JP4734696B2 - Polycarbonate diol copolymer and process for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid polycarbonate diol copolymer capable of easily producing a polyurethane because of being improved in workability, when producing this polyurethane containing 1,6-hexanediol(HDL) and 1,4- cyclohexanedimethanol(CHDM) as the diol component, and to provide the liquid polycarbonate diol copolymer having a stable and high reactivity in reacting with an isocyanate compound. SOLUTION: This liquid polycarbonate diol copolymer is composed of 1,6- hexanediol and 1,4-cyclohexanedimethanol, and further contains an ester interchanging catalyst heat-treated in the presense of a phosphorous triester.

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid polycarbonate diol copolymer containing 1,6-hexanediol (HDL) and 1,4-cyclohexanedimethanol (CHDM) as diol components. More specifically, the present invention relates to a liquid polycarbonate diol copolymer containing HDL and CHDM as diol components, which has a stable and high reactivity in the reaction with an isocyanate compound.
[0002]
[Prior art]
Polycarbonate diol is used as a raw material for producing polyurethane by reacting with an isocyanate compound. Among them, a polyurethane produced from a polycarbonate diol whose diol component is 1,6-hexanediol (HDL) is rich in flexibility, and is produced from a polycarbonate diol whose diol component is 1,4-cyclohexanedimethanol (CHDM). Polyurethane is very rigid. Therefore, if these two types of polycarbonate diols are blended to produce a polyurethane containing HDL and CHDM as diol components, it is considered possible to obtain a polyurethane having intermediate flexibility between the two.
[0003]
However, since both of the two types of polycarbonate diols are solid at room temperature, if these are blended to produce a polyurethane containing HDL and CHDM as diol components, the two types of polycarbonate diols are not used. It is necessary to mix by heating and melting each.
[0004]
Thus, when a polyurethane diol containing HDL and CHDM as a diol component is produced by blending a polycarbonate diol having a diol component of HDL and a polycarbonate diol having a diol component of CHDM, there is a great difficulty in workability. It was.
[0005]
Polycarbonate diol is usually produced by a transesterification reaction between a carbonate compound and a diol compound in the presence of a transesterification catalyst. However, this transesterification catalyst remains active unless it is deactivated. In addition, since the reaction between the polycarbonate diol and the isocyanate compound is also promoted, there is a problem that the reactivity is not constant in the reaction with the isocyanate compound even when the two types of polycarbonate diol are heated and melted and mixed. Was.
[0006]
For this reason, when it reacts with an isocyanate compound using the mixture of the said 2 types of polycarbonate diol, reaction control becomes difficult or complicated (for example, when the reaction scale becomes large, the reactivity falls remarkably in the late stage of the reaction) This causes problems such as rapid heat generation) or gelation of the reaction product during the reaction.
[0007]
In order to solve such a problem, conventionally, the transesterification catalyst is deactivated in advance with an acid or water, and then a catalyst is newly added in the reaction with the isocyanate compound to increase the reactivity of the polycarbonate diol. A complicated operation of adjustment is required (Japanese Patent Publication No. 8-26140).
[0008]
[Problems to be solved by the invention]
The present invention is a liquid which can be easily produced by improving workability when producing a polyurethane containing 1,6-hexanediol (HDL) and 1,4-cyclohexanedimethanol (CHDM) as diol components. It is an object of the present invention to provide a polycarbonate diol copolymer.
[0009]
In addition, the present invention improves the workability when producing a polyurethane containing 1,6-hexanediol (HDL) and 1,4-cyclohexanedimethanol (CHDM) as diol components, and easily produces the polyurethane. Another object of the present invention is to provide a liquid polycarbonate diol copolymer having high reactivity that is stable in reaction with an isocyanate compound.
[0010]
[Means for Solving the Problems]
The object of the present invention is solved by a polycarbonate diol copolymer which is liquid at room temperature, and the diol component is composed of 1,6-hexanediol and 1,4-cyclohexanedimethanol. Moreover, the subject of this invention is solved by the said polycarbonate diol copolymer containing the transesterification catalyst heat-processed in the presence of phosphorous acid triester.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the polycarbonate diol copolymer of the present invention, the diol component is composed of 1,6-hexanediol (hereinafter abbreviated as HDL) and 1,4-cyclohexanedimethanol (hereinafter abbreviated as CHDM), and is liquid at room temperature. belongs to. And this copolymer may contain 0 to 5000 ppm, preferably 0 to 3000 ppm of water. In the present invention, the term “liquid at normal temperature” refers to a state where the viscosity is less than 10,000 poise in the range of 10 to 40 ° C.
[0012]
As the polycarbonate diol copolymer as described above, specifically, HDL: CHDM (molar ratio) = 1: 2 to 2: 1, particularly HDL: CHDM (molar ratio) = 1: 1.5 to 1.5. The polycarbonate diol copolymer containing the transesterification catalyst which is -1 is mentioned preferably.
[0013]
The polycarbonate diol copolymer is prepared by a first method in which a polycarbonate diol (A) whose diol component is HDL and a polycarbonate diol (B) whose diol component is CHDM are transesterified in the presence of a transesterification catalyst. And CHDM can be suitably produced by a second method in which a transesterification reaction with a carbonate ester is carried out in the presence of a transesterification catalyst.
[0014]
[First method]
In the first method, the ratio of the transesterification reaction between the polycarbonate diol (A) and the polycarbonate diol (B) is not particularly limited as long as a polycarbonate diol copolymer that is liquid at room temperature can be obtained. (Molar ratio) = 1: 2 to 2: 1, particularly A: B (molar ratio) = 1: 1.5 to 1.5: 1.
[0015]
The polycarbonate diol (A) and the polycarbonate diol (B) can be obtained by a known method in which a diol (HDL or CHDM) corresponding to a carbonate ester or phosgene is reacted. Moreover, even if a polycarbonate diol (A) and a polycarbonate diol (B) use a commercial item, it does not interfere.
[0016]
As the carbonate ester, dialkyl carbonate (dimethyl carbonate, diethyl carbonate, etc.), diaryl carbonate (diphenyl carbonate, etc.), alkylene carbonate (ethylene carbonate, etc.) and the like are used. When the polycarbonate diol (A) or the polycarbonate diol (B) is obtained by reacting a carbonate ester with a corresponding diol, the transesterification catalyst described below is used in an amount of 0.001 to 0.1% by weight, particularly 0%, based on the diol. 0.001 to 0.01% by weight, and preferably used alone or in combination.
[0017]
The first method is, for example, a method in which a polycarbonate diol (A) and a polycarbonate diol (B) are charged at a predetermined ratio and reacted, or a molten polycarbonate diol (A) and a polycarbonate diol (B) are continuously mixed at a predetermined ratio. The reaction can be carried out batchwise or continuously, depending on the method of feeding and reacting.
[0018]
In the first method, the reaction temperature is preferably 50 to 300 ° C, particularly preferably 80 to 250 ° C. The reaction pressure may be ordinary pressure, but usually reduced pressure. The reaction atmosphere is usually an inert gas atmosphere such as nitrogen, argon or helium.
[0019]
In the first method, it is preferable to use a transesterification catalyst as necessary. That is, when the polycarbonate diol (A) or the polycarbonate diol (B) is obtained by reacting a carbonate ester with a corresponding diol, and the transesterification catalyst remains active in it, The reaction may be carried out as it is without adding the transesterification catalyst, but in other cases, it is preferable to newly add the transesterification catalyst for the reaction. The same applies when using a commercially available polycarbonate diol (A) or polycarbonate diol (B).
[0020]
In the first method, the transesterification catalyst can be used alone or in combination, and the amount used is 0.001 to 0.1% by weight based on the total amount of the polycarbonate diol (A) and the polycarbonate diol (B). In particular, the content is preferably 0.001 to 0.01% by weight.
[0021]
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.
[0022]
In the first method, the average molecular weight (number average molecular weight) of the polycarbonate diol copolymer is the number average molecular weight (determined from NMR or terminal hydroxyl value) of the polycarbonate diol (A) and the polycarbonate diol (B). Controlled by quantity. After the reaction, the produced polycarbonate diol copolymer can be obtained by cooling the reaction solution.
[0023]
[Second method]
In the second method, the ratio of HDL and CHDM is not particularly limited as long as a polycarbonate diol copolymer that is liquid at normal temperature is obtained, but HDL: CHDM (molar ratio) = 1: 2 to 2: 1, In particular, HDL: CHDM (molar ratio) = 1: 1.5 to 1.5: 1 is preferable.
[0024]
Examples of the carbonate ester used in the second method include dialkyl carbonate (dimethyl carbonate, diethyl carbonate, etc.), diaryl carbonate (diphenyl carbonate, etc.), alkylene carbonate (ethylene carbonate, etc.), and the like. It is preferable to appropriately select one that can efficiently extract by-product alcohol.
[0025]
The second method is performed in the same manner as the known method for obtaining the polycarbonate diol (A) or the polycarbonate diol (B) from the diol (HDL, CHDM) corresponding to the carbonate ester in the first method. The reaction conditions (carbonic acid ester usage, catalyst, reaction temperature, reaction pressure, reaction atmosphere, etc.) are also the same. The average molecular weight (number average molecular weight) of the polycarbonate diol copolymer is controlled by the charged amount of HDL and CHDM and the charged amount of carbonate ester.
[0026]
In addition, when the average molecular weight of the produced polycarbonate diol copolymer is smaller than the target molecular weight, the reaction is performed while distilling HDL or CHDM under reduced pressure, and conversely, the average molecular weight is larger than the target molecular weight. In this case, HDL or CHDM is added and the ester exchange reaction is further performed to obtain the target polycarbonate diol copolymer. After the reaction, the produced polycarbonate diol copolymer can be obtained by cooling the reaction solution.
[0027]
In this way, the diol component consists of HDL and CHDM (preferably HDL: CHDM (molar ratio) = 1: 2 to 2: 1, more preferably HDL: CHDM (molar ratio) = 1: 1.5 to 1. A polycarbonate diol copolymer that is liquid at room temperature can be obtained. This copolymer may contain 0 to 5000 ppm, preferably 0 to 3000 ppm of water.
[0028]
More preferably, the polycarbonate diol copolymer contains a transesterification catalyst that is heat-treated in the presence of phosphorous acid triester. That is, in the polycarbonate diol copolymer, it is more preferable that the transesterification catalyst used in the first method and the second method is directly heat-treated in the presence of phosphorous acid triester. By this heat treatment, it is possible to convert a polycarbonate diol copolymer whose reactivity with an isocyanate compound is not constant into a stable and highly reactive one. In the reaction, a stable high reaction rate constant is given, and a high isocyanate group conversion is also given.
[0029]
A polycarbonate diol copolymer containing a transesterification catalyst that has been heat-treated in the presence of phosphorous acid triester, for example, when diphenylmethane diisocyanate is used as an isocyanate compound (according to the method of Examples described later), is a late reaction (reaction) The average reaction rate constant at 50 to 60 minutes) 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 the reaction rate constant is stable. 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.
[0030]
Examples of the phosphorous acid triester include alkyl groups having 1 to 20 carbon atoms such as trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, trihexyl phosphite, and trioctyl phosphite. 6 to 20 carbon atoms such as trialkyl phosphite and triaralkyl phosphite containing aralkyl groups having 7 to 20 carbon atoms such as tribenzyl phosphite, triphenyl phosphite and tricresyl phosphite A triaryl phosphite containing an aryl group of A phosphorous acid triester containing a mixture of an alkyl group, an aralkyl group, and an aryl group can also be used.
[0031]
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. More preferred are trialkyl phosphites containing groups.
[0032]
In the heat treatment, phosphorous acid triester is used with respect to 1 mol of the transesterification catalyst (1 g atom of metal in the catalyst) contained in the polycarbonate diol copolymer obtained by the first method or the second method. It is preferable to use 0.8 to 10 mol, further 0.9 to 5 mol, particularly 1 to 2 mol.
[0033]
The temperature at which the polycarbonate diol copolymer 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.
[0034]
After completion of the heat treatment, the treatment liquid can be cooled to obtain a polycarbonate diol copolymer which is one of the present invention. This copolymer comprises a transesterification catalyst, phosphorous acid triester, and water in the above proportions. It can be used for the reaction with the isocyanate compound as it is (without adding a new catalyst, while containing the phosphorous acid triester).
[0035]
In addition, in the first method in which the polycarbonate diol (A) and the polycarbonate diol (B) are subjected to an ester exchange reaction, the heat treatment is performed before the ester exchange reaction, in which the ester exchange catalyst in the polycarbonate diol (A), the polycarbonate diol ( It may be performed in advance for each of the transesterification catalysts in B). In this case, the addition of a new catalyst in the transesterification reaction and the heat treatment in the presence of phosphorous acid triester with respect to the transesterification catalyst in the obtained polycarbonate diol copolymer are unnecessary.
[0036]
In the polycarbonate diol copolymer of the present invention obtained as described above, those having a number average molecular weight of 500 to 2,000 are more preferable as the polyurethane production raw material. In addition, reaction with an isocyanate compound can be performed according to a well-known method using diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, etc., for example.
[0037]
【Example】
Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, the reactivity of the polycarbonate diol in reaction with an isocyanate compound was evaluated by calculating | requiring the reaction rate constant of reaction with an isocyanate compound as follows.
[0038]
1. Determination of isocyanate groups
Two to three grams of a reaction solution of polycarbonate diol and isocyanate compound was sampled over time, added to a mixed solution of 10 ml of dibutylamine-THF solution and 20 ml of THF, stirred, and then 50 ml of THF and a bromophenol blue solution of an indicator were added thereto. Then, unconsumed dibutylamine was titrated with 0.1 mol / L (liter) 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.
[0039]
Dibutylamine-THF solution: a solution prepared by diluting 3.23 g of dibutylamine with THF to 250 ml
Bromophenol blue solution: A solution of 0.5 g of bromophenol blue in methanol to 50 ml
[0040]
2. Measurement of reaction rate constant
From the following equation, x / a (ax) was plotted against the reaction time t, and the reaction rate constant K in the reaction between the polycarbonate diol and the isocyanate compound was determined from the slope.
Kt = x / a (ax)
[0041]
However, each symbol is defined as follows.
K: Reaction rate constant when K = reaction rate = K [isocyanate group concentration] [hydroxyl group concentration of polycarbonate diol]
t: Reaction time
a: Initial concentration of isocyanate group (mol / g; number of moles of dibutylamine consumed per 1 g of reaction liquid at the time of charging measured by quantitative determination of isocyanate group)
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)
[0042]
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
[0043]
Example 1
In a reactor equipped with a stirrer and a thermometer, 200 g (0.40 mol) of a commercially available polycarbonate diol having an average molecular weight of 500 having a diol component of HDL (manufactured by Ube Industries) and a polycarbonate diol having an average molecular weight of 500 having a diol component of CHDM. A commercial product (200 g, 0.40 mol) (manufactured by Ube Industries) and titanium tetra-n-butoxide (40 mg) were charged, heated to 170 ° C., and stirred for 6 hours. At this time, the reaction was performed in a nitrogen stream under reduced pressure (200 mmHg). The two types of polycarbonate diols used as raw materials are synthesized by subjecting the corresponding diol compound and carbonate compound to a transesterification reaction in the presence of a transesterification catalyst, and subjecting the remaining catalyst to deactivation treatment.
[0044]
After completion of the reaction, the reaction solution was cooled to obtain a colorless and transparent liquid at room temperature. This product was confirmed to be a copolymer since the Tm of the starting polycarbonate diol disappeared from DSC. Further, from FD-MS and NMR, it was found that the raw material polycarbonate diol was randomly copolymerized. The number average molecular weight was 500 from the measurement of the terminal hydroxyl group.
[0045]
Comparative Example 1
300 g (0.60 mol) of a commercially available polycarbonate diol having an average molecular weight of 500 having a diol component of HDL (manufactured by Ube Industries) and 100 g (0.20 mol) of a commercially available polycarbonate diol having an average molecular weight of 500 having a diol component of CHDM (Ube) Manufactured by Kosan Co., Ltd.) and titanium tetra-n-butoxide 40 mg were carried out in the same manner as in Example 1.
As a result, the obtained product was a copolymer of raw material polycarbonate diol, but was a white opaque soft solid at room temperature. The number average molecular weight was 500.
[0046]
Example 2
In a reactor equipped with a stirrer, a thermometer, and a fractionation tube, 236.36 g (2.00 mol) of 1,6-hexanediol, 288.44 g (2.00 mol) of 1,4-cyclohexanedimethanol and carbonic acid were added. 360.32 g (4.00 mol) of dimethyl and 40 mg of tetra-n-butoxytitanium were charged and reacted at 95 to 160 ° C. while distilling off by-produced methanol. After almost no distillation of methanol, the pressure was reduced to 10 mmHg or less and the reaction was further continued for 4 hours. The reaction was performed in a nitrogen atmosphere.
[0047]
After completion of the reaction, the reaction solution is cooled and colorless and transparent at room temperature. liquid Got. From DSC, FD-MS, and NMR, this was the same raw material polycarbonate diol copolymer as in Example 1. The number average molecular weight was 590.
[0048]
Comparative Example 2
345.54 g (3.00 mol) of 1,6-hexanediol, 144.22 g (1.00 mol) of 1,4-cyclohexanedimethanol, 360.32 g (4.00 mol) of dimethyl carbonate and tetra-n-butoxy The same procedure as in Example 2 was performed except that 40 mg of titanium was charged.
As a result, the obtained product was a copolymer of raw material polycarbonate diol, but was a white opaque soft solid at room temperature. The number average molecular weight was 565.
[0049]
Example 3
[Heat treatment]
A 1000 ml glass flask was charged with 50 g of the polycarbonate diol copolymer obtained in Example 1 (0.1 mol as the polycarbonate diol copolymer and a water content of 700 ppm). To this, 4.41 mg of tributyl phosphite was added. (0.0176 mmol; 1.2 mol with respect to 1 g atom of titanium) was added and 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 50 g of a polycarbonate diol copolymer (liquid) having a stable and high reactivity. The water content is based on weight.
[0050]
[Reaction with isocyanate compound]
In a 1000 ml glass flask, 50 g of the polycarbonate diol copolymer obtained above and 500 g of 2-butanone were placed, and the mixture was heated and stirred at a bath temperature of 70 ° C. (liquid temperature of 65 ° C.). Next, 25 g (0.1 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.
[0051]
When the reaction solution was sampled over time and the isocyanate groups remaining in the reaction solution were quantified, the average reaction rate constant was 4.89 g / mol · sec at the beginning of the reaction (reaction start 10-20 minutes; hereinafter omitted). The reaction rate is 3.76 g / mole · second in the late reaction (starting from 50 to 60 minutes; hereinafter omitted), the rate constant decrease in the late reaction is small (reaction rate constant ratio: 0.77), and the reactivity is stable. It was. The average reaction rate constant in the entire reaction was 4.26 g / mol · sec. Moreover, the conversion rate of the isocyanate group after 1 hour was 84.4%. 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”.
[0052]
Reference example 1
[Reaction with isocyanate compound]
The reaction with the isocyanate compound was carried out in the same manner as in Example 3 except that 50 g of the polycarbonate diol copolymer was used as it was without performing heat treatment.
As a result, the average reaction rate constant was 2.75 g / mole · second at the beginning of the reaction and 1.67 g / mole · second at the end of the reaction, and the rate constant gradually decreased in the latter part of the reaction (reaction rate constant ratio: 0). .61), the reactivity was unstable. The average reaction rate constant for the entire reaction was also low at 2.45 g / mol · sec. Moreover, the conversion rate of the isocyanate group after 1 hour was 62.4%.
[0053]
Example 4
[Heat treatment]
The heat treatment was performed in the same manner as in Example 3 except that 50 g of the polycarbonate diol copolymer obtained in Example 2 (0.0847 mol as a polycarbonate diol and a water content of 300 ppm) was used.
[0054]
[Reaction with isocyanate compound]
The reaction with the isocyanate compound was carried out in the same manner as in Example 3 except that 50 g of the polycarbonate diol copolymer obtained by the heat treatment, 420 g of 2-butanone, and 21.2 g of 4,4′-diphenylmethane diisocyanate were used.
As a result, the average reaction rate constant was 4.84 g / mole · second at the beginning of the reaction and 3.80 g / mole · second at the later stage of the reaction, and the decrease in the rate constant in the later stage of the reaction was small (reaction rate constant ratio: 0.79). ), The reactivity was stable. The average reaction rate constant in the entire reaction was 4.35 g / mol · sec. Moreover, the conversion rate of the isocyanate group after 1 hour was 85.0%.
[0055]
Reference example 2
[Reaction with isocyanate compound]
The reaction with the isocyanate compound was carried out in the same manner as in Example 4 except that 50 g of the polycarbonate diol copolymer was used as it was without performing the heat treatment.
As a result, the average reaction rate constant was 3.07 g / mol · sec at the beginning of the reaction and 1.84 g / mol · sec at the end of the reaction, and the rate constant gradually decreased in the later stage of the reaction (reaction rate constant ratio: 0). .60), the reactivity was unstable. The average reaction rate constant for the entire reaction was also low at 2.65 g / mol · sec. Further, the conversion rate of the isocyanate group after 1 hour was 68.2%.
[0056]
【The invention's effect】
According to the present invention, when producing a polyurethane containing 1,6-hexanediol (HDL) and 1,4-cyclohexanedimethanol (CHDM) as diol components, the polyurethane can be easily produced with improved workability. A polycarbonate diol copolymer can be provided in which the diol component comprises 1,6-hexanediol and 1,4-cyclohexanedimethanol.
That is, since the polycarbonate diol copolymer of the present invention is in a liquid state at room temperature, a polycarbonate diol containing HDL as a diol component and a polycarbonate diol containing CHDM are mixed by heating and melting before use, respectively, as in the past. Therefore, the polyurethane can be easily produced with improved workability.
Further, according to the present invention, when a polyurethane containing 1,6-hexanediol (HDL) and 1,4-cyclohexanedimethanol (CHDM) as diol components is produced, the workability is improved and the polyurethane is easily produced. In addition, it is possible to provide a liquid polycarbonate diol copolymer having high reactivity which is stable in the reaction with an isocyanate compound.
That is, the polycarbonate diol copolymer of the present invention in which the transesterification catalyst is heat-treated in the presence of phosphorous acid triester has a stable and high reactivity in the reaction with the isocyanate compound (that is, the reaction with the isocyanate compound). In addition to the above effects, 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 increases rapidly). The reaction with the isocyanate compound can be carried out smoothly without causing problems such as the occurrence of excessive heat generation) or the problem that the reaction product gels during the reaction.

Claims (4)

  A transesterification catalyst selected from alkoxy or aryloxytitanium compounds and heat-treated in the presence of phosphorous acid triester, a number average molecular weight of 500 to 2000, and a diol component of 1,6-hexanediol: 1,4 Polycarbonate diol composition containing cyclohexanedimethanol (molar ratio) = 1: 2 to 2: 1 polycarbonate diol copolymer.   2. The polycarbonate diol composition according to claim 1, wherein the diol component is 1,6-hexanediol: 1,4-cyclohexanedimethanol (molar ratio) = 1: 1.5 to 1.5: 1.   A polycarbonate diol (A) having a diol component of 1,6-hexanediol and a polycarbonate diol (B) having a diol component of 1,4-cyclohexanedimethanol in the presence of a transesterification catalyst, A: B (molar ratio) The polycarbonate diol composition according to claim 1, wherein the transesterification reaction is performed at = 1: 2 to 2: 1, and then the obtained polycarbonate diol copolymer is heat-treated in the presence of a phosphorous acid triester. Manufacturing method.   Transesterification of 1,6-hexanediol (HDL) and 1,4-cyclohexanedimethanol (CHDM) with carbonate in the presence of a transesterification catalyst at HDL: CHDM (molar ratio) = 1: 2 to 2: 1 Then, the polycarbonate diol copolymer obtained is heat-treated in the presence of phosphorous acid triester, The method for producing a polycarbonate diol composition according to claim 1.