JP2002348265A - Carbonate compound having unsaturated bond and biodegradable resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a very useful carbonate compound having biodegradability and polymerizable unsaturated bonds as well as a composition containing the above compound. SOLUTION: The unsaturated bond containing carbonate compound having a structure where at least two molecules of aliphatic and/or alicyclic polyvalent alcohols having two or more hydroxyl groups combine with each other by carbonate bonds and also having a structure where two or more hydroxyl groups that do not contribute to the combination of polyvalent alcohols are substituted by functional groups shown by general formula (1), is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a carbonate compound having an unsaturated bond and a composition containing the same.

[0002]

2. Description of the Related Art Carbonate compounds are widely used industrially as molded articles, coatings, and film materials, and are indispensable industrial materials for producing various chemical products. Since it exhibits biodegradability due to the CO-O- bond, it has recently attracted attention as an environmentally compatible functional material that degrades in the natural environment.

[0003] Such carbonate compounds are usually
It is produced by dehydrochlorination using bisphenol A and phosgene as raw materials. That is, it has a skeleton formed from bisphenol A. However, such compounds are considered to have improved value as industrial materials by improving their biodegradability or imparting new functionality, and have been studied to apply them to various uses. There was room to do it.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, has biodegradability, and
An object of the present invention is to provide a carbonate compound having a polymerizable unsaturated bond and a high functionality, and a composition containing the carbonate compound.

[0005]

Means for Solving the Problems The present inventors have conducted various studies on carbonate compounds, and found that the carbonate compound has two molecules of an aliphatic polyhydric alcohol having at least two hydroxyl groups and / or an alicyclic polyhydric alcohol. Having a structure essential to the above, and two or more polyhydric alcohols are bonded to each other by a carbonate bond,
And, by having a structure in which two or more of the hydroxyl groups not participating in the bond are substituted with a specific functional group having an unsaturated bond, the compound has biodegradability derived from a carbonate bond, The inventors have found that the functionality such as polymerizability is exhibited by the unsaturated bond having a terminal structure, and have conceived that the above problem can be solved successfully. It has also been found that carbonate compounds having such an unsaturated bond have various forms, and compositions containing these are useful as industrial materials exhibiting high functionality. Further, when the carbonate compound has a structure having no aromatic ring, -O-CO-O-
It is conceivable that, in addition to having biodegradability due to bonding, it has good biodegradability due to being aliphatic, and has reached the present invention.

That is, the present invention essentially requires at least two molecules of an aliphatic polyhydric alcohol and / or alicyclic polyhydric alcohol having two or more hydroxyl groups, and at least two molecules of the polyhydric alcohol are mutually bonded by a carbonate bond. A carbonate compound having a structure formed by bonding, wherein two or more of the hydroxyl groups not participating in the bonding between the polyhydric alcohols are represented by the following general formula (1):

[0007]

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(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² is the same or different and represents an alkylene chain having 1 to 8 carbon atoms. M is an integer of 1 to 20.) ) Is a carbonate compound having an unsaturated bond having a structure substituted with a functional group represented by

The present invention is also a biodegradable resin composition containing the above-mentioned carbonate compound having an unsaturated bond in an amount of 5% by weight or more. Hereinafter, the present invention will be described in detail.

The carbonate compound having an unsaturated bond of the present invention essentially comprises at least two molecules of an aliphatic polyhydric alcohol and / or alicyclic polyhydric alcohol having two or more hydroxyl groups, and at least one of the polyhydric alcohols. It has a structure in which two molecules are bonded to each other by a carbonate bond. That is, the present invention has a structure in which aliphatic polyhydric alcohols and / or alicyclic polyhydric alcohols having two or more hydroxyl groups of two or more molecules constituting a carbonate compound are bonded to each other. Part or all have a structure in which they are bonded to each other by a carbonate bond at a hydroxyl group site. Such a structure is not limited to a structure formed by a raw material having essential aliphatic polyhydric alcohol and / or alicyclic polyhydric alcohol having two or more hydroxyl groups. A preferred form of the aliphatic polyhydric alcohol and / or alicyclic polyhydric alcohol having two or more hydroxyl groups forming such a structure is to have three or more hydroxyl groups. Further, it is preferable that the polyhydric alcohol has a structure in which all of the polyhydric alcohols are bonded to each other by a carbonate bond. The polyhydric alcohols forming such a structure may be all the same or different. In the carbonate compound having an unsaturated bond of the present invention, the above structure is essential,
It may or may not have another structure.

The present invention has a structure in which two or more hydroxyl groups which do not participate in the bonding between the polyhydric alcohols are substituted by the functional groups represented by the general formula (1). That is, two or more molecules of the polyhydric alcohol have a structure bonded to each other, but among all the hydroxyl groups of the two or more molecules of the polyhydric alcohol, two or more hydroxyl groups that do not participate in the bonding between the polyhydric alcohols are It has a structure substituted with a functional group represented by the general formula (1). Such a structure forms the terminal structure of the carbonate compound having an unsaturated bond according to the present invention, and has a polymerizable property by having an unsaturated bond, so that it has a multifunctional property. And so on. In a preferred embodiment of the present invention, a structure in which three or more hydroxyl groups not participating in the bonding between the polyhydric alcohols are substituted with the functional group represented by the general formula (1). Further, it is preferable that the polyhydric alcohol in which the hydroxyl group is substituted by the functional group represented by the general formula (1) is bonded to another polyhydric alcohol through a carbonate bond.

In the terminal structure represented by the general formula (1), one of the -O-CO-O- bonds is-(R ² O) m-
While CO-CR ¹ = CH ₂ is bonded, the other is bonded to an atomic group or the like constituted by a carbon chain. In the above general formula (1), if the number of carbon atoms of R ² or the number of m exceeds the above range, it becomes difficult to prepare a compound having a terminal structure represented by the general formula (1), and the cost of the carbonate compound is reduced. It rises and becomes unsuitable as an industrial material.

The number of the functional groups represented by the general formula (1), that is, the number of terminal structures represented by the general formula (1) in the molecule of the carbonate compound having an unsaturated bond of the present invention is 2 to 2 The number is preferably 20 and more preferably 3 to 20. All terminal structures may be the same or different. It is preferable that all of the terminal structures present in the compound have a terminal structure represented by the general formula (1), but a part of the terminal structure has a terminal structure represented by the general formula (1). You may. Further, it is preferable that all of the terminal structures represented by the general formula (1) are terminal structures in a structure in which at least two molecules of the polyhydric alcohol are bonded to each other by a carbonate bond.

The carbonate compound having an unsaturated bond of the present invention preferably has no aromatic ring. This is considered to have good biodegradability due to the aliphatic and / or alicyclic skeleton in addition to having biodegradability due to the -O-CO-O- bond. Thus, the value as an industrial material can be further increased.

The carbonate compound having an unsaturated bond of the present invention has the same or different terminal structure as described above.
It is preferable to have a structure in which two or more are bonded to an alkyl group or oxyalkylene group having 1 to 20 carbon atoms and 1 to 12 alkyl or oxyalkylene groups having the same carbon number of 1 to 20. Thereby, biodegradability is improved, and functionality such as polyfunctionality is improved. Such a compound has two or more alkyl groups or oxyalkylene groups having 1 to 20 carbon atoms.
The terminal structure is bonded to two or more of at least one of the alkyl group or the oxyalkylene group of
It has a structure in which 1 to 12 of the above terminal structures are bonded to 20 alkyl groups or oxyalkylene groups.

As an example of the carbonate compound having an unsaturated bond of the present invention, a compound having a structure in which two or more molecules of an aliphatic dihydric alcohol are essential is represented by the following general formula (2). A compound having a structure in which two or more aliphatic tetrahydric alcohol molecules are essential is represented by the following general formula (3). In these general formulas, all terminal structures are functional groups represented by the general formula (1).

[0017]

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[0018]

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In the above formula, X is the same or different and represents the above general formula (1). R ³ represents an alkyl group or an oxyalkylene group having 1 to 20 carbon atoms. n represents an integer of 2 to 12. p represents an integer of 1 to 100. In the general formula (3), the terminal structure represented by the general formula (1) is a structure in which six terminal structures are bonded to an alkyl group having 1 carbon atom.

The method for producing the carbonate compound having an unsaturated bond of the present invention is not particularly limited, and examples thereof include an aliphatic alcohol having an unsaturated bond and an aliphatic polyhydric alcohol having two or more hydroxyl groups and / or an alicyclic ring. A reaction method comprising reacting a reaction raw material containing a formula polyhydric alcohol and an alkyl carbonate as essential components in the presence of a Group I metal compound and / or a Group II metal compound, wherein the aliphatic alcohol having an unsaturated bond is General formula (4);

[0021]

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(Wherein R ¹ , R ² and m are the same as those described above). In this production method, since the carbonate compound is produced by transesterification of the alcohol and the alkyl carbonate, the alcohol is by-produced together with the carbonate compound.
Compared with the conventional production method using phosgene, the toxicity of the reaction raw materials and by-products is low, and the alcohol by-produced can be easily removed by distillation or the like, so that it can be produced with high safety and at low cost. . Further, since an alcohol having an unsaturated bond is indispensable as an alcohol, and an aliphatic polyhydric alcohol and / or an alicyclic polyhydric alcohol are used, a carbonate compound having an unsaturated bond is generated, and thus, Such a product has the utility of having an unsaturated bond and being an aliphatic and / or alicyclic skeleton in addition to the functionality of the carbonate compound.

In the above production method, an aliphatic and / or alicyclic alcohol having an unsaturated bond other than the compound represented by the general formula (4) may be used. Such aliphatic and / or alicyclic alcohols are not particularly restricted but include, for example, monohydric alcohols, polyhydric alcohols, etc., preferably having an unsaturated bond at the terminal, Preferably, the saturated bond has polymerizability. Such compounds include, for example, 1,14-
Tetradecanediol (meth) acrylate, 1,3-
Butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3
-(Meth) acryloyloxy-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-hydroxy-2,2
-Dimethylpropyl (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, dipropylene glycol (meth) Acrylate, tripropylene glycol (meth) acrylate,
Tetrapropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.
There is no particular limitation. One of these compounds may be used alone, or two or more of them may be used as a mixture.

Examples of the aliphatic polyhydric alcohol and / or alicyclic polyhydric alcohol having two or more hydroxyl groups which can be used in the above production method include polyhydric alcohols, polyhydroxyl resins such as polyester polyols and polyether polyols. Although a compound or the like can be used, it is not particularly limited. These compounds are 1
Only the species may be used, or two or more species may be appropriately used in combination. Among these, in the present invention, it is preferable to use polyhydroxy compounds such as polyhydric alcohols, polyester polyols and polyether polyols.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tetrapropylene glycol, polypropylene glycol, 2-methyl-1,3-methyl glycol. Propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, an adduct of bisphenol A with propylene oxide or ethylene oxide,
1,2,3,4-tetrahydroxybutane, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, 1,3-propanediol, 1,2
-Cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2,7-decalin glycol, 1,14- Tetradecanediol, 3-
(Meth) acryloyloxy-1,2-propanediol, 3-chloro-1,2-propanediol, 2,2-
Dimethyl-1,3-propanediol, pentaerythritol, dipentaerythritol, cyclohexanedimethanol, hydrogenated bisphenol A; monosaccharides such as glucose and fructose; polysaccharides such as mannitol, sorbitol, maltitol, lactose, cellulose and the like. Can be

Examples of the polyhydroxy compounds such as the above-mentioned polyester polyols and polyether polyols include polyester glycols obtained by reacting the above-mentioned polyhydric alcohols with polybasic acids and those obtained by reacting the above-mentioned polyhydric alcohols with glycols. Glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane- Propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, pentaerythritol Le - ethylene oxide adducts,
Pentaerythritol-propylene oxide adduct, pentaerythritol-tetrahydrofuran adduct, pentaerythritol-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, And dipentaerythritol-ethylene oxide-propylene oxide adducts. Among these polyhydroxy compounds, it is preferable to use an aliphatic and / or alicyclic polyhydric alcohol having three or more hydroxyl groups.

As the alkyl carbonate that can be used in the above-mentioned production method, for example, the alkyl group preferably has 1 to 12 carbon atoms. Examples of such an alkyl carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisobutyl carbonate, di-tert-butyl carbonate, diallyl carbonate, and di-tert-carbonate.
Examples include, but are not limited to, amyl carbonate, dipentyl carbonate, dihexyl carbonate, didodecyl carbonate, ethylene carbonate, propylene carbonate, and butylene carbonate. One of these compounds may be used alone, or two or more of them may be used as a mixture.

The weight ratio of the essential components in the above-mentioned reaction raw materials may be appropriately set according to the desired physical properties and use of the carbonate compound to be obtained. For example, the molar ratio of the aliphatic alcohol having an unsaturated bond represented by the general formula (4), the aliphatic polyhydric alcohol and / or the alicyclic polyhydric alcohol, and the alkyl carbonate is set to 10/1.
/ 10 to 1/10/1. More preferably, it is 8/1/8 to 1/8/1, and further preferably, it is 5/1/5 to 1/5/1.

In the above production method, the reaction raw materials are reacted in the presence of a Group I metal compound and / or a Group II metal compound. Each of these metal compounds can be used alone or in combination of two or more. The type thereof is not particularly limited, and oxides, hydroxides, carbonates, hydrogencarbonates, and alcoholates of Group I and Group II metals can be used. Phenolate, metal soap, acetylacetonate, and the like. Among these, it is preferable to use sodium and / or potassium compounds. Such compounds include sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium methoxide, sodium-tert-butoxide, sodium phenolate, sodium acetate, sodium octenoate, potassium hydroxide, potassium carbonate, potassium bicarbonate, Potassium methoxide, potassium ter
t-butoxide, potassium phenolate, potassium acetate, potassium octenoate and the like.

The amount of the Group I metal compound and / or Group II metal compound used is, for example, 100% by weight of the reaction raw material.
Is preferably 0.01 to 5% by weight.
Thereby, a carbonate compound having an unsaturated bond can be efficiently produced. More preferably, 0.
It is 0.5 to 2% by weight.

In the above-mentioned production method, it is also possible to prevent the polymerization of an aliphatic alcohol having an unsaturated bond or a carbonate compound having a polymerizable unsaturated bond, thereby stably producing the compound. It is preferred to use inhibitors. Examples of such a polymerization inhibitor include, for example,
Preferred are N-oxyls and the like, for example, 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-.
All, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 1-oxyl-2,2,
6,6-tetramethylpiperidin-4-yl-acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate, 1-oxyl-2,2,6 , 6-Tetramethylpiperidine-4
-Yl-stearate, 1-oxyl-2,2,6,6
-Tetramethylpiperidin-4-yl-4-t-butylbenzoate, bis (1-oxyl-2,2,6,6-
Tetramethylpiperidin-4-yl) succinate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (1-oxyl-
2,2,6,6-tetramethylpiperidin-4-yl)
n-butylmalonic acid ester, bis (1-oxyl-
2,2,6,6-tetramethylpiperidin-4-yl)
Phthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidine- 4-yl) adipamide, N- (1-oxyl-
2,2,6,6-tetramethylpiperidin-4-yl)
Caprolactam, N- (1-oxyl-2,2,6,6
-Tetramethylpiperidin-4-yl) dodecylsuccinimide, 2,4,6-tris- [N-butyl-N-
(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine, 1-oxyl-
2,2,6,6-tetramethylpiperidin-4-one and the like. These may be used alone or in combination of two or more.

The amount of the polymerization inhibitor to be used is preferably, for example, 0.001 to 1% by weight based on 100% by weight of the reaction raw material. More preferably, 0.00
5 to 0.5% by weight. As a method of using the polymerization inhibitor, it is preferable to mix the polymerization inhibitor with the reaction raw materials before performing the reaction.

The reaction method in the above production method includes:
For example, the reaction can be performed by preparing a mixture of reaction raw materials in which predetermined amounts of a reaction raw material, a group I metal compound and / or a group II metal compound, and a polymerization inhibitor are mixed, and heating the mixture. The reaction conditions such as the reaction temperature and pressure may be appropriately set according to the composition of the reaction raw materials used, the catalyst, and the like. For example, the reaction temperature is preferably set to 50 to 300 ° C. More preferably, it is 80 to 220 ° C. In addition, the reaction can be performed under normal pressure, pressure, vacuum conditions, and the like, and the reaction can be performed in various solvents.

In the above production method, since alcohol is generated during the reaction, it is preferable to remove the generated alcohol from the reaction system in order to improve the reaction efficiency. As a method of removing the generated alcohol from the reaction system,
For example, a method of separating and recovering with a condenser, a method of distilling out of the reaction system by azeotropy with various reaction solvents, a method of distilling off by reaction under reduced pressure, and the like are suitably applied. When unreacted raw materials and other by-products are contained in the obtained product, for example, the product after the reaction is washed with water and dried,
Unreacted raw materials and the like can be collected by an evaporator or the like. Thereby, a carbonate compound having an unsaturated bond having high purity can be obtained.

In the above production method, the aliphatic alcohol or fatty acid having an unsaturated bond represented by the general formula (4) in the reaction raw material may be used depending on the use of the carbonate compound having an unsaturated bond, desired physical properties, and the like. The kind and amount of the group polyhydric alcohol and / or the alicyclic polyhydric alcohol are appropriately set. In addition, by appropriately setting the type and amount of the group I metal compound and / or the group II metal compound, reaction conditions, and the like, the entire terminal structure of the carbonate compound having an unsaturated bond is represented by the general formula (1). It is possible to use a structure or a part of the structure as a hydroxyl group or an alkoxyl group.

The carbonate compound of the present invention has the formula -OC
Since it has good biodegradability due to the O-O-bond and has a polymerizable unsaturated bond, it can be used as a highly functional material. Further, by making the above compound an aliphatic carbonate compound,
It is possible to improve biodegradability. In addition, when the reaction is carried out in the presence of a group I metal compound and / or a group II metal compound, the color can be reduced.

The biodegradable resin composition of the present invention contains at least 5% by weight of a carbonate compound having an unsaturated bond, and one or more of these compounds can be used. If the amount is less than 5% by weight, the biodegradability is inferior, preferably 10 to 95% by weight, more preferably 15 to 90% by weight, further preferably 20% by weight.
~ 90% by weight. The weight ratio of the carbonate compound is a weight ratio when the total amount of the composition is 100% by weight.

In the biodegradable resin composition of the present invention, the compound having a terminal structure represented by the general formula (1) is -O-CO
Since it is a carbonate compound having an -O- bond, it has biodegradability due to this. Further, since the terminal structure represented by the general formula (1) has a polymerizable unsaturated bond, it is useful as a composition capable of exhibiting functionality such as polymerizability. in this way,
The biodegradable resin composition of the present invention contains a carbonate compound having a polymerizable unsaturated bond and has its functionality. Therefore, the biodegradable resin composition of the present invention, for example, as a curable composition,
The composition containing the polyfunctional compound can be used for various uses. As its application, it has good biodegradability, and is used for medical purposes and the like.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The obtained compound was identified by FT-NMR
The measurement was performed by measuring ¹ H-NMR and ¹³ C-NMR using UNITY PLUS 400 (manufactured by Varian). CDCl ₃ containing 0.05% tetramethylsilane was used as a measurement solvent.

Example 1 The following compounds were charged into a four-necked flask equipped with a gas inlet, a condenser, a thermometer, and a stirrer. Trimethylolpropane 8.05 g 2-hydroxyethyl methacrylate 25.77 g Diethyl carbonate 23.39 g Sodium hydroxide 0.54 g 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.1 g Dry air circulation The mixture was stirred at 100 ° C. for 8 hours, and only the generated ethanol was separated and collected by a condenser. After the reaction, the product was washed with water and dried, and an unreacted raw material was recovered by an evaporator. 40 g of a clear, colorless, viscous liquid were obtained. ¹ H-NMR of the compound contained in the obtained viscous liquid, ¹³ C-
When the NMR was measured, 1.93 ppm, 5.58 pp attributed to the methacryloyl group was determined from ¹ H-NMR.
m, a peak at 6.15 ppm, and a peak at 151.5 ppm attributed to a carbonate bond were confirmed from ¹³ C-NMR.

Example 2 The following compounds were charged into a four-necked flask equipped with a gas inlet, a condenser, a thermometer, and a stirrer. Glycerin 9.21 g Dimethyl carbonate 29.7 g 4-hydroxybutyl acrylate 47.6 g Potassium carbonate 0.42 g 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.05 g Under a stream of dry air, 80 The mixture was stirred at 8 ° C for 8 hours, and only the generated methanol was separated and collected by a condenser. After the reaction, the product was washed with water and dried, and an unreacted raw material was recovered by an evaporator. 55 g of a colorless viscous liquid were obtained. ¹ H-NMR, ¹³ C-NMR of compounds contained in the obtained viscous liquid
Was measured, it was found from ¹ H-NMR that 5.80 ppm, 6.05 ppm, and 6.4 were assigned to the acryloyl group.
A peak at 3 ppm and a peak at 151.5 ppm attributed to a carbonate bond were confirmed from ¹³ C-NMR.

Example 3 The following compounds were charged into a four-necked flask equipped with a gas inlet, a condenser, a thermometer, and a stirrer. Dipentaerythritol 25.4 g Diethyl carbonate 70.8 g Pentaerythritol trimethacrylate 204.2
g Sodium acetate 0.49 g 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.05 g Stir at 100 ° C. for 8 hours under a flow of dry air, and separate and collect only the generated ethanol with a condenser did. After the reaction, the product was washed with water and dried, and an unreacted raw material was recovered by an evaporator. 203 g of a colorless solid were obtained. When ¹ H-NMR and ¹³ C-NMR of the compound contained in the obtained viscous liquid were measured, the compounds were found to be 1.93 ppm, 5.58 ppm, 6.1 belonging to the methacryloyl group based on the ¹ H-NMR.
A peak of 5 ppm and a peak of 151.5 ppm attributed to a carbonate bond were confirmed from ¹³ C-NMR.

Example 4 The following compounds were charged into a four-necked flask equipped with a gas inlet, a condenser, a thermometer, and a stirrer. Sorbitol 18.2 g Diethyl carbonate 78.0 g Diethylene glycol acrylate 105.7 g Potassium acetylacetonate hemihydrate 1
47.22 g 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.05 g The mixture was stirred at 100 ° C. for 8 hours under a flow of dry air, and only the generated ethanol was separated and collected by a condenser. After the reaction, the product was washed with water and dried, and an unreacted raw material was recovered by an evaporator. 110 g of a colorless viscous liquid were obtained. ¹ H-NMR, ¹³ C-N of the compound contained in the obtained viscous liquid
As a result of measuring MR, 5.80 ppm and 6.05 ppm assigned to the acryloyl group were obtained from ¹ H-NMR,
A peak at 6.43 ppm and a peak at 151.5 ppm attributed to a carbonate bond were confirmed from ¹³ C-NMR.

Example 5 The following compounds were charged into a four-necked flask equipped with a gas inlet, a condenser, a thermometer, and a stirrer. Lactose 34.2 g dimethyl carbonate 79.3 g 2-hydroxyethyl acrylate 102.2 g sodium phenolate trihydrate 1.36 g 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl 0.05 g dry The mixture was stirred at 80 ° C. for 8 hours while flowing air, and only the generated ethanol was separated and collected by a condenser. After the reaction, the product was washed with water and dried, and an unreacted raw material was recovered by an evaporator. 118 g of a colorless viscous liquid were obtained. ¹ H-NMR, ¹³ C-NM of the compound contained in the obtained viscous liquid
The measured R, 5.80 ppm from ¹ H-NMR attributable to an acryloyl group, 6.05ppm, 6.
A peak at 43 ppm and a peak at 151.5 ppm attributed to a carbonate bond were confirmed from ¹³ C-NMR.

Comparative Example 1 The following compound was charged into a four-necked flask equipped with a gas inlet, a condenser, a thermometer, and a stirrer. 9.53 g of pentaerythritol 28.3 g of triphosgene 37.4 g of 2-hydroxyethyl methacrylate 40 g of potassium carbonate The mixture was stirred at 40 ° C. for 8 hours under a flow of dry air. During the reaction, phosgene gas which came out of the system was collected. After the reaction, the product was washed with water and dried, and an unreacted raw material was recovered by an evaporator.

Comparative Example 2 The following compound was charged into a four-necked flask equipped with a gas inlet, a condenser, a thermometer, and a stirrer. Tetraethylene glycol 13.5 g 2- (chlorocarbonyloxy) ethyl methacrylate
27.0 g pyridine 11.6 g The mixture was stirred at 40 ° C. for 8 hours under a flow of dry air. During the reaction, phosgene gas which came out of the system was collected. After the reaction, the product was washed with water and dried, and an unreacted raw material was recovered by an evaporator.

With respect to the compounds obtained in Examples 1 to 5,
Further, the structure was confirmed by mass (MS) spectrum measurement and elemental analysis. The measurement conditions of the mass (MS) spectrum are shown below.

(Mass Spectrum (Mass Spectrometry)) The mass spectrum was measured by a time-of-flight mass spectrometer Kompact M by a matrix-added laser desorption ionization method.
ALDI-III TOF mass spectrometer (K
(MALDI-TOF).
-MS). Α-Cyanocinnamic acid was used as a matrix, and lithium bromide was used as an ionizing agent.

¹ H—N of the compounds obtained in Examples 1 to 5
The measurement results of the MR spectrum, the ¹³ C-NMR spectrum and the mass spectrum, and the results of the elemental analysis are shown below. The measurement results of the ¹ H-NMR spectrum were as follows: chemical shift, spin coupling constant (s: singlet, d: doublet, t: triplet, q: quadruple, m: multiplet, br: broad Peak), relative number of hydrogen atoms, ¹³ C-NMR spectrum measurement result is chemical shift, mass spectrum (MALDI-TOF-MS) measurement result is molecular ion peak, elemental analysis result is compound The weight ratio (percentage) of carbon atoms, hydrogen atoms and oxygen atoms therein is shown.

Analysis of the compound contained in the viscous liquid obtained in Example 1 ¹ H-NMR: 0.96 (q, 3H), 1.25 (m,
2H), 1.93 (s, 9H), 3.9-4.2 (b
r, 6H), 4.3-4.5 (br, 12H), 5.5
8 (s, 3H), 6.15 (s, 3H); ¹³ C-NMR: 8.7, 18.4, 20.1, 31.
0, 66.4, 70.5, 71.3, 122.9, 13
8.0, 151.5, 165.0 MALDI-TOF-MS: 602.6 (M), 60
9.6 (M + Li) Elemental analysis: C, 53.8, H, 6.4, O, 39.8.

Analysis of the compound contained in the viscous liquid obtained in Example 2 ¹ H-NMR: 1.57 (m, 12 H), 4.16
(T, 12H), 4.40 (d, 4H), 5.15
(T, 1H), 5.80 (d, 3H), 6.05 (m,
3H), 6.43 (d, 3H) ^13C -NMR: 25.8, 26.5, 66.5, 70.
5, 71.2, 78.3, 128.6, 130.3, 1
51.5, 165.0 MALDI-TOF-MS: 602.5 (M), 60
9.4 (M + Li) Elemental analysis: C, 53.8, H, 6.4, O, 39.8.

Analysis of the compound contained in the viscous liquid obtained in Example 3 ¹ H-NMR: 1.93 (s, 54 H), 3.29
(S, 4H), 4.00-4.15 (m, 60H),
5.58 (d, 18H), 6.15 (d, 18H) ^13C -NMR: 18.4, 29.3, 64.1, 12
2.9, 138.0, 151.5, 165.0 MALDI-TOF-MS: 2452.5 (M), 24
59.4 (M + Li) Elemental analysis: C, 57.8, H, 6.3, O, 35.9.

Analysis of the compound contained in the viscous liquid obtained in Example ^{1 1} H-NMR: 3.50-3.80 (m, 24H)
4.20-4.45 (m, 28H), 5.12 (d, 2
H), 5.18 (m, 2H), 5.80 (d, 6H),
6.05 (m, 6H), 6.43 (d, 6H) ^13C -NMR: 67.5, 68.8, 69.2, 69.
6, 71.5, 73.0, 74.7, 128.6, 13
0.3, 151.5, 165.0 MALDI-TOF-MS: 1299.1 (M), 13
06.0 (M + Li) Elemental analysis: C, 49.9, H, 5.7, O, 44.4.

Analysis of the compound contained in the viscous liquid obtained in Example 5 ¹ H-NMR: 3.53 (t, 1 H), 4.15-5.
05 (m, 41H), 5.15-5.30 (t, 2
H) 5.45-5.70 (d, 1H), 5.80
(D, 8H), 6.05 (m, 10H), 6.43
(D, 10H), 6.66 (d, 1H) ^13C -NMR: 61.2, 63.8, 65.4, 66.
1, 69.3, 70.2, 70.5, 71.7, 74.
9, 76.5, 92.2, 98.7, 128.6, 13
0.3, 151.5, 165.0 MALDI-TOF-MS: 1479.2 (M), 14
86.1 (M + Li) Elemental analysis: C, 57.8, H, 6.2, O, 36.0.

[0056]

Industrial Applicability Since the carbonate compound having an unsaturated bond of the present invention has the above-mentioned constitution, it is biodegradable, and is an industrial material exhibiting high functionality by being polymerizable. It can be expected to be applied to various uses.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AB46 4J002 AA00X BG07W GB00 4J027 AB03 AB10 AB33 AC01 AC06 AJ06 CD07 4J100 AL66P AL67P BA08P BA22P CA01 CA03 JA50

Claims (2)

[Claims] An essential component is at least two molecules of an aliphatic polyhydric alcohol and / or alicyclic polyhydric alcohol having two or more hydroxyl groups, and at least two molecules of the polyhydric alcohol are bonded to each other by a carbonate bond. A carbonate compound having a structure represented by the following general formula (1): wherein at least two of the hydroxyl groups not participating in the bond between the polyhydric alcohols are represented by the following general formula (1): (Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² represents
The same or different, and represents an alkylene chain having 1 to 8 carbon atoms. m is an integer of 1 to 20. A) a carbonate compound having an unsaturated bond, wherein the carbonate compound has a structure substituted with a functional group represented by 2. A biodegradable resin composition comprising the carbonate compound having an unsaturated bond according to claim 1 in an amount of 5% by weight or more.