtained by swelling the polymer obtained in Example 16 with water (distilled water).

  Hereinafter, the novel polymer having an oxazolidinone structure of the present invention and the production method thereof will be specifically described.

  In this specification, the expression “containing” or “including” includes the concepts of “containing”, “including”, “consisting essentially only”, and “consisting only”.

1. Method for producing a polymer for manufacturing the present invention polymers, a monomer represented by the general formula (1) (hereinafter, referred to as "the general formula (1 monomer)", or "compound represented by the general formula (1)" There is also a step of polymerizing. The polymer compound obtained by the production method is a polymer having a structural unit (unit) represented by the general formula (2) in the molecule. Moreover, the polymer containing the structural unit represented by General formula (5) in a molecule | numerator can also be manufactured by chemically converting (modifying) the polymer obtained in this way.

  Hereinafter, description will be made by dividing into a process for producing a polymer by polymerization reaction of monomers and a process for chemically converting (modifying) the obtained polymer.

1.1 Polymerization Reaction A polymer containing a structural unit represented by the general formula (2) can be produced, for example, by subjecting a compound represented by the general formula (1) to a polymerization reaction. Moreover, it can manufacture by carrying out the copolymerization reaction of the compound represented with General formula (1), and another polymerizable monomer as needed.

  The polymerization method is not particularly limited, and known polymerization methods such as radical polymerization, ionic polymerization, coordination polymerization, rearrangement polymerization and the like can be applied. A radical polymerization method can be adopted as a polymerization method for producing a polymer containing a structural unit represented by a typical general formula (2). A specific production scheme is shown below.

(Wherein R ¹ represents a hydrogen atom or an organic group.
R ² and R ³ are the same or different and are a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hetero which may have a substituent. Represents an aryl group, or R ² and R ³ may combine with each other to form a ring with adjacent carbon atoms;
R ⁴ is the same or different and represents a hydrogen atom or a halogen atom. )
The organic group represented by R ¹ is a group containing a carbon atom, and may have an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a fluorine atom, a chlorine atom, etc.). Good.

Specific examples of the organic group represented by R ¹ include, but are not limited to, alkyl groups, aryl groups, heteroaryl groups, alkylcarbonyl groups, arylcarbonyl groups, heteroarylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyls. A group, a heteroaryloxycarbonyl group, an alkoxycarbonylalkyl group, an aryloxycarbonylalkyl group, or a heteroaryloxycarbonylalkyl group (these groups optionally have a substituent).

The alkyl group represented by R ^1, is not particularly limited, for example, linear, alkyl group having 1 to 10 carbon atoms, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and a cyclopentyl group. , N-hexyl group, cyclohexyl group, isohexyl group and the like, and C1-6 alkyl groups. Among them, preferred alkyl groups are a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The alkyl group is, for example, an alkenyl group (eg, vinyl group, allyl group, etc.), a halogen atom (eg, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group (eg, COOCH ₃ , COOC ₂ H ₅ etc.) 1 to 5 substituents such as an amide group and a hydroxyl group which may be protected.

The aryl group represented by R ^1, is not particularly limited, for example, monocyclic or bicyclic or more aryl groups. Specific examples of the aryl group include a phenyl group, a toluyl group, a xylyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Among them, preferred aryl groups are a phenyl group and a naphthyl group. Examples of the aryl group include an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester It may have 1 to 5 substituents such as a group (for example, COOCH ₃ , COOC ₂ H ₅ etc.), an amide group, and a hydroxyl group which may be protected.

The heteroaryl group represented by R ^1, is not particularly limited, for example, oxygen, nitrogen and / or sulfur atoms include heteroaryl groups containing in the ring. Specific examples of the heteroaryl group include a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an isoxazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolyl group, a quinolyl group, an isoquinolyl group, and a thiazolyl group. Etc. The heteroaryl group includes, for example, an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, ester group (e.g., COOCH _3, COOC ₂ H ₅ etc.), an amide group, a substituent of the hydroxyl group be protected may have 1-5.

The alkyl group represented by R ^1, is not particularly limited, for example, straight-chain, and a carbonyl group having an alkyl group having 1 to 10 carbon atoms, branched or cyclic. Specific examples of the alkylcarbonyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, n-valeryl group, isovaleryl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, and n-nonanoyl group. Group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanoyl group, cyclohexylcarbonyl group and the like. Alkyl groups of the alkyl group, for example, an alkenyl group (e.g., vinyl group, allyl group, etc.), a halogen atom (e.g., fluorine, chlorine, bromine), a carboxyl group, an ester group (e.g., COOCH _3, COOC ₂ H ₅ etc.), 1 to 5 substituents such as an amide group and an optionally protected hydroxyl group.

The arylcarbonyl group represented by R ¹ is not particularly limited, and examples thereof include monocyclic or bicyclic or more arylcarbonyl groups. Specific examples of the arylcarbonyl group include a benzoyl group, a toluylcarbonyl group, a xylylcarbonyl group, a naphthylcarbonyl group, an anthrylcarbonyl group, and a phenanthrylcarbonyl group. Examples of the aryl group of the arylcarbonyl group include an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.). , A carboxyl group, an ester group (for example, COOCH ₃ , COOC ₂ H _5, etc.), an amide group, and a hydroxyl group that may be protected may have 1 to 5 substituents.

The heteroarylcarbonyl group represented by R ¹ is not particularly limited, and examples thereof include a heteroarylcarbonyl group containing an oxygen, nitrogen and / or sulfur atom in the ring. Specific examples of the heteroarylcarbonyl group include a furylcarbonyl group, a thienylcarbonyl group, an imidazolylcarbonyl group, a pyrazolylcarbonyl group, an isoxazolylcarbonyl group, a pyridylcarbonyl group, a pyrazinylcarbonyl group, a pyrimidinylcarbonyl group, Examples include pyridazinylcarbonyl group, indolylcarbonyl group, quinolylcarbonyl group, isoquinolylcarbonyl group, thiazolylcarbonyl group and the like. Examples of the heteroaryl group of the heteroarylcarbonyl group include an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine). Etc.), a carboxyl group, an ester group (for example, COOCH ₃ , COOC ₂ H _5, etc.), an amide group, an optionally protected hydroxyl group, etc.

The alkoxycarbonyl group represented by R ^1, is not particularly limited, for example, straight-chain, and a carbonyl group having an alkoxy group having 1 to 10 carbon atoms, branched or cyclic. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a tertiary butoxycarbonyl group, and a 2,2,2-trichloroethoxycarbonyl group. Examples of the alkoxy group of the alkoxycarbonyl group include an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group (for example, COOCH ₃ , COOC, etc.). ₂ H ₅ etc.), 1 to 5 substituents such as an amide group and an optionally protected hydroxyl group.

The aryloxycarbonyl group represented by R ¹ is not particularly limited, and examples thereof include a monocyclic or bicyclic or higher aryloxycarbonyl group. Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, and a 2-naphthyloxycarbonyl group. Examples of the aryl group of the aryloxycarbonyl group include an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.). ), A carboxyl group, an ester group (for example, COOCH ₃ , COOC ₂ H _5, etc.), an amide group, and an optionally protected hydroxyl group, etc.

The heteroaryloxycarbonyl group represented by R ¹ is not particularly limited, and examples thereof include a heteroaryloxycarbonyl group containing an oxygen, nitrogen and / or sulfur atom in the ring. Specific examples of the heteroaryloxycarbonyl group include a furyloxycarbonyl group, a thienyloxycarbonyl group, an imidazolyloxycarbonyl group, a pyrazolyloxycarbonyl group, an isoxazolyloxycarbonyl group, a pyridyloxycarbonyl group, and a pyrazinyloxy group. Examples include carbonyl group, pyrimidinyloxycarbonyl group, pyridazinyloxycarbonyl group, indolyloxycarbonyl group, quinolyloxycarbonyl group, isoquinolyloxycarbonyl group, thiazolyloxycarbonyl group and the like. Examples of the heteroaryl group of the heteroaryloxycarbonyl group include an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, Bromine, etc.), carboxyl groups, ester groups (eg, COOCH ₃ , COOC ₂ H ₅ etc.), amide groups, and optionally substituted hydroxyl groups which may be protected.

The alkoxycarbonylalkyl group represented by R ¹ is not particularly limited, and examples thereof include a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms and a linear, branched or cyclic carbon group having 1 to 10 carbon atoms. An alkoxycarbonylalkyl group having an alkyl group can be mentioned. Specific examples of the alkoxycarbonylalkyl group include a methoxycarbonylethyl group and an ethoxycarbonylethyl group. The alkoxy group or alkyl group in the alkoxycarbonylalkyl group includes, for example, an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group (for example, COOCH ₃ , COOC ₂ H _5, etc.), amide group, optionally substituted 1 to 5 substituents such as hydroxyl group.

The aryloxycarbonylalkyl group represented by R ¹ is not particularly limited, and examples thereof include a monocyclic or bicyclic or higher aryl group and a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. An oxycarbonylalkyl group is mentioned. Specific examples of the aryloxycarbonylalkyl group include a phenoxycarbonylethyl group and a phenoxycarbonylpropyl group. The aryl group of the aryloxycarbonylalkyl group includes, for example, an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.). ), A carboxyl group, an ester group (for example, COOCH ₃ , COOC ₂ H _5, etc.), an amide group, and an optionally protected hydroxyl group, etc. The alkyl group of the aryloxycarbonylalkyl group includes, for example, an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group (for example, COOCH ₃ , COOC ₂ H ₅ etc.), amide group, optionally substituted 1-5 substituents such as hydroxyl group.

The heteroaryloxycarbonylalkyl group represented by R ¹ is not particularly limited, and for example, a heteroaryl group containing an oxygen, nitrogen and / or sulfur atom in the ring, and a straight, branched or cyclic carbon number of 1 And heteroaryloxycarbonylalkyl groups having 10 to 10 alkyl groups. Specific examples of the heteroaryloxycarbonylalkyl group include a furyloxycarbonylethyl group, a thienyloxycarbonylethyl group, an imidazolyloxycarbonylethyl group, a pyrazolyloxycarbonylethyl group, an isoxazolyloxycarbonylethyl group, and a pyridyloxycarbonyl group. Ethyl group, pyrazinyloxycarbonylethyl group, pyrimidinyloxycarbonylethyl group, pyridazinyloxycarbonylethyl group, indolyloxycarbonylethyl group, quinolyloxycarbonylethyl group, isoquinolyloxycarbonylethyl group, thiazolyl And a ruoxycarbonylethyl group. Examples of the heteroaryl group of the heteroaryloxycarbonylalkyl group include an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group), and a halogen atom (for example, fluorine, chlorine). , Bromine, etc.), carboxyl group, ester group (for example, COOCH ₃ , COOC ₂ H ₅ etc.), amide group, and optionally substituted 1 to 5 substituents such as a hydroxyl group which may be protected. Examples of the alkyl group of the heteroaryloxycarbonylalkyl group include an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group (for example, COOCH). ₃ , COOC ₂ H _5, etc.), an amide group, and 1 to 5 substituents such as an optionally protected hydroxyl group.

Examples of the alkyl group an alkyl group which may have a substituent represented by R ² and R ^3, is not particularly limited, for example, linear, alkyl group having 1 to 10 carbon atoms, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and a cyclopentyl group. , N-hexyl group, cyclohexyl group, isohexyl group and the like, and C1-6 alkyl groups. Among them, preferred alkyl groups are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, or tert-butyl group, more preferably methyl group, ethyl group. N-propyl group, isopropyl group, n-butyl group, s-butyl group or isobutyl group. The alkyl group is, for example, an alkenyl group (eg, vinyl group, allyl group, etc.), a halogen atom (eg, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group (eg, COOCH ₃ , COOC ₂ H ₅ etc.) 1 to 5 substituents such as an amide group and a hydroxyl group which may be protected.

The aryl group of the aryl group that may have a substituent represented by R ² and R ³ is not particularly limited, and examples thereof include a monocyclic or bicyclic or more aryl group. Specific examples of the aryl group include a phenyl group, a toluyl group, a xylyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Among them, a preferable aryl group is a phenyl group which may have a substituent, and more preferably an unsubstituted phenyl group. Examples of the aryl group include an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester It may have 1 to 5 substituents such as a group (for example, COOCH ₃ , COOC ₂ H ₅ etc.), an amide group, and a hydroxyl group which may be protected.

The heteroaryl group of the heteroaryl group which may have a substituent represented by R ² and R ³ is not particularly limited, and examples thereof include a heteroaryl group containing an oxygen, nitrogen and / or sulfur atom in the ring. Can be mentioned. Specific examples of the heteroaryl group include a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an isoxazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolyl group, a quinolyl group, an isoquinolyl group, and a thiazolyl group. Etc. The heteroaryl group includes, for example, an alkyl group (for example, C1-6 alkyl group), an alkenyl group (for example, vinyl group, allyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, ester group (e.g., COOCH _3, COOC ₂ H ₅ etc.), an amide group, a substituent of the hydroxyl group be protected may have 1-5.

R ² and R ³ may be bonded to each other to form a ring together with adjacent carbon atoms. For example, a 3- to 8-membered cyclic hydrocarbon is formed, and the cyclic hydrocarbon includes, for example, an alkyl group ( For example, C1-6 alkyl group), alkenyl group (for example, vinyl group, allyl group, etc.), halogen atom (for example, fluorine, chlorine, bromine, etc.), carboxyl group, ester group (for example, COOCH ₃ , COOC ₂ H ₅ ) and the like, and may have 1 to 5 substituents such as an amide group and an optionally protected hydroxyl group.

When R ² and R ³ are different, the carbon atom to which R ² and R ³ are bonded is an asymmetric carbon. The three-dimensional structure of the asymmetric carbon can be represented by an R isomer and an S isomer. The polymer containing the structural unit represented by the compound represented by the general formula (1) or the general formula (2) used in the present invention has a molar ratio of R-form and S-form in the range of 0: 100 to 100: 0. It is.

Examples of the halogen atom represented by R ⁴ include fluorine, chlorine, bromine, iodine and the like. Among them, preferred halogen atoms are fluorine, chlorine or bromine.

  The hydroxyl-protecting group is not particularly limited, and examples thereof include an alkyl group such as a methyl group; an aralkyl group such as a benzyl group; an acyl group such as a benzoyl group; and a trisubstituted silyl group such as a trialkylsilyl group. The type of hydroxyl protecting group or the deprotection method thereof can be referred to Green et al., Protective Groups in Organic Synthesis, 3rd Edition, 1999, John Wiley & Sons, Inc.

  In this specification, “n−” means normal, “s−” means secondary (sec−), and “t−” means tertiary (tert−).

Among the polymers containing the structural unit represented by the general formula (2), preferably R ¹ is an alkyl group, aryl group, heteroaryl group, alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl. A group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an alkoxycarbonylalkyl group, an aryloxycarbonylalkyl group, or a heteroaryloxycarbonylalkyl group (these groups optionally have a substituent). ,
R ² and R ³ are the same or different and are a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hetero which may have a substituent. An aryl group, or R ² and R ³ may be bonded together to form a ring with adjacent carbon atoms;
A polymer in which R ⁴ is a hydrogen atom or a halogen atom;
More preferably, R ¹ is an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group,
R ² and R ³ are the same or different and are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group which may have a substituent,
A polymer in which R ⁴ is a hydrogen atom or a halogen atom;
More preferably, R ¹ is an alkylcarbonyl group, an arylcarbonyl group, or an alkoxycarbonyl group,
R ² and R ³ are the same or different and each is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group or phenyl group. Yes,
A polymer in which R ⁴ is a hydrogen atom or a bromine atom.

Among the monomers represented by the general formula (1),
General formula (1a):

^{(Wherein, R 1a} represents a hydrogen atom or an organic group.
R ^2a and R ^3a are the same or different and are a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hetero which may have a substituent. Represents an aryl group, or R ² and R ³ may combine with each other to form a ring with adjacent carbon atoms;
R ^4a represents a hydrogen atom or a halogen atom.
The wavy line indicates that the stereochemistry of the double bond is E-form, Z-form, or a mixture of E-form and Z-form. However, the compounds represented by the following formulas (a) to (e) are excluded. )
Is preferable, and further,
General formula (1b):

(Wherein, R ^1b represents an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group.
R ^2b and R ^3b are the same or different and each represents a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group or isobutyl group, or R ^2b and R ^3b May combine with each other to form a ring with adjacent carbon atoms.
R ^4b represents a hydrogen atom or a halogen atom.
The wavy line indicates that the stereochemistry of the double bond is E-form, Z-form, or a mixture of E-form and Z-form. However, the compounds represented by the above formulas (a) to (e) are excluded. )
Is more preferable,
General formula (1c):

(Wherein R ^1c represents an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group,
R ^2c and R ^3c are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group or an isobutyl group, and R ^2c and R ^3c Among these, at least one shows a hydrogen atom.
R ^4c represents a hydrogen atom, a chlorine atom or a bromine atom.
The wavy line indicates that the stereochemistry of the double bond is E-form, Z-form, or a mixture of E-form and Z-form. However, the compounds represented by the above formulas (a) to (e) are excluded. )
Is more preferable,
Among them, general formula (1d):

(Wherein R ^1d represents an arylcarbonyl group,
R ^2d and R ^3d are the same or different and represent a hydrogen atom or an isobutyl group, and at least one of R ^2d and R ^3d represents a hydrogen atom.
R ^4d represents a hydrogen atom or a bromine atom.
The wavy line indicates that the stereochemistry of the double bond is E-form, Z-form, or a mixture of E-form and Z-form. )
Or a compound represented by
General formula (1e):

(Wherein R ^1e represents a carbonyl group having an alkoxy group having 1 to 10 carbon atoms,
R ^2e and R ^3e are the same or different and represent a hydrogen atom, a methyl or isobutyl group, and at least one of R ^2e and R ^3e represents a hydrogen atom.
R ^4e represents a hydrogen atom or a bromine atom.
The wavy line indicates that the stereochemistry of the double bond is E-form, Z-form, or a mixture of E-form and Z-form. )
Is more preferable,
The following compound (1-1) and compound (1-3) are particularly preferred.

  The polymer containing the structural unit represented by the general formula (2) can be produced by polymerizing the monomer represented by the general formula (1).

  In addition, a polymer including a structural unit (unit) represented by the general formula (2) and a structural unit (unit) derived from a polymerizable monomer other than the structural unit represented by the general formula (2) has a general formula It can be produced by copolymerizing the monomer compound represented by (1) and another polymerizable monomer.

  Examples of polymerizable monomers (hereinafter also referred to as “combined monomers”) include monomers having a double bond, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid, ( (Meth) acrylic acid (meth) acrylic acid ester monomers such as 2-hydroxyethyl and (meth) acrylic acid menthyl; α-acetoxyacrylic acid, α-acetoxymethyl acrylate, α-acetoxyacrylic acid menthyl, α-acetamidoacrylic acid , Α-acetamidomethyl acrylate, α-acetamidoacrylate menthol, methyl α-methoxyacrylate, menthyl α-methoxyacrylate, etc. Substituted monomer); cyclohexyl (meth) acrylate, (meth ) Unsaturated cycloalkyl group-containing unsaturated monomers (cycloalkyl group-containing (meth) acrylate ester) such as isobornyl acrylate and adamantyl (meth) acrylate; maleic acid, fumaric acid, dimethyl fumarate, dibutyl fumarate, itacon 2 or more carboxyl group-containing unsaturated monomers such as acid, ethyl itaconate, maleic anhydride, maleimide, N-cyclohexylmaleimide, N-phenylmaleimide; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N -Amine-containing unsaturated monomer ((meth) acrylic acid amide) such as hydroxyethyl (meth) acrylamide; styrene, α-methylstyrene, α-methoxystyrene, α-methoxy-2-methoxystyrene, 2-methylstyrene, 4 -Methylstyrene, 4-te aromatic vinyl monomers such as t-butoxystyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4-styrenesulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.); Heterocycle-containing vinyl monomers such as 2-vinylpyridine, 4-vinylpyridine, 2-vinylthiophene, 1-vinyl-2-pyrrolidone and vinylcarbazole; Vinylamides such as N-vinylacetamide and N-vinylbenzoylamide; Ethylene and propylene Α-olefins such as 1-hexene; diene monomers such as butadiene and isoprene; polyfunctional monomers such as divinylbenzene and 4,4′-divinylbiphenyl; (meth) acrylonitrile, methyl vinyl ketone, methyl isopropenyl ketone, ethyl vinyl Examples thereof include sulfide, vinyl benzoate, vinyl acetate, vinyl chloride, vinylidene chloride, ethyl α-cyanoacrylate, coumarin, and indene.

  Among these, (meth) acrylic acid ester monomers, aromatic vinyl monomers, and vinyl acetate monomers are preferable. In particular, methyl methacrylate, 2-hydroxylethyl methacrylate, n-butyl alkylate, acrylonitrile, styrene and vinyl acetate are more preferable.

  In this specification, (meth) acryl refers to methacryl and / or acryl, (meth) acrylo refers to methacrylo and / or acrylo, and (meth) acrylate refers to methacrylate and / or acrylate. Good (meth) acrylic acid means methacrylic acid and / or acrylic acid.

  In the present invention, when a combination monomer is used in addition to the monomer represented by the general formula (1), the charge ratio of the combination monomer in all monomers is generally preferably 99.9 mol% or less, preferably 0.1 to 0.1%. It is 99.9 mol%, More preferably, it is 0.1-90 mol%, More preferably, it is 0.1-80 mol%.

  The polymer containing the structural unit represented by the general formula (2) obtained by radical polymerization reaction has a molar fraction of units derived from the combined monomer of usually 99.9 mol% or less, preferably 0.1 to 0.1%. It is 99.9 mol%, More preferably, it is 0.1-90 mol%, More preferably, it is 0.1-80 mol%.

  The polymer obtained from the monomer represented by the general formula (1) and the concomitant monomer may contain the monomer represented by the general formula (1) as long as the polymer represented by the general formula (1) is contained. ) Alone, the glass transition temperature can be increased.

  Hereinafter, the specific manufacturing method of the polymer containing the structural unit represented by General formula (2) is demonstrated.

  The polymer containing the structural unit represented by the general formula (2) is produced by radical polymerization of the monomer represented by the general formula (1). Usually, the monomer represented by the general formula (1) and, if necessary, a radical polymerization initiator are mixed and stirred in a container substituted with an inert gas or a vacuum deaerated container.

  In the radical polymerization reaction, no solvent or a solvent (organic solvent or aqueous solvent) generally used in radical polymerization can be used. Examples of the organic solvent include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, chlorobenzene, dichlorobenzene, and trifluoro. Examples include methylbenzene and anisole. In addition, examples of the aqueous solvent include water and solvents containing methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyrocellosolve, 1-methoxy-2-propanol and the like as necessary.

  When a solvent is used, the amount of solvent used may be adjusted as appropriate. For example, the amount of the solvent used with respect to 1 mol of the monomer represented by the general formula (1) or with respect to 1 mol of all monomers including the monomer represented by the general formula (1) and the combined monomer in the case of copolymerization Is generally from 0.1 to 20 liters, preferably from 0.2 to 5 liters.

  The radical polymerization reaction can be carried out in the presence or absence of a radical polymerization initiator. Usually, it is preferable to carry out in the presence of a radical polymerization initiator. Of course, it is also possible to perform spontaneous thermal polymerization in the absence of a radical polymerization initiator, or radical polymerization by light irradiation in the presence or absence of a radical polymerization initiator. In the case of radical polymerization by light irradiation, polymerization is usually performed using a light source such as a mercury lamp or a xenon lamp. The light source can be appropriately selected depending on the type of monomer, the type of polymerization initiator, and the like.

  The radical polymerization reaction includes radical copolymerization in addition to radical homopolymerization of the monomer represented by the general formula (1). In the case of radical copolymerization, particularly living radical copolymerization, diblock and triblock copolymerization is possible. As the monomer capable of radical copolymerization, a monomer having a different structure among the monomers represented by the general formula (1), a monomer capable of radical polymerization other than the monomer represented by the general formula (1), and the like are used without limitation. be able to.

  The radical polymerization initiator is not particularly limited as long as it can be generally used for radical polymerization. For example, azo polymerization initiators, peroxides such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, redox polymerization In addition to initiators, photopolymerization initiators such as 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like can be mentioned. In addition to the above initiator, a living radical polymerization initiator system using an organic halogen substance (for example, ethyl 2-bromoisobutyrate), a nitroxide derivative, a thiocarbonyl substance, an organic tellurium substance or the like as an initiator or additive. Is mentioned.

  Of the radical polymerization initiators, an azo polymerization initiator is preferred, and specifically, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyro). Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis (2-methylpropane), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis [2- (3,4,5, 6-tetrahydropyrimidin-2-yl) propane] dihydrochloride and the like.

What is necessary is just to adjust suitably the usage-amount of a radical polymerization initiator with the polymer obtained. For example, with respect to 1 mol of the monomer represented by the general formula (1), or in the case of copolymerization, with respect to 1 mol of all monomers including the monomer represented by the general formula (1) and the combined monomer, usually 1 × 10 ⁻⁶ to ¹ mol, preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

  Of the above radical polymerization methods, the living radical polymerization method is particularly preferably employed. By this polymerization method, a polymer in which the molecular weight, molecular weight distribution, steric structure and the like are more highly controlled can be produced.

  As the living radical polymerization initiator, for example, an organic tellurium-mediated living radical polymerization initiator is preferable, and specifically, AIBN / di-n-butylditelluride (DBT), AIBN / diphenylditelluride, AIBN / ethyl 2-methyl. Examples include 2-methylterranyl-propionate, AIBN / ethyl 2-methyl-2-butylterranyl-propionate (EMBTP), AIBN / ethyl 2-methyl-2-phenylterranyl-propionate, AIBN / DBT / EMBTP, and the like.

In this case, the amount of AIBN used may be appropriately adjusted depending on the polymer obtained. For example, with respect to 1 mol of the monomer represented by the general formula (1), or in the case of copolymerization, with respect to 1 mol of all monomers including the monomer represented by the general formula (1), usually 1 × 10 ⁻⁶ it is to 1 mol, preferably ^{1 × 10 -4 ~1 × 10 -1} mol, more preferably ^{1 × 10 -3 ~1 × 10 -2} mol. The amount of organic tellurium used is based on 1 mol of the monomer represented by the general formula (1), or in the case of copolymerization, based on 1 mol of all monomers including the monomer represented by the general formula (1) and the combined monomer. Usually, it is 1 × 10 ⁻⁶ to ¹ mol, preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

  Among the living radical polymerizations, the production method of the block copolymer is as follows. This copolymer contains at least one monomer represented by the general formula (1), and in addition, the above combination monomers can be used. In the case of AB-type diblock copolymerization, for example, in the glove box or nitrogen-substituted glove box, the monomer represented by the general formula (1) is added to the radical initiator in the presence or absence of a solvent. Is added to react to obtain a polymer containing the structural unit represented by the general formula (2). Thereafter, a second monomer (a monomer represented by a different general formula (1) or a combination monomer) is mixed to obtain a copolymer. Further, the order of addition of the monomers may be reversed, and the monomer represented by the general formula (1) may be reacted after reacting the second monomer first. Furthermore, triblock copolymers such as ABA type and ABC type can also be produced by sequentially mixing the monomers after producing the above diblock copolymer.

  The reaction temperature and reaction time can be appropriately adjusted depending on the type of the monomer, the type of the polymerization initiator, and the like. Usually, it stirs about 0-180 degreeC and about 0.5-100 hours. Preferably, each is stirred at 30 to 100 ° C. for 1 to 30 hours. At this time, the pressure is usually a normal pressure. The pressure may be increased or decreased. At this time, examples of the inert gas include nitrogen, argon, helium and the like. Preferred inert gases are argon and nitrogen, and more preferably nitrogen.

  The degree of polymerization of the polymer obtained by the radical polymerization reaction of the present invention can be appropriately adjusted depending on the reaction time, initiator concentration, reaction temperature, solvent and the like. It is a polymer having a number average degree of polymerization of 10 to 20,000, particularly 50 to 5,000. The number average molecular weight (Mn) is about 500 to 4,000,000, and further about 5,000 to 1,000,000. As a method for measuring Mn and the weight average molecular weight (Mw), the GPC method described in Examples is adopted. In the present invention, a radical polymer having a molecular weight distribution (PDI = Mw / Mn) of 1.01 to 4, particularly 1.05 to 2.5 is usually obtained. Among these, the molecular weight distribution (PDI = Mw / Mn) of the living radical polymer is narrow and is controlled between 1.01 and 1.5, and further 1.05 to 1.3, particularly 1.1 to 1.25. Can be controlled within the range.

  There is no restriction | limiting in particular as glass transition temperature (Tg) of the polymer (hardened | cured material) of this invention, For example, it is preferable that it is 80-280 degreeC, and it is more preferable that it is 95-275 degreeC. The glass transition temperature can be measured by a differential scanning calorimetry (DSC method).

  There is no restriction | limiting in particular as light transmittance of the polymer of this invention, For example, it is preferable from a viewpoint used for an optical component that it has a light transmittance of 50% or more in conversion of thickness 1mm in wavelength 589nm. The light transmittance is more preferably 70% or more, more preferably 80% or more, and particularly preferably 85% or more in terms of thickness of 1 mm. Especially, if the light transmittance of 1 mm thickness conversion in wavelength 589nm is 50% or more, it will be easy to obtain the lens base material which has a more preferable property. The light transmittance in terms of 1 mm thickness in the present invention is obtained by molding a polymer to produce a 1.0 mm thick substrate, and an ultraviolet-visible absorption spectrum measuring apparatus (UV-1600PC, manufactured by Shimadzu Corporation). It is the value measured by.

  The refractive index of the polymer of the present invention is not particularly limited, and is adjusted to a desired refractive index depending on the type of substituent of the polymer of the present invention or when using other polymerizable monomers as a raw material. be able to. For example, when producing a polymer having a high refractive index, a polymer having a refractive index of 1.46 or more is preferable, and a polymer having a refractive index of 1.50 or more is more preferable.

1.2 Chemical conversion (modification) of polymer
The polymer obtained by the polymerization reaction described in 1.1 can be chemically converted (modified) by a ring-opening reaction (hydrolysis or the like). Thereby, the polymer which has various functional groups or physical properties can be manufactured. A specific conversion scheme is shown below.

(In the formula, R ^{1 to} R ⁴ are the same as described above. Y represents a hydrogen atom or a counter cation.)

[Hydrolysis]
The polymer containing the structural unit represented by the general formula (2) obtained above has an oxazolidin-5-one skeleton, and this is subjected to a hydrolysis reaction to have an amino group and a carboxyl group Convert to If necessary, the carboxyl group (carboxylic acid) can be converted into a salt.

  The polymer obtained by hydrolysis has the general formula (5):

(Wherein R ¹ , R ⁴ and Y are the same as above)
The structural unit represented by is included.

  Examples of the counter cation represented by Y include metal cations, ammonium, and onium of a nitrogen-containing organic compound. Examples of the metal cation include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium, barium and magnesium. Examples of the onium of the nitrogen-containing organic compound include (mono-, di-, tri-, or tetra-) alkyl ammonium, pyridinium, piperidinium, quinolinium, thiophenium, and the like.

  A polymer containing the structural unit represented by the general formula (2) is dissolved or swollen in water and an organic solvent (for example, an ether solvent such as THF, a halogenated hydrocarbon solvent such as chloroform), and a base or an acid. To hydrolyze. After completion of the reaction, the solvent is distilled off from the reaction solution, and a poor solvent (for example, methanol) is added to the residue to precipitate a polymer to obtain a hydrolyzate. In addition, when a part of filtered hydrolyzed polymer becomes water-insoluble, water can be added to a filtrate and only a water soluble part can be taken out as a hydrolyzate. Moreover, after completion | finish of reaction, a carboxylate can also be converted into carboxylic acid using an acid (for example, hydrochloric acid etc.) as needed.

As the hydrolysis reagent, examples of the acid include proton acids such as hydrochloric acid, sulfuric acid, nitric acid, fluorosulfonic acid, trichloroacetic acid, trifluoroacetic acid, and paratoluenesulfonic acid; Lewis acids such as BF ₃ and SnCl ₄ As the base, hydroxides of alkali metals such as NaOH and KOH; hydroxides of alkaline earth metals such as Be (OH) ₂ and Mg (OH) ₂ ; CH ₃ ONa, (CH ₃ ) ₃ OK And metal alkoxides. The acid or base can be used in the form of an aqueous solution as necessary.

  Hydrolysis can be carried out using a known method. For example, with respect to 1 g of the polymer containing the structural unit represented by the general formula (2), about 1 to 50 g of a base is used in a solvent (for example, water, ether solvent, halogenated hydrocarbon solvent, etc.) The reaction can be carried out at 0 to 150 ° C. for about 1 to 100 hours.

  In addition to the above chemical hydrolysis reagents, enzymatic hydrolysis can also be performed. Examples of the hydrolase that can be used include a group consisting of lipase, protease, phosphoesterase, esterase, cutinase, and combinations thereof. For enzymatic hydrolysis, known hydrolysis conditions can be selected as appropriate.

  The polymer containing the structural unit represented by the general formula (5) obtained as described above has a degree of polymerization, a molecular weight distribution, a meso-doublet of the polymer containing the structural unit represented by the general formula (2) ( The ratio (m: r) of the m) and the racemo duplex (r) is retained.

2. Production of Raw Material Monomer The monomer represented by the general formula (1) is produced by various methods. For example, Athelstan L. J. et al. Beckwith, et al. , Aust. J. et al. Chem. , 1993, 46, 1425-1430, the monomer of the general formula (1) can be produced. For example, the following route (reaction formula-1) can be exemplified.

[Reaction Formula-1]

^(Wherein, R 1 to R ³ and the wavy line are the same .X as above, .R ⁴ where represents a halogen atom, a hydrogen atom or a halogen atom.)

Examples of the alanine represented by the A process formula (6) include L-alanine, D-alanine, and a mixture thereof. As alanine, naturally occurring alanine can be used (green chemistry). That is, a polymer obtained by radical polymerization from an alanine-derived monomer is very important for practical industrialization.

  As the carbonyl compound represented by the general formula (7), known aldehydes and ketones can be widely used.

  Examples of such aldehydes include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, pivalaldehyde, valeraldehyde, trifluoroethanal, chloral, succinaldehyde, chlorofluoroacetaldehyde, menthone, cyclohexanecarbaldehyde, 2- Examples include pyrrole carbaldehyde, 3-pyridinecarbaldehyde, 2-furaldehyde, benzaldehyde, benzeneacetaldehyde, vanillin, piperonal, citronellal and the like.

  Examples of the ketone include methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl sec-butyl ketone, methyl tert-butyl ketone, acetophenone, 2-furylmethyl ketone, 2-acetonaphthone, 2 (3H) -pyrazinone, pyrrolidone and the like. .

  Of these carbonyl compounds, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, pivalaldehyde and the like are preferable, and isobutyraldehyde is more preferable.

The compound represented by the general formula (8) is a compound having a group corresponding to R ¹ of the monomer represented by the general formula (1) and a halogen atom, and a wide variety of known compounds can be used. Here, the halogen atom is fluorine, chlorine, bromine or the like.

  Examples of the compound represented by the general formula (8) include alkyl halide, aryl halide, alkylcarbonyl halide, arylcarbonyl halide, alkoxycarbonyl halide, aryloxycarbonyl halide, alkoxycarbonylalkyl halide, aryloxycarbonylalkyl halide and the like. Can be mentioned. Of these, benzoyl chloride and t-butoxycarbonyl chloride are preferred.

  A carbonyl compound represented by the general formula (7) (for example, isobutyraldehyde and the like), a compound represented by the general formula (8) and an alanine represented by the formula (6) are mixed with a solvent (for example, n-pentane or the like). In hydrocarbon solvents, etc., an acid catalyst (eg, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, etc.) or a base catalyst (eg, alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc.) as necessary In the presence of the product, the mixture is refluxed while azeotropically removing water using a reflux condenser equipped with a Dean-Stark fractionator, and subjected to a condensation reaction.

  The compound represented by the general formula (9) obtained by the condensation reaction can be isolated and purified by, for example, distillation under normal pressure or reduced pressure, column chromatography or the like. When the compound represented by the general formula (9) is a mixture of stereoisomers, it can be separated by using the isolation and purification methods described above.

  The temperature and time of the condensation reaction may be appropriately adjusted depending on the type of reagent. For example, the reaction temperature is usually about 0 to 180 ° C., preferably 0 to 80 ° C., more preferably 0 to 60 ° C. The reaction time is usually 0.5 to 100 hours, preferably 0.5 to 30 hours, more preferably 0.5 to 10 hours.

When the compound represented by the general formula (9) (hereinafter sometimes referred to as “methyl body”) uses L-alanine and carbonyl compounds different from R ² and R ³ as raw materials, the following general formula (9a) Or a mixture of two diastereomers represented by (9b).

(Wherein R ^{1 to} R ³ are the same as described above. * Represents an asymmetric carbon.)
In the compound represented by the general formula (9a) and the compound represented by the general formula (9b), one compound is highly purified (with a high diastereo ratio) in consideration of the improvement of the stereoregularity of the polymer after polymerization. ) Is preferably included. For example, the molar ratio of the compound represented by the general formula (9a) or (9b): the compound represented by the general formula (9b) or (9a) is 50:50 to 100: 0, preferably 80:20 to 100. : 0, more preferably 90:10 to 100: 0, particularly preferably 95: 5 to 100: 0.

  The methyl form (9) is derived from the methyl form (9) regardless of the ratio of the diastereomers of the compound represented by the general formula (9a) and the compound represented by the general formula (9b). Further, by using the monomer represented by the general formula (1) as a raw material, the obtained polymer of the present invention exhibits excellent performance such as having a high glass transition temperature.

In step A,
I) The alanine represented by the formula (6), the carbonyl compound represented by the general formula (7) and the compound represented by the general formula (8) can be reacted at once;
II) First, an alanine represented by the formula (6) and a carbonyl compound represented by the general formula (7) are reacted to produce an imino compound, and then the imino compound and the general formula (8) are represented. Or III) after reacting the alanine represented by formula (6) with the compound represented by general formula (8) to produce an N-substituted alanine compound The N-substituted alanine compound and the carbonyl compound represented by the general formula (7) can be reacted.

Step B Next, the compound represented by the general formula (9) obtained above is converted into a halogenating agent (for example, N-bromosuccinimide (NBS), N, for example) in the presence of a solvent (for example, carbon tetrachloride). -Chlorosuccinimide (NCS), N-iodosuccinimide (NIS), N, N-dibromohydantoin (NDBH), N-bromosaccharin (NBSA), bromine, chlorine, iodine, etc.) and radical initiators (eg 2,2 '-Azobis (isobutyronitrile) (AIBN) etc.) is reacted. Usually, the mixture is refluxed for a period of time in a flask equipped with a reflux condenser. After the reaction, the halogenated compound is obtained by a conventional method.

  Thereafter, a catalyst such as sodium iodide or potassium iodide is allowed to act on the halogenated compound in a solvent (eg, benzene, toluene, xylene, etc.). Usually, the above-mentioned catalyst is added to a halogenated compound solution and refluxed for a certain time. After the reaction, the solvent is distilled off, followed by isolation and purification by distillation to obtain the compound represented by the general formula (1).

The obtained monomer compound represented by the general formula (1) has an enantio-ratio of the asymmetric carbon (C *) to which R ² and R ³ are bonded (that is, the molar ratio of the R-form to the S-form). (S-form): S-form (R-form) = 100: 0 to 0: 100.

  The polymer containing the structural unit represented by the general formula (2) of the present invention exhibits excellent performance such as having a high glass transition temperature regardless of the ratio of R-form and S-form.

3. Use The polymer containing the structural unit represented by the general formula (2) of the present invention includes, for example, a bleach sterilization aid; a surfactant aid; a polymer flocculant; a chelating agent; a polymer electrolyte; Sanitary goods (polymer water-absorbing agent, ice pillow, etc.); Anti-fogging material (anti-fogging of glass); Adhesive; Ink material; Semiconductor sealing material; Photoresist material; Medical or environmental conservation materials; surface modifiers (such as coatings on metal surfaces of mobile phones and electronic devices); optical materials (lenses, optical fibers, semiconductor sealing materials, protective films, liquid crystal displays, light-absorbing materials for plasma display panels) , A photosensitive composition for forming a spacer for a liquid crystal display, etc.).

  Moreover, the polymer containing the structural unit represented by the general formula (5) of the present invention is a polyfunctional polymer having a hydrophilic amino group and a carboxyl group on the same carbon. Therefore, it has the characteristic property derived from this, For example, it can use as sanitary goods, such as a polymeric water absorbing agent and an ice pillow.

  The polymer containing the structural unit represented by the general formula (5) of the present invention can efficiently form chelates with various metal ions.

  Not only a homopolymer of the monomer represented by the general formula (1) but also a copolymer (copolymer) of the monomer represented by the general formula (1) and another polymerizable monomer (combined monomer), The polymer has an extremely high affinity for water. When the polymer is brought into contact with water, it swells to 50 to 3000 times its volume. In the case of a copolymer, the above properties (affinity for water) are exhibited if the monomer unit represented by the general formula (1) is about 10 to 100 mol%.

4). Optical Material Resin Composition The optical material resin composition of the present invention contains a polymer containing a structural unit represented by the general formula (2).

  The polymer containing the structural unit represented by the general formula (2) of the present invention exhibits a high glass transition temperature (heat resistance) and has excellent transparency and refractive index. Especially, it can use for optical materials, such as a lens, a film, an optical fiber, and a semiconductor sealing material.

  The resin composition for an optical material of the present invention can contain only one kind as the polymer of the present invention, or can contain two or more kinds in combination.

  In the resin composition for an optical material of the present invention, if necessary, an additive such as a polymer other than the polymer represented by the general formula (2), a dispersant, a plasticizer, a heat stabilizer, a release agent, It can mix | blend suitably in the range which does not prevent the effect of this invention.

  The ratio of the polymer of the present invention contained in the resin composition for an optical material of the present invention is not particularly limited as long as the polymer of the present invention is contained even a little.

  For example, the proportion of the polymer of the present invention contained in the resin composition for an optical material of the present invention is preferably 40 to 100% by weight, more preferably 60 to 100% by weight, and 80 to 100% by weight. More preferably it is.

5. Molded body The molded body of the present invention can be produced by molding the resin composition for optical materials of the present invention. The molded body of the present invention can be obtained by adding a solvent to the optical material resin composition and cast molding. The molded body of the present invention can be molded in a solid state without using a solvent by a technique such as injection molding or compression molding.

  The molded product of the present invention preferably has a maximum thickness of 0.1 mm or more. The maximum thickness is preferably 0.1 to 5 mm, and more preferably 1 to 3 mm. A molded body having these thicknesses is particularly useful as an optical component having a high refractive index. Such a thick molded body is generally not easy because it is difficult to remove the solvent even if it is manufactured by the solution casting method. However, if the resin composition for optical materials of the present invention is used, it is easy to mold and a complicated shape such as an aspherical surface can be easily realized. Thus, according to the present invention, it is possible to obtain a molded body having good transparency while utilizing high refractive index characteristics.

6). Optical Material The optical material of the present invention is obtained from a molded article having high refractive properties, high heat resistance and high light transmittance, and excellent optical properties. The optical material of the present invention is not particularly limited as long as the optical material is used in the field. For example, it can be suitably used as an optical component utilizing optical characteristics, particularly an optical component that transmits light (so-called passive optical component). Examples of the optical functional device including such an optical component include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), and optical fiber communication devices (optical waveguide, optical amplifier, etc.). And photographing devices such as cameras and videos.

  Examples of the optical component include a lens, a prism, a prism sheet, a panel (plate-shaped molded body), a film, an optical waveguide (film shape, fiber shape, etc.), an optical disk, and a semiconductor sealing agent. For such optical components, an optional coating layer (for example, a protective layer that prevents mechanical damage to the coated surface due to friction or abrasion; light having an undesirable wavelength that causes deterioration of inorganic particles, substrates, etc.) A light absorbing layer that absorbs; an optional additional functional layer such as a transmission shielding layer, an antiglare layer, an antireflection layer, a low refractive index layer, or the like that suppresses or prevents the transmission of reactive low molecules such as moisture and oxygen gas) It can be a multilayer structure.

7). Lens The optical material of the present invention is particularly suitable for a lens substrate. The lens of this invention is manufactured using the polymer containing the structural unit represented by General formula (2) of this invention. The lens substrate manufactured using the resin composition for optical materials of the present invention has high refractive properties, light transmittance, and light weight, and is excellent in optical properties. Moreover, about the polymer obtained by copolymerizing the monomer represented with General formula (1), and another polymerizable monomer (combination monomer), by adjusting suitably the kind and content of a combination monomer. The glass transition temperature, transmittance and refractive index of the lens substrate can be arbitrarily adjusted.

  The “lens substrate” in the present invention means a single member capable of exhibiting a lens function.

  A protective film, an antireflection film, a hard coat film, or the like can be formed on the surface of the lens substrate.

  The type or shape of the lens using the lens substrate of the present invention is not particularly limited. The lens substrate of the present invention includes, for example, a spectacle lens, an optical device lens, an optoelectronic lens, a laser lens, a pickup lens, an in-vehicle camera lens, a portable camera lens, a digital camera lens, an OHP lens, Used for microlens arrays and the like.

The present invention will be described in more detail with reference to examples, but is not limited thereto.
[measuring equipment]
In Examples and Comparative Examples, various physical properties were measured with the following equipment.
・¹ H-NMR: JEOL ECA-400WB (400 MHz)
IR: JASCO FT / IR-230
Optical rotation: JASCO P-1030
Separation and purification: Tosoh HLC-8020
Molecular weight (number average molecular weight Mn, weight average molecular weight Mw) and molecular weight distribution (Mw / Mn): GPC (gel permeation chromatography): Tosoh HLC-8220 (column-TSKgel G7000HHR + G5000HHR + G3000) polystyrene standard [Production of monomer]

Production Example 1 (Synthesis of N-benzoyl-2-isopropyl-4-methyleneoxazolidine-5-one (1-1))

(1) L-alanine 45.48 g (0.50 mol), sodium hydroxide 21.05 g (0.50 mol), ion-exchanged water 200 ml, and ethanol 100 ml were placed in a 500 ml eggplant-shaped flask equipped with a reflux tower. Was heated and stirred at 35 ° C. for 30 minutes. Then, the solvent was removed with the evaporator and the reaction mixture containing the sodium salt of L-alanine was obtained by making it dry using a vacuum pump.
(2) Next, 55.18 g (0.75 mol) of isobutyl aldehyde and 200 ml of n-pentane were placed in a 500 ml eggplant-shaped flask equipped with a reflux tower and Dean-Stark separator and refluxed for 12 hours. . After completion of the reaction, the reaction system was cooled to room temperature, and then the solvent was removed by an evaporator to obtain a white solid compound. Furthermore, this was fully dried with the vacuum pump, and the reaction mixture containing an imine compound was obtained.
(3) The reaction mixture of (2) above and 200 ml of dichloromethane were put into a 500 ml four-necked flask and stirred to form a suspension. While cooling the 500 ml four-necked flask with ice water, a solution of 14.1 g (0.50 mol) of benzoyl chloride in 150 ml of dichloromethane was added dropwise over 6 hours. And after completion | finish of dripping, it was made to react for 24 hours, stirring at room temperature. Then, it wash | cleaned one by one by water, 5% sodium hydrogencarbonate aqueous solution, sodium hydrogensulfite aqueous solution, and water. Subsequently, after drying with anhydrous magnesium sulfate, the solvent was removed by an evaporator, and 99.5 g (0.00%) of N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one (hereinafter referred to as “methyl body”). 4 mol) (yield: 80.5%). The methyl isomer was a mixture of trans isomer / cis isomer (stereostructure relationship between methyl group and isopropyl group) = 71.5: 28.5, and only the trans isomer was obtained by recrystallization.
(4) 10 g (40.4 mmol) of the obtained trans isomer, 14.4 g (80.8 mmol) of N-bromosuccinimide, 663.4 mg (4.0 mmol) of 2,2-azobisisobutyronitrile (AIBN), And 50 ml of carbon tetrachloride in a 100 ml eggplant type flask, cooled with ice water and irradiated with light (UV light source used: USHIO UIH-500C ultra-high pressure mercury lamp (500W) equipped with USHIO UI-501C parallel beam type) (The high-intensity light source device was used. USHIO HB-50110AA was used as the ultra-high pressure mercury lamp lighting device. The distance from the light source USHIO USH-500D ultra-high pressure mercury lamp to the reaction system is about 36 cm.) 3 Stir for hours. After completion of the reaction, the solid was removed by filtration, and the solvent was removed by an evaporator.

  The obtained reaction product, sodium iodide 24.2 mg (161.6 mmol), and acetone 50 ml were placed in a 100 ml eggplant flask equipped with a reflux tower and refluxed for 3 hours. Then, it washed sequentially with 5% anhydrous sodium thiosulfate aqueous solution and water. Then, after drying over anhydrous magnesium sulfate, the solvent was removed by an evaporator to obtain a mixture containing the target product.

  The mixture containing the target substance is the target substance by open column chromatography using silica gel (silica gel 60N (spherical, neutral) 63 to 210 μm) as a filler and n-hexane / acetone = 7/2 as a developing solvent. 7.2 g (29.4 mmol) of N-benzoyl-2-isopropyl-4-methyleneoxazolidine-5-one was obtained (yield: 72.7%). The compound obtained here was R-form: S-form = 0: 100.

With respect to N-benzoyl-2-isopropyl-4-methyleneoxazolidine-5-one obtained in Production Example 1, FIG. 1 shows a spectrum by ¹ H-NMR measurement, and FIG. 2 shows a spectrum by FT-IR measurement. .

N-benzoyl-2-isopropyl-4-methyleneoxazolidine-5-one:
^{IR (KBr, cm -1) 1636} (C = C), 1664 (C = O), 1798 (C = O), 2877~2973 (CH 3, CH)
¹ H-NMR (CDCl ₃ , ppm) 0.84 (d, J = 4.0 Hz, 3H), 1.04 (d, J = 4.0 Hz, 3H), 2.27 (m, 1H), 4 .85 (m, 1H), 5.51 (d, J = 2.0 Hz, 1H), 6.01 (d, J = 2.0 Hz, 1H), 7.41 (m, 5H)
[Α] _D = + 200.6 (the optical rotation of Na with respect to the D line, [compound] = 1.0 g / dl, in CHCl ₃ )

Production Example 2 (Synthesis of N-benzoyl-2-tert-butyl-4-methyleneoxazolidine-5-one (1-2))

  N-benzoyl-2-tert-butyl-4-methyl was prepared in the same manner as in Production Example 1 except that isobutyraldehyde in Production Example 1 (2) was replaced with 86.75 g (0.75 mol) of pivalaldehyde. 104.7 g (0.4 mol) of oxazolidine-5-one was obtained (yield: 80.1%).

  The methyl form was a mixture of trans form / cis form (stereostructure relationship between methyl group and isopropyl group) = 71.8: 28.2, and only the trans form was obtained by recrystallization.

  Using 10 g (38.3 mmol) of the trans isomer (N-benzoyl-2-tert-butyl-4-methyloxazolidine-5-one), N-benzoyl-2-tert-butyl-4-methyleneoxazolidine-5-one 6.8 g (yield: 68.5%) was obtained. The compound obtained here was R-form: S-form = 0: 100.

N-benzoyl-2-tert-butyl-4-methyleneoxazolidine-5-one: IR (KBr, cm ⁻¹ ) 1647 (C═C), 1679 (C═O), 1793 (C═O), 2875 2970 (CH ₃ , CH)
¹ H-NMR (CDCl ₃ , ppm) 1.00 (s, 9H), 4.58 (s, 1H), 5.42 (s, 1H), 6.17 (s, 1H), 7.53 ( m, 5H)
[Α] _D = −206.8 (the optical rotation of Na relative to the D line, [compound] = 1.0 g / dl, in CHCl ₃ )

Production Example 3 (Synthesis of N-tert-butoxycarbonyl 4-bromomethylene-2-methyloxazolidine-5-one (1-3))

(1) N-tert-butoxycarbonyl-L-alanine 50.9 g (0.27 mmol), acetaldehyde 35.6 g (0.81 mol), p-toluenesulfonic acid 1.0 g (0.005 mol) in a 100 ml flask And stirred at room temperature for 46 hours. Thereafter, benzene was added, washed with an aqueous sodium hydrogen carbonate solution and water, and dried using anhydrous magnesium sulfate. Then, the solvent benzene and unreacted acetaldehyde were distilled off with an evaporator, and N-tert-butoxycarbonyl-4- 24.9 g of methyl-2-methyloxazolidine-5-one was obtained (yield: 42.8%).

The methyl form was a mixture of trans form / cis form (stereostructure relationship between methyl group and isopropyl group) = 78.3: 21.7, and only the trans form was obtained by recrystallization.
(2) 8.0 g (37.2 mmol) of the obtained trans isomer, 11.7 g (74.3 mmol) of N-bromosuccinimide (NBS), 50 ml of carbon tetrachloride and 10 mg (0.06 mmol) of AIBN were placed in a 200 ml flask. The mixture was stirred for 3 hours while irradiating with a high-pressure mercury lamp under ice-cooling at 0 to 5 ° C. After completion of the reaction, the solid was removed by filtration, and the solvent was removed by an evaporator.

  Subsequently, the obtained reaction product, 22.3 mg (148.6 mmol) of sodium iodide and 200 ml of acetone were placed in a 200 ml eggplant flask equipped with a reflux tower and refluxed for 3 hours. Then, it was washed with 5% anhydrous sodium thiosulfate aqueous solution and water, and extracted with chloroform. Then, after drying over anhydrous magnesium sulfate, the solvent was removed by an evaporator to obtain a mixture containing the target product.

  The mixture containing the target product was obtained by subjecting the mixture to the target product by open column chromatography using silica gel (silica gel 60N (spherical, neutral) 63 to 210 μm) as a filler and n-hexane / ethyl acetate = 4/1 as a developing solvent. There was obtained 5.1 g of N-tert-butoxycarbonyl 4-bromomethylene-2-methyloxazolidine-5-one (yield: 46.9%) (from the starting N-tert-butoxycarbonyl-L-alanine). Yield 20.1%).

About the obtained N-tert-butoxycarbonyl 4-bromomethylene-2-methyloxazolidine-5-one, the spectrum by ¹ H-NMR measurement is shown in FIG. 3, and the spectrum by FT-IR measurement is shown in FIG.

N-tert-butoxycarbonyl 4-bromomethylene-2-methyloxazolidine-5-one:
IR (KBr, cm ⁻¹ ) 1651 (C═C), 1711 (C═O), 1801 (C═O)
¹ H-NMR (CDCl ₃ , ppm) 1.56 (s, 9H), 1.61 (d, J = 5.2 Hz, 3H), 5.57 (s, 1H), 5.80 (q, J = 5.2Hz, 1H)
_[Α] D = + 14.2 (optical rotation relative to D line of Na, [compound] = 1.0g / dl, in CHCl ₃₎

[Radical polymerization reaction]
Example 1

  In a glove box substituted with nitrogen, 490.5 mg (2 mmol) of the monomer (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) of Production Example 1 and 6.6 mg (0.04 mmol) of AIBN and a solvent were used. The mixture was adjusted to 1 ml with benzene and stirred at 60 ° C. for 2 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 2
In the glove box substituted with nitrogen, 49.1 mg (0.2 mmol) of the monomer (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) of Production Example 1 and 187.5 mg (1.8 mmol) of styrene, In addition, 0.8 mg (5 mmol) of AIBN and benzene as a solvent were adjusted to 1 ml, and the mixture was stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid) (Mn = 25000 (Mw / Mn = 1.32)). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 3
In a glove box substituted with nitrogen, 4.9 ml (0.02 mmol) of the monomer (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) of Production Example 1 and 206.2 mg (1.98 mmol) of styrene, In addition, 0.8 mg (5 mmol) of AIBN and benzene as a solvent were adjusted to 1 ml and stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid) (Mn = 23000 (Mw / Mn = 1.68)). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Comparative Example 1
In a glove box substituted with nitrogen, 1 ml (8.7 mmol) of styrene and 0.8 mg (4.9 mmol) of AIBN were stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 4
In a nitrogen-substituted glove box, 147.2 mg (0.6 mmol) of the monomer (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) of Production Example 1 and 140.2 mg (1.4 mmol) of methyl methacrylate ), And AIBN 0.8 mg (5 mmol) and benzene as a solvent, adjusted to 1 ml, and stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 5
In a nitrogen-substituted glove box, 49.1 mg (0.2 mmol) of the monomer of Production Example 1 (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) and 180.2 mg (1.8 mmol) of methyl methacrylate ), And AIBN 0.8 mg (5 mmol) and benzene as a solvent, adjusted to 1 ml, and stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid) (Mn = 23000 (Mw / Mn = 1.68)). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Comparative Example 2
In a glove box substituted with nitrogen, 1 ml (9.4 mmol) of methyl methacrylate and 0.8 mg (4.9 mmol) of AIBN were stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 6
In a nitrogen-substituted glove box, 49.1 mg (0.2 mmol) of the monomer (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) of Production Example 1 and 230.7 mg (1 mmol) of n-butyl acrylate 8 mmol), and 0.8 mg (5 mmol) of AIBN and benzene as a solvent, the mixture was adjusted to 1 ml and stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 7
In a nitrogen-substituted glove box, the monomer (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) 24.5 (0.1 mmol) and n-butyl acrylate 243.5 ml (1 0.9 mmol), and 0.8 mg (5 mmol) of AIBN and benzene as a solvent, the mixture was adjusted to 1 ml and stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Comparative Example 3
In a glove box substituted with nitrogen, 1 ml (6.9 mmol) of n-butyl acrylate and 0.8 mg (4.9 mmol) of AIBN were stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 8
In a nitrogen-substituted glove box, the monomer of Production Example 1 (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) 4.9 (0.02 mmol) and vinyl acetate 170.5 ml (1.98 mmol) And 0.8 mg (5 mmol) were stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 9
In a glove box substituted with nitrogen, 2.5 mg (0.01 mmol) of the monomer (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) of Production Example 1 and 171.3 ml (1.99 mmol) of vinyl acetate And 0.8 mg (5 mmol) of AIBN were stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.
Comparative Example 4
In a nitrogen-substituted glove box, 1 ml (10.8 mmol) of vinyl acetate and 0.8 mg (4.9 mmol) of AIBN were stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 10
In a nitrogen-substituted glove box, 49.1 mg (0.2 mmol) of the monomer (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) of Production Example 1 and 230.7 mg of 2-hydroxyethyl methacrylate ( 1.8 mmol), and AIBN 0.8 mg (5 mmol) and benzene as a solvent were adjusted to 1 ml and stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Example 11
In a glove box substituted with nitrogen, 24.5 mg (0.1 mmol) of the monomer of Production Example 1 (N-benzoyl-2-isopropyl-4-methyloxazolidine-5-one) and 234.3 mg of 2-hydroxyethyl methacrylate ( 1.9 mmol), and AIBN 0.8 mg (5 mmol) and benzene as a solvent were adjusted to 1 ml and stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Comparative Example 5
In a glove box substituted with nitrogen, 1 ml (8.2 mmol) of 2-hydroxyethyl methacrylate and 0.8 mg (4.9 mmol) of AIBN were stirred at 60 ° C. for 10 hours. After completion of the reaction, the solution was poured into a large amount of stirred n-hexane (about 20 times amount). The precipitated polymer was suction filtered at room temperature and dried to obtain the desired product (white solid). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

Examples 12-15
Each polymer was obtained in the same manner as in Example 1 except that the oxazolidinone monomer and other comonomers were changed to the types and content ratios shown in Table 1. The polymer obtained in Example 12 had Mn = 14000 (Mw / Mn = 1.32). The polymer obtained in Example 13 had Mn = 11000 (Mw / Mn = 1.26). The polymer obtained in Example 14 exceeded the detection limit and was not measurable (Mn was 1.5 million or more). The polymer obtained in Example 15 had Mn = 47000 (Mw / Mn = 1.81). Using the obtained polymer, glass transition temperature (Tg), transmittance and refractive index were measured. The results are shown in Table 1.

<Glass transition temperature>
Each polymer solution was poured into a metal dish having a diameter of about 4 cm covered with aluminum foil so that the thickness after curing was 100 μm, the solvent was dried at 100 ° C. for 10 minutes, and cured at 130 ° C. for 2 hours. The aluminum foil was peeled off from the cured product, and the inflection point when measured under the following measurement conditions using a differential thermal scanning calorimeter (DSC22 (manufactured by SII Nanotechnology)) was defined as the glass transition temperature (° C.). .

<Light transmittance>
Each polymer was molded to produce a small piece having a thickness of 1.0 mm, and measured with an ultraviolet-visible absorption spectrum measuring apparatus “UV-1600PC” (manufactured by Shimadzu Corporation).

<Refractive index>
Each polymer was compression-molded by heating to produce a film having a thickness of 200 μm, and measured with an Abbe refractometer (“Atago New Abbe Refractometer” manufactured by Atago Co., Ltd.) using light having a wavelength of 589 nm.

  The oxazolidines in Table 1 are compounds shown in the following (1-1) to (1-3).

  From the results of Table 1 above, it was shown that the polymers obtained in Examples 1 to 15 had excellent transmittance and high refractive index, and had a high glass transition temperature.

  On the other hand, although the polymers obtained in Comparative Examples 1 to 5 were excellent in transmittance and refractive index, the glass transition temperature was low.

  From the above, the polymer of the present invention can be used in fields where excellent transmittance, refractive index, and glass transition temperature are required, and can be suitably used particularly for lenses, films, optical fibers, semiconductor sealing materials, and the like. Is.

[Ring-opening reaction (hydrolysis)]
Example 16

  1.00 g of the polymer produced in Example 1 and 300 ml of THF were placed in a flask, 300 ml of aqueous potassium hydroxide (KOH) solution (5 g of KOH) was added, and the mixture was reacted at 80 ° C. for 48 hours. After completion of the reaction, THF was removed by an evaporator, and methanol was added to the residue to precipitate a polymer. Thereafter, the precipitated polymer was suction filtered at room temperature and dried. Subsequently, the polymer was purified using a dialysis membrane (Spectrum, Spectrapore 7, fractional molecular weight 3,500). The yield of the purified hydrolyzed polymer was 0.47 g (92.1% yield).

About the hydrolyzed polymer obtained in Example 16, the spectrum by FT-IR measurement was shown in FIG.
IR (KBr, cm ⁻¹ ) 1590 (br, NH ₂ ), 1690 (br, C═O), 3420 (br, OK)
In FIG. 5, peaks indicating amino groups and COOK groups were observed, confirming that the target hydrolyzed polymer.

Example 17
1 g of the polymer produced in Example 16 was washed several times with 3000 ml of water and then vacuum-dried for 2 days. When water was added to this polymer and swollen, it was found that the water was easily absorbed and the weight increased to about 1000 times the weight of the polymer after drying and swollen. FIG. 6 shows a photograph of the hydrogel after the polymer was swollen in water (distilled water).

  Thus, the polymer produced in Example 16 can be suitably used for sanitary articles such as a polymer water-absorbing agent and an ice pillow.

Claims (10)

General formula (2):
(Wherein R ¹ represents a hydrogen atom or an organic group.
R ² and R ³ are the same or different and are a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hetero which may have a substituent. Represents an aryl group, or R ² and R ³ may combine with each other to form a ring with adjacent carbon atoms;
R ⁴ represents a hydrogen atom or a halogen atom. )
The polymer containing the structural unit represented by these. The group represented by R ¹ is an alkyl group, aryl group, heteroaryl group, alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkoxycarbonylalkyl group The polymer according to claim 1, wherein the polymer is an aryloxycarbonylalkyl group or a heteroaryloxycarbonylalkyl group (these groups may have a substituent). Furthermore, the polymer of Claim 1 or 2 containing the structural unit derived from polymerizable monomers other than the structural unit represented by General formula (2). The polymer according to any one of claims 1 to 3,
General formula (1):
(Wherein, R ⁴ represents a hydrogen atom or a halogen atom. Wavy line, the double bond stereochemistry E-form, Z form, or .R ¹ ~ indicating that it is a mixture of E-form and Z-form R ³ is the same as described above), and a polymer obtained by copolymerizing a monomer represented by the above and another polymerizable monomer. A method for producing a polymer according to claim 1 or 2,
General formula (1):
(Wherein, R ⁴ represents a hydrogen atom or a halogen atom. Wavy line, the double bond stereochemistry E-form, Z form, or .R ¹ ~ indicating that it is a mixture of E-form and Z-form R ³ is the same as above.)
A production method comprising a step of polymerizing a monomer represented by: A method for producing a polymer according to claim 3 or 4,
General formula (1):
(Wherein, R ⁴ represents a hydrogen atom or a halogen atom. Wavy line, the double bond stereochemistry E-form, Z form, or .R ¹ ~ indicating that it is a mixture of E-form and Z-form R ³ is the same as above.)
A production method comprising a step of copolymerizing a monomer represented by the above and another polymerizable monomer. General formula (5):
(Wherein R ¹ represents a hydrogen atom or an organic group.
R ⁴ represents a hydrogen atom or a halogen atom.
Y represents a hydrogen atom or a counter cation. )
A process for producing a polymer comprising a structural unit represented by
The manufacturing method provided with the process of hydrolyzing the polymer of Claim 1. The resin composition for optical materials using the polymer as described in any one of Claims 1-4. The molded object using the polymer as described in any one of Claims 1-4. The optical material using the polymer as described in any one of Claims 1-4.