JP2017165845A - Method for producing lactone ring-containing polymer, polymer and lactone ring-containing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polymer having a lactone ring structure in the main chain (lactone ring-containing polymer), that does not exist in the prior art.SOLUTION: Provided is a method for producing lactone ring-containing polymer by allowing an elimination reaction of protecting group against a copolymer (C) having, as a constitutional unit, a unit (A) derived from a propenoic acid ester in which a hydroxyl group protected by a protective group is bonded to a carbon atom at the 2-position and a unit (B) derived from a (meth)acrylic acid ester, and a cyclization reaction between unit (A) and unit (B) to proceed, and produce a polymer with lactone ring structure in the main chain.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a lactone ring-containing polymer having a lactone ring structure in the main chain, a novel polymer that can be used in the method, and a novel lactone ring-containing polymer that can be produced by the method.

  As a transparent thermoplastic polymer, for example, acrylic polymer, polycycloolefin, polycarbonate, polystyrene, and polyester are known. Among them, the acrylic polymer has characteristics such as high optical transparency and a good balance of weather resistance, mechanical strength, molding processability and surface hardness. Transparent thermoplastic polymers are widely used in applications of optical members such as lenses, prisms, optical fibers, and optical films.

  One type of acrylic polymer is a polymer having a ring structure in the main chain. For example, Patent Document 1 (Japanese Patent Laid-Open No. 2006-96960) discloses an acrylic polymer having a lactone ring structure in the main chain, and Patent Document 2 (Japanese Patent Laid-Open No. 2006-328334) includes glutarimide in the main chain. Acrylic polymers having a structure are disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 2007-31537), each of which has an N-substituted maleimide structure in the main chain. In general, the glass transition temperature (Tg) of an acrylic polymer is as high as about 100 ° C., but these documents describe that acrylic polymers having a ring structure in the main chain exhibit a higher Tg. Yes. When the Tg of the polymer is increased, the heat resistance of a member containing the polymer, for example, the above-described optical member is improved. When the heat resistance of the optical member is improved, the recent strong demand for products including the optical member, as a specific example, the light source, power supply unit, There is an increased possibility of being able to meet the design requirements for arranging optical members in the vicinity of heating elements such as batteries and circuit boards.

  As a method for producing a lactone ring-containing polymer, Patent Document 1 discloses that a lactone cyclization condensation reaction proceeds for a polymer containing an acrylic ester unit containing a hydroxy group, for example, a methyl 2-hydroxymethyl acrylate unit. Is disclosed.

Japanese Unexamined Patent Publication No. 2006-96960 JP 2006-328334 A JP 2007-31537 A

  One of the objects of the present invention is a method for producing a lactone ring-containing polymer having a lactone ring structure in the main chain, and an object is to provide an unprecedented production method.

  The method for producing a lactone ring-containing polymer of the present invention comprises a unit (A) derived from a propenoic acid ester in which a hydroxy group protected by a protecting group is bonded to the carbon atom at the 2-position, and a unit derived from a (meth) acrylic acid ester. For the copolymer (C) having (B) as a structural unit, the elimination reaction of the protective group and the cyclization reaction between the unit (A) and the unit (B) are allowed to proceed, This is a method for obtaining a polymer having a lactone ring structure in the main chain.

  The polymer of the present invention comprises a propenoic acid ester-derived unit (A) in which a hydroxy group protected by a protecting group is bonded to the 2-position carbon atom, and a (meth) acrylic acid ester-derived unit (B). It is a polymer having as a structural unit.

  The lactone ring-containing polymer of the present invention has a propenoic acid ester unit (A) having a lactone ring structure in the main chain and a hydroxy group protected by a protecting group bonded to the carbon atom at the 2-position as a constituent unit.

  According to the present invention, it is a method for producing a lactone ring-containing polymer having a lactone ring structure in the main chain, and an unprecedented production method can be achieved.

It is a figure which shows the measurement result (NMR profile) of the < ¹ > H-nuclear magnetic resonance (NMR) with respect to the copolymer (C-1) produced in manufacture example 2. FIG. 1 is a diagram showing a ¹ H-NMR profile of a lactone ring-containing polymer (D-1) produced in Example 1. FIG. 3 is a diagram showing a ¹ H-NMR profile of a lactone ring-containing polymer (D-2) produced in Example 2. FIG. FIG. 4 is a diagram showing a ¹ H-NMR profile of a lactone ring-containing polymer (D-3) produced in Example 3.

  In the method for producing a lactone ring-containing polymer of the present invention, a unit (A) derived from a propenoic acid ester in which a hydroxy group protected by a protecting group is bonded to a carbon atom at the 2-position, and a unit derived from a (meth) acrylic acid ester For the copolymer (C) having (B) as a structural unit, a protective group elimination reaction and a cyclization reaction between the units (A) and (B) are allowed to proceed to the main chain. A polymer having a lactone ring structure (lactone ring-containing polymer) is obtained. Copolymer (C) is a precursor polymer in which a lactone ring-containing polymer is formed by elimination reaction and cyclization reaction.

  This manufacturing method has the following features, for example.

  One feature is that a lactone ring-containing polymer having a lactone ring structure that is a 5-membered ring in the main chain can be efficiently produced from the stage of a specific monomer. The precursor polymer for producing a lactone ring-containing polymer that is a 5-membered ring is, for example, a monomer group including a monomer in which a hydroxy group is bonded to a carbon atom located in the main chain of the precursor polymer after polymerization. Formed by polymerization. However, such monomers are susceptible to isomerization similar to that seen with vinyl alcohol monomers. On the other hand, in the production method of the present invention, as a precursor polymer for producing a lactone ring-containing polymer, a propenoic acid ester-derived unit (A) in which a hydroxy group protected by a protective group is bonded to a carbon atom at the 2-position. And the copolymer (C) which has the unit (B) derived from (meth) acrylic acid ester as a structural unit is used. By protecting the hydroxy group with a protecting group, the copolymer (C) as a precursor polymer can be formed while suppressing the above-mentioned isomerization. In this production method, the copolymer (C) The cyclization reaction can proceed smoothly with the elimination reaction of the protecting group. For this reason, in the manufacturing method of this invention, the lactone ring containing polymer which has a lactone ring structure which is a 5-membered ring in a principal chain can be efficiently manufactured from the stage of a specific monomer.

  Another feature is that a lactone ring-containing polymer in which a protecting group remains can be produced by controlling the elimination reaction of the protecting group. In such a lactone ring-containing polymer, it is possible to obtain properties and / or functions reflecting the presence of the protecting group, for example, properties and / or functions reflecting the properties and / or functions of the protecting group itself. As an example, when the protecting group is a silicon-based group, it is expected to exhibit characteristics and / or functions as a Si-containing polymer. Specific examples thereof include changes in properties such as refractive index, surface hardness, wettability, and compatibility with other resins. In general, the silicon group present in the side chain of the polymer has low heat resistance and is easily thermally decomposed. However, in the lactone ring-containing polymer produced by the production method of the present invention, the lactone ring structure of the main chain The main chain of the polymer is largely distorted and is sterically crowded. Contrary to such common technical knowledge, high heat resistance is maintained even in a state in which a silicon group remains (that is, a state having a silicon group). It is possible to realize.

  In addition to these characteristics, the production method of the present invention further includes a lactone ring-containing polymer and a molding process of the polymer or a resin composition containing the polymer (hereinafter simply referred to as “lactone ring-containing polymer”). The effect of suppressing the occurrence of gelation and foaming at the time of molding of the coalesced ") is also expected.

  In Patent Document 1, a cyclization reaction is performed on a precursor polymer having, as constituent units, an acrylic ester unit (X) containing a hydroxy group and a (meth) acrylic ester unit (Y) containing no hydroxy group. To form a lactone ring-containing polymer. The cyclization reaction proceeds between the unit (X) and the unit (Y) adjacent to each other, but this precursor polymer is a pure random polymer, and three or more units (X) are continuous in the molecular chain. There is a part to do. Then, the units (X) other than the unit (X) located at both ends of the continuous portion remain as they are during the cyclization reaction and after the cyclization reaction, that is, the obtained lactone ring-containing polymer has a hydroxy group. Will remain. The more hydroxy groups remain, the higher the content of the unit (X) in the precursor polymer. As a result of studies, the present inventors have found that this residual hydroxy group is one of the causes of gelation and foaming during the formation of the lactone ring-containing polymer and during the molding process. This is because the residual hydroxy group induces crosslinking between molecular chains of the polymer, typically crosslinking between molecular chains from which alcohol is eliminated. Cross-linking causes gelation and detached alcohol causes foaming.

  On the other hand, in the production method of the present invention, a propenoic acid ester-derived unit (A) in which a hydroxy group protected by a protecting group is bonded to the 2-position carbon atom, and a (meth) acrylic acid ester-derived unit (B) A lactone ring-containing polymer is formed by allowing a cyclization reaction to proceed on the copolymer (C) having as a structural unit. Copolymer (C) is a monomer containing, for example, a propenoic acid ester monomer in which a hydroxy group protected by a protective group is bonded to the carbon atom at the 2-position, and a (meth) acrylic acid ester monomer In this case, since the homopolymerizability of the former monomer is lowered due to the presence of the protecting group, the number and frequency of continuous units (A) in the copolymer (C) are increased. , Lower than the conventional precursor polymer. For this reason, the number of hydroxy groups remaining in the copolymer (C) when the cyclization reaction proceeds and the number of hydroxy groups remaining in the lactone ring-containing polymer obtained through the reaction is reduced. The occurrence of gelation and foaming during the formation of the ring-containing polymer and during the molding process is suppressed.

  Depending on the kind of the protecting group, the homopolymerizability of the propenoic acid ester monomer protected by the group is lost. At this time, the continuity of the unit (A) in the copolymer (C) is most suppressed, and the occurrence of gelation and foaming is most suppressed during the formation of the lactone ring-containing polymer and during the molding process.

  The effect of using the copolymer (C) for the formation of the lactone ring-containing polymer is not necessarily limited to the direct effect of suppressing the occurrence of gelation and foaming. The fact that the number and frequency of continuous units (A) in the copolymer (C) is lower than in the past means that the content of the unit (A) in the copolymer (C) as the precursor polymer can be made larger than in the past. Means. This is because even when the content rate is increased, the occurrence of gelation and foaming during the formation of the lactone ring-containing polymer and during the molding process can be suppressed. And being able to enlarge the content rate of the unit (A) in a copolymer (C) brings about the improvement of the freedom degree of control of the characteristic which the formed lactone ring containing polymer shows. The characteristics are, for example, thermal characteristics and optical characteristics. The thermal property is, for example, Tg of a lactone ring-containing polymer. As a more specific example, it is possible to form a lactone ring-containing polymer having a higher Tg while suppressing the occurrence of gelation and foaming during formation and molding. By improving the degree of freedom of control of such characteristics, it is possible to meet further demands in conventional applications such as optical applications, and for example, application of lactone ring-containing polymers to applications that require further heat resistance. Expansion is expected. The degree of increase in Tg due to introduction of a lactone ring structure into the main chain is greater when the lactone ring is a 5-membered ring than when it is a 6-membered ring.

  The unit (A) is not limited as long as it is a unit derived from a propenoic acid ester in which a hydroxy group protected by a protecting group is bonded to the 2-position carbon atom. The unit (A) is, for example, a unit represented by the following formula (1).

R ^{1 in} Formula (1) is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain oxygen. R ² is a protecting group.

  The organic residue is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a propyl group; an unsaturated aliphatic carbonization having 1 to 20 carbon atoms such as an ethenyl group or a propenyl group. A hydrogen group; an aromatic hydrocarbon group having 1 to 20 carbon atoms such as a phenyl group or a naphthyl group; in the alkyl group, the unsaturated aliphatic hydrocarbon group, and the aromatic hydrocarbon group, One or more is a group substituted by at least one group selected from a carboxyl group, an ether group and an ester group.

R ¹ is preferably a hydrogen atom; an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group.

The unit represented by the formula (1) is a structural unit derived from the monomer represented by the following formula (2) (formed by polymerization of the monomer). R ^1, R ² of formula (2) are the same as R ^1, R ² of formula (1).

Monomer represented by the formula (2), the hydroxy group of 2-hydroxy-propenoic acid ester was protected by a protecting group R ^2, it is a 2-hydroxy-propenoic acid ester derivative. That is, the unit represented by the formula (1) can also be expressed as a 2-hydroxypropenoic acid ester unit in which a hydroxy group is protected by a protecting group, or simply a 2-hydroxypropenoic acid ester derivative unit.

The monomer in the state before the hydroxy group is protected by the protective group R ² is, for example, 2-hydroxypropenoic acid, 2-hydroxypropenoic acid methyl, 2-hydroxypropenoic acid ethyl, 2-hydroxypropenoic acid n- Propyl, isopropyl 2-hydroxypropenoate, n-butyl 2-hydroxypropenoate, isobutyl 2-hydroxypropenoate, t-butyl 2-hydroxypropenoate, n-octyl 2-hydroxypropenoate, isooctyl 2-hydroxypropenoate, 2-hydroxyhexyl 2-hydroxypropenoate, stearyl 2-hydroxypropenoate, cyclopentyl 2-hydroxypropenoate, cyclohexyl 2-hydroxypropenoate, phenyl 2-hydroxypropenoate, o-methoxyphenyl 2-hydroxypropenoate 2-hydroxypropenoic acid p-methoxyphenyl, 2-hydroxypropenoic acid p-nitrophenyl, 2-hydroxypropenoic acid o-methylphenyl, 2-hydroxypropenoic acid p-methylphenyl, 2-hydroxypropenoic acid p-t-butyl Phenyl. Among these monomers, methyl 2-hydroxypropenoate, ethyl 2-hydroxypropenoate, n-butyl 2-hydroxypropenoate, 2-ethylhexyl 2-hydroxypropenoate are converted into units (B) by polymerization ( From the viewpoint of copolymerization with the (meth) acrylate monomer and the stability of the cyclization reaction as the copolymer (C), and from the viewpoint of high effect of improving the Tg of the lactone ring-containing polymer. Is preferably methyl 2-hydroxypropenoate (HPM).

The protecting group R ² is at least one selected from, for example, a silicon group, an acetal group, a benzyl group and derivatives thereof, an acetyl group, and a benzoyl group. These groups, when forming the copolymer (C), have the effect of reducing the homopolymerization of a monomer (for example, a 2-hydroxypropenoic acid ester derivative) containing a hydroxy group protected by a protective group. In addition to being high, when a lactone ring-containing polymer is formed from the copolymer (C), it is easily detached from the monomer, and the cyclization of the copolymer (C) is hardly inhibited.

  The silicon group that is a protective group is not limited, and is at least one selected from, for example, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group, and a triisopropylsilyl group. The acetal group which is a protective group is not limited, and for example, at least selected from a methoxymethyl group, a tetrahydropyranyl group, an ethoxyethyl group, a methoxyethyl group, a methylthiomethyl group, a benzoyloxymethyl group, and a methoxyethoxymethyl group One type. The benzyl group which is a protecting group and its derivative are, for example, at least one selected from a benzyl group, a p-methylphenylbenzyl group and a p-methoxyphenylbenzyl group.

  Protecting groups are trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, triisopropylsilyl group, methoxymethyl group, tetrahydropyranyl group, ethoxyethyl group, methoxyethyl group, methylthiomethyl group , A benzoyloxymethyl group, a methoxyethoxymethyl group, a benzyl group, an acetyl group, and a benzoyl group.

  The protective group is a silicon group and an acetal group from the viewpoint that the action of lowering the homopolymerizability is particularly high and elimination is more reliable when the lactone ring-containing polymer is formed from the copolymer (C). Groups are preferred.

  The unit (B) is not limited as long as it is a unit derived from a (meth) acrylic acid ester (a unit formed by polymerization of a (meth) acrylic acid ester monomer). The unit (B) may or may not have a hydroxy group, but is typically a (meth) acrylic acid ester unit having no hydroxy group. The (meth) acrylic acid ester unit is, for example, acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and benzyl acrylate. Esters by polymerization of monomers of methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, etc. A unit to be formed. Among them, since the lactone ring-containing polymer obtained after cyclization is excellent in cyclization reactivity with the unit (A) and has high heat resistance and optical transparency, the unit (B) is methyl methacrylate. (MMA) units are preferred.

  The copolymer (C) may have two or more types of units (A) and / or two or more types of units (B) as constituent units.

  The content rate of the unit (A) in the copolymer (C) (ratio of the unit (A) in all the structural units of the copolymer (C)) is, for example, 1 to 60 mol%. As described above, the number of consecutive units (A) in the copolymer (C) and the frequency thereof can be made lower than those of the conventional precursor polymer by the arrangement of the protecting group, thereby forming the lactone ring-containing polymer. Further, since the occurrence of gelation and foaming during the molding process can be suppressed, the content of the unit (A) in the copolymer (C) can be increased.

The content rate of each structural unit which comprises a polymer can be evaluated by a well-known method, for example, < ¹ > H-nuclear magnetic resonance (NMR) method and / or infrared spectroscopy (IR) method.

  The copolymer (C) may have a structural unit other than the unit (A) and the unit (B).

The structural unit is, for example, a hydroxy group-containing propenoic acid ester unit in which the hydroxy group is not protected by a protecting group. An example of such a structural unit is shown in the following formula (3). R ¹ of formula (3) is the same as R ¹ of formula (1).

The structural unit other than the unit (A) and the unit (B) is, for example, a unit formed by polymerization of an unsaturated carboxylic acid and / or a unit formed by polymerization of a monomer represented by the following formula (4). It is. R ^{3 in} Formula (4) is a hydrogen atom or a methyl group, and X is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, —C (═O ) R ⁴ group or —C—O—R ⁵ group. Ac is an acetyl group, R ⁴ and R ⁵ are hydrogen atoms or groups exemplified as the organic residue in formula (1).

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, and α-substituted methacrylic acid. Among these, at least one selected from acrylic acid and methacrylic acid is preferable.

  Examples of the monomer represented by the formula (4) include styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. Among these, at least one selected from styrene and acrylonitrile is preferable.

  When the copolymer (C) has structural units other than the units (A) and (B), the content of the structural unit in the copolymer (C) is, for example, 0.1 to 30 mol%, The upper limit is preferably 20 mol% or less, and more preferably 15 mol% or less.

  Copolymer (C) is a novel polymer. This novel polymer can have each composition and each characteristic of copolymer (C) explained above in arbitrary combinations.

  The molecular weight of the copolymer (C) is not limited. For example, the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is 50,000 to 500,000, preferably 80,000 to 400,000, more preferably Is 100,000 to 300,000.

  Although a copolymer (C) is not specifically limited, About the molecular weight distribution (Mw / Mn), it can take the range of 1-5, 1.2-4.5, and also 1.5-4, for example. Mw and number average molecular weight Mn can be measured by GPC.

  The formation method of a copolymer (C) is not limited. Copolymer (C) is a monomer containing, for example, a propenoic acid ester monomer in which a hydroxy group protected by a protective group is bonded to the carbon atom at the 2-position, and a (meth) acrylic acid ester monomer It can be formed by group copolymerization. Examples of the former and latter monomers are as described above.

  The copolymerization method of the monomer group is not limited. As long as a copolymer (C) is obtained, arbitrary polymerization processes can be implemented.

  More specifically, the copolymerization is performed, for example, by solution polymerization. When the copolymer (C) is formed by solution polymerization, the polymerization product contains the polymerization solvent used for the polymerization in addition to the copolymer (C). C) need not be taken out as a solid. Depending on the type of copolymer (C), the polymerization product may be subjected to a desorption reaction and a cyclization reaction to form a lactone ring-containing polymer from the copolymer (C) while containing a solvent. You can also. Of course, after taking out the copolymer (C) as a solid, these reactions may be carried out again in a state suitable for elimination reaction and / or cyclization reaction.

  When the copolymer (C) is formed by solution polymerization, the polymerization solvent used is, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, dimethyl sulfoxide ( DMSO), tetrahydrofuran. Of these, aromatic hydrocarbons and ketones are preferable, and toluene and methyl isobutyl ketone are particularly preferable.

  When the copolymer (C) is polymerized, a polymerization initiator can be used as necessary. The polymerization initiator is not limited. For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl peroxide Organic peroxides such as 2-ethylhexanoate; 2,2′-azobis (isobutyronitrile); (AIBN), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis ( 2-methylisobutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile). Two or more polymerization initiators may be used. The usage-amount of a polymerization initiator can be suitably set according to a combination of monomers or polymerization conditions, and is not limited.

  In order to form the copolymer (C) having a structural unit other than the unit (A) and the unit (B), the monomer group may further include a monomer in which the structural unit is formed by polymerization.

  The monomer group used for copolymerization includes two or more propenoic acid ester monomers in which a hydroxy group protected by a protective group is bonded to the carbon atom at the 2-position, and / or a (meth) acrylic acid ester monomer Can contain two or more.

In the production method of the present invention, the elimination reaction of the protecting group R ² and the cyclization reaction between the unit (A) and the unit (B) are allowed to proceed with respect to the copolymer (C), so that the main chain has a lactone. A lactone ring-containing polymer having a ring structure is formed.

In the elimination reaction, the protecting group R ² is eliminated from the unit (A) of the copolymer (C). As long as the protecting group can be eliminated, the specific means for proceeding with the elimination reaction is not limited. The elimination reaction can be carried out, for example, by at least one selected from application of heat to the copolymer (C), change in the environment of the copolymer (C), and use of a elimination agent. The environmental change is, for example, a change to an acidic atmosphere or a basic atmosphere, or a change to a reducing atmosphere, and can be carried out by using an acid or a base and using a reducing agent, respectively. The release agent is, for example, a fluorine compound. These means may be arbitrarily combined. Each means to combine may be implemented simultaneously or in steps. Specific means for proceeding the elimination reaction can be selected depending on the constitution of the copolymer (C) and the kind of the protecting group.

  An example of a combination of a protecting group and specific means is at least one selected from the group consisting of a silicon-based protecting group, application of heat, change to an acidic atmosphere (for example, use of an acid), and use of a leaving agent. is there. For acetal-based protecting groups, heat is applied and / or changes to an acidic atmosphere. This is a change to a reducing atmosphere for the protecting group which is a benzyl group and its derivative. For protecting groups that are acetyl and benzoyl groups, a change to a basic atmosphere and / or a change to a reducing atmosphere.

  In the elimination reaction, it is sufficient that at least a part of the protecting groups can be eliminated from the unit (A), and of course, all the protecting groups may be eliminated from the unit (A). By removing some of the protecting groups from the unit (A), a lactone ring-containing polymer in which the protecting groups remain after the cyclization reaction can be obtained. That is, in the production method of the present invention, the elimination reaction may be allowed to proceed so that a part of the protective group remains after the reaction to form a lactone ring-containing polymer having a protective group. The degree of elimination of the protecting group from the unit (A) (from the copolymer (C)) is, for example, the time of elimination reaction, the temperature at which the elimination reaction proceeds, the addition amount and addition concentration of acid or base, the reduction The addition amount and concentration of the agent, the addition amount and concentration of the desorbing agent, and when the elimination reaction proceeds in the solution system, can be controlled by the composition of the solution system.

  When the elimination reaction proceeds by applying heat, the temperature varies depending on the type of protecting group, but for example, in the case of silicon-based and acetal-based protecting groups, it is about 100 to 300 ° C.

  When the elimination reaction proceeds by changing to an acidic atmosphere, for example, an acidic substance may be added to the atmosphere in which the copolymer (C) is placed. The acidic substance is not limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid compounds, and organic acids such as sulfonic acids such as methanesulfonic acid and paratoluenesulfonic acid, and carboxylic acids such as formic acid and acetic acid. . Along with the acidic substance, water and / or an alcohol such as methanol or ethanol may be added.

  When the elimination reaction proceeds by changing to a basic atmosphere, for example, a basic substance may be added to the atmosphere in which the copolymer (C) is placed. The basic substance is not limited, and examples thereof include alkali metals, alkaline earth metals, salts thereof, and hydroxides. Along with the basic substance, water and / or an alcohol such as methanol or ethanol may be added.

  When the elimination reaction proceeds by changing to a reducing atmosphere, for example, a reducing substance may be added to the atmosphere in which the copolymer (C) is placed. The reducing substance is not limited and is, for example, a metal hydride. Metal hydride may be generated in the above atmosphere by adding metal and hydrogen.

  When the elimination reaction is allowed to proceed by using the elimination agent, for example, the elimination agent may be added to the atmosphere in which the copolymer (C) is placed. Examples of the fluorine-based compound as a desorbing agent include hydrogen fluoride salts such as hydrogen fluoride and tetrabutylammonium fluoride, and metal fluorides such as cesium fluoride.

In the cyclization reaction, the cyclization condensation reaction proceeds between the hydroxy group of the unit (A) and the ester group of the unit (B) exposed by the removal of the protective group R ² by the elimination reaction, and thereby the lactone A ring structure is formed in the main chain of the polymer. The cyclization reaction is a kind of transesterification reaction that proceeds in the molecular chain of the copolymer (C), and is a reaction in which alcohol is by-produced. The copolymer from which the protective group is eliminated from the copolymer (C) can also be regarded as a precursor polymer that becomes a lactone ring-containing polymer by a cyclization reaction.

The specific means for causing the cyclization reaction to proceed is not limited. The cyclization reaction can be carried out, for example, by applying heat to the copolymer (C) from which the protecting group R ² is eliminated and / or changing the environment of the copolymer (C). The change in the environment is, for example, the change exemplified in the explanation of the elimination reaction, and specific examples are acidic or basic in the atmosphere in which the copolymer (C) from which the protecting group R ² is eliminated is placed. It is a change to. A cyclization catalyst that controls the cyclization reaction, typically that promotes the cyclization reaction, may be used in combination. A known catalyst can be used as the cyclization catalyst.

  When heat is applied to advance the cyclization reaction, the temperature is, for example, 100 to 300 ° C, preferably 150 to 250 ° C.

When the cyclization reaction proceeds by changing to an acidic atmosphere, for example, an acidic substance may be added to the atmosphere in which the copolymer (C) from which the protecting group R ² is eliminated is placed. The acidic substance is not limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid compounds, and organic acids such as sulfonic acids such as methanesulfonic acid and paratoluenesulfonic acid, and carboxylic acids such as formic acid and acetic acid. .

When the cyclization reaction proceeds by changing to a basic atmosphere, for example, a basic substance may be added to the atmosphere in which the copolymer (C) from which the protecting group R ² is eliminated is placed. The basic substance is not limited, and examples thereof include alkali metals, alkaline earth metals, salts thereof, and hydroxides.

  The cyclization reaction is a dealcoholization condensation reaction. For this reason, by reducing the atmosphere of the cyclization reaction, alcohol as a by-product may be actively removed, thereby promoting the cyclization reaction.

  In the cyclization reaction, at least the cyclization reaction between the unit (A) and the unit (B) proceeds. At this time, a further cyclization reaction may proceed between the unit (A) or the unit (B) and another structural unit constituting the copolymer (C).

  The elimination reaction and the cyclization reaction may proceed separately, or may proceed at the same time as long as the conditions for both reactions are prepared. Further, the elimination reaction, or both the elimination reaction and the cyclization reaction can be continued from the formation of the copolymer (C) if the conditions for these reactions and the polymerization conditions for the copolymer (C) are aligned. May be implemented.

  It is also possible to employ a method of proceeding the elimination reaction and the cyclization reaction by mixing the copolymer (C) and 0.001 mol% to 50 mol% of acid with respect to the protective group. In this case, the protecting group is, for example, a silicon group or an acetal group. A silicon group and an acetal group are protecting groups that are eliminated by an acid when used as a protecting group for a hydroxy group.

  In this method (low-capacity acid method), an acid having a number of moles of 50 mol% or less of the number of moles of the protecting group to be eliminated (the number of moles of the hydroxy group from which the protecting group is eliminated) is used. This means that when an average acid molecule is assumed, the acid molecule is involved in the removal of the protective group at least twice. In this sense, the low capacity acid method removes the protective group. A catalytic amount of acid is used.

  The use of such an acid for removing the protecting group can reduce the amount of acid remaining in the copolymer after removal of the protecting group and the lactone ring-containing polymer obtained after the cyclization reaction, for example. This brings a great merit in industrial production of these copolymers and lactone ring-containing polymers.

  One advantage is that the process of removing the remaining acid can be simplified or unnecessary. As described later, since the acid remaining in the polymer may adversely affect the polymer, it is preferable to remove the remaining acid. The ability to simplify or eliminate this treatment reduces the production cost of the lactone ring-containing polymer.

  Another advantage is that it is often difficult to remove the acid remaining in the polymer. For low molecular weight compounds, various methods for removing the remaining acid, such as reprecipitation, liquid separation, neutralization, and chromatograph, can be selected depending on the situation. However, in the case of a polymer, the methods that can be selected are limited particularly because the solvent in which the polymer dissolves is limited. Alternatively, even if there is a method that can be selected, the remaining acid cannot often be sufficiently removed. According to the low-capacity acid method, such a problem can be avoided.

  Another advantage is that the acid remaining in the polymer can adversely affect the polymer even if it can be removed later, but the low volume acid method can avoid this risk. is there. The adverse effects are, for example, a decrease in molecular weight due to the cleavage of the polymer molecular chain by acid, the occurrence of coloring, and a decrease in properties. The deterioration of the properties is caused, for example, by degradation products generated by acid. Examples of properties are thermal properties such as Tg, optical properties such as transparency and birefringence. This merit becomes particularly remarkable when a lactone ring-containing polymer used for an optical member is produced, for example.

  More specifically, the lactone ring-containing polymer can be used for an optical member such as an optical film, but the low-capacity acid method suppresses a decrease in optical properties of the obtained lactone ring-containing polymer. The suppression of the deterioration of the thermal characteristics, for example, the decrease of Tg, also works advantageously when the obtained lactone ring-containing polymer is used for an optical member. An optical member composed of a lactone ring-containing polymer having a high Tg has high heat resistance. Since this is possible, the design of the image display device and the degree of freedom in design are improved.

  However, it is not essential to adopt the low-capacity acid method for the elimination reaction.

  A specific method for proceeding the elimination reaction by the low-capacity acid method is that the copolymer (C) and the acid (0.001 mol% to 50 mol%) with respect to the protective group contained in the copolymer (C). And the protective group can be eliminated from the copolymer (C) (the copolymer (C) can be deprotected). The elimination of the protective group, that is, the progression of the elimination reaction, is preferably performed in a solution system in which the copolymer (C), the acid, and the copolymer after the elimination of the protective group are dissolved.

  The solvent constituting such a solution system can be selected according to the type of the copolymer (C), the acid and the copolymer after elimination of the protective group. Solvents include, for example, aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and acetone; ethers such as tetrahydrofuran; halomethanes such as methylene chloride and chloroform; amides such as dimethylacetamide and dimethylformamide; dimethyl sulfoxide It is. An example of the combination of the acid and the solvent is that the acid is at least one selected from organic sulfonic acids such as para-toluenesulfonic acid and methanesulfonic acid; hydrochloric acid; and phosphoric acid compounds such as phosphoric acid and phosphoric acid ester. Is a combination which is at least one selected from aromatic hydrocarbons, ketones and ethers.

  When the elimination reaction proceeds in the solution system, the concentration of the copolymer (C) in the solution system is, for example, 10 to 80% by mass, preferably 25 to 60% by mass.

  The amount of the acid mixed with the copolymer (C) is 0.001 mol% to 50 mol%, preferably 0.05 mol% to 20 mol, based on the protective group contained in the copolymer (C). %, More preferably 0.5 mol% to 10 mol%. When the amount of the acid mixed with the copolymer (C) is less than 0.001 mol%, the elimination reaction cannot be sufficiently progressed or even if it can be allowed to proceed, it is necessary for the elimination reaction. The time is very long. When the amount of the acid mixed with the copolymer (C) exceeds 50 mol%, the merit of employing the low-capacity acid method is reduced.

  Examples of acids used in the low-capacity acid method include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid compounds (phosphoric acid, phosphorous acid, phosphoric acid ester) and sulfones such as methanesulfonic acid and paratoluenesulfonic acid. These are carboxylic acids such as acids, formic acid and acetic acid, and metal carboxylates.

  An organic acid can be selected as the acid. When the acid is an organic acid, it is easy to use a water-insoluble solvent when the elimination reaction proceeds in the solution system, so that the degree of freedom in selecting an organic solvent as the solvent increases. The organic acid is, for example, an organic sulfonic acid such as methanesulfonic acid or paratoluenesulfonic acid, a carboxylic acid such as phosphoric acid ester, formic acid or acetic acid, or a metal carboxylate, preferably an organic sulfonic acid. In particular, p-toluenesulfonic acid is particularly preferable.

  The elimination reaction of the low-capacity acid method may be performed in the presence of a polar solvent, and at this time, the elimination reaction can proceed more efficiently. This is presumably because the elimination of the protecting group is promoted by the direct bonding of the polar solvent and the protecting group in the low-capacity acid method system. In order to remove the protecting group in the presence of a polar solvent, for example, the elimination reaction may be allowed to proceed in the solution system to which a polar solvent is further added.

  A polar solvent is not limited, For example, it is at least 1 sort (s) chosen from water and alcohol. Alcohol is a C1-C10 alcohol, for example, Preferably they are methanol, ethanol, propanol, and isopropanol.

  When the elimination reaction of the low-capacity acid method is performed in the presence of a polar solvent, the amount of the polar solvent is, for example, 0.1 mol% to 10000 mol% with respect to the protective group of the copolymer (C). 1 mol%-1000 mol% are preferable, and 5 mol%-500 mol% are more preferable. For example, the elimination reaction can be allowed to proceed in the solution system to which an amount of polar solvent in these ranges is further added. When the amount of the polar solvent is within these ranges, the elimination reaction in the low-capacity acid method can proceed more efficiently. Note that the presence of an excessive polar solvent in the solution system may reduce the solubility of the copolymer (C) in the solution system.

  The elimination reaction of the low-capacity acid method may proceed while applying heat. By applying heat, for example, applying heat to the solution system, the elimination reaction can proceed more efficiently. When heat is applied, the specific temperature varies depending on the type of protecting group, but is, for example, about 30 to 300 ° C.

  Even when a part of the protecting group present in the copolymer (C) is eliminated, the amount of the acid used for the elimination reaction is within the above-mentioned range, more specifically, the protection present in the copolymer (C). 0.001 mol% to 50 mol% of the group.

  In the low-capacity acid method, the cyclization reaction to the copolymer formed by the elimination of the protective group can proceed together with the elimination reaction of the protective group. More specifically, depending on the composition of the copolymer (C) and / or the cyclization catalyst described later, the cyclization reaction can proceed in an atmosphere of a catalytic amount of acid used for the elimination reaction. Sometimes, both elimination and cyclization can proceed. A catalyst for controlling the cyclization reaction, typically, a cyclization catalyst for promoting the cyclization reaction may be used in combination. A known catalyst can be used as the cyclization catalyst.

The lactone ring-containing polymer (D) obtained by the production method of the present invention has a lactone ring structure in its main chain. The specific structure of the lactone ring structure to be formed is not particularly limited, but is typically a 5-membered lactone ring structure, for example, a structure represented by the following formula (5). R ¹ of formula (5) is the same as R ¹ of formula (1), R ⁶ is a hydrogen atom (when the unit (B) is an acrylic ester unit) or a methyl group (unit (B) is methacrylic acid ester Unit).

The polymer (D) is at least one unit selected from the unit (A), the unit in which the protecting group R ² is eliminated from the unit (A), and the unit (B), which remain unreacted during the cyclization reaction. As a structural unit. When it has a unit (A), it becomes a lactone ring-containing polymer (D) having a protecting group. Moreover, a polymer (D) can further have the said structural unit, when the copolymer (C) has structural units other than a unit (A) and a unit (B).

  The polymer (D) is typically a thermoplastic polymer. The polymer (D) can be, for example, an amorphous polymer.

Unit (B) is a (meth) acrylic acid ester unit. The unit (A) has an acrylate unit. For this reason, the lactone ring structure formed by the cyclization reaction between the unit (A) and the unit (B) is a derivative of a (meth) acrylic acid ester unit. In addition, the polymer (D) is at least one selected from the unit (A), the unit in which the protecting group R ² is eliminated from the unit (A), and the unit (B) remaining unreacted during the cyclization reaction. These units can be included as structural units. For this reason, if the sum total of the content rate of the lactone ring structure and the content rate of the (meth) acrylic acid ester unit in the polymer (D) is 50% by mass or more, the polymer (D) is an acrylic polymer. At this time, the polymer (D) has characteristics because it is an acrylic polymer, for example, high transparency, high surface gloss and weather resistance, and a high balance of mechanical strength, molding processability and surface hardness. sell.

  The content of the lactone ring structure in the polymer (D) can be made larger than that of the conventional lactone ring-containing polymer because it can suppress the occurrence of gelation and foaming during its formation and molding. is there. Specifically, the content of the lactone ring structure in the polymer (D) can be, for example, 10 to 100% by mass.

  The molecular weight of the polymer (D) is not limited. For example, the weight average molecular weight Mw measured by GPC is 50,000 to 500,000, preferably 80,000 to 400,000, more preferably 100,000 to 300,000. .

  Although a polymer (D) is not specifically limited, About the molecular weight distribution (Mw / Mn), it can take the range of 1-5, 1.2-4.5, and also 1.5-4, for example. Mw and number average molecular weight Mn can be measured by GPC.

  The polymer (D) has characteristics based on the lactone ring structure of the main chain. The characteristics are, for example, thermal characteristics and optical characteristics.

  The thermal characteristic is, for example, Tg, and the Tg of the lactone ring-containing polymer (D) is higher than that when the main chain does not have a lactone ring structure. The Tg of the lactone ring-containing polymer (D) is, for example, 100 ° C. or higher, and can be 130 ° C. or higher, 150 ° C. or higher, and further 180 ° C. or higher depending on the configuration and content of the lactone ring structure. In the lactone ring-containing polymer (D), such a high Tg is achieved, for example, while suppressing the occurrence of gelation and foaming during the formation of the polymer (D) and during the molding process.

  In addition, the lactone ring-containing polymer (D) has a higher Tg when the content of the lactone ring structure is the same as that of the lactone ring-containing polymer formed by the conventional production method. This is considered to be based on the fact that the lactone ring structure is more uniformly arranged in the molecular chain of the lactone ring-containing polymer due to the effects described above.

  And when the lactone ring structure which a polymer (D) has in a principal chain is a 5-membered ring, compared with the case where it is a 6-membered ring, the polymer (D) shown at the time of the content rate of the same lactone ring structure Tg tends to be higher.

  The optical characteristic is, for example, a birefringence characteristic. The lactone ring structure located in the main chain improves the birefringence expression (phase difference expression) of the polymer. The lactone ring structure has an effect of imparting positive intrinsic birefringence to the polymer (D). The positive or negative of the intrinsic birefringence as the polymer (D) is determined by the balance between the birefringence characteristics of the respective structural units of the polymer (D).

  The polymer (D) may further have other properties based on the main chain lactone ring structure. An example of another characteristic is a high pyrolysis start temperature. The polymer (D) is not particularly limited, but may have a thermal decomposition onset temperature of, for example, 230 ° C. or higher, 280 ° C. or higher, and further 300 ° C. or higher depending on the configuration of the polymer. When the polymer (D) has such a high thermal decomposition starting temperature, for example, when the polymer (D) is subjected to various types of processing such as film formation, decomposition of the polymer can be suppressed.

  Another example of other properties is high mechanical properties. For example, the polymer (D) can have high strength and / or hardness. Among these, regarding the strength, the polymer (D) can exhibit a breaking strength (breaking energy) of, for example, 3 mJ or more, and depending on the configuration of the polymer, 5 mJ or more, and further 7 mJ. The upper limit of the breaking strength is not limited, but is, for example, 50 mJ. The breaking strength is a value when formed into an unstretched film having a thickness of 100 μm, and the forming into the unstretched film at the time of measuring the breaking strength is performed through melting of the polymer at Tg + 150 ° C. Specifically, the breaking strength is the height when the film is broken (breaking height) by performing a test of dropping a sphere with a mass of 0.0054 kg and a diameter of 10 mm on the formed unstretched film. ) Average value (15 average values). Whether or not the film has been destroyed is determined by visually confirming whether or not deformation has been observed on the surface of the film after falling onto the film. When the deformation is confirmed, it can be determined that the film is broken.

Fracture energy (mJ) = sphere mass (kg) × fracture height average value (mm) × 9.8 (m / sec ² )

Further, the polymer for the hardness (D), for example 150 N / mm ² or more, depending on the configuration of the polymer, 160 N / mm ² or more, further can exhibit 170N / mm ² or more Martens hardness. The Martens hardness is a value when molded into an unstretched film having a thickness of 100 μm, and the molding into the unstretched film at the time of measuring the Martens hardness is performed by melting the polymer at Tg + 150 ° C. Specifically, Martens hardness is based on ISO-14477-1 using an ultra-micro hardness meter (for example, Fisherscope HM-2000 available from Fischer Instruments) for the formed unstretched film. The method is evaluated. Evaluation is carried out with the unstretched film fixed to the glass substrate. A typical example of measurement conditions uses a quadrangular pyramidal indenter (face-to-face angle a = 136 °); maximum test load 1 mN; application time 20 seconds when load is applied; creep time 5 seconds; application when load is reduced Time 20 seconds; measurement temperature room temperature.

  Based on these characteristics, the lactone ring-containing polymer (D) can be used for various applications. The application is, for example, an optical member. The above-described thermal and optical properties of the lactone ring-containing polymer (D) can be advantageous characteristics of the optical member. Another advantage of the optical member is that the lactone ring-containing polymer (D) is excellent in transparency and heat resistance, and is less gelled and foamed during formation and molding. sell. The optical member is, for example, an optical lens, an optical prism, an optical film, an optical fiber, or an optical disk.

  The shape of the optical member is not particularly limited, and is, for example, a film (optical film). The specific use of the optical film is not particularly limited. For example, a birefringent film, a retardation film, a viewing angle compensation film, a light diffusion film, and a reflection film used in image display devices such as liquid crystal displays, plasma displays, and organic EL displays. A film, an antireflection film, an antiglare film, a brightness enhancement film, a pixel part (light emitting part) protective film, a polarizer protective film, and an ultraviolet absorbing film.

  Other uses of the lactone ring-containing polymer (D) include, for example, signboards / displays, weak electrical / industrial parts, photosensitive electronic materials, automotive parts such as automobiles, building materials / shopping, coating materials, protection for depainting. These include miscellaneous goods such as films, lighting fixtures, large water tanks, mirrors, textiles, stationery, and tableware, cosmetics, and foods.

  When the lactone ring-containing polymer (D) has a protecting group, it can have characteristics derived from the protecting group. Examples of characteristics include refractive index derived from Si atoms contained in the group, surface hardness, wettability, and the like when the protecting group is a silicon group. In addition, as described above, the silicon group present in the side chain of the polymer usually has low heat resistance and is likely to be thermally decomposed. However, in the lactone-containing polymer (D), the heavy chain is present due to the lactone ring structure of the main chain. It is possible to realize high heat resistance even in the state where the silicon group remains, contrary to such common technical knowledge, because the main chain of the coalescence is large and sterically mixed. High heat resistance is manifested, for example, by a thermal decomposition starting temperature of 300 ° C. or higher. Depending on the specific configuration of the polymer (D) including the type and content (residual amount) of the protecting group, a thermal decomposition starting temperature of 310 ° C. or higher can be achieved. Such high heat resistance can be a merit of using the polymer (D) for each application described above. In addition, the thermal decomposition start temperature of a general acrylic polymer is much lower. For example, the thermal decomposition start temperature of simple polymethyl methacrylate (PMMA) is about 220 ° C.

  The lactone ring-containing polymer (D) can be molded into various shapes depending on the application. Formable shapes are, for example, films, sheets, plates, disks, blocks, balls, lenses, rods, strands, cords and fibers. The method for forming the lactone ring-containing polymer (D) into these shapes may be a known method.

  The lactone ring-containing polymer (D) may be used alone, or may be used as a resin composition (E) containing the lactone ring-containing polymer (D) and other polymers and / or additives. .

  The other polymer is not limited, but when the resin composition (E) is used for an application requiring transparency such as an optical member, the lactone ring-containing polymer (D) and the other polymer are compatible with each other. Keep in mind that you need to. Another polymer is, for example, a thermoplastic polymer. Specific examples of other polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, and poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride and chlorinated vinyl resins; Styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polylactic acid, Biodegradable polyester such as polybutylene succinate; polyamide such as nylon 6, nylon 66, nylon 610; polyacetal; polycarbonate; cellulose triacetate, cellulose acetate Cellulose polymers such as lopionate and cellulose acetate butyrate; polyphenylene oxide; polyphenylene sulfide; polyether ether ketone; polyether nitrile; polysulfone; polyethersulfone; polyoxypentylene; polyamidoimide; It is a rubbery polymer such as a blended ABS resin or ASA resin.

  Additives are, for example, ultraviolet absorbers, antioxidants, lubricants, antistatic agents, plasticizers, fluidizers, colorants, dyes, flame retardants, and fillers.

  The resin composition (E) may contain two or more kinds of other polymers and / or two or more kinds of additives.

  The content rate of the lactone ring containing polymer (D) in a resin composition (E) can be freely set according to the characteristic calculated | required as a resin composition (E). The lactone ring-containing polymer (D) may be a main component of the resin composition (E). A main component means a component with the largest content rate in a resin composition. The content rate of the main component is, for example, 50% by mass or more, and may be 60% by mass or more, 70% by mass or more, 80% by mass or more, and further 90% by mass or more.

  The content of the other polymer in the resin composition (E) can be freely set according to the characteristics required for the resin composition (E). The total content of other polymers in the resin composition (E) is, for example, 50% by mass or less, and may be 40% by mass or less. The content of the additive in the resin composition (E) can also be freely set according to the characteristics required for the resin composition (E). The total content of the additives in the resin composition (E) is, for example, 5 parts by mass or less with respect to 100 parts by mass of the lactone ring-containing polymer (D).

The content of each polymer contained in the resin composition can be evaluated by a known method, for example, ¹ H-NMR method and / or IR method.

  The resin composition (E) is, for example, a thermoplastic resin composition.

  The formation method of the resin composition (E) is not limited. For example, it can be formed by mixing the lactone ring-containing polymer (D) and the other polymer and / or additive by a known mixing method. Mixing can be carried out, for example, by pre-blending with a mixer such as an omni mixer and then kneading the resulting mixture. A kneading machine is not specifically limited, For example, well-known kneading machines, such as extruders, such as a single screw extruder and a twin screw extruder, and a pressure kneader, can be used. The resin composition (E) includes a lactone ring-containing polymer (D) formed by the production method of the present invention. For this reason, about resin composition (E), generation | occurrence | production of the gelatinization and foaming at the time of the formation and shaping | molding process can be suppressed, for example.

  The resin composition (E) has characteristics based on the type and content of the lactone ring-containing polymer (D), the polymer and the additive contained in the composition (E). The characteristics are, for example, the above-described thermal characteristics and optical characteristics. Resin composition (E) shows high Tg, for example. The Tg of the resin composition (E) is, for example, 100 ° C. or more, and depending on the configuration and content of the lactone ring-containing polymer (D) contained in the composition, 120 ° C. or more, 130 ° C. or more, It can be 150 ° C or higher. In the resin composition (E), such a high Tg is achieved, for example, while suppressing the occurrence of gelation and foaming during formation and molding.

  The resin composition (E) can be used for the same applications as the lactone ring-containing polymer (D).

  The lactone ring-containing polymer (D) or the resin composition (E) can be molded to form a resin molded body (F). The resin molded body (F) is composed of a lactone ring-containing polymer (D) or a resin composition (E).

  The shape of the resin molded body (F) is not limited and is, for example, a film, a sheet, a plate, a disk, a block, a ball, a lens, a rod, a strand, a cord, or a fiber.

  The resin molded body (F) has characteristics based on the characteristics of the lactone ring-containing polymer (D) or the resin composition (E) constituting the molded body.

  The use of the resin molding (F) is the same as that of the lactone ring-containing polymer (D) and the resin composition (E).

  The formation method of a resin molding (F) is not limited. The resin molded body (F) can be formed by molding the lactone ring-containing polymer (D) or the resin composition (E) by a known molding technique such as a melt extrusion method, a casting method, or a press molding method.

  The resin molded body (F) has characteristics based on the characteristics of the lactone ring-containing polymer (D) or the resin composition (E). The characteristics are, for example, the above-described thermal characteristics and optical characteristics. And in the resin molding (F), generation | occurrence | production of gelling and foaming is suppressed, and this becomes a point especially advantageous for use as an optical member of the resin molding (F). This is because gel and foam become optical defects which are serious defects as an optical member.

  Copolymer (C) is a novel polymer. This polymer comprises a unit (A) derived from a propenoic acid ester in which a hydroxy group protected by a protective group is bonded to the carbon atom at the 2-position, and a unit (B) derived from a (meth) acrylic acid ester. Have as.

About a structure, content rate, a characteristic, a specific example, etc. of a unit (A) and a unit (B) and a copolymer (C), it is as the said description. The unit (A) is, for example, a unit represented by the following formula (1). R ^{1 in} Formula (1) is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain oxygen. R ² is a protecting group.

The lactone ring-containing polymer (D) in which the protective group remains is a novel polymer. This polymer has, as a structural unit, a propenoic acid ester unit (A) having a lactone ring structure in the main chain and having a hydroxy group protected by a protecting group bonded to a carbon atom at the 2-position. The constitution, content, characteristics, specific examples, etc. of the unit (A), the lactone ring structure and the lactone ring-containing polymer (D) are as described above. The unit (A) is, for example, a unit represented by the following formula (1). R ^{1 in} Formula (1) is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain oxygen. R ² is a protecting group.

The specific structure of the lactone ring structure is not particularly limited, but is typically a 5-membered lactone ring structure, for example, a structure represented by the following formula (5). R ¹ of formula (5) is the same as R ¹ of formula (1), R ⁶ is a hydrogen atom (when the unit (B) is an acrylic ester unit) or a methyl group (unit (B) is methacrylic acid ester Unit).

  The examples illustrate the invention in more detail. The present invention is not limited to the examples shown below.

  Initially, the evaluation method of each polymer produced in the present Example is shown.

[Content of each structural unit in the copolymer (C)]
The content rate of each structural unit which the copolymer (C) has was calculated | required from the area ratio of the < ¹ > H-NMR profile obtained by performing a < ¹ > H-NMR measurement with respect to the copolymer (C). Specifically, from the area ratio of the peak near the chemical shift 0 to 0.5 ppm derived from the trimethylsilyl group and the peak near 3.5 to 4.0 ppm derived from the methyl group of the methyl ester group in the profile. Asked. ^{For 1} H-NMR measurement, a nuclear magnetic resonance spectrometer (manufactured by BRUKER, AV300M) was used, and deuterated chloroform (manufactured by Wako Pure Chemical Industries) was used as a measurement solvent.

[Glass transition temperature (Tg)]
The Tg of the produced lactone ring-containing polymer and polymethyl methacrylate (PMMA), which is a polymer of the comparative example, was determined in accordance with the provisions of JIS K7121. Specifically, using a differential scanning calorimeter (Rigaku, Thermo plus EVO DSC-8230), a sample of about 10 mg was heated from room temperature to 300 ° C. (temperature increase rate 20 ° C./min) in a nitrogen gas atmosphere. From the DSC curve obtained in this way, the starting point method was used for evaluation. Α-alumina was used as a reference.

[Pyrolysis start temperature (DyTGA)]
DyTGA of PMMA which is the produced lactone ring-containing polymer and the polymer of the comparative example was obtained by dynamic TG measurement on these polymers. Specifically, it is as follows.

  Using a differential type differential thermal balance apparatus (Rigaku, Thermo plus2 Tg-8120), a sample of about 10 mg was heated from room temperature to 500 ° C. in a nitrogen gas atmosphere. At this time, when the mass decrease rate of the sample during temperature increase is 0.005 mass% / second or less, the temperature increase rate is 10 ° C./minute, and when it exceeds 0.005 mass% / second, the mass decrease rate is The temperature was raised by using stepwise isothermal control together so as to keep 0.005 mass% / second or less. The temperature at which stepwise isothermal control was first performed in order to maintain the mass reduction rate (the lowest temperature with stepwise isothermal control) was defined as DyTGA of the polymer.

[Molecular weight]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer (C), the produced lactone ring-containing polymer, and the PMMA of the comparative example were determined using gel permeation chromatography (GPC). It was determined under the following measurement conditions in terms of standard polystyrene.
Measurement system: “GPC system HLC-8220” manufactured by Tosoh Corporation
Developing solvent: N, N-dimethylformamide (Wako Pure Chemical Industries, special grade)
Solvent flow rate: 1 mL / min Standard sample: TSK standard polystyrene (“PS-oligomer kit” manufactured by Tosoh Corporation)
Measurement side column configuration: Guard column ("TSK guardcolumn ALPHA" manufactured by Tosoh Corporation), separation column ("TSK Gel ALPHA-5000" manufactured by Tosoh Corporation, "TSK Gel ALPHA-2500"), two in series connection

(Production Example 1: Preparation of methyl 2-trimethylsiloxypropenoate monomer)
In Production Example 1, a 2-hydroxypropenoic acid methyl monomer having a hydroxy group protected by a trimethylsilyl group (TMS group), which is a protective group, is converted into a unit (A) by polymerization, that is, methyl 2-trimethylsiloxypropenoate. A monomer (TMS-HPM) was prepared.

  First, a dropping funnel, a condenser tube and a thermometer were attached to a three-necked flask having an internal volume of 200 mL, and methyl pyruvate monomer (31 mmol, 3.2 g), chlorotrimethylsilane (TMS-Cl; 35 mmol, 3.8 g) were attached thereto. ), And tetrahydrofuran (THF; 40 mL) was added as a solvent. Next, a mixture of triethylamine (42 mmol, 4.3 g) and THF (25 mL) was dropped into the flask via a dropping funnel at room temperature over 10 minutes, and then stirred at room temperature for 3 hours. After completion of the reaction, hexane (40 mL) was charged into the flask, the contents of the flask were filtered, and the obtained liquid was subjected to a liquid separation treatment with water and saturated brine to extract an organic layer. Next, after drying the extracted organic layer with sodium sulfate, the solvent was distilled off to obtain a transparent liquid. Next, the obtained liquid was isolated by neutral silica gel chromatography to obtain 3.4 g (19.5 mmol) of TMS-HPM monomer in a yield of 63%.

(Production Example 2: Production of copolymer (C-1))
A TMS-HPM monomer produced in Production Example 1 and a methyl methacrylate (MMA) monomer are copolymerized to produce a TMS-HPM unit as unit (A) and an MMA unit as unit (B). The copolymer (C-1) which has as a structural unit was produced.

Specifically, the TMS-HPM monomer (5 mmol, 0.87 g) prepared in Production Example 1 and the MMA monomer (45 mmol, 4.5 g) were charged into a pressure-resistant tube having an internal volume of 100 mL. Thereafter, 10.7 mg of AIBN as an initiator and 3.6 g of toluene as a solvent were further added. Next, after bubbling nitrogen inside the tube for 2 minutes, the tube was sealed and immersed in an oil bath at 65 ° C. for 8 hours. Next, the contents of the tube were dissolved in chloroform and reprecipitated with hexane, and then the solvent was removed. Thus, the copolymerization of the TMS-HPM monomer and the MMA monomer was advanced to obtain a white solid copolymer (C-1) which is a TMS-HPM / MMA copolymer. It was 20 mol% when the content rate of the TMS-HPM unit in a copolymer (C-1) was evaluated by < ¹ > H-NMR. In addition, the copolymer (C-1) had a weight average molecular weight of 150,000 and a number average molecular weight of 89,000. FIG. 1 shows the ¹ H-NMR profile of the copolymer (C-1).

(Production Example 3: Production of copolymer (C-2))
Except that the amount of MMA monomer charged into the pressure tube was 95 mmol (9.5 g), the amount of AIBN was 20.7 mg, and the amount of toluene was 6.9 g, TMS-HPM / A white solid copolymer (C-2), which is an MMA copolymer, was obtained. When the content of TMS-HPM units in the copolymer (C-2) was evaluated by ¹ H-NMR, it was 10 mol%. The copolymer (C-2) had a weight average molecular weight of 194,000 and a number average molecular weight of 121,000.

Example 1
In Example 1, a lactone ring-containing polymer was obtained by allowing the copolymer (C-1) produced in Production Example 2 to proceed with a protecting group (TMS group) elimination reaction and a cyclization reaction. Specifically, it is as follows.

First, in an autoclave having an internal volume of 100 mL, 2 g of the copolymer (C-1) prepared in Production Example 2 was dissolved in 18 mL of methyl ethyl ketone (MEK). Next, 26 mg of paratoluenesulfonic acid (4.3 mol% with respect to the protective group of the copolymer (C-1)) and 0.22 g of methanol were added to the autoclave, and the autoclave was further purged with nitrogen. Thereafter, the whole was heat-treated for 3.5 hours using an oil bath maintained at 250 ° C. Next, after the heat-treated liquid was cooled to room temperature and taken out from the autoclave, it was dried in a vacuum oven maintained at 240 ° C. to obtain a lactone ring-containing polymer (D-1). In this reaction, the elimination reaction and the cyclization reaction proceeded together. More specifically, in the copolymer (C-1) formed by the elimination reaction and from which the protective group was eliminated, the cyclization reaction proceeded rapidly after elimination of the protective group. ^{As a} result of confirmation by ¹ H-NMR, no residual protecting group was observed in the obtained lactone ring-containing polymer (D-1) (the content of TMS-HPM units in the polymer (D-1) is 0 mol%).

The lactone ring-containing polymer (D-1) thus obtained had a weight average molecular weight of 115,000, a number average molecular weight of 54,000, Tg of 137 ° C., and DyTGA of 310 ° C. ^As confirmed by ¹ H-NMR, the lactone ring structure of the polymer (D-1) in the main chain had the structure represented by formula (5) (where R ¹ and R ⁶ are methyl groups). . The content of the lactone ring structure in the polymer (D-1) is 25 mol%, that is, the elimination reaction of the protecting group of the TMS-HPM unit and the cyclization with the MMA unit in the copolymer (C-1). The reaction was completely progressing. FIG. 2 shows the ¹ H-NMR profile of the lactone ring-containing polymer (D-1). Each of the above-mentioned matters found for the lactone ring-containing polymer (D-1) produced in Example 1 is that the peak near the chemical shift of 0 to 0.5 ppm derived from the trimethylsilyl group disappears in the profile. And an area ratio between a peak near 0.7 to 1.5 ppm derived from the methyl group directly bonded to the main chain and a peak near 3.4 to 4.0 ppm derived from the methyl group of the methyl ester group. It was.

(Example 2)
20 mg of paratoluenesulfonic acid (3.3 mol% with respect to the protective group of the copolymer (C-1)) and 0.17 g of methanol were used, and the heat treatment time was 2 hours. In the same manner as in Example 1, a lactone ring-containing polymer (D-2) was obtained. ^When confirmed by ¹ H-NMR, the resulting lactone ring-containing polymer (D-2) was found to have residual protecting groups (the content of TMS-HPM units in the polymer (D-2) was 3). Mol%).

The weight average molecular weight of the lactone ring-containing polymer (D-2) thus obtained was 17,000, the number average molecular weight was 55,000, Tg was 134 ° C., and DyTGA was 310 ° C. The lactone ring structure that the polymer (D-2) has in the main chain was the same as in Example 1, and the content of the lactone ring structure in the polymer (D-2) was 20.5 mol%. FIG. 3 shows the ¹ H-NMR profile of the lactone ring-containing polymer (D-2). Each of the above items found for the lactone ring-containing polymer (D-2) produced in Example 2 was directly bonded to the main chain of a peak near the chemical shift of 0 to 0.5 ppm derived from the trimethylsilyl group in the profile. This was confirmed by the area ratio of the peak around 0.7 to 1.5 ppm derived from the methyl group and the peak around 3.4 to 4.0 ppm derived from the methyl group of the methyl ester group.

(Example 3)
6 mg of paratoluenesulfonic acid (1 mol% based on the protective group of the copolymer (C-1)) and 0.05 g of methanol were used, except that the heat treatment time was 1.5 hours. In the same manner as in Example 1, a lactone ring-containing polymer (D-3) was obtained. ^When confirmed by ¹ H-NMR, the resulting lactone ring-containing polymer (D-3) was found to have residual protecting groups (the content of TMS-HPM units in the polymer (D-3) was 18). Mol%).

The thus obtained lactone ring-containing polymer (D-3) had a weight average molecular weight of 11,000,000, a number average molecular weight of 62,000, Tg of 130 ° C., and DyTGA of 310 ° C. The lactone ring structure that the polymer (D-3) has in the main chain was the same as in Example 1, and the content of the lactone ring structure in the polymer (D-3) was 2 mol%. FIG. 4 shows the ¹ H-NMR profile of the lactone ring-containing polymer (D-3). Each of the above-mentioned matters found for the lactone ring-containing polymer (D-3) produced in Example 3 was directly bonded to the main chain, a peak near the chemical shift of 0 to 0.5 ppm derived from the trimethylsilyl group in the profile. This was confirmed by the area ratio of the peak around 0.7 to 1.5 ppm derived from the methyl group and the peak around 3.4 to 4.0 ppm derived from the methyl group of the methyl ester group.

Example 4
While using the copolymer (C-2) produced in Production Example 3 instead of the copolymer (C-1) produced in Production Example 2, 12 mg of paratoluenesulfonic acid (copolymer (C-2) Lactone ring-containing polymer (D-4) in the same manner as in Example 1, except that 3.7 mol% of the protecting group contained in the solvent and 0.1 g of methanol were used and the heat treatment time was 2 hours. ) ^{As a} result of confirmation by ¹ H-NMR, no residual protective group was observed in the obtained lactone ring-containing polymer (D-4) (the content of TMS-HPM units in the polymer (D-4) is 0 mol%).

  The lactone ring-containing polymer (D-4) thus obtained had a weight average molecular weight of 145,000, a number average molecular weight of 74,000, Tg of 124 ° C., and DyTGA of 315 ° C. The lactone ring structure of the polymer (D-4) in the main chain was the same as in Example 1. The content of the lactone ring structure in the polymer (D-4) is 11.1 mol%, that is, the elimination reaction of the protecting group of the TMS-HPM unit and the MMA unit in the copolymer (C-2). The cyclization reaction was completely in progress. Each of the above items found for the lactone ring-containing polymer (D-4) produced in Example 4 is that the peak near the chemical shift of 0 to 0.5 ppm derived from the trimethylsilyl group disappears in the profile. And an area ratio between a peak near 0.7 to 1.5 ppm derived from the methyl group directly bonded to the main chain and a peak near 3.4 to 4.0 ppm derived from the methyl group of the methyl ester group. It was.

  The results of Example 1-4 are summarized in Table 1 below together with the weight average molecular weight, number average molecular weight, Tg, and DyTGA values of polymethyl methacrylate (PMMA) prepared as a polymer of the comparative example.

  The lactone ring-containing polymer obtained by the production method of the present invention can be used for the same applications as conventional lactone ring-containing polymers.

Claims (11)

  A copolymer having, as constituent units, a propenoic acid ester-derived unit (A) in which a hydroxy group protected by a protecting group is bonded to the 2-position carbon atom, and a (meth) acrylic acid ester-derived unit (B). A lactone that obtains a polymer having a lactone ring structure in the main chain by allowing the elimination reaction of the protecting group and the cyclization reaction between the units (A) and (B) to proceed with respect to (C) A method for producing a ring-containing polymer. The method for producing a lactone ring-containing polymer according to claim 1, wherein the unit (A) is a unit represented by the following formula (1).

R ^{1 in} Formula (1) is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain oxygen. R ² is the protecting group.   2. The elimination reaction is allowed to proceed by at least one selected from application of heat to the copolymer (C), change of the environment of the copolymer (C), and use of an elimination agent. 2. A process for producing a lactone ring-containing polymer as described in 2.   3. The elimination reaction and the cyclization reaction are allowed to proceed by mixing the copolymer (C) and 0.001 mol% to 50 mol% of an acid with respect to the protecting group. A process for producing a lactone ring-containing polymer as described in 1.   The method for producing a lactone ring-containing polymer according to claim 4, wherein the acid is an organic acid.   A monomer comprising the copolymer (C), a propenoic acid ester monomer in which a hydroxy group protected by the protective group is bonded to a carbon atom at the 2-position, and a (meth) acrylic acid ester monomer The method for producing a lactone ring-containing polymer according to any one of claims 1 to 5, which is formed by copolymerization of a group.   The lactone ring-containing polymer according to claim 1, wherein the polymer having the protecting group is obtained by allowing the elimination reaction to proceed so that a part of the protecting group remains after the reaction. Manufacturing method.   The polymer which has as a structural unit the unit (A) derived from the propenoic ester which the hydroxyl group protected by the protecting group couple | bonded with the 2-position carbon atom, and the unit (B) derived from (meth) acrylic ester. The polymer according to claim 8, wherein the unit (A) is a unit represented by the following formula (1).

R ^{1 in} Formula (1) is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain oxygen. R ² is the protecting group. Has a lactone ring structure in the main chain,
A lactone ring-containing polymer having, as a structural unit, a propenoic acid ester unit (A) in which a hydroxy group protected by a protecting group is bonded to a carbon atom at the 2-position. The lactone ring-containing polymer according to claim 10, wherein the unit (A) is a unit represented by the following formula (1).

R ^{1 in} Formula (1) is a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain oxygen. R ² is the protecting group.

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