JP2011191687A - Optical element having photoelasticity - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical element having photoelasticity which is amorphism; in which the birefringence is extensive and changes in the linear manner to the stress or the distortion from the outside ; and in which birefringence control is easy. <P>SOLUTION: The optical element having photoelasticity, including an aliphatic polycarbonate which is expressed in the general formula (1), which is obtained as epoxide and carbon oxide bond alternately, and which does not include an ether bond component that can be detected by<SP>1</SP>H-NMR analysis, is characterized by having a stress optic coefficient within the range of 0.1 to 2.0 GPa<SP>-1</SP>. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an optical element having photoelasticity. The present invention also relates to an optical element having photoelasticity, which is amorphous and has a birefringence that changes linearly in a wide range with respect to external stress or strain, and the birefringence is easily controlled.

In the field of manufacturing synthetic resins including polycarbonate, the use of carbon dioxide as a carbon source is an important issue from the viewpoint of resource utilization and environmental protection. Polycarbonate has excellent properties such as impact resistance, lightness, transparency, and heat resistance. Among them, aliphatic polycarbonate is biodegradable, so it has a low environmental impact and is an important resin. I can say that.
In addition, various methods for producing polycarbonate and the like using carbon dioxide as a carbon source have been studied. For example, methods using a zinc complex, an aluminum complex, a porphyrin complex, a salen complex (Patent Document 1), etc. as a catalyst are studied. Has been.
Therefore, finding a new use of an aliphatic polycarbonate using carbon dioxide as a carbon source is meaningful from the viewpoint of resource utilization and environmental protection.

  In the field of optical resins, in order to prevent a decrease in transparency due to light scattering by microcrystals, a resin having a large side chain, for example, PMMA, or some mobility after dropping the main chain mobility. Resin having steric hindrance, such as polycarbonate having a bisphenol skeleton, is used. However, since the change of birefringence is very small due to the influence of the side chain, PMMA cannot be used as an optical element that utilizes the birefringence of a material such as a retardation film. In addition, the polycarbonate having a bisphenol skeleton has a large intrinsic birefringence and has a rigid benzene ring unit, so the change in birefringence when stress is applied is remarkably large, so that it can be used as an optical element. However, it was necessary to control the stress with very high accuracy, and it was difficult to put it to practical use.

  Further, in order to manufacture an optical device having a complicated function using an optical element, a dynamic optical element capable of dynamically changing optical characteristics by an external input is required. Currently, devices that use liquid crystalline molecules are used for such applications, but in a dynamic optical device that uses liquid crystals, the optical functionality changes depending on the voltage applied from the outside. In addition, a complicated electric circuit for controlling the voltage is necessary, and in order to maintain a certain optical characteristic, it is necessary to continue to apply the voltage, which leads to the complexity of the device incorporating the voltage and the increase in power consumption. . Therefore, there is a demand for an optical element whose characteristics can be changed by an input other than electricity, or an optical element which maintains its optical characteristics even when input given from outside is stopped.

JP 2009-215529 A

As described above, in the field of optical elements, there are optical elements that are amorphous and have a birefringence that changes linearly over a wide range with respect to external stress or strain and that control of birefringence is simple. It is desired. Further, there is a strong demand for a dynamic optical element in which birefringence changes with respect to external stress or strain in a temperature environment that is normally used or a temperature close thereto.
Accordingly, an object of the present invention is to provide an optical element having photoelasticity, including a specific aliphatic polycarbonate having the above characteristics.

（式中、Ｒ¹及びＲ²は、同一又は異なり、水素原子、置換若しくは非置換のアルキル基であるか、又はＲ¹とＲ²とが互いに結合して置換若しくは非置換の脂肪族環を形成する）
で表される、エポキシドと二酸化炭素とが交互に結合して得られ且つ¹Ｈ−ＮＭＲ分析により検出可能なエーテル結合成分を含まない脂肪族ポリカーボネートを含む、光弾性を有する光学素子であって、０．１〜２．０ＧＰａ^-1の範囲の応力光学係数を有することを特徴とする光学素子により、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies in order to solve the above problems, the present inventors have found that the following general formula (1):

(Wherein R ¹ and R ² are the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or R ¹ and R ² are bonded to each other to form a substituted or unsubstituted aliphatic ring. Form)
An optical element having photoelasticity, comprising an aliphatic polycarbonate obtained by alternately bonding epoxides and carbon dioxide, and containing no ether bond component detectable by ¹ H-NMR analysis, It has been found that the above-mentioned problems can be solved by an optical element having a stress optical coefficient in the range of 0.1 to 2.0 GPa ⁻¹ , and the present invention has been completed.

（式中、Ｒ¹及びＲ²は、同一又は異なり、水素原子、置換若しくは非置換のアルキル基であるか、又はＲ¹とＲ²とが互いに結合して置換若しくは非置換の脂肪族環を形成する）
で表される、エポキシドと二酸化炭素とが交互に結合して得られ且つ¹Ｈ−ＮＭＲ分析により検出可能なエーテル結合成分を含まない脂肪族ポリカーボネートを含む、光弾性を有する光学素子であって、
０．１〜２．０ＧＰａ^-1の範囲の応力光学係数を有することを特徴とする、
上記光学素子。 Specifically, the present invention relates to the following aspects.
[Aspect 1]
The following general formula (1):

(Wherein R ¹ and R ² are the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or R ¹ and R ² are bonded to each other to form a substituted or unsubstituted aliphatic ring. Form)
An optical element having photoelasticity, comprising an aliphatic polycarbonate obtained by alternately bonding epoxides and carbon dioxide, and containing no ether bond component detectable by ¹ H-NMR analysis,
Having a stress optical coefficient in the range of 0.1-2.0 GPa ⁻¹ ,
The optical element.

[Aspect 2]
At a tensile rate of 1000% / min, the film was stretched to a strain of 400%, the stress value and birefringence value were plotted as the x-axis and y-axis, respectively, and the coefficient of determination was 0.95 when regressed with a straight line passing through the origin. The optical element according to aspect 1, which is the above.
[Aspect 3]
The optical element according to aspect 1 or 2, wherein the epoxide is ethylene oxide or propylene oxide.

（式中、Ｒ_ａは、それぞれ独立して、Ｈ、炭素数１〜１０のアルキル基若しくは炭素数３〜１０のシクロアルキル基、置換若しくは非置換の炭素数６〜２０のアリール基、炭素数１〜１０のアルコキシ基、炭素数２〜１０のアシル基、炭素数２〜１０のアシロキシ基、Ｆ、Ｃｌ、Ｂｒ、Ｉ、又は−Ｓｉ（Ｒ_ｂ）₂−Ｒ_ｃ−Ｘ（式中、Ｒ_ｂは、それぞれ独立して、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、又は置換若しくは非置換の炭素数６〜２０のアリール基から選択され、Ｒ_ｃは、炭素数１〜８の二価の炭化水素基であり、Ｘは、Ｆ、Ｃｌ、Ｂｒ又はＩから選択される。）から選択されるが、Ｒ_ａの少なくとも１つは−Ｓｉ（Ｒ_ｂ）₂−Ｒ_ｃ−Ｘであり、Ｒ_ｄは、各ベンゼン環上の０〜３個の置換基であって、それぞれ独立して、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、置換若しくは非置換の炭素数６〜２０のアリール基、炭素数１〜１０のアルコキシ基、炭素数２〜１０のアシル基、炭素数２〜１０のアシロキシ基、又はＦ、Ｃｌ、Ｂｒ若しくはＩから選択され、Ｙは、２個の炭素原子を介して２個のイミノ窒素を連結する二価の連結基であって、その２個の炭素原子に１又は複数の、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、又は置換若しくは非置換の炭素数６〜２０のアリール基が結合していてもよく、あるいはその２個の炭素原子が置換又は非置換の、飽和若しくは不飽和の脂肪族環又は芳香環の一部を構成してもよく、Ｚは、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、及びアリールオキシドからなる群から選択されるアニオン性配位子である）
で表されるコバルト錯体である、態様１〜３のいずれか１つに記載の光学素子。 [Aspect 4]
The catalyst used for the synthesis of the aliphatic polycarbonate is represented by the following general formula (I):

(In the formula, each R _a is independently H, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or carbon number. An alkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, F, Cl, Br, I, or —Si (R _b ) ₂ —R _c —X (wherein R _b is independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R _c is A divalent hydrocarbon group having 1 to 8 carbon atoms, wherein X is selected from F, Cl, Br or I.), but at least one of R _a is —Si (R _b ) _2- R _c -X, where R _d is 0-3 substituents on each benzene ring. Each independently, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, Selected from an acyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or F, Cl, Br, or I, and Y is a group that connects two imino nitrogens through two carbon atoms. A valent connecting group having two or more carbon atoms having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 20 carbon atoms May be bonded to each other, or the two carbon atoms may form a part of a substituted or unsubstituted, saturated or unsaturated aliphatic ring or aromatic ring, and Z is F ^{-, Cl -, Br -,} I -, N 3 -, aliphatic Cal Kishirato, aromatic carboxylate, alkoxide, and an anionic ligand selected from the group consisting of aryloxides)
The optical element as described in any one of the aspects 1-3 which is a cobalt complex represented by these.

[Aspect 5]
The optical element according to any one of aspects 1 to 4, having a stress optical coefficient in the range of 0.3 to 1.0 GPa ⁻¹ .
[Aspect 6]
The optical element according to aspect 5, having a breaking elongation of 100% or more at 25 ° C., and an elongation recovery rate after elongation of 100% is 90% or more.

[Aspect 7]
The optical element according to any one of aspects 1 to 6, which is selected from the group consisting of a shutter, a phase difference plate, and a wavelength filter.
[Aspect 8]
The apparatus containing the optical element as described in any one of aspect 1-7.

The optical element having photoelasticity of the present invention is amorphous, and birefringence changes linearly over a wide range with respect to external stress or strain, and birefringence can be easily controlled.
Moreover, the optical element having photoelasticity of the present invention is a dynamic optical element whose birefringence changes with respect to external stress or strain in a temperature environment or a temperature close to it.
Furthermore, since the optical element having photoelasticity of the present invention contains aliphatic polycarbonate having carbon dioxide as a part of the raw material and biodegradability, it has high environmental adaptability.

FIG. 1 is a schematic diagram of an optical delay measurement system. FIG. 2 is a diagram showing the relationship between strain and birefringence of the PPC manufactured in Manufacturing Example 1. FIG. 3 is a diagram showing the relationship between strain and birefringence of the PEC produced in Production Example 2. FIG. 4 is a diagram showing the relationship between time and birefringence of the PPC manufactured in Manufacturing Example 1. FIG. 5 is a diagram showing the relationship between time and birefringence of the PEC manufactured in Manufacturing Example 2. FIG. 6 is a diagram illustrating the relationship between stress and birefringence in the PPC manufactured in Manufacturing Example 1. FIG. 7 is a diagram illustrating the relationship between stress and birefringence of the PEC manufactured in Manufacturing Example 2. FIG. 8 is a diagram showing the relationship between stress and birefringence in TOPAS ™ 6015 used in Comparative Example 1. FIG. 9 is a schematic diagram of the shutter unit used in the second embodiment.

で表されるエポキシドにおいて、Ｒ¹及びＲ²は、同一又は異なり、水素原子、置換若しくは非置換のアルキル基であるか、又はＲ¹とＲ²とが互いに結合して置換若しくは非置換の脂肪族環を形成することができる。 The optical element having photoelasticity of the present invention will be described in detail below.
[Aliphatic polycarbonate]
General formula (1) used as a raw material for the aliphatic polycarbonate used in the present invention:

And R ¹ and R ² are the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or R ¹ and R ² are bonded to each other to form a substituted or unsubstituted fat. A family ring can be formed.

The alkyl group for R ¹ and R ² is preferably a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. , N-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 2-hexyl Group, 3-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 3,3- Dimethyl-n-butyl group, n-heptyl group, 2-heptyl group, 1-ethyl-1,2-dimethyl-n-propyl group, 1-ethyl-2,2-dimethyl-n-propyl group, n-octyl Group, n-no A nyl group, n-decyl group, etc. are mentioned, More preferably, it is a methyl group. The alkyl group is substituted with one or more substituents selected from, for example, a hydroxy group, an amino group, a carboxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, and an aromatic group. May be.

R ¹ and R ² may be bonded to each other to form a substituted or unsubstituted aliphatic ring, and preferably a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms. For example, when R ¹ and R ² are bonded to each other via — (CH ₂ ) ₄ —, a cyclohexane ring is formed. The ring thus formed is selected from, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. It may be substituted with two or more substituents.

Specific examples of particularly preferable epoxides represented by the general formula (1) include the following formulas (1-1) to (1-3).

  Of the epoxides of the formulas (1-1) to (1-3), ethylene oxide represented by the formula (1-1) and propylene oxide represented by the formula (1-2) are particularly preferable.

で表され、ここでＲ¹及びＲ²は上記の通りである。 The aliphatic polycarbonate used in the present invention has the general formula (2):

Where R ¹ and R ² are as described above.

  The number average molecular weight of the aliphatic polycarbonate represented by the general formula (2) is preferably about 5,000 to 1,000,000, more preferably about 10,000 to 200,000, particularly preferably about 50,000. It is in the range of ~ 130,000.

The aliphatic polycarbonate used in the present invention preferably has a breaking elongation of at least 100%, more preferably has a breaking elongation of at least 200%, and at least 400 at a temperature at which the aliphatic polycarbonate can be molded. It is further preferred to have a% elongation at break and most preferably at least 400%. By having the above elongation at break, it can have a wide range of birefringence values, including the birefringence values of optical elements formed from conventional TOPAS, due to the stress associated with strain during molding, and formed from conventional TOPAS The optical element made can be replaced.
In the present specification, the “breaking elongation” means the amount of strain at break when the sample is stretched at a predetermined temperature under conditions of an initial sample length of 5 mm and 1000% / min.

  Further, the aliphatic polycarbonate used in the present invention preferably has a breaking elongation of at least 100% at 25 ° C., more preferably has a breaking elongation of at least 200%, and a breaking elongation of at least 400%. And most preferably has a breaking elongation of at least 400%.

  Furthermore, the aliphatic polycarbonate used in the present invention preferably has an elongation recovery rate after 100% elongation of 90% or more, more preferably 95% or more, further preferably 99% or more, Most preferably, it is 99.5% or more. By having the breaking elongation and elongation recovery characteristics at 25 ° C., which is close to normal room temperature, the optical element including the aliphatic polycarbonate has its optical characteristics due to application of stress, strain, etc. in a normal use environment. It can be used as a dynamic optical element that can be adjusted. Furthermore, when birefringence is controlled by strain, it is necessary to supply energy from the outside such as a motor to adjust the strain. After the adjustment, if the strain is fixed by screwing, a brake mechanism, etc., then Since the optical characteristics can be maintained without supplying energy, it can be an element that consumes much less energy than a liquid crystal element that requires constant voltage application.

In the present specification, the “elongation recovery rate” means that a sample having an initial sample length of 20 mm is stretched to a strain amount of 100% under the condition of 100% / min, and then 100% / min. The sample is then shrunk to 0% under the conditions of the following, then the sample is removed from the testing machine, the sample length L (mm) is measured,
Elongation recovery rate (%) = (2-L / 20) × 100
Means the value calculated according to

Specific examples of particularly preferable aliphatic polycarbonates represented by the general formula (2) include those represented by the following formulas (3-1) to (3-3).

  Of the formulas (3-1) to (3-3), the polyethylene carbonate represented by the formula (3-1) and the polypropylene carbonate represented by the formula (3-2) are particularly preferable.

The aliphatic polycarbonate used in the present invention is an aliphatic polycarbonate obtained by alternately bonding epoxide and carbon dioxide and containing no ether bond component detectable by ¹ H-NMR analysis. As long as it is a method capable of polymerizing a compound that exhibits the above, it can be produced by any method. For example, JP 2009-215529 A, JP 2008-285545 A, US It can be produced according to the methods disclosed in Japanese Patent Application Publication No. 2006/89252, International Publication Nos. 2008/150033 and 2009/137540.

のコバルト錯体を用いて重合することができる。上記式（Ｉ）のコバルト触媒は、特に、ポリプロピレンカーボネートの合成に適している。 The aliphatic polycarbonate used in the present invention is also represented by the following formula (I):

It can superpose | polymerize using a cobalt complex. The cobalt catalyst of the above formula (I) is particularly suitable for the synthesis of polypropylene carbonate.

In the above formula (I), each R _a is independently H, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted, 6 to 20 carbon atoms, preferably Is an aryl group having 6 to 14 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, F, Cl, Br, I, or -Si (R _b ) selected from ₂ -R _c -X, wherein at least one of R _a is -Si (R _b ) ₂ -R _c -X. Here, —Si (R _b ) ₂ —R _c —X represents a silyl substituent, and each R _b independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, and R _c is 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably carbon atoms. 1 to 3 divalent hydrocarbon groups, X is selected from F, Cl, Br or I.

Specific examples of R _{b in} the silyl substituent —Si (R _b ) ₂ —R _c —X include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec A linear or branched alkyl group such as a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group Cycloalkyl group such as cyclodecyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,6-xylyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, anthryl group, etc. Or a substituted aryl group or the like. Specific examples of R _c include methylene group, ethylene group, propylene group, methylmethylene group, dimethylmethylene group, ethylmethylene group, methylethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and the like. And a linear or branched divalent hydrocarbon group. R _b is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a phenyl group, more preferably a methyl group, an ethyl group, or a phenyl group, and particularly preferably a methyl group. preferable. R _c is preferably a methylene group, an ethylene group or a propylene group, more preferably a methylene group. X is preferably Cl, Br or I, and more preferably Cl.

Specific examples of _Ra include H: methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Linear or branched alkyl groups such as heptyl group, octyl group, nonyl group, decyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group; phenyl group, o-tolyl A substituted or unsubstituted aryl group such as a group, m-tolyl group, p-tolyl group, 2,6-xylyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, anthryl group; methoxy group, ethoxy group, Vinyloxy group, n-propoxy group, isopropoxy group, allyloxy group, n-butoxy group, isobutoxy group, sec-butoxy group, Alkoxy groups such as xyloxy group, octyloxy group, decyloxy group; acyl groups such as acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, pivaloyl group, hexanoyl group, heptanoyl group, octanoyl group, decanoyl group; acetoxy group An acyloxy group such as propionyloxy group and butyryloxy group; F, Cl, Br, I; fluoromethyldimethylsilyl group, chloromethyldimethylsilyl group, bromomethyldimethylsilyl group, iodomethyldimethylsilyl group, chloromethyldiethylsilyl group, Chloromethyldi (isopropyl) silyl group, chloromethyldiphenylsilyl group, (1-chloroethyl) dimethylsilyl group, (2-chloroethyl) dimethylsilyl group, (2-chloropropyl) dimethylsilyl group, (3-chloropro Le) dimethylsilyl group, (4-chlorobutyl) dimethylsilyl group, (6-chloro-hexyl) dimethylsilyl group, and a silyl substituent such as (8-chloro-octyl) dimethylsilyl group. When R _a is other than _a silyl substituent, H, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group Cyclohexyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,6-xylyl group, mesityl group, methoxy group, ethoxy group, vinyloxy group, n-propoxy group, isopropoxy group, An allyloxy group, an acetyl group, an acetoxy group, F, Cl, Br, or I is preferable, and a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, or a phenyl group is more preferable, A tert-butyl group is particularly preferred. When R _a is a silyl substituent, it is preferably a chloromethyldimethylsilyl group, a (2-chloroethyl) dimethylsilyl group, or a (3-chloropropyl) dimethylsilyl group, and preferably a chloromethyldimethylsilyl group. More preferred. More preferably, both R _a are silyl substituents.

R _d is 0 to 3 substituents on each benzene ring and each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted, An aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or F, Cl, Br Alternatively, it is selected from I. Specific examples of R _d include the organic groups described above for R _a other than the silyl substituent, and include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, an n-butyl group, an isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,6-xylyl group, mesityl group, methoxy group, ethoxy group, Vinyloxy group, n-propoxy group, isopropoxy group, allyloxy group, acetyl group, acetoxy group, F, Cl, Br, or I are preferable, methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl Group or a phenyl group is more preferable, and a tert-butyl group is particularly preferable. R _d is preferably one for each benzene ring, and at this time, the position of R _d is preferably the 3-position of the site corresponding to the salicylaldehyde of the ligand.

  Y is a divalent linking group that connects two imino nitrogens through two carbon atoms. In the two carbon atoms, one or a plurality of alkyl groups having 1 to 10 carbon atoms or cycloalkyl groups having 3 to 10 carbon atoms, or substituted or unsubstituted, 6 to 20 carbon atoms, preferably 6 carbon atoms ~ 14 aryl groups may be bonded. Examples of the group bonded to the carbon atom of the divalent linking group Y include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc., linear or branched alkyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, etc. A cycloalkyl group such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,6-xylyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, anthryl group, etc. A substituted aryl group can be mentioned. Further, in the divalent linking group Y, the two carbon atoms may constitute a part of a substituted or unsubstituted saturated or unsaturated aliphatic ring or aromatic ring. Examples of such saturated or unsaturated aliphatic ring or aromatic ring include a cyclohexane ring, a cyclohexene ring, a benzene ring, etc., and these aliphatic ring or aromatic ring include, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, substituted with one or more substituents such as alkyl group such as tert-butyl group, aryl group such as phenyl group, naphthyl group, etc. Also good.

  Specific examples of such a divalent linking group Y include an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms as described above, or a substituted or unsubstituted aryl having 6 to 20 carbon atoms. An ethylene group which may be substituted with a group, which is unsubstituted or substituted with one or more methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, or phenyl groups It is preferable that As a specific example of the divalent linking group Y, a substituted or unsubstituted cycloalkylene group (for example, cyclohexane-1,2-diyl group) in which two adjacent carbon atoms are each bonded to another imino nitrogen. ) Or a phenylene group (for example, 1,2-phenylene group). Of these, a cyclohexane-1,2-diyl group is preferred.

Z is an anionic ligand selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carboxylate, alkoxide, and aryloxide. The anionic ligand may have nucleophilicity with respect to the epoxide carbon of the epoxide. Specific examples of Z include aliphatic carboxylates such as F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , acetate, trifluoroacetate, trichloroacetate, propionate, cyclohexylcarboxylate; benzoate, p- methyl benzoate, 3,5-dichloro benzoate, 3,5-bis (trifluoromethyl) benzoate, 4-dimethylamino benzoate, 4-tert-butyl benzoate, pentafluorophenyl benzoate ^(- OBzF _5), Aromatic carboxylates such as naphthalenecarboxylate; alkoxides such as methoxide, ethoxide, propoxide, isopropoxide; phenoxide, o-nitrophenoxide, p-nitrophenoxide, m-nitrophenoxide, 2,4-dinitrophenoxide, 3, 5-Gini Rofenokishido, 3,5-difluoro phenoxide, 3,5-bis (trifluoromethyl) phenoxide, 1-naphthoxide, aryloxide such as 2-naphthoxide and the like. Z is preferably F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , acetate, trifluoroacetate, trichloroacetate, benzoate, or pentafluorobenzoate, and F ⁻ , Cl ⁻ , Br ⁻ , I ^-, trifluoroacetate, trichloroacetate acetate or more preferably pentafluoro benzoate,, F ^-, Cl ^- or particularly preferably pentafluoro benzoate.

又は次の式（ＩＩＩ）：

（式中、Ｒ_ｃ、Ｘ及びＺは上述の通りである。）
で表されるものが好ましい。 Among the cobalt complexes described above, the following formula (II):

Or the following formula (III):

(Wherein R _c , X and Z are as described above.)
The thing represented by these is preferable.

又は次の式（Ｖ）：

（式中、Ｚは上述の通りである。）
で表されるものがより好ましく、式（ＩＶ）で表されるものが特に好ましい。 Among the cobalt complexes described above, the following formula (IV):

Or the following formula (V):

(Wherein Z is as described above.)
What is represented by these is more preferable, and what is represented by Formula (IV) is especially preferable.

  Copolymerization of epoxide and carbon dioxide can also be performed using a catalyst system in which a promoter is combined with the cobalt complex. By using the cocatalyst in combination, the reaction rate of the copolymerization can be increased and / or the alternating regularity of the copolymer can be increased, and / or the production of cyclic carbonate as a byproduct can be suppressed.

（式中、Ｒ⁴は、それぞれ独立して、炭素数１〜２０のアルキル基若しくは炭素数３〜２０のシクロアルキル基、又は置換若しくは非置換の炭素数６〜２０のアリール基であり、Ｒ⁵は、イミダゾリウム環の炭素上の０〜３個の置換基であって、それぞれ独立して、炭素数１〜２０のアルキル基若しくは炭素数３〜２０のシクロアルキル基、又は置換若しくは非置換の炭素数６〜２０のアリール基である。）からなる群から選択されるリン及び／又は窒素を含むカチオンと、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、及びアリールオキシドからなる群から選択されるアニオンとの塩を使用できる。 An example of a cocatalyst that can be combined with the cobalt complex is a salt composed of a cation containing phosphorus and / or nitrogen and a counter anion. As such a cocatalyst, the following formula:
[R ³ ₄ N] ⁺ ,
[R ³ ₄ P] ⁺ or [R ³ ₃ P = N = PR ³ ₃ ] ⁺
(In the formula, each R ³ independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.) And formula (VI):

(In the formula, each R ⁴ independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; ⁵ is 0 to 3 substituents on carbon of the imidazolium ring, each independently an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, or substituted or unsubstituted And a cation containing phosphorus and / or nitrogen selected from the group consisting of: F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate , Salts with anions selected from the group consisting of aromatic carboxylates, alkoxides, and aryloxides.

Specific examples of R ^{3 in} the cation [R ³ ₄ N] ⁺ , [R ³ ₄ P] ⁺ , and [R ³ ₃ P═N = PR ³ ₃ ] ⁺ constituting the salt include a methyl group, an ethyl group, n-propyl, isopropyl, allyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, etc. A linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group; a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, Examples thereof include substituted or unsubstituted aryl groups such as 2,6-xylyl group, mesityl group, 1-naphthyl group, 2-naphthyl group and anthryl group. Specific examples of R ⁴ and R ⁵ in the imidazolium of formula (VI) include linear or branched alkyl groups, cycloalkyl groups, and substituted or unsubstituted aryl groups as described above for R ³ . These R ³ , R ⁴ and R ⁵ are the above cations ([R ³ ₄ N] ⁺ , [R ³ ₄ P] ⁺ , [R ³ ₃ P = N = PR ³ ₃ ] ⁺ , of the formula (VI) The imidazolium) as a whole can be selected and combined so as to exert a steric effect advantageous to the copolymerization reaction, that is, to have an appropriate bulkiness.

As the cation constituting the salt, [R ³ ₄ N] ⁺ , [R ³ ₃ P = N = PR ³ ₃ ] ⁺ , or imidazolium of the formula (VI) is preferably used, and [R ³ ₃ P = N = PR ³ ₃ ] ⁺ is more preferred.

Specific examples of quaternary ammonium [R ³ ₄ N] ⁺ include tetrabutylammonium, tetrahexylammonium, tricyclohexylmethylammonium, trimethylphenylammonium and the like.
Specific examples of quaternary phosphonium [R ³ ₄ P] ⁺ include tetrabutylphosphonium, tetrahexylphosphonium, tetracyclohexylphosphonium, tetraphenylphosphonium, tetra (methoxyphenyl) phosphonium and the like.

Specific examples of bis (phosphoranylidene) ammonium [R ³ ₃ P═N═PR ³ ₃ ] ⁺ include bis (tributylphosphoranylidene) ammonium, bis (ethyldiphenylphosphoranylidene) ammonium, bis (n-butyldiphenylphosphorani). Ridene) ammonium, bis (dimethylphenylphosphoranylidene) ammonium, bis (triphenylphosphoranylidene) ammonium, bis (tolylphosphoranylidene) ammonium, bis (trinaphthylphosphoranylidene) ammonium and the like. Among these, bis (triphenylphosphoranylidene) ammonium is preferable.

  Specific examples of imidazoliums of formula (VI) include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1,3-diethylimidazolium, 1-ethyl-2,3-dimethyl-imidazolium. 1-butyl-3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-hexyl-3-methylimidazolium and the like.

Examples of the anion constituting the salt include those described above with respect to Z. F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , acetate, trifluoroacetate, trichloroacetate, benzoate, or pentafluorobenzoate it is preferred, F is ^{-, Cl -, Br -,} I -, trifluoroacetate, trichloroacetate acetate, or more preferably pentafluoro benzoate, F ^-, Cl ^- or pentafluoro benzoate It is particularly preferred.

Examples of the salt composed of the cation and the anion include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium acetate, tetrabutylphosphonium chloride, tetraphenylphosphonium chloride, bis (triphenylphosphoranylidene) ammonium fluoride (PPNF). ), Bis (triphenylphosphoranylidene) ammonium chloride (PPNCl), bis (triphenylphosphoranylidene) ammonium pentafluorobenzoate (PPNOBzF ₅ ), 1,3-dimethylimidazolium chloride, 1-ethyl-2,3 - dimethyl - imidazolium chloride and the like, PPNF, is PPNCl and PPNOBzF ₅ preferred.

  In a catalyst system combining a cobalt complex and a cocatalyst, the cobalt complex is preferably a compound of formula (II) or formula (III), more preferably a compound of formula (IV) or formula (V). It is particularly preferable to use a compound of formula (IV).

（式中、Ｚは、Ｆ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、及びアリールオキシドからなる群から選択されるアニオン性配位子である。）で表される化合物と、［Ｒ³ ₃Ｐ＝Ｎ＝ＰＲ³ ₃］⁺（式中、Ｒ³は、それぞれ独立して、炭素数１〜２０のアルキル基若しくは炭素数３〜２０のシクロアルキル基、又は置換若しくは非置換の炭素数６〜２０のアリール基である。）で表されるリン及び窒素を含むカチオン、並びにＦ^-、Ｃｌ^-、Ｂｒ^-、Ｉ^-、Ｎ₃ ^-、脂肪族カルボキシラート、芳香族カルボキシラート、アルコキシド、及びアリールオキシドからなる群から選択されるアニオンの塩からなる助触媒とを含むものがより好ましく、ここで、Ｚがペンタフルオロベンゾアートであり、助触媒がビス（トリフェニルホスホラニリデン）アンモニウムクロリドであることが特に好ましい。 In such a catalyst system,
Formula (IV):

Wherein Z is an anionic ligand selected from the group consisting of F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , N ₃ ⁻ , aliphatic carboxylate, aromatic carboxylate, alkoxide, and aryloxide. And a compound represented by [R ³ ₃ P = N = PR ³ ₃ ] ⁺ , wherein R ³ is independently an alkyl group having 1 to 20 carbon atoms or 3 to 3 carbon atoms. A cycloalkyl group of 20 or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms) and a cation containing phosphorus and nitrogen, and F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ and N _3. ^- , More preferably comprising a cocatalyst consisting of a salt of an anion selected from the group consisting of aliphatic carboxylates, aromatic carboxylates, alkoxides, and aryloxides, wherein Z is pentafluorobenzoate And the cocatalyst is particularly preferably bis (triphenylphosphoranylidene) ammonium chloride.

  The copolymerization of epoxide and carbon dioxide can be performed using a known polymerization reaction apparatus capable of being pressurized, for example, an autoclave. The reaction temperature for copolymerization can generally be about 0 ° C. or higher and about 100 ° C. or lower, preferably about 10 ° C. or higher and about 90 ° C. or lower, and is about 20 ° C. or higher and about 60 ° C. or lower. Is more preferable. When the copolymerization is performed at a low temperature, the formation of cyclic carbonate can be suppressed, and when the copolymerization is performed at a high temperature, the reaction rate is increased and TOF and / or TON can be improved. When the cobalt complex of the present invention is used, copolymerization can be carried out in a wider temperature range than conventional catalysts or catalyst systems.

  The partial pressure of carbon dioxide during copolymerization can generally be about 0.1 MPa or more and about 10 MPa or less, preferably about 5 MPa or less, and more preferably about 2 MPa or less. An inert gas such as nitrogen or argon may be present in the reaction atmosphere together with carbon dioxide.

  The molar ratio of the epoxide to the catalyst cobalt complex can generally be epoxide: cobalt complex = about 1000: 1 or more, preferably about 2000: 1 or more. The cobalt complex may be copolymerized under a very low complex concentration such as epoxide: cobalt complex = about 4000: 1 or more, about 8000: 1 or more, or about 32000: 1 or more by appropriately raising the reaction temperature. it can. Since the reaction time generally becomes long when the complex concentration is low, it is general that the epoxide: cobalt complex is about 100,000: 1 or less, or about 50000: 1 or less. The amount of co-catalyst used as needed can generally be about 0.1 to about 10 moles, preferably about 0.3 to about 5 moles, per mole of cobalt complex. More preferably from about 0.5 to about 1.5 moles.

  Copolymerization may be performed without a solvent, or may be performed using a solvent as necessary. Examples of usable solvents include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, amides such as dimethylformamide, ethers such as 1,2-dimethoxyethane, and combinations thereof. Dichloromethane, toluene, dimethylformamide and 1,2-dimethoxyethane are preferred, and dichloromethane and 1,2-dimethoxyethane are more preferred. When a solvent is used, the amount can generally be about 0.1 to about 100 parts by weight, preferably about 0.2 to about 50 parts by weight, based on 1 part by weight of epoxide, More preferred is 0.5 to about 20 parts by weight.

  After the desired amount of epoxide has been polymerized, a known post-treatment can be performed. For example, hydrochloric acid, methanol, hydrochloric acid / methanol mixture or the like can be added to the reaction mixture as a reaction terminator, and the reaction can be terminated by raising the temperature and / or stirring as necessary. Thereafter, for example, the polymer may be reprecipitated using methanol, hexane or the like as a poor solvent, and the complex may be extracted from the solid mixture using a Soxhlet extractor. In addition, the polymer may be further purified using a known means such as column chromatography.

[Optical element having photoelasticity]
Stress optical coefficient of the optical element having the optical elasticity of the present invention is in the range of 0.1～2.0GPa ^-1, preferably in the range of 0.2～1.5GPa ^-1, and most preferably 0 In the range of 3 to 1.0 GPa ⁻¹ . If the stress optical coefficient is less than 0.1 GPa ⁻¹ , sufficient birefringence does not occur even if strain, stress, etc. are added, and it may not be used as an optical element, and if it exceeds 2.0 GPa ^−1. Depending on the shape of the optical element, excessive birefringence may remain due to the history of stress applied during molding.
The stress optical coefficient is preferably measured at a temperature above Tg of the polycarbonate, and more preferably at a temperature of Tg + 10 ° C. or higher of the polycarbonate.

The stress optical coefficient can be measured by the apparatus and measurement principle described below.
[Optical delay measurement system]
A schematic diagram of an optical delay measurement system used for measurement is shown in FIG.
The optical delay measurement system 1 includes a He-Ne laser oscillator (manufactured by Autech, LGK 7786P100) (not shown), polarizing plates 2, 2 ′ and 2 ″, ¼λ plates 3 and 3 ′, a rotating polarizing plate 4, a beam splitter (not shown), and light receivers 5 and 5 ′. A indicates the penetration direction of the incident laser beam, and identifiers 6 and 7 indicate the sample and the coordinate system, respectively.

The incident laser light is split into two by a beam splitter, the intensity of light that has passed through the sample 6 (hereinafter referred to as “measurement light”), and the light that does not pass through the sample 6 (hereinafter referred to as “reference light”). ) Is measured as a voltage by the light receivers 5 and 5 ′, respectively. The optical delay is measured by comparing the phase angle of the measurement light with the phase angle of the reference light.
The rotational speed of the rotating polarizing plate 4 is 2500 rpm.

-Data collection-
Using an A / D converter (manufactured by KEYENCE, NR-500), the load data of the tensile tester, the amount of reference light and the amount of measurement light of the optical delay measurement system are digitized, and the sampling period is 500 μs (2 kHz). To sample.

（式中、Ｓ₀は試料の初期断面積であり、ｄ₀は初期厚みであり、ｌ₀は初期長であり、そしてΔｌは長さの変化量である）
と表すことができる。 -Analysis-
The phase difference between the reference light and the measurement light is calculated from the maximum value obtained by calculating a cross-correlation function of data every 200 data (0.1 seconds). The change in thickness of the sample during the stretching process is determined on the assumption of uniform affine deformation.
The cross-sectional area S (t) and thickness d (t) of the sample are respectively expressed by the following formulas (a) and (b):

(Where S ₀ is the initial cross-sectional area of the sample, d ₀ is the initial thickness, l ₀ is the initial length, and Δl is the change in length)
It can be expressed as.

（式中、Ｌ（ｔ）は延伸時の加重であり、Г（ｔ）は延伸時の光学遅延である）
と表せる。
複屈折を縦軸、応力を横軸にとったグラフを作成し、解析したデータをプロットすると、直線の傾きが、応力光学係数となる。 The stress σ (t) and birefringence Δn (t) are respectively expressed by the following formulas (c) and (d):

(Where L (t) is the weight during stretching and Γ (t) is the optical delay during stretching)
It can be expressed.
When a graph with birefringence on the vertical axis and stress on the horizontal axis is created and the analyzed data is plotted, the slope of the straight line becomes the stress optical coefficient.

The principle of optical delay measurement is as follows.
As shown in FIG. 1, an α-β orthogonal coordinate system with the vertical direction as the α axis relative to the traveling direction of light, and an xy orthogonal coordinate system obtained by rotating the α-β orthogonal coordinate system 45 ° to the left. think of. The He—Ne laser light, which is a monochromatic light source, becomes circularly polarized light when passing through the ¼λ plate 3, and becomes linearly polarized light after passing through the rotating polarizing plate 4 (frequency 42 Hz).

After passing through the rotating polarizer 4, the x-axis and y-axis direction, the electric field vector component E _x and E _y of the light, respectively, the following formula (e) and (f):
E _x = Asinφ (t) sinωt (e)
E _y = A cos φ (t) sinωt (f)
(Where A is the amplitude, ω is the angular frequency of the laser beam, and φ (t) is the rotation angle of the rotating polarizer 4)
It becomes.

により表わすことができる。 The time average I _ref (t) of the reference light intensity is expressed by the following equation (g) when the attenuation at the half mirror is ignored.

Can be represented by

により表わすことができる。 On the other hand, the electric field vector components E _x and E _y in the x-axis and y-axis directions after passing through the ¼λ plate 3 ′ are respectively expressed by the following equations (h) and (i):

Can be represented by

となる。 Accordingly, the electric field vector components E _α and E _β in the α-axis and β-axis directions are respectively expressed by the following equations (j) and (k):

It becomes.

と表すことができる。 When the sample 6 has optical anisotropy and E _α has a phase difference of δ with respect to E _β , the electric field vector components E _α and E _β after passing through the sample are respectively expressed by the following formulas ( l) and (m):

It can be expressed as.

となり、
測定光強度の時間平均Ｉ_meas（ｔ）は次の式（ｏ）：

となる。 Therefore, the component E _x in the x direction at the light receiver 5 is expressed by the following equation (n):

And
The time average I _meas (t) of the measurement light intensity is expressed by the following formula (o):

It becomes.

と表され、参照光は測定光に対しδの位相差を有することになる。
当該δが、試料の、α方向の、β方向に対する光学遅延となる。 Considering that the light intensity is attenuated by reflection or the like on the surfaces of the beam splitter, the polarizing plates 2, 2 ′ and 2 ″ and the sample 6, the equations (g) and (o) are respectively expressed by the following equations: (P) and (q):

The reference light has a phase difference of δ with respect to the measurement light.
The δ is an optical delay of the sample in the α direction with respect to the β direction.

  The optical element having photoelasticity of the present invention is preferably stretched to a strain of 400%, more preferably to 500%, and most preferably to 600% at a tensile rate of 1000% / min. The coefficient of determination when plotting as the x-axis and y-axis, respectively, and regressing with a straight line passing through the origin, is preferably 0.95 or more, more preferably 0.97 or more, and most preferably 0.98 or more. . If the determination coefficient is 0.95 or less, the change in birefringence with respect to the stress applied to the element is poor in linearity, and it may be difficult to control optical functionality.

The optical element having photoelasticity of the present invention is not particularly limited as long as it is an element utilizing photoelastic characteristics, and examples thereof include a shutter, a phase difference plate, and a wavelength filter.
In addition, examples of the device including the optical element of the present invention include a window with a shade mechanism that can change the transparency stepwise, a lamp that can freely change the color, a display that can change the viewing angle according to the surrounding environment, and the like. Can be mentioned.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these Examples.
The ¹ H-NMR spectrum of the compound obtained in this example was measured using JNM-JNM-ECP500 (500 MHz) and JEOL-made JNM-ECS400 (400 MHz). The molecular weight of polycarbonate is measured using tetrahydrofuran or chloroform as an eluent using a high-performance liquid chromatography system (DG660B, PU713, UV702, RI704, CO631A) manufactured by GL Sciences and two KF-804F columns manufactured by SHODEX ( 40 ° C., 1.0 mL / min), measured based on polystyrene standards, and measured by analysis software (EZ Chrom Elite manufactured by Scientific Software).

[Preparation of catalyst]
Toluene, tetrahydrofuran (hereinafter referred to as “THF”), hexane, and diethyl ether used as solvents in the following synthesis examples were passed through dehydrated grade reagents obtained from Kanto Chemical Co., Ltd. through a solvent purification apparatus manufactured by Glass Contour. We used what we did. As methanol and ethanol, those obtained from Kanto Chemical Co., Ltd. as dehydrating grade reagents were used as they were. Further, ethyl acetate obtained from Wako Pure Chemical Industries, Ltd. was used as it was.

  As the tert-butyllithium n-pentane solution, triethylamine, and cobalt acetate, those obtained from Kanto Chemical Co. were used as they were. For chloromethyldimethylsilyl chloride and pentafluorobenzoic acid, reagents obtained from Tokyo Chemical Industry Co., Ltd. and (1R, 2R) -diaminocyclohexane were used as they were from Wako Pure Chemical Industries, Ltd. For magnesium chloride and paraformaldehyde, reagents obtained from Aldrich were used as they were.

  4-Bromo-2-tert-butylphenol and 3-tert-butyl-5-[(3'-chloropropyl) dimethylsilyl] salicylaldehyde used as raw materials in the following ligand synthesis are described in J. Am. Am. Chem. Soc. , 2007, 129, 8082 were used.

[Synthesis Example A: Synthesis of Cobalt Complex (1)]
[A-1: Synthesis of silyl-substituted salicylaldehyde]
In an Ar atmosphere, 5.4 g of 4-bromo-2-tert-butylphenol was dissolved in 200 mL of THF and cooled to −78 ° C. Then, 41 mL of tert-butyllithium (1.6 M n-pentane solution) was added over 2 hours. It was dripped. After dropping, the mixture was stirred at -78 ° C for 2 hours, and 7.1 mL of chloromethyldimethylsilyl chloride was added. The solution was gradually warmed to room temperature and stirred for 4 hours, after which 300 mL of water was added and stirred for 4 hours. Extraction was performed with 200 mL of ethyl acetate, and the organic layer was concentrated under reduced pressure. The resulting yellow oil was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1, Rf = 0.47) to give 6.3 g of 2-tert-butyl-4-[(chloromethyl) dimethylsilyl] phenol. Was obtained as a pale yellow oil (yield 79%).
¹ H-NMR (CDCl ₃ , 500 MHz) δ 7.43 (s, 1H), 7.25 (dd, 1H), 6.69 (d, 1H), 4.84 (s, 1H), 2.92 ( s, 2H), 1.41 (s, 9H), 0.38 (s, 6H) ppm

2.1 g of 2-tert-butyl-4-[(chloromethyl) dimethylsilyl] phenol, 3.5 mL of triethylamine, and 2.62 g of magnesium chloride were stirred in 120 mL of THF at room temperature for 30 minutes. The paraformaldehyde 0.8g was added there and it recirculate | refluxed for 3 hours. After the reaction, 100 mL of ethyl acetate and 100 mL of water were added, and the mixture was stirred at room temperature for 30 minutes, followed by liquid separation. The aqueous layer was further extracted with 100 mL of ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate, and then the volatile matter was concentrated under reduced pressure. The resulting pale yellow oil was subjected to silica gel column chromatography (hexane: ethyl acetate = 20: 1, Rf = 0.09). Purified. 1.4 g of 3-tert-butyl-5-[(chloromethyl) dimethylsilyl] salicylaldehyde was obtained as a white solid (yield 63%).
¹ H-NMR (CDCl ₃ , 500 MHz) δ 11.89 (s, 1H), 9.90 (s, 1H), 7.67 (s, 1H), 7.56 (s, 1H), 2.94 ( s, 2H), 1.42 (s, 9H), 0.43 (s, 6H) ppm

[A-2: Synthesis of salen ligand]
3-tert-butyl-5-[(chloromethyl) dimethylsilyl] salicylaldehyde (808.9 mg) and (1R, 2R) -diaminocyclohexane (136 mg) were stirred in 20 mL of absolute ethanol at room temperature for 6 hours. After concentrating the volatile components under reduced pressure, the precipitate was filtered and washed with 5 mL of cold hexane to obtain 770 mg of a salen compound as a yellow powder (yield 85%).
¹ H-NMR (CDCl ₃ , 500 MHz) δ 14.10 (s, 2H), 8.31 (s, 2H), 7.39 (s, 2H), 7.15 (s, 2H), 3.37 ( t, 2H), 2.84 (s, 4H), 2.07-1.68 (m, 8H), 1.40 (s, 18H), 0.33 (s, 12H) ppm

[A-3: Synthesis of cobalt complex]
Under an Ar atmosphere, 770 mg of salen ligand was dissolved in a mixture of 5 mL of dehydrated methanol and 1 mL of toluene, 212 mg of anhydrous cobalt acetate was added thereto, and the mixture was stirred at room temperature for 3 hours. The resulting precipitate was collected by filtration and washed with 5 mL of cold methanol to obtain a red powdery cobalt (II) complex. This was dissolved in 10 mL of methylene chloride, 240 mg of pentafluorobenzoic acid was added, and the mixture was stirred under air for 15 hours. After concentrating the volatile components under reduced pressure, the residue was washed with cold hexane to obtain 527 mg of cobalt (III) complex (1) as a greenish brown solid (yield 48%).
¹ H-NMR (DMSO-d ₆ , 500 MHz) δ 7.93 (s, 2H), 7.55 (s, 2H), 7.41 (s, 2H), 3.65 (m, 2H), 3. 14 (s, 4H), 2.05-1.85 (m, 8H), 1.73 (s, 18H), 0.37 (s, 6H), 0.23 (s, 6H) ppm

[Synthesis Example B: Synthesis of Cobalt Complex (2)]
[B-1: Synthesis of salen ligand]
3-tert-butyl-5-[(3′-chloropropyl) dimethylsilyl] salicylaldehyde (313 mg) and (1R, 2R) -diaminocyclohexane (57 mg) were dissolved in ethanol (10 mL), and the mixture was stirred at room temperature for 12 hours. After distilling off the volatiles under reduced pressure, the residue was washed with 1 mL of cold hexane to obtain 330 mg of a salen compound as a yellow powder (yield 94%).
¹ H-NMR (CDCl ₃ , 500 MHz) δ 14.11 (s, 2H), 8.45 (s, 2H), 7.34 (s, 2H), 7.23 (s, 2H), 3.53- 3.44 (m, 6H), 2.00-1.93 (m, 2H), 1.90-1.68 (m, 14H), 1.40 (s, 18H), 0.70 (t, 4H), 0.26 (s, 6H), 0.21 (s, 6H) ppm

[B-2: Synthesis of cobalt complex]
Under an Ar atmosphere, 200 mg of salen ligand was dissolved in 2 mL of methylene chloride, 50 mg of anhydrous cobalt acetate was added thereto, and the mixture was stirred at room temperature for 2 hours. Volatile components were distilled off under reduced pressure, and then washed with 1 mL of diethyl ether to obtain a red powdery cobalt (II) complex. This was dissolved in a mixture of 2 mL of methylene chloride and 2 mL of toluene, 60 mg of pentafluorobenzoic acid was added, and the mixture was stirred under air for 16 hours. After concentrating the volatiles under reduced pressure, the residue was washed with 5 mL of cold hexane to obtain 162 mg of cobalt (III) complex (2) as a green brown powder (yield 60%).
¹ H-NMR (DMSO-d6,500 MHz) δ 7.91 (s, 2H), 7.52 (s, 2H), 7.42 (s, 2H), 3.63-3.57 (m, 6H) , 2.04-1.80 (m, 6H), 1.77 (s, 18H), 1.71-1.55 (m, 8H), 0.76 (t, 4H), 0.31 (s) , 6H), 0.24 (s, 6H) ppm

[Synthesis Example C: Synthesis of Cobalt-Asymmetric Salen Complex (3)]
[C-1: Synthesis of asymmetric salen ligand]
Under an Ar atmosphere, (R, R) -cyclohexanediamine monohydrochloride (216 mg, 1.74 mmol), 3,5-di-tert-butylsalicylaldehyde (336 mg, 1.74 mmol), and molecular sieves 4A (200 mg) Were stirred in a mixed solvent of absolute ethanol (6 mL) and anhydrous methanol (6 mL) at room temperature for 4 hours. 3-tert-butyl-5-[(chloromethyl) dimethylsilyl] salicylaldehyde (648 mg, 1.74 mmol) and triethylamine (0.4 mL, 2.88 mmol) were dissolved in methylene chloride (12 mL). The solution was added and stirred at room temperature for 4 hours. The reaction solution was filtered using silica gel, the silica gel was washed with methylene chloride, and the filtrate was concentrated. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1, Rf = 0.57) to obtain a yellow solid (701 mg) (yield 67%).
¹ H-NMR (CDCl ₃ , 500 MHz) δ 14.10 (s, 2H), 8.31 (s, 1H), 8.12 (s, 1H), 7.39-7.15 (m, 4H), 3.37 (t, 2H), 2.84 (s, 2H), 2.07-1.68 (m, 8H), 1.40 (s, 18H), 1.25 (s, 9H), 0 .33 (s, 6H) ppm

[C-2: Synthesis of cobalt complex]
Under an Ar atmosphere, an asymmetric salen ligand (700 mg, 1.17 mmol) was dissolved in a mixture of 5 mL of dehydrated methanol and 1 mL of toluene, to which was added anhydrous cobalt acetate (207 mg, 1.28 mmol), and the mixture was stirred at room temperature for 3 hours. did. The resulting precipitate was collected by filtration and washed with 5 mL of cold methanol to obtain a red powdery cobalt (II) complex. This was dissolved in 10 mL of methylene chloride, pentafluorobenzoic acid (270 mg, 1.28 mmol) was added, and the mixture was stirred under air for 15 hours. After concentrating the volatiles under reduced pressure, the residue was washed with cold hexane to obtain 512 mg of cobalt (III) complex as a greenish brown solid (yield 51%).
¹ H-NMR (DMSO-d ₆ , 500 MHz) δ 7.96 (s, 1H), 7.87 (s, 1H), 7.77 (s, 1H), 7.48 (m, 3H), 3. 59 (m, 2H), 3.11 (s, 2H), 2.01-1.92 (m, 8H), 1.75 (s, 18H), 1.32 (s, 9H), 0.37 (S, 6H) ppm

[Synthesis Example D: Synthesis of Cobalt Complex (4)]
[D-1: Synthesis of salen ligand]
Under an Ar atmosphere, 600 mg of the salen ligand of Synthesis Example A and 347 mg of sodium iodide were dissolved in 10 mL of acetonitrile and stirred at 90 ° C. for 24 hours. The resulting precipitate was filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in 20 mL of methylene chloride, washed with 10 mL of saturated aqueous sodium bicarbonate and then with 10 mL of saturated brine, and the organic layer was dried over sodium sulfate and concentrated under reduced pressure. Then, 643 mg of salen ligand in which chlorine was substituted with iodine was obtained as a yellow powder (yield 82%).
¹ H-NMR (CDCl ₃ , 500 MHz) δ 14.09 (s, 2H), 8.30 (s, 2H), 7.39 (s, 2H), 7.14 (s, 2H), 3.33 ( t, 2H), 2.07 (s, 4H), 1.98-1.74 (m, 8H), 1.40 (s, 18H), 0.36 (s, 12H) ppm

[D-2: Synthesis of cobalt complex]
Under an Ar atmosphere, 100 mg of the ligand was dissolved in 5 mL of methylene chloride, 22 mg of cobalt acetate was added, and the mixture was stirred at room temperature for 2 hours. The volatile matter was distilled off under reduced pressure and then dried under vacuum for 3 hours to obtain a red solid. This was dissolved in 5 mL of toluene, 28 mg of pentafluorobenzoic acid was added, and the mixture was stirred at room temperature under air for 15 hours. Volatiles were distilled off under reduced pressure, and the residue was washed with cold hexane to obtain 99 mg of cobalt complex (4) as a dark green powder (yield 75%).
¹ H-NMR (DMSO-d ₆ , 500 MHz) δ 8.30 (s, 2H), 7.39 (s, 2H), 7.14 (s, 2H), 3.33 (t, 2H), 2. 07 (s, 4H), 1.98-1.74 (m, 8H), 1.40 (s, 18H), 0.36 (s, 12H) ppm

[Production Example 1 Production of polypropylene carbonate]
A stainless steel autoclave with an internal volume of 3 L was charged with 393 mg of cobalt complex (1), bis (triphenylphosphoranylidene) ammonium chloride (hereinafter referred to as “PPNCl”) (purchased from Strem Co. from methylene chloride / diethyl ether. 246 mg (used after recrystallization) was added, and the atmosphere was replaced with an Ar atmosphere. Then, 600 mL of propylene oxide (20,000 mol with respect to 1 mol of cobalt complex (1)) and 1.4 MPa of carbon dioxide were charged at 107 ° C. at 107 ° C. Reacted for hours. Since the pressure of carbon dioxide decreased with the progress of the reaction, carbon dioxide was additionally injected to a pressure of 1.8 MPa when the system pressure dropped to 0.8 MPa. After measuring ¹ H-NMR, the content was dissolved in methylene chloride, washed with 1N hydrochloric acid, and precipitated with methanol to obtain 282 g of polypropylene carbonate (PPC) as a white solid. The polypropylene carbonate had a refractive index of 1.47 and a Tg of 39 ° C.
The refractive index was measured with an interference microscope (Carzice Jena Interfaco), and the Tg was measured with DSC (TA Instruments QSC Q100) with a sample amount of 5 mg and a heating rate of 10 ° C./min. Measured under conditions.

As shown below, the obtained polypropylene carbonate does not contain cyclic carbonate and polyether by ¹ H-NMR, that is, the obtained polypropylene carbonate has epoxide (propylene oxide) and carbon dioxide alternately bonded. It was confirmed that it was a polypropylene carbonate containing no ether bond component obtained by 1H-NMR analysis.
Polycarbonate: Cyclic carbonate: Polyether = 100: 0: 0, Yield: 32%, TOF: 60 h ⁻¹ , TON: 441 g / g-cat (the mass of the catalyst was calculated as the total amount of cobalt complex and PPNCl) , M _n = 101,400, M _w / M _n = 1.53

[Production Example 2 Production of polyethylene carbonate]
In a stainless steel autoclave having an internal volume of 3 L, 252 mg of cobalt complex (3-2) described in [0063] of JP-A-2009-215529, bis (triphenylphosphoranylidene) ammonium fluoride (hereinafter referred to as “PPNF”) 272 mg) was added, and the atmosphere was replaced with an Ar atmosphere. Then, 600 mL of ethylene oxide (25,000 mol with respect to 1 mol of cobalt complex) and 2.0 MPa of carbon dioxide were charged and reacted at 43 ° C. for 90 hours. After measuring ¹ H-NMR, the content was dissolved in methylene chloride, washed with 1N hydrochloric acid, and precipitated with methanol to obtain 324 g of polyethylene carbonate (PEC) as a white solid. The polyethylene carbonate had a refractive index of 1.46 and a Tg (° C.) of 15 ° C.

As shown below, the obtained polyethylene carbonate does not contain cyclic carbonate and polyether by ¹ H-NMR, that is, the obtained polyethylene carbonate has epoxide (ethylene oxide) and carbon dioxide alternately bonded. And was found to be a polyethylene carbonate containing no ether bond component detectable by 1H-NMR analysis.
Polycarbonate: Cyclic carbonate: Polyether = 100: 0: 0, Yield: 30%, TOF: 83h ⁻¹ , TON: 618 g / g-cat (the mass of the catalyst was calculated as the total amount of cobalt complex and PPNF) , M _n = 96,700, M _w / M _n = 1.41

[Example 1]
In Production Examples 1 and 2, the produced PPC and PEC were molded into a film-like sample for tensile test at 100 ° C. using a heating press.
Using the optical delay measurement system described above and a desktop tensile tester (manufactured by Imoto Seisakusho, tensile / compression small tester (with a 200 ° C. constant temperature bath)), the change in birefringence during deformation was measured.
The measurement conditions are as follows.
Initial sample length: 5 mm
Tensile speed: 1000% / min (50mm / min)
Measurement temperature: PEC is room temperature (about 24 ° C), PPC is 50 ° C
He-Ne laser light: linearly polarized light, wavelength 543 nm
The breaking elongation and elongation recovery rate at 25 ° C. were measured using the above-described desktop tensile tester.

  The relationship between strain and birefringence is shown in FIGS. 2 and 3 for PPC and PEC, respectively. 2 and 3, it can be seen that the PPC and PEC produced in Production Examples 1 and 2 are flexible and exhibit high elongation at break. It can also be seen that strain and stress have a proportional relationship up to a range of at least about 600% strain.

Next, stretching was stopped when the strain and the birefringence were proportional to each other at a strain of 600%, and thereafter, the stretching was relaxed under a constant strain condition, and the relationship between time and birefringence was measured. The results of PPC and PEC are shown in FIG. 4 and Table 5, respectively.
4 and 5, it can be seen that the PPC and PEC produced in Production Examples 1 and 2 continue to maintain the proportional relationship between stress and birefringence even during relaxation.

The relationship between stress and birefringence for PPC and PEC is shown in FIGS. 6 and 7, respectively. In FIG. 6, when each plot was regressed with a straight line passing through the origin, a relational expression y = 0.52x was obtained, and the determination coefficient was 0.98. Similarly, in FIG. 7, a relational expression y = 0.56x was obtained, and the determination coefficient was 0.99.
From the inclination of the above relational expression, a stress optical coefficient of PPC of 0.52 GPa ⁻¹ and a stress optical coefficient of PEC of 0.56 GPa ⁻¹ were obtained.

  Furthermore, when the breaking elongation of the PEC tensile test sample was measured at 25 ° C., the breaking elongation was 1060%, which showed very high deformability. Further, when the extension recovery rate of this film was measured, it showed a very high extension recovery rate of 99.6%. Therefore, it is suggested that the PEC can be used as a dynamic element that applies repeated strain, load, and the like at room temperature.

[Comparative Example 1]
A sample for tensile test was molded at 180 ° C. using TOPAS ™ 6015 (Tg: 158 ° C.) commercially available from TOPAS ADVANCED POLYMERS GmbH. The change in birefringence was measured according to the conditions of Example 1 except that the measurement temperature was 175 ° C. and the strain rate was 500% / min. However, the breaking elongation of TOPAS under the above conditions was as low as about 80%. Therefore, the film was stretched to a strain of 40%, which is equal to or lower than the breaking elongation, and then the relaxation process was evaluated under a constant strain. The relationship between stress and birefringence is shown in FIG. When the plot of FIG. 8 was regressed with a straight line passing through the origin, a relationship of y = 1.53x was obtained and the coefficient of determination was 0.99. As a result, a stress optical coefficient of 1.53 GPa ⁻¹ of TOPAS (trademark) 6015 was obtained.

[Example 2]
A PEC film-like test piece was produced in the same manner as in Example 1, and the shutter unit shown in FIG. 9 was produced. In the shutter unit 8 shown in FIG. 9, a PEC test piece 10 is disposed between two polarizing plates 9 and 9 ′ whose polarization directions are set to be different from each other by 90 °. When the shutter unit 8 is placed on the paper on which characters are written, the light is blocked by the polarizing plates 9 and 9 'in a state where no distortion is applied to the PEC sample piece 10, and the characters behind the unit are read. Was impossible. Next, when 25% strain was applied to the PEC test piece 10 along the polarization direction of the polarizing plates 9 and 9 ′ and the direction B having an angle of 45 °, birefringence occurred in the PEC test piece. The polarization direction changed, the light was transmitted, and the characters behind the unit could be read.

DESCRIPTION OF SYMBOLS 1 Optical delay measuring system 2, 2 ', 2''Polarizing plate 3, 3' 1/4 (lambda) board 4 Rotating polarizing plate 5, 5 'Light receiver 6 Sample 7 Coordinate system 8 Shutter unit 9, 9' Polarizing film 10 PEC test Fragment

Claims (8)

The following general formula (1):

(Wherein R ¹ and R ² are the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or R ¹ and R ² are bonded to each other to form a substituted or unsubstituted aliphatic ring. Form)
An optical element having photoelasticity, comprising an aliphatic polycarbonate obtained by alternately bonding epoxides and carbon dioxide, and containing no ether bond component detectable by ¹ H-NMR analysis,
Having a stress optical coefficient in the range of 0.1-2.0 GPa ⁻¹ ,
The optical element.   At a tensile rate of 1000% / min, the film was stretched to a strain of 400%, the stress value and birefringence value were plotted as the x-axis and y-axis, respectively, and the coefficient of determination was 0.95 when regressed with a straight line passing through the origin. The optical element according to claim 1, which is as described above.   The optical element according to claim 1, wherein the epoxide is ethylene oxide or propylene oxide. The catalyst used for the synthesis of the aliphatic polycarbonate is represented by the following general formula (I):

(In the formula, each R _a is independently H, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or carbon number. An alkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, F, Cl, Br, I, or —Si (R _b ) ₂ —R _c —X (wherein R _b is independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R _c is A divalent hydrocarbon group having 1 to 8 carbon atoms, wherein X is selected from F, Cl, Br or I.), but at least one of R _a is —Si (R _b ) _2- R _c -X, where R _d is 0-3 substituents on each benzene ring. Each independently, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, Selected from an acyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or F, Cl, Br, or I, and Y is a group that connects two imino nitrogens through two carbon atoms. A valent connecting group having two or more carbon atoms having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 20 carbon atoms May be bonded to each other, or the two carbon atoms may form a part of a substituted or unsubstituted, saturated or unsaturated aliphatic ring or aromatic ring, and Z is F ^{-, Cl -, Br -,} I -, N 3 -, aliphatic Cal Kishirato, aromatic carboxylate, alkoxide, and an anionic ligand selected from the group consisting of aryloxides)
The optical element as described in any one of Claims 1-3 which is a cobalt complex represented by these. The optical element according to claim 1, which has a stress optical coefficient in a range of 0.3 to 1.0 GPa ⁻¹ .   The optical element according to claim 5, having an elongation at break of 100% or more at 25 ° C., and an elongation recovery rate after elongation of 100% is 90% or more.   The optical element as described in any one of Claims 1-6 selected from the group which consists of a shutter, a phase difference plate, and a wavelength filter.   The apparatus containing the optical element as described in any one of Claims 1-7.

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