JPH10306157A - Novel polyaryl alkyl carbonate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer having an excellent heat resistance by effecting the reaction of inserting an oxirane or cyclohexene oxide into a polyaryl carbonate in the presence of a quaternary onium salt or a crown ether complex. SOLUTION: This polyaryl alkyl carbonate is represented by formula I [wherein R1 and R2 are each a 1-4C alkyl; R3 is a substituent represented by formula II or III (wherein R4 is allyl or the like; R5 and R6 are each a 1-4 C alkyl; and c and d are each 0-5); a and b are each 0-4; and n>2] or formula IV. This compound is obtained by dissolving 1 mol. of a polyaryl carbonate represented by formula V and 2-10 mol. of at least one member selected among cyclohexene oxide and oxiranes represented by formula VI, etc., in a solvent (e.g. chlorobenzene), adding a quaternary onium salt (e.g. tetra-n-butylammonium chloride) or a crown ether complex catalyst (e.g. 18-crown-6-ether/KCl complex) to the solution and effecting the reaction of inserting the oxirane into the polyaryl carbonate at 50-250 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel polyaryl-alkyl carbonate obtained by an insertion reaction of an oxirane into a polyaryl carbonate, and a method for producing the same. More specifically, the novel polyaryl-alkyl carbonate represented by the general formula (I) and a quaternary onium salt or a crown ether complex as a catalyst in a reaction solvent at a temperature of 50 to 250 ° C. The present invention relates to a novel method for producing a polyaryl-alkyl carbonate, comprising reacting an oxirane with a polyaryl carbonate represented by the formula (1) at a ratio of 2 to 10 mol per mol of the polyaryl carbonate.

The novel polyaryl-alkyl carbonate of the present invention represented by the general formula (I) is excellent in mechanical strength such as toughness and impact resistance, and is also excellent in heat resistance, aging resistance, etc. Building materials, auto parts,
It can be used for various applications such as tools, machine parts, electric appliances, electric insulation materials, and various molded products, laminating agents, coating agents, films and sheet products. It is also useful as a curing agent for epoxy resins. Furthermore, this polymer is an ordered polymer having high reactivity and can be further chemically modified, so that the use of a new functional polymer as an excellent raw material for synthesis can be greatly expected.

[0003]

2. Description of the Related Art Ordinary polymers are synthesized from the viewpoint of the synthesis of polymers with highly regulated arrangements, or from the viewpoint of the material properties of polymers, along with the regulation of stereoregularity and molecular weight. This is an important research topic in. There have been several reports on the synthesis of ordered polymers in which the sequence order is regulated. For example, the addition reaction of an oxirane compound or a thiirane compound with various active esters proceeds quantitatively and regioselectively under mild conditions by using a quaternary onium salt or a crown ether complex as a catalyst. Is known (T. Iizawa, A. Goto and T. Nishikubo, Bull.
m. Japan, 62 , 597 (1989)). Therefore, as an example of applying this reaction to the insertion reaction of a low-molecular compound into a polymer having an active chemical bond in the main chain, there is a research example on the insertion reaction of an oxirane compound into a polyaryl ester. According to the report, it is reported that the use of a quaternary onium salt as a catalyst allows an oxirane compound to be inserted into an aryl ester bond of a polymer main chain to give a polyalkyl ester having a novel skeleton ( T.Nishikubo, T.Shimokawa, T.Hirano, A.Shiina, J.Poly
m. Sci. Chem., 27 , 2519 (1989), etc.).

[0004] As an example of a report on the insertion reaction of a low-molecular compound into such a polymer, Yokozawa et al.
kozawa, M.Nishimori, S.Mizukami, T.Endo, Macromolecule
s, 29 , 8017 (1996)) and the synthesis of alternating copolymers by the insertion reaction of ε-caprolactam into polycarbonate by Hoeker et al. (B. Wurm, H. Keul and H. Hoeker, Macro.
molecules, 25 , 2977 (1992)), and the insertion reaction of quinone into polysilane by Tanaka et al. (M. Tanaka, H. Yamasita, Ch.
em. Lett, 1547 (1992)), Sonoda et al., insertion of cyclic siloxanes into polycarbonate (K. Yokota, TK).
akuchi, N.Fukui, T.Kuroda, Y.Morimoto, E.Hamaya, I.Mur
ase and R. Sonoda, Polym. J., 29 , 58 (1997)). According to this method, if a low-molecular compound is inserted into a polymer main chain in a quantitative and regioselective manner, it becomes possible to synthesize an ordered polymer having a new sequence. Since various types of ordered polymers can be synthesized by variously changing the condensed polymer or the low molecular compound used, it is extremely useful as a method for synthesizing ordered polymers. Furthermore, this method is very interesting from the viewpoint of the synthesis of a functional polymer, since a polymer can be easily functionalized by using a cyclic compound having a functional group.

[0005] On the other hand, polycarbonate is a condensation polymer which is currently used in various fields as an engineering plastic because of its excellent mechanical strength and heat resistance. ing. Epoxy resin is a relatively brittle material having poor impact resistance, but by using polycarbonate as a curing agent, the following reaction formula (V)

[0006]

Embedded image

[0007] With the progress of the epoxy resin, the strength of the epoxy resin after curing is expected to be improved (Y. Yu, JP Bell, J. Poly).
m. Sci, A, 26 , 247 (1988), MSLi, CCMMa, JLChen,
MSLu, FCChang, Polymer, 37, 3899 (1966) and TMD
on, JPBell, J. Polym. Sci., A, 34 , 2103 (1966), etc.).

[0008]

The curing reaction represented by the above reaction formula (V) utilizes an insertion reaction of an epoxy group into a carbonate bond in the main chain. However, this reaction is currently used only for research and application for the purpose of curing epoxy resin, and the fact is that there is no study focusing on the insertion reaction of epoxy group into carbonate bond. . Further, in the curing reaction of the epoxy resin in the prior art as shown in the above reaction formula (V), since the reaction is carried out at a high temperature using a Lewis base such as an amine as a catalyst, a five-membered ring carbonate is formed by a ring opening reaction. There was a problem such as the side reaction of
(MSLi, CCMMa, JLChen, MLLin, FCChang, Macrom
olecules, 29 , 499 (1996), etc.). An object of the present invention is to provide a novel polyaryl-alkyl carbonate which can be expected to be used as an excellent synthetic raw material of a new functional polymer by exhibiting excellent mechanical strength, heat resistance, aging resistance and reactivity. And a method for producing the same.

[0009]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have proposed a method for synthesizing a new ordered polymer by inserting a cyclic compound into a polymer main chain. After extensive studies on the insertion reaction of various oxiranes into the aryl carbonate, the reaction formula (V)
The curing reaction of the epoxy resin with polycarbonate as shown in (1) is performed under mild conditions using a neutral catalyst such as a quaternary onium salt to suppress side reactions and proceed quantitatively and regioselectively. Therefore, by applying this reaction to the insertion reaction of oxiranes into the aryl carbonate bond in the polycarbonate main chain, the knowledge that a novel ordered polyaryl-alkyl carbonate can be synthesized, Using 2 to 10 moles of oxiranes per mole of polyaryl carbonate, in the presence of a quaternary onium salt or crown ether complex as a catalyst, preferably in an aprotic non-polar solvent at a temperature of 50 to 250 ° C, By performing an insertion reaction of oxiranes into a polyaryl carbonate, a novel polyaryl carbonate is obtained. Reel - found that alkyl carbonate is obtained, and have completed the present invention.

That is, the first invention according to claim 1 is a compound represented by the general formula (I):

Embedded image (However, in the general formula (I), R ₁ and R ₂ are each an alkyl group having 1 to 4 carbon atoms, and
₃ is

[0011]

Embedded image and

Embedded image Wherein R ₄ is an allyl group, an acryloyl group, a methacryloyl group, or a substituent selected from the group consisting of
An alkyl group having 4 carbon atoms, R ₅ and R ₆ are each an alkyl group having 1 to 4 carbon atoms, and c and d are each an integer of 0 to 5) And a and b are each an integer of 0 to 4, and n is an integer of 2 or more. Note that R ₁ ,
R ₂ and R _{4 to} R ₆ may be the same or different from each other), or the following general formula (II)

[0012]

Embedded image (However, in the general formula (II), R ₁ , R ₂ , a and b
Are respectively R ₁ , R ₂ , and R ₁ in the general formula (I).
a and b), which can be achieved by providing a novel polyaryl-alkyl carbonate represented by the formula:

In a second aspect of the present invention, a compound represented by the following general formula (III) is used in the presence of a quaternary onium salt or a crown ether complex as a reaction catalyst.

[0014]

Embedded image (Wherein, R ₁ and R ₂ are each an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and a and b are each an integer of 0 to 4 And n is an integer of 2 or more) with respect to the polyaryl carbonate represented by the formula (IV):

[0015]

Embedded image (However, in the general formula (IV), R ₃ is

[0016]

Embedded image and

Embedded image R ₄ is an allyl group, an acryloyl group, a methacryloyl group, or a substituent selected from 1-4.
An alkyl group having ₅ carbon atoms, and R ₅ and R
₆ is an alkyl group having 1 to 4 carbon atoms, and R _{4 to} R ₆ may be the same or different, and c and d are each an integer of 0 to 5) Wherein one kind of oxirane selected from the group consisting of the compounds represented by the formula (1) is subjected to an insertion reaction at a ratio of 2 to 10 moles per 1 mole of the polyaryl carbonate. This can be achieved by providing a method for producing an alkyl carbonate.

According to a third aspect of the present invention, the reaction catalyst is tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-butylammonium acetate, n-butylphosphonium chloride, tetra n-butylphosphonium bromide,
The n-butylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide and one or more quaternary phosphonium salts selected from the group consisting of tetraphenylphosphonium iodides, The method for producing a novel polyaryl-alkyl carbonate according to the second invention and the fourth invention according to the fourth invention are characterized in that the reaction catalyst is 18-crown-6-ether / potassium chloride complex, 18-crown-6 complex. Or one or more crown ether complexes selected from the group consisting of -ether / potassium bromide complex and 18-crown-6-ether / potassium iodide complex,
The present invention can be attained by providing a method for producing a novel polyaryl-alkyl carbonate according to the second invention.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyaryl-alkyl carbonate of the present invention comprises
This is a novel polymer obtained by subjecting one kind of oxiranes to an insertion reaction into a polyaryl carbonate by a method described below. That is, the polymer is represented by the general formula (I) (wherein R ₁ and R ₂ are each 1 to 4
R ₃ is an alkyl group having ₃ carbon atoms.

[0019]

Embedded image and

Embedded image

Wherein R ₄ is an allyl group, an acryloyl group, a methacryloyl group or an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₆ are each , An alkyl group having 1 to 4 carbon atoms, c and d are
A and b are each an integer of 0 to 4, and n is an integer of 2 or more, preferably 2 or more and 1000 or less. Note that R ₁ , R ₂
And R _{4 to} R ₆ may be the same or different from each other) or the general formula (II) (wherein R ₁ ,
R ₂ , a and b each represent a novel polyaryl-alkyl carbonate represented by the same general meaning as R ₁ , R ₂ , a and b in formula (I).

In the general formula (I),
R ₁ , R ₂ , R ₅ and R ₆ are specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group, respectively. A lower alkyl group having 1 to 4 carbon atoms selected from the group consisting of groups; Also, R
₄ is an allyl group, an acryloyl group, a methacryloyl group,
A substituent selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. In the present invention, in the general formula (I), a and b are both 0, and R ₃ is

[0022]

Embedded image (Where c is 0) represented by the following general formula (VI):

[0023]

Embedded image (Wherein, in the general formula (VI), n is an integer of 2 or more, preferably 2 to 1000), a and b are both 0, and R ₃ is

[0024]

Embedded image Wherein R ₄ is an n-butyl group, represented by the following general formula (VII):

[0025]

Embedded image (However, in the general formula (VII), n is an integer of 2 or more, preferably 2 to 1000).

The polyaryl-alkyl carbonate obtained in the present invention has a number average molecular weight (M
n) (measured by GPC method (standard polystyrene conversion)) is 1000 or more, preferably 5000 to 300,000, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn)
Is preferably 1.0 to 10.0, and more preferably 1.0 to 5.0.

Next, a method for producing the polyaryl-alkyl carbonate of the present invention will be described. In the method of the present invention, the polyaryl carbonate used as one of the raw materials is represented by the general formula (III) (wherein R ₁ and R
₂ is an alkyl group having 1 to 4 carbon atoms, each of which may be the same or different; a and b are each an integer of 0 to 4; , Preferably an integer of 2 to 1000). In the present invention, the polyaryl carbonate is, for example, 2,2-bis (4′-
Oxyphenyl) propane (so-called bisphenol A) or at least one of the 4'-oxyphenyl groups
Two hydrogen atoms are methyl, ethyl, n-propyl,
Isopropyl group, n-butyl group, isobutyl group, sec
A bisphenol A derivative substituted with a lower alkyl group having 1 to 4 carbon atoms selected from the group consisting of -butyl group and tert-butyl group; dimethyl carbonate, dialkyl carbonate such as diethyl carbonate or diaryl carbonate such as diphenyl carbonate Having a number average molecular weight (Mn) (measured by GPC method (standard polystyrene conversion)) of 500 or more, preferably 2500.
~ 200,000 commercially available ones are used. Among these polyaryl carbonates, a and b are both 0 in the above general formula (III), that is, a polyaryl carbonate derived from bisphenol A is particularly preferred.

The other starting material in the process of the present invention is cyclohexene oxide and the above-mentioned general formula (IV)
(Wherein, R ₃ is

[0029]

Embedded image and

Embedded image

A substituent selected from the group consisting of
R ₄ is an allyl group, an acryloyl group, a methacryloyl group or an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₆ are each an alkyl group having 1 to 4 carbon atoms; _{4 to} R ₆ may be the same or different, and c and d are each 0 to 5
Are monofunctional oxiranes selected from the group consisting of compounds represented by the formula: In this case, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Specific examples can be given. In the method of the present invention, among these oxiranes, cyclohexene oxide and R ₃ in the general formula (IV) are the same.

[0031]

Embedded image In the case of the substituent represented by, allyl glycidyl ether in which R ₄ is an allyl group, n-type in which R ₄ is an n-butyl group
Butyl glycidyl ether, glycidyl methacrylate glycidyl acrylate and R ₄ R ₄ is an acryloyl group is a methacryloyl group, R ₃ is

[0032]

Embedded image In the case of the substituent represented by, R ₅ is a methyl group and c is 1
Cresyl glycidyl ether, phenyl glycidyl ether where c is 0, and R ₃ is

[0033]

Embedded image In the case of the substituent represented by, styrene oxide in which d is 0 is preferable, and n-butyl glycidyl ether and phenyl glycidyl ether are particularly preferable. In the method of the present invention, one of the above oxiranes is used alone, but two or more may be used in combination. It is also possible to use bifunctional oxiranes such as 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether. In this case, a cross-linking reaction occurs during the insertion reaction into the polyaryl carbonate. Since it seems to proceed, it is particularly necessary to take measures such as controlling the reaction temperature and reaction time to suppress the crosslinking reaction.

In the method of the present invention, the compound represented by the general formula (II)
The polyaryl carbonate represented by I) is subjected to an insertion reaction with cyclohexene oxide and one type of oxirane selected from the group consisting of the compound represented by the general formula (IV), thereby obtaining the compound represented by the general formula (I). A polyaryl-alkyl carbonate is obtained, which is an example of an unprecedented insertion reaction in which two equivalents of oxirane react in a stepwise fashion with one carbonate linking species. Therefore, the amount of the oxiranes selected from cyclohexene oxide and the compound represented by the general formula (IV) is 2 to 10 mol, preferably 2 to 5 mol per mol of the polyaryl carbonate represented by the general formula (III). Desirably it is molar. When the amount of the oxiranes used is less than 2 moles per mole of the polyaryl carbonate, the regioselective insertion reaction of the oxiranes into the polyaryl carbonate does not proceed, and the highly sequence-regulated regular polyaryl- Alkyl carbonate cannot be obtained. On the other hand, the amount of oxiranes used is 10 per mole of polyaryl carbonate.
Even if it is more than mol, the insertion ratio of oxirane into the polyaryl carbonate main chain does not improve any more,
Since the amount of water present in the used oxiranes also increases, the molecular weight of the polyaryl-alkyl carbonate produced by the hydrolysis tends to easily decrease, which is not preferable.

The insertion reaction of an oxirane selected from the group consisting of cyclohexene oxide and the compound represented by the general formula (IV) into the polyaryl carbonate represented by the general formula (III) is carried out in a reaction solvent. It is desirable. As the reaction solvent of the present invention, those having an action of dissolving or swelling the polyaryl carbonate and / or the oxiranes and having no reactivity with the polyaryl carbonate and the oxiranes may be used. Examples of such reaction solvents include ether compounds such as chlorobenzene, o-dichlorobenzene, nitrobenzene, tetrahydrofuran, anisole and diglyme (diethylene glycol dimethyl ether), formamide, N, N-dimethylformamide (DMF), N, N-dimethylacetamide ( DMA
c) and hexamethylphosphoric triamide (HMPA)
Amide compounds such as dimethyl sulfoxide (DMS
O), sulfolane, tetramethylurea, N-methyl-2
-Various solvents from non-polar or low-polar solvents such as pyrrolidone (NMP) to high-polar solvents. These solvents may be used alone or as a mixture of two or more. In the method of the present invention, chlorobenzene, o
The use of aprotic non-polar solvents such as dichlorobenzene, anisole is preferred. In addition, as described above,
Aprotic polar solvents such as DMSO, DMAc, DMF, HMPA and NMP can also be used,
Hydrolysis of the polyaryl-alkyl carbonate by water in these polar solvents, or a possibility that these polar solvents may act as nucleophiles and cause a side reaction to lower the insertion rate or decrease the molecular weight of the polyaryl-alkyl carbonate. . Further, in the method of the present invention, a mixture of an organic solvent which forms a homogeneous phase with the above-mentioned reaction solvent and has no reactivity with the above-mentioned polyaryl carbonate or oxiranes, and a reaction solvent thereof can also be used. As the organic solvent, n-hexane, n-
Aliphatic hydrocarbons such as octane, aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone and methyl propyl ketone; halogenated aliphatic hydrocarbons such as dichloromethane and dichloroethane; and dioxane. Specific examples are given below.

The amount of the reaction solvent used may be at least an amount sufficient to dissolve or swell the polyaryl carbonate and / or the oxiranes. Not only the type of reaction solvent used, but also the polyaryl carbonate is used. And the insertion reaction conditions such as the charged amount of the oxiranes, the type and amount of the catalyst described below, the reaction temperature, the reaction time, and the like. Further, in the insertion reaction, the polyaryl carbonate and / or the oxiranes are mixed in a reaction solvent. Or swells with the reaction solvent, so it is difficult to define them unequivocally. Therefore, for example, when an aprotic non-polar solvent such as chlorobenzene, o-chlorobenzene, or anisole is used as the reaction solvent, the amount of the reaction solvent used is 0.01 to 5 times (volume / volume) of the polyaryl carbonate. Weight ratio), preferably 0.1 to 5 times (volume /
(Weight ratio). If the amount is less than 0.01 times, the polyaryl carbonate and / or the oxiranes are not sufficiently dissolved in the reaction solvent, and the reaction proceeds in a heterogeneous system. It is not preferable because regioselective insertion reaction becomes difficult and orderly polyaryl-alkyl carbonate cannot be obtained. On the other hand, even if the aprotic non-polar solvent is used in an amount more than 5 times, the rate of hydrolysis of the polyaryl-alkyl carbonate caused by water contained in the reaction solvent increases, or the oxiranes and the polyaryl The molecular weight of the resulting polyaryl-alkyl carbonate decreases, for example, due to a decrease in the probability of contact with the carbonate bond in the carbonate main chain, and also in the recovery of the reaction solvent from the reaction system by a method described below. It is not profitable because it consumes more energy than necessary.

In the method of the present invention, the insertion reaction of the oxiranes into the polyaryl carbonate does not proceed at all even in the absence of a catalyst even at a high temperature, and a tertiary amine such as triethylamine or tetra-n-butylammonium Quaternary onium salts having a low nucleophilic counter anion, such as hexafluorophosphate (TBAPF ₆ ), also have no catalytic effect. That is, the presence of a quaternary onium salt or a crown ether complex having a counter anion having an appropriate nucleophilicity as a catalyst is indispensable. The catalyst is capable of forming the polyaryl-alkyl carbonate of the present invention represented by the general formula (I) by the insertion reaction of the oxiranes into the polyaryl carbonate, which is performed as shown in the following formula (VIII). It has a promoting effect.

[0038]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a,
b, c, d and n are each R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b,
Represents the same meaning as c, d and n. )

The quaternary onium salt of the catalyst in the method of the present invention is represented by the following general formula (IX)

[0040]

Embedded image

(Wherein, R _{7 to} R ₁₃ represent a hydrogen atom, a hydroxyalkyl group, an alkyl group, an aryl group or an aralkyl group which may be the same or different,
When these are alkyl groups or aralkyl groups, they are linear, branched or cyclic hydrocarbon groups having 1 to 30 carbon atoms. M ₁ represents a nitrogen, phosphorus, arsenic or antimony atom, M ₂ represents an oxygen, sulfur, selenium or tin atom, and M ₃ represents an iodine atom. X is a halogen atom,
1 selected from the group consisting of a hydroxyl group, an alkoxide, an acetate group, a carbonate group, a bicarbonate group, a dihydrogen phosphate group and a bisulfate group
Which represents a valent anion).

Specifically, in the general formula (IX),
An ammonium compound wherein M ₁ is a nitrogen atom, M ₁
Phosphonium compounds when but a phosphorus atom, arsonium compounds when M ₁ is arsenic atom, stibonium compounds when M ₁ is an antimony atom, oxonium compound when M ₂ is an oxygen atom, M ₂ is sulfur Examples include a sulfonium compound when it is an atom, a selenonium compound when M ₂ is a selenium atom, a stannonium compound when M ₂ is a tin atom, and an iodonium compound when M ₃ is an iodine atom. As specific examples of the above ammonium compounds, tetra n-butylammonium chloride (TBAC), tetra n-butylammonium bromide (TBAB), and tetra n-butylammonium iodide (TBA)
I) and other tetra-n-butylammonium halides (T
BAX) and tetra n-butylammonium acetate (TBAAc). Specific examples of the above phosphonium compound include tetra-n-butylphosphonium chloride (TBPC), tetra-n-butylphosphonium bromide (TBPB) and tetra-n-butylphosphonium bromide (TBPB).
Tetra n-butyl phosphonium halides (TBPX) such as butyl phosphonium iodide (TBPI) and tetraphenyl phosphonium chloride (TPP)
C), tetraphenylphosphonium bromide (TPP
B) and tetraphenylphosphonium halides (TPPX) such as tetraphenylphosphonium iodide (TPPI).

In the method of the present invention, among the quaternary onium salt catalysts mentioned above, TBPX such as TBPC, TBPB and TBPI, TPPX such as TPPC, TPPB and TPPI, TBAX such as TBAC, TBAB and TBAI, and TBAAc The use of phosphonium compounds or ammonium compounds such as TBPC, T
The use of PPC, TBAC and TBAAc is particularly preferred. In other words, counter anion Cl ^- and OAc ^- Using quaternary onium salt having, although polymers with high insertion rate and relatively high molecular weight is obtained, the counter anion Br ^- and I
^When a quaternary onium salt having-is used, the insertion ratio and the molecular weight of the polymer tend to decrease. This indicates that the insertion reaction is highly dependent on the nucleophilicity of the counter anion of the catalyst, and that Cl has a moderate nucleophilicity.
^- and OAc ^- is considered because it is most effective. In the method of the present invention, two or more kinds selected from the above quaternary onium salts may be mixed and used as a catalyst.

On the other hand, the crown ether complex of the catalyst in the method of the present invention includes 18-crown-6-ether / potassium chloride complex, 18-crown-6-ether / potassium bromide complex and 18-crown-6-ether / Potassium iodide complex and the like. Among these crown ether complexes, the use of an 18-crown-6-ether / potassium chloride complex is preferred. In the method of the present invention, two or more kinds selected from the above-mentioned crown ether complexes may be used in combination as a catalyst, or may be used in combination with the quaternary onium salt. However, when a crown ether complex is used as a catalyst, a polymer having a high molecular weight can be obtained. However, the increase in the molecular weight is not due to the insertion reaction of the oxiranes, but is caused by the polymer terminal generated by hydrolysis of the obtained polymer. In some cases, the phenolic hydroxyl group causes a transesterification reaction with a carbonate bond in the polymer main chain. Therefore, as the catalyst, it is preferable to use the quaternary onium salt which does not cause such a transesterification reaction, and when using a crown ether complex catalyst, it is necessary to devise such a measure that the reaction time described later is not too long. It is.

The amount of the above-mentioned quaternary onium salt or crown ether complex as a catalyst required for the insertion reaction depends on the charged amount of the polyaryl carbonate or the oxiranes, the type and used amount of the reaction solvent, the reaction temperature. , Depends on the insertion reaction conditions such as reaction pressure and reaction time, etc., and cannot be limited unconditionally.
It is desirable that the content be 15 mol%, preferably 1 to 10 mol%, particularly preferably 1 to 5 mol%. When the amount of the catalyst is more than 15 mol% based on the oxiranes, the amount of water contained in the catalyst increases, so that the obtained polyaryl-alkyl carbonate is easily hydrolyzed, and the ring-closing reaction and the like are caused. Since the side reaction also proceeds at the same time as the hydrolysis, the rate of insertion of the oxirane into the main chain of the polyaryl carbonate and the molecular weight of the obtained polyaryl-alkyl carbonate are reduced. Further, the amount of the catalyst used is 1 mol% with respect to the oxiranes.
If the amount is smaller, the insertion reaction of the oxiranes into the polyaryl carbonate does not proceed sufficiently, so that a high-molecular-weight ordered polyaryl-alkyl carbonate cannot be obtained in a high yield, which is not preferable. In order to surely prevent the occurrence of these undesired phenomena, the amount of the catalyst used should be within the above-mentioned preferred range, and more particularly within the particularly preferred range.

The insertion reaction of the oxiranes into the polyaryl carbonate in the production method of the present invention needs to proceed in a solution in a homogeneous system. That is, in a state where the polyaryl carbonate and / or the oxiranes are dissolved in the reaction solvent, or
It is necessary to perform the insertion reaction in a state where the polyaryl carbonate and / or the oxiranes are swollen with the reaction solvent. For this purpose, the reaction solvent should be maintained in a liquid state during the progress of the insertion reaction. It is. Therefore, the reaction temperature must be at least 50 ° C. or higher so that the polyaryl carbonate and / or the oxiranes are dissolved in the reaction solvent or swollen with the reaction solvent. . However, in this case, if the reaction temperature exceeds 250 ° C., undesired thermal decomposition reaction of the product polyaryl-alkyl carbonate occurs at the same time, so the reaction temperature in the insertion reaction of the present invention is 50 to 25.
Preferably it is in the range of 0 ° C.

In the reaction for inserting the oxirane into the polyaryl carbonate in the production method of the present invention, the reaction pressure is not particularly limited, and the reaction can be carried out at any of reduced pressure, normal pressure and increased pressure. is there. However, in the case of pressurization, pressure resistance performance is required of the manufacturing equipment, and in the case of decompression, pressure reduction equipment is required. However, as described above, during the progress of the insertion reaction,
Needless to say, pressure conditions must be maintained so that the reaction solvent can maintain a liquid state. Therefore, depending on the set reaction temperature, the insertion reaction may need to be performed under pressurized conditions, for example, in an autoclave. In addition, the above-mentioned insertion reaction has a higher reaction rate as the temperature is higher. Therefore, when it is necessary to increase the yield or molecular weight of the obtained polyaryl-alkyl carbonate, the reaction temperature should be as high as possible within the range described above. Is good. However, when the temperature at the time of the insertion reaction is too high, the insertion reaction does not proceed quantitatively and regioselectively due to the occurrence of side reactions such as a hydrolysis reaction and a ring closing reaction, and the heat resistance of the resulting polyaryl-alkyl carbonate. Quality and mechanical properties may be adversely affected, and the polyaryl carbonate, oxiranes, reaction solvent, etc. used may be thermally unstable. Therefore, in such a case, it is preferable to reduce the pressure of the reaction system and maintain the reaction temperature low.

The reaction time in the production method of the present invention also depends on the amount of the polyaryl carbonate and the oxiranes charged, the type and amount of the reaction solvent, the type and amount of the catalyst, and the reaction temperature and reaction pressure. Although it depends on the insertion reaction conditions, it is about 1 to 80 hours, preferably about 5 to 50 hours, more preferably about 1 to 50 hours.
About 0 to 30 hours is desirable. In the insertion reaction of the present invention, hydrolysis and side reactions tend to occur in the initial stage, and the molecular weight of the obtained polyaryl-alkyl carbonate tends to decrease. It is not preferable because it corresponds to the time zone. Further, even if it is longer than about 80 hours, further improvement in the yield and molecular weight of the target product polyaryl-alkyl carbonate cannot be expected, and the obtained polyaryl-alkyl carbonate suffers from a prolonged heat history. However, it is not preferable because the quality may be deteriorated due to thermal deterioration.

The insertion reaction in the method of the present invention is preferably performed while stirring by an appropriate method such as mechanical stirring using a stirrer. Also, the insertion reaction in the method of the present invention is carried out in a degassed closed apparatus or in an inert gas atmosphere to prevent undesirable hydrolysis and oxidation of the resulting ordered polyaryl-alkyl carbonate. It is preferably performed below. As the inert gas, a rare gas such as an argon gas or a helium gas can be suitably used in addition to the nitrogen gas.

In the present invention, the method for producing the polyaryl-alkyl carbonate represented by the general formula (I) by the insertion reaction of the oxiranes into the polyaryl carbonate is not particularly limited.
What is necessary is just to carry out according to a conventional method, and it can implement with either a batch type or a continuous type. For example, after dissolving or swelling a predetermined amount of the polyaryl carbonate and / or the oxiranes in a predetermined amount of the reaction solvent, the solution is supplied to a reaction device equipped with a suitable stirrer and heating device, and further, a predetermined amount is used as a catalyst. The above-mentioned quaternary onium salt or crown ether complex is added, and the mixture is heated to a predetermined temperature while stirring at normal pressure or under a predetermined reduced or increased pressure, and the reaction may be performed for a predetermined time. In this case, the oxiranes can be added in appropriate amounts without adding a predetermined amount at once. Further, the quaternary onium salt or crown ether complex of the catalyst also,
The required amount may be added to the reaction system at one time, or may be added in appropriate portions. Accordingly, the reactor used is not particularly limited, and an autoclave, a batch reactor, a single- or multi-tank continuous reactor, a tubular continuous reactor, and the like are used. Furthermore, in the method of the present invention, as described above, when a bifunctional oxirane is used as the oxirane raw material, the insertion is performed in order to prevent the generation of an intermolecular cross-linkage based on a crosslinking reaction during the insertion reaction. At the time of the reaction, consideration must be given to the selection of reaction conditions that are as mild as possible within the ranges of the reaction temperature and reaction time described above.

In the method of the present invention, subsequently, the reaction solution obtained as described above is added to a precipitation solvent, and left for a suitable period (for example, about 24 hours) to obtain the above-mentioned general formula (I) A precipitate of the polyaryl-alkyl carbonate represented by the formula is obtained. The precipitation solvent may be any poor solvent for the polyaryl-alkyl carbonate, for example, water, methanol, ethanol, n-
Propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and sec-
Room temperature liquid alcohols having 1 to 4 carbon atoms such as butyl alcohol, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, methyl propyl ether,
Methyl isopropyl ether, methyl butyl ether,
Ethers such as methyl isobutyl ether, phenetole, diphenyl ether and dioxane; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone and methyl isobutyl ketone; and aliphatic carbons such as n-hexane and n-octane Examples thereof include hydrogens, aromatic hydrocarbons such as benzene, toluene and xylene, and a mixture of two or more selected from these organic solvents. Among them, methanol,
Ethanol, diethyl ether, diisobutyl ether, acetone, methyl ethyl ketone and methyl isobutyl ketone are preferred, and methanol and ethanol are particularly preferred.

The amount of the precipitation solvent is preferably 1 to 100 times (volume ratio) the amount of the reaction solution. If the amount is less than 1 time, precipitation of the polyaryl-alkyl carbonate from the reaction solution is not sufficiently performed, which is not preferable. If the amount used is more than 100 times, not only the further effect of the precipitation solvent cannot be expected, but also if the above-mentioned organic solvent is used as the precipitation solvent and it is intended to recover it, There is a problem that more energy is required for recovering the precipitation solvent, which is not economically preferable.

The reaction mixture containing the precipitate obtained by injecting the reaction solution into the precipitation solvent is separated into a solid (precipitate) by a known method such as filtration or centrifugation. Prior to injecting the reaction solution into the precipitation solvent, the reaction solution may be diluted with a good solvent described below. In the method of the present invention, the solid matter comprising the polyaryl-alkyl carbonate separated and recovered is dissolved again in a good solvent. Such a good solvent may be any solvent that has an action of dissolving the solid composed of the polyaryl-alkyl carbonate and does not react with the solid, and may be dichloromethane, dichloroethane, chloroform, trichloroethane, trichloroethylene, tetrachloroethylene, or the like. Preferable examples include halogenated aliphatic hydrocarbons such as carbon chloride, tetrachloroethane, and tetrachloroethylene. In addition, the same kind of reaction solvent as used in the above-described insertion reaction of the oxirane into the polyaryl carbonate may be used, and specifically, chlorobenzene, o-dichlorobenzene, nitrobenzene, tetrahydrofuran, anisole and diglyme Amide compounds such as formamide, DMF, DMAc and HMPA, DMSO, sulfolane, tetramethylurea and N
A variety of solvents can be used, from non-polar or less polar solvents to more polar solvents, such as MP. These solvents may be used alone or as a mixture of two or more. And in the present invention, among the above-mentioned good solvents, chloroform, carbon tetrachloride, DMSO,
The use of DMAc, HMPA and NMP is preferred, the use of chloroform and carbon tetrachloride is particularly preferred. Further, similarly to the reaction solvent, n-hexane, n-hexane, which forms a homogeneous phase with these good solvents and has no reactivity with the solid of the polyaryl-alkyl carbonate,
Mixtures of these good solvents with aliphatic hydrocarbons such as octane, ketones such as acetone, methyl ethyl ketone and methyl propyl ketone, and organic solvents such as dioxane may be used.

The amount of the good solvent used may be any amount that is sufficient to dissolve the solid of the above-mentioned polyaryl-alkyl carbonate, and is preferably 1 to 60 times (volume / weight) the solid. . When the amount of the good solvent used is less than 1 time, the solid is not sufficiently dissolved in the good solvent, and the recovery of the polyaryl-alkyl carbonate of the target product by the subsequent reprecipitation purification becomes insufficient. And
If the amount of the good solvent exceeds 60 times, more energy is required than necessary for the recovery and reuse of the good solvent, which is not profitable.

Next, the above solution containing the target product polyaryl-alkyl carbonate (that is, a good solvent in which the polyaryl-alkyl carbonate is dissolved) is added again to the above-mentioned precipitation solvent, and is then added for an appropriate period (for example, about one day and night). After leaving the target product to stand, the solid content (precipitate of the target product) is separated and recovered by a known method such as filtration or centrifugation.
In this case, the amount of the precipitation solvent used is the same as in the case of the above-described polyaryl-alkyl, as in the case of separating and recovering the solid containing the polyaryl-alkyl carbonate by injecting the reaction solution obtained by the insertion reaction into the precipitation solvent. It may be 1 to 100 times (volume ratio) the amount of the solution containing carbonate. In the method of the present invention, as described above, the operation of dissolving the solid containing the target product, polyaryl-alkyl carbonate, in a good solvent, the operation of injecting the solution into the precipitation solvent, and the resulting precipitate By repeating a series of reprecipitation / purification operations of the target product at least once, preferably 2-3 times, comprising a separation / recovery operation by filtration or centrifugation of the polyaryl-
It is desirable to remove and purify impurities such as residual reaction solvent from the solid containing alkyl carbonate. In the repetition of the above-described series of reprecipitation and purification operations, it is easy to collect and reuse the good solvent and the precipitation solvent (poor solvent) from the filtrate obtained when separating and recovering the solid matter of the polyaryl-alkyl carbonate. As for the good solvent, the same solvent as the reaction solvent used in the insertion reaction of the oxiranes into the polyaryl carbonate is used for the good solvent, and the reaction obtained by the insertion reaction is used for the precipitation solvent. It is preferable to use the same kind of solvent as the precipitation solvent used for separation / recovery of the solid matter of the polyaryl-alkyl carbonate from the solution, but the present invention is not limited thereto. It may be different in each reprecipitation purification operation. Unless the recovery and reuse of the precipitation solvent from the filtrate is taken into account, it is needless to say that water is most preferably used as the precipitation solvent economically.

In the production method of the present invention, the solid matter of the polyaryl-alkyl carbonate obtained as described above is finally treated at a temperature of 100 ° C. or less by a known method such as hot air drying, vacuum drying and freeze drying. By drying, the target product polyaryl-alkyl carbonate represented by the general formula (I) is obtained.

When the solid containing polyaryl-alkyl carbonate is recovered from the reaction mixture containing the precipitate obtained by injecting the reaction solution into the precipitation solvent by filtration, centrifugation, etc. The filtrate obtained in the reprecipitation purification operation of the solid contains unreacted oxiranes, a reaction solvent, a catalyst, a solvent for dissolving the precipitate (good solvent), a precipitation solvent (poor solvent), and the like. These may be recovered, if necessary, and then subjected to distillation, column chromatography such as liquid chromatography, recrystallization, selective solvent extraction, and JP-A-5-125021.
A known separation operation method, such as a pervaporation method or a vapor permeation method using a permselective membrane disclosed in Japanese Patent Application Laid-Open No. 6-157407, or the like, may be used alone or in an appropriate combination. Thus, each of the above substances can be isolated and reused.

[0058]

Next, the method of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the method of the present invention is not limited by these Examples and Comparative Examples. In the following Examples and Comparative Examples, the characteristics of the raw material polyaryl carbonate and the product polyaryl-alkyl carbonate were determined by the following methods.

(1) Elemental analysis of polyaryl-alkyl carbonate 240C CHNS / O manufactured by PerkinElmer Co., Ltd.
The measurement was performed using an analyzer.

(2) Number average molecular weight of polyaryl carbonate and polyaryl-alkyl carbonate (M
n) and the ratio of the weight average molecular weight to the number average molecular weight (Mw /
Mn) Gel permeation chromatography (G) using tetrahydrofuran (THF) as an eluate under the following conditions
PC). Measuring instrument: HLC-8020 manufactured by Tosoh Corporation Column: TSKgelG1000H Standard substance: polystyrene Solvent: tetrahydrofuran (THF)

(3) Infrared absorption spectrum (IR) of polyaryl carbonate and polyaryl-alkyl carbonate was measured by the following method using an IR-700 Fourier infrared spectrophotometer manufactured by JASCO Corporation. (Film method) A polyaryl carbonate sample and a polyaryl-alkyl carbonate sample from which water has been removed by drying under reduced pressure at 60 ° C. for 10 hours or more are each adjusted to a concentration of about 5% by weight in tetrahydrofuran (dehydrated according to a conventional method and distilled). ) And dried gently on a plastic petri dish to prepare a film.

(4) Nuclear magnetic resonance spectrum ( ¹ H-NMR) of polyaryl carbonate and polyaryl-alkyl carbonate: JMN-α-500 (500 MH) manufactured by JEOL Ltd.
z) Nuclear magnetic resonance apparatus or JMN- manufactured by JEOL Ltd.
FX-200 (200 MHz) nuclear magnetic resonance apparatus was used. 50 mg of a polyaryl carbonate sample and a polyaryl-alkyl carbonate sample, each of which was dried under reduced pressure at 60 ° C. for 10
The solution was dissolved in ml of CDCl ₃ (deuterated chloroform manufactured by Aldrich Chem. Co. (USA), internal standard: tetramethylsilane (TMS)), and ¹ H-NMR was measured.

(5) Nuclear magnetic resonance spectrum ( ¹³ C-NMR) of polyaryl carbonate and polyaryl-alkyl carbonate: JMN-α-500 (125 MHz, manufactured by JEOL Ltd.)
z) Nuclear magnetic resonance apparatus or JMN- manufactured by JEOL Ltd.
FX-200 (50 MHz) nuclear magnetic resonance apparatus was used. A 50 mg polyaryl carbonate sample and a 50 mg polyaryl-alkyl carbonate sample, each of which was dried under reduced pressure at 60 ° C. for 10 hours or more to remove water, was about 0.5 m each.
l of CDCl ₃ (deuterated chloroform manufactured by Aldrich Chem. Co. (USA), internal standard: tetramethylsilane (TMS)) and ¹³ C-NMR was measured.

(6) Insertion ratio of oxiranes into polyaryl carbonate In the ¹ H-NMR spectrum of polyaryl-alkyl carbonate determined in the above section (4), methyl protons derived from polyaryl carbonate and oxiranes are derived. The insertion ratio of oxiranes was determined from the integral ratio of methine protons.

The reagents and solvents used in the following Examples and Comparative Examples have been subjected to the following pretreatment. (A) Solvent Anisole was obtained by pre-drying a commercially available product with magnesium sulfate, and then adding sodium to purify by distillation. Also, N, N
-Dimethylacetamide (hereinafter abbreviated as "DMAc"),
Chlorobenzene, N-methyl-2-pyrrolidone (hereinafter abbreviated as “NMP”) and N, N-dimethylformamide (hereinafter abbreviated as “DMF”) are each commercially available products that have been pre-dried with calcium hydride and then dried with calcium hydride. Was purified by distillation under reduced pressure.

(B) Polyaryl carbonate Commercial product (Aldrich Chem. Co. (USA), trade name: N)
o. 18,162-5, weight average molecular weight (Mw): 64
000 (GPC method)) was purified by reprecipitation twice using chloroform as a good solvent and n-hexane as a poor solvent.

(C) Oxirane Phenyl glycidyl ether (hereinafter abbreviated as “PGE”), n-butyl glycidyl ether (hereinafter “BGE”)
), Styrene oxide (hereinafter abbreviated as “SO”) and cyclohexene oxide (hereinafter abbreviated as “CHO”)
Was purified by vacuum distillation in the presence of calcium hydride after adding calcium hydride to a commercially available product and pre-drying.

(D) Catalyst Tetra n-butylammonium bromide (hereinafter referred to as “TB
AB ") was purified by recrystallizing a commercially available product with dehydrated ethyl acetate. As other quaternary onium salts and 18-crown-6-ether (18-C-6), commercially available products were used as they were. Triethylamine (hereinafter abbreviated as “TEA”) was obtained by drying a commercially available product over calcium hydride and then purifying it by distillation.

Example 1 0.012 g (0.04 mmol) of tetra-n-butylphosphonium chloride (hereinafter abbreviated as "TBPC") as a catalyst in an ampoule tube in a dry bag (humidity <10%), so that the catalyst concentration was PGE 2 mol%)
Was weighed, a rotor was put therein, and dried under reduced pressure at 60 ° C. for 5 hours. Then, in a dry bag (humidity <10%), 0.254 g (1 mmol, number average molecular weight (hereinafter abbreviated as “Mn”) = 29800, polyaryl carbonate (hereinafter abbreviated as “PC”) = 29800 in an ampoule tube was added. Ratio of molecular weight to number average molecular weight (hereinafter abbreviated as “Mw / Mn”) = 1.5
1), 0.300 g (2 mmol) of PGE and 1.25 ml of chlorobenzene as a reaction solvent (therefore, the concentration of PC relative to the solvent (hereinafter referred to as “monomer concentration”) was 0.8 mol / l). Subsequently, a two-way cock was connected to the ampoule tube, taken out of the dry bag in a hermetically sealed state, and degassed and sealed. Then, the ampoule tube was immersed in an oil bath at 100 ° C. and
GE insertion reaction was performed. After completion of the reaction, the reaction mixture was diluted with about 3 ml of chloroform, poured into 100 ml of methanol, and allowed to stand for 16 hours to precipitate a polymer.

Therefore, the methanol solution containing the polymer precipitate was separated by filtration through a glass filter, and the recovered polymer was purified by reprecipitation using chloroform as a good solvent and methanol as a poor solvent (that is, 5 ml of the recovered polymer). After dissolving in chloroform,
of methanol to precipitate the polymer). Then, the methanol solution containing the polymer precipitate was separated by filtration with a glass filter, and the obtained polymer was dried under reduced pressure in a desiccator at room temperature.
Obtained in a yield of 4 g. Therefore, as shown in Table 1, the yield of the obtained polymer was 98%,
n = 16600 and Mw / Mn = 1.84. The results of elemental analysis were as follows. Elemental analysis (C ₃₄ H ₃₄ O ₇₎ Calculated (%) C: 73.63 H: 6.18 Found (%) C: 73.57 H: 6.35

Further, in order to determine the chemical structure of this polymer and to determine the insertion ratio of PGE into PC, the infrared absorption spectrum (I
R spectrum) and nuclear magnetic resonance spectrum ( ¹ H
-NMR spectrum and ¹³ C-NMR spectrum). IR spectrum of the obtained polymer, ¹ H
-NMR spectrum and ¹³ C-NMR spectrum
These are shown in FIGS. 1, 2 and 3 in comparison with those of the raw material PC. The results (spectral data) of the IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement are as follows.
Each was as follows. IR (Film, cm ^-1 ): 1749 (νC = O, ca
rbonate), 1599, 1497 (νC = C, a
romantic), 1272, 1079 (νC-O-
C, ether), 1235, 1182 (νO-C-
O, carbonate). ¹ H-NMR (200 MHz, CDCl ₃ , TMS) δ
(Ppm): 1.41 to 1.75 (bs, 6H,
^{H a), 4.05~4.40 (bs,} 8.0H,
^{H b), 5.20~5.50 (m,} 2.0H, H c),
6.60 to 7.40 (m, 18.0H, aromati
cH). ¹³ C-NMR (125 MHz, CDCl ₃ , TMS) δ
^{(Ppm): 30.99 (C 1} ), 41.69
(C ² ), 65.84 (C ³ ), 74.66 (C ⁴ ),
114.01, 114.62, 121.31, 127.
76,129.46,143.76,156.07,1
58.23 (aromatic C), 154.16
(C ^5). In addition, P to the PC determined from the ¹ H-NMR measurement results
The GE insertion rate was 100%. From this, PC
It was found that two molecules of PGE were quantitatively inserted into one of the carbonate bonds. Then, the ¹ H-N
From the spectrum data of MR and ¹³ C-NMR, PG
It has been found that β-β cleavage of E is selectively proceeding,
In addition to this, from the results of the above elemental analysis and IR measurement,
The obtained white polymer was found to be an ordered polyaryl-alkyl carbonate represented by the following general formula (X) and having a well-arranged sequence.

[0072]

Embedded image

However, the molecular weight of the polyaryl-alkyl carbonate after the insertion reaction (Mn = 16600)
Is smaller than the molecular weight of PC before the insertion reaction (Mn = 29800), which is considered to be due to cleavage of the polymer main chain due to side reactions such as hydrolysis and ring closure reaction.

Example 2 The same operation as in Example 1 was carried out except that the reaction time was changed to 72 hours and set to 24 hours, to obtain 0.55 g of a white polymer. The yield of the polymer, Mn and Mw
/ Mn, as shown in Table 1, was 98% and 13%, respectively.
900 and 1.84. The insertion ratio of the obtained polymer was 95%, as determined from ¹ H-NMR spectrum data. Further, from the results of IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement performed on the obtained polymer, the obtained white polymer was found to be an ordered polyaryl-alkyl represented by the general formula (X). It turned out to be carbonate.

Examples 3 to 5 In Example 3, 5 ml (monomer concentration: 0.2 mol / l) was used instead of 1.25 ml (monomer concentration: 0.8 mol / l) of chlorobenzene as a reaction solvent. In the case of Example 4, 2.5 ml (monomer concentration: 0.4 mol /
l), and in Example 5 except that the amount was 1.67 ml (monomer concentration: 0.6 mol / l).
The same operation as described above was performed. The Mn of the obtained white polymer and the insertion ratio determined from ¹ H-NMR spectrum data were as shown in Table 1, respectively. In Examples 3 to 5, from the results of IR measurement, ¹ H-NMR measurement, and ¹³ C-NMR measurement performed on the obtained polymer, the obtained white polymers were each represented by the general formula (X) Is found to be an ordered polyaryl-alkyl carbonate represented by From the results of Examples 2 to 5 above, in the insertion reaction of PGE into PC using TBPC as a catalyst, as the monomer concentration becomes higher (that is, the amount of the reaction solvent decreases), the molecular weight of the obtained polymer becomes higher. It was also found that the insertion rate tended to increase.

Example 6 Instead of 0.300 g (2 mmol) of PGE, BGE
Except that 0.260 g (2 mmol) was used, the insertion reaction of BGE into PC was performed in exactly the same manner as in Example 1. The obtained polymer had a yield of 0.49 g (yield: 95%), Mn = 11400, and Mw / Mn =
1.53. The results of IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement (spectral data) of the obtained polymer were as follows, respectively.

[0077]

Embedded image

IR (Film, cm ^-1 ): 1747 (ν
C = O, carbonate), 1608, 1510
(ΝC = C, aromatic), 1268, 1075
(ΝC-OC, ether), 1239, 1182
(ΝO-CO, carbonate). ¹ H-NMR (200 MHz, CDCl ₃ , TMS) δ
(Ppm): 0.70 to 1.00 (m, 6.1H,
^{H g), 1.10~1.75 (m,} 14.0H, H a,
^{H f), 3.30~3.60 (m,} 3.9H, H c),
^{3.60~3.80 (m, 4.0H, H d} ), 4.05
-4.30 (bs, 4.0H, ^Hb ), 5.10-5.
^{25 (m, 2.0H, H c} ), 6.60~7.40
(M, 8.0H, aromatic H). Further, B to PC determined from the ¹ H-NMR measurement results
The GE insertion rate was 100%. From this, PG
As in the case of E, it was found that the insertion reaction of BGE into PC proceeded quantitatively. Further, from the above ¹ H-NMR and ¹³ C-NMR spectrum data, it was revealed that β-β cleavage of BGE was selectively proceeding similarly to the case of PGE.

Example 7 Instead of 0.300 g (2 mmol) of PGE, SO.
Except that 240 g (2 mmol) was used, the same operation as in Example 1 was performed, and an insertion reaction of SO into PC was performed. The obtained polymer had a yield of 0.46 g (yield: 93%), Mn = 6100, and Mw / Mn =
1.51. The results of IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement (spectral data) of the obtained polymer were as follows, respectively.

[0080]

Embedded image

IR (Film, cm ^-1 ): 1751 (ν
C = O, carbonate), 1606, 1508
(ΝC = C, aromatic), 1263, 1079
(ΝC-OC, ether), 1234, 1182
(ΝO-CO, carbonate). ¹ H-NMR (200 MHz, CDCl ₃ , TMS) δ
(Ppm): 1.41 to 1.75 (bs, 6.0H, H
^a ), 3.95 to 4.50 (m, 3.7H, ^Hb ),
^{5.20~6.10 (m, 1.8H, H c} ), 6.60
~ 7.70 (m, 17.3H, aromatic
H). Further, from the results of ¹ H-NMR measurement, the insertion ratio of SO into PC was 90%, and the ratio of β: α cleavage of SO was β: α =
It was confirmed that the progress was at 8: 2. This is SO
It is considered that, unlike PGE and BGE, carbon at the α-position easily forms a stable cation.

Example 8 Instead of 0.300 g (2 mmol) of PGE, CHO was used.
Except that 0.196 g (2 mmol) was used, the same operation as in Example 1 was performed to perform a reaction of inserting CHO into PC. The obtained polymer had a yield of 0.16 g.
(Yield: 36%), Mn = 3400, Mw / Mn
= 1.42. The results of IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement (spectral data) of the obtained polymer were as follows, respectively.

[0083]

Embedded image

IR (Film, cm ^-1 ): 1768 (ν
C = O, carbonate), 1606, 1505
(ΝC = C, aromatic), 1081 (νC-O
-C, ether), 1230, 1194 (νO-C-
O, carbonate). ¹ H-NMR (200 MHz, CDCl ₃ , TMS) δ
(Ppm): 1.20 to 2.00 (bs, 8.1H, H
^a , ^Hb ), 4.20-4.40 (m, 0.3H,
^{H c), 4.80~5.10 (m,} 0.4H, H d),
6.60 to 7.40 (m, 8.0H, aromatic
H). Further, C to PC determined from the ¹ H-NMR measurement results
The HO insertion rate was 20%. PG insertion rate is PG
The lower reason compared to E, BGE and SO is that CH
It is considered that O has a cyclohexane ring on the back side of the oxirane ring, so that the quaternary onium salt is not easily coordinated to the oxirane ring, and the reaction did not proceed much.

[0085]

[Table 1]

Examples 9 to 11 The amount of TBPC used as a catalyst was 0.012 g (0.02 g).
Instead of 4 mmol, catalyst concentration: 2 mol% based on PGE, in the case of Example 9, 0.024 g (0.08 mmol, catalyst concentration: 4 mol% based on PGE), Example 10
0.035 g (0.12 mmol, catalyst concentration:
Exactly the same operation as in Example 1 except that the amount was 6 mol% based on PGE) and 0.059 g (0.20 mmol, catalyst concentration: 10 mol% based on PGE) in Example 11. Was done. Mn of the obtained white polymer,
And the insertion rates determined from the ¹ H-NMR spectrum data were as shown in Table 2, respectively. In Examples 9 to 11, the obtained polymer was analyzed by IR
From the results of the measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement, it was found that each of the obtained white polymers was an ordered polyaryl-alkyl carbonate represented by the general formula (X). Was. Then, from the results of Examples 9 to 11 and the result of Example 1 described above, it can be seen that the insertion ratio of PGE into the polymer and the molecular weight of the polymer decrease as the amount of the catalyst increases. This is because the amount of water contained in TBPC also increases with an increase in the amount of catalyst, so that the obtained polymer is easily hydrolyzed, and side reactions such as a ring closure reaction are also proceeding simultaneously with the hydrolysis. It is considered something.

Example 12 Instead of 0.012 g (0.04 mmol, catalyst concentration: 2 mol% based on PGE) of TBPC as a catalyst, tetra n-butylammonium chloride (hereinafter referred to as “TBA”) was used.
Except that 0.011 g (0.04 mmol, catalyst concentration: 2 mol% based on PGE) was used, the same operation as in Example 2 was performed, and 0.53 g (yield: 9
(6%) of a white polymer. As shown in Table 2, Mn and Mw / Mn of this polymer were 105, respectively.
00 and 1.67. The insertion ratio of the obtained polymer was 95%, as determined from ¹ H-NMR spectrum data. Further, from the results of IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement performed on the obtained polymer, the obtained white polymer was found to be an ordered polyaryl-alkyl represented by the general formula (X). It turned out to be carbonate.

Examples 13 to 16 In Example 13, tetra-n-butylammonium acetate (hereinafter referred to as "catalyst: 2 mol% based on PGE") was used in place of 0.012 g (0.04 mmol, catalyst concentration: 2 mol% based on PGE) as a catalyst. 0.012 g (abbreviated as "TBAAc").
04 mmol, catalyst concentration: 2 mol% based on PGE)
In the case of Example 14, 0.014 g of TBAB (0.0
4 mmol, catalyst concentration: 2 mol% based on PGE)
In the case of Example 15, 0.015 g of tetra n-butylammonium iodide (hereinafter abbreviated as “TBAI”)
(0.04 mmol, catalyst concentration: 2 mol% based on PGE), and in Example 16, tetra n-butylphosphonium bromide (hereinafter abbreviated as “TBPB”).
PGE was inserted into PC in exactly the same manner as in Example 2 except that 014 g (0.04 mmol, catalyst concentration: 2 mol% based on PGE) was used. The yield of the obtained white polymer, Mn and Mw / Mn, and the insertion ratio determined from ¹ H-NMR spectrum data were as shown in Table 2, respectively. In Examples 13 to 16, from the results of performing IR measurement, ¹ H-NMR measurement, and ¹³ C-NMR measurement on the obtained polymers, the obtained white polymers were each represented by the general formula (X). Is found to be an ordered polyaryl-alkyl carbonate represented by Example 1
From the results of 2 to 16 and the result of Example 2 described above, when TBPC, TBAC and TBAAc were used as the catalyst, a high insertion ratio and a relatively high molecular weight polymer were obtained. However, TBAB, TBPB and TBAI were used. In this case, it was found that the insertion rate and the molecular weight decreased in the order of TBAB, TBPB> TBAI. This is considered to be due to the fact that the insertion reaction largely depends on the nucleophilicity of the counter anion of the catalyst.

[0089]

[Table 2]

Examples 17 to 19 In Example 17, 18-crown-6-ether / chloride was used in place of 0.012 g (0.04 mmol, catalyst concentration: 2 mol% based on PGE) of TBPC as a catalyst. Potassium complex (hereinafter abbreviated as "18-C-6 / KCl complex") 0.014 g [0.04 mmol (18-C-6:
KCl = 0.011 g: 0.003 g), catalyst concentration: P
2 mol% based on GE], and 18-
Crown-6-ether / potassium bromide complex (hereinafter referred to as "1
8-6-C-6 / KBr complex ").
04 mmol (18-C-6: KBr = 0.011 g:
0.005 g), catalyst concentration: 2 mol% based on PGE]
And in the case of Example 19 an 18-crown-6-ether / potassium iodide complex (hereinafter "18-C-6 / K
Abbreviated as "I complex") 0.018 g [0.04 mmol (1
8-C-6: KI = 0.011 g: 0.007 g), catalyst concentration: 2 mol% based on PGE], except that PGE was inserted into PC in the same manner as in Example 2. Was done. The yield of the obtained white polymer, Mn and Mw / Mn, and the insertion ratio determined from ¹ H-NMR spectrum data were as shown in Table 3, respectively. In Examples 17 to 19, the obtained polymer was subjected to IR measurement, ¹ H-NMR measurement and ¹³ C
From the result of -NMR measurement, it was found that each of the obtained white polymers was an ordered polyaryl-alkyl carbonate represented by the general formula (X).

Comparative Example 1 The addition amount of TBPC as a catalyst was 0.012 g (0.0
The same operation as in Example 2 was carried out except that the amount was changed to 0 g instead of 4 mmol, the catalyst concentration: 2 mol% based on PGE), that is, the catalyst was not added at all.
As shown in Table 3, the insertion ratio of the obtained polymer obtained from ¹ H-NMR spectrum data was 0%, and it was confirmed that the target product, polyaryl-alkyl carbonate, was not obtained at all.

COMPARATIVE EXAMPLE 2 The catalyst was replaced with 0.012 g (0.04 mmol, catalyst concentration: 2 mol% based on PGE) of TBPC.
EA 0.004 g (0.04 mmol, catalyst concentration: PG
Example 2 except that 2 mol%) was used.
The same operation as described above was performed. Of the obtained polymer ¹ H-
The insertion ratio determined from the NMR spectrum data is shown in Table 3.
0%, as shown in the figure, the polyaryl-
It was confirmed that no alkyl carbonate was obtained. This is considered to be because TEA is a catalyst having a counter anion having low nucleophilicity, whereas the insertion reaction largely depends on the nucleophilicity of the counter anion of the catalyst.

Comparative Example 3 As a catalyst, tetra-n-butylammonium hexafluorophosphate (hereinafter abbreviated as “TBAPF ₆ ”) was used in place of 0.012 g (0.04 mmol, catalyst concentration: 2 mol% based on PGE) of TBPC. 0.016 g (0.
The same operation as in Example 2 was performed, except that the amount of the catalyst was 0.4 mmol and the catalyst concentration was 2 mol% based on PGE). As shown in Table 3, the insertion ratio of the obtained polymer obtained from ¹ H-NMR spectrum data was 0%, and it was confirmed that the target product, polyaryl-alkyl carbonate, was not obtained at all. This is presumably because TBAPF ₆ is a quaternary onium salt catalyst having a counter anion with low nucleophilicity, whereas the insertion reaction largely depends on the nucleophilicity of the counter anion of the catalyst.

[0094]

[Table 3]

Examples 20 to 24 In Example 20, 5 ml (monomer concentration: 0.2 ml / l) was used instead of 1.25 ml (monomer concentration: 0.8 ml / l) of the reaction solvent. Example 2
1, 2.5 ml (monomer concentration: 0.4 ml /
l), 2 ml in Example 22 (monomer concentration: 0.1
5 ml / l), 1.67 ml (monomer concentration: 0.6 ml / l) in Example 23, and 1.43 ml (monomer concentration: 0.7 ml / l) in Example 24. The same operation as in Example 17 was performed.
Yield of white polymer obtained, Mn and Mw / M
n and the insertion ratio determined from the ¹ H-NMR spectrum data were as shown in Table 4, respectively. Further, in Examples 20 to 24, from the results of performing IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement on the obtained polymer, the obtained white polymers were each represented by the general formula (X) Is found to be an ordered polyaryl-alkyl carbonate represented by From the results of Examples 20 to 24, it was found that 18-C-6 / KC
In the insertion reaction of PGE into PC using 1 complex,
As in the case of using TBPC as the catalyst (in the case of Examples 2 to 5), as the monomer concentration increases (that is, the amount of the reaction solvent decreases), the molecular weight and insertion ratio of the obtained polymer increase. However, when the monomer concentration is 0.7 mol / l, the insertion ratio is 1
00%.

Examples 25 and 26 The reaction time was changed to 24 hours, and
Time, in the case of Example 26, except for 72 hours,
In exactly the same manner as in Example 17, the insertion of PGE into the PC was
Responded. The yield of white polymer obtained, Mn and
And Mw / Mn, and¹H-NMR spectrum data
Are respectively as shown in Table 4.
there were. In Examples 25 and 26,
Measurement of the polymer ¹H-NMR measurement and
¹³From the result of the C-NMR measurement, the obtained white
The limers are each defined by the general formula (X).
May be an orderly polyaryl-alkyl carbonate
understood. The results of Examples 25 and 26, and
From the results of Example 17, as the reaction time was increased,
The molecular weight and insertion rate of the polymers produced tend to increase
It can be seen that the molecular weight distribution gradually widens.
Revealed. After 72 hours, the reaction solution is very viscous.
It was a terrible thing.

[0097]

[Table 4]

Example 27 Anisole 1.25 was replaced with chlorobenzene 1.25 ml (monomer concentration: 0.8 mol / l).
ml (monomer concentration: 0.8 mol / l), the same operation as in Example 2 was carried out to obtain 0.54 g
A white polymer (yield: 98%) was obtained. Mn and Mw / Mn of this polymer were 12100 and 1.80, respectively, as shown in Table 5. The insertion ratio of the obtained polymer was 93%, which was determined from ¹ H-NMR spectrum data. Further, the obtained polymer was subjected to IR measurement, ¹ H-NMR measurement and ¹³ C-N
From the result of the MR measurement, it was found that each of the obtained white polymers was an ordered polyaryl-alkyl carbonate represented by the general formula (X).

Examples 28 to 30 In Examples 28, 29 and 30, the reaction solvent was 1.25 ml of chlorobenzene (monomer concentration: 0.8 mol).
/ L), 1.25 ml of DMAc (concentration of monomer: 0.8 mol / l) and 1.25 ml of DMF, respectively
(Monomer concentration: 0.8 mol / l) and NMP1.
The same operation as in Example 2 was performed except that the amount was 25 ml (monomer concentration: 0.8 mol / l). The yield of the obtained white polymer, Mn and Mw / Mn, and the insertion ratio determined from ¹ H-NMR spectrum data were as shown in Table 5, respectively. In Examples 28 to 30, the obtained polymer was analyzed by IR.
From the results of the measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement, it was found that each of the obtained white polymers was an ordered polyaryl-alkyl carbonate represented by the general formula (X). Was. Examples 27 to 3
0 and the results of Example 2 described above, when an aprotic non-polar solvent such as chlorobenzene or anisole is used, the molecular weight and insertion ratio of the obtained polymer are relatively high, but the other It has been found that when a protic polar solvent is used, the resulting polymer has a low molecular weight and low insertion ratio. This causes hydrolysis of the obtained polymer by water in the polar solvent, and causes the same side reaction as when a polar solvent acts as a nucleophilic species and a catalyst having a highly nucleophilic counter anion is used, and the insertion rate is reduced. It is considered that the molecular weight and the molecular weight were reduced.

Examples 31 to 34 The reaction time was changed to 72 hours, and 6 hours (for Example 31), 12 hours (for Example 32), 18 hours (for Example 33) and 48 hours (for Example 33). Except in the case of Example 34), the P
GE insertion reaction was performed. M of the obtained white polymer
n and the insertion ratio determined from the ¹ H-NMR spectrum data were as shown in Table 5, respectively. Further, in Examples 31 to 34, from the results of performing IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement on the obtained polymer, the obtained white polymers were each represented by the general formula (X) Is found to be an ordered polyaryl-alkyl carbonate represented by From the results of Examples 31 to 34 and the results of Examples 1 and 2 described above, the molecular weight and the insertion ratio of the obtained polymer increase as the reaction time increases, but the molecular weight decreases to Mn = 5000 in the early stage of the reaction. It was suggested that hydrolysis and side reactions of the polymer obtained in the initial stage of the reaction were likely to occur.

[0101]

[Table 5]

Example 35 Insertion of PGE into PC in exactly the same manner as in Example 2 except that the amount of PGE used was changed to 0.300 g (2 mmol) to 0.361 g (2.4 mmol). The reaction was performed. The resulting white polymer had a yield of 0.55 g.
(Yield: 99%), Mn = 13800, Mw / M
n = 1.69. In addition, ¹ H of the obtained polymer
-Insertion rate determined from NMR spectrum data is 10
It was 0%. In addition, the IR
From the results of the measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement, it was found that the obtained white polymer was an ordered polyaryl-alkyl carbonate represented by the general formula (X).

Examples 36 and 37 The amount of PGE used was changed to 0.300 g (2 mmol).
In the case of Example 36, 0.421 g (2.8 mm
0.481 g (3.2 mm) in Example 37.
PC) in exactly the same manner as in Example 2 except that
A PGE insertion reaction was performed. White polymer obtained
Mn, and¹H-NMR spectrum data
The insertion rates obtained were as shown in Table 6.
Was. In Examples 36 and 37,
IR measurement on the limer, ¹H-NMR measurement and¹³C
-White polymer obtained from the result of NMR measurement
Is a regularity represented by the general formula (X),
It is found to be a polyaryl-alkyl carbonate.
Was. Results of Examples 35 to 37 and results of Example 1 described above
From the results, using 2 equivalents by using PGE in excess
100% insertion rate in less time than if
I understood. In addition, even if PGE is excessively used, the insertion rate is 10%.
Polyant that does not exceed 0% and already has 2 molecules of PGE inserted
No insertion reaction takes place in urea-alkyl carbonate.
It became clear that there was none. However, the molecular weight is
There is a tendency that the excess amount of PGE decreases,
Means that if the amount of PGE increases, the water present in the PGE
As the amount increases, the molecular weight decreases due to hydrolysis.
It is considered that this is also likely to occur.

[0104]

[Table 6]

[0105]

As described above, according to the present invention, a novel ordered polyaryl-alkyl carbonate having excellent mechanical strength, heat resistance, aging resistance, reactivity and the like can be obtained. Further, according to the method of the present invention, the insertion reaction of the oxirane into the polyaryl carbonate is carried out quantitatively and in a mild condition in the presence of a quaternary onium salt catalyst or a crown ether complex catalyst while suppressing side reactions. It can be performed regioselectively, and thus the above-mentioned polyaryl-alkyl carbonate can be efficiently produced. Therefore, the novel polyaryl-alkyl carbonates of the present invention can be used in household products,
Building materials, automotive parts, tools, machine parts, electrical appliances,
Various molded products such as electrical insulating materials, laminating agents, coating agents, films, sheet products, can be used in application fields such as epoxy resin curing agents, in particular, by utilizing the high reactivity of the polymer, The use of the new functional polymer as an excellent raw material for synthesis can be greatly expected.

[Brief description of the drawings]

FIG. 1 is a view showing a comparison between an IR spectrum of a polyaryl-alkyl carbonate obtained in Example 1 and an IR spectrum of a raw material polyaryl carbonate.

It is a diagram comparatively showing ¹ H-NMR spectrum of ¹ H-NMR spectrum and the raw material of polyaryl carbonate alkyl carbonate - [2] polyaryl obtained in Example 1.

It is a diagram comparatively showing ¹³ C-NMR spectrum of ¹³ C-NMR spectrum and the raw material of polyaryl carbonate alkyl carbonate - [3] polyaryl obtained in Example 1.

Claims (4)

[Claims] 1. A compound of the general formula (I) (However, in the general formula (I), R ₁ and R ₂ are each an alkyl group having 1 to 4 carbon atoms, and
₃ is And Wherein R ₄ is an allyl group, an acryloyl group, a methacryloyl group, or a substituent selected from the group consisting of
An alkyl group having 4 carbon atoms, R ₅ and R ₆ are each an alkyl group having 1 to 4 carbon atoms, and c and d are each an integer of 0 to 5) And a and b are each an integer of 0 to 4, and n is an integer of 2 or more. Note that R ₁ ,
R ₂ and R _{4 to} R ₆ may be the same or different from each other), or the following general formula (II): (However, in the general formula (II), R ₁ , R ₂ , a and b
Are respectively R ₁ , R ₂ , and R ₁ in the general formula (I).
the same meanings as a and b). 2. In the presence of a quaternary onium salt or a crown ether complex as a reaction catalyst, the following general formula (III): (Wherein, R ₁ and R ₂ are each an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and a and b are each an integer of 0 to 4 And n is an integer of 2 or more), to cyclohexene oxide and the following general formula (IV) (However, in the general formula (IV), R ₃ is And R ₄ is an allyl group, an acryloyl group, a methacryloyl group, or a substituent selected from 1-4.
An alkyl group having ₅ carbon atoms, and R ₅ and R
₆ is an alkyl group having 1 to 4 carbon atoms, and R _{4 to} R ₆ may be the same or different, and c and d are each an integer of 0 to 5) 2. The novel polyaryl-alkyl according to claim 1, wherein one kind of oxirane selected from the group consisting of the compounds represented by the formula is subjected to an insertion reaction at a ratio of 2 to 10 mol per 1 mol of the polyaryl carbonate. Method for producing carbonate. 3. The reaction catalyst is tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-butylammonium acetate, tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide 1, selected from the group consisting of tetra-n-butylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide and tetraphenylphosphonium iodide
The method for producing a novel polyaryl-alkyl carbonate according to claim 2, wherein the method is a kind or two or more kinds of quaternary phosphonium salts. 4. The reaction catalyst is selected from the group consisting of 18-crown-6-ether / potassium chloride complex, 18-crown-6-ether / potassium bromide complex and 18-crown-6-ether / potassium iodide complex. The method for producing a novel polyaryl-alkyl carbonate according to claim 2, wherein the method is one or more crown ether complexes.