JP2008121029A - Method for producing urethanization catalyst-containing polycarbonate diol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily producing a urethanization catalyst-containing polycarbonate diol capable of solving conventional problems and having stable reactivity in urethanization (urethanization reactivity), exhibiting stable and high reactivity in urethanization with an isocyanate compound in particular. <P>SOLUTION: The method for producing the urethanization catalyst-containing polycarbonate diol is characterized by thermally treating a polycarbonate diol containing a transesterification catalyst in the presence of a phosphite triester. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a urethane diol-containing polycarbonate diol. More specifically, a urethanization catalyst-containing polycarbonate diol having a stable reactivity (urethanization reactivity) in the urethanization reaction, that is, a urethanization catalyst-containing polycarbonate diol having a high stability in the urethanization reaction with an isocyanate compound. Regarding the method. Polycarbonate diol is a compound useful as a raw material for various urethane compounds. In the present invention, urethanization means "converting (polycarbonate diol) to urethane".

  Polycarbonate diol is produced by a transesterification reaction between a carbonate compound and a diol compound in the presence of a transesterification catalyst, but usually contains a transesterification catalyst as active unless deactivation treatment is performed. .

  For this reason, the polycarbonate diol (transesterification catalyst-containing polycarbonate diol) obtained as described above promotes the urethanization reaction of the polycarbonate diol with an isocyanate compound, so that the urethanization reaction, that is, the isocyanate compound The reactivity (urethanization reactivity) in the urethanization reaction due to is not constant.

  Therefore, when the urethanization reaction is carried out using such a polycarbonate diol, the reaction control becomes difficult or complicated (for example, the reactivity is remarkably lowered in the later stage of the reaction, and the reaction scale is rapidly increased, the heat is rapidly increased. Or a reaction product gelled during the reaction. Moreover, when using an aliphatic isocyanate compound as an isocyanate compound, there existed a problem that the urethanization reactivity of polycarbonate diol was very low.

In order to solve such problems, conventionally, the transesterification catalyst is deactivated in advance with acid or water, and then a urethanization catalyst is newly added during the urethanization reaction to urethanize the polycarbonate diol. The complicated operation of adjusting the sex was necessary (for example, Patent Document 1).
Japanese Patent Publication No. 8-26140

  This invention makes it a subject to provide the manufacturing method of the urethanization catalyst containing polycarbonate diol which can solve the above problems. That is, the present invention relates to a urethanization catalyst-containing polycarbonate diol having a stable reactivity (urethanization reactivity) in a urethanation reaction, particularly a urethanization catalyst-containing polycarbonate diol having a high stability in a urethanization reaction with an isocyanate compound. It is an object to provide a method that can be easily manufactured.

  The object of the present invention is solved by a process for producing a polycarbonate diol containing a urethanization catalyst, characterized by heat-treating a polycarbonate diol containing a transesterification catalyst in the presence of a phosphorous acid triester.

  According to the present invention, a method for producing a urethanization catalyst-containing polycarbonate diol having a stable reactivity (urethanization reactivity) in a urethanization reaction, that is, a urethanization catalyst-containing polycarbonate having a high reactivity stable in a urethanization reaction with an isocyanate compound A method for easily producing a diol can be provided. In addition, according to the present invention, the transesterification catalyst-containing polycarbonate diol in which the reactivity (urethanization reactivity) in the urethanization reaction with an isocyanate compound is unstable and causes various problems, the urethanization reactivity is stable and the reaction It can be converted into a polycarbonate diol having a high urethanization catalyst content. That is, the transesterification catalyst contained in the polycarbonate diol is heat-treated in the presence of phosphorous acid triester to stabilize the urethanization catalyst activity of the transesterification catalyst (maintain high activity). Can do. At the same time, the conversion rate of the isocyanate compound (isocyanate group) in the urethanization reaction can be increased. The urethanization catalyst-containing polycarbonate diol having a stable urethanization reactivity of the present invention has a stable and high reactivity in the urethanization reaction with an isocyanate compound (that is, the reaction rate constant of the urethanization reaction with the isocyanate compound is stable). And the reaction control becomes difficult or complicated (for example, the reactivity is significantly reduced in the late stage of the reaction, and the reaction scale becomes large, causing a rapid exotherm), or the reaction product gels during the reaction. Thus, the urethanization reaction with the isocyanate compound can be carried out smoothly without causing problems such as these. In addition, the urethanization reaction with an aliphatic isocyanate compound can also be carried out smoothly overcoming the problem that the reactivity is very low.

  The polycarbonate diol containing a transesterification catalyst (transesterification catalyst-containing polycarbonate diol) used in the present invention is obtained by subjecting a carbonate compound and a diol compound to a transesterification reaction in the presence of a transesterification catalyst. In addition, the polycarbonate diol produced | generated by this transesterification has a molecular terminal substantially hydroxyl group as shown by following Formula.

（式中、Ｒはジオール化合物の残基を表す。ｎはポリカーボネートジオールの平均重合度を表し、特に制限されない実数であるが、好ましくは１〜１００、更に好ましくは１〜５０の実数である。）

(In the formula, R represents the residue of the diol compound. N represents the average degree of polymerization of the polycarbonate diol, and is a real number that is not particularly limited, but is preferably a real number of 1 to 100, more preferably 1 to 50). )

  The transesterification catalyst-containing polycarbonate diol contains the transesterification catalyst in the transesterification reaction between the carbonate compound and the diol compound as it is, but the transesterification catalyst content is 0.001 to 1 mol of the polycarbonate diol. It is preferably 30 mmol, more preferably 0.001 to 15 mmol, particularly preferably 0.003 to 8 mmol. The transesterification catalyst-containing polycarbonate diol may contain 0 to 5000 ppm, preferably 0 to 3000 ppm, more preferably 0 to 2000 ppm. However, the water content is based on weight.

  Examples of the transesterification catalyst include C4-C40 alkoxy or aryloxy titanium compounds such as tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetraphenoxytitanium, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, etc. Preferred examples thereof include organic tin compounds having 2 to 40 carbon atoms, and alkoxyaluminum compounds having 3 to 30 carbon atoms such as triethoxyaluminum, triisopropoxyaluminum, and tri-s-butoxyaluminum. Among these transesterification catalysts, the titanium compound is particularly preferable.

  The transesterification catalyst may be used alone or in plural in the transesterification reaction, but is 0.001 to 5 mmol, more preferably 0.001 to 3 mmol, especially 0 to 1 mol of the diol compound. It is preferably used at a ratio of 0.003 to 1 mmol.

  Examples of the carbonate compound include dialkyl carbonates containing an alkyl group having 1 to 10 carbon atoms such as dimethyl carbonate, diethyl carbonate and dibutyl carbonate, and diaralkyl carbonates containing an aralkyl group having 7 to 10 carbon atoms such as dibenzyl carbonate. And diaryl carbonate containing an aryl group having 6 to 10 carbon atoms such as diphenyl carbonate, and alkylene carbonate containing an alkylene group having 2 to 10 carbon atoms such as ethylene carbonate and propylene carbonate.

  The carbonate compound may be used alone or in plural in the transesterification reaction, but it is preferably used in a proportion of 0.5 to 1.5 mol with respect to 1 mol of the diol compound. In addition, it is preferable to select suitably the carbonate compound which can extract byproduct alcohol derived from this compound efficiently.

  The diol compound is preferably a diol compound (aliphatic diol) having hydroxyl groups at both ends of an alkylene group having 3 to 25 carbon atoms (residue of the diol compound). This alkylene group contains various isomers and may have at least one alkyl group having 1 to 6 carbon atoms, aralkyl group having 7 to 10 carbon atoms, or aryl group having 6 to 12 carbon atoms as a substituent. Moreover, the carbon chain of the alkylene group may contain at least one ether bond, and may contain an alicyclic structure. The diol compound may be used alone or in combination.

  Specific examples of the diol compound include the following compounds. That is, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,20-eicosanediol,

2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3 -Propanediol, 1,3-butanediol, neopentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentane Diol, 1,5-hexanediol, 2-ethyl-1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,4-heptanediol, 2-methyl-1,8-octanediol, etc. The alkylene group is an isomer or has an alkyl group as a substituent,

1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,7-norbornanediol, 2,2'-bis (4-hydroxycyclohexyl) propane, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol , A carbon chain of an alkylene group such as 1,4-cyclohexanediethanol includes an alicyclic structure,

Carbon chains of alkylene groups such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol and the like containing an ether bond,

Examples include those in which the carbon chain of an alkylene group such as tetrahydrofuran dimethanol and 1,4-bis (hydroxyethoxy) cyclohexane contains an alicyclic structure and an ether bond.

  The diol compound includes aromatic rings such as p-xylene diol, p-tetrachloroxylene diol, 1,4-bis (hydroxyethoxy) benzene, 2,2-bis [(4-hydroxyethoxy) phenyl] propane. Or a polyol compound such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, or the like, alone or in combination, and is 25% by weight or less, more preferably 20% by weight or less, particularly 15% or less. It may be contained in a proportion of not more than% by weight.

  The transesterification catalyst-containing polycarbonate diol used in the present invention is obtained by subjecting a carbonate compound and a diol compound to an ester exchange reaction in the presence of an ester exchange catalyst. Commercially available polycarbonate diol can be used as long as it is obtained (transesterification catalyst-containing polycarbonate diol).

  The transesterification reaction can be performed in one step, two steps, or three steps according to a known method. For example, using a reactor equipped with a distillation apparatus (distillation tower, etc.), in the presence of a transesterification catalyst, the alcohol produced as a by-product is extracted by distillation and the carbonate compound and diol compound are reacted until almost no alcohol is distilled off. Thus, the polycarbonate diol may be produced in one step. At this time, the carbonate compound may be initially charged in its entirety, or may be added continuously or sequentially to the diol compound.

  Further, if necessary (in order to adjust the molecular weight), the transesterification catalyst is allowed to exist as it is, and the polycarbonate diol produced in one step is further subjected to a polycondensation reaction between molecules while similarly extracting the by-product diol compound. Thus, the polycarbonate diol having the target molecular weight may be produced in two stages. In the present invention, the entire reaction including the condensation polymerization reaction in this case is treated as a transesterification reaction.

  If necessary (to adjust the molecular weight), a diol compound is added to the polycarbonate diol produced in one step, the transesterification catalyst is left as it is, and the polycarbonate diol and the diol compound are further transesterified. Thus, the polycarbonate diol having the target molecular weight may be produced in two stages. Alternatively, a polycarbonate diol having a target molecular weight may be produced in three stages by adding a diol compound to the polycarbonate diol produced in two stages including the above condensation polymerization reaction and further performing a transesterification reaction.

  When the transesterification reaction is performed in one stage, the reaction temperature is preferably 100 to 210 ° C., and the reaction pressure is not particularly limited, but is preferably normal pressure or reduced pressure of 50 to 500 mmHg. However, it is preferable that the reaction temperature and the reaction pressure are such that the by-produced alcohol is distilled and the diol compound is not substantially distilled. The reaction can be performed in an atmosphere of air, carbon dioxide gas, or an inert gas (nitrogen, argon, helium, etc.) or in an air stream, but is preferably performed in an inert gas atmosphere or in an air stream.

  When the transesterification reaction is carried out in two stages by further subjecting the produced polycarbonate diol to a polycondensation reaction between molecules, the reaction temperature is preferably 150 to 240 ° C., more preferably 150 to 230 ° C., and the reaction pressure is 0. A reduced pressure of about 1 to 50 mmHg is preferable. As the catalyst, the transesterification catalyst can be used as it is. The by-produced diol compound is preferably extracted by distillation, and the reaction atmosphere is preferably the same as described above. The extracted diol compound can be reused in a transesterification reaction with a carbonate compound.

  Further, when the transesterification reaction is carried out in two or three stages by adding a diol compound to the produced polycarbonate diol and further carrying out the transesterification reaction, the reaction conditions such as the reaction temperature and the reaction pressure are the same as the transesterification reaction described above. This is similar to the case of performing in stages.

  After the transesterification reaction is completed in one stage, two stages, or three stages, the reaction liquid is cooled as it is, whereby a transesterification catalyst-containing polycarbonate diol can be obtained. As described above, this transesterification catalyst-containing polycarbonate diol has a molecular end that is substantially a hydroxyl group, and contains the transesterification catalyst and water in the above proportions.

  In the present invention, the transesterification catalyst-containing polycarbonate diol obtained as described above (the reactivity in the urethanization reaction with an isocyanate compound (urethanization reactivity) is unstable and causes various problems as described above), By heat-treating in the presence of phosphorous acid triester, it can be converted to a urethanized catalyst-containing polycarbonate diol having stable urethanization reactivity. That is, the urethanization catalyst-containing polycarbonate diol of the present invention is obtained by heat-treating a transesterification catalyst-containing polycarbonate diol in the presence of phosphorous acid triester. And this urethanation-reactive urethanization catalyst-containing polycarbonate diol is also highly urethanization-reactive.

  Thus, in the present invention, the transesterification catalyst contained in the polycarbonate diol is heat-treated in the presence of phosphorous acid triester to stabilize the activity of the transesterification catalyst as a urethanization catalyst. (Maintain high activity). And the conversion rate of the isocyanate compound (isocyanate group) in a urethanation reaction can also be made high.

  In the heat treatment, the transesterification catalyst-containing polycarbonate diol may be used alone or in combination. In addition, the polycarbonate diol is converted into a lactone (butyrolactone, caprolactone, laurolactone, etc.) containing an alkylene group having 2 to 20 carbon atoms, or an alkylene carbonate (ethylene carbonate, 1, 2 or 2) containing an alkylene group having 2 to 20 carbon atoms. -Propylene carbonate, 1,3-propylene carbonate, 2,2-dimethylpropylene carbonate, etc.), and further copolymerized with ring-opening polymers of these lactones and alkylene carbonates It may be. The alkylene group of this alkylene carbonate may have an isomer or a substituent as in the alkylene group in the diol compound.

  Examples of the phosphorous acid triester used in the present invention include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, trihexyl phosphite, trioctyl phosphite, etc. Trialkyl phosphites containing 20 alkyl groups, triaralkyl phosphites containing aralkyl groups having 7 to 20 carbon atoms such as tribenzyl phosphite, triphenyl phosphites, tricresyl phosphites, etc. And triaryl phosphite containing an aryl group having 6 to 20 carbon atoms. Moreover, the phosphorous acid triester which contains a mixed alkyl group, an aralkyl group, and an aryl group can also be mentioned.

  Among the phosphorous acid triesters, trialkyl phosphites are preferred, and among them, alkyls having 3 to 20 carbon atoms such as tripropyl phosphite, tributyl phosphite, trihexyl phosphite, trioctyl phosphite, etc. Particular preference is given to trialkyl phosphites containing groups.

  In the heat treatment, phosphorous acid triester is used in an amount of 0.8 to 10 mol, more preferably 0 to 1 mol of the transesterification catalyst (1 g atom of metal in the catalyst) used in the transesterification reaction of the carbonate compound and the diol compound. It is preferable to use it at 9-5 mol, especially 1-2 mol.

  The temperature at which the transesterification catalyst-containing polycarbonate diol is heat-treated in the presence of phosphorous acid triester is preferably 70 to 145 ° C, more preferably 80 to 145 ° C, and particularly preferably 95 to 135 ° C. The atmosphere during the heat treatment is preferably an atmosphere of an inert gas such as helium, nitrogen, argon, carbon dioxide, or an air stream. The pressure may be any of reduced pressure, normal pressure, and increased pressure. Although heat processing time changes with conditions, it is 0.5 to 24 hours normally.

  After completion of the heat treatment, the treatment liquid can be cooled to obtain the urethanization catalyst-containing polycarbonate diol of the present invention. This urethanization catalyst-containing polycarbonate diol comprises the transesterification catalyst, phosphorous acid triester, and water in the above proportions. And can be used in a urethanization reaction with an isocyanate compound as it is (without adding a new catalyst and containing a phosphorous acid triester). In addition, the urethanation reaction by an isocyanate compound can be performed in accordance with a well-known method using diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, etc., for example.

  The urethanization catalyst-containing polycarbonate diol of the present invention thus obtained has a stable urethanization reactivity and a high urethanization reactivity. That is, it has a stable and high reactivity in the urethanization reaction with the isocyanate compound (the reaction rate constant of the urethanization reaction with the isocyanate compound is stable and high).

  For example, in a urethanization reaction using diphenylmethane diisocyanate as an isocyanate compound (according to the method of Examples described later), the urethanization catalyst-containing polycarbonate diol of the present invention is an average reaction rate in the late stage of reaction (reaction start 50 to 60 minutes). The constant is 0.7 times or more of the average reaction rate constant at the beginning of the reaction (10 to 20 minutes from the start of the reaction), and although the rate constant is slightly decreased in the later stage of the reaction, the degree is not remarkable, and the reaction rate constant is stable. It is what. And if it sees in the whole reaction, an average reaction rate constant is a thing with a high reaction rate in the range of 4-5 g / mol * sec.

  In addition, in the urethanization reaction using dicyclohexylmethane diisocyanate as an isocyanate compound (according to the method of Examples described later), the average reaction rate constant in the late stage of the reaction (reaction start 2 to 5 hours) is the initial reaction (reaction start 10 to 10). The average reaction rate constant of 60 minutes) is 0.6 times or more, and although the rate constant is slightly decreased in the latter stage of the reaction, the degree is not so remarkable and the reaction rate constant is stable. And if it sees in the whole reaction, an average reaction rate constant is the range of 0.2-0.5 g / mol * sec, and a reaction rate is high.

  The urethanized catalyst-containing polycarbonate diol may be used alone or in combination, and may be further copolymerized with the above lactone or alkylene carbonate, or further with these ring-opened polymers. It may be copolymerized and used for the urethanization reaction.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, the reactivity in the urethanation reaction by the isocyanate compound of polycarbonate diol was evaluated by calculating | requiring the reaction rate constant of a urethanation reaction as follows.

1. Quantification of Isocyanate Group 2-3 g of the reaction solution of the urethanization reaction of polycarbonate diol with isocyanate compound was sampled over time, added to a mixed solution of 10 ml of dibutylamine-THF solution and 20 ml of THF, and stirred, and then 50 ml of THF was added to this. And an indicator bromophenol blue solution were added, and unconsumed dibutylamine was titrated with 0.1 mol / L (liter) of hydrochloric acid. From the difference between the titration value and the blank experiment, the isocyanate group (in moles) remaining in the reaction solution was determined. In addition, THF represents tetrahydrofuran, and each solution is as follows.

  Dibutylamine-THF solution: A solution in which 3.23 g of dibutylamine was diluted with THF to 250 ml Bromophenol blue solution: A solution in which 0.5 g of bromophenol blue was 50 ml in methanol

2. Measurement of reaction rate constant of urethanization reaction From the following formula, x / a (ax) was plotted against reaction time t, and the reaction rate constant K of urethanization reaction was determined from the slope.
Kt = x / a (ax)

However, each symbol is defined as follows.
K: reaction rate = K [isocyanate group concentration] [reaction rate constant when polycarbonate diol has a concentration] t: reaction time a: initial concentration of isocyanate group (mol / g; measured by quantification of isocyanate group) Consumed dibutylamine moles per gram of reaction liquid at the time of charging)
a-x: Concentration of isocyanate group after time t (mol / g; number of moles of dibutylamine consumed per gram of reaction liquid after time t measured by quantitative determination of isocyanate group)
x: Consumption isocyanate group concentration after time t (mol / g)

Moreover, the isocyanate group conversion rate was calculated | required as follows.
Isocyanate group conversion (%) = 100 × (number of moles of charged isocyanate group−number of moles of remaining isocyanate group) / number of moles of charged isocyanate group

Example 1
[Production of polycarbonate diol (polyester diol containing transesterification catalyst)]
In a 1 L (liter) glass flask equipped with a distillation column, 427 g (4.74 mol) of dimethyl carbonate, 560 g (4.74 mol) of 1,6-hexanediol, and 0.054 g (0.16 of tetrabutoxytitanium). The reaction mixture was stirred at a reaction temperature of 100 to 200 ° C. for 5 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring.

  Next, after further distilling off the mixture of methanol and dimethyl carbonate at a reduced pressure of 100 mmHg, the mixture was further reacted for 8 hours at 160 to 200 ° C. under a reduced pressure of 1 to 5 mmHg while distilling off 1,6-hexanediol. 537 g of polycarbonate diol (polyester diol containing a transesterification catalyst) was obtained. This polycarbonate diol had a hydroxyl value of 56.1 mgKOH / g, an average molecular weight of 2000, and a hue (APHA) of 15. In addition, reaction operation was performed in nitrogen stream and the average molecular weight was calculated | required from the hydroxyl value.

[Heat treatment]
In a 500 ml glass flask, 100 g of the transesterification catalyst-containing polycarbonate diol obtained above (0.05 mol as polycarbonate diol, titanium content 14 ppm, water content 700 ppm) was added, and tributyl phosphite 8. 78 mg (0.0351 mmol; 1.2 mol based on 1 g atom of titanium) was added, and the mixture was heat-treated for 2 hours with stirring at 130 ° C. in a nitrogen stream. After completion of the heat treatment, the treatment liquid was cooled to obtain 100 g of a urethanized catalyst-containing polycarbonate diol. The titanium content and water content are based on weight.

[Urethaneization reaction]
100 g of the urethanized catalyst-containing polycarbonate diol and 225 g of 2-butanone obtained above were placed in a 500 ml glass flask, and the mixture was heated and stirred at a bath temperature of 70 ° C. (liquid temperature of 65 ° C.). Next, 12.51 g (0.05 mol) of 4,4′-diphenylmethane diisocyanate was added, followed by heating and stirring at the same temperature. The reaction operation was performed in a nitrogen stream.

  When the reaction solution was sampled over time and the isocyanate groups remaining in the reaction solution were quantified, the average reaction rate constant of the urethanization reaction was 4.81 g at the beginning of the reaction (reaction start 10-20 minutes; hereinafter omitted). / Mol · sec, 3.67 g / mol · sec in the late reaction (reaction start 50 to 60 minutes; hereinafter omitted), the decrease in the rate constant in the late reaction is small (reaction rate constant ratio: 0.76), and the reaction Sex was stable. The average reaction rate constant over the entire reaction was 4.44 g / mol · sec. Moreover, the conversion rate of the isocyanate group after 1 hour was 82.4%. The average reaction rate constant is determined by the least square method, and the reaction rate constant ratio means “average reaction rate constant in the late reaction stage: average reaction rate constant in the initial reaction stage”.

Comparative Example 1
[Urethaneization reaction]
The urethanization reaction was performed in the same manner as in Example 1 except that 100 g of the transesterification catalyst-containing polycarbonate diol was used as it was without performing the heat treatment. As a result, the average reaction rate constant of the urethanization reaction was 2.94 g / mole · second in the early stage of the reaction and 1.88 g / mole · second in the later stage of the reaction. Constant ratio: 0.64), reactivity was unstable. The average reaction rate constant for the entire reaction was also low at 2.73 g / mol · sec. Moreover, the conversion rate of the isocyanate group after 1 hour was 65.6%.

Example 2
[Heat treatment]
Heat treatment was carried out in the same manner as in Example 1 except that 100 g of a polycarbonate diol containing a transesterification catalyst having a different moisture absorption obtained in Example 1 (0.05 mol as polycarbonate diol, titanium content 14 ppm, water content 300 ppm) was used. Went.

[Urethaneization reaction]
A urethanization reaction was performed in the same manner as in Example 1 except that 100 g of the urethanization catalyst-containing polycarbonate diol obtained above was used. As a result, the average reaction rate constant of the urethanization reaction was 4.83 g / mol · sec at the beginning of the reaction and 3.69 g / mol · sec at the end of the reaction, and the decrease in the rate constant in the late reaction was small (reaction rate constant ratio). : 0.76), the reactivity was stable. The average reaction rate constant in the entire reaction was 4.43 g / mol · sec. Moreover, the conversion rate of the isocyanate group after 1 hour was 82.3%.

Example 3
[Heat treatment]
The heat treatment was performed in the same manner as in Example 2 except that the heating temperature was changed to 100 ° C.

[Urethaneization reaction]
A urethanization reaction was performed in the same manner as in Example 1 except that 100 g of the urethanization catalyst-containing polycarbonate diol obtained above was used. As a result, the average reaction rate constant of the urethanization reaction was 4.77 g / mol · sec at the beginning of the reaction and 3.62 g / mol · sec at the end of the reaction, and the decrease in the rate constant in the late reaction was small (reaction rate constant ratio). : 0.76), the reactivity was stable. The average reaction rate constant in the entire reaction was 4.38 g / mol · sec. Moreover, the conversion rate of the isocyanate group after 1 hour was 81.9%.

Comparative Example 2
[Urethaneization reaction]
The urethanization reaction was performed in the same manner as in Example 2 except that 100 g of the transesterification catalyst-containing polycarbonate diol was used as it was without performing the heat treatment. As a result, the average reaction rate constant of the urethanization reaction was 4.57 g / mole · second in the early stage of the reaction and 2.36 g / mole · second in the late stage of the reaction, and the rate constant decreased in the late stage of the reaction (reaction rate constant ratio). : 0.52), the reactivity was unstable. The average reaction rate constant for the entire reaction was 4.12. Moreover, the conversion rate of the isocyanate group after 1 hour was 86.8%.

Example 4
[Heat treatment]
The same operation as in Example 1 was performed.

[Urethaneization reaction]
The urethanization reaction was carried out in the same manner as in Example 1 except that the amount of 2-butanone was changed to 56.6 g and the isocyanate compound was replaced with 13.4 g (0.05 mol) of 4,4′-dicyclohexylmethane diisocyanate. went. As a result, the average reaction rate constant of the urethanization reaction was 0.497 g / mole / second at the beginning of the reaction (reaction start 10 to 60 minutes; hereinafter omitted), and the late reaction (reaction start 2 to 5 hours; hereinafter omitted). 0.369 g / mole · second, the decrease in the rate constant in the late reaction was small (reaction rate constant ratio: 0.74), and the reactivity was stable. The average reaction rate constant in the entire reaction was 0.421 g / mol · sec. Further, the conversion rate of the isocyanate group after 5 hours was 82.8%.

Example 5
[Heat treatment]
The same procedure as in Example 1 was conducted except that the phosphorous acid triester was changed to 4.35 mg (0.0351 mmol) of trimethyl phosphite.

[Urethaneization reaction]
A urethanization reaction was performed in the same manner as in Example 4 except that 100 g of the urethanization catalyst-containing polycarbonate diol obtained above was used. As a result, the average reaction rate constant of the urethanization reaction was 0.360 g / mole · second in the early stage of the reaction and 0.238 g / mole · second in the late stage of the reaction, and the decrease in the rate constant in the late stage of the reaction was small (reaction rate constant ratio). : 0.66), the reactivity was stable. The average reaction rate constant in the entire reaction was 0.290 g / mol · sec. Further, the conversion rate of the isocyanate group after 5 hours was 78.9%.

Example 6
[Heat treatment]
The same procedure as in Example 1 was conducted except that 10.9 mg (0.0351 mmol) of triphenyl phosphite was used instead of phosphorous acid triester.

[Urethaneization reaction]
A urethanization reaction was performed in the same manner as in Example 4 except that 100 g of the urethanization catalyst-containing polycarbonate diol obtained above was used. As a result, the average reaction rate constant of the urethanization reaction was 0.342 g / mole · second in the early stage of the reaction and 0.234 g / mole · second in the late stage of the reaction, and the decrease in the rate constant in the late stage of the reaction was small (reaction rate constant ratio). : 0.68), the reactivity was stable. The average reaction rate constant in the entire reaction was 0.283 g / mol · sec. Further, the conversion rate of the isocyanate group after 5 hours was 73.2%.

Comparative Example 3
[Urethaneization reaction]
The urethanization reaction was performed in the same manner as in Example 4 except that 100 g of the transesterification catalyst-containing polycarbonate diol was used as it was without performing the heat treatment. As a result, the average reaction rate constant of the urethanization reaction was 0.114 g / mol · sec at the beginning of the reaction and 0.055 g / mol · sec at the end of the reaction. : 0.48), the reactivity was unstable. The average reaction rate constant for the entire reaction was also low at 0.066 g / mol · sec. Further, the conversion rate of the isocyanate group after 5 hours was 39.8%.

Example 7
[Heat treatment]
The same operation as in Example 2 was performed.

[Urethaneization reaction]
The urethanization reaction was carried out in the same manner as in Example 2 except that the amount of 2-butanone was changed to 56.6 g and the isocyanate compound was replaced with 13.4 g (0.05 mol) of 4,4'-dicyclohexylmethane diisocyanate. went. As a result, the average reaction rate constant of the urethanization reaction was 0.383 g / mole · second in the early stage of reaction and 0.326 g / mole · second in the late stage of reaction, and the decrease in the rate constant in the late stage of reaction was small (reaction rate constant ratio). : 0.85), the reactivity was stable. The average reaction rate constant in the entire reaction was 0.351 g / mol · sec. Further, the conversion rate of the isocyanate group after 5 hours was 79.7%.

Comparative Example 4
[Urethaneization reaction]
A urethanization reaction was carried out in the same manner as in Example 7 except that 100 g of the transesterification catalyst-containing polycarbonate diol was used as it was without performing heat treatment. As a result, the average reaction rate constant of the urethanization reaction was 0.191 g / mole · second in the early stage of the reaction and 0.067 g / mole · second in the later stage of the reaction, and the rate constant decreased in the later stage of the reaction (reaction rate constant ratio). : 0.35), the reactivity was unstable. The average reaction rate constant for the entire reaction was also low at 0.090 g / mol · sec. Further, the conversion rate of the isocyanate group after 5 hours was 58.2%.

Comparative Example 5
[Heat treatment]
The heat treatment was performed in the same manner as in Example 1 except that 7.37 mg (0.0351 mmol) of dibutyl phosphate was used instead of the phosphorous acid triester.

[Urethaneization reaction]
A urethanization reaction was performed in the same manner as in Example 1 except that 100 g of the urethanization catalyst-containing polycarbonate diol obtained above was used. As a result, the average reaction rate constant of the urethanization reaction was 0.051 g / mole · second in the early stage of the reaction and 0.043 g / mole · second in the later stage of the reaction. Constant ratio: 0.84), and the average reaction rate constant in the whole reaction was also very low at 0.045 g / mol · sec. Moreover, the conversion rate of the isocyanate group after 1 hour was only 4.0%.

Claims (9)

  A method for producing a polycarbonate diol containing a urethanization catalyst for a raw material of a urethane compound, comprising heat-treating a polycarbonate diol containing a transesterification catalyst in the presence of a phosphorous acid triester, and heating with a phosphorous acid triester The treated urethanization catalyst-containing polycarbonate diol has an average reaction rate constant of urethanation reaction with diphenylmethane diisocyanate at 65 ° C. of 4 to 5 g / mol · sec.   A method for producing a polycarbonate diol containing a urethanization catalyst for a raw material of a urethane compound, comprising heat-treating a polycarbonate diol containing a transesterification catalyst in the presence of a phosphorous acid triester, and heating with a phosphorous acid triester The treated urethanized catalyst-containing polycarbonate diol has an average reaction rate constant of urethanization reaction with dicyclohexylmethane diisocyanate at 65 ° C. of 0.2 to 0.5 g / mol · sec.   The urethane diol catalyst for urethane compound raw materials according to claim 1 or 2, wherein the polycarbonate diol containing a transesterification catalyst is obtained by subjecting a carbonate compound and a diol compound to a transesterification reaction in the presence of a transesterification catalyst. A method for producing polycarbonate diol.   The method for producing a polycarbonate diol containing a urethanization catalyst for a raw material of a urethane compound according to any one of claims 1 to 3, wherein the transesterification catalyst is an alkoxy or aryloxytitanium compound, an organic tin compound, or an alkoxyaluminum compound. .   The urethanization catalyst-containing polycarbonate diol for a raw material of a urethane compound according to any one of claims 1 to 4, wherein the phosphorous acid triester is heat-treated in the presence of 0.8 to 10 times mol of the transesterification catalyst. Production method.   The manufacturing method of the urethane-ized catalyst containing polycarbonate diol for the raw materials of the urethane compound of any one of Claims 1-5 whose heat processing temperature is 70-145 degreeC.   A polycarbonate diol containing a urethanization catalyst for a raw material of a urethane compound, obtained by the production method according to any one of claims 1 to 6.   A step of obtaining a urethane diol-containing catalyst-containing polycarbonate diol for a urethane compound raw material by the production method according to claim 1, and a urethane compound-containing urethanized catalyst-containing polycarbonate diol and an isocyanate compound for the obtained urethane compound. A method for producing a urethane compound, comprising a step of reacting.   A urethane compound obtained by the production method according to claim 8.