JP2013166852A - Polycarbonate diol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate diol suitable as a starting material of polyurethanes and thermoplastic elastomers and as a material of paints and adhesives.SOLUTION: A polycarbonate diol has repeating units represented by formula (A): -O-R-O-(C=O)- (R represents a 2-15C divalent aliphatic or alicyclic hydrocarbon) and terminal hydroxyl groups, wherein the repeating units represented by the formula (A) include repeating units in which R in the formula (A) is represented by 4, 5 and 6C divalent aliphatic hydrocarbons and which account for 80-100 mol% of the repeating units represented by the formula (A), and the respective repeating units in which R in the formula (A) is represented by 4, 5 and 6C divalent aliphatic hydrocarbons account for 10-80 mol%.

Description

  The present invention relates to a polycarbonate diol suitable as a raw material for polyurethane, thermoplastic elastomer and the like, and further as a constituent material for paints and adhesives. More specifically, the present invention is liquid at room temperature and easy to handle. When used as a paint or when polyurethane is produced by polymerization, it is possible to reduce the amount of solvent used, and toughness and high resistance. The present invention relates to a polycarbonate diol capable of obtaining a polyurethane having chemical properties.

  Polycarbonate diol is known as a material excellent in hydrolysis resistance, light resistance, oxidation degradation resistance, heat resistance and the like as a soft segment such as polyurethane and thermoplastic elastomer. However, polycarbonate diol using 1,6-hexanediol as a main raw material is a solid at room temperature due to its high crystallinity, and a large amount of solvent is required when it is used as a paint or when polyurethane is produced by polymerization. There was an inconvenience that the handling was hindered.

  In order to solve such inconvenience, various liquid polycarbonate diols have been disclosed. For example, a polycarbonate diol that is liquid at room temperature, in which the diol component is composed of 1,6-hexanediol and 1,4-cyclohexanedimethanol, is disclosed (see Patent Document 1). Further, a polycarbonate diol obtained by using 3-methyl-1,5-pentanediol as a main glycol raw material is disclosed (see Patent Document 2). Although these polycarbonate diols are liquid at room temperature, they have the disadvantage that the strength of the resulting polyurethane is reduced compared to polycarbonate diols using 1,6-hexanediol as the main raw material.

  As described above, in the conventional techniques, there is no polycarbonate diol that can be easily handled because it is low in crystallinity and is liquid at room temperature, and can obtain a polyurethane having toughness and chemical resistance.

JP 2011-84751 A International Publication No. 2007/108198

  The present invention provides a polycarbonate diol that is easy to handle because it has low crystallinity and is liquid at room temperature, and can reduce the amount of solvent used when it is used as a paint or when polyurethane is produced by polymerization. For the purpose. Moreover, it aims at providing the polycarbonate diol which can obtain the polyurethane which has toughness and high chemical resistance.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a repeating unit represented by the formula (A) in a polycarbonate diol having a repeating unit represented by the following formula (A) and a terminal hydroxyl group. It has been found that the object can be achieved by forming with repeating units having a specific structure and proportion, and the present invention has been made.

［２］上記式（Ｂ）と（Ｃ）と（Ｄ）で表される繰り返し単位の合計に対して、式（Ｂ）で表される繰り返し単位が１５〜４０モル％であることを特徴とする上記［１］項に記載のポリカーボネートジオール。
［３］式（Ｃ）と（Ｄ）で表される繰り返し単位の割合がモル比で４０：６０〜８５：１５であることを特徴とする上記［２］項に記載のポリカーボネートジオール。
［４］８０℃に加熱し、次いで室温まで冷却したときに液状であることを特徴とする上記［１］〜［３］項のいずれか１項に記載のポリカーボネートジオール。 That is, the configuration of the present invention is as follows.
[1] A polycarbonate diol having a repeating unit represented by the following formula (A) and a terminal hydroxyl group, wherein the repeating unit represented by the formula (A) is represented by the following formulas (B), (C) and (D The total number of repeating units represented by formulas (B), (C), and (D) is 80 to 100 mol% of the repeating units represented by formula (A). Each repeating unit represented by the formula (B) or (C) or (D) is 10 to 80 mol based on the total of the repeating units represented by the formulas (B), (C) and (D). % Polycarbonate diol, characterized by

[2] The repeating unit represented by the formula (B) is 15 to 40 mol% with respect to the total of the repeating units represented by the formulas (B), (C) and (D). The polycarbonate diol as described in the above item [1].
[3] The polycarbonate diol as described in the above item [2], wherein the ratio of the repeating units represented by the formulas (C) and (D) is 40:60 to 85:15 in molar ratio.
[4] The polycarbonate diol as described in any one of [1] to [3] above, which is liquid when heated to 80 ° C. and then cooled to room temperature.

Since the polycarbonate according to the present invention is low in crystallinity and liquid at room temperature, it is easy to handle, and when used as a paint or when polyurethane is produced by polymerization, the amount of solvent used can be reduced. Further, by using the polycarbonate according to the present invention, a polyurethane having toughness and high chemical resistance can be obtained. Because of these characteristics, the polycarbonate diol according to the present invention can be suitably used as a raw material for polyurethanes, thermoplastic elastomers and the like, and further as a constituent material for paints and adhesives.
The term “liquid” as used herein means a state in which, even when it is tilted in a transparent container, it exhibits fluidity, and further, the scenery behind can be confirmed through the transparent container. In addition, “normal temperature” here includes, for example, a temperature range including 5 ° C. to 40 ° C., normally including 10 ° C. to 35 ° C., and more typically including 15 ° C. to 30 ° C.

Hereinafter, the present invention will be specifically described.
The polycarbonate diol of the present invention has a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and the repeating unit represented by the formula (A) is represented by the following formulas (B), (C) and (D ), And the total of the repeating units represented by the formulas (B), (C), and (D) is 80 to 100 mol% of the repeating unit represented by the formula (A). . If the total ratio of the repeating units represented by the formulas (B), (C) and (D) in the repeating unit represented by the formula (A) is within this range, the polycarbonate is liquid at room temperature, A rich polyurethane having chemical resistance can be obtained. This ratio is more preferably 90 to 100 mol%.
In the polycarbonate diol, the ratio of the repeating unit represented by the formula (A) is preferably 95 mol% or more and 100 mol% or less, more preferably 97 mol% or more and 100 mol% or less, and further preferably 99 mol% or more. 100 mol% or less.

  In the polycarbonate diol of the present invention, each repeating unit represented by the formula (B) or (C) or (D) is added to the total of the repeating units represented by the formulas (B), (C), and (D). It is 10-80 mol% with respect to. If the ratio of each repeating unit represented by the formula (B) or (C) or (D) is within this range, the crystallinity of the polycarbonate is low, it is liquid at room temperature, and has toughness and chemical resistance. A polyurethane can be obtained.

  Furthermore, in the polycarbonate diol of the present invention, the repeating unit represented by the formula (B) is 15 to 40 mol% with respect to the total repeating units represented by the formulas (B), (C) and (D). Yes, and / or the ratio of the repeating units represented by formulas (C) and (D) is preferably 40:60 to 85:15 in molar ratio. By setting the ratio of each repeating unit within these ranges, it is possible to achieve further reduction in the crystallinity of the polycarbonate and improvement in toughness and chemical resistance of the resulting polyurethane. The repeating unit represented by the formula (B) is 20 to 35 mol% with respect to the total repeating units represented by the formulas (B), (C), and (D) and / or the formula (C ) And (D) when the ratio of the repeating units is 40:60 to 85:15 in terms of molar ratio, the toughness and chemical resistance of the resulting polyurethane can be further improved.

  The polycarbonate diol of the present invention is preferably in a liquid state at room temperature after being left in the state of production or ambient conditions. The polycarbonate diol is more preferably liquid when heated to 80 ° C. and then cooled to room temperature.

Moreover, the polycarbonate diol of this invention can also contain the structure represented by the repeating unit of following formula (E) in the molecule | numerator in order to provide a softness | flexibility.

  The method for introducing the repeating unit of the above formula (E) into the polycarbonate diol molecule is not particularly limited. For example, polyoxyethylene glycol, polyoxyethylene propylene glycol, polyoxyethylene tetramethylene glycol, polyoxytetramethylene Ether-based polyols such as glycol and polyoxypropylene glycol may be added to the raw material diol, and alkylene oxides such as ethylene oxide and / or propylene oxide may be added during the polymerization.

  In the polycarbonate diol of the present invention, the content of the repeating unit of the formula (E) in the molecule is not particularly limited as long as it does not affect the present invention. And chemical resistance may decrease. Therefore, when the repeating unit represented by the formula (E) is introduced into the polycarbonate diol, the carbonate repeating unit represented by the formula (A) is represented by the formula (E) (the structure derived from the ether). The repeating unit is preferably 0.05 to 5 mol%, more preferably 0.05 to 3 mol%.

  The number average molecular weight of the polycarbonate diol of the present invention is preferably 300 to 5,000. If the number average molecular weight of the polycarbonate diol is 300 or more, the low temperature characteristics of the resulting polyurethane will be good. If the number average molecular weight of the polycarbonate diol is 5000 or less, when used as a constituent material of a paint, the solid content concentration of the paint is not limited, and the molding processability of the resulting polyurethane is not lowered, which is preferable. . The number average molecular weight of the polycarbonate diol is more preferably 450 to 3000.

  The method for producing the polycarbonate diol used in the present invention is not particularly limited. For example, it can be produced by various methods described in Schnell, Polymer Reviews Vol. 9, p9-20 (1994).

  The polycarbonate diol of the present invention uses 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol as diol raw materials. Usually, the above three diols are mixed to obtain a diol raw material. A diol mixture obtained by hydrogenating a dibasic acid mixture containing succinic acid, glutaric acid, and adipic acid can also be used as a raw material without being separated into diols such as 1,4-butanediol. In that case, a specific diol can be additionally used according to the repeating unit composition of the polycarbonate diol.

  In addition to the above three diols, ethylene glycol, 1,3-propanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11- Diols having no side chain such as undecanediol, 1,12-dodecanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3- Diols having side chains such as propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 2-bis 4-hydroxycyclohexyl) - cyclic diols such as propane, may be used one or more kinds of diol as a raw material. The amount of these diols is not particularly limited, but is usually 0.1% with respect to the total number of moles of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol used. It is preferable that it is 10 mol%. If this ratio is 0.1 to 10 mol%, a polyurethane having toughness and chemical resistance is obtained, which is preferable. If this ratio is 0.1-5 mol%, it is more preferable.

  Furthermore, a compound having 3 or more hydroxyl groups per molecule, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol and the like can be used within the range not impairing the performance of the polycarbonate diol of the present invention. If too many compounds having 3 or more hydroxyl groups in one molecule are used, gelation occurs due to crosslinking during the polymerization reaction of the polycarbonate. Therefore, even when a compound having three or more hydroxyl groups in one molecule is used, the compound is a total mole of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol used. It is preferable to make it 0.1-5 mol% with respect to a number. This ratio is more preferably 0.1 to 1 mol%.

  The polycarbonate diol of the present invention includes, as examples of carbonates as raw materials, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate, diaryl carbonates such as diphenyl carbonate, ethylene carbonate, trimethylene carbonate, 1,2- Examples include alkylene carbonates such as propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. Of these, one or more carbonates can be used as a raw material. From the viewpoint of easy availability and easy setting of conditions for the polymerization reaction, it is preferable to use dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, or ethylene carbonate.

  In the production of the polycarbonate diol of the present invention, a catalyst may or may not be added. When adding a catalyst, it can select freely from a normal transesterification catalyst. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium and other metals, salts, alkoxides, organic compounds Used. Particularly preferred are titanium, tin and lead compounds. Moreover, the usage-amount of a catalyst is 0.00001 to 0.1% of the polycarbonate diol weight normally obtained.

  As an example of a method for producing a polycarbonate diol, a method using dimethyl carbonate as a carbonate will be described. The production of the polycarbonate diol can be carried out in two stages. Diol and dimethyl carbonate are mixed at a molar ratio of 20: 1 to 1:10, reacted at 100 to 300 ° C. under normal pressure or reduced pressure, and the resulting methanol is removed as a mixture with dimethyl carbonate to reduce the A molecular weight polycarbonate diol can be obtained. Next, heating is performed at 160 to 250 ° C. under reduced pressure to remove unreacted diol and dimethyl carbonate and to condense low molecular weight polycarbonate diol to obtain polycarbonate diol having a predetermined molecular weight.

  The polycarbonate diol of the present invention can be used as a constituent material for paints and adhesives, as a raw material for polyurethane and thermoplastic elastomers, and for applications such as polyester and polyimide modifiers. In particular, when used as a constituent material for paints, it is easy to handle, can reduce the amount of solvent used, and provides a coating film that is tough and has a good balance of performance such as chemical resistance, hydrolysis resistance, and heat resistance. It is done. Further, when used as a raw material for polyurethane or thermoplastic elastomer, it is possible to reduce the solvent used for polymerization, and to obtain a polyurethane or thermoplastic elastomer that is tough and excellent in chemical resistance.

The paint and thermoplastic polyurethane can be obtained using the polycarbonate diol and polyisocyanate of the present invention.
Examples of the polyisocyanate used include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof (TDI), crude TDI, diphenylmethane-4,4′-diisocyanate (MDI), crude MDI, Known aromatic diisocyanates such as naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), phenylene diisocyanate, 4 , 4′-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (hydrogenated XDI), etc. Aliphatic diisocyanates, isocyanurate-modified products of these isocyanates, carbodiimidization-modified products, biuret-modified products, and the like. These organic polyisocyanates may be used alone or in combination of two or more. These organic polyisocyanates may be used by masking isocyanate groups with a blocking agent.

  Further, in the reaction of polycarbonate diol and polyisocyanate, a chain extender can be used as a copolymerization component if desired. As the chain extender, a conventional chain extender in the polyurethane industry, that is, water, a low molecular polyol, a polyamine and the like can be used. Examples of chain extenders include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1 , 1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, xylylene glycol, low molecular polyols such as bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, ethylenediamine, hexamethylenediamine, isophoronediamine, Polyamines such as xylylenediamine, diphenyldiamine, and diaminodiphenylmethane are listed. These chain extenders may be used alone or in combination of two or more.

  As a method for producing a paint, a production method known in the industry is used. For example, as a paint, a two-component solvent-based coating composition in which a main component composed of polycarbonate diol and a curing agent composed of organic polyisocyanate are mixed immediately before coating, an isocyanate end group obtained by reacting polycarbonate diol and organic polyisocyanate. -Pack type solvent-based coating composition comprising a urethane prepolymer having a one-component solvent-based coating composition comprising a polyurethane resin obtained by reacting polycarbonate diol, organic polyisocyanate and chain extender, or one-pack type An aqueous coating composition can be produced.

  Examples of the paint include a curing accelerator (catalyst), a filler, a dispersant, a flame retardant, a dye, an organic or inorganic pigment, a release agent, a fluidity modifier, a plasticizer, an antioxidant, An ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, a coloring agent, a solvent, etc. can be added.

  Solvents for paint include dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, xylene, ethyl cellosolve, ethyl acetate, butyl acetate, ethanol, isopropanol , N-butanol, water and the like. The paint can be used by mixing one or more of these solvents.

As a method for producing the thermoplastic polyurethane, a technique of polyurethane reaction known in the polyurethane industry is used. For example, a thermoplastic polyurethane can be produced by reacting the polycarbonate diol of the present invention with an organic polyisocyanate under atmospheric pressure from room temperature to 200 ° C. When a chain extender is used, it may be added from the beginning of the reaction or may be added from the middle of the reaction. For the method for producing thermoplastic polyurethane, reference can be made, for example, to US Pat. No. 5,070,173.
In the polyurethane reaction, a known polymerization catalyst or solvent may be used. The polymerization catalyst used is not particularly limited, and examples thereof include dibutyltin dilaurate.

  It is desirable to add a stabilizer such as a heat stabilizer (for example, an antioxidant) or a light stabilizer to the thermoplastic polyurethane. Further, a plasticizer, an inorganic filler, a lubricant, a colorant, silicon oil, a foaming agent, a flame retardant, and the like may be added.

Next, the present invention will be described with reference to examples and comparative examples.
The following examples are given to illustrate the present invention and are not intended to limit the scope of the invention in any way.
The physical property values shown in the following examples and comparative examples were measured by the following methods.

1. Determination of the composition of the polycarbonate diol 1 g of a sample is weighed into a 100 ml eggplant flask, charged with 30 g of ethanol and 4 g of potassium hydroxide, and heated in an oil bath at 100 ° C. for 1 hour. After cooling to room temperature, add 1-2 drops of phenolphthalein to the indicator and neutralize with hydrochloric acid. After cooling in the refrigerator for 3 hours and removing the precipitated salt by filtration, GC analysis was performed. The GC analysis uses a gas chromatography GC14B (manufactured by Shimadzu Corporation) with a DB-WAX (manufactured by J & W, USA) 30 m and a film thickness of 0.25 μm as a column, and diethylene glycol diethyl ester as an internal standard. A flame ionization detector (FID) was used. The temperature rising profile of the column was maintained at 60 ° C. for 5 minutes and then heated to 250 ° C. at 10 ° C./min.

In the polycarbonate diol, the ratio of the total repeating units represented by the formula (B), the formula (C), and the formula (D) to the repeating unit represented by the formula (A) (abbreviated as the main component ratio) is GC analysis. Based on the results, the following formula (1) was used.
Main component ratio (mol%) = {(B + C + D) / A} × 100 (1)
A: Number of moles of all diols
B: Number of moles of 1,4-butanediol
C: Number of moles of 1,5-pentanediol
D: Number of moles of 1,6-hexanediol

In the polycarbonate diol, the ratio of the repeating unit represented by the formula (B), the formula (C), or the formula (D) to the total of the repeating units of the formulas (B), (C), and (D) is the result of GC analysis. Based on the following formulas (2) to (4).
Ratio (mol%) of formula (B) = B / (B + C + D) × 100 (2)
Ratio of formula (C) (mol%) = C / (B + C + D) × 100 (3)
Ratio of formula (D) (mol%) = D / (B + C + D) × 100 (4)

In the present invention, the ratio (molar ratio) of the repeating units represented by the formulas (C) and (D) is represented by the following formula (5) based on the result of GC analysis.
Formula (C): Formula (D) (molar ratio) = C: D (5)

2. Determination of the molecular weight of the polycarbonate diol The number average molecular weight of the polycarbonate diol was determined by determining the hydroxyl value by the “neutralization titration method (JIS K0070-1992)” in which titration was performed with an ethanol solution of potassium hydroxide using acetic anhydride and pyridine. It calculated using Formula (6).
Number average molecular weight = 2 / (OH value × 10 ⁻³ /56.1) (6)

3. Determination of the viscosity of the polycarbonate diol The viscosity of the polycarbonate diol was measured at a measurement temperature of 70 ° C. by a method using a cone-plate rotational viscometer (JIS K1557-2007). In addition, the viscosity here was represented as a relative value with respect to the viscosity of the polycarbonate diol (PC-17) obtained by the following comparative example 2.

4). Confirmation of properties of polycarbonate diol Polycarbonate diol heated to 80 ° C. was placed in a transparent sample bottle, and the state cooled to room temperature was visually observed. The case where it is transparent and has a slight fluidity when the sample bottle is tilted is expressed as liquid, and the case where it is opaque and does not change even when the sample bottle is tilted is expressed as solid.

5. Mechanical Properties of Polyurethane Film A polyurethane film obtained from polycarbonate diol was cut into a 10 mm × 80 mm strip and cured for 3 days in a temperature-controlled room at 23 ° C. and 50% RH. Using a Tensilon tensile tester (ORIENTEC, RTC-1250A), the distance between checks is 50 mm, the tensile speed is 100 mm / min, 100% tensile stress (stress when the film is stretched 50 mm; unit: MPa), and the breaking strength ( Unit: MPa) and elongation at break (unit:%) were measured.

6). Oil resistance (chemical resistance) of polyurethane film
0.1 g of oleic acid was attached to a test piece obtained by cutting a polyurethane film obtained from a polycarbonate diol into a strip of 10 mm × 80 mm, and allowed to stand at 20 ° C. for 4 hours. The oil resistance was evaluated as ◎ when there was no change in appearance, ◯ when there was almost no change in appearance, △ when there was a very small bulge, and x when there was a clear bulge.

[Example 1]
840 g (7.1 mol) of diethyl carbonate, 240 g (2.7 mol) of 1,4-butanediol, 1,5-pentane in a 2 L glass flask equipped with a rectification column packed with a regular packing and a stirrer 360 g (3.5 mol) of diol and 175 g (1.5 mol) of 1,6-hexanediol were charged. As a catalyst, 0.5 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. While gradually increasing the reaction temperature from 150 ° C. to 190 ° C., the reaction was carried out for 15 hours while distilling off the resulting mixture of ethanol and dimethyl carbonate. Thereafter, the pressure was reduced to 15 kPa, and the mixture was further reacted at 190 ° C. for 8 hours while distilling off a mixture of ethanol and diethyl carbonate. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-1.

[Example 2]
The reaction was carried out using the apparatus shown in Example 1. 760 g (8.6 mol) of ethylene carbonate, 210 g (2.3 mol) of 1,4-butanediol, 550 g (5.3 mol) of 1,5-pentanediol, and 115 g (1.0 mol) of 1,6-hexanediol ) Prepared. As a catalyst, 0.5 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. While gradually increasing the reaction temperature from 150 ° C. to 190 ° C., the reaction was carried out for 15 hours while distilling off the mixture of ethylene glycol and ethylene carbonate produced. Thereafter, the pressure was reduced to 14 kPa, and the reaction was further performed at 190 ° C. for 8 hours while distilling off the diol and ethylene carbonate. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-2.

[Example 3]
740 g (8.4 mol) of ethylene carbonate, 170 g (1.9 mol) of 1,4-butanediol, 390 g (3.8 mol) of 1,5-pentanediol, and 330 g (2.8 mol) of 1,6-hexanediol ) The reaction was carried out using the apparatus of Example 1 under the conditions shown in Example 2 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-3.

[Example 4]
750 g (8.5 mol) of ethylene carbonate, 250 g (2.8 mol) of 1,4-butanediol, 370 g (3.6 mol) of 1,5-pentanediol, and 265 g (2.3 mol) of 1,6-hexanediol ) The reaction was carried out using the apparatus of Example 1 under the conditions shown in Example 2 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-4.

[Example 5]
740 g (8.4 mol) of ethylene carbonate, 190 g (2.1 mol) of 1,4-butanediol, 430 g (4.1 mol) of 1,5-pentanediol, and 260 g (2.2 mol) of 1,6-hexanediol ) The reaction was carried out using the apparatus of Example 1 under the conditions shown in Example 2 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-5.

[Example 6]
750 g (8.5 mol) of ethylene carbonate, 230 g (2.6 mol) of 1,4-butanediol, 330 g (3.2 mol) of 1,5-pentanediol, 330 g (2.8 mol) of 1,6-hexanediol ) The reaction was carried out using the apparatus of Example 1 under the conditions shown in Example 2 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-6.

[Example 7]
750 g (8.5 mol) of ethylene carbonate, 210 g (2.3 mol) of 1,4-butanediol, 490 g (4.7 mol) of 1,5-pentanediol, and 175 g (1.5 mol) of 1,6-hexanediol ) The reaction was carried out using the apparatus of Example 1 under the conditions shown in Example 2 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-7.

[Example 8]
880 g (7.5 mol) of diethyl carbonate, 285 g (3.2 mol) of 1,4-butanediol, 410 g (3.9 mol) of 1,5-pentanediol, and 100 g (0.9 mol) of 1,6-hexanediol ) The reaction was carried out under the conditions shown in Example 1 using the apparatus of Example 1 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-8.

[Example 9]
830 g (7.0 mol) of diethyl carbonate, 125 g (1.4 mol) of 1,4-butanediol, 480 g (4.6 mol) of 1,5-pentanediol, and 180 g (1.5 mol) of 1,6-hexanediol ) The reaction was carried out under the conditions shown in Example 1 using the apparatus of Example 1 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-9.

[Example 10]
Diethyl carbonate 840 g (7.1 mol), 1,4-butanediol 85 g (0.9 mol), 1,5-pentanediol 520 g (5.0 mol), 1,6-hexanediol 200 g (1.7 mol) ) The reaction was carried out under the conditions shown in Example 1 using the apparatus of Example 1 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-10.

[Example 11]
860 g (7.3 mol) of diethyl carbonate, 360 g (4.0 mol) of 1,4-butanediol, 320 g (3.1 mol) of 1,5-pentanediol, and 90 g (0.8 mol) of 1,6-hexanediol ) The reaction was carried out under the conditions shown in Example 1 using the apparatus of Example 1 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-11.

[Example 12]
850 g (7.2 mol) of diethyl carbonate, 150 g (1.7 mol) of 1,4-butanediol, 260 g (2.5 mol) of 1,5-pentanediol, and 420 g (3.6 mol) of 1,6-hexanediol ) The reaction was carried out under the conditions shown in Example 1 using the apparatus of Example 1 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-12.

[Example 13]
850 g (7.2 mol) of diethyl carbonate, 155 g (1.7 mol) of 1,4-butanediol, 180 g (1.7 mol) of 1,5-pentanediol, and 500 g (4.2 mol) of 1,6-hexanediol ) The reaction was carried out under the conditions shown in Example 1 using the apparatus of Example 1 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-13.

[Example 14]
860 g (7.3 mol) of diethyl carbonate, 130 g (1.4 mol) of 1,4-butanediol, 580 g (5.6 mol) of 1,5-pentanediol, and 95 g (0.8 mol) of 1,6-hexanediol ) The reaction was carried out under the conditions shown in Example 1 using the apparatus of Example 1 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-14.

[Example 15]
760 g (8.6 mol) of ethylene carbonate, 240 g (2.7 mol) of 1,4-butanediol, 390 g (3.8 mol) of 1,5-pentanediol, and 260 g (2.2 mol) of 1,6-hexanediol ) And 3-methyl-1,5-pentanediol were charged under the conditions shown in Example 2 using the apparatus of Example 1 except that 170 g (1.4 mol) was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-15.

[Comparative Example 1]
Using the apparatus shown in Example 1, 800 g (6.8 mol) of diethyl carbonate and 850 g (7.2 mol) of 1,6-hexanediol were charged. As a catalyst, 0.5 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. While gradually increasing the reaction temperature from 150 ° C. to 190 ° C., the reaction was carried out for 15 hours while distilling off the resulting mixture of ethanol and dimethyl carbonate. Thereafter, the pressure was reduced to 15 kPa, and the mixture was further reacted at 190 ° C. for 8 hours while distilling off a mixture of ethanol and diethyl carbonate. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-16.

[Comparative Example 2]
The reaction was performed under the conditions shown in Comparative Example 1 using the apparatus of Example 1, except that 900 g (7.6 mol) of diethyl carbonate and 730 g (8.1 mol) of 1,4-butanediol were charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-17.

[Comparative Example 3]
Using the apparatus shown in Comparative Example 1, 780 g (8.8 mol) of ethylene carbonate, 55 g (0.6 mol) of 1,4-butanediol, 800 g (7.7 mol) of 1,5-pentanediol, 1,6 -65 g (0.6 mol) of hexanediol was charged. As a catalyst, 0.5 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. While gradually increasing the reaction temperature from 150 ° C. to 190 ° C., the reaction was carried out for 15 hours while distilling off the mixture of ethylene glycol and ethylene carbonate produced. Thereafter, the pressure was reduced to 14 kPa, and the reaction was further performed at 190 ° C. for 8 hours while distilling off the diol and ethylene carbonate. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-18.

[Comparative Example 4]
750 g (8.5 mol) of ethylene carbonate, 370 g (4.1 mol) of 1,4-butanediol, 20 g (0.2 mol) of 1,5-pentanediol, and 500 g (4.2 mol) of 1,6-hexanediol ) A reaction was carried out under the conditions shown in Comparative Example 3 using the apparatus of Example 1 except for charging. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-19.

[Comparative Example 5]
700 g (8.0 mol) of ethylene carbonate, 10 g (0.1 mol) of 1,4-butanediol, 540 g (5.2 mol) of 1,5-pentanediol, and 380 g (3.2 mol) of 1,6-hexanediol ) A reaction was carried out under the conditions shown in Comparative Example 3 using the apparatus of Example 1 except for charging. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-20.

[Comparative Example 6]
760 g (8.6 mol) of ethylene carbonate, 270 g (3.0 mol) of 1,4-butanediol, 570 g (5.5 mol) of 1,5-pentanediol, and 20 g (0.2 mol) of 1,6-hexanediol ) A reaction was carried out under the conditions shown in Comparative Example 3 using the apparatus of Example 1 except for charging. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-21.

[Comparative Example 7]
780 g (6.6 mol) of diethyl carbonate, 10 g (0.1 mol) of 1,4-butanediol, 600 g (4.2 mol) of 1,4-cyclohexanedimethanol, 300 g (2.5 mol) of 1,6-hexanediol ) A reaction was carried out under the conditions shown in Comparative Example 1 using the apparatus of Example 1 except that it was charged. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is abbreviated as PC-22.

[Application Example 1]
A reactor equipped with a stirrer, a thermometer, and a cooling tube was charged with 200 g of PC-1 obtained in Example 1, 34 g of hexamethylene diisocyanate, and 0.02 g of dibutyltin dilaurate as a catalyst, and reacted at 70 ° C. for 5 hours. A prepolymer of terminal NCO was obtained. After adding 600 g of dimethylformamide as a solvent and dissolving, 17 g of isophoronediamine as a chain extender was added and stirred at 35 ° C. for 1 hour. The obtained polyurethane resin solution was cast on a glass plate, allowed to stand at room temperature for 30 minutes to evaporate the solvent, and then placed in a dryer at 100 ° C. for 2 hours to be dried. The properties of the polyurethane film were evaluated and are shown in Table 2.

[Application Examples 2 to 21]
A polyurethane film was obtained under the conditions shown in Application Example 1 using PC-2 to 21 as the polycarbonate diol. The properties of the polyurethane film were evaluated and are shown in Table 2. In addition, since the polyurethane resin solution using PC-22 had a high viscosity and a uniform polyurethane film could not be obtained, physical properties were not evaluated.

  The polycarbonate diol of the present invention is liquid at room temperature and easy to handle, and when used as a paint or when a polyurethane resin is produced by polymerization, the amount of solvent used can be reduced. Moreover, as demonstrated in the above-mentioned Examples, when the polycarbonate diol of the present invention is used as a raw material for polyurethane and thermoplastic elastomer, it is possible to obtain polyurethane and thermoplastic elastomer having high toughness and chemical resistance. Therefore, the polycarbonate diol of the present invention can be suitably used as a raw material for polyurethanes, thermoplastic elastomers and the like, and further as a constituent material for paints and adhesives.

Claims (4)

A polycarbonate diol having a repeating unit represented by the following formula (A) and a terminal hydroxyl group, wherein the repeating unit represented by the formula (A) is represented by the following formulas (B), (C) and (D). The total of the repeating units represented by the formulas (B), (C), and (D) is 80 to 100 mol% of the repeating units represented by the formula (A), Each repeating unit represented by B) or (C) or (D) is 10 to 80 mol% with respect to the total repeating units represented by formulas (B), (C) and (D). A polycarbonate diol characterized by that.

  The repeating unit represented by the formula (B) is 15 to 40 mol% with respect to the total repeating units represented by the formulas (B), (C) and (D). 1. The polycarbonate diol according to 1.   The polycarbonate diol according to claim 1 or 2, wherein the ratio of the repeating units represented by the formulas (C) and (D) is 40:60 to 85:15 in terms of molar ratio.   The polycarbonate diol according to any one of claims 1 to 3, which is liquid when heated to 80 ° C and then cooled to room temperature.