WO2020008879A1

WO2020008879A1 - (meth)acrylate-terminated polycarbonate oligomer

Info

Publication number: WO2020008879A1
Application number: PCT/JP2019/024236
Authority: WO
Inventors: 充孝尾▲崎▼; 健須藤
Original assignee: 本州化学工業株式会社
Priority date: 2018-07-05
Filing date: 2019-06-19
Publication date: 2020-01-09
Also published as: JPWO2020008879A1; TW202006010A; KR20210029159A; CN112424259B; CN112424259A; TWI794523B; KR102637355B1; JP7253548B2

Abstract

The present invention addresses the problem of providing a (meth)acrylate-terminated polycarbonate oligomer as a starting material for a UV curable (meth)acrylic resin that is used as a UV curable hard coating agent or the like, said (meth)acrylate-terminated polycarbonate oligomer having excellent solvent solubility and excellent compatibility with a polyfunctional (meth)acrylic monomer. The present invention provides, as a solution, a (meth)acrylate-terminated polycarbonate oligomer which is characterized by being represented by formula (1) and/or formula (2) and by having a weight average molecular weight (Mw) within the range of from 500 to 10,000 (inclusive).

Description

Terminal (meth) acrylate polycarbonate oligomer

The present invention relates to a terminal (meth) acrylate polycarbonate oligomer having good solvent solubility.

Resin materials are widely used as engineering plastics because of their advantages such as light weight, low cost, and excellent workability.However, their surface hardness, scratch resistance, and chemical resistance are inferior to glass and metal. Therefore, it is not used as a substitute material as it is. In order to improve these disadvantages of the resin material, a hard coat treatment is performed to form a resin thin film of a material different from the base resin on the resin surface, protect the base resin from external factors, and modify the surface. Is commonly done. For the formation of the hard coat layer, a system is used in which a hard coat agent is applied to the resin surface of the base material, dried, and then irradiated with radiation such as an electron beam or ultraviolet rays (UV) as required, and then cured. (For example, Patent Documents 1 and 2). Above all, UV-curable hard coat agents using UV-curable resins can be processed at lower temperatures and in a shorter time than conventional hard coat agents. I have.
In this UV-curable hard coating agent, a polyfunctional (meth) acrylic monomer such as pentaerythritol (meth) acrylate is used as a main component. What has high compatibility is demanded.

JP 2010-024255 A JP 2016-011365 A

The present invention has been made in view of the above circumstances, and has been described as a raw material of a UV-curable (meth) acrylic resin used for a UV-curable hard coat agent and the like, which is compatible with a polyfunctional (meth) acrylic monomer. Another object of the present invention is to provide a terminal (meth) acrylate polycarbonate oligomer having excellent solvent solubility.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, in the terminal (meth) acrylate polycarbonate represented by the following formula (1) and / or (2), the weight average molecular weight (Mw) is specific. The present inventors have found that oligomers within the range have excellent compatibility with polyfunctional (meth) acrylic monomers and good solvent solubility, and have completed the present invention.

The present invention is as follows.
1. A terminal (meth) acrylate polycarbonate oligomer represented by the following formulas (1) and / or (2) and having a weight average molecular weight (Mw) in a range of 500 or more and 10,000 or less.

(In the formulas (1) and (2), R ₁ to R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, 8 represents an alkoxy group or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ₅ each independently represents a hydrogen atom or a methyl group, and R ₆ and R ₇ each independently represent hydrogen. X represents an atom or an alkyl group having 1 to 14 carbon atoms, X represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 or more, provided that R ₆ and R _{7 have} the same number of carbon atoms. Is not more than 14, and two oxygen atoms bonded to X do not bond to the same carbon atom of X.)

The terminal (meth) acrylate polycarbonate oligomer according to the present invention has a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less, so that it can be used with a polyfunctional (meth) acrylic monomer such as pentaerythritol-based (meth) acrylate. Since it has excellent compatibility and good solvent solubility, it is optimal as a raw material for a UV-curable hard coat agent, and exhibits an industrially advantageous effect that a smooth coating film can be formed by UV curing.

1 is a ¹ H-NMR spectrum chart of a terminal (meth) acrylate polycarbonate oligomer (1c) synthesized in Example 1. 5 is a ¹ H-NMR spectrum chart of a terminal (meth) acrylate polycarbonate oligomer (1d) synthesized in Example 2.

Hereinafter, the terminal (meth) acrylate polycarbonate oligomer of the present invention will be described in detail.
The terminal (meth) acrylate polycarbonate oligomer of the present invention is, as illustrated in the following reaction formula, a polycarbonate oligomer represented by the formula (A) and a (meth) acrylate agent such as (meth) acrylic acid chloride. A compound represented by the following formula (1) and / or (2) having a weight average molecular weight (Mw) in the range of 500 to 10,000 obtained by the reaction.

(The definitions of R ₁ to R ₇ , X, and n in the reaction formula are the same as in the above formulas (1) and (2).)

<About the polycarbonate oligomer represented by the formula (A)>
The chemical structure of the terminal (meth) acrylate polycarbonate oligomer of the present invention will be described by describing in detail the polycarbonate oligomer represented by the following formula (A), which is a raw material for the synthesis. That is, specific examples of R ₁ to R ₄ , R ₆ , R ₇ , X and n in the formula (A), preferred chemical groups and substituents thereof represent the terminal (meth) acrylate polycarbonate oligomer of the present invention. , And are the same as R ₁ to R ₇ , X, and n in the formula (1) or (2).

(The definitions of R ₁ to R ₇ , X, and n in the formula (A) are the same as those in the above formulas (1) and (2).)
In the above formula (A), when any of R ₁ , R ₂ , R ₃ and R ₄ is an alkyl group having 1 to 8 carbon atoms, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. It is a linear or branched alkyl group, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an isobutyl group. Such an alkyl group may have a substituent such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms, as long as the effects of the present invention are not impaired.
When any of R ₁ , R ₂ , R ₃ and R ₄ is a cycloalkyl group having 5 to 12 carbon atoms, the cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms. Specifically, for example, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group and the like can be mentioned. Examples of such a cycloalkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and phenyl groups as long as the effects of the present invention are not impaired. And the like.
When any of R ₁ , R ₂ , R ₃ and R ₄ is an alkoxy group having 1 to 8 carbon atoms, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. It is a chain alkoxy group, and specific examples include a methoxy group and an ethoxy group. Such an alkoxy group may have a substituent such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms, as long as the effects of the present application are not impaired.
Further, when any of R ₁ , R ₂ , R ₃ and R ₄ is an aromatic hydrocarbon group having 6 to 12 carbon atoms, the aromatic hydrocarbon group is specifically, for example, phenyl And naphthyl groups. In such an aromatic hydrocarbon group, for example, an alkyl group having 1 to 4 carbon atoms and / or an alkoxy group having 1 to 4 carbon atoms is in a range of 1 to 3 as long as the effects of the present invention are not impaired. It may be substituted.
The position where the substituents of R ₁ , R ₂ , R ₃ and R ₄ are bonded is preferably ortho to the oxygen atom bonded to the benzene ring.
In the above formula (A), when either R ₆ or R ₇ is an alkyl group having 1 to 14 carbon atoms, the alkyl group is preferably a linear or branched chain having 1 to 12 carbon atoms. Alkyl group, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group , N-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. However, the total number of carbon atoms of R ₆ and R ₇ must be 14 or less.
In the above formula (A), X is, specifically, an ethylene group, an n-propylene group, a propane-1,2-diyl group, an n-butylene group, a butane-1,3-diyl group, a butane-1, A 2-diyl group and a butane-2,3-diyl group, among which an ethylene group, an n-propylene group, a propane-1,2-diyl group and an n-butylene group are preferable, and an ethylene group, a propane-1,2 -Diyl group is more preferable, and ethylene group is particularly preferable.

As the polycarbonate oligomer represented by the formula (A), those produced by any conventionally known production method can be used. Specific examples include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Among them, it is industrially advantageous to use an interfacial polymerization method, a melt transesterification method, or a solid phase transesterification method of a prepolymer. Among them, a melt transesterification method using no phosgene and a solid phase transesterification method of a prepolymer by a melt transesterification method are particularly preferable. The above-mentioned production method is carried out using a dihydroxy compound represented by the following formula (B) and a carbonate ester-forming agent.

(The definitions of R ₁ to R ₄ , R ₆ , R ₇ and X in the formula (B) are the same as those in the above formulas (1) and (2).)

<About the dihydroxy compound represented by the formula (B)>
Specific examples of the dihydroxy compound represented by the formula (B) include, for example, bis (4- (2-hydroxyethoxy) phenyl) methane, 2,2-bis (4- (2-hydroxyethoxy) phenyl) Propane, 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) propane, 1,1-bis (4- (2-hydroxyethoxy) phenyl) ethane, 2,2-bis (4- (2-hydroxyethoxy) phenyl) -4-methylpentane, 2,2-bis (4- (2-hydroxyethoxy) phenyl) butane, 1,1-bis (4- (2-hydroxyethoxy) phenyl) dodecane, etc. Is mentioned.
In the polymerization reaction, such a dihydroxy compound may be used alone or as a mixture of two or more kinds at an arbitrary ratio.

<About carbonate ester forming agent>
Specific examples of the carbonate-forming agent to be reacted with the dihydroxy compound represented by the formula (B) include, for example, diaryl carbonate such as diphenyl carbonate, ditolyl carbonate, bis (m-cresyl) carbonate, dimethyl carbonate, diethyl Examples thereof include dialkyl carbonates such as carbonate and dicyclohexyl carbonate; alkylaryl carbonates such as methylphenyl carbonate, ethylphenyl carbonate and cyclohexylphenyl carbonate; and diester carbonates such as dialkenyl carbonate such as divinyl carbonate, diisopropenyl carbonate and dipropenyl carbonate. Furthermore, a dihalogenated carbonyl compound such as phosgene and the like, and triphosgene are also included. Of these, diaryl carbonate is preferred, and diphenyl carbonate is particularly preferred.

<About the melt transesterification method>
As a method for producing the polycarbonate oligomer represented by the formula (A), a melt transesterification method will be described.
In the case of using a dihydroxy compound represented by the formula (B) and diphenyl carbonate as a carbonate ester-forming agent, a method of the melt transesterification reaction is performed in the presence of a catalyst in an inert gas atmosphere at normal pressure or reduced pressure. The stirring is carried out while heating, and the formed phenol is distilled off. In general, the desired molecular weight and terminal hydroxyl group amount are adjusted by adjusting the mixing ratio of the dihydroxy compound represented by the formula (B) and the carbonate ester forming agent and the degree of reduced pressure during the transesterification reaction. The polycarbonate oligomer represented can be obtained.
In order to obtain the polycarbonate oligomer represented by the formula (A), the mixing ratio of the dihydroxy compound represented by the formula (B) and the carbonate-forming agent is based on 1 mol of the dihydroxy compound represented by the formula (B). The carbonic acid ester-forming agent is usually used in a molar amount of 0.2 to 1.0, preferably 0.25 to 0.95, more preferably 0.3 to 0.90.
In the case of the melt transesterification reaction, a transesterification catalyst is used as needed in order to increase the reaction rate. The transesterification catalyst is not particularly limited, and examples thereof include lithium, sodium, cesium hydroxides, carbonates, inorganic alkali metal compounds such as hydrogen carbonate compounds, alcoholates, and organic alkali metal compounds such as organic carboxylate. Alkali metal compounds; hydroxides such as beryllium and magnesium, inorganic alkaline earth metal compounds such as carbonates, alcoholates, organic alkaline earth metal compounds such as organic carboxylates, etc .; alkaline earth metal compounds such as tetramethylboron; Basic boron compounds such as sodium salts, calcium salts, and magnesium salts such as tetraethylboron and butyltriphenylboron; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine; or derived from these compounds Basic phosphorus compounds such as quaternary phosphonium salts; Use of a basic ammonium compound such as tramethylammonium hydroxide, tetraethylammonium hydroxide, or tetrabutylammonium hydroxide; known transesterification catalysts such as amine compounds such as 4-aminopyridine, 2-dimethylaminoimidazole, and aminoquinoline Can be. Among them, alkali metal compounds are preferable, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferable.
The amount of the catalyst used is within a range that does not cause a problem in the quality of the produced oligomer due to the catalyst residue, and a suitable addition amount varies depending on the type of the catalyst. ) Is usually 0.05 to 100 μmol, preferably 0.08 to 50 μmol, more preferably 0.1 to 20 μmol, and still more preferably 0.1 to 5 μmol, per 1 mol of the dihydroxy compound represented by the formula (1). . The catalyst may be added as it is, or may be added after being dissolved in a solvent. As the solvent, for example, a solvent that does not affect the reaction such as water and phenol is preferable.
Regarding the reaction conditions for the melt transesterification reaction, the temperature is usually in the range of 120 to 360 ° C, preferably in the range of 150 to 280 ° C, and more preferably in the range of 180 to 260 ° C. If the reaction temperature is too low, the transesterification does not proceed, and if the reaction temperature is too high, side reactions such as decomposition proceed, which is not preferable. The reaction is preferably performed under reduced pressure. The reaction pressure is preferably a pressure at which the carbonate forming agent as a raw material cannot be distilled out of the system at the reaction temperature, and a by-product such as phenol can be distilled off. Under such reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.

<About (meth) acrylation>
As exemplified in the above reaction formula, the terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) and / or (2) of the present invention comprises a polycarbonate oligomer represented by the formula (A) and (meth) It is obtained by reaction with a (meth) acrylate agent such as acrylic acid chloride.
Specific examples of the (meth) acrylic agent include acrylic acid chloride, methacrylic acid chloride, acrylic acid, methacrylic acid, and the like.
The amount of the (meth) acrylate agent used is determined based on the total terminal hydroxyl groups of the polycarbonate oligomer represented by the formula (A) when the (meth) acrylate polycarbonate oligomer having both ends is represented by the formula (1). The (meth) acrylate is used usually in an amount of 1.0 to 2.5 moles, preferably 1.1 to 2.0 moles, and more preferably 1.15 to 1.5 moles.
When a one-terminal (meth) acrylate polycarbonate oligomer represented by the formula (2) is obtained, a (meth) acrylate is usually added to all terminal hydroxyl groups of the polycarbonate oligomer represented by the formula (A). It is used in an amount of 0.5 to 1.5 moles, preferably 0.55 to 1.25 moles, and more preferably 0.6 to 1.0 moles.
For example, when a (meth) acrylic acid chloride is used to acrylate a polycarbonate oligomer represented by the formula (A), chloride ions are generated in the form of hydrogen chloride. Therefore, it is preferable to use a hydrogen chloride scavenger in combination. . As a hydrogen chloride scavenger, any basic substance can be used. As the inorganic basic substance, an alkali metal carbonate or bicarbonate can be used. Tertiary amines can be used as the organic basic substance. Examples of the tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl-diamylamine, N, N- Aliphatic amines such as diisopropylethylamine, N, N-dimethyl-cyclohexylamine, N, N-diethyl-cyclohexylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline; pyridine, picoline, N Heterocyclic amines such as N, N-dimethylaminopyridine; Fats such as 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene And cyclic amines.
The amount of the hydrogen chloride scavenger to be used is 0.8 to 10 moles, preferably 0.9 to 8 moles, particularly preferably 0.9 mole, relative to the moles of the (meth) acrylate agent usually used. Is about 1.0 to 7 times mol. If the amount of the hydrogen chloride scavenger is less than 0.8 times the number of moles of the (meth) acrylate, the generated hydrogen chloride cannot be completely captured, and the polycarbonate oligomer represented by the formula (A) as a raw material or the target substance cannot be used. There is a possibility that the terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) or (2) will be decomposed to lower the purity of the target product. On the other hand, if the amount of the hydrogen chloride scavenger exceeds 10 times the number of moles of the (meth) acrylate, the removal of the hydrogen chloride scavenger is not only complicated but also not economical, which is not preferable.

In this (meth) acrylation reaction, the solvent used may be any solvent that can uniformly mix the used raw materials and the like, and specifically, halogenated hydrocarbons such as methylene chloride, tetrahydrofuran, dioxane, Chlorobenzene and the like can be mentioned. The amount of the solvent used is not particularly limited, but is usually 0.5 to 100 times by weight, preferably 1 to 50 times by weight, particularly preferably 2 to 10 times by weight, based on the polycarbonate oligomer represented by the formula (A). Weight times.
The (meth) acrylation reaction is carried out at a relatively low temperature, usually at -50 to 100 ° C, preferably at -30 to 80 ° C, particularly preferably at -15 to 60 ° C. If the reaction temperature exceeds 100 ° C., a side reaction occurs, leading to a decrease in the yield of the target product. On the other hand, when the temperature is lower than -50 ° C., the reaction rate becomes slow and the required time is too long, which is not economical.
As a reaction procedure, a method in which a polycarbonate oligomer represented by the formula (A) and a (meth) acrylate are mixed in a solvent in advance and a hydrogen chloride scavenger is added thereto, )) And a hydrogen chloride scavenger in a solvent, and adding a (meth) acrylate to the mixture. In these methods, the hydrogen chloride scavenger or the (meth) acrylic agent to be added later may be used after being diluted with a solvent.
During the reaction, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-di-tert-butyl-4-methylphenol (BHT) and the like may be added as a polymerization inhibitor.

<Post-treatment and purification of (meth) acrylation>
In the (meth) acrylation reaction, a basic substance which is a hydrogen chloride scavenger is often added in excess, and especially an organic basic substance is represented by the formula (1) and / or (2) which is the target substance. Since it remains in the organic solvent together with the terminal (meth) acrylate polycarbonate oligomer represented and easily causes undesired phenomena such as coloring and decomposition, it is preferable to remove it by washing after the reaction. In order to wash and remove the organic basic substance, it is preferable to wash with an aqueous solution of an acidic substance. The acidic substance to be used is not particularly limited, but examples of the inorganic acidic substance include hydrochloric acid, sulfuric acid, and nitric acid, and examples of the organic acidic substance include, for example, formic acid, acetic acid, and propionic acid. Carboxylic acids such as butyric acid; and sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid. Among them, an organic acidic substance having a low acidity is more preferable. After removing the hydrogen chloride scavenger, it is preferable to subsequently carry out water washing.
It is preferable that the obtained terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) and / or (2) is obtained as a precipitate by adding a poor solvent to a dissolved solution. Specific examples of the poor solvent include an aliphatic alcohol solvent having 1 to 6 carbon atoms such as methanol, ethanol, and propanol, or a mixture of the aliphatic alcohol solvent and water.

<About terminal (meth) acrylate polycarbonate oligomer>
Specific examples of preferred compounds of the terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) and / or (2) of the present invention are shown below.

Preferred compounds of the both-terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) are as follows. N in the formulas (1a) to (1d) is an integer of 1 or more, and the weight average molecular weight (Mw) is in the range of 500 to 10,000.

Preferred compounds of the one-terminal (meth) acrylate polycarbonate oligomer represented by the formula (2) are as follows. In the formulas (2a) to (2d), n is an integer of 1 or more, but the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.

The terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) and / or (2) of the present invention has a weight average molecular weight (Mw) in a range of 500 or more and 10,000 or less, and among them, 1,000 or more. The range is preferably 8,000 or less, more preferably 2,000 or more and 6,000 or less. It is preferable that the weight average molecular weight (Mw) is within this range, since good solubility in an organic solvent can be obtained.
When the terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) and / or (2) of the present invention is used as a component of a UV-curable hard coat agent, a pentaerythritol-based Since it has excellent compatibility with polyfunctional (meth) acrylic monomers such as (meth) acrylate, it has an industrially advantageous effect that a smooth coating film can be formed by UV curing.
The terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) and / or (2) of the present invention can be used as a raw material for a 3D printer or a heat source such as an epoxy resin in addition to a raw material for a UV-curable hard coat agent. Useful as a modifier for cured resins.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
The weight average molecular weight (Mw) in the following examples was measured by gel permeation chromatography. The analysis method is as follows.
<Analysis method>
1. Gel permeation chromatography (oligomer analysis)
Equipment: Tosoh Corporation HLC-8320GPC
Flow rate: 0.35 ml / min, mobile phase: tetrahydrofuran, injection volume: 10 μl
Column: TSKgel guardcolumn SuperMP (HZ) -N, TSKgel SuperMultipore HZ-N x 3 detectors: RI,
Analysis method: Relative molecular weight in terms of polystyrene.
Polystyrene standard: A-500, A-2500, A-5000, F-1, F-2, F-4 manufactured by Tosoh Corporation
(Polymer analysis)
Equipment: Tosoh Corporation HLC-8320GPC
Flow rate: 1.0 ml / min, mobile phase: tetrahydrofuran, injection volume: 100 μl
Column: TSKgel guardcolumn HXL-L TSKgel G2000HXL x 2 + TSKgel G3000HXL + TSKgel G4000HXL
Detector: RI,
Analysis method: Relative molecular weight in terms of polystyrene.
Polystyrene standard product: PStQuick E, F manufactured by Tosoh Corporation (E: F-40, F-4, A-5000, A-1000, F: F-20, F-2, A-2500, A-500)
2. Measurement of terminal hydroxyl concentration Using ¹ H-NMR, using TCE (1,1,1,2-tetrachloroethane) as an internal standard, using bisphenol A and bisphenol C as samples, and preparing a calibration curve of the weight ratio with TCE did. The phenol terminal weight was determined by a method for determining the phenol terminal weight from this calibration curve.
Apparatus: Ascend ™ 400 manufactured by BRUKER
2. Measurement conditions: room temperature, 120 integrations Identification of Chemical Structure It was carried out by ¹ H-NMR measurement using the same apparatus as in “2.” above.

<Reference Example 1> Synthesis of polycarbonate oligomer (Aa)

In a four-necked flask equipped with a thermometer, stirrer, and condenser, 388.6 g (1.1 mol) of 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) propane and diphenyl carbonate 169 were added. After charging the reaction vessel with nitrogen, 0.82 g of a 0.09% cesium carbonate aqueous solution was added at 110 ° C. After the temperature was raised to 200 ° C., the degree of vacuum was adjusted to 0.3 kPa, and the reaction was carried out for 2 hours while distilling off the generated phenol, to obtain 383.4 g of a reaction-terminated liquid.
Next, 372.6 g of the obtained reaction-terminated liquid was charged into a four-necked flask equipped with a thermometer, a stirrer, and a cooler, dissolved in 745.2 g of toluene, and 2235.6 g of methanol was added. For a minute. The solution of the upper layer separated by standing for 30 minutes was drawn out, 558.9 g of toluene and 2235.6 g of methanol were added to the obtained lower layer solution, and the same stirring, standing, and extraction of the upper layer solution were performed twice. . Thereafter, the solvent was concentrated to obtain 193.5 g of a polycarbonate oligomer (Aa). The weight average molecular weight of the obtained polycarbonate oligomer was 4630 (gel permeation chromatography), and the terminal hydroxyl concentration was 0.67 mmol / g.

<Example 1> Synthesis of terminal acrylate polycarbonate oligomer (1c) 80.3 g of the polycarbonate oligomer (Aa) obtained in Reference Example 1 was placed in a four-necked flask equipped with a thermometer, a stirrer, and a cooler. After the atmosphere in the reaction vessel was replaced with nitrogen, 7.3 g (0.08 mol) of acrylic acid chloride, 120.5 g of dichloromethane and 4.0 mg of methquinone were added under a nitrogen stream. At 10 ° C., a mixed solution of 10.9 g (0.11 mol) of triethylamine and 40.2 g of dichloromethane was added over 2 hours. After further stirring at 10 ° C. for 1 hour, 825 g of water and 960 g of methanol were added. After stirring for 1 hour, the solution of the upper layer separated by standing was taken out, and 960 g of methanol was further added and stirred. After stirring for 1 hour, the solution of the upper layer separated by standing was drawn out, and 320 g of methanol was further added and stirred. After stirring for 2 hours, the precipitate was separated by filtration and dried to obtain 79.3 g of a powdery terminal acrylate polycarbonate oligomer (1c).
The weight average molecular weight of the obtained terminal acrylate polycarbonate oligomer (1c) was 5,211 (gel permeation chromatography). ^{From the result of the 1} H-NMR analysis, it was confirmed that it was an acrylate polycarbonate oligomer having both ends represented by the above formula (1c). FIG. 1 shows a ¹ H-NMR spectrum chart of the obtained terminal acrylate polycarbonate oligomer (1c).
When 2.0 g of the obtained terminal acrylate polycarbonate oligomer (1c) and 10.0 g of cyclohexanone were mixed, a transparent solution was obtained. Further, when 8.0 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 0.5 g of Irgacure (184) were mixed, a clear solution was obtained.
The obtained terminal acrylate polycarbonate oligomer (1c) showed good solubility in organic solvents such as cyclohexanone, and was found to be excellent in compatibility with pentaerythritol tetraacrylate which is a polyfunctional acrylate.

<Example 2> Synthesis of terminal methacrylate polycarbonate oligomer (1d) 96 g of the polycarbonate oligomer (Aa) obtained in Reference Example 1 was charged into a four-necked flask equipped with a thermometer, a stirrer, and a cooler, and reacted. After the vessel was replaced with nitrogen, 8.5 g (0.08 mol) of methacrylic acid chloride, 120.4 g of dichloromethane, and 4.6 mg of methquinone were added under a nitrogen stream. At 10 ° C., 10.9 g (0.11 mol) of triethylamine was added over 30 minutes. After stirring was further continued at 10 ° C. for 2 hours, 825 g of water and 960 g of methanol were added. After stirring for 1 hour, the solution of the separated upper layer was left standing and separated, and 960 g of methanol was further added and stirred. After stirring for 2 hours, the precipitate was filtered off, and a washing step of redispersing the obtained wet cake in 960 g of methanol was performed. Thereafter, the precipitate was separated by filtration and dried to obtain 56.1 g of a powdery terminal methacrylate polycarbonate oligomer (1d).
The weight average molecular weight of the obtained terminal methacrylate polycarbonate oligomer (1d) was 4,734 (gel permeation chromatography). ^{From the} result of ¹ H-NMR analysis, it was confirmed that the oligomer was a methacrylate polycarbonate oligomer having both ends represented by the above formula (1d). FIG. 2 shows a ¹ H-NMR spectrum chart of the obtained terminal methacrylate polycarbonate oligomer (1d).
When 2.0 g of the obtained terminal methacrylate polycarbonate oligomer (1d) and 10.0 g of cyclohexanone were mixed, a transparent solution was obtained. Further, when 8.0 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 0.5 g of Irgacure (184) were mixed, a clear solution was obtained.
The resulting terminal methacrylate polycarbonate oligomer (1d) showed good solubility in organic solvents such as cyclohexanone, and was found to be excellent in compatibility with pentaerythritol tetraacrylate, which is a polyfunctional acrylate.

Comparative Example 1 Synthesis of Terminal Diacrylic Polycarbonate In a four-necked flask equipped with a thermometer, a stirrer, and a condenser, 246.1 g (1.08 mol) of 2,2-bis (4-hydroxyphenyl) propane was added. 237.1 g (1.12 mol) of diphenyl carbonate was added, the reaction vessel was purged with nitrogen, and at 110 ° C., 0.9 g of a 0.08% cesium carbonate aqueous solution was added. After the temperature was raised to 220 ° C., the reaction was carried out at normal pressure for 40 minutes, and while the generated phenol was distilled, the degree of vacuum was raised to 13.3 kPa over 80 minutes. After the temperature was raised to 240 ° C., the pressure was reduced over 40 minutes. Was set to 0.8 kPa. The temperature was further raised to 285 ° C., and the reaction was performed at 0.7 kPa for 7 hours. 250 g of the reaction-terminated liquid was obtained.
Next, a solution obtained by dissolving 150.0 g of the obtained reaction-terminated liquid in 530.0 g of dichloromethane was dropped into 1850 g of methanol to precipitate the desired product. After stirring for 1 hour, the precipitate was separated by filtration and dried to obtain a powdery polycarbonate.
The weight average molecular weight of the obtained polycarbonate was 31,240 (gel permeation chromatography), and the terminal hydroxyl concentration was 0.13 mmol / g.
Next, 13.6 g of the obtained polycarbonate was placed in a four-necked flask equipped with a thermometer, a stirrer, and a cooler, and the reaction vessel was replaced with nitrogen. Then, 0.3 g (0.003 mol) of acrylic acid chloride was added. After adding 47.6 g of dichloromethane under a nitrogen stream, 0.4 g (0.004 mol) of triethylamine was added at 15 ° C. After stirring for 2 hours, the reaction solution was added to 163 g of methanol to precipitate the desired product. Thereafter, the precipitate was separated by filtration and dried, and 14.1 g of the obtained wet cake was dissolved in 47.6 g of dichloromethane. The solution was added to 163 g of methanol to precipitate. Thereafter, the precipitate was separated by filtration and dried to obtain 13 g of a white powdery compound.
From the result of ¹ H-NMR analysis of the obtained compound, it was confirmed that it was a terminal diacryl polycarbonate.
8.0 g of cyclohexanone was used with respect to 0.4 g of terminal diacryl polycarbonate, but did not dissolve. Further, a mixture of 0.6 g of terminal diacrylic polycarbonate, 2.4 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 3.0 g of dichloromethane, using dichloromethane instead of cyclohexanone, is in a cloudy state, and a transparent solution is obtained. I couldn't get it.

According to the above results, the terminal (meth) acrylate polycarbonate oligomer represented by the formula (1) and / or (2) of the present invention has a weight average molecular weight (Mw) within a specific range. It has been found that the compound has good solubility in a solvent and has excellent compatibility with a polyfunctional acrylate or the like.

Claims

A terminal (meth) acrylate polycarbonate oligomer represented by the following formulas (1) and / or (2) and having a weight average molecular weight (Mw) in a range of 500 or more and 10,000 or less.

(In the formulas (1) and (2), R 1 to R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, 8 represents an alkoxy group or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R 5 each independently represents a hydrogen atom or a methyl group, and R 6 and R 7 each independently represent hydrogen. X represents an atom or an alkyl group having 1 to 14 carbon atoms, X represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 or more, provided that R 6 and R 7 have the same number of carbon atoms. Is not more than 14, and two oxygen atoms bonded to X do not bond to the same carbon atom of X.)