TW202006010A - Terminal (meth)acrylate polycarbonate oligomer - Google Patents

Abstract

An objective of the present invention is to provide a terminal (meth)acrylate polycarbonate oligomer which acts as a raw material for UV curable (meth)acrylic resins used in UV curable hard coating agents, or the like, and has excellent compatibility with polyfunctional (meth)acrylic monomers and solvent solubility. As a solution, the present invention provides a terminal (meth)acrylate polycarbonate oligomer represented by the formula (1) and/or (2), and has a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less.

Description

Terminal (meth)acrylate polycarbonate oligomer

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

Resin materials are widely used as engineering plastics because of their advantages such as light weight, low cost, and excellent processability. However, they are not because of poor surface hardness, scratch resistance, chemical resistance, etc. compared to glass and metal systems. Used directly as a substitute material. In order to improve these shortcomings of resin materials, a hard coating process is usually performed. This hard coating process is to form a resin film made of a different material from the resin of the substrate on the surface of the resin to protect the resin of the substrate from external factors The effect is to seek surface modification. The hard coat layer is formed by applying a hard coat agent to the resin surface of the base material and drying it, and then irradiating with electron beams, ultraviolet rays (UV), or other radiation to harden it if necessary (for example, Patent Documents 1 and 2). Among them, the UV-curable hard coating agent using a UV-curable resin can be processed at a low temperature and in a short time compared to the conventional hard coating agent system, so it is highly productive and develops various applications.

Since this UV-curable hard coating agent uses polyfunctional (meth)acrylic monomers such as neopentyl alcohol (meth)acrylate as the main component, it is required that the formulated component system and these polyfunctional (meth) ) Those with higher compatibility of acrylic monomers.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2010-024255

[Patent Document 2] Japanese Patent Application Publication No. 2016-011365

The present invention was created in view of the above circumstances, and aims to provide a terminal (meth)acrylate polycarbonate oligomer which is used as a UV When a raw material of UV-curable (meth)acrylic resin such as a hardening type hard coat agent is used, it is a compound having excellent compatibility with a polyfunctional (meth)acrylic monomer and excellent solvent solubility.

In order to solve the above-mentioned problems, the inventors have carefully studied and found that the weight average molecular weight (Mw) in the terminal (meth)acrylate polycarbonate represented by the following formula (1) and/or formula (2) is specific The oligomers in the range are excellent in compatibility with polyfunctional (meth)acrylic monomers and have good solvent solubility, and the present invention has been completed.

The present invention is as follows.

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

(式(1)、式(2)中，R₁至R₄係各自獨立地表示氫原子、碳原子數1至8的烷基、碳數5至12的環烷基、碳原子數1至8的烷氧基、或碳原子數6至12的芳香族烴基，R₅係各自獨立地表示氫原子或甲基，R₆、R₇係各自獨立地表示氫原子或碳原子數1至14的烷基，X係表示碳原子數2至4的伸烷基，n為1以上的整數；惟，R₆及R₇的碳原子數之合計為14以下，鍵結於X之2個氧原子並不鍵結在X的同一個碳原子上)。

(In formula (1) and formula (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, and 1 to 1 carbon atom) 8 alkoxy groups, or aromatic hydrocarbon groups 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 a hydrogen atom or 1 to 14 carbon atoms Alkyl group, X represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 or more; however, the total number of carbon atoms of R ₆ and R ₇ is 14 or less, which is bonded to two oxygens of X The atom is not bonded to the same carbon atom of X).

According to the terminal (meth)acrylate polycarbonate oligomer of the present invention, since the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less, it is multifunctional with neopentyl alcohol (meth)acrylate and the like. (Meth)acrylic monomer has excellent compatibility and good solvent solubility, so it is most suitable as a raw material for UV-curing hard coating agent, and it can play a role in forming a smooth coating film by UV curing. For beneficial effects.

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

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

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 a compound represented by the following formula (1) and/or the following formula (2), and the following formula (1) and/or the following formula ( 2) The compound represented by the following reaction formula can be obtained by reacting a polycarbonate oligomer represented by formula (A) with a (meth)acrylating agent such as (meth)acryloyl chloride. Those having a weight average molecular weight (Mw) of 500 or more and 10,000 or less.

or

(反應式中的R₁至R₇、X、n之定義係與上述的式(1)、式(2)相同)。

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

<About polycarbonate oligomer represented by formula (A)>

The chemical structure of the terminal (meth)acrylate polycarbonate oligomer of the present invention is explained in detail by the polycarbonate oligomer represented by the following formula (A) of its synthetic raw material get on. That is, the specific examples of R ₁ to R ₄ , R ₆ , R ₇ , X, n in formula (A), preferred chemical groups and substituents thereof, etc. are related to the terminal (methyl ) R ₁ to R ₇ , X, and n in the formula (1) or formula (2) of the acrylate polycarbonate oligomer are the same.

(式(A)中的R₁至R₇、X、n的定義係與上述的式(1)、式(2)相同)。

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

In the above formula (A), when any one 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 1 to 4 carbon atoms The linear or branched chain alkyl group specifically includes, for example, methyl, ethyl, n-propyl, isopropyl, isobutyl and the like. Such an alkyl group may have a substituent such as a phenyl group and an alkoxy group having 1 to 4 carbon atoms in a range that does not impair the effects of the present invention.

When any one 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 Examples of the above include cyclohexyl, cyclopentyl, and cycloheptyl. Such a cycloalkyl group may have, for example, a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group within a range that does not impair the effects of the present invention Etc. substituents.

Furthermore, when any one 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 chain having 1 to 4 carbon atoms The alkoxy group in the form of a branch or a chain may be specifically exemplified by methoxy, ethoxy and the like. Such an alkoxy group may have a substituent such as a phenyl group, an alkoxy group having 1 to 4 carbon atoms and the like within a range that does not impair the effects of the present application.

In addition, when any one of R ₁ , R ₂ , R ₃ and R ₄ is an aromatic hydrocarbon group having 6 to 12 carbon atoms, specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group . Such an aromatic hydrocarbon group may be within a range that does not impair the effects of the present invention, for example, an alkyl group having 1 to 4 carbon atoms and/or an alkoxy group having 1 to 4 carbon atoms is substituted by about 1 to 3.

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 of the pair.

In the above formula (A), when any one of R ₆ and R ₇ is an alkyl group having 1 to 14 carbon atoms, the alkyl group is preferably a linear or branched carbon atom having 1 to 12 carbon atoms. Branched-chain alkyl, specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl , N-nonyl, n-decyl, n-eleven, n-twelve, etc. However, the total number of carbon atoms of R ₆ and R ₇ must be 14 or less.

In the above formula (A), X specifically represents ethylidene, n-propylene, propane-1,2-diyl, n-butylene, butane-1,3-diyl, butane- 1,2-diyl, butane-2,3-diyl, especially ethyl, n-propyl, propane-1,2-diyl, n-butyl, preferably ethyl, propane -1,2-Diyl is more preferred, and ethylidene is particularly preferred.

The polycarbonate oligomer represented by formula (A) can be produced by any conventionally well-known production method. Specifically, for example, there may be mentioned 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, the solid-phase transesterification method using the interfacial polymerization method, the melt transesterification method, and the prepolymer is particularly industrially advantageous. Among these methods, the melt transesterification method without using phosgene and the solid phase transesterification method of the prepolymer by the melt transesterification method are particularly preferable. The above production method is performed using a dihydroxy compound represented by the following formula (B) and a carbonate forming agent.

(式(B)中的R₁至R₄、R₆、R₇、X的定義係與上述的式(1)、式(2)相同)。

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

<About dihydroxy compound represented by formula (B)>

Specific examples of the dihydroxy compound represented by formula (B) include bis(4-(2-hydroxyethoxy)phenyl)methane, 2,2-bis(4-(2-hydroxyethyl Oxy)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)benzene Group) butane, 1,1-bis (4- (2-hydroxyethoxy) phenyl) dodecane and so on.

In the polymerization reaction, such a dihydroxy compound may be used alone, or two or more kinds may be mixed and used in an arbitrary ratio.

<About carbonate forming agent>

Examples of the carbonate forming agent that reacts with the dihydroxy compound represented by formula (B) include, for example, diphenyl carbonate, di(tolyl) carbonate (ditolyl carbonate), and bis(carbonate). Diaryl carbonates such as tolyl) esters; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dicyclohexyl carbonate; methyl phenyl carbonate, ethyl phenyl carbonate, and cyclohexyl phenyl carbonate Such as alkyl aryl carbonate; or divinyl carbonate, diisopropylene carbonate, dipropylene carbonate and other diene carbonate and other carbonate diesters. Moreover, dihalogenated carbonyl compounds, such as phosgene, and triphosgene can also be mentioned. Among these, diaryl carbonate is preferred, and diphenyl carbonate is particularly preferred.

<About molten transesterification method>

As a method for producing a polycarbonate oligomer represented by formula (A), a melt transesterification method will be described.

As a method of molten transesterification reaction, when the dihydroxy compound represented by formula (B) and diphenyl carbonate as a carbonate forming agent are used, it is inert at normal pressure or reduced pressure in the presence of a catalyst The gas atmosphere is heated while stirring, and the generated phenol is distilled off. Generally speaking, by adjusting the mixing ratio of the dihydroxy compound represented by formula (B) and the carbonate forming agent, and the degree of reduced pressure during the transesterification reaction, the formula (A) adjusted to the desired molecular weight and the amount of terminal hydroxyl groups can be obtained ) Indicates a polycarbonate oligomer.

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 1 mole relative to the dihydroxy compound represented by the formula (B) The carbonate forming agent used is usually 0.2 to 1.0 mole times, preferably 0.25 to 0.95 mole times, more preferably 0.3 to 0.90 mole times.

In the melt transesterification reaction, in order to increase the reaction rate, a transesterification catalyst can be used as necessary. The transesterification catalyst is not particularly limited. For example, inorganic alkali metal compounds such as hydroxides of lithium, sodium and cesium, carbonates and bicarbonates, organic bases such as alcoholates and organic carboxylates can be used. Alkali metal compounds such as metal compounds; alkaline earth metal compounds such as hydroxides of beryllium and magnesium, inorganic alkaline earth metal compounds such as carbonates, organic alkaline earth metal compounds such as alcoholates and organic carboxylates; tetramethylboron, tetraethyl Basic boron compounds such as sodium salts, calcium salts, magnesium salts such as boronic acid, butyl triphenyl boron, etc.; trivalent phosphorus compounds such as triethylphosphine, tri-n-propylphosphine, or the fourth grade derived from these compounds Basic phosphorus compounds such as phosphonium salts; basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; 4-aminopyridine, 2-dimethylaminoimidazole, and aminoquinoline Well-known transesterification catalysts such as amine compounds. Among them, alkali metal compounds are particularly preferred, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferred.

The amount of catalyst used can be used within a range that does not cause problems in the quality of oligomers generated due to catalyst residues, and the preferred amount of addition will vary depending on the type of catalyst and cannot be generalized, but generally For example: relative to 1 mole of the dihydroxy compound represented by formula (B), it is usually 0.05 to 100 micromolar (μmol), preferably 0.08 to 50 micromolar, more preferably 0.1 to 20 micromolar, Still more preferably, it is 0.1 to 5 micromolar. The catalyst may be added directly or dissolved in a solvent. The solvent is preferably water or phenol, which does not affect the reaction.

The reaction conditions of the molten transesterification reaction are 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. When the reaction temperature is too low, the transesterification reaction cannot be carried out, and when the reaction temperature is high, side reactions such as decomposition reaction are carried out, which is not good. The reaction system is preferably carried out under reduced pressure. The reaction pressure is preferably such that the carbonate forming agent of the raw material does not distill out of the system at the reaction temperature, and the by-products 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 formula (1) and/or formula (2) of the present invention is a polycarbonate represented by formula (A) The oligomer is obtained by the reaction of (meth)acrylic agent such as (meth)acryloyl chloride.

Specific examples of (meth)acrylating agents include acrylic chloride, methacrylic chloride, acrylic acid, and methacrylic acid.

When obtaining both terminal (meth)acrylate polycarbonate oligomers represented by formula (1), (meth)acrylating agent The amount used is usually 1.0 to 2.5 mole times, preferably 1.1 to 2.0 mole times, more preferably 1.15 to 1.5 mole times.

When a (meth)acrylate polycarbonate oligomer having one terminal represented by formula (2) is obtained, the (meth)acrylating agent is relative to all terminal hydroxyl groups of the polycarbonate oligomer represented by formula (A) The amount used is usually 0.5 to 1.5 mole times, preferably 0.55 to 1.25 mole times, more preferably 0.6 to 1.0 mole times.

For example, when (meth)acryloyl chloride is used to acrylate the polycarbonate oligomer represented by formula (A), since chloride ions are generated in the form of hydrogen chloride, it is preferable to use a hydrogen chloride supplement. Hydrogen chloride supplements can be used if they are alkaline substances. Inorganic alkaline substances can be used: alkali metal carbonates, bicarbonates, etc. For organic alkaline substances, tertiary amines can be used. Examples of the tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl Aliphatic amines such as di-pentylamine, N,N-diisopropylethylamine, N,N-dimethyl-cyclohexylamine, N,N-diethyl-cyclohexylamine; N,N-di Aromatic amines such as toluidine, N,N-diethylaniline; heterocyclic amines such as pyridine, picoline, N,N-dimethylaminopyridine; 1,8-diazabicyclo[5.4 .0] Alicyclic amines such as undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, etc.

The amount of hydrogen chloride supplement used is usually 0.8 to 10 times the molar amount, preferably 0.9 to 8 times the molar amount, particularly preferably 1.0 to 7 times the molar amount relative to the number of moles of the (meth)acrylating agent used Around ears. When the molar number of hydrogen chloride supplement relative to the (meth)acrylic agent is less than 0.8 times, the generated hydrogen chloride cannot be completely captured, and the polycarbonate represented by the raw material formula (A) is oligomerized. The terminal (meth)acrylate polycarbonate oligomer represented by the formula (1) or formula (2) of the target or target decomposes, which may cause the purity of the target to decrease. In addition, when the number of moles of hydrogen chloride supplement relative to the (meth)acrylic agent is more than 10 times the number of moles, not only the removal of hydrogen chloride supplement becomes cumbersome, but also the economic efficiency is poor, so it is not good.

烷、氯苯等。溶劑的使用量並無特別限定，通常係相對於式(A)表示之聚碳酸酯寡聚物為0.5至100重量倍，較佳為1至50重量倍，特佳為2至10重量倍。 In this (meth)acrylation reaction, the solvent used may be a solvent that can uniformly mix the raw materials used, and specific examples include halogenated hydrocarbons such as dichloromethane and tetrahydrofuran. ,two

Alkane, chlorobenzene, etc. The amount of the solvent used is not particularly limited, but it is usually 0.5 to 100 times the weight of the polycarbonate oligomer represented by the formula (A), preferably 1 to 50 times the weight, and particularly preferably 2 to 10 times the weight.

The reaction of (meth)acrylation is carried out at a relatively low temperature, usually -50 to 100°C, preferably -30 to 80°C, particularly preferably -15 to 60°C. When the reaction temperature exceeds 100°C, a side reaction occurs, and the yield of the target product is reduced. In addition, when the temperature is less than -50℃, the reaction speed becomes slow and the time spent is too long, and the economic benefit is poor.

The reaction procedure includes: mixing the polycarbonate oligomer represented by the formula (A) and the (meth)acrylating agent in a solvent in advance, and then adding a hydrogen chloride supplement to it; first expressing the formula (A) The polycarbonate oligomer and the hydrogen chloride supplement are mixed in the solvent, and then add the (meth) acrylate agent. In these methods, the subsequently added hydrogen chloride supplement and (meth)acrylic agent can also be used in a diluted state with a solvent.

、2,6-二-第三丁基-4-甲酚(BHT)等作為聚合抑制劑。 In addition, during the reaction, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine may be added

, 2,6-di-tert-butyl-4-cresol (BHT), etc. as polymerization inhibitors.

<About post-treatment and purification of (meth) acrylic acid>

In the (meth)acrylation reaction, the alkaline substances belonging to the hydrogen chloride supplement are mostly added in excess, especially the organic alkaline substances and the ends represented by formula (1) and/or formula (2) belonging to the target (Meth)acrylate polycarbonate oligomers remain in the organic solvent together, and are likely to cause undesirable phenomena such as coloring and decomposition. Therefore, it is preferably removed by washing after the reaction. In order to wash and remove the organic alkaline substance, it is preferable to wash with an aqueous solution of an acid substance. The acidic substance used is not particularly limited. Inorganic acidic substances include, for example, hydrochloric acid, sulfuric acid, and nitric acid, and organic acidic substances include, for example, carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid; methanesulfonic acid and trifluoromethane Sulfonic acid, p-toluenesulfonic acid and other sulfonic acids. Among them, organic acidic substances with lower acidity are particularly preferred. Preferably, after removing the hydrogen chloride supplement, water washing is performed.

The obtained terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or formula (2) is preferably added by adding a poor solvent to the dissolved solution The method of obtaining the precipitate. Specific examples of the poor solvent include aliphatic alcohol solvents 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>

Regarding preferred compounds of the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or formula (2) of the present invention, specific examples are shown below.

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

Formula (2) represents a preferred compound of one terminal (meth)acrylate polycarbonate oligomer as described below. In formula (2a) to formula (2d), n is an integer of 1 or more, and 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 formula (1) and/or formula (2) of the present invention has a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less, especially 1,000 or more The range of 8,000 or less is more preferable, and the range of 2,000 or more and 6,000 or less is more preferable. When the weight average molecular weight (Mw) is within this range, it is preferable because it can obtain good solubility in organic solvents.

In addition, when the terminal (meth)acrylate polycarbonate oligomer represented by the formula (1) and/or formula (2) of the present invention is used as a component of the UV-curable hard coating agent, it is the main component Multifunctional (meth)acrylic monomers such as neopentaerythritol (meth)acrylate are excellent in compatibility, so they can exert industrially advantageous effects that can form a smooth coating film by UV curing.

The terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or formula (2) of the present invention is also used as a 3D printer in addition to being a raw material for UV-curable hard coating agent Modifier for thermoforming resins such as raw materials for molding and epoxy resin.

[Example]

Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited by these examples.

In the following examples, the weight average molecular weight (Mw) was measured using gel permeation chromatography. The analysis method is as follows.

<Analysis method>

1. Determination by gel permeation chromatography

(Analysis of oligomers)

Device: HLC-8320GPC manufactured by TOSOH Corporation

Flow rate: 0.35ml/min, mobile phase: tetrahydrofuran, injection volume: 10μl

Column: TSKgel guardcolumn Super MP(HZ)-N, TSKgel Super Multipore HZ-N×3

Detector: RI,

Analysis method: It is assumed to be relative molecular weight in terms of polystyrene.

Polystyrene specimens: A-500, A-2500, A-5000, F-1, F-2, F-4 manufactured by TOSOH Corporation

(Analysis of polymers)

Device: HLC-8320GPC manufactured by TOSOH Corporation

Flow rate: 1.0ml/min, mobile phase: tetrahydrofuran, injection volume: 100μl

Column: TSKgel guardcolumn HXL-L TSKgel G2000HXL×2pcs+TSKgel G3000HXL+TSKgel G4000HXL

Detector: RI,

Analysis method: It is assumed to be relative molecular weight in terms of polystyrene.

Polystyrene specimen: PStQuickE, F (E: F-40, F-4, A-5000, A-1000, F: F-20, F-2, A-2500, A-500) manufactured by TOSOH Corporation

2. Determination of terminal hydroxyl group concentration

Using ¹ H-NMR, TCE (1,1,1,2-tetrachloroethane) was used as an internal standard, and bisphenol A and bisphenol C were used as specimens to prepare a calibration curve for the weight ratio to TCE. Quantification was carried out by calculating the weight of phenol end from the calibration curve.

Device: Ascend TM400 manufactured by BRUKER

Measurement conditions: room temperature, 120 cumulative times

3. Identification of chemical structure

It was implemented by ¹ H-NMR measurement using the same equipment as the above "2."

<Reference Example 1> Synthesis of polycarbonate oligomer (A-a)

In a four-necked flask equipped with a thermometer, a stirrer, and a cooler, add 388.6g (1.1 mol) of 2,2-bis(4-(2-hydroxyethoxy)-3-methylphenyl)propane and diphenyl carbonate After 169.2g (0.8mol) of the ester was substituted with nitrogen in the reaction vessel, 0.82g of a 0.09% cesium carbonate aqueous solution was added at 110°C. After the temperature was raised to 200° C., the degree of reduced pressure was adjusted to 0.3 kPa, and the produced phenol was reacted while being distilled off over 2 hours to obtain 383.4 g of a reaction-finished liquid.

Next, 372.6 g of the obtained reaction end liquid was added to a four-necked flask equipped with a thermometer, a stirrer, and a cooler, and it was dissolved in 745.2 g of toluene, and 2235.6 g of methanol was further added and stirred at room temperature for 30 minutes. After standing for 30 minutes, the separated upper layer solution was extracted, 558.9 g of toluene and 2235.6 g of methanol were added to the obtained lower layer solution, and stirring, standing, and extraction of the upper layer solution were performed twice in the same manner. Thereafter, 193.5 g of polycarbonate oligomer (A-a) was obtained by concentrating the solvent. The weight average molecular weight of the obtained polycarbonate oligomer was 4630 (gel permeation chromatography), and the terminal hydroxyl group concentration was 0.67 mmol/g.

<Example 1> Synthesis of terminal acrylate polycarbonate oligomer (1c)

To a four-necked flask equipped with a thermometer, a stirrer, and a cooler, 80.3 g of the polycarbonate oligomer (Aa) obtained in Reference Example 1 was added, and after replacing the reaction vessel with hydrogen, 7.3 g of propylene acetyl chloride was added under a nitrogen flow. 0.08 mol), dichloromethane 120.5g, hydroquinone monomethyl ether (methoquinone) 4.0mg. A mixed solution of 10.9 g (0.11 mol) of triethylamine and 40.2 g of dichloromethane was added at 10° C. for 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 separated upper layer solution was allowed to stand and was extracted, and 960 g of methanol was added and stirred. After stirring for 1 hour, it was allowed to stand and the separated upper layer solution was extracted, and then 320 g of methanol was added and stirred. After stirring for 2 hours, the precipitate was separated by filtration and dried to obtain 79.3 g of 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 analysis results of ¹ H-NMR, it was confirmed that they were both terminal acrylic polycarbonate oligomers represented by the above formula (1c). The ¹ H-NMR spectrum chart of the obtained terminal acrylate polycarbonate oligomer (1c) is shown in FIG. 1.

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. When 8.0 g of neopentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 0.5 g of IRGACURE (184) are further mixed, a transparent solution can be obtained.

The obtained terminal acrylate polycarbonate oligomer (1c) exhibits good solubility in organic solvents such as cyclohexanone, and it is known that it is superior to neopentaerythritol tetraacrylate which is a polyfunctional acrylate Compatibility.

<Example 2> Synthesis of terminal methacrylate polycarbonate oligomer (1d)

96 g of the polycarbonate oligomer (Aa) obtained in Reference Example 1 was added to a four-necked flask equipped with a thermometer, a stirrer, and a cooler, and after replacing the reaction vessel with nitrogen, 8.5 g of methacryloyl chloride was added under a nitrogen flow. (0.08 mol), dichloromethane 120.4g, p-methoxyphenol 4.6mg. 10.9 g (0.11 mole) of triethylamine was added at 10° C. for 30 minutes. After further stirring at 10°C for 2 hours, 825 g of water and 960 g of methanol were added, and after stirring for 1 hour, the separated upper layer solution was allowed to stand still and 960 g of methanol was added and stirred. After stirring for 2 hours, the precipitate was filtered and separated, and then the washing step of redispersing the obtained wet cake in 960 g of methanol was performed. After that, the precipitate was separated by filtration and dried to obtain 56.1 g of powdered 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 analysis results of ¹ H-NMR, it was confirmed that they were both terminal methacrylate polycarbonate oligomers represented by the above formula (1d). The ¹ H-NMR spectrum chart of the obtained terminal methacrylate polycarbonate oligomer (1d) is shown in FIG. 2.

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. When 8.0 g of neopentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 0.5 g of IRGACURE (184) are further mixed, a transparent solution can be obtained.

The obtained terminal methacrylate polycarbonate oligomer (1d) exhibits good solubility in organic solvents such as cyclohexanone, and it is known that it is a polyfunctional acrylate-based neopentyl alcohol tetraacrylate Has excellent compatibility.

<Comparative Example 1> Synthesis of terminal dipropenyl polycarbonate

In a four-necked flask equipped with a thermometer, a stirrer, and a cooler, add 246.1 g (1.08 mol) of 2,2-bis(4-hydroxyphenyl)propane and 237.1 g (1.12 mol) of diphenyl carbonate, and place the reaction vessel After nitrogen substitution, 0.9 g of 0.08% cesium carbonate aqueous solution was added at 110°C. After the temperature was raised to 220, the reaction was performed at normal pressure for 40 minutes to distill the generated phenol, while the pressure reduction degree was 13.3 kPa in 80 minutes and the temperature was raised to 240°C, and then the pressure reduction degree was 40 minutes Becomes 0.8kPa. The temperature was further increased to 285°C, and the reaction was performed at 0.7 kPa for 7 hours. 250 g of the reaction completion liquid was obtained.

Next, 150.0 g of the obtained reaction end liquid was dissolved in 530.0 g of dichloromethane to form a solution, and this solution was dropped into 1850 g of methanol to precipitate the target substance. After stirring for 1 hour, the precipitate was separated by filtration and dried to obtain powdery polycarbonate.

The weight average molecular weight of the obtained polycarbonate was 31,240 (gel permeation chromatography), and the terminal hydroxyl group concentration was 0.13 millimoles/g.

Then, 13.6 g of the obtained polycarbonate was added to a four-necked flask equipped with a thermometer, a stirrer, and a cooler, and after the reaction vessel was replaced with nitrogen, 0.3 g (0.003 mole) of propylene acetyl chloride was added under a nitrogen flow. 47.6 g of methylene chloride, and then, 0.4 g (0.004 mole) 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 target substance. Subsequently, the precipitate was separated by filtration and dried, and 14.1 g of the obtained wet cake was dissolved in 47.6 g of methylene chloride, and the dissolved liquid was added to 163 g of methanol to precipitate it. After that, the precipitate was separated by filtration and dried to obtain 13 g of a white powdery compound.

From the analysis result of ¹ H-NMR of the obtained compound, it was confirmed that it was terminal dipropenyl polycarbonate.

Cyclohexanone 8.0 g was used for 0.4 g of terminal dipropenyl polycarbonate, but it did not dissolve. Furthermore, dichloromethane was used instead of cyclohexanone, and a mixture of 0.6 g of terminal dipropenyl polycarbonate, 2.4 g of neopentyl tetraacrylate, which is a polyfunctional acrylate, and 3.0 g of dichloromethane was White turbid state, and failed to get a transparent solution.

From the above results, it can be seen that the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or formula (2) of the present invention is prepared by making the weight average molecular weight (Mw) within a specific range Among them, it shows good solubility in organic solvents, and has excellent compatibility with polyfunctional acrylates and the like.

Claims (1)

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

In formula (1) and formula (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, and 1 to 8 carbon atoms Alkoxy group, or 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 represents a hydrogen atom or 1 to 14 carbon atoms Alkyl group, X represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 or more; however, the total number of carbon atoms of R ₆ and R ₇ is 14 or less, which is bonded to 2 oxygen atoms of X It is not bonded to the same carbon atom of X.

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