JP2023103002A - Polyether polycarbonate diol and method for producing the same - Google Patents

Abstract

To provide a polyether polycarbonate diol that enables the production of a polyurethane suitable for synthetic leather or the like, having excellent chemical resistance, and having a weight average molecular weight of about 150,000 to 200,000.SOLUTION: A polyether polycarbonate diol comprises a structural unit represented by the following formula (1) of 0.1 mass% or more and 3.5 mass% or less, and has a hydroxyl value of 11.0 mg-KOH/g or more and 320 mg-KOH/g or less. Preferably, the polyether polycarbonate diol further comprises a structural unit represented by the following formula (2). (In the formula (1), m is an integer of 1 or greater). (In the formula (2), R1 and R2 each denote a hydrogen atom or a C1-2 alkyl group, and n is an integer of 1 or greater).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polyether polycarbonate diol used as a raw material for polyurethane, polyurethane urea, etc., and a method for producing the same. The present invention also relates to a method for producing polyurethane using this polyether polycarbonate diol.

Polyurethanes are used in a wide range of applications such as urethane foams, paints, adhesives, sealants and elastomers. Polyurethane is composed of a hard segment composed of isocyanate and a chain extender and a soft segment composed mainly of polyol. Polyol, one of the main raw materials of polyurethane, is classified into polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, acrylic polyol, etc. according to the difference in molecular chain structure, and polyol is selected according to the required performance of polyurethane. Among polyether polyols, polytetramethylene ether glycol (hereinafter sometimes abbreviated as PTMG) has high crystallinity, and therefore the polyurethane obtained by reaction with isocyanates exhibits excellent wear resistance, hydrolysis resistance, and tear resistance. The main uses of such polyurethanes are spandex, thermoplastic elastomers, thermoset elastomers, artificial leather, synthetic leather and the like.

Due to such excellent properties, polyurethanes obtained from polytetramethylene ether glycol are used in a variety of applications, but polytetramethylene ether glycol has a high melting point and viscosity, which poses problems in terms of handling.

In Patent Document 1, a polyether polyol that is liquid at room temperature is obtained by introducing a methyl group into the side chains of some polymer units to make it amorphous.
A polyether polycarbonate diol (hereinafter sometimes abbreviated as PEPCD) produced from polytetramethylene ether glycol having a small molecular weight is known as a room-temperature liquid polyol (Patent Document 2).

JP-A-61-120830 JP-A-2002-256069

The polyurethane obtained from the polyether polyol of Patent Document 1 has the drawback of low durability.
According to PEPCD of Patent Document 2, durability is improved, but it is difficult to control urethane polymerization reactivity, and it is not possible to obtain polyurethane having a weight average molecular weight of about 200,000, which is used for synthetic leather and the like.
In addition, although chemical resistance is also emphasized in polyurethane used for synthetic leather and the like, chemical resistance is not studied in Patent Documents 1 and 2.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a polyether polycarbonate diol (hereinafter sometimes abbreviated as PEPCD) that can be suitably used for synthetic leather and the like, has excellent chemical resistance, and can produce polyurethane having a weight average molecular weight of about 150,000 to 200,000.

As a result of intensive studies aimed at solving the above problems, the present inventors have found that by using a polyether polycarbonate diol containing specific structural units in a specific ratio and having a hydroxyl value within a specific range as a starting material for urethane production, the urethane polymerization reaction can be easily controlled, rapid polymerization reaction can be suppressed, and a polyurethane having a desired molecular weight and excellent chemical resistance can be obtained.
The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] A polyether polycarbonate diol containing 0.1% by mass or more and 3.5% by mass or less of a structural unit represented by the following formula (1) and having a hydroxyl value of 11.0 mg-KOH/g or more and 320 mg-KOH/g or less.

(In the above formula (1), m is an integer of 1 or more.)

[2] The polyether polycarbonate diol according to [1], further comprising a structural unit represented by the following formula (2).

(In formula (2) above, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and n is an integer of 1 or more.)

[3] The polyether polycarbonate diol according to [1] or [2], wherein the ratio of the total number of alkoxy terminal groups and aryloxy terminal groups to the total number of terminal groups is 0.20% or more and 7.5% or less.

[4] The polyether polycarbonate diol of [3], wherein the alkoxy end groups comprise butoxy end groups.

[5] A method for producing a polyether polycarbonate diol according to any one of [1] to [4], comprising the step of reacting a polyalkylene ether glycol with a carbonate compound, wherein the carbonate compound is ethylene carbonate.

[6] The method for producing a polyether polycarbonate diol according to [5], wherein the polyalkylene ether glycol contains polytetramethylene ether glycol.

[7] The method for producing a polyether polycarbonate diol according to [5] or [6], wherein the polyalkylene ether glycol has a hydroxyl value of 50.0 mg-KOH/g or more and 550 mg-KOH/g or less.

[8] A method for producing polyurethane using the polyether polycarbonate diol according to any one of [1] to [4].

According to the polyether polycarbonate diol of the present invention, it is possible to produce a polyurethane having excellent chemical resistance and a weight average molecular weight of about 150,000 to 200,000, which can be suitably used for synthetic leather and the like.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in more detail, but the present invention is not limited to the embodiments described below as long as the gist thereof is not exceeded.

[Polyether polycarbonate diol]
The polyether polycarbonate diol (hereinafter sometimes abbreviated as "PEPCD") of the present invention is a polyether polycarbonate diol containing 0.1% by mass or more and 3.5% by mass or less of a structural unit represented by the following formula (1) (hereinafter sometimes referred to as "structural unit (1)") and having a hydroxyl value of 11.0 mg-KOH/g or more and 320 mg-KOH/g or less. The PEPCD of the present invention preferably further contains a structural unit represented by the following formula (2) (hereinafter sometimes referred to as "structural unit (2)").

(In the above formula (1), m is an integer of 1 or more.)

(In formula (2) above, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and n is an integer of 1 or more.)

The content ratio of the structural unit (1) in PEPCD and the content ratio of the structural unit (2) described later can be measured by the method described in Examples below.

<Structural unit (1)>
In the formula (1) representing the structural unit (1), m is an integer of 1 or more, preferably 1-5, more preferably 1-3.

If the content of the structural unit (1) in PEPCD is less than 0.1% by mass, the chemical resistance of the polyurethane synthesized using the PEPCD as a raw material may be lowered. On the other hand, if the content of the structural unit (1) exceeds 3.5% by mass, the chemical resistance of the polyurethane synthesized using the PEPCD as a starting material may be lowered and the mechanical strength may be lowered. The content of structural unit (1) in PEPCD of the present invention is preferably 0.3 to 3.0% by mass, more preferably 0.5 to 2.5% by mass, and particularly preferably 0.6 to 2.0% by mass.

Structural unit (1) is a structural unit that can be introduced into PEPCD by using ethylene glycol, diethylene glycol, triethylene glycol, ethylene carbonate, or the like as a raw material when producing PEPCD. In order to contain structural unit (1) in PEPCD at the above content ratio, for example, the concentration or amount of the compound may be adjusted during PEPCD production.

<Structural unit (2)>
The PEPCD of the present invention preferably contains structural unit (2) together with structural unit (1).
In formula (2) representing structural unit (2), n is an integer of 1 or more, preferably 2 to 45, more preferably 3 to 30, even more preferably 3 to 15, and particularly preferably 3 to 10.
Each of R ¹ and R ² is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 carbon atom, particularly preferably a hydrogen atom.

The content of the structural unit (2) in the PEPCD of the present invention is preferably 80% by mass or more and 99% by mass or less. If the content of the structural unit (2) is at least the above lower limit, the chemical resistance of the polyurethane synthesized using PEPCD may be improved. If it is less than the above upper limit, flexibility of polyurethane synthesized using PEPCD may be improved. The content of structural unit (2) is more preferably 85% by mass or more and 98% by mass or less, and more preferably 86% by mass or more and 97% by mass or less.

Structural unit (2) is a structural unit introduced into PEPCD by a polyalkylene ether glycol such as polytetramethylene ether glycol, which will be described later. In order to make the content of structural unit (2) in PEPCD within the above range, for example, the concentration of polytetramethylene ether glycol or the amount of polytetramethylene ether glycol may be adjusted during the production of PEPCD.
The PEPCD of the present invention may contain only one type of structural unit (2), or may contain two or more types of structural units (2) having different values of m, R ¹ and R ² in formula (2).

<Other structural units>
The PEPCD of the present invention may contain structural units other than structural unit (1) and structural unit (2).
Other structural units include structural units derived from diol compounds having 7 to 50 carbon atoms and introduced into PEPCD. The PEPCD of the present invention may contain only one of these other structural units, or may contain two or more.

However, the PEPCD of the present invention contains the structural unit (1) and the structural unit (2), and from the viewpoint of effectively obtaining the above effects, the content of other structural units in the PEPCD of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably does not contain other structural units.

<Hydroxyl value and number average molecular weight of PEPCD>
The lower limit of the hydroxyl value of the PEPCD of the present invention is usually 11.0 mg-KOH/g, preferably 22.4 mg-KOH/g, more preferably 28.1 mg-KOH/g, more preferably 37.4 mg-KOH/g, and the upper limit is usually 320 mg-KOH/g, preferably 187.0 mg-KOH/g, more preferably 140.3 mg-KOH/g, more preferably 112.2 mg-KOH. /g. When the hydroxyl value is at least the above lower limit, the viscosity does not become too high, and there is a tendency that handling becomes easy when the PEPCD is used as a raw material to produce a polyurethane.

The molecular weight of the PEPCD of the present invention is not particularly limited, but preferably the number average molecular weight (Mn) calculated from hydroxyl groups has a lower limit of usually 600, preferably 800, more preferably 1000, and an upper limit of usually 5000, preferably 4000, more preferably 3000. When the number average molecular weight (Mn) of PEPCD is 600 or more, the obtained polyurethane has sufficient flexibility, and when it is 5000 or less, the viscosity does not become too high and the handling is excellent.

Here, the hydroxyl value and number average molecular weight (Mn) of PEPCD are measured by the methods described in Examples below.

<Ratio of terminal alkoxy/aryloxy>
In the PEPCD of the present invention, the ratio of the total number of alkoxy terminal groups and the number of aryloxy terminal groups to the total number of terminal groups (hereinafter sometimes referred to as "terminal alkoxy/aryloxy ratio") is preferably 0.20% or more and 7.5% or less.

PEPCD refers to "a compound having repeating units of polyether polycarbonate", and the PEPCD of the present invention is usually composed of a mixture of a plurality of compounds having repeating units of polyether polycarbonate and having different terminal groups.

PEPCD is usually produced by reacting a carbonate compound such as an alkylene carbonate, a dialkyl carbonate, or a diaryl carbonate with a polyether polyol compound, and optionally with a diol compound different from the polyether polyol compound used. In this reaction, along with PEPCD having hydroxyl groups at both ends, which is the target product, alkoxy terminal groups are produced as by-products due to the reaction between the dialkyl carbonate and the polyether polyol compound, and aryloxy terminal groups are generated due to the reaction between the diaryl carbonate and the polyether polyol compound (hereinafter, these alkoxy terminal groups and aryloxy terminal groups may be collectively referred to as "alkoxy/aryloxy terminal groups").
In addition, these alkoxy/aryloxy ends may be brought into the reaction system as impurities in the polyether polyol compound such as PTMG used as a starting material for PEPCD production, and mixed into the resulting PEPCD.
In addition, the alkoxy/aryloxy terminus is mixed with PEPCD by heating during the purification process of PEPCD.
By controlling the amount of alkoxy/aryloxy terminals produced as reaction by-products and the amount of alkoxy/aryloxy terminals mixed into the reaction system as a result of being mixed into the raw material compound and mixed into the product so that the ratio of the terminal alkoxy/aryloxy groups is 0.2% or more and 7.5% or less, the urethane polymerization reaction can be easily controlled and a rapid polymerization reaction can be suppressed to produce a polyurethane having a desired molecular weight suitable for various uses as a polyurethane.

When the terminal alkoxy/aryloxy ratio is 7.5% or less, the urethane polymerization reaction can proceed sufficiently. On the other hand, when the terminal alkoxy/aryloxy ratio is 0.20% or more, the urethane polymerization reaction rate does not become too fast, and the reaction control is easy.
In the PEPCD of the present invention, the terminal alkoxy/aryloxy ratio is more preferably 0.20% to 7.0%, still more preferably 0.30% to 6.5%, particularly preferably 0.30% to 6.0%, and most preferably 0.40% to 5.5%.

The terminal alkoxy/aryloxy ratio of PEPCD and the later-described butoxy terminal ratio are measured by the method described in Examples below.

<Alkoxy/Aryloxy Termination>
The alkoxy/aryloxy terminals contained in the PEPCD of the present invention are mainly derived from the polyether polyol compound and carbonate compound, which are raw materials for the production of PEPCD, as described above.

The alkoxy terminal group includes methoxy terminal, ethoxy terminal, propioxy terminal, butoxy terminal, etc. From the viewpoint of PEPCD quality, methoxy terminal or butoxy terminal is preferable, and butoxy terminal is more preferable.

Specific examples of aryloxy end groups include substituted or unsubstituted phenoxy end groups.

The PEPCD of the present invention may contain only one type of these alkoxy/aryloxy termini, or may contain two or more types. When two or more alkoxy/aryloxy termini are included, the total content of these should be within the above range.

The PEPCD of the present invention preferably contains a butoxy terminal as an alkoxy/aryloxy terminal, particularly from the viewpoint of controlling the urethane polymerization reaction. When the PEPCD of the present invention contains a butoxy terminal as an alkoxy/aryloxy terminal, the content is preferably 0.01% or more and 2.0% or less based on the total terminals of the PEPCD. If the butoxy terminal content is too high, the progress of urethane polymerization may be inhibited. If the content of the butoxy terminal is too low, the urethane polymerization reaction rate becomes too fast, which may make it difficult to control the polymerization. A more preferable content of butoxy ends is 0.02 to 1.5%, and particularly preferably 0.05 to 1.0%.

<Method for controlling terminal alkoxy/aryloxy ratio>
Although the method for controlling the terminal alkoxy/aryloxy ratio of the PEPCD of the present invention is not particularly limited,
(1) A method of mixing PEPCD containing an alkoxy/aryloxy end with a PEPCD not containing an alkoxy/aryloxy end (2) A method of adjusting the concentration of alkoxy/aryloxy ends in PEPCD containing an alkoxy/aryloxy end by distillation, extraction, or the like. Examples include a method of controlling the amount of alkoxy/aryloxy terminals as a product by adjusting the pH of the solution.

[Method for producing PEPCD]
The PEPCD of the present invention is produced by reacting a carbonate compound containing ethylene carbonate as an essential component and a polyether polyol compound containing polyalkylene ether glycol as an essential component, according to a normal PEPCD manufacturing method, except that the content ratio of the structural unit (1) and the structural unit (2), preferably the terminal alkoxy/aryloxy ratio, is controlled. During the reaction, if necessary, a diol compound different from the polyether polyol compound may be copolymerized.

(Carbonate compound)
Alkylene carbonate, dialkyl carbonate, and diaryl carbonate can be used as the carbonate compound, but in the present invention, at least ethylene carbonate is used as the carbonate compound for quality during PEPCD production. That is, by using ethylene carbonate, it is possible to obtain high-quality PEPCD with little coloration.

Alkylene carbonates other than ethylene carbonate include propylene carbonate and butylene carbonate.
Dialkyl carbonates include symmetric dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and dibutyl carbonate, and asymmetric dialkyl carbonates such as methyl ethyl carbonate.
Diaryl carbonates include symmetric diaryl carbonates such as diphenyl carbonate and dinaphthyl carbonate, as well as asymmetric diaryl carbonates such as phenylnaphthyl carbonate.
Chlorocarbonates such as methyl chlorocarbonate and phenyl chlorocarbonate, phosgene and its equivalents, and carbon dioxide gas can also be used as the carbonate source.

Among carbonate compounds other than ethylene carbonate, alkylene carbonate or dialkyl carbonate is preferred, and dimethyl carbonate is more preferred.
The above carbonate compounds may be used alone or in combination of two or more. It is preferable to control the amount of ethylene carbonate used so that PEPCD that satisfies the content ratio of the structural unit (1) is obtained.

(polyalkylene ether glycol)
As the polyalkylene ether glycol used for producing the PEPCD of the present invention, a polyalkylene ether glycol represented by the following formula (3) can be used.

(In the above formula (3), n, R ¹ and R ² have the same meanings as in the above formula (2), and preferred ones are also the same.)

Specific examples of polyalkylene ether glycol include polytetramethylene ether glycol (PTMG), tetrahydrofuran-3-methyltetrahydrofuran copolymer, and the like.
These may be used individually by 1 type, and may be used in mixture of 2 or more types.
Among these, PTMG is preferably used from the viewpoint of chemical resistance of urethane using PEPCD.

The hydroxyl value of the raw material polyalkylene ether glycol such as PTMG is preferably 50.0 mg-KOH/g or more and 550 mg-KOH/g or less, particularly 100 mg-KOH/g or more and 540 mg-KOH/g or less, particularly 200 mg-KOH/g or more and 530 mg-KOH/g or less, from the viewpoint of tensile properties and durability of the obtained polyurethane. A polyalkylene ether glycol having a hydroxyl value of 550 mg-KOH/g or less can suppress the crystallinity of the resulting PEPCD and increase in melting point. Further, when the hydroxyl value of the polyalkylene ether glycol is 50.0 mg-KOH/g or more, the resulting PEPCD does not have too high a viscosity and is excellent in handleability.
The polyalkylene ether glycol preferably has a number average molecular weight (Mn) of 100 or more and 3000 or less, especially 150 or more and 2000 or less, particularly 200 or more and 850 or less, as determined from hydroxyl groups, from the viewpoint of tensile properties and durability of the obtained polyurethane. If the polyalkylene ether glycol has a number average molecular weight of 100 or more, it is possible to suppress the increase in crystallinity and melting point of the resulting PEPCD. Moreover, if the number average molecular weight of the polyalkylene ether glycol is 3000 or less, the obtained PEPCD does not have too high a viscosity and is excellent in handleability.

Here, the hydroxyl value and number average molecular weight (Mn) of the polyalkylene ether glycol are measured by the methods described in Examples below.

(Other polyether polyol compounds)
Polyether polyol compounds other than polyalkylene ether glycols may be used in the production of the PEPCD of the present invention. Polyether polyol compounds can be produced by ring-opening polymerization of cyclic ethers.

The number of carbon atoms constituting the cyclic ether is usually 2-10, preferably 3-7.
Specific examples of cyclic ethers include tetrahydrofuran (THF), ethylene oxide, propylene oxide, oxetane, tetrahydropyran, oxepane, and 1,4-dioxane. A cyclic ether in which a part of the cyclic hydrocarbon chain is substituted with an alkyl group, a halogen atom, or the like can also be used. Specific examples include 3-methyl-tetrahydrofuran and 2-methyltetrahydrofuran. One type of these cyclic ethers may be used alone, or two or more types may be mixed and used, but it is preferable to use one type.

Examples of polyether polyol compounds other than polyalkylene ether glycol include low molecular weight polyether polyols such as diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol, polyethylene glycol having a number average molecular weight of 100 to 3000 determined from hydroxyl groups, polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of THF and 3-methyl-tetrahydrofuran, and dipropylene glycol polyethylene glycol.
These may be used individually by 1 type, and may be used in mixture of 2 or more types.

(Diol compound)
When producing PEPCD, if necessary, a diol compound other than the polyether polyol compound may be copolymerized. Examples of the diol compound include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol, 2-methyl-14-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Examples include chain alkyldiols such as decanediol and 1,12-dodecanediol, and cyclic alkyldiols such as cyclohexanedimethanol and isosorbide.
These other diol compounds may be used singly or in combination of two or more.

(Ratio of raw materials used)
In the production of PEPCD, the amount of the carbonate compound used is not particularly limited, but usually the molar ratio to 1 mol of the polyether polyol compound such as polyalkylene ether glycol, the lower limit is preferably 0.35, more preferably 0.50, more preferably 0.60, and the upper limit is preferably 1.00, more preferably 0.98, more preferably 0.97. When the amount of the carbonate compound used is not more than the above upper limit, the proportion of PEPCD obtained that does not have a hydroxyl terminal group can be suppressed, and the number average molecular weight can be easily controlled within a predetermined range. When the amount of the carbonate compound used is at least the above lower limit, the polymerization is easily allowed to progress to a predetermined number average molecular weight.

When the other diol compound described above is used, the amount of the other diol compound to be used is preferably 0.05, more preferably 0.10, and still more preferably 0.20, and the upper limit is preferably 2.0, more preferably 1.0, and further preferably 0.60, as a molar ratio to 1 mol of the polyether polyol compound such as polyalkylene ether glycol. In this case, the amount of the carbonate compound used is preferably within the above range in terms of a molar ratio to 1 mol of the total of the polyether polyol compound such as polyalkylene ether glycol and the other diol compound.

(catalyst)
When producing PEPCD, it is preferable to use a catalyst that is used in the transesterification reaction. This catalyst includes metal, metal, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal oxide, metal, etc., metal such as lithium, sodium, sodium, sodium, sodium, potassium, cesium, calcium, culcium, carium, barium, zinc, aluminum, titanium, germanium, tin, lead, antimonium, metal oxide, etc. Patiently, alkaline metal, alkaline earth, zinc, titanium, lead, carbonate, carbonate, borate, carbonic acid, carbonate, oxide, and organic metal compounds, especially organic titanium compounds and organic magnesium compounds.

The amount of the transesterification catalyst used is preferably 10 μmol or more and 1500 μmol or less, and the lower limit is more preferably 20 μmol, further preferably 30 μmol, and particularly preferably 50 μmol, relative to 1 mol of the total of the polyether polyol compound such as polyalkylene ether glycol as a starting material and other diol compounds that are optionally used. The upper limit is more preferably 1000 μmol, still more preferably 500 μmol, particularly preferably 300 μmol, most preferably 200 μmol. When the amount of catalyst is at least the above lower limit, the reaction time can be shortened, the production efficiency can be improved, and the coloring of the resulting PEPCD can be suppressed. Further, when the amount of the catalyst is equal to or less than the above upper limit, coloration of PEPCD and coloration during polyurethane production are suppressed, and the urethane polymerization reaction rate does not become too fast, tending to facilitate reaction control.

(Reaction conditions)
The reaction temperature during the production of PEPCD is usually 70 to 250°C, preferably 80 to 220°C. At the initial stage of the reaction, the temperature is preferably near the boiling point of the raw material carbonate compound, specifically 100 to 150° C., and as the reaction progresses, the temperature is gradually raised to allow the reaction to proceed further. Reaction by-products such as alcohol and phenol are separated by distillation. At this time, if the raw material carbonate compound is also distilled together with the distilled alcohol, etc., and there is a large amount of loss, it is preferable to use a reactor equipped with a plate column or a packed column to suppress the amount of loss. In order to reduce loss, the distilled raw material carbonate compound may be recovered and recycled to the reaction system for use. When there is a loss of the raw material carbonate compound, the theoretical molar ratio of the raw material carbonate compound and the polyether polyol compound such as polyalkylene ether glycol or other diol compound for PEPCD production is n moles of the carbonate compound, but the polyether polyol compound such as polyalkylene ether glycol or other diol compound (n + 1) moles, but considering the loss, it is preferably 1.1 to 1.3 times the theoretical molar ratio. A polyether polyol compound such as polyalkylene ether glycol or other diol compound may be charged at the initial stage of the reaction or may be added during the reaction.

[Additive]
Various additives can be added to the PEPCD of the present invention as necessary.
For example, an antioxidant can be added to the PEPCD of the present invention to inhibit deterioration due to oxidation. In this case, the antioxidant concentration in the PEPCD after addition of the antioxidant is usually 10 weight ppm or more, preferably 50 weight ppm or more, more preferably 100 weight ppm or more, usually 1000 weight ppm or less, preferably 500 weight ppm or less, more preferably 300 weight ppm or less.
If the antioxidant concentration is equal to or less than the above upper limit, the problem of clogging due to solid deposition can be suppressed in the process. On the other hand, if the concentration of the antioxidant is equal to or higher than the above lower limit, the effect of preventing the oxidation reaction will be sufficient.
As the antioxidant, 2,6-di-tert-butyl-p-cresol (BHT) is preferable from the viewpoint of effect and stability.

[Use of PEPCD]
The PEPCD of the present invention is useful as a polyurethane raw material suitable for applications such as elastic fibers, thermoplastic polyurethanes, and coating materials because of its excellent urethane polymerization reaction controllability.
In such applications, a polyurethane solution or aqueous polyurethane emulsion can be produced from the PEPCD of the present invention.
Uses of the PEPCD of the present invention are further described below.
The PEPCD of the present invention can be used as a raw material for UV-curable paints, electron beam-curable paints, plastic coatings, molding agents for lenses, sealants, adhesives, etc. by modifying the ends.
The PEPCD of the present invention can be used to disperse nanomaterials such as nanofiber cellulose, carbon nanofibers, and metal nanoparticles.

<Water-based polyurethane emulsion>
When the PEPCD of the present invention is used to produce an aqueous polyurethane emulsion, a compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is mixed to form a prepolymer when the polyol containing the PEPCD of the present invention is reacted with excess polyisocyanate to form a prepolymer, and the hydrophilic functional group is subjected to a neutralization and chlorination process, an emulsification process by adding water, and a chain extension reaction process to form an aqueous polyurethane emulsion.

As used herein, the hydrophilic functional group of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is, for example, a carboxyl group or a sulfonic acid group, which is neutralizable with an alkaline group. In addition, the isocyanate-reactive group is a group that generally reacts with isocyanate to form a urethane bond or a urea bond, such as a hydroxyl group, a primary amino group, or a secondary amino group, and these may be mixed in the same molecule.

Specific examples of compounds having at least one hydrophilic functional group and at least two isocyanate-reactive groups include 2,2'-dimethylolpropionic acid, 2,2-methylolbutyric acid, 2,2'-dimethylolvaleric acid, and the like. Also included are diaminocarboxylic acids such as lysine, cystine, 3,5-diaminocarboxylic acid and the like. These may be used individually by 1 type, and may use 2 or more types together. When these are actually used, they can be neutralized with amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine and triethanolamine, and alkaline compounds such as sodium hydroxide, potassium hydroxide and ammonia.

When producing a water-based polyurethane emulsion, the lower limit of the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups used is preferably 1% by weight, more preferably 5% by weight, and even more preferably 10% by weight, based on the total weight of the PEPCD of the present invention and other polyols, in order to improve the dispersibility in water. On the other hand, in order to maintain the properties of the polycarbonate diol, the upper limit is preferably 50% by weight, more preferably 40% by weight, and even more preferably 30% by weight.

When producing an aqueous polyurethane emulsion, the reaction may be carried out in the presence of a solvent such as methyl ethyl ketone, acetone, or N-methyl-2-pyrrolidone in the prepolymer step, or may be carried out without a solvent. Moreover, when using a solvent, it is preferable to distill off the solvent by distillation after manufacturing an aqueous emulsion.

When the PEPCD of the present invention is used as a raw material to produce a solvent-free aqueous polyurethane emulsion, the upper limit of the number average molecular weight obtained from the hydroxyl value of the PEPCD used is preferably 5,000, more preferably 4,500, and still more preferably 4,000. The lower limit of the number average molecular weight of PEPCD is preferably 300, more preferably 500, and even more preferably 800. If the number average molecular weight determined from the hydroxyl value is within the above range, there is a tendency that emulsification is facilitated.

In the synthesis or storage of aqueous polyurethane emulsions, anionic surfactants typified by higher fatty acids, resin acids, acidic fatty alcohols, sulfate esters, higher alkyl sulfonates, alkylaryl sulfonates, sulfonated castor oil, and sulfosuccinic acid esters; cationic surfactants such as primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, and pyridinium salts; or nonionic surfactants typified by known reaction products of ethylene oxide and long-chain fatty alcohols or phenols. and the like may be used together to maintain emulsion stability.

Further, when making an aqueous polyurethane emulsion, an emulsion can be produced by mechanically mixing water with a prepolymer solution in an organic solvent in the presence of an emulsifier at high shear, if necessary without the neutralization and chlorination step.

The water-based polyurethane emulsion thus produced can be used for various purposes. In particular, there is a recent demand for chemical raw materials with low environmental impact, and it is possible to replace conventional products for the purpose of not using organic solvents.

Specific uses of water-based polyurethane emulsions include, for example, coating agents, water-based paints, adhesives, synthetic leathers, and artificial leathers. In particular, the water-based polyurethane emulsion produced using the PEPCD of the present invention contains alkoxy/aryloxy terminals so that the PEPCD has a predetermined alkoxy/aryloxy terminal ratio. Therefore, it is flexible and can be used more effectively as a coating agent than conventional water-based polyurethane emulsions using polycarbonate diols or PTMG. In particular, compared to conventional water-based polyurethane emulsions using PTMG, it has a hydrophilic group, so it has a good affinity for water, and the PEPCD of the present invention having a higher molecular weight can be used. In addition, the excellent dispersibility in water increases the degree of freedom in molecular design of the water-based polyurethane emulsion, and it is possible to achieve matte properties by adjusting the composition.

The storage stability of polyurethane solutions and water-based polyurethane emulsions produced using the PEPCD of the present invention using an organic solvent and/or water can be measured by adjusting the concentration of polyurethane in the solution or emulsion (hereinafter sometimes referred to as "solid content concentration") to 1 to 80% by weight, storing the solution or emulsion under specific temperature conditions, and then visually measuring the presence or absence of changes in the solution or emulsion. For example, in the case of a polyurethane solution (N,N-dimethylformamide/toluene mixed solution, solid content concentration of 30% by weight) produced by the two-step method of the present invention using PEPCD, 4,4'-dicyclohexylmethane diisocyanate and isophoronediamine, the period during which no change is visually observed in the polyurethane solution when stored at 10°C is preferably 1 month, more preferably 3 months or more, and even more preferably 6 months or more.

[Method for producing polyurethane]
The method for producing the polyurethane of the present invention is a method for producing a polyurethane using the PEPCD of the present invention, and generally, a raw material containing the PEPCD of the present invention and a compound having a plurality of isocyanate groups (hereinafter sometimes referred to as a "polyisocyanate compound" or "polyisocyanate") is subjected to an addition polymerization reaction to produce a polyurethane (hereinafter sometimes referred to as the "polyurethane of the present invention").
The method for producing the polyurethane of the present invention is characterized by using the PEPCD of the present invention, and generally, the polyurethane of the present invention can be produced by an ordinary polyurethane formation reaction except that the PEPCD of the present invention, a polyisocyanate compound and a chain extender are used.

For example, the polyurethane of the present invention can be produced by reacting the PEPCD of the present invention with a polyisocyanate compound and a chain extender at a temperature ranging from room temperature to 200°C.
Further, the PEPCD of the present invention and an excess polyisocyanate compound are first reacted to produce a prepolymer having terminal isocyanate groups, and then a chain extender is used to increase the degree of polymerization to produce the polyurethane of the present invention.

<Polyisocyanate compound>
The polyisocyanate compound used as a raw material for producing the polyurethane of the present invention may have two or more isocyanate groups, and includes various known aliphatic, alicyclic or aromatic polyisocyanate compounds.

For example, aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer diisocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group; ,4'-Dicyclohexylmethane diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane. Aromatic diisocyanate compounds such as dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethylxylylene diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

Among these, aromatic polyisocyanate compounds are preferred because of their reactivity with PEPCD and the high curability of the resulting polyurethane, and 4,4'-diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI"), toluene diisocyanate (TDI), and xylylene diisocyanate are particularly preferred because they are industrially available in large quantities at low cost.

<Chain extender>
The chain extender used as a raw material for producing the polyurethane of the present invention is a low-molecular-weight compound having at least two active hydrogens that react with isocyanate groups, and is selected from polyols and polyamines.

Specific examples thereof include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; Branched diols such as diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol and dimer diol diols having an ether group such as diethylene glycol and propylene glycol; diols having an alicyclic structure such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 1,4-dihydroxyethylcyclohexane; diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene and 4,4'-methylenebis(hydroxyethylbenzene); hydroxyamines such as ethanolamine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), polyamines such as xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, N,N'-diaminopiperazine;

One of these chain extenders may be used alone, or two or more thereof may be used in combination.

Among these, ethylene glycol, 1,4-butanediol, and 1,6-hexanediol are preferred in terms of excellent flexibility and elastic recovery due to excellent phase separation of the soft segment and hard segment of the polyurethane obtained, and industrial availability in large quantities at low cost.

<Chain terminating agent>
When producing the polyurethane of the present invention, a chain terminating agent having one active hydrogen group can be used as necessary for the purpose of controlling the molecular weight of the resulting polyurethane.
Examples of these chain terminators include aliphatic monools having one hydroxyl group such as methanol, ethanol, propanol, butanol and hexanol, and aliphatic monoamines having one amino group such as diethylamine, dibutylamine, n-butylamine, monoethanolamine, diethanolamine and morpholine.
These may be used individually by 1 type, and may use 2 or more types together.

<Catalyst>
Known urethane polymerization catalysts typified by amine-based catalysts such as triethylamine, N-ethylmorpholine, and triethylenediamine, acid-based catalysts such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid, tin-based compounds such as trimethyltin laurate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin dineodecanate, and organic metal salts such as titanium-based compounds, can also be used in the polyurethane-forming reaction during the production of the polyurethane of the present invention. A urethane polymerization catalyst may be used individually by 1 type, and may use 2 or more types together.

<Polyol other than PEPCD of the present invention>
In the polyurethane-forming reaction when producing the polyurethane of the present invention, a polyol other than the PEPCD of the present invention may be used in combination, if necessary. Here, the polyol other than PEPCD of the present invention is not particularly limited as long as it is used in ordinary polyurethane production, and examples thereof include polyester polyol, polycaprolactone polyol, polycarbonate polyol, and polyether polyol. Among these, polyether polyols are preferable, and polytetramethylene ether glycol is particularly preferable because it can obtain urethane physical properties close to those of PEPCD. Here, the weight ratio of the PEPCD of the present invention to the combined weight of the PEPCD of the present invention and other polyols is preferably 30% or more, more preferably 50% or more, and even more preferably 90% or more. When the weight ratio of the PEPCD of the present invention is at least the above lower limit, the controllability of the urethane polymerization reaction and the flexibility of the resulting polyurethane are improved.

<Method for producing polyurethane>
As a method for producing the polyurethane of the present invention using the above-mentioned reaction reagents, production methods generally used experimentally or industrially can be used.
Examples thereof include a method in which the PEPCD of the present invention, other polyols, polyisocyanate compounds and chain extenders that are used as necessary are mixed together and reacted together (hereinafter sometimes referred to as "one-step method"), and a method in which the PEPCD of the present invention, other polyols and polyisocyanate compounds that are used as necessary are first reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer and the chain extender are reacted (hereinafter referred to as "two-step method"). ), etc.

The two-step method involves the step of preparing an isocyanate intermediate at both ends corresponding to the soft segment of the polyurethane by previously reacting the PEPCD of the present invention and other polyols with 1 equivalent or more of a polyisocyanate compound. In this way, if the prepolymer is once prepared and then reacted with a chain extender, it may be easier to adjust the molecular weight of the soft segment portion, and it is useful when it is necessary to ensure phase separation between the soft segment and the hard segment.

(single stage method)
The one-step method, which is also called a one-shot method, is a method in which the PEPCD of the present invention, other polyols, a polyisocyanate compound and a chain extender are charged all at once to carry out the reaction.
The amount of the polyisocyanate compound used in the one-step method is not particularly limited, but when the total number of hydroxyl groups of the PEPCD of the present invention and other polyols and the total number of hydroxyl groups and amino groups of the chain extender is 1 equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents. Equivalents, more preferably 1.5 equivalents, particularly preferably 1.1 equivalents.

If the amount of the polyisocyanate compound used is less than or equal to the above upper limit, there is no risk that unreacted isocyanate groups will cause a side reaction and the resulting polyurethane will become too viscous to be difficult to handle or its flexibility will be impaired.

The amount of the chain extender used is not particularly limited, but when the number obtained by subtracting the total number of hydroxyl groups of the PEPCD of the present invention and other polyols from the number of isocyanate groups of the polyisocyanate compound is taken as 1 equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, and even more preferably 1.5 equivalents. amount, particularly preferably 1.1 equivalents. If the amount of the chain extender is less than or equal to the above upper limit, the resulting polyurethane tends to dissolve easily in a solvent and is easy to process.

(two-step method)
The two-step method, also called a prepolymer method, mainly includes the following methods.
(a) A method in which the PEPCD of the present invention, other polyols, and an excess polyisocyanate compound are reacted in advance at a reaction equivalent ratio of polyisocyanate compound/(PEPCD of the present invention and other polyols) exceeding 1 to 10.0 or less to produce a prepolymer having an isocyanate group at the molecular chain end, and then adding a chain extender to the prepolymer to produce a polyurethane.
(b) A method in which a polyisocyanate compound is reacted in advance with an excess of the PEPCD of the present invention and other polyols at a reaction equivalent ratio of polyisocyanate compound/(PEPCD of the present invention and other polyols) of 0.1 or more to less than 1.0 to produce a prepolymer having hydroxyl group ends, and then reacting this with a polyisocyanate compound having an isocyanate group end as a chain extender to produce a polyurethane.

The two-step method can be carried out without solvent or in the presence of solvent.
Polyurethane production by the two-step method can be carried out by any one of the methods (1) to (3) described below.
(1) Without using a solvent, the polyisocyanate compound, the PEPCD of the present invention, and other polyols are directly reacted to synthesize a prepolymer, which is directly used for the chain extension reaction.
(2) A prepolymer is synthesized by the method of (1), then dissolved in a solvent and used for subsequent chain extension reaction.
(3) Using a solvent from the beginning, the polyisocyanate compound, the PEPCD of the present invention, and other polyols are reacted, and then the chain extension reaction is performed.

In the case of method (1), in the chain extension reaction, it is important to obtain the polyurethane in a form coexisting with the solvent by a method such as dissolving the chain extender in the solvent or dissolving the prepolymer and the chain extender in the solvent at the same time.
The amount of the polyisocyanate compound used in the two-step method (a) is not particularly limited, but the lower limit is preferably more than 1.0 equivalents, more preferably 1.2 equivalents, still more preferably 1.5 equivalents, and the upper limit is preferably 10.0 equivalents, more preferably 5.0 equivalents, and still more preferably 3.0 equivalents, as the number of isocyanate groups when the total number of hydroxyl groups of the PEPCD of the present invention and other polyols is 1 equivalent. There is.

If the amount of the polyisocyanate compound used is less than or equal to the above upper limit, side reactions due to excess isocyanate groups tend to be suppressed and the desired physical properties of the polyurethane tend to be easily achieved.
The amount of the chain extender used is not particularly limited, but the lower limit is preferably 0.1 equivalents, more preferably 0.5 equivalents, and still more preferably 0.8 equivalents, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, and still more preferably 2.0 equivalents, relative to the number of equivalents of isocyanate groups contained in the prepolymer.

For the purpose of adjusting the molecular weight, monofunctional organic amines and alcohols may coexist during the chain extension reaction.
In the two-step method (b), the amount of the polyisocyanate compound to be used when preparing a prepolymer having a hydroxyl group at its end is not particularly limited, but the lower limit is preferably 0.1 equivalent, more preferably 0.5 equivalent, still more preferably 0.7 equivalent, and the upper limit is preferably 0.99 equivalent, more preferably 0.98, as the number of isocyanate groups when the total number of hydroxyl groups of the PEPCD of the present invention and other polyols is taken as 1 equivalent. Equivalents, more preferably 0.97 equivalents.

If the amount of the polyisocyanate compound used is at least the above lower limit, the process for obtaining the desired molecular weight in the subsequent chain extension reaction tends to be too long, and production efficiency tends to be good.
The amount of the chain extender used is not particularly limited, but when the total number of hydroxyl groups of the PEPCD of the present invention used in the prepolymer and the other polyol is 1 equivalent, the total equivalent including the equivalent of the isocyanate group used in the prepolymer is preferably 0.7 equivalent, more preferably 0.8 equivalent, still more preferably 0.9 equivalent, and the upper limit is preferably less than 1.0 equivalent, more preferably 0.99 equivalent, and further preferably 0.9 equivalent. It is in the range of 8 equivalents.

For the purpose of adjusting the molecular weight, monofunctional organic amines and alcohols may coexist during the chain extension reaction.
The chain extension reaction is usually carried out at 0° C. to 250° C., but this temperature varies depending on the amount of solvent, reactivity of raw materials used, reaction equipment, etc., and is not particularly limited. If the temperature is equal to or higher than the above lower limit, the reaction progresses quickly, and the raw materials and polymer are highly soluble, so that the production time is shortened. If the temperature is equal to or lower than the above upper limit, side reactions and decomposition of the resulting polyurethane can be suppressed. The chain extension reaction may be performed under reduced pressure while defoaming.

Moreover, a catalyst, a stabilizer, etc. can also be added to a chain extension reaction as needed.
Examples of the catalyst include compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid. Examples of stabilizers include compounds such as 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N,N'-di-2-naphthyl-1,4-phenylenediamine, and tris(dinonylphenyl)phosphite. If the chain extender is highly reactive such as a short-chain aliphatic amine, the reaction may be carried out without adding a catalyst.
A reaction inhibitor such as tris(2-ethylhexyl) phosphite can also be used.

<Additive>
Various additives such as heat stabilizers, light stabilizers, colorants, fillers, stabilizers, ultraviolet absorbers, antioxidants, anti-adhesives, flame retardants, anti-aging agents, and inorganic fillers can be added or mixed with the polyurethane of the present invention as long as the properties of the polyurethane of the present invention are not impaired.

Compounds that can be used as heat stabilizers include phosphoric acid, aliphatic, aromatic or alkyl-substituted aromatic esters of phosphorous acid, hypophosphorous acid derivatives, phosphorus compounds such as phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diphosphites, and dialkylbisphenol A diphosphites; Compounds containing sulfur such as thiodipropionate; and tin compounds such as tin malate and dibutyltin monoxide can be used.

Specific examples of the hindered phenol compound include "Irganox 1010" (trade name: manufactured by BASF Japan Ltd.), "Irganox 1520" (trade name: manufactured by BASF Japan Ltd.), and "Irganox 245" (trade name: manufactured by BASF Japan Ltd.).
Phosphorus compounds include "PEP-36", "PEP-24G", "HP-10" (all trade names: manufactured by ADEKA Corporation), and "Irgafos 168" (trade name: manufactured by BASF Japan Ltd.).

Specific examples of sulfur-containing compounds include thioether compounds such as dilaurylthiopropionate (DLTP) and distearylthiopropionate (DSTP).
Examples of light stabilizers include benzotriazole-based and benzophenone-based compounds. Specifically, "TINUVIN622LD", "TINUVIN765" (manufactured by Ciba Specialty Chemicals Co., Ltd.), "SANOL LS-2626", "SANOL LS-765" (manufactured by Sankyo Co., Ltd.) and the like can be used.

Examples of ultraviolet absorbers include "TINUVIN328" and "TINUVIN234" (manufactured by Ciba Specialty Chemicals Co., Ltd.).

Examples of the coloring agent include dyes such as direct dyes, acid dyes, basic dyes, and metal complex dyes; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide, and mica; and organic pigments such as coupling azo, condensed azo, anthraquinone, thioindigo, dioxazone, and phthalocyanine pigments.

Examples of inorganic fillers include short glass fibers, carbon fibers, alumina, talc, graphite, melamine, and clay.

Examples of flame retardants include additive and reactive flame retardants such as phosphorous and halogen containing organic compounds, bromine or chlorine containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide and the like.

These additives may be used alone, or two or more of them may be used in any combination and ratio.

Regarding the amount of these additives added, the lower limit is preferably 0.01% by weight, more preferably 0.05% by weight, and still more preferably 0.1% by weight, and the upper limit is preferably 10% by weight, more preferably 5% by weight, and even more preferably 1% by weight, as a weight ratio to polyurethane. If the amount of the additive added is at least the above lower limit, the effect of the addition can be sufficiently obtained, and if the amount is below the above upper limit, there is no risk of precipitation or turbidity in the polyurethane.

<Molecular Weight of Polyurethane>
The molecular weight of the polyurethane of the present invention is appropriately adjusted according to its use and is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 50,000 to 400,000, more preferably 100,000 to 300,000, and even more preferably 150,000 to 200,000. When Mw is at least the above lower limit, sufficient strength and hardness can be obtained, and when it is at most the above upper limit, there is a tendency for excellent handleability such as workability.

<Usage of Polyurethane>
Since the polyurethane of the present invention has excellent chemical resistance, solvent resistance, good flexibility, and mechanical strength, it can be widely used for foams, elastomers, elastic fibers, paints, fibers, adhesives, adhesives, flooring materials, sealants, medical materials, artificial leathers, synthetic leathers, coating agents, water-based polyurethane paints, active energy ray-curable polymer compositions, and the like.

In particular, when the use of polyuretan of the invention is used for applications such as artificial leather, synthetic leather, waterproof cloth, water -based polyurethane, adhesive, elastic fiber, medical material, flooring, paint, coating, etc. Therefore, it is possible to give a good characteristics that is highly durable, flexible, and resistant to physical impacts, such as touching human skin, using cosmetic drugs and alcohol for disinfecting. Moreover, it can be suitably used for automobile applications where heat resistance is required and outdoor applications where weather resistance is required.

The polyurethanes of the invention can be used in polyurethane elastomers, such as cast polyurethane elastomers. Specific uses include rolling rolls, paper manufacturing rolls, office equipment, rolls such as pretension rolls, solid tires and casters for forklifts, automobile vehicle nutrams, bogies, trucks, etc. Industrial products include conveyor belt idlers, guide rolls, pulleys, steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, and the like. It can also be used for OA equipment belts, paper feed rolls, copying cleaning blades, snow plows, toothed belts, surf rollers and the like.

The polyurethanes of the invention also find application as thermoplastic elastomers. For example, it can be used for tubes and hoses, spiral tubes, fire hoses, etc. in pneumatic equipment used in the food and medical fields, coating equipment, analytical equipment, physical and chemical equipment, metering pumps, water treatment equipment, industrial robots, and the like. In addition, it is used as a belt such as a round belt, a V belt, a flat belt, etc. in various transmission mechanisms, spinning machines, packing machines, printing machines, and the like. It can also be used for heel tops and soles of footwear, couplings, packings, pole joints, bushes, gears, machine parts such as rolls, sporting goods, leisure goods, watch belts and the like. Automobile parts include oil stoppers, gearboxes, spacers, chassis parts, interior parts, and tire chain substitutes. Also, it can be used for films such as keyboard films and films for automobiles, curled cords, cable sheaths, bellows, conveyor belts, flexible containers, binders, synthetic leathers, dipping products, adhesives and the like.

The polyurethane elastomer made of the polyurethane of the present invention can also be a foamed polyurethane elastomer or polyurethane foam. Examples of methods for foaming or foaming polyurethane elastomers include chemical foaming using water and mechanical foaming such as mechanical floss, as well as spray foaming, slabs, injection, hard foams obtained by molding, and flexible foams obtained by slabs and molding.
Specific uses of foamed polyurethane elastomers or polyurethane foams include electronic devices, railroad rails, thermal insulation and vibration-proof materials for construction, automobile seats, automobile ceiling cushions, bedding such as mattresses, insoles, midsoles and shoe soles.

The polyurethane of the present invention can also be applied as a solvent-based two-component paint, and can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, and sporting goods. It can also be used for automobile repair as tar epoxy urethane.

The polyurethane of the present invention can be used as a component of moisture-curable one-component paints, blocked isocyanate-based solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, ultraviolet-curable paints, water-based urethane paints, and the like. It can be applied to white coats for

The polyurethane of the present invention can also be applied as an adhesive or adhesive to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, etc. It can also be used as a component of low temperature adhesives and hot melts.
The polyurethane of the present invention can be used as a binder for magnetic recording media, inks, castings, baked bricks, graft materials, microcapsules, granular fertilizers, granular agricultural chemicals, polymer cement mortar, resin mortar, rubber chip binders, recycled foams, glass fiber sizing, and the like.

The polyurethane of the present invention can be used as a component of a fiber processing agent for shrink-proofing, wrinkle-proofing, water-repellent finishing, and the like.

When the polyurethane of the present invention is used as an elastic fiber, the fiberization method is not particularly limited as long as it can be spun. For example, a melt spinning method can be employed in which the material is pelletized, melted, and spun directly through a spinneret. When the elastic fiber is obtained from the polyurethane of the present invention by melt spinning, the spinning temperature is preferably 250°C or lower, more preferably 200°C or higher and 235°C or lower.

The elastic fibers made of the polyurethane of the present invention can be used as they are as bare yarns, or can be coated with other fibers and used as covered yarns. Other fibers include known fibers such as polyamide fiber, wool, cotton, polyester fiber, etc. Among them, polyester fiber is preferably used. In addition, the elastic fibers made of the polyurethane of the present invention may contain a dyeing type disperse dye.

The polyurethane of the present invention can be used as a sealant/caulk for concrete walls, induced joints, around sashes, wall-type PC (Precast Concrete) joints, ALC (Autoclaved Light-weight Concrete) joints, board joints, composite glass sealants, heat insulating sash sealants, automobile sealants, roof waterproof sheets, and the like.

The polyurethane of the present invention can be used as a medical material, such as tubes, catheters, artificial hearts, artificial blood vessels, artificial valves, etc. as blood compatible materials, and catheters, tubes, bags, surgical gloves, artificial kidney potting materials, etc. as disposable materials.

By modifying the terminal, the polyurethane of the present invention can be used as a raw material for UV curable coatings, electron beam curable coatings, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating compositions, and the like.

[Usage of Polyurethane]
Uses of the polyurethane of the present invention are described in detail below for each application.

<Moisture-permeable waterproof film, moisture-permeable waterproof membrane, moisture-permeable waterproof fabric>
The polyurethane using the PEPCD of the present invention has excellent performance as a moisture-permeable waterproof film. Polyester polyols and polyether polyols are mainly used as polyurethane raw materials for moisture-permeable and waterproofing, but polyester polyols have a fatal drawback of poor hydrolysis resistance. On the other hand, urethane using polyether polyol has the disadvantage of being inferior in light resistance and heat resistance. More recently, polyurethanes for moisture-permeable waterproof fabrics have been developed in which durability such as hydrolysis resistance is improved by using polycarbonate diol (PCD) or ester-modified polycarbonate diol. However, moisture-permeable waterproof cloth using polycarbonate diol can exhibit moisture permeability by forming micropores by a wet manufacturing method, but when it is made into a film, it cannot have sufficient moisture-permeable performance. Therefore, polyethylene glycol (PEG) and polycarbonate diol are sometimes blended and used, but there are problems such as poor mixability, insufficient strength, poor adhesion and poor texture.

Since PEPCD consists of ether bonds and carbonate bonds, it has a high oxygen content and can exhibit sufficient moisture permeability even in a non-porous type. In other words, it is a polyol that combines the moisture permeability of PEG and the durability of PCD in one polyol. Therefore, it is possible to achieve a water pressure resistance of 10,000 mm or more, and further 20,000 mm or more. In addition, moisture permeability of 10,000 g/m ² -24 hrs or more, further 15,000 g/m ² -24 hrs or more can be exhibited.

In addition, since PEPCD has carbonate bonds and can exhibit sufficient strength and water pressure resistance, it can be designed as a porous type. In the case of a porous type, the moisture permeability is even better, and even if the thickness is increased, the water pressure resistance can be 10,000 mm or more, and further 20,000 mm or more. In addition, moisture permeability of 10,000 g/m ² -24 hrs or more, further 15,000 g/m ² -24 hrs or more can be exhibited.

Any method can be used to form the moisture-permeable and waterproof coating film. As a manufacturing method of the non-porous type, for example, release paper is coated with a polyurethane solution for a skin layer to which an antiblocking agent or pigment is added to prevent films from sticking together, and dried to form a film. Then, a polyurethane solution for an adhesive layer comprising polyurethane, a cross-linking agent, a solvent, a catalyst, etc. is coated thereon, and the adhesive layer is adhered to the substrate by pressure bonding. The solvent in the adhesive layer is volatilized in a dryer, and the curing reaction is completed by aging. By peeling off the release paper, a non-porous membrane type moisture-permeable waterproof fabric is obtained.

The polyurethane using the PEPCD of the present invention can also be applied to the coating of porous type moisture-permeable waterproof fabrics. As a method for manufacturing the porous type, for example, a substrate that has been pretreated so that the solution does not enter more than necessary is coated with the polyurethane solution for the skin layer and immersed in a coagulation bath. During the immersion, the solvent in the polyurethane solution is extracted, the resin is precipitated and solidified, and a porous polyurethane layer having many voids is formed. After drying, a microporous membrane type moisture-permeable waterproof fabric is obtained. PEPCD has moderate hydrophilicity and flexibility due to the balance of carbonate bonds and ether bonds, and gives a moisture-permeable waterproof fabric that is excellent not only in terms of moisture-permeable and waterproof performance but also in terms of comfort when worn.

The moisture-permeable waterproof fabric produced using the PEPCD of the present invention is suitably used for outdoor rainwear, windbreakers, winter wear, shoes, tents, rucksacks, bags, shoes and the like.

<Cellulose nanofiber treatment agent>
The polyurethane using the PEPCD of the present invention can be used as a cellulose nanofiber treatment agent. Cellulose nanofibers (CNF) are ultrafine fibrous substances with a diameter of 3 to 50 nm and an aspect ratio (fiber length/fiber width) of 100 or more, and are obtained by defibrating plant fibers derived from wood, bamboo, etc. by various methods. The features of CNF are light (specific gravity 1.3 to 1.5 g/cm ³ , about 1/5 that of steel), strong (strength 3 GPa, about 5 times that of steel), large specific surface area (250 m ² /g or more), high adsorption properties, hard (tensile modulus of elasticity about 140 GPa, equivalent to aramid fiber), small thermal expansion and contraction (linear expansion coefficient 0.1 to 0.2 ppm/K, about 1/50 that of glass), heat equivalent to glass. It is an extremely promising material as a reinforcing filler for various plastics because of its excellent biocompatibility. However, it is difficult to knead strong hydrophilic CNF into hydrophobic plastics, which has been a big problem for its widespread use.
By controlling the ether bond concentration in the polyol, the polyurethane using the PEPCD of the present invention becomes a polymer having moderate hydrophilicity, and can be adsorbed on the surface of CNF as a polyurethane emulsion. As a result, the polarity of the CNF surface can be converted to hydrophobic, making it possible to knead into hydrophobic general-purpose resins such as polypropylene, polyethylene, PET, PBT, polycarbonate, polyamide, and the like. CNF finely and uniformly dispersed in the resin forms a strong network, exerts an efficient reinforcing effect, increases the strength and elastic modulus, and can significantly reduce the coefficient of linear expansion.

<Automotive interior paint>
Polyurethanes using the PEPCD of the present invention can be used in automotive interior paints. Large plastic parts used for automobile interiors are usually painted for the purpose of concealing and protecting their molding defects and at the same time imparting design properties. The environment in which they are used is where they are touched by human hands and exposed to strong direct sunlight, so high light resistance, heat resistance, chemical resistance, and scratch resistance are required, as well as good tactile sensation and advanced design. In addition, in order to improve productivity and save energy, low-temperature drying and curing properties in a short period of time are required.
Polyurethane using PEPCD of the present invention has high durability and excellent touch feeling by controlling the concentration and molecular weight of carbonate bonds and ether bonds, and the number of functional groups. In addition, since the compression set is small, it becomes a self-healing coating film in which scratched by fingernails or the like is naturally repaired. Therefore, it can be used as a main agent for paints for automobile interior parts such as instrument panels and center consoles.

<Paint for Home Appliance Housing>
Polyurethanes using the PEPCD of the present invention can be used as paints for home appliance casings. Plastic housings of home electric appliances are sometimes painted for the purpose of antiglare, antifouling, protection, tactile sensation, and designability. In addition to adhesion to substrates such as polystyrene, ABS, and polycarbonate, the coating film requires chemical resistance to acids, alkalis, oils and fats, spray paintability, low-temperature drying properties, and scratch resistance during transportation due to packaging materials.
Polyurethane using PEPCD of the present invention can be used as a main ingredient of home appliance casing paint by controlling carbonate bond/ether bond concentration, adjusting molecular weight and number of functional groups, selecting diisocyanate and chain extender, hard segment content and adjusting molecular weight.

<Gravure ink>
Polyurethanes using the PEPCD of the present invention can be used in gravure inks. Gravure inks can print long films and papers at high speed, and can provide multi-color, high-definition printed matter. Gravure inks for packaging are required to have a high degree of printability, and in particular, requirements for ink resolubility, acid resistance, alkali resistance, and oil resistance after printing are severe.
Polyurethane using PEPCD of the present invention can be used as a binder resin for gravure ink for packaging due to the durability derived from polycarbonate and the solubility obtained by adjusting the ether bond concentration.
Further, gravure inks for building materials are required to have weather resistance, stain resistance, and blocking resistance to prevent blocking due to winding during printing. Polyurethane using PEPCD of the present invention has high weather resistance derived from polycarbonate, controls the number of functional groups, and optimizes the ether bond concentration to increase re-solubility. By controlling the concentration of urethane bonds and urea bonds introduced by a diamine-based chain extender, blocking on the back surface of the film can be suppressed, and it can be used as a binder resin for gravure ink for printing various films for building materials.

<Architectural exterior paint>
Polyurethanes using the PEPCD of the present invention can be used in architectural exterior paints. Architectural exterior paints are required to have a high-gloss appearance, stain resistance, and high weather resistance to withstand long periods of wind, rain, and sunlight. On the other hand, there is a shift from conventional solvent-based to weak solvent-based, which is less irritating, and water-based, which is more environmentally friendly, is progressing. It is becoming difficult to maintain the required performance due to water-based systems.
Polyurethane using the PEPCD of the present invention can be made finer in emulsion particle size by controlling the carbonate bond/ether bond concentration and optimizing hydrophilicity, and when used as a water-based paint, a highly glossy appearance with less unevenness on the surface of the coating film can be obtained. In addition, due to its high weather resistance derived from polycarbonate, it is ideal as a resin for building exterior paints. Furthermore, by maximizing the hydrophilicity of the coating film surface, a low-staining coating film is formed that weakens the adhesion of lipophilic contaminants and facilitates cleaning.

<Rooftop waterproofing>
Polyurethanes using the PEPCD of the present invention can be used for roof waterproofing. Rooftop waterproofing includes sheet waterproofing and coating film waterproofing. Conventionally, a cured coating film obtained by cross-linking an aromatic diamine of a prepolymer obtained from polypropylene glycol and diisocyanate has been widely used for coating film waterproofing. Although these are easier to install than sheet waterproofing, they have low weather resistance and a short service life, and the repair period is about half that of sheet waterproofing, about 10 years.
Polyurethane using PEPCD of the present invention has high weather resistance derived from polycarbonate and can exhibit high waterproof performance by appropriately controlling the ether bond concentration and adjusting the number of functional groups.

<Sealants for information electronic materials>
The polyurethane using the PEPCD of the present invention can be used as a sealant for information electronic materials. In various fields of information electronic materials, various sealants are used to protect various functional elements from the environment. These sealing agents are required to have barrier properties, heat resistance, hydrolysis resistance, transparency, light resistance, adhesiveness, flexibility, mechanical strength and the like.
Polyurethane using PEPCD of the present invention has high weather resistance derived from polycarbonate, and by controlling the polyether bond concentration and the number of functional groups, the oxygen and water vapor barrier properties are enhanced, and by adjusting the type of diisocyanate, chain extender, and hard segment content, other required performance can be adjusted in a well-balanced manner, and it can be used as a resin for sealing agents such as light emitting elements of flat panel displays and solar cell panels.

<Ultra-low hardness, low compression set, non-foam resin>
Polyurethanes with PEPCD of the present invention can be used in ultra-low hardness, low compression set non-foam resins. In order to reduce the hardness, it is necessary to introduce a flexible ether structure to increase the molecular weight between cross-links and increase the flexibility of the molecular chain. Also, in order to achieve a low compression strain, it is necessary to increase the number of functional groups and reduce the loss of the crosslinked structure as much as possible. PEG lacks mechanical properties, PTMG is difficult to polyfunctionalize, and PPG has low reactivity due to the terminal OH group binding to a secondary carbon and olefinizes at a certain rate due to dehydration, so none of them can be used for this purpose.
As long as a polyfunctional alcohol having an OH group bonded to a primary carbon is used as a raw material, the PEPCD of the present invention inevitably leaves an OH group bonded to a primary carbon with high reactivity at the end, so that a polyurethane having a completely crosslinked structure can be obtained while increasing the molecular weight between crosslinks. Since it has high weather resistance derived from polycarbonate, it is effective as a material for various special rolls used in printers and copiers as a non-foam molded product with high durability, flexibility and compression set comparable to foam.

<Polyurethane flexible foam>
Polyurethanes using the PEPCD of the present invention can be used in flexible polyurethane foams. In order to reduce the hardness, it is necessary to introduce a flexible ether structure to increase the molecular weight between cross-links and increase the flexibility of the molecular chain. Also, in order to achieve a low compression strain, it is necessary to increase the number of functional groups and reduce the loss of the crosslinked structure as much as possible. PEG lacks mechanical properties, PTMG is difficult to polyfunctionalize, and PPG has low reactivity due to the terminal OH group binding to a secondary carbon and olefinizes at a certain rate due to dehydration, so none of them can be used for this purpose.
As long as a polyfunctional alcohol having an OH group bonded to a primary carbon is used as a raw material, the PEPCD of the present invention always has a highly reactive OH group bonded to the primary carbon at the terminal, so that a polyurethane with a completely crosslinked structure can be obtained while increasing the molecular weight between crosslinks. Since it has high weather resistance derived from polycarbonate, it is highly durable, flexible, low compression set, and high impact resilience. Effective as a material. This characteristic is particularly noticeable in high-density foams having a foaming density of 0.1 g/cc or more.

[Urethane (meth)acrylate resin]
A urethane (meth)acrylate oligomer (hereinafter sometimes referred to as "urethane (meth)acrylate oligomer of the present invention") can be produced by subjecting the PEPCD of the present invention to an addition reaction with a polyisocyanate and a hydroxyalkyl (meth)acrylate. When a polyol, which is another raw material compound, and a chain extender, etc. are used in combination, the urethane (meth)acrylate oligomer can be produced by subjecting the polyisocyanate to an addition reaction of these other raw material compounds. The urethane (meth)acrylate of the present invention gives an active energy ray-curable resin composition by blending with other raw materials. This active energy ray-curable resin composition can be widely used in various surface processing fields and cast molding applications. This active energy ray-curable resin composition, when cured to form a cured film, is characterized by excellent balance between hardness and elongation, solvent resistance, and handleability, and can be used as a raw material for UV-curable coatings, electron beam-curable coatings, photosensitive resin compositions for flexographic printing plates, and photocurable optical fiber coating compositions.

The urethane (meth)acrylate-based oligomer of the present invention can be produced by adding polyisocyanate, hydroxyalkyl (meth)acrylate and, if necessary, other compounds in addition to the PEPCD of the present invention. Polyisocyanates usable for producing urethane (meth)acrylate oligomers include polyisocyanates such as tris(isocyanatohexyl)isocyanurate in addition to the above organic diisocyanates.
In addition, the usable hydroxyalkyl (meth)acrylate is not particularly limited as long as it is a compound having both one or more hydroxyl groups and one or more (meth)acryloyl groups, as typified by 2-hydroxyethyl (meth)acrylate. Furthermore, in addition to the PEPCD of the present invention, a compound having at least two active hydrogens such as other polyols and/or polyamines may be added, or any combination thereof may be used.

The active energy ray-curable resin composition containing the urethane (meth)acrylate-based oligomer of the present invention may be mixed with an active energy ray-reactive monomer other than the urethane (meth)acrylate-based oligomer of the present invention, an active energy ray-curable oligomer, a polymerization initiator, a photoenhancer, and other additives.

The cured film of the active energy ray-curable resin composition containing the urethane (meth)acrylate-based oligomer of the present invention can be a film having excellent stain resistance and protection against general household contaminants such as ink and ethanol.
A laminate using the cured film as a coating on various substrates has excellent design and surface protection properties, and can be used as a film for painting substitutes.

[Applications of polyester elastomer]
The PEPCD of the present invention can be used as a polyester elastomer. Polyester-based elastomers are copolymers composed of hard segments mainly composed of aromatic polyesters and soft segments mainly composed of aliphatic polyethers, aliphatic polyesters or aliphatic polycarbonates. When the PEPCD of the present invention is used as a constituent component of the soft segment of the polyester-based elastomer, physical properties such as heat resistance and water resistance are superior to those in which aliphatic polyethers and aliphatic polyesters are used. In addition, compared to known polycarbonate polyols, it is a polyether carbonate ester elastomer that has fluidity when melted, that is, a melt flow rate suitable for blow molding and extrusion molding, and has an excellent balance with mechanical strength and other physical properties, and can be suitably used for various molding materials such as fibers, films, and sheets, such as elastic threads and molding materials for boots, gears, tubes, and packings. Specifically, it can be effectively applied to applications such as joint boots for automobiles, household appliance parts, etc., which require heat resistance and durability, and electric wire coating materials.

[Uses of (meth)acrylic resin]
The PEPCD of the present invention can be derived into novel (meth)acrylates by (meth)acrylating one or both of the terminal hydroxyl groups. Any of an anhydride, a halide, and an ester of the corresponding (meth)acrylate may be used in the method for producing the (meth)acrylate.
This (meth)acrylate is blended with other raw materials to give an active energy ray-polymerizable composition ((meth)acrylic resin).

This active energy ray-polymerizable composition has the property of being cured by polymerization in a short time with an active energy ray such as ultraviolet rays, and is generally excellent in transparency, making it possible to give the cured product excellent properties such as toughness, flexibility, scratch resistance, and chemical resistance. From this point, it can be used in various fields such as a coating agent for plastics, a lens molding agent, a sealing agent, and an adhesive agent.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

〔Evaluation methods〕
Evaluation methods for the PEPCD and polyurethane obtained in the following examples and comparative examples are as follows.
[Hydroxyl value and number average molecular weight of PEPCD and PTMG]
The hydroxyl values of PEPCD and PTMG were measured by a method using an isocyanating reagent according to the method of ASTM E1899-16.
Furthermore, the number average molecular weight (Mn) was obtained from the measured hydroxyl value by the following formula (I).
Number average molecular weight = 2 × 56.1 / (hydroxyl value × 10 ^-3 ) (I)

[Composition analysis of PEPCD]
Structural units constituting PEPCD and their mass ratios were calculated by ¹ H-NMR analysis of PEPCD. Specifically, PEPCD was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (ECZ-400 manufactured by JEOL Ltd.) was measured, and from the signal position of each component, the molar ratio of the structural unit was obtained, and the molar ratio was converted to the mass ratio using the molecular weight of the structural unit.
When analysis by ¹ H-NMR and analysis of signal positions are difficult, the mass of each dihydroxy compound obtained by hydrolysis with an alkali can be analyzed by gas chromatography (hereinafter "GC"). Specifically, the following method is used.
0.5 g of PEPCD is precisely weighed into a 100 mL flask, dissolved in 5 mL of THF, and 45 mL of methanol is added. After that, 5 mL of a 25 mass % NaOH aqueous solution is added, a condenser is set in a 100 mL flask, and methanol is refluxed at 70 to 75° C. for 30 minutes for hydrolysis. 6N-HCl is added to the obtained reaction solution until it becomes neutral. The concentration of each dihydroxy compound is determined by GC analysis of the solution after the volume is finally adjusted to 100 mL with THF. A calibration curve for each dihydroxy compound with respect to the internal standard is prepared, and the mass ratio of each dihydroxy compound in PEPCD is calculated from the concentration thereof. The mass ratio of the hydrolyzate of each structural unit obtained here is defined as the mass ratio of each structural unit.

[Percentage of terminal alkoxy/aryloxy and butoxy terminal of PEPCD]
PEPCD was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (ECZ-400 manufactured by JEOL Ltd.) was measured, and calculation was performed from the integral value of the signal of each component.
—OCH ₃ end group: δ 3.33 (s, 3H)
—OCH ₂ CH ₂ CH ₂ CH ₃ end group: δ 0.91 (t, 3H)
There is a possibility that the above-described signal values may deviate due to differences in the structure of PEPCD. The detection limit of the terminal alkoxy/aryloxy ratio of this ¹ H-NMR measurement method is 0.01%.

[Polyurethane molecular weight]
Polyurethane was dissolved in dimethylacetamide to prepare a dimethylacetamide solution having a concentration of 0.14% by mass. Using a GPC apparatus [manufactured by Tosoh Corporation, product name "HLC-8220" (column: TskgelGMH-XL, 2 columns)], the dimethylacetamide solution was injected, and the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyurethane were measured in terms of standard polystyrene.

[Polyurethane Room Temperature Tensile Test]
A test piece of 1 cm × 15 cm was cut out from a polyurethane film (thickness 50 to 100 μm), and this test piece was subjected to a tensile test according to JIS K6301 (2010) using a tensile tester (manufactured by Orientec, product name “Tensilon UTM-III-100”) at a chuck distance of 50 mm and a tensile speed of 500 mm/min at a temperature of 23 ° C. and a relative humidity of 55%.

[Polyurethane chemical resistance test]
A test piece of 3 cm×3 cm was cut from a polyurethane film (thickness 50-100 μm). The test piece was placed in a 250 mL glass bottle containing 50 mL of oleic acid or 50 mL of ethanol as a test solvent, and allowed to stand at 80° C. for 16 hours. After the test, the test piece was taken out and lightly wiped with a paper wiper, and the mass was measured with a precision balance to calculate the rate of change in mass from before the test (increase rate, hereinafter referred to as "wetting rate"). A wetness ratio closer to 0% indicates better chemical resistance.

[Compound abbreviation]
Abbreviations of compounds in Examples and Comparative Examples are as follows.
PTMG: Polytetramethylene ether glycol having a hydroxyl value of 521.9 mg-KOH/g and a number average molecular weight of 215, manufactured by Mitsubishi Chemical Corporation EC: ethylene carbonate, manufactured by Mitsubishi Chemical Corporation Mg (acac) ₂ : magnesium (II) acetylacetonate, manufactured by Tokyo Chemical Industry Co., Ltd. 1,4BD: 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation MDI: 4,4'-diphenylmethane diisocyanate, manufactured by Tokyo Chemical Industry Co., Ltd.

[Manufacture and evaluation of PEPCD]
[Example 1]
515 g of PTMG, 285 g of EC, and 250 mg of Mg(acac) ₂ were placed in a 1 L glass four-necked flask equipped with a magnetic stirrer, a distillate trap, a pressure regulator, and a distillation column containing a 30 mmφ ordered packing, and the flask was purged with nitrogen gas. After lowering the pressure to 80 to 40 kPa while stirring, the internal temperature was raised to 150° C., and the reaction was carried out for 12 hours while removing ethylene glycol and EC from the system (first stage of reaction).
After that, 1.1 mL of an 8.5% aqueous solution of phosphoric acid was added to the product to deactivate the catalyst. Thereafter, the packed distillation column was removed, and residual monomers were removed at 168-178° C. under 1 kPa to obtain crude PEPCD.
The obtained crude PEPCD was sent to a thin film distillation apparatus at a flow rate of 20 g/min, and subjected to thin film distillation (temperature: 210°C, pressure: 53 Pa) to obtain PEPCD-1. As the thin-film distillation apparatus, a molecular distillation apparatus MS-300 special type manufactured by Shibata Scientific Co., Ltd. with an internal condenser having a diameter of 50 mm, a height of 200 mm and an area of 0.0314 m 2 and a jacket was used. Table 1 shows the analytical results and the like of the obtained PEPCD-1.

[Example 2]
PEPCD-2 was produced in the same manner as in Example 1, except that the pressure in the first reaction stage was 50 to 30 kPa and the reaction time was 7 hours. Table 1 shows the analysis results of the obtained PEPCD-2.

[Example 3]
After completion of the first reaction step, 37 g of EC was then added, the pressure was lowered to 40 to 20 kPa, and the reaction was carried out at 150° C. for 8 hours (second reaction step). Table 1 shows the analysis results of the obtained PEPCD-3.

[Comparative Example 1]
PEPCD-4 was produced in the same manner as in Example 1 except that 292 g of dimethyl carbonate was used instead of EC. Table 1 shows the analysis results of the obtained PEPCD-4.

[Comparative Example 2]
In Example 1, after purging with nitrogen gas, the internal temperature was raised to 150° C. while stirring to heat and dissolve the contents. Then, after reacting at normal pressure for 2 hours, the pressure was lowered to 80 to 40 kPa, and reaction was carried out for 12 hours while removing ethylene glycol and EC from the system. Then, 37 g of EC was added, the pressure was lowered to 40-20 kPa, and the reaction was carried out at 150° C. for 8 hours. Otherwise, PEPCD-5 was produced in the same manner as in Example 1. Table 1 shows the analysis results and the like of the obtained PEPCD-5.

[Production and Evaluation of Polyurethane]
[Example 4]
Using PEPCD-1 as a raw material, a polyurethane was produced by the following procedure.
A separable flask equipped with a thermocouple, a cooling tube and a stirrer is placed on an oil bath at 60 ° C., 54.86 g of PEPCD-1 preheated to 80 ° C., 5.5 g of 1,4BG, and 211.9 g of dehydrated N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) are added, and then 30.9 g of MDI is added. The temperature was raised to 80° C. in about an hour. After reaching 80°C, 0.0133 g of Neostan U-830 (manufactured by Nitto Kasei Co., Ltd.) was added as a urethanization catalyst, and the mixture was further stirred at 80°C for about 2 hours. After that, MDI was added in portions so that the equivalent amount of NCO to OH was around 1.0, and the mixture was further stirred for 1 hour to obtain a polyurethane solution. This polyurethane solution was applied on a fluororesin sheet with an applicator to a uniform thickness and dried with a dryer to obtain a polyurethane film. Table 2 shows the properties and physical properties of this polyurethane.

[Example 5]
A polyurethane and a polyurethane film were produced in the same manner as in Example 4 except that 49.8 g of PEPCD-2, 4.5 g of 1,4BG, 184.7 g of dehydrated N,N-dimethylformamide, 25.5 g of MDI, and 0.0138 g of Neostan U-830 were used.

[Example 6]
A polyurethane and a polyurethane film were produced in the same manner as in Example 4 except that 69.5 g of PEPCD-3, 6.5 g of 1,4BG, 243.8 g of dehydrated N,N-dimethylformamide, 27.3 g of MDI, and 0.0209 g of Neostan U-830 were used.

[Comparative Example 3]
A polyurethane and a polyurethane film were produced in the same manner as in Example 4 except that 74.1 g of PEPCD-4, 6.4 g of 1,4BG, 250.3 g of dehydrated N,N-dimethylformamide, 28.2 g of MDI, and 0.0201 g of Neostan U-830 were used.

[Comparative Example 4]
A polyurethane and a polyurethane film were produced in the same manner as in Example 4 except that 52.0 g of PEPCD-5, 2.6 g of 1,4BG, 159.8 g of dehydrated N,N-dimethylformamide, 14.6 g of MDI, and 0.0105 g of Neostan U-830 were used.

As is clear from the results of Examples 4 to 6, the polyurethanes produced using PEPCD-1 to 3 corresponding to the PEPCD of the present invention produced in Examples 1 to 3 had low swelling when oleic acid and ethanol adhered, and excellent chemical resistance.
On the other hand, the polyurethanes of Comparative Examples 3 and 4, which were produced using PEPCD-4 and 5 produced in Comparative Examples 1 and 2, had large swelling amounts in oleic acid and ethanol, and were inferior in chemical resistance.
From this result, it can be seen that the PEPCD of the present invention can produce polyurethane having excellent chemical resistance and a weight average molecular weight of about 150,000 to 200,000, which can be suitably used for synthetic leather and the like.

Claims (8)

A polyether polycarbonate diol containing 0.1% by mass or more and 3.5% by mass or less of a structural unit represented by the following formula (1) and having a hydroxyl value of 11.0 mg-KOH/g or more and 320 mg-KOH/g or less.

(In the above formula (1), m is an integer of 1 or more.) The polyether polycarbonate diol according to claim 1, further comprising a structural unit represented by the following formula (2).

(In formula (2) above, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and n is an integer of 1 or more.) 3. The polyether polycarbonate diol according to claim 1, wherein the ratio of the sum of the number of alkoxy terminal groups and the number of aryloxy terminal groups to the total number of terminal groups is 0.20% or more and 7.5% or less. 4. The polyether polycarbonate diol of claim 3, wherein said alkoxy end groups comprise butoxy end groups. A method for producing the polyether polycarbonate diol according to any one of claims 1 to 4,
A method for producing a polyether polycarbonate diol, comprising the step of reacting a polyalkylene ether glycol with a carbonate compound, wherein the carbonate compound is ethylene carbonate. 6. The method for producing a polyether polycarbonate diol according to claim 5, wherein said polyalkylene ether glycol comprises polytetramethylene ether glycol. 7. The method for producing a polyether polycarbonate diol according to claim 5 or 6, wherein the polyalkylene ether glycol has a hydroxyl value of 50.0 mg-KOH/g or more and 550 mg-KOH/g or less. A method for producing polyurethane using the polyether polycarbonate diol according to any one of claims 1 to 4.