JP5552866B2 - Method for producing polycarbonate polyol polyacrylate - Google Patents

Description

  The present invention relates to a method for producing a polycarbonate polyol polyacrylate compound (a compound in which a hydroxyl group of a polycarbonate polyol is acrylated with an acrylate compound). More specifically, the present invention relates to a method for producing a polycarbonate polyol polyacrylate compound in the presence of a catalyst from a polycarbonate polyol and a vinyl acrylate compound.

  The polycarbonate polyol polyacrylate compound is a compound useful as a raw material for inks, paints, coating materials, adhesives, photocurable resins, crosslinking agents, electrolyte materials, and other resins. For example, Patent Document 1 discloses a film-shaped optical waveguide using polycarbonate polyol polyacrylate.

As a method for producing a polycarbonate polyol polyacrylate compound, a method in which a polycarbonate polyol and acrylic acid are reacted in the presence of a proton acid catalyst such as p-toluenesulfonic acid is known (for example, see Patent Document 2).
However, this method has a big problem concerning the quality of the product that the obtained polycarbonate polyol polyacrylate compound is colored brown. Furthermore, in this method, since the raw material acrylic acid is used in excess, even after synthesis, even if they are removed by neutralization and washing with water, the resulting product contains an acid catalyst and sulfur content resulting from the raw material. There is a problem that impurities remain and quality deterioration (bad odor, metal corrosion) easily occurs.

  In addition, a method for producing a polycarbonate polyol polyacrylate compound by reacting a polycarbonate polyol and an alkyl acrylate ester compound in the presence of an organometallic catalyst while extracting the alcohol to be produced is known (for example, see Patent Document 3). However, this method has a problem that when the by-product alcohol is distilled off, the raw material alkyl acrylate azeotropes and may come out of the reaction system, and complicated operations are required to avoid this. What was required was an issue.

JP 2009-157125 A JP 2002-25335 A JP 2001-151730 A

  An object of the present invention is to provide a method for solving the above-described problems in the prior art. Specifically, an object of the present invention is to provide a method for producing a simple polycarbonate polyol polyacrylate compound that does not require a distillation operation of by-product alcohol.

  As a result of intensive studies to solve the problems, the present inventors require a complicated by-product distillation operation during the reaction by transesterification of polycarbonate polyol and vinyl acrylate compound in the presence of a catalyst. However, a novel industrial production process for obtaining a polycarbonate polyol polyacrylate compound was found and the present invention was achieved.

  That is, the subject of this invention is solved by the manufacturing method of the polycarbonate polyol polyacrylate compound characterized by making linear or branched polycarbonate polyol and a vinyl acrylate compound react in presence of a catalyst.

  According to the present invention, it is possible to provide a method for producing a polycarbonate polyol polyacrylate compound that does not require a complicated operation of distilling off by-products.

  In addition, vinyl alcohol produces | generates as a by-product by using the compound which has the molecular structure of acrylic acid vinyl ester for reaction with polycarbonate polyol. Since this compound is immediately isomerized to a keto-type carbonyl compound, it is considered that there is an effect of shifting the equilibrium of the reaction to the production system. In addition, there is an effect that side reactions caused by by-product alcohol are suppressed. This achieves a high conversion to acrylate. Furthermore, alcohol is removed from the reaction system by immediately isomerizing the by-product alcohol. Therefore, it is possible to carry out the conversion reaction of the polycarbonate polyol without carrying out the complicated operation of carrying out the reaction without removing the acrylate as the reaction raw material azeotropically and removing the alcohol from the system.

(Polyol range)
The polycarbonate polyol used in the present invention has a carbonic acid ester structure in the molecular structure and has two or more hydroxyl groups at the terminal, and has a branched structure even if it is linear. May be. For example, a polycarbonate polyol can be represented by the formula (I):

(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 carbon atoms may be replaced by a divalent aromatic group, a divalent heterocyclic group, an oxygen atom or a sulfur atom, or It is a divalent group, and n represents an average degree of polymerization and is a number of 1 to 50).

  Examples of the divalent group composed of one or more of a linear, branched or cyclic alkylene group include, for example, a divalent group consisting of a linear or branched alkylene group-cyclic alkylene group, Chain- or branched-chain alkylene group-cyclic alkylene group-divalent group composed of linear or branched alkylene group, cyclic alkylene group-linear or branched alkylene group-cyclic alkylene The bivalent group which consists of is mentioned.

The linear or branched alkylene group preferably has 1 to 25 carbon atoms, more preferably 2 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, pentylene group, hexylene group, heptylene group, octylene group, and decylene group, preferably a butylene group, hexyl cyclohexylene group.

  The number of carbon atoms of the cyclic alkylene group is preferably 3 to 25, and more preferably 5 to 10. As the cyclic alkylene group, a cycloalkylene having 3 to 12 carbon atoms is preferable, and examples thereof include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and the like. A cyclohexylene group is preferred.

  The above divalent group may have a substituent and / or one or more carbon atoms other than the terminal 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, benzene-1,4-dimethylene group).

  Examples of the substituent include a linear or branched alkyl group having 1 to 6 carbon atoms (for example, a methyl group and an ethyl group), a cycloalkyl group having 3 to 12 carbon atoms (for example, a cyclohexyl group), and a carbon atom. 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) ), Halogen atoms (for example, fluorine atom, chlorine atom), hydroxyl group and the like.

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.

R ¹ is preferably a propylene group, butylene group, pentylene group, hexylene group, 3-methyl pentylene group, 1,4-cyclohexylene hexylene, 1,4-cyclohexane dimethylene group, 1,4-benzenedicarboxylic methylene group It is.

In the formula (I), 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 terminal group determination by ¹ H-NMR.

Any polycarbonate polyol produced by any known method can be used as the polycarbonate polyol. For example, an aliphatic dihydric alcohol (HO—R ¹ —OH) having an alkylene group having 4 to 25 carbon atoms (preferably 4 to 15 carbon atoms) corresponding to R ¹ in the formula (I) and a carbonate ester ( For example, transesterification with dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, etc.), ring-opening polymerization of a cyclic carbonate having an alkylene group having 2 to 25 carbon atoms (preferably 2 to 15 carbon atoms), Or what was manufactured by reaction of the said aliphatic dihydric alcohol, chloroformate, or phosgene etc. can be used. Among these production methods, the transesterification reaction between the aliphatic dihydric alcohol having an alkylene group having 4 to 25 carbon atoms (preferably 4 to 15 carbon atoms) and a carbonate is preferable.

Non-limiting examples of the dihydric alcohol include, for example, the following compounds. That is, 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-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl- Those having a trimethylene moiety such as 1,3-propanediol, those having a tetramethylene moiety such as 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2 , 2-diethyl-1,5-pentanediol, 1,5-hexanediol and other pentamethylene moieties, 1,6-hexanediol, 2-ethyl Those having a hexamethylene moiety such as 1,6-hexanediol, those having a heptamethylene moiety such as 1,7-heptanediol, and octane such as 1,8-octanediol and 2-methyl-1,8-octanediol Examples thereof include those having a methylene moiety, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,20-eicosanediol and the like. In addition, R ¹ is a dihydric alcohol corresponding to a cycloalkylene group having 4 to 15 carbon atoms. Specifically, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4- Dimethanol and cyclohexane-1,4-diethanol. In addition, 2,2-bis (4-hydroxycyclohexyl) propane or the like, in which R ¹ is a dihydric alcohol corresponding to cycloalkylene-linear or branched alkylene-cycloalkylene, can also be used. In addition, 2,2-bis (4-hydroxycyclohexyl) propane or the like, in which R ¹ is a dihydric alcohol corresponding to cycloalkylene-linear or branched alkylene-cycloalkylene, can also be used.

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

In addition, for the purpose of producing a polycarbonate polyol having a branched structure, ¹ on R ¹ such as 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 1,2,6-hexanetriol, etc. Polyhydric alcohols having three or more hydroxyl groups in which two or more hydrogen atoms are substituted with hydroxyl groups can also be used.

Furthermore, the thing which is the alkylene group substituted by the bivalent aromatic group by which R < ¹ > is unsubstituted or substituted by the halogen atom, such as p-xylylene diol, p-tetrachloro xylylene diol, is also used. can do. In addition, R ¹ is one or more oxygen atoms and one or more divalent aromatics such as 1,4-bis (hydroxyethoxy) benzene and 2,2-bis [(4-hydroxyethoxy) phenyl] propane. Those that are alkylene groups replaced by groups can also be used. The dihydric alcohol in which R ¹ has a divalent aromatic group is preferably 25% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less based on the entire dihydric alcohol.

In the polycarbonate polyol used in the present invention, each R ¹ may be the same or different between different unit structures. That is, when a polycarbonate polyol is obtained by a transesterification reaction between a dihydric alcohol and a carbonate ester or a reaction between a dihydric alcohol and a chloroformate or phosgene, the dihydric alcohol is one kind alone or two or more kinds. You may use together. Moreover, when polycarbonate polyol is obtained by ring-opening polymerization of cyclic carbonate, cyclic carbonate may be used alone or in combination of two or more.

(Vinyl acrylate range)
Examples of the vinyl acrylate compound used in the present invention include formula (II):

(Where
R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
R ³ is a hydrogen atom or a compound represented by a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.

In the formula (II), non-limiting examples of R ² include, for example, a hydrogen atom, a methyl group, and an ethyl group. Non-limiting examples of R ³ include, for example, a hydrogen atom, a methyl group, and an ethyl group. Propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, cyclopentyl group, cyclohexyl group and the like.

R ² is preferably a hydrogen atom or a methyl group. R ³ is preferably a hydrogen atom or a methyl group.

  Non-limiting examples of the vinyl acrylate compound of formula (II) include, for example, the following compounds. That is, acrylic acid alkenyl esters such as vinyl acrylate and isopropenyl acrylate, and methacrylic acid alkenyl esters such as vinyl methacrylate and isopropenyl methacrylate are listed. Of these, vinyl acrylate and vinyl methacrylate are preferred.

  The vinyl acrylate compound of the formula (II) may be used alone or in combination of two or more.

The amount of the vinyl acrylate compound used is 0.5 to 60 mol, more preferably 1.2 to 10 mol, based on 1 mol of free hydroxyl group in the polycarbonate polyol, from the viewpoint of adjusting the acrylate conversion rate of the hydroxyl group. preferable. The number of moles of polycarbonate polyol is calculated from the average molecular weight determined from ¹ H-NMR (terminal hydroxyl value) (for example, Polymer Experimental Studies Vol. 18 (polymer magnetic resonance), page 283, Kyoritsu Shuppan (1975). (See Annual Report)).

(Catalyst range)
The catalyst used in the present invention is not particularly limited as long as it is a transesterification catalyst. Examples of the transesterification catalyst include metal compounds such as titanium, tin, aluminum, zinc, copper, nickel, and iron, and proton acids such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and cationic ion exchange resins. And inorganic bases such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, and organic bases such as sodium methoxide, sodium ethoxide and potassium t-butoxide.

  Non-limiting examples of the metal compound include organic titanium compounds having 4 to 40 carbon atoms such as tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, and tetraphenoxy titanium, or dibutyltin. Organic tin compounds having an alkyl group, aryl group, or acyloxy group having 2 to 40 carbon atoms such as oxide, diphenyltin oxide, dibutyltin acetate, dibutyltin laurate, tin 2-ethylhexanoate, and carbon such as triisopropoxyaluminum Organoaluminum compounds having an alkoxy group of 3 to 30 atoms, zinc inorganic acid salts or organic acid salts such as zinc chloride and zinc acetate, copper inorganic acid salts or organic acids such as cupric chloride and copper acetate Of salt, nickel chloride, nickel acetate, etc. Machine and or organic acid salts, inorganic acid salts of iron such as ferric chloride.

  Among these catalysts, the organic titanium compounds, organotin compounds, and organoaluminum compounds are preferable, but the organic titanium compounds are more preferable. Examples of the organic titanium compound include, but are not limited to, tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetraphenoxy titanium, and the like.

  The amount of the catalyst used varies depending on the catalyst type, reaction conditions, etc., but the catalyst is 0.00001 to 0.3 mol, more preferably 0.0001 to 0.2 mol, especially 0.001 to 1 mol per mol of polycarbonate polyol. The ratio is preferably 0.1 mol. A single catalyst or a plurality of catalysts can be used.

(Reaction temperature)
The reaction temperature may be in a range where the reaction proceeds and the raw materials and products are not decomposed, and is usually 40 to 250 ° C, preferably 50 to 200 ° C, more preferably 60 to 180 ° C. The reaction pressure is not particularly limited as long as the reaction proceeds, and may be any of normal pressure, pressurization, and reduced pressure. The reaction atmosphere may be in the air, but is preferably in an inert gas atmosphere such as helium, nitrogen, or argon, or in an air stream. In addition, although reaction time changes with reaction conditions etc., it is the range of 0.1 to 100 hours normally.

(Polymerization inhibitor)
In order to prevent polymerization of the acrylate moiety, the reaction is preferably performed in the presence of a polymerization inhibitor. 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, per 1 mol of the polycarbonate polyol.

(solvent)
Moreover, it is preferable to perform the said reaction using a solvent as needed. The solvent is not particularly limited as long as it achieves the reaction temperature, dissolves the reaction product, and does not inhibit the reaction. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cyclooctane, cyclodecane, cyclododecane, and petroleum ether, aliphatic halogenated hydrocarbons such as dichloroethane and chloroform, benzene, and toluene. Aromatic hydrocarbons such as xylene, ethylbenzene and isopropylbenzene, and aromatic halogenated hydrocarbons such as chlorobenzene and chlorotoluene are used. Of these solvents, aromatic hydrocarbons and aromatic halogenated hydrocarbons are preferable, and among these, toluene and xylene are more preferable.
The amount of the solvent used is preferably 50 g or less, more preferably 0.01 to 40 g, particularly preferably 0.05 to 30 g based on 1 g of the polycarbonate polyol.

(Catalyst deactivation)
In the present invention, it is preferable to deactivate the catalyst after completion of the reaction. This catalyst deactivation is performed by adding at least one deactivator such as base, water, phosphate ester (dibutyl phosphate, etc.), phosphoric acid or the like to the reaction solution. When the above organic titanium compound, organotin compound, or organoaluminum compound is used as the catalyst, it is preferable to deactivate with at least one deactivator among water, phosphate ester, and phosphoric acid. It is particularly preferable to deactivate. Among the deactivators, the base is preferably used when the protonic acid is deactivated.

  The addition amount of the deactivator is preferably 1 to 5000 mol, more preferably 2 to 2000 mol, per 1 mol of the catalyst. The temperature at which the catalyst is deactivated is preferably 20 to 130 ° C, more preferably 30 to 120 ° C, and particularly preferably 50 to 110 ° C. Although the time in that case changes with other conditions, it is about 0.01 to 20 hours normally.

  After deactivation of the catalyst, insoluble matters are preferably removed by filtration or centrifugation. Thereafter, the produced polycarbonate polyol polyacrylate compound (compound in which the hydroxyl group of the polycarbonate polyol is acrylated with an acrylate compound) is obtained by distilling low-boiling components (such as an acrylate compound or a solvent) in the reaction solution at normal pressure or under reduced pressure. It can obtain by removing. The removal of the low boiling point component may be performed before the catalyst deactivation.

  The temperature at which the low-boiling components are removed by distillation varies depending on the acrylate compound, the solvent, etc., but the bath temperature is usually 20 to 120 ° C. If necessary, distillation may be carried out at a high temperature of 120 to 250 ° C., preferably 120 to 200 ° C. under reduced pressure, in order to remove a small amount of residual low boiling point components and low molecular weight components of the polycarbonate polyol polyacrylate compound. The recovered solvent and acrylic ester compound can be purified and reused as necessary.

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 average molecular weight and average polymerization degree of the polycarbonate polyol and the polycarbonate polyol polyacrylate compound were determined from ¹ H-NMR.

Example 1
Polycarbonate diol (UH-100: average molecular weight 1000, average degree of polymerization 7.0: Ube Industries, Ltd .: 1,6-hexanediol and dimethyl carbonate were reacted with a glass flask having an internal volume of 200 ml equipped with a reflux apparatus. (Obtained polycarbonate diol) 10.0 g (0.01 mol), vinyl methacrylate 5.6 g (0.05 mol), p-methoxyphenol 0.02 g, tetrabutoxy titanium 0.034 g (0.10 mmol), Then, 50 ml of toluene was added, and the mixture was heated and stirred for 9 hours at a bath temperature of 120 ° C. in a nitrogen stream under normal pressure. During this time, cooling water at 10 ° C. was flowed through the reflux apparatus to perform total reflux.
After the reaction, 0.6 g of water was added to the reaction solution and stirred at a bath temperature of 90 ° C. for 2 hours. Subsequently, insoluble matters were removed by suction filtration, and the filtrate was distilled off under reduced pressure using a rotary evaporator. The residue was then dried under reduced pressure for 2 hours in a desiccator at 60 ° C. to obtain 13.09 g of a transparent polycarbonate diol acrylate compound. . From ¹ H-NMR, this product had a terminal acrylate conversion ratio (ratio in which the terminal hydroxyl group of the starting polycarbonate diol was acrylated) of 89.7% and an average polymerization degree of 7.2.

Comparative Example 1
Polycarbonate diol (UH-100: average molecular weight 1000, average degree of polymerization 7.0: Ube Industries, Ltd .: 1,6-hexanediol and dimethyl carbonate were reacted with a glass flask having an internal volume of 200 ml equipped with a reflux apparatus. Obtained polycarbonate diol) 10. 0 g (0.01 mol), 5.0 g (0.05 mol) of methyl methacrylate, 0.02 g of p-methoxyphenol, 0.034 g (0.10 mmol) of tetrabutoxytitanium, and 50 ml of toluene were added under normal pressure. The mixture was heated and stirred in a nitrogen stream at a bath temperature of 120 ° C. for 9 hours. During this time, cooling water at 10 ° C. was flowed through the reflux apparatus to perform total reflux.
After the reaction, 0.6 g of water was added to the reaction solution and stirred at a bath temperature of 90 ° C. for 2 hours. Next, insoluble matters were removed by suction filtration, and the filtrate was distilled off under reduced pressure using a rotary evaporator. The residue was dried under reduced pressure for 2 hours in a desiccator at 60 ° C. to obtain 13.50 g of a transparent polycarbonate diol acrylate compound. It was. From ¹ H-NMR, this product had a terminal acrylate conversion rate (a ratio of the terminal hydroxyl group of the starting polycarbonate diol of acrylated) of 31.2% and an average degree of polymerization of 7.0.

  As is clear from the above results, the acrylated reaction using vinyl methacrylate has a higher hydroxyl group acrylate ratio than the acrylated reaction using methyl methacrylate. Furthermore, the reaction may be performed only under reflux conditions that do not require evaporation of by-product alcohol, and is excellent as a simple method for synthesizing a polycarbonate polyol polyacrylate compound in that sufficient purification can be achieved only by filtration and drying under reduced pressure. .

  According to the present invention, it is possible to provide a method for producing a polycarbonate polyol polyacrylate compound (a compound in which a hydroxyl group of a polycarbonate polyol is acrylated) that does not require a complicated operation of distilling off by-products. That is, according to the present invention, a high-quality polycarbonate polyol polyacrylate compound can be produced by a simple operation using readily available raw materials.

Claims (2)

Formula (I):

(Where
R ¹ is the same or different and is a propylene group, butylene group, pentylene group, hexylene group, 3-methylpentylene group, 1,4-cyclohexylene group, 1,4-cyclohexanedimethylene group and 1,4-cyclohexane. A divalent group selected from the group consisting of benzenedimethylene groups;
n represents the average degree of polymerization and is a number from 1 to 50)
A polycarbonate polyol represented by formula (II):

(Where
R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
R ³ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms)
A polycarbonate polyol characterized by reacting with a vinyl acrylate compound represented by the formula (I) in the presence of one or more metal catalysts having transesterification ability selected from organotitanium compounds having an alkoxy group or an aryloxy group. A method for producing a polyacrylate compound. The catalyst is deactivated with deactivating agent after the reaction process according to claim 1, polycarbonate polyol polyacrylate compound according.