JP6323340B2 - Polycarbonate diol diacrylate compound composition and method for producing the same - Google Patents

Description

  The present invention relates to a polycarbonate diol diacrylate compound composition, a process for its production, its use as a curable composition for adhesives, and an adhesive comprising the curable composition for adhesives, and a polycarbonate diol diacrylate compound composition The invention relates to a reactor for production.

  The polycarbonate diol diacrylate compound composition is useful as a raw material for, for example, inks, paints, coating materials, adhesives, photocurable resins, crosslinking agents, electrolyte materials, and other resins. Specifically, JP-A-2009-157125 discloses a film-like optical waveguide using a polycarbonate diol diacrylate compound composition.

  The polycarbonate diol diacrylate compound composition is a composition of a polycarbonate diol diacrylate compound and a compound whose terminal is modified. In the above-mentioned use, the oligomer component may be eluted (bleed out) after the curing treatment, and may cause quality deterioration. Therefore, non-polymerizable compounds such as polycarbonate diol compounds and polycarbonate diol compounds that are not completely acrylated are used. There is a need for a polycarbonate diol diacrylate compound composition that is low in contamination and has a sufficiently large amount of polycarbonate diol diacrylate compound.

  In particular, since a purification method such as distillation and crystallization cannot be applied to a polycarbonate diol diacrylate compound composition, there is a method for directly producing a polycarbonate diol diacrylate compound composition in which a terminal hydroxy group is sufficiently acrylated. It has been demanded.

  In recent years, as a method for producing a polycarbonate diol diacrylate compound composition, for example, a method by reacting a polycarbonate diol and an unsaturated carboxylic acid ester compound in the presence of an organometallic catalyst while extracting the generated alcohol is known. (For example, refer to JP 2001-151730 A). However, the residue of the metal component derived from the organometallic catalyst can cause deterioration in quality, and therefore, a decomposition and recovery process of the catalyst component is required. Further, in the polycarbonate diol diacrylate compound composition obtained by this method, the mixing of the polycarbonate diol compound and the polycarbonate diol compound not completely acrylated has not been sufficiently reduced.

  International Publication No. 2011-122520 discloses a method for producing a polycarbonate diol diacrylate compound composition by reacting a polycarbonate diol with a vinyl (meth) acrylate compound in the presence of a hydrolase.

  JP 2011-207975 discloses a method for producing a polycarbonate diol diacrylate compound composition by reacting a polycarbonate diol with a (meth) acrylic acid ester compound in the presence of a hydrolase.

JP 2009-157125 A JP 2001-151730 A International Publication No. 2011-122520 JP 2011-207975 A

However, in the method described in International Publication No. 2011-122520, a polycarbonate diol diacrylate compound composition in which contamination of a polycarbonate diol compound or a polycarbonate diol compound not completely acrylated is reduced is obtained. It is difficult to obtain a vinyl (meth) acrylate compound. Therefore, it has been desired to propose a production method using readily available raw materials (for example, alkyl acrylate ester).
On the other hand, the polycarbonate diol diacrylate compound composition obtained by the method described in Japanese Patent Application Laid-Open No. 2011-207975 has not been sufficiently reduced in the mixing of the polycarbonate diol compound or the polycarbonate diol compound that is not completely acrylated. .

  An object of the present invention is to solve the above-described problems in the prior art. Specifically, it is to provide a polycarbonate diol diacrylate compound composition in which the polycarbonate diol compound and the polycarbonate diol compound which is not completely acrylated are little mixed and the abundance of the polycarbonate diol diacrylate compound is sufficiently large. . In particular, it is to provide a composition obtained from a polycarbonate diol and an unsaturated carboxylic acid ester compound without using a protic acid or a metal component.

  Another object of the present invention is to provide a method for producing the polycarbonate diol diacrylate compound composition.

The present invention includes the following aspects.
The first aspect of the present invention includes two or more kinds of polycarbonate derivatives represented by the formula (10), and the ratio of terminal functional groups measured by proton nuclear magnetic resonance method is a hydroxy group; 0.01-1. Polycarbonate having a range of 99 mol%, R ³ represented by formula (7); 0.01 to 1.99 mol%, group represented by formula (8); 98.00 to 99.98 mol% It is a diol diacrylate compound composition.

In the formula, X and Y are each independently a hydrogen atom, R ³ or a group represented by the formula (8), and R ¹ is the same or different and is a linear, branched or cyclic alkylene group. Wherein the divalent group may have a substituent and / or one or more non-terminal methylene groups are divalent aromatic groups, It may be replaced by a divalent heterocyclic group, an oxygen atom or a sulfur atom, or is a divalent group of a bridged carbocyclic ring, n represents the average degree of polymerization and is a number from 1 to 50 , R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. Group, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

A second aspect of the present invention is the formula (1)

(In the formula, R ¹ is the same or different and is a divalent group composed of one or more of a linear, branched or cyclic alkylene group, and the divalent group has a substituent. And / or one or more non-terminal methylene groups may be replaced with a divalent aromatic group, a divalent heterocyclic group, an oxygen atom or a sulfur atom, or A divalent group of a bridging carbocyclic ring, and each n independently represents an average degree of polymerization and is a number of 1 to 50), and a formula (7)

(Wherein R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³ is a linear or branched chain having 1 to 12 carbon atoms or A cyclic alkyl group, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.) In the presence of lipase. And a method for producing a polycarbonate diol diacrylate compound composition, comprising the step of contacting the resulting reaction mixture with a molecular sieve.

  According to the present invention, there is provided a polycarbonate diol diacrylate compound composition and a method for producing the same, in which the polycarbonate diol compound and the polycarbonate diol compound which is not completely acrylated are mixed little and the amount of the polycarbonate diol diacrylate compound is sufficiently large. Can be provided. The polycarbonate diol diacrylate compound composition of the present invention can be suitably used for a curable composition for adhesives and the like.

It is an example of the block diagram of the apparatus used for reaction by a distribution | circulation continuous type. It is another example of the block diagram of the apparatus used for reaction by a continuous flow type.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Further, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

(Polycarbonatediol diacrylate compound composition)
The polycarbonate diol diacrylate compound composition of the present invention (hereinafter also simply referred to as “composition”) includes two or more types of polycarbonate derivatives represented by the formula (10), and has a terminal end measured by proton nuclear magnetic resonance. The proportion of the functional group is a hydroxy group; 0.01 to 1.99 mol%, R ³ ; 0.01 to 1.99 mol%, a group represented by the formula (8); 98.00 to 99.98 mol% It is the composition containing the polycarbonate diol diacrylate compound which is the range shown by these. The polycarbonate diol diacrylate compound means a compound represented by the formula (10), wherein X and Y are represented by a group represented by the formula (8), and R ² in the formula (8) is limited to a hydrogen atom. Is not to be done.

In the formula, X and Y are each independently a hydrogen atom, R ³ or a group represented by the formula (8), and R ¹ is the same or different and is a linear, branched or cyclic alkylene group. Wherein the divalent group may have a substituent and / or one or more non-terminal methylene groups are divalent aromatic groups, It may be replaced by a divalent heterocyclic group, an oxygen atom or a sulfur atom, or is a divalent group of a bridged carbocyclic ring, n represents the average degree of polymerization and is a number from 1 to 50 , R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. Group, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. In addition, the wavy line in Formula (8) shows a coupling position.

The polycarbonate diol diacrylate compound composition of the present invention is preferably a polycarbonate diol compound represented by the formula (1), a polycarbonate diol monoacrylate compound represented by the formula (2), and a polycarbonate diol represented by the formula (3). (Monoalkyl ether) monoacrylate compound, polycarbonate diol monoalkyl ether compound represented by formula (4), and at least one selected from the group consisting of polycarbonate diol dialkyl ether compounds represented by formula (5), and formula ( The proportion of the functional group at the terminal, which is measured by proton nuclear magnetic resonance method, includes the polycarbonate diol diacrylate compound represented by 6) is a hydroxy group; 0.01 to 1.99 mol%, R ³ ; 0.01 to 1.99 Le%, based on the formula (8) which is a range indicated by 98.00 to 99.98 mol%, a polycarbonate diol diacrylate compound composition.

In the formula, R ¹ is the same or different and is a divalent group composed of one or more of a linear, branched or cyclic alkylene group, and the divalent group has a substituent. And / or one or more non-terminal methylene groups may be replaced by a divalent aromatic group, a divalent heterocyclic group, an oxygen atom or a sulfur atom, or a bridge A divalent group of a carbocyclic ring, each n independently represents an average degree of polymerization and is a number of 1 to 50, and R ² is a hydrogen atom or a linear or branched group having 1 to 4 carbon atoms. R ³ is a linear alkyl group having 1 to 12 carbon atoms, a branched or cyclic alkyl group, an aralkyl group having 7 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms. It is a group.

式中、Ｒ^２は、上記と同義である。

In the formula, R ² has the same meaning as described above.

The composition is a composition containing, as a main component, a compound represented by the formula (10), wherein X and Y are groups represented by the formula (8), that is, a compound represented by the formula (6). The composition of the compound group represented by the formula (10) contained in the composition or the composition of the compound group represented by the formulas (1) to (6) includes a hydroxy group in the terminal functional group, R ³ and the formula (8). Are selected so as to be in a predetermined range. The composition contains a compound represented by the formula (10) or a compound represented by the formulas (1) to (6) as a main component, and may further contain other components such as an organic solvent. The total content of the compound represented by the formula (10) or the compound represented by the formulas (1) to (6) is, for example, 90% by mass or more, and preferably 98% by mass or more. It is more preferable to consist of the compound shown by Formula (10) or the compound shown by Formula (1)-(6). Here, “substantially” means allowing other components to be contained as impurities.

In the composition, when the total amount of terminal functional groups measured by proton nuclear magnetic resonance method is 100 mol%, the amount of R ³ in the terminal functional groups is 0.01 to 1.99 mol%. The crosslink density can be improved by setting the content to 0.01 to 1.00 mol%, more preferably 0.01 to 0.50 mol%. Further, the amount of the hydroxy group in the terminal functional group is 0.01 to 1.99 mol%, preferably 0.01 to 1.00 mol%, more preferably 0.01 to 0.50 mol%. Thus, in addition to improving the cross-linking density, it can be applied to applications that dislike the presence of active hydrogen such as non-aqueous electrolytes.

  In addition to the above, the amount of the group represented by the formula (8) in the terminal functional group is 98.00 to 99.98 mol%, preferably 99.00 to 99.98 mol%, more preferably By setting it as 99.50-99.98 mol%, the amount of non-polymerizable compounds can be sufficiently reduced, and bleeding out of the cured product of the composition can be suppressed.

The composition includes at least one selected from the group consisting of compounds represented by formulas (1) to (5) and a compound represented by formula (6), wherein the hydroxy group in the terminal functional group The abundance is 0.01 to 1.99 mol%, the abundance of R ³ is 0.01 to 1.99 mol%, and the abundance of the group represented by formula (8) is 98.000 to 99.98 mol%. If it is the range of these, you may combine these compounds how. The compound represented by the formulas (1) to (5) may be only one of the compounds represented by the formulas (1) to (5) (in this case, the compound represented by the formula (4)) A combination of two or more of the compounds represented by formulas (1) to (5), or a combination including all of the compounds represented by formulas (1) to (5). Preferably, the compound shown by Formula (2) is included.

The abundance of the hydroxy group, R ³ and the group represented by formula (8) in the terminal functional group is measured by a proton nuclear magnetic resonance method. Specifically, the following procedure can be used.
(1) The proton nuclear magnetic resonance spectrum of the polycarbonate diol diacrylate compound composition is measured.
(2) Observation in each group from the integral value of the signal corresponding to R ³ in the proton nuclear magnetic resonance spectrum, the integral value of the signal corresponding to the hydroxy group, and the integral value of the signal corresponding to the group represented by the formula (8) In consideration of the number of protons to be produced, the total amount of the hydroxy group, R ³ and each group represented by the formula (8) is converted to 100 mol%, and the abundance of each group is calculated.
The measurement conditions of the proton nuclear magnetic resonance spectrum are not particularly limited as long as the presence of the hydroxy group, R ³ and the group represented by formula (8) can be measured with a desired accuracy.

  The polycarbonate diol diacrylate compound composition of the present invention can be efficiently produced, for example, by the production method described later.

(Method for producing polycarbonate diol diacrylate compound composition)
The process for producing the polycarbonate diol diacrylate compound composition of the present invention comprises the formula (1)

(In the formula, R ¹ is the same or different and is a divalent group composed of one or more of a linear, branched or cyclic alkylene group, and the divalent group has a substituent. And / or one or more non-terminal methylene groups may be replaced with a divalent aromatic group, a divalent heterocyclic group, an oxygen atom or a sulfur atom, or And a polycarbonate diol compound represented by formula (7): n is a divalent group of a bridged carbocycle, and n represents an average degree of polymerization and is a number from 1 to 50.

(Wherein R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³ is a linear or branched chain having 1 to 12 carbon atoms or A cyclic alkyl group, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.) In the presence of lipase. And a step of contacting the resulting reaction mixture with a molecular sieve. In the method for producing a polycarbonate diol diacrylate compound composition, the step of obtaining the reaction mixture and the step of bringing the reaction mixture into contact with the molecular sieve may be performed sequentially in different tanks or in the same tank. Also good.

  The reaction mixture includes a raw material mixture containing a polycarbonate diol represented by the formula (1), an unsaturated carboxylic acid ester compound represented by the formula (7), and an organic solvent, a polymerization inhibitor, and the like that are included as necessary, a lipase, Can be obtained by bringing them into contact with each other. By contacting the raw material mixture with lipase, a reaction mixture in which at least a part of the terminal hydroxy group of the polycarbonate diol is converted to an unsaturated carboxylic acid ester by an ester exchange reaction of the unsaturated carboxylic acid ester compound is obtained.

(Polycarbonate diol)
The polycarbonate diol used in the present invention has the formula (1):

(In the formula, R ¹ is the same or different and is a divalent group composed of one or more of a linear, branched or cyclic alkylene group, and the divalent group has a substituent. And / or one or more non-terminal methylene groups may be replaced with a divalent aromatic group, a divalent heterocyclic group, an oxygen atom or a sulfur atom, or A divalent group of a bridged carbocyclic ring,
n represents the average degree of polymerization and is a number from 1 to 50).
That is, R ¹ is a linear alkylene group, a branched alkylene group, a cyclic alkylene group, a divalent aromatic group, a divalent heterocyclic group, an oxygen atom, a sulfur atom, or a divalent group of a bridged carbocycle. A divalent group having at least one non-aromatic carbon atom at both ends, and the divalent group may have a substituent.

  Examples of the divalent group composed of one or more linear, branched or cyclic alkylene groups include, for example, a linear alkylene group, a branched alkylene group, a cyclic alkylene group, and a linear group. Or a branched alkylene group-a divalent group consisting of a cyclic alkylene group, a linear or branched alkylene group-a cyclic alkylene group-a divalent group consisting of a linear or branched alkylene group, Examples thereof include a divalent group composed of a cyclic alkylene group-a linear or branched alkylene group-a cyclic alkylene.

The number of carbon atoms of the linear alkylene group is preferably 1 to 25, more preferably 3 to 25, still more preferably 3 to 12, and particularly preferably 4 to 12. . Examples of the linear alkylene group (linear alkanediyl group) include a propylene group, a butylene group, a pentene group, a hexene group, a heptene group, an octene group, and a decene group, preferably a propylene group, It is a butylene group, a pentene group or a hexene group.
The number of carbon atoms of the branched alkylene group is preferably 3 to 25, more preferably 3 to 12, and still more preferably 4 to 12. Examples of branched alkylene groups (branched alkanediyl groups) include isopropylene group, isobutylene group, isopentene group, 3-methylpentene group, 2,4-diethyl-1,5-pentene group, and the like. Preferably, it is a 3-methylpentene group or a 2,4-diethyl-1,5-pentene group.

  The number of carbon atoms in the cyclic alkylene group is preferably 3 to 25, more preferably 3 to 12, and still more preferably 5 to 10. As the cyclic alkylene group, a cycloalkylene group having 3 to 12 carbon atoms (cycloalkanediyl group) is preferable. For example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclo Examples include an octylene group, and a cyclohexylene group is preferable.

  Examples of the divalent group consisting of the linear or branched alkylene group-cyclic alkylene group-linear or branched alkylene group include cyclopentane-1,3-dimethylene group, cyclohexane-1 , 4-dimethylene group and the like, preferably cyclohexane-1,4-dimethylene group.

  The above divalent group may have a substituent and / or one or more non-terminal methylene groups are divalent aromatic groups (for example, phenylene group, naphthylene group), divalent hetero groups. It may be substituted with a cyclic group (for example, pyridanyl group), an oxygen atom or a sulfur atom. For example, a benzene-1,4-dimethylene group corresponds to an alkylene group in which a non-terminal methylene group is replaced with a divalent aromatic group.

  Examples of the substituent include linear or branched alkyl groups having 1 to 6 carbon atoms (for example, methyl group and ethyl group), cycloalkyl groups having 3 to 12 carbon atoms (for example, cyclohexyl group), carbon atoms Aralkyl group having 7 to 10 carbon atoms (for example, benzyl group), aryl group having 6 to 12 carbon atoms (for example, phenyl group, tolyl group), alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group) ) And halogen atoms (for example, fluorine atom, chlorine atom).

R ¹ may be a divalent group of a bridged carbocycle. Here, the “bridged carbocycle” refers to a carbocycle in which two carbons that are not adjacent to each other are bridged by a bridging group or a direct bond. The divalent group of the bridged carbocycle is preferably a divalent group of a bridged carbocycle having 6 to 10 carbon atoms, such as bicyclo- [2.1.1] -hexane-diyl, bicyclo- [2.2. 1] -heptane-diyl, bicyclo- [2.2.2] -octane-diyl, bicyclo- [3.3.0] -octane-diyl, bicyclo- [4.3.0] -nonane-diyl, bicyclo -[4.4.0] -octane-diyl, adamantane-diyl and the like.

R ¹ is preferably a propylene group (propanediyl group), a butylene group (butanediyl group), a pentene group (pentanediyl group), a hexene group (hexanediyl group), or a 3-methylpentene group (3-methylpentanediyl group). And at least one selected from the group consisting of a cyclohexane-1,4-dimethylene group and a benzene-1,4-dimethylene group.

  In Formula (1), n represents an average degree of polymerization and is a number of 1 to 50, preferably 3 to 20. The average degree of polymerization can be measured by a proton nuclear magnetic resonance method.

The polycarbonate diol of the formula (1) may be produced by any method. For example, by a transesterification reaction between a dihydric alcohol (HO—R ¹ —OH) having a group corresponding to R ¹ in the formula (1) and a carbonate (eg, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate). The polycarbonate diol manufactured and the polycarbonate diol manufactured by reaction of said dihydric alcohol, chloroformate, or phosgene can be used. Examples of the dihydric alcohol include aliphatic dihydric alcohols having an alkylene group having 1 to 25 carbon atoms (preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms). Alternatively, a polycarbonate diol produced by ring-opening polymerization of a cyclic carbonate or the like can be used. Examples of the cyclic carbonate include cyclic carbonates having an alkylene group having 1 to 25 carbon atoms (preferably 3 to 12 carbon atoms, more preferably 4 to 12 carbon atoms).

Among them, it was produced by a transesterification reaction between an aliphatic dihydric alcohol having an alkylene group having 1 to 25 carbon atoms (preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms) and a carbonate. Polycarbonate diol is preferred. Examples of such aliphatic dihydric alcohols, R ¹ is a linear or branched dihydric alcohol corresponding to an alkylene group having a carbon number of 1 to 25, R ¹ is a carbon atom number of 3-25 cycloalkylene A divalent alcohol corresponding to the group, R ¹ is a linear or branched alkylene group-a cyclic alkylene group-a divalent group consisting of a linear or branched alkylene group, and R ¹ is a cycloalkylene-direct Examples thereof include dihydric alcohols corresponding to linear or branched alkylene-cycloalkylene.
Specific examples of the dihydric alcohol in which R ¹ represents a linear or branched alkylene group having 1 to 25 carbon atoms include 2-methyl-1,3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl- Those having a trimethylene moiety such as 2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 1,4-butane Those having a tetramethylene moiety such as diol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,5-pentanediol, 1, Those having a pentamethylene moiety such as 5-hexanediol, those having a hexamethylene moiety such as 1,6-hexanediol and 2-ethyl-1,6-hexanediol, and hepta such as 1,7-heptanediol Those having a methylene portion, those having an octamethylene portion of 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11 -Undecanediol, 1,12-dodecanediol, 1,20-eicosanediol and the like. Specific examples of the dihydric alcohol in which R ¹ corresponds to a cycloalkylene group having 3 to 25 carbon atoms include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, and the like. Can be mentioned. Specific examples of the divalent group in which R ¹ is a linear or branched alkylene group-cyclic alkylene group-linear or branched alkylene group include cyclohexane-1,4-dimethanol, cyclohexane -1,4-diethanol and the like. Specific examples of the dihydric alcohol in which R ¹ corresponds to cycloalkylene-linear or branched alkylene-cycloalkylene include 2,2-bis (4-hydroxycyclohexyl) propane.

In addition, dihydric alcohols other than those described above can also be used. For example, a non-terminal methylene group of R ¹ such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol or the like is an oxygen atom. Linear or branched alkylene in which the non-terminal methylene group of R ¹ such as 1,4-bis (hydroxyethoxy) cyclohexane or the like is replaced with an oxygen atom -Cycloalkylene-one that is a linear or branched alkylene group, or R ¹ such as 2,5-tetrahydrofuran dimethanol is a linear or branched alkylene-the non-terminal methylene group is replaced by an oxygen atom Cycloalkylene-linear or branched al It can also be used as an alkylene group. In addition, 2,7-norbornanediol, which is a divalent alcohol having a bridged carbocyclic ring, can also be used.

Furthermore, the divalent methylene group of R ¹ such as p-xylylene diol, p-tetrachloroxylylene diol, and benzene-1,4-dimethanol is unsubstituted or substituted with a halogen atom. Those which are alkylene groups replaced by aromatic groups can also be used. In addition, the non-terminal methylene group of R ¹ such as 1,4-bis (hydroxyethoxy) benzene and 2,2-bis [(4-hydroxyethoxy) phenyl] propane has one or more oxygen atoms and one or more Those having an alkylene group substituted with a divalent aromatic group can also be used. When R ¹ contains a dihydric alcohol having a divalent aromatic group, the content is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably with respect to the entire divalent alcohol. Is 15% by mass or less.

In the polycarbonate diol used in the present invention, R ¹ may be used alone or in combination of two or more. That is, when the polycarbonate diol is obtained by a transesterification reaction between a dihydric alcohol and a carbonate ester or a reaction between the dihydric alcohol and a chloroformate or phosgene, the dihydric alcohol is used alone or in combination of two or more. May be used in combination. Moreover, when polycarbonate diol is obtained by ring-opening polymerization of a cyclic carbonate, the cyclic carbonate may be used alone or in combination of two or more.

Polycarbonate diol of the formula (1), from the terms of good handling property, preferably R ¹ is a propylene group (propanediyl group), butylene group (butanediyl group), pentene group (pentanediyl group), hexene group (hexanediyl group) Polycarbonate diol which is at least one selected from the group consisting of 3-methylpentene group (3-methylpentanediyl group), cyclohexane-1,4-dimethylene group and benzene-1,4-dimethylene group. The polycarbonate diol of the formula (1) may be used alone or in combination of two or more.

(Unsaturated carboxylic acid ester compound)
The unsaturated carboxylic acid ester compound used in the present invention has the formula (7):

(Wherein R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³ is a linear or branched chain having 1 to 12 carbon atoms or A cyclic alkyl group, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.).

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group.
Among these, R ² is preferably a hydrogen atom or a methyl group.

The linear, branched or cyclic alkyl group having 1 to 12 carbon atoms in R ³ is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. A linear, branched or cyclic alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 2 carbon atoms (methyl group or ethyl group) is still more preferable.
Examples of the alkyl group in R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopropyl group, A cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ³ include a benzyl group and a phenethyl group. Examples of the aryl group having 6 to 10 carbon atoms in R ³ include a phenyl group and a tolyl group.

Among these, as R ³ , a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable, and a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms is preferable. More preferred is a methyl group or an ethyl group.

  Examples of the unsaturated carboxylic acid ester compound represented by the formula (7) include linear alkyl alkyl esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl methacrylate, and isopropyl acrylate. And acrylic acid branched or cyclic alkyl esters such as cyclohexyl methacrylate. Among these, at least one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate is preferable.

  The amount of the unsaturated carboxylic acid ester compound of the formula (7) used is preferably 2.0 to 60 mol, more preferably 2.2 to 45 mol, relative to 1 mol of the polycarbonate diol. More preferably, it is 0-45 mol. The number of moles of polycarbonate diol is calculated from the average molecular weight determined by the proton nuclear magnetic resonance method (see, for example, Polymer Experiments Vol. 18 (Polymer Magnetic Resonance), page 283, Kyoritsu Shuppan (published in 1975)). .

(Lipase)
The lipase used in the present invention is not particularly limited, but preferably a lipase derived from Burkholderia cepacia (for example, Amano PS (manufactured by Amano Enzyme)), Pseudomonas sp. (Pseudomonas) lipase (eg, LIP-301 (manufactured by Toyobo Co., Ltd.)), a lipase (eg, Lipase OF (manufactured by Meito Sangyo Co., Ltd.)), and alkali genes -It is at least 1 sort (s) selected from the group which consists of lipase (For example, Lipase PLG (made by a name sugar industry company)) which originates in SP (Alcaligenes sp.). Particularly preferred is a lipase originating from Burkholderia cepacia. These are lipases exhibiting low alcohol-carbonate exchange activity while exhibiting alcohol-ester exchange activity, which is advantageous in the present invention. Among the above lipases, lipases originating from Burkholderia cepacia (for example, Amano PS (manufactured by Amano Enzyme) and Amano PS are used because of a small decrease in the degree of polymerization of the polycarbonate chain. -CI (Amano PS / ceramic carrier adsorption, manufactured by Amano Enzyme)) is more preferable.

  The above lipase was obtained from a recombinant culture obtained by introducing a gene encoding a lipase obtained from the above microorganism into an appropriate host such as yeast or filamentous fungus. May be.

  Recombinant DNA techniques used for the expression of recombinant lipases are known in the art. The amino acid sequences used for the lipase recombinants are not limited to those originating from microorganisms as described above. For example, one or several amino acids are deleted, substituted or added in these amino acid sequences. A protein (lipase) having an amino acid sequence and having hydrolytic activity can be preferably used in the present invention. Alternatively, a protein (lipase) comprising these amino acid sequences and an amino acid sequence having a sequence identity (homology) of, for example, 90% or more, preferably 95%, more preferably 97% or more and having hydrolytic activity. It can be suitably used in the present invention.

  The form of these lipases is not particularly limited, and may be a crude enzyme or an immobilized lipase.

The immobilized lipase refers to a lipase supported on an immobilization carrier by adsorption or the like. Immobilization carriers include celite, diatomaceous earth, kaolinite, silica gel, molecular sieves, porous glass, activated carbon, calcium carbonate, ceramics and other inorganic carriers, ceramic powder, polyvinyl alcohol, polypropylene, chitosan, ion exchange resin, hydrophobic adsorption Examples thereof include organic polymers such as resins, chelate resins, and synthetic adsorption resins. As the immobilization carrier, a hydrophobic adsorption resin is particularly preferable from the viewpoint of high lipase adsorption power. Among the hydrophobic adsorption resins, porous particles are preferable because they have a large surface area and can increase the amount of lipase adsorbed.
Examples of the monomer constituting the hydrophobic adsorption resin include styrene, divinylbenzene, acrylic acid, acrylic acid ester and the like. The hydrophobic adsorption resin may be a homopolymer composed of one of these monomers or a copolymer composed of two or more of the monomers.
The magnitude | size of a porous particle is not specifically limited, For example, it can be set as 0.05-10.0 mm, and it is preferable that it is 0.10-2.0 mm. The BET specific surface area of the porous particles is preferably 10~2000m ² / g, more preferably 50~1500m ² / g.

  Immobilized lipase or lipase may be used alone or in combination of two or more.

  The amount of the immobilized lipase used is preferably 0.001 g to 10 g, more preferably 0.01 g to 2 g, and particularly preferably 0.05 g to 2 g with respect to 1 g of the polycarbonate diol of the formula (1). The amount of lipase used can be appropriately selected according to the hydrolysis activity of the lipase. The amount of lipase used is preferably 0.01 mg to 10 g, more preferably 0.1 mg to 1 g, further preferably 1 mg to 0.1 g per 1 g of polycarbonate diol.

  In the present invention, the reaction system in which the polycarbonate diol and the unsaturated carboxylic acid ester compound are reacted in the presence of lipase is not particularly limited, and includes a batch system or a continuous flow system in which an enzyme is immobilized. Yes, it can be done in any way.

(Range of solvent)
The reaction in the present invention can be performed using an organic solvent or without a solvent. The organic solvent is not particularly limited as long as it can dissolve the substrate and does not deactivate the lipase.

  Examples of the organic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, and cycloheptane; aromatic hydrocarbons such as benzene, toluene, and xylene. ; Ethers such as diethyl ether, t-butyl methyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane; ketones such as acetone and methyl ethyl ketone; from the group consisting of nitriles such as acetonitrile and propionitrile; There may be mentioned at least one selected. Preferably, it is at least one selected from the group consisting of n-hexane, n-heptane, cyclopentane, cyclohexane, toluene, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran and acetonitrile, and more preferably n -At least one selected from the group consisting of hexane, n-heptane, cyclohexane, toluene, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether and acetonitrile, particularly preferably n-heptane, cyclohexane, toluene and t- It is at least one selected from the group consisting of butyl methyl ether. These organic solvents may be used alone or in combination of two or more.

  The amount of the organic solvent used is preferably 0.1 to 100 mL, more preferably 0.5 to 50 mL, and particularly preferably 0.5 to 10 mL with respect to 1 g of the polycarbonate diol of the formula (1).

  The reaction in the present invention is preferably carried out in the presence of a polymerization inhibitor in order to prevent polymerization of the acrylate moiety. The polymerization inhibitor is not particularly limited as long as it is normally used. For example, phenol, cresol, hydroquinone, t-butylhydroquinone, p-methoxyphenol (methoquinone), 2,6-di-t-butyl-4 -Methylphenol, phenothiazine, etc. can be used. The amount of the polymerization inhibitor used is preferably 0.000001 to 0.05 mol, more preferably 0.000002 to 0.03 mol, relative to 1 mol of the polycarbonate diol.

(Contact process with molecular sieve)
In the present invention, after the reaction, the obtained reaction mixture is brought into contact with a molecular sieve. As a result, the alcohol by-produced by the reaction can be brought into a state not involving the raw material polycarbonate diol compound without being removed from the reaction mixture under reduced pressure and / or heating. As a result, the reaction proceeds promptly and lipase inactivation can be prevented.

  The molecular sieve is preferably a molecular sieve having an effective pore size of 1 to 10 cm (angstrom, 0.1 nm to 1 nm), more preferably at least one selected from the group consisting of natural zeolite and synthetic zeolite. It is a molecular sieve. Specifically, for example, zeolite (preferably molecular sieve (trade name)) is used.

(Zeolite)
As the zeolite, preferably used is a zeolite membrane in which zeolite is formed into a membrane on a porous support. As the zeolite membrane, a Y-type zeolite membrane is preferably used in which a Y-type zeolite is formed into a membrane on a porous support.
The contact between the zeolite membrane and the reaction mixture is performed by bringing the reaction mixture into contact with one side of the zeolite membrane, selectively permeating alcohol from the reaction mixture to the other side, and removing the permeated alcohol as alcohol vapor. Is preferred.

(Molecular sieve)
As the molecular sieve (trade name), molecular sieve 4A, molecular sieve 5A and the like are preferably used, and molecular sieve 4A is more preferably used.
The contact between the molecular sieve and the reaction mixture is preferably a method in which the molecular sieve is directly immersed in the reaction mixture or a method in which the reaction mixture is circulated through a column packed with the molecular sieve.

  The amount of molecular sieve used is not particularly limited and can be appropriately selected according to the type of molecular sieve. The amount of molecular sieve used is, for example, preferably 50 to 20,000 g, more preferably 100 to 10,000 g, and further preferably 500 to 5,000 g, per 1 mol of polycarbonate diol. preferable.

(Reaction temperature, pressure range)
In this invention, reaction temperature can be suitably selected according to the kind of lipase, etc., for example, can be 0-100 degreeC, Preferably it is 10-90 degreeC, More preferably, it is 30-70 degreeC. is there. In particular, it is preferable to select the reaction temperature according to the optimum temperature of the lipase to be used.

  In the present invention, the reaction pressure is not particularly limited, and the reaction can be performed under normal pressure or reduced pressure.

(Reaction form)
The reaction in the present invention can be carried out in either a batch reactor or a flow reactor. The “reaction tank” for carrying out the reaction and the tank for carrying out the contacting step with the molecular sieve (hereinafter also referred to as “molecular sieve tank”) may be the same or different. The production of the polycarbonate diol diacrylate compound composition can also be carried out while continuously circulating the reaction mixture (hereinafter also referred to as “circulation continuous type”).

When the reaction is carried out in a continuous flow mode, the concentration of the polycarbonate diol compound in the reaction solution is preferably 10 to 50% by mass relative to the total mass of the reaction system, and the concentration of the unsaturated carboxylic acid ester compound is It is preferable to set it as 5-30 mass% with respect to the total mass of a reaction system. Moreover, the liquid flow rate of the reaction mixture is preferably 0.5 to 400 mm / min, and more preferably 1 to 200 mm / min. The liquid flow rate (mm / min) is the cross-sectional area of the packed bed (mm ² ), which is the amount of liquid fed per minute (mm ³ / min) (or liquid feed rate (10 ⁻³ mL / min)). The value expressed by the quotient divided by. When the pressure inside the packed column increases by increasing the liquid flow rate, it becomes difficult to pass the liquid and an enzyme packed column with high pressure resistance is required. Therefore, it is preferable that the liquid passage speed is 400 mm / min or less. Further, from the viewpoint of productivity, it is preferable that the liquid flow rate is 1 mm / min or more. Since the expression activity of the immobilized enzyme changes depending on the flow rate, the reaction can be performed according to the desired production capacity and manufacturing cost by selecting the optimal flow rate and determining the reaction conditions. it can. The flow time of the reaction solution in the reaction vessel can be in the range of 30 seconds to 6 hours.

(Distributed continuous reactor)
The continuous flow reaction apparatus of the present invention is a reaction apparatus for producing the polycarbonate diol diacrylate compound composition of the present invention, and includes a reaction tank containing lipase, a molecular sieve tank containing molecular sieve, and a raw material before the reaction. The mixture and the reaction solution filling tank containing the reaction mixture after the reaction are sequentially connected so as to be able to circulate, and further, a flow continuous type configured to include a liquid feed pump for feeding the raw material mixture and the reaction mixture. This is a device that performs the reaction.
For example, a polycarbonate diol diacrylate compound composition can be efficiently produced by using the continuous flow reactor in the above-described method for producing a polycarbonate diol diacrylate compound composition.

As an apparatus for carrying out the reaction in a continuous flow mode, FIG. FIG. 1 shows that a reaction tank 1 containing lipase, a molecular sieve tank 2 containing molecular sieve, and a reaction liquid filling tank 3 containing a raw material mixture before reaction and a reaction mixture after reaction can be circulated sequentially. FIG. 2 is a schematic diagram of a continuous flow reactor for producing a polycarbonate diol diacrylate compound composition that is connected and further includes a liquid feed pump 4 that feeds a raw material mixture and a reaction mixture; It is preferably used in the method. By using the reaction apparatus, the reaction can be carried out continuously, and the place where the ratio of the terminal acrylate group is sufficiently increased (so-called reaction end point) can be determined.
A continuous flow reactor whose one embodiment is shown as a block diagram in FIG. 2 is also preferably used. In FIG. 2, a reaction vessel 5 containing lipase and a reaction vessel 6 containing a molecular sieve and containing a raw material mixture before reaction and a reaction mixture after reaction are connected so as to be able to circulate, and further, the raw material mixture and A liquid feed pump 7 for feeding the reaction mixture is included.

  When the reaction is carried out batchwise, the reaction time can be appropriately selected according to the type of lipase, the amount used, the reaction temperature, etc., for example, 0.1 to 720 hours, preferably 1 -360 hours, more preferably 2-240 hours.

Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
In addition, the qualitative and quantitative determination of the functional group at the end was measured by a proton nuclear magnetic resonance method, and the average molecular weight and the degree of polymerization were calculated from the measurement results by a proton nuclear magnetic resonance method. Here, in proton nuclear magnetic resonance, a measurement sample is prepared using CDCl ₃ as a solvent, and a ¹ H-NMR spectrum is obtained at 25 ° C. using a nuclear magnetic resonance spectrum measuring apparatus JNM-AL400 manufactured by JEOL. Measured and implemented.

Example 1 (Preparation of immobilized lipase PS)
Lipase PS “Amano” SDH (manufactured by Amano Enzyme) 150 g of 100 mM phosphate buffer solution (pH 7.0) and pure water were dissolved by adding 0.6 L, and the volume was adjusted to 3 L to prepare an immobilization solution. Thereto was added 600 g of a porous resin carrier (LEWATIT VPOC 1600, manufactured by LANXESS), and the mixture was stirred at 6 ° C. for 12 hours. Thereafter, the carrier was recovered by decantation, washed with pure water, and dried under reduced pressure to obtain immobilized lipase PS (352 g).

Example 2 (Production of a polycarbonate diol diacrylate compound composition in a batch system)
10.0 g of polycarbonate diol (UM90 (1/3) 1,6-hexanediol / 1,4-cyclohexanedimethanol copolymer carbonate diol (molar ratio = 1: 3): average molecular weight 900: manufactured by Ube Industries) 011 mol) was added 37.8 g (0.439 mol) of acrylic acid methyl ester, 10 mg of p-methoxyphenol and 10.0 g of molecular sieve 4A (1/16) as a polymerization inhibitor, and reacted for 24 hours while stirring.
Specifically, the reaction solution and 2.5 g of immobilized lipase PS prepared in Example 1 were added to a 100 ml glass reactor equipped with a cooling tube, and reacted at 40 ° C. for 24 hours with stirring (300 rpm). . At this time, after the polycarbonate diol and acrylic acid methyl ester reacted, the reaction mixture contacted the molecular sieve 4A.
After completion of the reaction, the reaction mixture was filtered through a 0.2 μm filter, and unreacted methyl acrylate and by-product alcohol components were distilled off from the filtrate under reduced pressure using a rotary evaporator. Dry under reduced pressure for hours.
The proportion of terminal acrylate groups in the resulting polycarbonate diol diacrylate compound composition is over 99.00 mol%, hydroxy groups are only less than 0.50 mol%, methyl groups are only less than 0.50 mol%. there were.

Example 3 (Preparation of polycarbonate diol diacrylate compound composition in batch mode)
In Example 2, the reaction was performed in the same manner as in Example 1 except that 50 ml of heptane was used as a solvent and the reaction time was 48 hours.
As a result, the ratio of the terminal acrylate group of the obtained polycarbonate diol diacrylate compound composition exceeds 99.00 mol%, the hydroxy group is less than 0.50 mol%, and the methyl group is only 0.50 mol. %.

Example 4 (Production of polycarbonate diol diacrylate compound composition in a batch system)
In Example 2, the reaction was performed in the same manner as in Example 1 except that 50 ml of t-butyl methyl ether was used as a solvent and the reaction time was 48 hours.
As a result, the ratio of the terminal acrylate group of the obtained polycarbonate diol diacrylate compound composition exceeds 99.00 mol%, the hydroxy group is less than 0.50 mol%, and the methyl group is only 0.50 mol. %.

Example 5 (Production of polycarbonate diol diacrylate compound composition in continuous flow)
For the reaction, a reaction apparatus shown as a configuration diagram in FIG. 1 was used.
Reaction tank 1 (inner diameter 30 mm × 300 mm, pore size 5 μm with glass filter); 75 g of immobilized lipase PS prepared in Example 1 was filled and kept at 40 ° C.
Molecular sieve tank 2: 200.0 g of molecular sieve 4A (1/16) was added.
Reaction liquid filling tank 3 (internal volume 1 L); polycarbonate diol (UM90 (1/3) 1,6-hexanediol / 1,4-cyclohexanedimethanol copolymer carbonate diol (molar ratio = 1: 3): average molecular weight 900 : Ube Industries, Ltd.) 200.0 g (0.22 mol) and acrylic acid methyl ester 700.0 g (8.14 mol) and p-methoxyphenol 20 mg as a polymerization inhibitor were added to prepare a raw material mixture.
From the reaction liquid filling tank 3, the raw material mixture was supplied to the reaction tank 1 by the liquid feed pump 4, and the reaction between the polycarbonate diol and acrylic acid methyl ester was carried out at 40 ° C. in the presence of lipase. The reaction mixture circulated through the reaction vessel 1 and was carried to the molecular sieve vessel 2 where it contacted the molecular sieve. Thereafter, the contact liquid was carried to the reaction liquid filling tank 3. Furthermore, it was supplied to the reaction tank 1 by the liquid feed pump 4, and the reaction and contact with the molecular sieve were repeated (continuous flow).
After 144 hours, since the proportion of the acrylate group at the end of the polycarbonate diol diacrylate compound composition accumulated in the reaction solution filling tank 3 exceeded 99 mol%, the reaction mixture was stopped from flowing.
The reaction mixture was collected, and the solvent of the obtained reaction mixture was distilled off under reduced pressure using a rotary evaporator, and then the residue was dried under reduced pressure in a 60 ° C. desiccator for 2 hours.
The proportion of terminal acrylate groups in the resulting polycarbonate diol diacrylate compound composition is over 99.00 mol%, hydroxy groups are only less than 0.50 mol%, methyl groups are only less than 0.50 mol%. there were.

Example 6 (Production of polycarbonate diol diacrylate compound composition in continuous flow)
For the reaction, a reaction apparatus shown as a configuration diagram in FIG. 1 was used.
Reaction tank 1 (inner diameter 50 mm × length 200 mm, pore size 5 μm with glass filter); 151.2 g of the immobilized lipase PS prepared in Example 1 was filled and kept at 35 to 45 ° C. with a ribbon heater.
Molecular sieve tank 2 (inner diameter 80 mm × length 200 mm, with pore size 5 μm glass filter); 873.9 g of molecular sieve 4A (1/8) was added.
Reaction liquid filling tank 3 (internal volume 5 L separable flask); polycarbonate diol (UM90 (1/3) 1,6-hexanediol / 1,4-cyclohexanedimethanol copolymer carbonate diol (molar ratio = 1: 3): Average molecular weight 910: A raw material mixture was prepared by adding 2675.8 g (31.1 mol) of methyl acrylate and 0.16 g of p-methoxyphenol as a polymerization inhibitor to 706.2 g (0.78 mol) manufactured by Ube Industries. The filling tank 3 was kept at 40 to 42 ° C. with an oil bath.
From the reaction liquid filling tank 3, the raw material mixture was supplied to the reaction tank 1 by the liquid feed pump 4, and the reaction between the polycarbonate diol and methyl acrylate was carried out at 35 to 45 ° C. in the presence of lipase. The reaction mixture circulated through the reaction vessel 1 and was carried to the molecular sieve vessel 2 where it contacted the molecular sieve. Thereafter, the contact liquid was carried to the reaction liquid filling tank 3. Furthermore, it was supplied to the reaction tank 1 by the liquid feed pump 4, and the reaction and contact with the molecular sieve were repeated (continuous flow).
After 87 hours, since the proportion of the acrylate group at the end of the polycarbonate diol diacrylate compound composition accumulated in the reaction solution filling tank 3 exceeded 99 mol%, the reaction mixture was stopped from flowing.
The reaction mixture was collected, and the solvent of the obtained reaction mixture was distilled off under reduced pressure using a rotary evaporator. Further, the residue was distilled off under reduced pressure at 60 ° C. oil bath at a vacuum degree of 1 mmHg (133 Pa) for 2 hours.
The resulting polycarbonate diol diacrylate compound composition had a terminal acrylate group ratio of 99.1 mol%, a hydroxyl group of only 0.3 mol%, and a carbonate methyl group of only 0.6 mol%.

Example 7 (Production of polycarbonate diol diacrylate compound composition in continuous flow)
For the reaction, a reaction apparatus shown as a configuration diagram in FIG. 2 was used.
Reaction tank 5 (inner diameter 15 mm × 100 mm, pore size 5 μm with glass filter); 5.8 g of immobilized lipase PS prepared in Example 1 was filled and kept at 40 ° C.
Reaction tank 6 (internal volume 0.25 L); UH-200 (poly (1,6-hexanediol carbonate)) diol: average molecular weight 2000: manufactured by Ube Industries) 40.0 g (0.02 mol) methyl acrylate 68 .9 g (0.80 mol) and 80 ml of t-butyl methyl ether were added and dissolved, and then 20.0 g of molecular sieve 4A (1/16) and 10 mg of p-methoxyphenol as a polymerization inhibitor were added to prepare a raw material mixture. did.
From the reaction liquid tank 6, the raw material mixture was supplied to the reaction tank 5 by the liquid feed pump 7, and the reaction between the polycarbonate diol and acrylic acid methyl ester was carried out at 40 ° C. in the presence of lipase. The reaction mixture circulated through the reaction vessel 5 and contacted with the molecular sieve in the reaction vessel 6. Furthermore, it was supplied to the reaction tank 5 by the liquid feed pump 7, and the reaction and contact with the molecular sieve were repeated (continuous flow).
After 168 hours, since the proportion of the acrylate group at the end of the polycarbonate diol diacrylate compound composition accumulated in the reaction solution tank 6 exceeded 99 mol%, the reaction mixture was stopped from flowing.
The reaction mixture was recovered and the solvent was distilled off under reduced pressure using a rotary evaporator, and then the residue was dried under reduced pressure in a 60 ° C. desiccator for 2 hours to obtain 40.85 g of a colorless polycarbonate diol diacrylate compound composition.
The ratio of the terminal acrylate group of the obtained polycarbonate diol diacrylate compound composition exceeded 99 mol%, the hydroxy group was only 0.2 mol%, and the methyl group was only 0.5 mol%.

(Adhesion test)
A polycarbonate diol diacrylate compound composition (Test Example 1) having a terminal acrylate group ratio of 99.1 mol% synthesized in Example 6 and a polycarbonate diol (UM90 (1/3) 1 in Example 6). , 6-hexanediol / 1,4-cyclohexanedimethanol copolymer carbonate diol (molar ratio = 1: 3): average molecular weight 900: manufactured by Ube Industries, Ltd. was added, and the ratio of terminal acrylate groups was 98.0 mol. %, 94.9 mol%, 78.6 mol% and 49.5 mol% were prepared as polycarbonate diol diacrylate compound compositions (Test Examples 2 to 5).
To 2 g of each polycarbonate diol diacrylate compound composition, 0.5 g of an ethyl acetate solution in which the initiator was dissolved (0.05 g of initiator IRGACURE 819 dissolved in 1 g of ethyl acetate) was added. The prepared solution was applied onto a 150 mm × 70 mm polystyrene (PS) or ABS resin substrate so that the coating thickness after drying was 50 μm. After drying the solvent in an oven at 80 ° C. for 30 minutes, the surface is covered with a PET film, and a UV irradiation device (manufactured by Sen Special Light Source Co., Ltd.) is used to cure the coating film with an integrated light quantity of 1000 mJ / cm ^2. Formed.
Using a dedicated jig, 11 cuts were made in the coating film at 2 mm intervals in the vertical and horizontal directions to make 100 squares. A cellophane tape was applied to the entire mass and rubbed with an eraser for good adhesion. The cellophane tape was peeled off vigorously, and the adhesion to the substrate was evaluated. The test was terminated if even one cell was peeled off, and the test was repeated up to 10 times until peeled off. The number of cells remaining without being peeled on the substrate surface after the test was completed and the number of times the test was conducted until peeling were taken as the evaluation results. The evaluation results are shown in Table 1. In addition, the evaluation result of adhesiveness was described as x / 100 (y), where x is the number of cells remaining without being peeled and y is the number of tests performed before peeling.
The polycarbonate diol diacrylate compound composition having an acrylate group ratio of 99.1 mol% is 97/100 (1) for polystyrene (PS) and 98/100 (2) for ABS, and has good adhesion to the substrate. It was good. On the other hand, the polycarbonate diol diacrylate compound composition with 94.9 mol% of acrylate groups was 48/100 (1) and 85/100 (2) with ABS, indicating a decrease in adhesion.

  The present invention relates to a polycarbonate diol diacrylate composition and a method for producing the same. The polycarbonate diol diacrylate compound composition is a compound useful as a raw material for, for example, inks, paints, coating materials, adhesives, photocurable resins, crosslinking agents, electrolyte materials, and other resins.

  The disclosures of Japanese Patent Application No. 2013-021107 and Japanese Patent Application No. 2013-105254 are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims (9)

Formula (1)

(Where
R ¹ is the same or different and is a divalent group composed of one or more of a linear, branched or cyclic alkylene group, and the divalent group may have a substituent. And / or one or more non-terminal methylene groups may be replaced by a divalent aromatic group, a divalent heterocyclic group, an oxygen atom or a sulfur atom, or A divalent group,
n represents the average degree of polymerization each independently, and is a number of 1-50. )
A polycarbonate diol compound represented by formula (7):

(Where
R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
R ³ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. )
Bulk hydreria cepacia (Pseudomonas cepacia) using an unsaturated carboxylic acid ester compound represented by the formula ( 1) using at least one organic solvent selected from the group consisting of heptane and t-butyl methyl ether or without solvent A process for producing a polycarbonate diol diacrylate compound composition comprising the steps of obtaining a reaction mixture by reacting in the presence of a lipase originating from (Burkholderia cepacia) , and contacting the resulting reaction mixture with a molecular sieve. Molecular sieve, is a molecular sieve having an effective pore size of 0.1Nm～1nm, The method according to claim 1 polycarbonate diol diacrylate compound composition. The method for producing a polycarbonate diol diacrylate compound composition according to claim 2 , wherein the molecular sieve is at least one molecular sieve selected from the group consisting of natural zeolite and synthetic zeolite. Method of manufacturing R ² is a polycarbonate diol diacrylate compound composition according to any one of claim 1 to 3 which is a hydrogen atom or a methyl group. R ³ is straight-chain C1-4 method of polycarbonate diol diacrylate compound composition according to any one of claims 1 to 4, which is a branched or cyclic alkyl group. The ratio of the terminal functional group measured by a proton nuclear magnetic resonance method includes two or more kinds of polycarbonate derivatives represented by the formula (10).
Hydroxy group; 0.01 to 1.99 mol%,
R ³ ; 0.01 to 1.99 mol%,
Group represented by formula (8); 98.00 to 99.98 mol%
A polycarbonate diol diacrylate compound composition, which is a range represented by the formula ( 1), which contains at least one organic solvent selected from the group consisting of heptane and t-butyl methyl ether, or is solvent- free. A reaction apparatus for the production of a compound composition comprising a reaction vessel containing a lipase originating from Burkholderia cepacia , a molecular sieve vessel containing a molecular sieve, and a pre-reaction vessel The raw material mixture and the reaction liquid filling tank containing the reaction mixture after the reaction are sequentially connected so as to be able to circulate, and further, a flow continuous type configured to include a liquid feed pump for feeding the raw material mixture and the reaction mixture Reactor.

(Where
X and Y are each independently a hydrogen atom, R ³ or a group represented by formula (8);
R ¹ is the same or different and is a divalent group composed of one or more of a linear, branched or cyclic alkylene group, and the divalent group may have a substituent. And / or one or more non-terminal methylene groups may be replaced by a divalent aromatic group, a divalent heterocyclic group, an oxygen atom or a sulfur atom, or A divalent group,
n represents each independently an average degree of polymerization, and is a number of 1 to 50,
R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
R ³ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. ) A polycarbonate diol compound represented by the formula (1):
A polycarbonate diol monoacrylate compound represented by the formula (2):
Polycarbonate diol (monoalkyl ether) monoacrylate compound represented by formula (3),
At least one selected from the group consisting of a polycarbonate diol monoalkyl ether compound represented by the formula (4) and a polycarbonate diol dialkyl ether compound represented by the formula (5);
A polycarbonate diol diacrylate compound represented by the formula (6),
The proportion of terminal functional groups measured by proton nuclear magnetic resonance is
Hydroxy group; 0.01 to 1.99 mol%,
R ³ ; 0.01 to 1.99 mol%,
Group represented by formula (8); 98.00 to 99.98 mol%
A polycarbonate diol diacrylate compound composition, which is a range represented by the formula ( 1), which contains at least one organic solvent selected from the group consisting of heptane and t-butyl methyl ether, or is solvent- free. A reaction apparatus for the production of a compound composition, comprising a reaction vessel comprising a lipase originating from Burkholderia cepacia , a molecular sieve vessel comprising a molecular sieve, and a pre-reaction vessel The raw material mixture and the reaction liquid filling tank containing the reaction mixture after the reaction are sequentially connected so as to be able to circulate, and further, a flow continuous type configured to include a liquid feed pump for feeding the raw material mixture and the reaction mixture Reactor.

(Where
R ¹ is the same or different and is a divalent group composed of one or more of a linear, branched or cyclic alkylene group, and the divalent group may have a substituent. And / or one or more non-terminal methylene groups may be replaced by a divalent aromatic group, a divalent heterocyclic group, an oxygen atom or a sulfur atom, or A divalent group,
n represents each independently an average degree of polymerization, and is a number of 1 to 50,
R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
R ³ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. )

(Where
R ² has the same meaning as described above. ) The reaction apparatus according to claim 6 or 7, wherein R ² is a hydrogen atom or a methyl group. The reaction apparatus according to any one of claims 6 to 8, wherein R ³ is a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.

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