KR102637355B1 - Terminal (meth)acrylate polycarbonate oligomer - Google Patents

Abstract

The present invention provides a terminal (meth)acrylate polycarbonate oligomer with excellent compatibility with polyfunctional (meth)acrylic monomers and solvent solubility as a raw material for UV curable (meth)acrylic resin used in UV curable hard coating agents, etc. Make it an assignment.
In order to solve the above problems, the present invention provides a terminal (meth)acrylate polycarbonate represented by formula (1) and/or (2), characterized in that the weight average molecular weight (Mw) is in the range of 500 to 10,000. Oligomers are provided.

Description

Terminal (meth)acrylate polycarbonate oligomer

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

Resin materials are widely used as engineering plastics due to their advantages such as being lightweight, inexpensive, and have excellent processability. However, since they are inferior to glass or metal in terms of surface hardness, scratch resistance, and chemical resistance, they are not used as replacement materials. does not exist. In order to improve these defects of resin materials, a hard coating treatment is generally performed to form a thin film of a resin made of a different material from the resin of the base material on the surface of the resin, protect the resin of the base material from external factors, and achieve surface modification. I'm losing. For the formation of this hard coating layer, a system is adopted in which a hard coating agent is applied to the resin surface of the substrate, dried, and then cured by irradiating radiation such as electron beams or ultraviolet rays (UV) as necessary (for example, patent document 1, 2). Among these, UV-curable hard coatings using UV-curable resins can be processed at lower temperatures and in a shorter time than conventional hard coatings, and thus have high productivity and are being developed for various uses.

Since this UV-curable hard coating agent uses multifunctional (meth)acrylic monomers such as pentaerythritol-based (meth)acrylate as its main ingredient, the ingredients mixed are required to have high compatibility with these multifunctional (meth)acrylic monomers. It is becoming.

Japanese Patent Publication No. 2010-024255 Japanese Patent Publication No. 2016-011365

The present invention was made against the background of the above-mentioned circumstances, and is a raw material for UV-curable (meth)acrylic resin used in UV-curable hard coating agents, etc., and has excellent compatibility with polyfunctional (meth)acrylic monomers and excellent solvent solubility at the terminal (meth)acrylic resin. ) The purpose is to provide an acrylate polycarbonate oligomer.

As a result of intensive study to solve the above-mentioned problem, the present inventors have found that, in the terminal (meth)acrylate polycarbonate represented by the formula (1) and/or (2) below, an oligomer having a weight average molecular weight (Mw) in a specific range discovered that it had excellent compatibility with polyfunctional (meth)acrylic monomers and good solvent solubility, and completed the present invention.

The present invention is as follows.

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

(In formulas (1) and (2), R ₁ to _{R 4} are each independently a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 5 to 12 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, or a carbon source. represents an aromatic hydrocarbon group with 6 to 12 carbon atoms, R ₅ each independently represents a hydrogen atom or a methyl group, R ₆ and R ₇ each independently represent a hydrogen atom or an alkyl group with 1 to 14 carbon atoms, and Represents an alkylene group of ~4, and n is an integer greater than or equal to 1. However, the total number of carbon atoms of R ₆ and R ₇ is 14 or less, and the two oxygen atoms bonded to No.)

Since the terminal (meth)acrylate polycarbonate oligomer according to the present invention has a weight average molecular weight (Mw) in the range of 500 to 10,000, it can be used with polyfunctional (meth)acrylic monomers 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 coating agent, and has the industrially advantageous effect of being able to form a smooth coating film by UV curing.

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

Below, 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 obtained by reaction of a polycarbonate oligomer represented by formula (A) and a (meth)acrylating agent such as (meth)acrylic acid chloride, as illustrated in the reaction formula below. , a compound represented by the following formula (1) and/or the following formula (2), with a weight average molecular weight (Mw) in the range of 500 to 10,000.

(In the reaction formula, the integers of R ₁ to R ₇ ,

<About the 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 explaining in detail the polycarbonate oligomer represented by the formula (A) below, which is the raw material for synthesis. That is, specific examples of R ₁ to _{R 4} , R ₆ , R ₇ , The same as R ₁ to R ₇ , X, and n in (1) or (2).

(In Formula (A), the integers of R ₁ to R ₄ , R ₆ , R ₇ ,

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 a linear or branched alkyl group having 1 to 4 carbon atoms. It is an alkyl group, and specifically, examples include methyl group, ethyl group, n-propyl group, isopropyl group, and isobutyl group. Such 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 effect of the present invention is not impaired.

When any one of R ₁ , R ₂ , R ₃ and R ₄ is a cycloalkyl group with 5 to 12 carbon atoms, the cycloalkyl group is preferably a cycloalkyl group with 5 to 7 carbon atoms, and specifically, for example, cycloalkyl group with 5 to 7 carbon atoms. Hexyl group, cyclopentyl group, cycloheptyl group, etc. can be mentioned. Such a cycloalkyl group may have a substituent such as, for example, a straight-chain or branched alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, or a phenyl group, as long as the effect of the present invention is not impaired.

In addition, 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 straight-chain or branched alkoxy group having 1 to 4 carbon atoms, and specific Examples of this include methoxy group, ethoxy group, etc. This 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 effect of the present invention is not impaired.

Additionally, 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. These aromatic hydrocarbon groups may be substituted with, for example, 1 to 3 alkyl groups of 1 to 4 carbon atoms and/or alkoxy groups of 1 to 4 carbon atoms, as long as the effects of the present invention are not impaired.

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 alkyl group having 1 to 12 carbon atoms, and 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, etc. However, the total number of carbon atoms of R ₆ and R ₇ must be 14 or less.

In the formula (A), It represents a diyl group and butane-2,3-diyl group, and among them, ethylene group, n-propylene group, propane-1,2-diyl group, and n-butylene group are preferable, and ethylene group and propane-1,2-di A diary group is more preferable, and an ethylene group is particularly preferable.

The polycarbonate oligomer represented by formula (A) can be produced by any conventionally known production method. Specifically, examples include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Among them, it is industrially advantageous to use the interfacial polymerization method, the melt transesterification method, and the solid-phase transesterification method of the prepolymer. Among these, a melt transesterification method that does not use phosgene and a solid-phase transesterification method of a prepolymer using a melt transesterification method are particularly preferable. The above production method is carried out using a dihydroxy compound represented by the formula (B) below and a carbonate ester forming agent.

(In Formula (B), the integers of R ₁ to R ₄ , R ₆ , R ₇ , and

<About the dihydroxy compound represented by formula (B)>

As a dihydroxy compound represented by formula (B), specifically, for example, bis(4-(2-hydroxyethoxy)phenyl)methane, 2,2-bis(4-(2-hydroxy Toxy)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. are mentioned.

During the polymerization reaction, these dihydroxy compounds may be used alone or in combination of two or more types in an arbitrary ratio.

＜About carbonic acid ester forming agent＞

Specific examples of the carbonate ester forming agent for reacting with the dihydroxy compound represented by formula (B) include diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, and bis(m-cresyl)carbonate, and dimethyl. Dialkyl carbonates such as carbonate, diethyl carbonate, and dicyclohexyl carbonate; alkylaryl carbonates such as methylphenyl carbonate, ethylphenyl carbonate, and cyclohexylphenyl carbonate; or carbonates such as divinyl carbonate, diisopropenyl carbonate, and dipropenyl carbonate. Carbonic diesters such as dialkenyl can be mentioned. Additionally, dihalogenated carbonyl compounds such as phosgene and triphosgene can also be mentioned. Among these, diaryl carbonate is preferable and diphenyl carbonate is particularly preferable.

＜About melt transesterification method＞

The melt transesterification method will be described as a method for producing the polycarbonate oligomer represented by formula (A).

As a method of melt transesterification reaction, when using a dihydroxy compound represented by formula (B) and diphenyl carbonate as a carbonate ester forming agent, heating is performed in an inert gas atmosphere at normal or reduced pressure in the presence of a catalyst. This is carried out by stirring and allowing the produced phenol to flow out. Usually, the mixing ratio of the dihydroxy compound represented by formula (B) and the carbonate ester forming agent or the degree of pressure reduction during the transesterification reaction is adjusted to adjust the desired molecular weight and terminal hydroxyl group content, such as formula (A). The indicated polycarbonate oligomer can be obtained.

To obtain the polycarbonate oligomer represented by formula (A), the mixing ratio of the dihydroxy compound represented by formula (B) and the carbonate ester former is 1 mole of the dihydroxy compound represented by formula (B). The carbonate ester forming agent is usually used in an amount of 0.2 to 1.0 mole, preferably 0.25 to 0.95 mole, and more preferably 0.3 to 0.90 mole.

To increase the reaction rate during the molten transesterification reaction, a transesterification catalyst is used as needed. There are no particular restrictions on the transesterification catalyst, and examples include alkali metal compounds such as inorganic alkali metal compounds such as hydroxide, carbonate, and hydrogen carbonate compounds of lithium, sodium, and cesium, and organic alkali metal compounds such as alcoholates and organic carboxylates. ；Alkaline earth metal compounds such as hydroxides such as beryllium and magnesium, inorganic alkaline earth metal compounds such as carbonates, and organic alkaline earth metal compounds such as alcoholates and organic carboxylates; Tetramethyl boron, tetraethyl boron, butyltriphenyl boron basic boron compounds such as sodium salts, calcium salts, and magnesium salts; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine; or basic phosphorus such as quaternary phosphonium salts derived from these compounds. Compounds; Basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; Known amine compounds such as 4-aminopyridine, 2-dimethylaminoimidazole, and aminoquinoline Transesterification catalysts can be used. Among them, alkali metal compounds are preferable, and cesium compounds such as cesium carbonate and cesium hydroxide are especially preferable.

The amount of catalyst used is within a range that does not cause problems with the quality of the oligomers produced due to catalyst residues. Since the appropriate addition amount varies depending on the type of catalyst, it cannot be stated uniformly, but can be roughly expressed, for example, in formula (B). It is usually 0.05 to 100 μmole, preferably 0.08 to 50 μmole, more preferably 0.1 to 20 μmole, and still more preferably 0.1 to 5 μmole, per mole of the dihydroxy compound displayed. The catalyst may be added as is or may be added by dissolving it in a solvent. A solvent that does not affect the reaction of water, phenol, etc., for example, is preferable.

The reaction conditions for the melt transesterification reaction are usually in the range of 120 to 360°C, preferably in the range of 150 to 280°C, more preferably in the range of 180 to 260°C. If the reaction temperature is too low, the transesterification reaction will not proceed, and if the reaction temperature is too high, side reactions such as decomposition reaction will proceed, which is undesirable. The reaction is preferably carried out under reduced pressure. The reaction pressure is preferably a pressure at which the carbonate ester forming agent as a raw material does not flow out of the system and by-products such as phenol can flow out at the reaction temperature. Under these reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.

＜About (meth)acrylicization＞

As illustrated in the above reaction formula, the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or (2) of the present invention is a polycarbonate oligomer represented by formula (A) and (meth) ) It is obtained by reaction with a (meth)acrylating agent such as acrylic acid chloride.

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

When obtaining a (meth)acrylate polycarbonate oligomer at both ends represented by formula (1), the amount of (meth)acrylating agent used is (meth) relative to all terminal hydroxyl groups of the polycarbonate oligomer represented by formula (A). ) The acrylic agent is usually used in an amount of 1.0 to 2.5 mole, preferably 1.1 to 2.0 mole, and more preferably 1.15 to 1.5 mole.

When obtaining a one-terminal (meth)acrylate polycarbonate oligomer represented by formula (2), the (meth)acrylating agent is usually added at an amount of 0.5 to 1.5% relative to all terminal hydroxyl groups of the polycarbonate oligomer represented by formula (A). It is used at a molar ratio, preferably 0.55 to 1.25 molar ratio, and more preferably 0.6 to 1.0 molar ratio.

For example, when (meth)acrylic acid chloride is used to acrylate the polycarbonate oligomer represented by formula (A), chloride ions are generated in the form of hydrogen chloride, so it is preferable to use a hydrogen chloride scavenger in combination. Any basic substance can be used as a hydrogen chloride trap. As the inorganic basic material, carbonate or hydrogen carbonate of an alkali metal can be used. Tertiary amines can be used as the organic basic substance. Tertiary amines include, for example, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, and N-ethyl-amine. Aliphatic amines such as diamylamine, N,N-diisopropylethylamine, N,N-dimethyl-cyclohexylamine, and N,N-diethyl-cyclohexylamine; N,N-dimethylaniline, N,N- Aromatic amines such as diethylaniline; Heterocyclic amines such as pyridine, picoline, and N,N-dimethylaminopyridine; 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-dia and alicyclic amines such as zabicyclo[4.3.0]non-5-ene.

The amount of the hydrogen chloride scavenger used is usually 0.8 to 10 times the mole number of the (meth)acrylating agent used, preferably 0.9 to 8 times the mole, and particularly preferably 1.0 to 7 times the mole number. If the hydrogen chloride trapping agent is less than 0.8 times the mole number of the (meth)acrylating agent, the generated hydrogen chloride cannot be completely captured, and the polycarbonate oligomer represented by formula (A) of the raw material or the target product of formula (1) or (2) cannot be completely captured. There is a risk that the terminal (meth)acrylate polycarbonate oligomer indicated by ) may be decomposed, causing a decrease in the purity of the target product. Additionally, if the hydrogen chloride scavenger exceeds 10 times the mole number of the (meth)acrylic agent, it is not preferable because removal of the hydrogen chloride scavenger not only becomes complicated but is also uneconomical.

The solvent used in this (meth)acrylation reaction can be any solvent that can uniformly mix the raw materials used, etc. Specifically, halogenated hydrocarbons such as methylene chloride, tetrahydrofuran, dioxane, chlorobenzene, etc. I can hear it. The amount of solvent used is not particularly limited, but is usually 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, and particularly preferably 2 to 10 parts by weight, based on the polycarbonate oligomer represented by formula (A).

The (meth)acrylation reaction is carried out at a relatively low temperature, usually -50 to 100°C, preferably -30 to 80°C, particularly preferably -15 to 60°C. If the reaction temperature exceeds 100°C, side reactions occur, leading to a decrease in the yield of the target product. In addition, below -50°C, the reaction rate is slow and takes too much time, making it uneconomical.

As a reaction procedure, the polycarbonate oligomer represented by formula (A) and a (meth)acrylating agent are mixed in advance in a solvent and a hydrogen chloride scavenger is added thereto. First, the polycarbonate oligomer represented by formula (A) is mixed. There is a method of mixing a carbonate oligomer and a hydrogen chloride scavenger in a solvent and adding a (meth)acrylating agent thereto. In these methods, the hydrogen chloride trapping agent or (meth)acrylating agent added later may be used in a state diluted in a solvent.

Additionally, as a polymerization inhibitor during the reaction, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-di-tert-butyl-4-methylphenol (BHT), etc. may be added.

＜Post-processing and purification of (meth)acrylation＞

In the (meth)acrylation reaction, the basic substance as a hydrogen chloride scavenger is often added in excess, and in particular, the organic basic substance is the terminal (meth)acrylate polycarbonate oligomer represented by the target formula (1) and/or (2). Since it remains in the organic solvent and tends to cause undesirable phenomena such as coloring and decomposition, it is preferable to remove it during cleaning after the reaction. In order to wash and remove organic basic substances, it is preferable to wash with an aqueous solution of an acidic substance. There is no particular limitation on the acidic substance used, but examples of inorganic acidic substances include hydrochloric acid, sulfuric acid, and nitric acid, and examples of organic acidic substances include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, and methane. There are sulfonic acids such as sulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Among them, organic acidic substances with low acidity are more preferable. After removing the hydrogen chloride scavenger, it is desirable to continue washing with water.

The obtained terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or (2) is preferably obtained as a precipitate by adding a poor solvent to the dissolved solution. Specific examples of the poor solvent include aliphatic alcohol solvents having 1 to 6 carbon atoms such as methanol, ethanol, and propanol, or mixtures of the aliphatic alcohol solvent and water.

＜About terminal (meth)acrylate polycarbonate oligomer＞

Specific examples of preferred compounds of terminal (meth)acrylate polycarbonate oligomers represented by formula (1) and/or (2) of the present invention are given below.

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

The terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or (2) of the present invention has a weight average molecular weight (Mw) in the range of 500 to 10,000, especially in the range of 1,000 to 8,000. It is preferable, and a range of 2,000 or more and 6,000 or less is more preferable. If the weight average molecular weight (Mw) is within this range, it is preferable because good solubility in organic solvents is obtained.

In addition, when the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or (2) of the present invention is used as a component of a UV curable hard coating agent, pentaerythritol-based (meth)acrylate as the main component is used. Since it has excellent compatibility with polyfunctional (meth)acrylic monomers such as polyfunctional (meth)acrylic monomers, it exhibits the industrially advantageous effect of being able to form a smooth coating film by UV curing.

The terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or (2) of the present invention is used as a raw material for modeling materials for 3D printers and as a modifier for thermosetting resins such as epoxy resins, in addition to raw materials for UV curable hard coating agents. It is useful as

Example

The present invention will be described in detail below by way of examples, but the present invention is not limited to these examples.

In addition, the weight average molecular weight (Mw) in the examples below was measured by gel permeation chromatography. The analysis method is as follows.

＜Analysis method＞

1. Gel permeation chromatography measurement

(Analysis of oligomers)

Device: HLC-8320GPC manufactured by Tosoh Corporation

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

Column: TSKgel guardcolumn SuperMP(HZ)-N, TSKgel SuperMultiporeHZ-N x 3

Detector: RI,

Analysis method: Use the relative molecular weight converted to polystyrene.

Polystyrene standard product: A-500, A-2500, A-5000, F-1, F-2, F-4 manufactured by Tosoh Co., Ltd.

(Analysis of polymers)

Device: HLC-8320GPC manufactured by Tosoh Corporation

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

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

Detector: RI,

Analysis method: Use the relative molecular weight converted to polystyrene.

Polystyrene standard product: PStQuick E, F manufactured by Tosoh Co., Ltd. (E: F-40, F-4, A-5000, A-1000, F: F-20, F-2, A-2500, A-500)

2. Determination of terminal hydroxyl concentration

Using ^1H -NMR, a calibration curve of the weight ratio with TCE was created using TCE (1,1,1,2-tetrachloroethane) as an internal standard and bisphenol A and bisphenol C as standards. It was quantified by calculating the phenol terminal weight from this calibration curve.

Device: Ascend ^TM 400 manufactured by BRUKER

Measurement conditions: room temperature, integration count 120 times

3. Identification of chemical structure

It was carried out by ¹ H-NMR measurement using the same equipment as in “2.” above.

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

388.6 g (1.1 mol) of 2,2-bis(4-(2-hydroxyethoxy)-3-methylphenyl)propane and 169.2 g (0.8 mol) of diphenyl carbonate in a four-necked flask equipped with a thermometer, stirrer, and condenser. After the reaction vessel was purged with nitrogen, 0.82 g of 0.09% cesium carbonate aqueous solution was added at 110°C. After raising the temperature to 200°C, the degree of reduced pressure was adjusted to 0.3 kPa, and the reaction was carried out for 2 hours while flowing out the produced phenol, to obtain 383.4 g of the reaction solution.

Next, 372.6 g of the obtained reaction solution was placed in a four-necked flask equipped with a thermometer, stirrer, and condenser, and dissolved in 745.2 g of toluene. Additionally, 2235.6 g of methanol was added, and the mixture was stirred at room temperature for 30 minutes. After standing for 30 minutes, the separated upper layer solution was removed. To the obtained lower layer solution, 558.9 g of toluene and 2235.6 g of methanol were added, and the same stirring, standing, and removal of the upper layer solution were performed twice. After that, the solvent was concentrated to obtain 193.5 g of polycarbonate oligomer (A-a). 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 (A-a) obtained in Reference Example 1 was placed in a four-necked flask equipped with a thermometer, stirrer, and condenser, and the reaction vessel was purged with nitrogen, followed by 7.3 g (0.08 mol) of acrylic acid chloride and dichloromethane. 120.5 g and 4.0 mg of methoquinone were added under a nitrogen stream. A mixed solution of 10.9 g (0.11 mol) of triethylamine and 40.2 g of dichloromethane was added over 2 hours at 10°C. After continuing to stir at 10°C for an additional hour, 825 g of water and 960 g of methanol were added, and after stirring for 1 hour, the solution was allowed to stand, the separated upper layer solution was removed, and 960 g of methanol was further added and stirred. . After stirring for 1 hour, the solution in the separated upper layer was removed, and 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 it was a both-terminal acrylate polycarbonate oligomer shown in the above formula (1c). Figure 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. Additionally, 8.0 g of pentaerythritol tetraacrylate, which is a multifunctional acrylate, and 0.5 g of Irgacure (184) were mixed, and a transparent solution was obtained.

It was revealed that the obtained terminal acrylate polycarbonate oligomer (1c) exhibits good solubility in organic solvents such as cyclohexanone, and also has excellent compatibility with pentaerythritol tetraacrylate, which is a multifunctional acrylate.

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

96 g of polycarbonate oligomer (A-a) obtained in Reference Example 1 was placed in a four-necked flask equipped with a thermometer, stirrer, and condenser, and the reaction vessel was purged with nitrogen, followed by 8.5 g (0.08 mol) of methacrylic acid chloride, 120.4 g of dichloromethane and 4.6 mg of methoquinone were added under a nitrogen stream. 10.9 g (0.11 mole) of triethylamine was added over 30 minutes at 10°C. After continuing to stir for an additional 2 hours at 10°C, 825 g of water and 960 g of methanol were added, and after stirring for 1 hour, the solution was left to stand and the separated upper layer solution was removed, and 960 g of methanol was further added and stirred. . After stirring for 2 hours, the precipitate was separated by filtration, and a washing step was further performed in which the obtained wet cake was redispersed in 960 g of methanol. Thereafter, the precipitate was separated by filtration and dried to obtain 56.1 g of 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 analysis results of ¹ H-NMR, it was confirmed that it was a both-terminal methacrylate polycarbonate oligomer shown in the above formula (1d). Figure 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. Additionally, 8.0 g of pentaerythritol tetraacrylate, which is a multifunctional acrylate, and 0.5 g of Irgacure (184) were mixed, and a transparent solution was obtained.

It was revealed that the obtained terminal methacrylate polycarbonate oligomer (1d) exhibits good solubility in organic solvents such as cyclohexanone, and also has excellent compatibility with pentaerythritol tetraacrylate, which is a polyfunctional acrylate.

<Comparative Example 1> Synthesis of terminal diacryl polycarbonate

246.1 g (1.08 mol) of 2,2-bis(4-hydroxyphenyl)propane and 237.1 g (1.12 mol) of diphenyl carbonate were added to a four-necked flask equipped with a thermometer, stirrer, and condenser, and the reaction vessel was purged with nitrogen. Afterwards, 0.9 g of 0.08% cesium carbonate aqueous solution was added at 110°C. After raising the temperature to 220°C, the reaction was carried out at normal pressure for 40 minutes, and while discharging the produced phenol, the degree of reduced pressure was set to 13.3 kPa over 80 minutes. After raising the temperature to 240°C, the degree of reduced pressure was adjusted to 0.8 kPa over 40 minutes. . The temperature was further raised to 285°C, reaction was performed at 0.7 kPa for 7 hours, and 250 g of the reaction solution was obtained.

Next, 150.0 g of the obtained reaction solution was dissolved in 530.0 g of dichloromethane, and the solution was added dropwise into 1850 g of methanol to precipitate the target product. 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 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, stirrer, and condenser, and after purging the reaction vessel with nitrogen, 0.3 g (0.003 mol) of acrylic acid chloride and 47.6 g of dichloromethane were added under a nitrogen stream. Afterwards, 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 product. Thereafter, the precipitate was separated by filtration and dried. 14.1 g of the resulting wet cake was dissolved in 47.6 g of dichloromethane, and the solution was added to 163 g of methanol to cause precipitation. Afterwards, the precipitate was separated by filtration and dried to obtain 13 g of the compound in the form of white powder.

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

8.0 g of cyclohexanone was used for 0.4 g of terminal diacryl polycarbonate, but it did not dissolve. In addition, dichloromethane was used instead of cyclohexanone, and the mixture of 0.6 g of terminal diacryl polycarbonate, 2.4 g of pentaerythritol tetraacrylate, a multifunctional acrylate, and 3.0 g of dichloromethane was cloudy and a transparent solution. couldn't get it

From the above results, the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or (2) of the present invention has good solubility in organic solvents by setting the weight average molecular weight (Mw) within a specific range. It has also become clear that it has excellent compatibility with multifunctional acrylates and the like.

Claims (1)

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


(In formulas (1) and (2), R ₁ to _{R 4} are each independently a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 5 to 12 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, or a carbon source. represents an aromatic hydrocarbon group with 6 to 12 carbon atoms, R ₅ each independently represents a hydrogen atom or a methyl group, R ₆ and R ₇ each independently represent a hydrogen atom or an alkyl group with 1 to 14 carbon atoms, and Represents an alkylene group of ~4, and n is an integer greater than or equal to 1. However, the total number of carbon atoms of R ₆ and R ₇ is 14 or less, and the two oxygen atoms bonded to No.)