JP2023151035A - Polymerizable composition and polycarbonate resin - Google Patents

Abstract

To provide a polycarbonate resin having excellent heat resistance.SOLUTION: A polymerizable composition contains a polymerizable monomer such as cyclohexene carbonate, wherein the polymerizable monomer is a mixture containing an (R, R) isomer and an (S, S) isomer in stereochemistry of two adjacent carbon atoms to which a carbonate group is bonded, and any one ratio of the (R, R) isomer and the (S, S) isomer is 60 mol% or more and 90 mol% or less with respect to the total amount of the (R, R) isomer and the (S, S) isomer.SELECTED DRAWING: None

Description

The present invention relates to a polymerizable composition and a polycarbonate resin.

Polycarbonate resin is an engineering plastic with excellent heat resistance. In recent years, polycarbonate resins have been required to be lighter and lower in cost, as well as having excellent heat resistance and optical properties. In order to meet such demands, special aromatic polycarbonate resins based on aromatic skeletons are being actively developed.

On the other hand, polycarbonate resins having an aliphatic structure, particularly an alicyclic structure, are being developed as resins to replace aromatic polycarbonates. Alicyclic polycarbonates tend to have better light resistance and optical properties than polycarbonate resins having aromatic rings such as bisphenol A. For example, Patent Document 1 discloses a polycyclic alicyclic polycarbonate resin that has excellent transparency, heat resistance, and color tone. In addition, polycarbonate is being developed using not only petroleum raw materials but also raw materials derived from biomass such as plants. For example, Patent Document 2 discloses a polycarbonate resin using isosorbide that can be derived from starch as a raw material.

Among such alicyclic polycarbonate resins, poly(cyclohexene carbonate) having a cyclohexane carbonate structure is the simplest polycarbonate having a saturated six-membered carbon ring corresponding to a benzene ring. It is widely known that poly(cyclohexene carbonate) can be synthesized by the reaction of cyclohexene oxide and carbon dioxide, as shown in Patent Document 3, for example. Furthermore, as described in Patent Document 4 and Non-Patent Document 1, it is known that poly(cyclohexene carbonate) can be obtained by ring-opening polymerization of 1,2-cyclohexene carbonate.

Patent No. 4774610 Patent No. 6507495 Patent No. 5403537 JP 2019-108547 Publication

Macromolecules 2014, 47, 4230-4235. Journal of Polymer Research 2011, 18, 1177-1183. Journal of the American Chemical Society 2012, 134, 5682-5688.

When the present inventors examined in detail conventional alicyclic polycarbonate resins including those described in the above-mentioned literature, it was found that the heat resistance was insufficient.

For example, Patent Document 3 describes poly(cyclohexene carbonate) synthesized from cyclohexene oxide from carbon dioxide, but it is shown that an ether bond different from a carbonate bond exists.

Generally, it is known that main chain cleavage tends to start from thermally unstable parts such as unsaturated bonds and heterogeneous bonds, and even in polycarbonate resins, in order to increase heat resistance, it is necessary to cleave other than carbonate bonds. It is considered desirable not to include heterogeneous bonds.

Furthermore, Non-Patent Document 2 describes that adding zinc to poly(cyclohexene carbonate) promotes thermal decomposition accompanied by decarboxylation. Such a decomposition promoting effect is expected to occur not only with zinc, but also with transition metal elements and Group 12 and 13 elements, which have relatively high Lewis acidity, and from the perspective of suppressing thermal decomposition, such It is considered preferable that the material does not contain metal elements.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate resin having excellent heat resistance.

As a result of intensive research to solve the above problems, the present inventors discovered that it is possible to provide a polycarbonate resin with excellent heat resistance by controlling the enantiomeric ratio in the polymer within a specific range. The invention was completed.

That is, the present invention is as follows.
[1]
The following formula (1):
(In formula (1), A is an optionally substituted divalent alicyclic moiety.)
Contains a polymerizable monomer represented by
The polymerizable monomer is a mixture containing an (R,R) form and an (S,S) form in the stereochemistry of two adjacent carbon atoms to which the carbonate group of the formula (1) is bonded, and
The proportion of either one of the (R,R) form and the (S,S) form is 60 mol% or more and 90 mol% of the total amount of the (R,R) form and the (S,S) form. A polymerizable composition as follows.
[2]
Structural unit represented by the following formula (2):
(In formula (2), A is an optionally substituted divalent alicyclic moiety.)
A polycarbonate resin having
The polycarbonate resin contains structural units of the (R, R) form and (S, S) form in the stereochemistry of two adjacent carbon atoms to which carbonate groups are bonded in the structural unit represented by formula (2),
The proportion of either one of the (R,R) form and the (S,S) form is 60 mol% or more and 90 mol% of the total amount of the (R,R) form and the (S,S) form. The following is
A polycarbonate resin having a weight average molecular weight of 100,000 or more and 500,000 or less.
[3]
The polycarbonate resin according to [2], wherein the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is 1.8 or more and 4.0 or less.
[4]
The polycarbonate resin according to [2] or [3], wherein the content of metal elements from Groups 3 to 13 of the periodic table is 1 ppm or less.
[5]
The polycarbonate resin according to any one of [2] to [4], which has a weight loss rate of 10% by mass or less at 150 to 270°C when the methanol-insoluble content is heated in a nitrogen atmosphere by thermogravimetry.
[6]
A polycarbonate resin composition containing the polycarbonate resin according to any one of [2] to [5] and an antioxidant.
[7]
An optical component containing the polycarbonate resin according to any one of [2] to [5] or the polycarbonate resin composition according to claim [6].
[8]
Use of the polycarbonate resin according to any one of [2] to [5] or the polycarbonate resin composition according to [6] as a material for optical components.
[9]
The method for producing a polycarbonate resin according to any one of [2] to [5], comprising a polymerization step of obtaining the polycarbonate resin by ring-opening polymerization of the polymerizable composition according to [1]. Production method.

According to the present invention, a polycarbonate resin having excellent heat resistance can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to this embodiment, and can be implemented with various modifications within the scope of the gist.

<Polymerizable composition>
The polymerizable composition of this embodiment has the following formula (1):
(In formula (1), A is an optionally substituted divalent alicyclic moiety.)
Contains a polymerizable monomer represented by
The polymerizable monomer is a mixture containing an (R,R) form and an (S,S) form in the stereochemistry of two adjacent carbon atoms to which the carbonate group of the formula (1) is bonded, and
The proportion of either the (R,R) form or the (S,S) form is 60% or more and 90% of the total amount of the (R,R) form and the (S,S) form. It is as follows.
The polymerizable composition of this embodiment has the above-mentioned characteristics and can provide a polycarbonate resin having excellent heat resistance.
In the polymerizable composition of the present embodiment, the ratio of one of the (R,R) body and the (S,S) body is such that the ratio of the (R,R) body and the (S,S) body is It is preferably 60% or more and 90% or less, more preferably 70% or more and 90% or less of the total amount. The polymerizable composition of the present embodiment provides a polycarbonate resin having even better heat resistance when the ratio of either the (R,R) body or the (S,S) body is within the above range. can.
In this specification, the term "carbonate group" means a divalent substituent represented by -OC(=O)O-.

In formula (1), A is an optionally substituted divalent alicyclic moiety. From the viewpoint of achieving the effects of the present invention more effectively and reliably, in formula (1), A is preferably a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, or a cyclooctylene group. , cyclononanylene group, and cyclodecylene group. From the same viewpoint, in formula (1), A is more preferably a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, or a cyclooctylene group. From the same viewpoint, A in formula (1) is more preferably a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, or a cycloheptylene group. It is preferable that the alicyclic moiety A is unsubstituted.

In this embodiment, the alicyclic moiety A in formula (1) may be substituted with a substituent. Substituents include, but are not particularly limited to, hydroxyl groups, phosphoric acid groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and 1 to 30 carbon atoms. a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or a linear, branched, or cyclic group having 1 to 30 carbon atoms. Examples include aliphatic hydrocarbon groups. From the viewpoint of achieving the effects of the present invention more effectively and reliably, when the alicyclic moiety A is substituted, the substituent is preferably a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an ester having 1 to 11 carbon atoms. acyl group having 1 to 11 carbon atoms, and a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms. From the same viewpoint, when the alicyclic moiety A is substituted, the substituent is more preferably a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a linear, branched, or cyclic carbon number 1 group. -1 or more substituents selected from the group consisting of 30 aliphatic hydrocarbon groups. From the same viewpoint, when the alicyclic moiety A is substituted, the substituent is more preferably an alkoxy group having 1 to 20 carbon atoms, and a linear, branched, or cyclic carbon number 1 to 30 group. is one or more substituents selected from the group consisting of aliphatic hydrocarbon groups. Examples of various substituents and suitable substituents are as shown in the following formula (1A).

The polymerizable monomer according to this embodiment has the following formula (1A):
(In formula (1A), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a hydroxyl group, a phosphoric acid group, a carbon number of 6 to 20 aryl group, aralkyl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, silyl group having 1 to 30 carbon atoms, silylalkoxy group having 1 to 30 carbon atoms, ester group having 1 to 30 carbon atoms , an acyl group having 1 to 30 carbon atoms, or a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, or R ¹ to R ⁸ are may form a cyclic structure together with a carbon element, and in the cyclic structure, R ¹ to R ⁸ are bonded to each other via an alkylene group or a carbonate group, and the alkylene group is Acid group, amino group, alkoxy group having 1 to 20 carbon atoms, ester group having 1 to 20 carbon atoms, or unsubstituted linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms The alkoxy group, silyl group, silylalkoxy group, ester group, acyl group, aliphatic hydrocarbon group may be substituted with a hydroxyl group, or a carbonyl group may be inserted into the main chain. It may be substituted with a phosphoric acid group, an amino group, an alkoxy group, or an ester group, and the aralkyl group and the aryl group may be substituted with an alkyl group having 1 to 20 carbon atoms. is an integer from 0 to 5.) is preferably a polymerizable monomer represented by the following.

In the present embodiment, in formula (1A), R ¹ to R ⁸ are each independently a hydrogen atom, a hydroxyl group, a phosphoric acid group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, Alkoxy group having 1 to 10 carbon atoms, silyl group having 1 to 30 carbon atoms, silylalkoxy group having 1 to 30 carbon atoms, ester group having 1 to 30 carbon atoms, acyl group having 1 to 30 carbon atoms, or straight chain It is a branched, or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms. From the viewpoint of achieving the effects of the present invention more effectively and reliably, in formula (1A), R ¹ to R ⁸ preferably each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbon One or more types selected from the group consisting of an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, and a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms. is a substituent. From the same viewpoint, in formula (1A), R ¹ to R ⁸ are more preferably each independently a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and a linear, branched, or one or more substituents selected from the group consisting of cyclic alkyl groups having 1 to 30 carbon atoms. From the same viewpoint, in formula (1A), R ¹ to R ⁸ are each independently a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, and a linear, branched, or cyclic is one or more substituents selected from the group consisting of aliphatic hydrocarbon groups having 1 to 30 carbon atoms.

In the present embodiment, R ¹ to R ⁸ in formula (1A) may be bonded to each other via an alkylene group or a carbonate group (-OC(=O)O- group) to form a cyclic structure. , the alkylene group may be substituted with a hydroxyl group, a phosphoric acid group, an alkoxy group, or an ester group. From the viewpoint of achieving the effects of the present invention more reliably and effectively, when R ¹ to R ⁸ are bonded to each other via an alkylene group to form a cyclic structure, the number of carbon atoms in the alkylene group is preferably 1 to 1. 20, more preferably 1-15, even more preferably 1-12. Furthermore, from the same viewpoint, the substituent that the alkylene group has is preferably a hydroxyl group, an alkoxy group, or an ester group, and more preferably a hydroxyl group or an alkoxy group. From the same viewpoint, when R ¹ to R ⁸ form a cyclic structure, the cyclic structure is preferably formed via an unsubstituted alkylene group. Examples of the unsubstituted alkylene group include, but are not limited to, a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, and a 1,3-cyclopentylene group. , 1,6-hexylene group, 1,3-cyclohexylene group, and 1,4-cyclohexylene group.

When R ¹ to R ⁸ form a cyclic structure, it is preferred that any two of R ¹ to R ⁸ form a cyclic structure together.

The phosphoric acid group in the above formula (1A) may be unsubstituted or substituted. That is, it may be a mono-substituted phosphoric acid group or a di-substituted phosphoric acid group. From the viewpoint of achieving the effects of the present invention more effectively and reliably, when the phosphoric acid group is substituted, the substituent is an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. It is preferable that there be. From the same viewpoint, the phosphoric acid group in the above formula (1A) is preferably unsubstituted.

The aryl group having 6 to 20 carbon atoms in the above formula (1A) is not particularly limited, but includes, for example, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, tetramethylphenyl group, pentamethylphenyl group, ethyl An aryl group having an unsubstituted or alkyl group such as a phenyl group, a propylphenyl group, a diisopropylphenyl group, an aryl group having an alkoxy group such as a 4-methoxyphenyl group, a 3,5-dimethoxyphenyl group, etc. , biphenyl group, naphthyl group, and anthracenyl group.

The aralkyl group having 6 to 20 carbon atoms in the above formula (1A) is not particularly limited, but includes unsubstituted or aralkyl groups having an alkyl group such as benzyl group, 4-methylbenzyl group, phenethyl group, etc. Examples include aralkyl groups having an alkoxy group such as , 4-methoxybenzyl group, and 3,5-dimethoxybenzyl group, as well as diphenylmethyl group, naphthylmethyl group, and anthracenylmethyl group.

The alkoxy group having 1 to 20 carbon atoms in the above formula (1A) is not particularly limited, but includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a cyclopentyloxy group, a hexyloxy group, and a cyclohexyloxy group. group, heptyloxy group, octyloxy group, nonanyloxy group, decyloxy group, phenoxy group, benzyloxy group, vinyloxy group, and allyloxy group.

The silyl group having 1 to 30 carbon atoms in the above formula (1A) is not particularly limited, but includes, for example, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, triphenylsilyl group, tert-butyldimethylsilyl group, di- Examples include tert-butylisobutylsilyl group and tert-butyldiphenylsilyl group.

The silylalkoxy group having 1 to 30 carbon atoms in the above formula (1A) is not particularly limited, but includes, for example, a trimethylsilylmethoxy group, a trimethylsilylethoxy group, a trimethylsilylphenoxy group, a trimethylsilylbenzyloxy group, a triethylsilylmethoxy group, and a triethylsilylethoxy group. group, triethylsilylphenoxy group, triethylsilylbenzyloxy group, triisopropylsilylmethoxy group, triisopropylsilylethoxy group, triisopropylsilylphenoxy group, triisopropylsilylbenzyloxy group, triphenylsilylmethoxy group, triphenylsilylethoxy group, Triphenylsilylphenoxy group, triphenylsilylbenzyloxy group, tert-butyldimethylsilylmethoxy group, tert-butyldimethylsilylethoxy group, tert-butyldimethylsilylphenoxy group, tert-butyldimethylsilylbenzyloxy group, di-tert- Butylisobutylsilylmethoxy group, di-tert-butylisobutylsilylethoxy group, di-tert-butylisobutylsilylphenoxy group, di-tert-butylisobutylsilylbenzyloxy group, tert-butyldiphenylsilylmethoxy group, tert-butyldiphenylsilyl Examples include ethoxy group, tert-butyldiphenylsilylphenoxy group, and tert-butyldiphenylsilylbenzyloxy group.

The ester group having 1 to 30 carbon atoms in the above formula (1A) is not particularly limited, but includes, for example, a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, a pentyl ester group, a cyclopentyl ester group, and a hexyl ester group. group, cyclohexyl ester group, heptyl ester group, octyl ester group, nonanyl ester group, decyl ester group, phenyl ester group, benzyl ester group, vinyl ester group, and allyl ester group.

The acyl group having 1 to 30 carbon atoms in the above formula (1A) is not particularly limited, but includes, for example, formyl group, acetyl group, propionyl group, butyryl group, valeryl group, and benzoyl group.

The aliphatic hydrocarbon group in the above formula (1A) may be saturated or unsaturated, but from the viewpoint of improving thermal stability, it is preferably saturated (alkyl group). The linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms in the above formula (1A) is not particularly limited, but includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Butyl group, isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 1-norbornyl group, 2-norbornyl group, n-octyl group, 1-bicyclo [2.2.2] Octyl group, 2-bicyclo[2.2.2]octyl group, n-nonanyl group, n-decyl group, 1-adamantyl group, 2-adamantyl group, decahydronaphthyl group, and tetra A cyclododecyl group is mentioned.

<Polycarbonate resin>
The polycarbonate resin of this embodiment has a structural unit represented by the following formula (2):
(In formula (2), A is an optionally substituted divalent alicyclic moiety.)
A polycarbonate resin having
The polycarbonate resin contains structural units of the (R, R) form and (S, S) form in the stereochemistry of two adjacent carbon atoms to which carbonate groups are bonded in the structural unit represented by formula (2),
The proportion of either the (R,R) form or the (S,S) form is 60% or more and 90% of the total amount of the (R,R) form and the (S,S) form. The following is
The weight average molecular weight is 100,000 or more and 500,000 or less.

In addition, in formula (2), A is an optionally substituted divalent alicyclic moiety as described in relation to formula (1).

The polycarbonate resin of this embodiment has a structural unit represented by the following formula (2A):
It is preferable that the polycarbonate resin has the following.

In addition, in formula (2A), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and n are as explained in relation to formula (1A).

The polycarbonate resin of this embodiment has excellent heat resistance by having the above configuration. This factor is considered to be as follows, but the factor is not limited to this.

Since the polycarbonate resin of this embodiment has an excessive enantiomeric ratio of either the (R, R) body or the (S, S) body, the (R, R) bodies or (S, S) bodies are continuous. The probability of arranging them increases. As a result, it is thought that the blockiness of the enantiomeric arrangement increases and the intermolecular force of the highly blocky parts of the polymer chain increases, thereby improving heat resistance while maintaining amorphousness.
In the polycarbonate resin of the present embodiment, the ratio of either the (R,R) body or the (S,S) body is the total amount of the (R,R) body and the (S,S) body. It is preferably 60% or more and 90% or less, more preferably 70% or more and 90% or less. The polycarbonate resin of the present embodiment has even better heat resistance when the ratio of either the (R,R) body or the (S,S) body is within the above range.
The ratio of the (R,R) form and the (S,S) form is, for example, the ratio of the (R,R) form and (S,S) form of a diol produced by hydrolyzing a polycarbonate resin with an alkali. The ratio can be measured by analyzing the ratio using gas chromatography or high performance liquid chromatography.

Non-Patent Document 3 describes poly(cyclohexene carbonate) in which the proportion of one enantiomer is excessive, but chemical species with ether bonds different from carbonate bonds have been observed, and different species that can be the starting point of thermal decomposition have been observed. Challenges remain in the synthesis of bond-free polycarbonate rings. Further, there is no mention of heat resistance such as thermal decomposition of the resin, and the polycarbonate resin described in Non-Patent Document 3 does not have sufficient reliability in heat resistance, and there is room for improvement.

In the polycarbonate resin of this embodiment, the weight average molecular weight (hereinafter also referred to as "Mw") in terms of polystyrene measured by size exclusion chromatography (SEC) is 100,000 or more and 500,000 or less. The polycarbonate resin of this embodiment can be easily molded by having Mw within the above range. Further, such a polycarbonate resin has excellent heat resistance. From the same viewpoint, the Mw of the polycarbonate resin of this embodiment is more preferably 100,000 or more and 450,000 or less, and still more preferably 100,000 or more and 400,0000 or less. Moreover, the upper limit of Mw of the polycarbonate resin of this embodiment may be 300,000. The weight average molecular weight of the polycarbonate resin by size exclusion chromatography can be specifically measured by the method described in the Examples.

In the polycarbonate resin of this embodiment, in order to control the weight average molecular weight (Mw) within the above range, it is sufficient to adjust the ratio of the polymerizable monomer and the polymerization initiator as appropriate, and also by the manufacturing method described below. What is necessary is to manufacture polycarbonate resin. By controlling the amount of polymerization initiator added to the polymerizable monomer within a specific range, the polymerization reaction tends to proceed at a good conversion rate and the Mw can be increased.

The polycarbonate resin of this embodiment preferably has a ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 1.8 or more and 4.0 or less. The polycarbonate resin of this embodiment tends to have even better heat resistance when Mw/Mn is within the above range. From the same viewpoint, Mw/Mn of the polycarbonate resin of this embodiment is more preferably 1.8 or more and 3.5 or less, and even more preferably 1.8 or more and 3.0 or less.

The polycarbonate resin of this embodiment preferably has a content of metal elements from Groups 3 to 13 of the periodic table of 1 ppm or less. Examples of metal elements from Groups 3 to 13 of the periodic table include, but are not limited to, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, and ruthenium. , osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, aluminum, gallium, indium, and thallium. Since the content of the metal element is 1 ppm or less, the polycarbonate resin of this embodiment can suppress the promotion of thermal decomposition caused by the metal element, as described in Non-Patent Document 2, and has further heat resistance. It tends to be of superior quality. From the same viewpoint, in the polycarbonate resin of this embodiment, the content of the metal element is more preferably 0.8 ppm or less, still more preferably 0.5 ppm or less. Moreover, in the polycarbonate resin of this embodiment, the lower limit of the content of the metal element may be 0 ppm. The content of the above metal elements can be measured by inductively coupled plasma mass spectrometry (ICP-MS).

In the polycarbonate resin of the present embodiment, the weight loss rate at 150 to 270° C. when the methanol-insoluble content is heated in a nitrogen atmosphere by thermogravimetry is preferably 10% by mass or less. It is preferable to reduce the weight loss rate from 150°C, which is considered to be higher than the glass transition temperature (Tg) of general alicyclic polycarbonate resins, to about 270°C, which is considered to be the upper limit of the cylinder temperature during molding. When the weight reduction rate of the polycarbonate resin of the present embodiment is within the above range, it tends to be possible to suppress discoloration and molding defects caused by main chain scission. From the same point of view, in the polycarbonate resin of this embodiment, the weight loss rate at 150 to 270°C when the methanol-insoluble content is heated in a nitrogen atmosphere by thermogravimetric measurement is more preferably 8% by mass or less, and Preferably it is 5% by mass or less. In the polycarbonate resin of the present embodiment, the lower limit of the weight loss rate at 150 to 270°C when the methanol-insoluble content is heated in a nitrogen atmosphere by thermogravimetry is not particularly limited, but is, for example, 0.1% by mass. .

<Polycarbonate resin composition>
The polycarbonate resin composition of this embodiment contains the above polycarbonate resin and an antioxidant.

By containing an antioxidant, the polycarbonate resin composition of this embodiment can further prevent deterioration due to heat and shearing during molding, and therefore can further improve the heat resistance of the polycarbonate resin composition. can. Furthermore, by containing an antioxidant, the polycarbonate resin composition of this embodiment can further prevent the polycarbonate resin from being oxidized during use, thereby further improving the light resistance of the polycarbonate resin composition. can be done.

The antioxidant in the polycarbonate resin composition of this embodiment is not particularly limited, and examples thereof include hindered phenol-based antioxidants and phosphorus-based antioxidants.

Examples of hindered phenolic antioxidants include, but are not limited to, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate]), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), Irganox 1330 (Irganox 1330: 3,3',3'',5,5' , 5''-hex-t-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol), Irganox 3114 (Irganox3114:1,3,5- Tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), Irganox 3125, Adekastab AO-60 (pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]), Adekastab AO-80 (3,9-bis{2-[3-(3- Cyanox 1790 ), Sumilizer GA-80, Sumilizer GS: 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di acrylate -tert-pentylphenyl), and Sumilizer GM (2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl acrylate). . These may be used alone or in combination of two or more.

Phosphorous antioxidants are not particularly limited, but include, for example, Irgafos 168 (Irgafos 168: Tris(2,4-di-t-butylphenyl) phosphite), Irgafos 12 (Irgafos 12: Tris[2-[[2, 4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine), ADKSTAB HP-10 :2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite), ADKSTAB PEP36 (ADKSTAB PEP36: bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol di ADKSTAB PEP36A (bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite), Sumilizer butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine), and GSY P101 (tetrakis(2,4-di-t-butyl-5methylphenyl)4,4'-biphenylene diphosphonite).These may be used alone or in combination of two or more. Good too.

The polycarbonate resin contained in the polycarbonate resin composition of this embodiment is the same as the above-described polycarbonate resin, and its preferred embodiments are also the same.

In the polycarbonate resin composition of the present embodiment, the content of the polycarbonate resin is preferably 50% by mass or more and 99% by mass or less based on the entire resin composition, from the viewpoint of more effectively and reliably achieving the effects of the present invention. It is more preferably 60% by mass or more and 99% by mass or less, and even more preferably 65% by mass or more and 99% by mass or less.

In the polycarbonate resin composition of the present embodiment, the content of the antioxidant is preferably 0.001% by mass based on the entire resin composition from the viewpoint of further preventing deterioration due to heat and shearing during molding. The content is 1% by mass or less, more preferably 0.003% by mass or more and 1% by mass or less, and still more preferably 0.005% by mass or more and 1% by mass or less.

<Optical parts>
The optical component of this embodiment contains the above polycarbonate resin or the above polycarbonate resin composition.

The above polycarbonate resin or the above polycarbonate resin composition contained in the optical component of this embodiment tends to have a small photoelastic coefficient and an in-plane retardation due to molecular orientation. Therefore, the optical component of this embodiment tends to be less likely to exhibit stress birefringence and orientational birefringence. Therefore, the optical component of this embodiment tends to be able to suppress birefringence during use. Furthermore, the above-mentioned polycarbonate resin or the above-mentioned polycarbonate resin composition contained in the optical component of this embodiment has excellent heat resistance as described above. Therefore, the optical component of this embodiment is less likely to deteriorate over time and can be used for a longer period of time than conventional optical components.

Optical components in this embodiment include, but are not particularly limited to, optical lenses such as cameras, telescopes, microscopes, projectors, and vehicle lenses, and optical components such as diffusers, light guide plates, polarizing plates, and retardation films. An example is film. The optical component of this embodiment can be obtained by appropriately processing the above-mentioned polycarbonate resin or the above-mentioned polycarbonate resin composition, such as molding, so that it has a shape suitable for its use.

<Production method of polycarbonate resin>
The method for producing a polycarbonate resin of the present embodiment includes a polymerization step of obtaining a polycarbonate resin by subjecting the polymerizable composition to ring-opening polymerization.

(Polymerization initiator)
In the manufacturing method of this embodiment, the polymerization initiator for ring-opening polymerization of the polymerizable composition is not particularly limited, and examples thereof include acid catalysts, base catalysts, and enzyme catalysts. Examples of the base catalyst include, but are not particularly limited to, cyclic amines such as alkyl metals, metal alkoxides, metal amides, metal organic acid salts, cyclic monoamines and cyclic diamines (particularly cyclic diamine compounds having an amidine skeleton), and guanidine skeletons. Examples include triamine compounds having a nitrogen atom, and heterocyclic compounds containing a nitrogen atom. Examples of the alkyl metal include, but are not limited to, organolithium such as methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and phenyllithium, methylmagnesium halide, ethylmagnesium halide, and propylmagnesium halide. , phenylmagnesium halide, trimethylaluminum, and triethylaluminum. Among them, methyllithium, n-butyllithium, or sec-butyllithium is preferably used. The metal ion in the metal alkoxide is not particularly limited, but includes, for example, alkali metal and alkaline earth metal ions, with alkali metal being preferred. Examples of alkoxide ions include, but are not limited to, methoxide, ethoxide, propoxide, butoxide, phenoxide, and benzyloxide. Note that phenoxide and benzyl oxide may have a substituent on the aromatic ring. Examples of metal amides include, but are not limited to, lithium amide, sodium amide, potassium amide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. The organic acid ion in the metal organic acid salt is not particularly limited, but includes, for example, a carboxylic acid ion having 1 to 10 carbon atoms. Examples of the metal in the metal organic acid salt include, but are not limited to, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, and tin. Further, the base catalyst is not particularly limited, but includes, for example, an organic base. The organic base is not particularly limited, but for example, 1,4-diazabicyclo-[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). , 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), diphenylguanidine ( DPG), N,N-dimethyl-4-aminopyridine (DMAP), imidazole, pyrimidine, purine, and phosphazene bases. From the viewpoint of achieving the effects of the present invention more effectively and reliably, the polymerization initiator used in the production method of this embodiment is preferably an alkyl metal, a metal alkoxide, or a metal amide, and more preferably a metal alkoxide or a metal amide. It is.

The amount of the polymerization initiator used in the polymerization step of the method for producing polycarbonate resin of this embodiment may be adjusted as appropriate depending on the target molecular weight of the polycarbonate resin. From the viewpoint of controlling the weight average molecular weight (Mw) of the polycarbonate resin in the range of 10,000 to 500,000, the amount of the polymerization initiator used is calculated based on the amount of substance relative to the cyclic carbonate (A1), which is a ring-opening polymerizable monomer. The content is preferably 0.0001 mol% or more and 4 mol% or less, more preferably 0.0001 mol% or more and 2 mol% or less, and even more preferably 0.0001 mol% or more and 1 mol% or less. Furthermore, the above polymerization initiators may be used alone or in combination of two or more.

(Polymerization terminator)
In the method for producing a polycarbonate resin of the present embodiment, a polymerization terminator may be used in addition to the polymerization initiator from the viewpoint of controlling the average molecular weight of the resulting polycarbonate resin. Examples of the polymerization terminator include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, metaphosphoric acid, formic acid, acetic acid, and propionic acid. , butyric acid, lactic acid, citric acid, ascorbic acid, gluconic acid, oxalic acid, tartaric acid, Meldrum's acid, and benzoic acid.

(Additive)
In the method for producing polycarbonate resin of this embodiment, additives are added in addition to the polymerization initiator from the viewpoint of controlling the molecular weight of the resulting polycarbonate resin and from the viewpoint of expressing various properties by controlling the terminal structure. May be used. Examples of additives include, but are not limited to, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, dodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 5-norbornene-2. - monoalcohols such as methanol, 1-adamantanol, 2-adamantanol, trimethylsilylmethanol, phenol, benzyl alcohol, and p-methylbenzyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, Dialcohols such as 1,3-butanediol, 1,4-butanediol, hexanediol, nonanediol, tetramethylene glycol, and polyethylene glycol, such as glycerol, sorbitol, xylitol, ribitol, erythritol, and triethanolamine Included are polyhydric alcohols, methyl lactate, and ethyl lactate. Further, the above additives may be used alone or in combination of two or more.

(reaction temperature)
In the method for producing a polycarbonate resin of this embodiment, the reaction temperature in the polymerization step is not particularly limited as long as it is within a range that allows production of the polycarbonate resin of this embodiment, but is preferably 0°C or higher and 150°C or lower. , more preferably 0°C or more and 130°C or less, still more preferably 0°C or more and 120°C or less. When the reaction temperature in the polymerization step is within the above range, it becomes easier to control the weight average molecular weight of the resulting polycarbonate resin within the range of 100,000 to 500,000.

(solvent)
In the method for producing polycarbonate resin of this embodiment, a solvent may or may not be used. Examples of the solvent include, but are not limited to, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, tert-butyl methyl ether, and propylene. Ether solvents such as glycol monomethyl ether acetate, halogen solvents such as methylene chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane, saturated hydrocarbons such as hexane, heptane, octane, nonane, cyclohexane, and methylcyclohexane. Solvents, aromatic hydrocarbon solvents such as toluene, xylene, o-xylene, m-xylene, p-xylene, and cresol, as well as acetone, 2-butanone, 2-pentanone, 3-pentanone, cyclopentanone, Examples include ketone solvents such as cyclohexanone and methyl isobutyl ketone.

The present invention will be explained in more detail using Examples and Comparative Examples, but the present invention is not limited by these Examples and the like.

In this specification, the physical properties of polycarbonate resin were measured as follows.

( ^1H -NMR measurement)
^{A 1} H-NMR spectrum of the polycarbonate resin was obtained by performing NMR measurements as described below using an NMR device manufactured by JEOL Ltd. (product name: ECZ400S) and a TFH probe. Note that the reference peak of the heavy solvent was 7.26 ppm when chloroform-d was used, and the measurement was performed with the number of integrations set to 32.

(Measurement of molecular weight)
A solution prepared by adding 2.0 g of tetrahydrofuran to 0.02 g of polycarbonate resin was used as the measurement sample, and the weight of the polycarbonate resin was measured using a high-speed GPC device (manufactured by Tosoh Corporation, product name "HLC-8420GPC"). The average molecular weight was measured. As columns, TSK guard columns SuperH-H, TSKgel SuperHM-H, TSKgel SuperHM-H, TSKgel SuperH2000, and TSKgel SuperH1000 (all product names manufactured by Tosoh Corporation) were connected in series and used. The column temperature was 40° C., and analysis was performed at a rate of 0.60 mL/min using tetrahydrofuran as the mobile phase. An RI detector was used as a detector. A calibration curve was created using polystyrene standard samples (molecular weight: 2520000, 1240000, 552000, 277000, 130000, 66000, 34800, 19700, 8680, 3470, 1306, 370) manufactured by Polymer Standards Service as standard samples. . Based on the calibration curve thus created, the number average molecular weight and weight average molecular weight of the polycarbonate resin were determined.

[Synthesis example]
((S,S)-trans-1,2-cyclohexene carbonate)
(S,S)-trans-1,2-cyclohexanediol (4.11 g, 35.4 mmol) was weighed into a 200 mL three-necked flask, and the inside of the flask was purged with nitrogen. After adding dehydrated tetrahydrofuran (100 mL) and ethyl chloroformate (8.78 g, 80.9 mmol) into the flask, immerse the flask in an ice bath and cool the internal temperature to 3°C while stirring using a magnetic stirrer. did. Triethylamine (8.58 g, 84.8 mmol) was slowly added dropwise using an addition funnel. When the flask was removed from the ice bath and stirred at room temperature for an additional 3 hours, residual diol was confirmed, so triethylamine (8.99 g, 88.9 mmol) and triethylamine (9.0283 g, 83.2 mmol) were added twice. It was added in portions. After confirming the disappearance of the diol, 0.40 g of ethanol was added, the precipitate was removed by vacuum filtration, and the filtrate was concentrated using an evaporator. The concentrated residue was dissolved in chloroform (20 mL), passed through silica gel (20 g) to remove colored components, and then washed with water (100 mL). The organic layer was dehydrated with magnesium sulfate and concentrated using an evaporator. The concentrated residue was redissolved in chloroform (1 mL) and dropped into heptane (100 mL) cooled in an ice bath, and the precipitated solid was collected by vacuum filtration. The collected solid was dried at 40°C for 12 hours using a vacuum dryer to produce (S,S)-trans-1,2-cyclohexene carbonate (hereinafter also referred to as (S,S)-t-CHC) ( 1.54 g) was obtained.
Note that (R,R)-trans-1,2-cyclohexene carbonate (hereinafter also referred to as (R,R)-t-CHC) is almost equivalent to (S,S)-t-CHC, and the above It can be synthesized by a method similar to the method for synthesizing (S,S)-t-CHC described above.

[Example 1]
(R,R)-t-CHC: (S,S)-t-CHC (0.99 g, 6 .97 mmol) and racemic t-CHC (1.00 g, 7.05 mmol) were weighed out to prepare a polymerizable composition, and the inside of the flask was purged with nitrogen. After adding dehydrated m-xylene (7.84 g) into the flask, the mixture was stirred using a magnetic stirrer to completely dissolve the polymerizable composition. 0.98 g was taken out from this polymerizable composition solution and its moisture value was analyzed using a Karl Fischer apparatus. Separately, a solution of potassium tert-butoxide in tetrahydrofuran (1.0 M, 0.40 mL, 0.40 mmol) was weighed into a dried 30 mL Schlenk tube, diluted with dehydrated m-xylene (3.60 mL), and the initiator solution was dissolved. was prepared. In the flask, while stirring the polymerizable composition solution (8.85 g), 0.06 mL of the prepared initiator solution was added, and the mixture was stirred at 25°C for 30 minutes to perform a ring-opening polymerization reaction of the polymerizable composition. . Acetic acid (0.0039 g) was added into the flask to stop the reaction, and a polymerization solution was obtained.

Subsequently, in order to evaluate the methanol-insoluble matter, a reprecipitation operation was performed as follows. 7.98g of the polymerization solution was sampled and diluted with 28.6g of acetone. The diluted solution was added to 345 g of methanol to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was vacuum dried at 100° C. for 8 hours to obtain a polycarbonate resin. When the obtained polycarbonate resin was heated in a nitrogen atmosphere, the thermal weight loss rate at 150 to 270°C was 1.8% by mass. Further, since no metal elements from Groups 3 to 13 of the periodic table are used, the content of metal elements from Groups 3 to 13 of the periodic table in this polymer is 1 ppm or less.

[Example 2]
(R,R)-t-CHC: 0.84 g of (S,S)-t-CHC as a polymerizable composition so that (S,S)-t-CHC=15 mol%:85 mol%, A polycarbonate resin was obtained by carrying out the polymerization reaction and reprecipitation operation in the same manner as in Example 1, except that 0.36 g of racemic t-CHC was used. When the obtained polycarbonate resin was heated in a nitrogen atmosphere, the thermal weight loss rate at 150 to 270°C was 2.6% by mass. Further, since no metal elements from Groups 3 to 13 of the periodic table are used, the content of metal elements from Groups 3 to 13 of the periodic table in this polymer is 1 ppm or less.

[Comparative example 1]
The same method as in Example 1 except that only racemic t-CHC was used as the polymerizable composition ((R,R)-t-CHC:(S,S)-t-CHC=50:50). Polycarbonate resin was obtained by performing a polymerization reaction and a reprecipitation operation. When the obtained polycarbonate resin was heated in a nitrogen atmosphere, the thermal weight loss rate at 150 to 270°C was 13.3% by mass. Further, since no metal elements from Groups 3 to 13 of the periodic table are used, the content of metal elements from Groups 3 to 13 of the periodic table in this polymer is 1 ppm or less.

[Comparative example 2]
Example 1 except that only (S,S)-t-CHC was used as the polymerizable composition ((R,R)-t-CHC:(S,S)-t-CHC=0:100) Polycarbonate resin was obtained by carrying out a polymerization reaction in the same manner as described above. When the obtained polycarbonate resin was heated in a nitrogen atmosphere, the thermal weight loss rate at 150 to 270°C was 45.9% by mass. Further, since no metal elements from Groups 3 to 13 of the periodic table are used, the content of metal elements from Groups 3 to 13 of the periodic table in this polymer is 1 ppm or less.

Table 1 shows the physical properties of the polycarbonate resins obtained in Examples and Comparative Examples.

From Table 1, it was shown that the polycarbonate resin of the example had a smaller weight loss rate at 150 to 270°C and had excellent heat resistance than the polycarbonate resin of the comparative example.

The polycarbonate resin, polycarbonate resin composition, and optical molded article containing them of the present invention are industrially useful in the fields of various optical materials such as optical lens materials, optical devices, materials for optical parts, and display materials. availability.

Claims (9)

The following formula (1):
(In formula (1), A is an optionally substituted divalent alicyclic moiety.)
Contains a polymerizable monomer represented by
The polymerizable monomer is a mixture containing an (R,R) form and an (S,S) form in the stereochemistry of two adjacent carbon atoms to which the carbonate group of the formula (1) is bonded, and
The proportion of either one of the (R,R) form and the (S,S) form is 60 mol% or more and 90 mol% of the total amount of the (R,R) form and the (S,S) form. A polymerizable composition as follows. Structural unit represented by the following formula (2):
(In formula (2), A is an optionally substituted divalent alicyclic moiety.)
A polycarbonate resin having
The polycarbonate resin contains structural units of the (R, R) form and (S, S) form in the stereochemistry of two adjacent carbon atoms to which carbonate groups are bonded in the structural unit represented by formula (2),
The proportion of either one of the (R,R) form and the (S,S) form is 60 mol% or more and 90 mol% of the total amount of the (R,R) form and the (S,S) form. The following is
A polycarbonate resin having a weight average molecular weight of 100,000 or more and 500,000 or less. The polycarbonate resin according to claim 2, wherein the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is 1.8 or more and 4.0 or less. The polycarbonate resin according to claim 2 or 3, wherein the content of metal elements from Groups 3 to 13 of the periodic table is 1 ppm or less. The polycarbonate resin according to any one of claims 2 to 4, wherein the weight loss rate at 150 to 270 ° C. when the methanol-insoluble content is heated in a nitrogen atmosphere by thermogravimetry is 10% by mass or less. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 2 to 5 and an antioxidant. An optical component comprising the polycarbonate resin according to any one of claims 2 to 5 or the polycarbonate resin composition according to claim 6. Use of the polycarbonate resin according to any one of claims 2 to 5 or the polycarbonate resin composition according to claim 6 as a material for optical components. A method for producing a polycarbonate resin according to any one of claims 2 to 5, comprising a polymerization step of obtaining the polycarbonate resin by ring-opening polymerization of the polymerizable composition according to claim 1. Production method.