JP2022120570A - Polyether polycarbonate diol and method for producing the same - Google Patents

Abstract

To provide a polyether polycarbonate diol that serves as the raw material for polyurethane and has balanced physical properties such as flexibility, low temperature properties (e.g. low temperature flexibility), mechanical strength, solvent resistance, and hydrolysis resistance.SOLUTION: A polyether polycarbonate diol has a polyalkylene ether glycol-derived constitutional unit A and a C7-50 diol compound-derived constitutional unit B. A method for producing the polyether polycarbonate diol includes the step in which: in the presence of a catalyst, a polyalkylene ether glycol with a hydroxyl value of 220 mg-KOH/g or more and 750 mg-KOH/g or less, a C7-50 diol compound and a carbonate compound are reacted with each other.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 polyurethanes 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. be. Among polyether polyols, polytetramethylene ether glycol (hereinafter sometimes abbreviated as PTMG) has high crystallinity, so the polyurethane obtained by reaction with isocyanates has excellent abrasion resistance and hydrolysis resistance. Tear resistance. The main uses of such polyurethanes are spandex, thermoplastic elastomers, thermoset elastomers, artificial leather, synthetic leather and the like.

Because of these excellent properties, polyurethanes obtained from polytetramethylene ether glycol are used in a variety of applications. In terms of applications, there is still room for improvement in durability such as chemical resistance of the resulting polyurethane.

As a method for improving the physical properties of polytetramethylene glycol, a method of linking with a carbonate bond is known. For example, 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 1).

JP-A-2002-256069

According to Patent Document 1, a room-temperature liquid polyol is obtained, but this PEPCD is a polyurethane that satisfies hydrolysis resistance, mechanical strength, chemical resistance, flexibility, etc. in a well-balanced manner as a polyurethane used for synthetic leather and the like. could not get

The present invention has been made in view of the above problems. The object is to provide an ether polycarbonate diol.

As a result of intensive studies to solve the above problems, the present inventors have found that a polyether polycarbonate diol containing a structural unit derived from a polyalkylene ether glycol and a structural unit derived from a diol compound having 7 to 50 carbon atoms can be used as a polyurethane raw material. The inventors have found that by using this, it is possible to obtain a polyurethane having an excellent balance of physical properties, which has good flexibility, low-temperature properties such as low-temperature flexibility, mechanical strength, solvent resistance, hydrolysis resistance, and the like.
The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] Containing a structural unit derived from polyalkylene ether glycol (hereinafter referred to as "structural unit A") and a structural unit derived from a diol compound having 7 to 50 carbon atoms (hereinafter referred to as "structural unit B") Polyether polycarbonate diol.
[2] The polyether polycarbonate diol according to [1], which has a hydroxyl value of 20 mg-KOH/g or more and 450 mg-KOH/g or less.
[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 0.01% or more and 7.0% or less.
[4] The polyether polycarbonate diol according to any one of [1] to [3], wherein the structural unit A contains a structural unit derived from polytetramethylene glycol.
[5] Any one of [1] to [4], wherein the ratio of the mass of the structural unit B to the total mass of the structural unit A and the mass of the structural unit B is 0.5% or more and 50% or less The polyether polycarbonate diol described in .
[6] The polyether polycarbonate diol according to any one of [3] to [5], wherein the alkoxy end groups comprise methoxy end groups.
[7] The polyether polycarbonate diol according to any one of [3] to [6], wherein the alkoxy terminal groups comprise butoxy terminal groups.
[8] A polyether polycarbonate diol composition containing the polyether polycarbonate diol according to any one of [1] to [7] and a metal, wherein the metal is zinc and Group 2 of the long period periodic table A polyether polycarbonate diol composition which is at least one selected from the group consisting of metals.
[9] The polyether polycarbonate diol composition according to [8], wherein the content of the metal is 1 mass ppm or more and 500 mass ppm or less.
[10] A method for producing a polyether polycarbonate diol according to any one of [1] to [7], comprising: A method for producing a polyether polycarbonate diol comprising a step of reacting an alkylene ether glycol, a diol compound having 7 to 50 carbon atoms and a carbonate compound.
[11] The method for producing a polyether polycarbonate diol according to [10], wherein the carbonate compound is an alkylene carbonate.
[12] A composition in which the catalyst comprises at least one metal (M) selected from zinc and Group 2 metals of the long period periodic table, and at least one compound represented by the following formula (1): , or the method for producing a polyether polycarbonate diol according to [10] or [11], which is a composition comprising at least one salt represented by the following formula (2) and a precursor thereof.

(In the formula, R ₁ and R ₃ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom and has an oxygen atom. R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, and the hydrocarbon group may be substituted with a halogen atom or may have an oxygen atom. M represents zinc or a metal of group 2 of the long period periodic table, and n=2.)
[13] A polyurethane containing a structural unit derived from the polyether polycarbonate diol according to any one of [1] to [7].
[14] A method for producing a polyurethane by subjecting raw materials containing the polyether polycarbonate diol according to any one of [1] to [7] and a compound having a plurality of isocyanate groups to an addition polymerization reaction.

According to the polyether polycarbonate diol of the present invention, it is possible to produce a polyurethane having an excellent balance of physical properties such as low-temperature properties such as flexibility and low-temperature flexibility, mechanical strength, solvent resistance and hydrolysis resistance.

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 of the present invention is not exceeded.

[Polyether polycarbonate diol]
The polyether carbonate diol (hereinafter sometimes abbreviated as "PEPCD") of the present invention contains a structural unit A derived from a polyalkylene ether glycol and a structural unit B derived from a diol compound having 7 to 50 carbon atoms. It is a polyether polycarbonate diol.
The PEPCD of the present invention is synonymous with the PEPCD composition described in the explanation of the metal content (remaining catalyst metal amount of PEPCD) below.

In the present invention, the polyether polycarbonate diol refers to "a compound having repeating units of polyether polycarbonate", and the polyether polycarbonate diol of the present invention usually has repeating units of polyether polycarbonate and has different terminal groups. It is configured as a mixture of multiple types of compounds having

PEPCD is 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.

<Structure of PEPCD>
The PEPCD of the present invention contains a structural unit A derived from a polyalkylene ether glycol and a structural unit B derived from a diol compound having 7 to 50 carbon atoms, and has good solvent resistance, mechanical strength, and flexibility when made into a polyurethane. , low-temperature properties such as low-temperature flexibility and hydrolysis resistance can be combined.

As long as the PEPCD of the present invention contains the structural unit A and the structural unit B, they may be a copolymer or a mixture of different types of PEPCD. Therefore, it is preferably a copolymer. In the case of copolymers, either block copolymers or random copolymers may be used, but PEPCD, which is a random copolymer, is preferable because it has good low-temperature properties and flexibility.

The mass ratio of structural unit A and structural unit B to all structural units of PEPCD of the present invention can be determined by gas chromatography analysis of each dihydroxy compound obtained by hydrolyzing PEPCD with an alkali.
It can also be obtained by identifying the molar ratio of each structural unit by ¹ H-NMR and converting the molar ratio into the mass ratio of each structure. It can also be calculated from the ratio of the mass of each diol compound reacted during polymerization to the mass of the obtained polyether polycarbonate diol. The mass ratio of the structural unit A and the structural unit B introduced into the PEPCD can also be calculated from the weight of the diol used in charging the PEPCD, the amount of by-products, and the amount of distillation.

The content of the structural unit A in the PEPCD of the present invention is not particularly limited. If the amount is too high, the hydrophilicity of the resulting polyurethane may increase, resulting in insufficient hydrolysis resistance and reduced mechanical strength. The content of structural unit A in PEPCD of the present invention is preferably 15% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. The upper limit is preferably 99.5% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less.
If the content of the structural unit B in the PEPCD of the present invention is too small, the hydrolysis resistance will be insufficient, and if it is too large, the mechanical strength and solvent resistance of the polyurethane may not be sufficient. . In order to obtain the effects of including the structural unit A and the structural unit B in a well-balanced manner, the ratio of the mass of the structural unit B to the sum of the masses of the structural unit A and the structural unit B contained in the PEPCD of the present invention is preferably 0.5 to 50% by mass, more preferably 1 to 45% by mass, even more preferably 2 to 40% by mass, further preferably 3 to 35% by mass, Most preferably it is between 5 and 35%.

If the PEPCD of the present invention contains the structural unit A and the structural unit B, other structural units other than the structural unit A and the structural unit B, that is, a polyalkylene ether glycol and a diol compound having 7 to 50 carbon atoms It may contain structural units derived from other dihydroxy compounds. In this case, the content of other structural units is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 20% by mass or less, and most preferably 10% by mass or less, relative to the total structural units of PEPCD. . If the ratio of other structural units is large, the balance of solvent resistance, flexibility, etc. may be impaired.

Each compound constituting structural unit A, structural unit B, and other structural units will be described later.

<Hydroxyl value, number average molecular weight, and molecular weight distribution of PEPCD>
The hydroxyl value of the PEPCD of the present invention is not particularly limited, but the lower limit of the hydroxyl value is usually 11 mg-KOH/g, preferably 20 mg-KOH/g, more preferably 22.4 mg-KOH/g, more preferably 22.4 mg-KOH/g. Is 28.1 mg-KOH / g, particularly preferably 37.4 mg-KOH / g, the upper limit is 450 mg-KOH / g, preferably 320 mg-KOH / g, more preferably 187.0 mg-KOH / g, more preferably is 140.3 mg-KOH/g, particularly 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 handling tends to be easy when the PEPCD is used as a raw material to produce a polyurethane. tend to be better.

Further, in the PEPCD of the present invention, hydrolyzates of structural unit A and structural unit B can be obtained by hydrolysis. The hydrolyzate corresponds to the raw material used in the production of PEPCD. The hydroxyl value of the hydrolyzate of structural unit A is preferably 220 mg-KOH/g or more and 750 mg-KOH/g or less. Within the above range, the PEPCD may be inhibited from raising the crystallinity and melting point. Further, when the hydroxyl value of the hydrolyzate of the structural unit A is 750 mg-KOH/g or less, the PEPCD has a suitable viscosity and may be excellent in handleability. The hydroxyl value of the hydrolyzate of structural unit A is more preferably 280 mg-KOH/g or more, more preferably 370 mg-KOH/g or more, and more preferably 700 mg-KOH/g or less, It is more preferably 660 mg-KOH/g or less.
The method of hydrolysis of PEPCD is as described in the Examples section.

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 of PEPCD and its hydrolyzate, and the number average molecular weight (Mn) of PEPCD are measured, for example, by the following methods.

<Hydroxyl value/number average molecular weight>
The hydroxyl value of PEPCD is measured by a method using an isocyanating reagent according to ASTM E1899-16.
From the measured hydroxyl value, the number average molecular weight (Mn) is determined by the following formula (I).
Number average molecular weight = 2 × 56.1 / (hydroxyl value × 10 ^-3 ) (I)

The molecular weight distribution (Mw/Mn) of the PEPCD of the present invention is usually 1 or more, preferably 1.2 or more, more preferably 1.5 or more, while the upper limit is usually 3 or less, preferably 2.5 or less, and more It is preferably 2.2 or less.
When the molecular weight distribution is 3 or less, an increase in high molecular weight and an increase in viscosity are suppressed, and in addition to being excellent in handleability, various physical properties of polyurethane such as tensile strength tend to be improved. On the other hand, the lower limit of molecular weight distribution is usually 1 or more.
Here, the molecular weight distribution of PEPCD is a value measured by the following method.

<Molecular weight distribution (Mw/Mn)>
After preparing a tetrahydrofuran solution of PEPCD, the weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) [manufactured by Tosoh Corporation, product name “HLC-8220”, column: TskgelSuperHZM-N (4 columns)]. was divided by the number average molecular weight (Mn), and the value (Mw/Mn) was defined as the molecular weight distribution of PEPCD. A POLYTETRAHYDROFURAN calibration kit from POLYMER LABORATORIES, UK was used for GPC calibration.

<APHA value>
The color of the PEPCD of the present invention is preferably 50 or less in terms of Hazen color number (in accordance with JIS K0071-1: 1998) (hereinafter referred to as "APHA value"), and 40 or less. More preferably, it is 30 or less. If the APHA value exceeds 50, the color tone of the resulting polyurethane may deteriorate, the commercial value may decrease, or the heat stability may deteriorate.

In order to make the APHA value 50 or less, the selection of the type and amount of catalyst during PEPCD production, thermal history, the concentration of monohydroxy compounds during and after polymerization, and the concentration of unreacted monomers are comprehensively controlled. There is a need. Light shielding during and after polycondensation is also effective. It is also important to set the number-average molecular weight of PEPCD and select the type of dihydroxy compound used as a monomer. In particular, PEPCD, which is made from an aliphatic dihydroxy compound having an alcoholic hydroxyl group, exhibits various excellent properties such as flexibility, water resistance, and light resistance when processed into polyurethane. It is not easy to reduce the APHA value to 60 or less because the thermal history and the coloration due to the catalyst tend to become more marked than when the APHA value is reduced.

<Ratio of terminal alkoxy/aryloxy>
PEPCD is 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. In its production, along with the target product, PEPCD having hydroxyl groups at both ends, as by-products, alkoxy terminal groups resulting from the reaction of a dialkyl carbonate with a polyether polyol compound and reaction of a diaryl carbonate with a polyether polyol compound Aryloxy terminal groups may be generated (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 raw material for PEPCD production, and may be mixed in the obtained PEPCD.
Alkoxy/aryloxy termini may also be mixed into PEPCD by heating during the purification process of PEPCD.
That is, by controlling the amount of alkoxy/aryloxy terminals generated as reaction by-products and the amount of alkoxy/aryloxy terminals mixed in the raw material compound and brought into the reaction system, the amount of alkoxy/aryloxy terminals mixed in the product can be controlled to a specified amount.

In the PEPCD of the present invention, the ratio of the total number of alkoxy terminal groups and the number of aryloxy terminal groups (terminal alkoxy/aryloxy ratio) to the total number of terminal groups is preferably 0.01 to 7.0%. When the terminal alkoxy/aryloxy ratio is 7.0% or less, the urethane polymerization reaction proceeds sufficiently, and a polyurethane having a sufficient molecular weight and high mechanical strength can be obtained. The terminal alkoxy/aryloxy ratio of the PEPCD of the present invention is more preferably 5.0% or less, still more preferably 3.0% or less, particularly preferably 2.0% or less, and preferably 1.0% or less. It is most preferred from the viewpoint of the mechanical properties and solvent resistance of the polyurethane to be used.
On the other hand, when the terminal alkoxy/aryloxy ratio is 0.01% or more, the urethane polymerization reaction rate does not become too fast, the reaction is easy to control, and a polyurethane having a desired molecular weight can be obtained. % or more, it becomes easier to control the reaction. That is, the terminal alkoxy/aryloxy ratio of the PEPCD of the present invention is preferably 0.01% or more, more preferably 0.1% or more, and even more preferably 0.2% or more.

The terminal alkoxy/aryloxy ratio of PEPCD is measured by the method described in the Examples section below.

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

The alkoxy terminal group includes methoxy terminal, ethoxy terminal, propioxy terminal, butoxy terminal and the like, and preferably methoxy terminal or butoxy terminal from the viewpoint of PEPCD quality.

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.

<Method for controlling terminal alkoxy/aryloxy ratio>
The method for controlling the terminal alkoxy/aryloxy ratio of the PEPCD of the present invention is not particularly limited,
(1) Method of mixing PEPCD containing alkoxy/aryloxy ends and PEPCD not containing alkoxy/aryloxy ends (2) Adjusting the concentration of alkoxy/aryloxy ends in PEPCD containing alkoxy/aryloxy ends by operations such as distillation and extraction (3) A method of controlling the content of alkoxy/aryloxy terminals in polyether polyol compounds, carbonate compounds, and diol compounds that are raw materials for PEPCD A method of controlling the amount of aryloxy terminals by adjusting the pH of the solution and the like can be mentioned.

<Melt viscosity>
The PEPCD of the present invention has a melt viscosity of 100 mPa.s at 40° C. measured by the method described in Examples below. s or more, especially 300 mPa.s or more. s or more, especially 500 mPa.s or more. s above 100000 mPa.s. s or less, especially 10000 mPa.s or less. s or less, especially 7000 mPa.s or less. s or less, or even 5000 mPa.s or less. s or less. When the melt viscosity of PEPCD is at least the above lower limit, the degree of polymerization of PEPCD is sufficient, and urethane produced using this tends to have excellent flexibility and elastic recovery. It is preferable because the handleability of the polyurethane obtained by using it is improved and the production efficiency is not lowered.

<Glass transition temperature>
The glass transition temperature (Tg) of the PEPCD of the present invention measured by a differential scanning calorimeter (hereinafter sometimes referred to as "DSC") is preferably −40° C. or less, more preferably −50° C. or less, and further It is preferably -60°C or lower. When the Tg of PEPCD is too high, the Tg of the polyurethane becomes high, and the flexibility at low temperature is lowered, the elongation at break is lowered, and the properties may be deteriorated. However, if the Tg is too low, the elastic modulus tends to be too low or the tackiness tends to be strong when made into polyurethane.

[Method for producing polyether polycarbonate diol]
The production method of the PEPCD of the present invention is not particularly defined as long as the target PEPCD is obtained, but it is usually produced by reacting a polyether polyol compound and a diol compound having 7 to 50 carbon atoms with a carbonate compound. During the reaction, if necessary, a diol compound different from the polyether polyol compound and the diol compound having 7 to 50 carbon atoms may be copolymerized. Moreover, in the manufacturing process, a catalyst, an additive, and the like may be added as necessary.
Preferably, the PEPCD of the present invention is a step of reacting a polyalkylene ether glycol having a hydroxyl value of 220 mg-KOH/g or more and 750 mg-KOH/g or less, a diol compound having 7 to 50 carbon atoms, and a carbonate compound in the presence of a catalyst. Produced by the method for producing a polyether polycarbonate diol of the present invention containing. More preferably, at that time, the terminal alkoxy/aryloxy ratio is controlled.

<Carbonate compound>
Alkylene carbonate, dialkyl carbonate, and diaryl carbonate can be used as the carbonate compound.

Alkylene carbonates include ethylene carbonate, propylene carbonate, butylene carbonate, and the like.
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 these, from the viewpoint of ease of control of the total ratio of the number of alkoxy terminal groups and the number of aryloxy terminal groups to the total number of terminal groups, alkylene carbonate or dialkyl carbonate are preferred, and ethylene carbonate and dimethyl carbonate are more preferred. Alkylene carbonates such as ethylene carbonate are preferred.
In addition, said carbonate compound may be used individually by 1 type, and may be used in mixture of 2 or more types.

<Polyether polyol compound>
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 kind of these cyclic ethers may be used alone, or two or more kinds may be mixed and used, but it is preferable to use one kind.

Specific polyether polyol compounds include low-molecular-weight polyether polyols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and dipropylene glycol; Examples include copolymers of ethylene and propylene oxide, polyalkylene ether glycols such as polytetramethylene ether glycol (PTMG), copolymers of THF and 3-methyl-tetrahydrofuran, and dipropylene glycol polyethylene glycol.

Among these, a polyalkylene having a hydroxyl value of 220 mg-KOH/g or more and 750 mg-KOH/g or less, particularly 280 mg-KOH/g or more and 700 mg-KOH/g or less, especially 370 mg-KOH/g or more and 660 mg-KOH/g or less Ether glycol is preferable from the viewpoint of tensile properties and durability of the obtained polyurethane. A polyalkylene ether glycol having a hydroxyl value of 750 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 220 mg-KOH/g or more, the resulting PEPCD does not have too high a viscosity and is excellent in handleability.
Further, the polyalkylene ether glycol has a number average molecular weight (Mn) of 100 or more and 3000 or less, especially 150 or more and 2000 or less, especially 200 or more and 850 or less, as determined from hydroxyl groups. is preferable from the viewpoint of 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. Further, when 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 of the polyalkylene ether glycol and the number average molecular weight (Mn) obtained from the hydroxyl value are measured in the same manner as the hydroxyl value and number average molecular weight (Mn) of the PEPCD of the present invention described above.

As the polyalkylene ether glycol, polytetramethylene glycol (PTMG) is preferable because it has an excellent balance of flexibility, low-temperature flexibility, mechanical strength, hydrolysis resistance, low-temperature flexibility, solvent resistance, and the like.

THF, which is a raw material for PTMG, can be obtained by a conventionally known production method. For example, 1,4-butanediol obtained by obtaining diacetoxybutene, which is an intermediate obtained by performing an acetoxylation reaction using raw material butadiene, acetic acid and oxygen, and then hydrogenating and hydrolyzing the diacetoxybutene. A method of obtaining 1,4-butanediol obtained by hydrogenating maleic acid, succinic acid, maleic anhydride and/or fumaric acid as raw materials by cyclodehydration; Acetylene A method of obtaining 1,4-butanediol obtained by hydrogenating butynediol obtained by contacting with an aqueous formaldehyde solution using as a raw material; 1,4-butanediol obtained by cyclodehydration; A method of obtaining 1,4-butanediol obtained by hydrogenating succinic acid obtained by a fermentation method; A method of obtaining 1,4-butanediol by cyclization dehydration; A method of obtaining 1,4-butanediol obtained by direct fermentation from biomass such as sugar - A method of obtaining by cyclodehydration of butanediol; A method of obtaining by decarbonylation and reduction of furfural obtained from biomass;

<Diol compound having 7 to 50 carbon atoms>
Although the structure of the diol compound having 7 to 50 carbon atoms from which the structural unit B is derived is not particularly limited, the following compounds may be mentioned. The diol compound having 7 to 50 carbon atoms from which the structural unit B is derived is a diol compound having no ether bond.
Linear diols include 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1 ,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,12-octadecanediol, 1,20-eicosanediol and the like.
As side chain diols, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,6-hexanediol, 3-butyl-1,5-pentanediol , 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, 2,2-dibutyl-1,3-propanediol and the like.
Cyclic diols include dimer diol, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane, 1,3-cyclohexanedimethanol, 2,7-norbornanediol, tricyclo[5.2.1 .02,6] decanedimethanol and the like.
These diol compounds may be used alone or in combination of two or more. These diols may also be contained as impurities in raw materials such as other diol compounds.

If the number of carbon atoms in the diol compound to be used is 6 or less, the density of the carbonate groups increases and aggregates, resulting in insufficient flexibility of the resulting polyurethane or improved crystallinity, resulting in an increase in Tg and a low temperature. Flexibility is impaired, and hydrolysis resistance is lowered due to decreased hydrophobicity. On the other hand, when the number of carbon atoms in the diol compound used exceeds 50, the ratio of fat-soluble aliphatic diols increases, resulting in insufficient solvent resistance of the resulting polyurethane, lowering the density of carbonate groups, and lowering the mechanical strength. may decrease, or the compatibility during polyurethane synthesis may decrease. Therefore, in the present invention, a diol compound having 7 to 50 carbon atoms is used.

A diol compound having 7 to 50 carbon atoms is preferable from the viewpoint of the flexibility and hydrolysis resistance of the resulting polyurethane. It preferably has 8 to 30 carbon atoms, more preferably 8 to 20 carbon atoms.
Further, a diol compound having 8 to 12 carbon atoms is more preferable because it has an excellent balance of solvent resistance and flexibility when made into a polyurethane, and specifically, 1,8-octanediol and 1,9-nonanediol. , 1,10-decanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,12-dodecanediol and the like are preferable. On the other hand, diol compounds having 15 or more carbon atoms such as 1,18-octadecanediol, 1,12-octadecanediol, 1,20-eicosandiol and dimer diol are preferred from the viewpoint of hydrolysis resistance and low-temperature flexibility. .
Cyclic diols or side chain diols are preferred from the viewpoint of the mechanical strength of the resulting polyurethane, and linear diols are preferred from the viewpoint of excellent balance between flexibility and mechanical strength.
Further, by using a combination of diol compounds having different carbon numbers, the crystallinity may be lowered and the flexibility may be improved.

Structural unit A and structural unit B contained in the PEPCD of the present invention are preferably plant-derived from the viewpoint of reducing environmental load. Compounds derived from the structural unit A that can be applied as plant-derived include PTMG produced from the above-mentioned plant-derived THF and the like. Compounds derived from the structural unit B that can be applied as derived from plants include 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tride Candiol, 1,12-octadecanediol, 1,20-eicosanediol, dimerdiol and the like can be mentioned.

<Other dihydroxy compounds>
In the production of the PEPCD of the present invention, as long as the effect of the present invention is not impaired, that is, within the range of the upper limit of the content of the other structural units or less, compounds other than the compounds from which the structural units A and B are derived Other dihydroxy compounds (hereinafter sometimes referred to as "other dihydroxy compounds") may also be used. Other dihydroxy compounds other than diol compounds having 7 to 50 carbon atoms include linear dihydroxy compounds, dihydroxy compounds having an ether group, dihydroxy compounds having a branched chain, dihydroxy compounds containing a cyclic group, and the like. are mentioned. More specifically, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1, Chain alkyl diols such as 6-hexanediol, side chain alkyl diols such as 2-methyl-1,4-butanediol, 2-methylpropanediol and neopentyl glycol, and cyclic alkyl diols such as cyclohexanedimethanol and isosorbide. be done.
These other dihydroxy compounds may be used singly or in combination of two or more.

<Halogen component>
If halogen components such as chloride ions, bromide ions, and fluoride ions are contained in the raw material compound used as the raw material for the production of PEPCD, it will be involved in the polycarbonate formation reaction and further in the polyurethane formation of the obtained PEPCD. The smaller the content, the better, since it may affect the performance or cause coloration. Usually, the upper limit of the content of the halogen component in the polyether polyol compound, diol compound, and carbonate compound used in the production of the PEPCD of the present invention is usually 10 ppm, preferably 5 ppm, more preferably 10 ppm, preferably 5 ppm, more preferably as a halogen mass with respect to these masses. 1 ppm.
Moreover, these halogen components may be incorporated as an internal structure or terminal structure of PEPCD. In that case, the content is preferably as small as possible, and the mass content of halogen in the PEPCD of the present invention is usually 10 ppm or less, preferably 5 ppm or less, more preferably 1 ppm or less.

<Ratio of raw materials used>
In the production of PEPCD, the amount of the carbonate compound used is not particularly limited, but usually the lower limit is preferably 0.35, more preferably 0.50, and more preferably 0.50, as a molar ratio with respect to 1 mol of the total of the polyether polyol compound and the diol compound. It is preferably 0.60, and the upper limit is preferably 1.00, more preferably 0.98, still more preferably 0.97. If the amount of the carbonate compound used is not more than the above upper limit, the ratio of the PEPCD obtained that does not have a hydroxyl terminal group can be suppressed, and the number average molecular weight can be easily controlled within the 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.

<Transesterification catalyst>
The PEPCD of the present invention is obtained by polycondensing a polyether polyol compound, which is a compound from which the structural unit A is derived, and a diol compound having 7 to 50 carbon atoms, which is a compound from which the structural unit B is derived, and a carbonate compound, by transesterification. can be manufactured by

When producing the PEPCD of the present invention, a transesterification catalyst (hereinafter sometimes referred to as a catalyst) can be used as necessary to promote polymerization.
As the transesterification catalyst, any compound generally considered to have transesterification ability can be used without limitation.

Examples of transesterification catalysts include compounds of long period periodic table (hereinafter simply referred to as "periodic table") Group 1 metals such as lithium, sodium, potassium, rubidium, cesium, etc.; magnesium, calcium, strontium, Compounds of Group 2 metals of the periodic table such as barium; compounds of Group 4 metals of the periodic table such as titanium and zirconium; compounds of Group 5 metals of the periodic table such as hafnium; compounds of group 9 metals of the periodic table such as cobalt; Compounds of Group 12 metals of the periodic table such as zinc; Compounds of Group 13 metals of the periodic table such as aluminum; Compounds of Group 14 metals of the periodic table such as germanium, tin and lead; Group 15 of the periodic table such as antimony and bismuth Metal compounds; compounds of lanthanide metals such as lanthanum, cerium, europium, ytterbium, and the like. Among these, from the viewpoint of increasing the transesterification reaction rate, periodic table group 1 metal compounds, periodic table group 2 metal compounds, periodic table group 4 metal compounds, periodic table group 5 metal compounds, A compound of a metal of Group 9 of the periodic table, a compound of a metal of Group 12 of the periodic table, a compound of a metal of Group 13 of the periodic table, a compound of a metal of Group 14 of the periodic table, a compound of a metal of Group 1 of the periodic table, a compound of a metal of Group 1 of the periodic table, Compounds of Group 2 metals are more preferred, and compounds of Group 2 metals of the periodic table are even more preferred. Among the compounds of Group 1 metals of the periodic table, lithium, potassium and sodium compounds are preferred, lithium and sodium compounds are more preferred, and sodium compounds are even more preferred. Among the compounds of Group 2 metals of the periodic table, compounds of magnesium, calcium and barium are preferred, compounds of calcium and magnesium are more preferred, and compounds of magnesium are even more preferred. These metal compounds are mainly used as hydroxides, salts and the like. Examples of salts when used as salts include halide salts such as chlorides, bromides and iodides; carboxylates such as acetates, formates and benzoates; sulfonates such as romethanesulfonic acid; phosphorus-containing salts such as phosphates, hydrogen phosphates and dihydrogen phosphates; acetylacetonate salts; Catalyst metals can also be used as alkoxides such as methoxides and ethoxides.

Among these, preferably, at least one metal selected from group 2 metals of the periodic table, such as acetate, nitrate, sulfate, carbonate, phosphate, hydroxide, halide, acetylacetonate salt, Alkoxides are used, more preferably acetates and acetylacetonates of Group 2 metals of the periodic table are used, and more preferably acetates, carbonates and acetylacetonates of magnesium and calcium are used, and from the viewpoint of reactivity Most preferably magnesium acetylacetonate is used.

The catalyst used for the production of PEPCD of the present invention contains at least one metal (M) selected from zinc and metals of Group 2 of the periodic table and at least one compound represented by the following formula (1). A composition (hereinafter sometimes referred to as "catalyst composition (1)"), or at least one salt represented by the following formula (2) and a composition containing them as precursors (hereinafter referred to as "catalyst Composition (2)” may be mentioned as a preferred one.

(In the formula, R ₁ and R ₃ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom and has an oxygen atom. may
R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, and the hydrocarbon group may be substituted with a halogen atom or may have an oxygen atom.
M represents zinc or a metal of group 2 of the periodic table and n=2. )

The stable form of zinc or a group 2 metal compound of the periodic table usually includes the form of a salt represented by the above formula (2). Therefore, it is effective to use the catalyst composition (2). However, when it is difficult to obtain a salt, or when it is desired to arbitrarily adjust the composition ratio of zinc or a Group 2 metal of the periodic table and the compound represented by the above formula (1), the metal compound and the above A catalyst composition (1) with a compound having a structure represented by formula (1) may also be used.
Moreover, the catalyst composition (1) and the catalyst composition (2) may be used in combination.

As a method for preparing the catalyst composition (2), for example, as shown in the above formula (3), using a method similar to the method for synthesizing a metal acetylacetone salt, a metal halide salt and A method of preparing catalyst composition (2) by reacting with an acetylacetone analogue, or preparing catalyst composition (2) by exchanging a metal alkoxide with an acetylacetone analogue as shown in the following formula (4) However, it is not limited to this.

(In formulas (3) and (4) above, R ₁ , R ₂ , R ₃ , M and n are as defined in formula (2) above, X is a halogen atom, and R ₅ is an arbitrary hydrocarbon group. is.)

The catalyst compositions (1) and (2) may be prepared in advance and mixed with a polyether polyol compound, a diol compound having 7 to 50 carbon atoms and a carbonate compound as raw material monomers, and each component may be mixed with an arbitrary You may mix with a raw material monomer in order.

In addition to these catalyst compositions (1) and (2), a basic compound such as a transition metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound is used in combination. is also possible.

In the above formulas (1) and (2), each of R ₁ and R ₃ is independently a monovalent is preferably a hydrocarbon group, which may be substituted with a halogen atom or may have an oxygen atom, and may be a monovalent hydrocarbon group having 1 to 7 carbon atoms. It is more preferable from the viewpoints of easiness of interaction with the metal (M) inside, solubility as a catalyst composition, thermal stability and low coloration. R ₂ is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms or a halogen atom which may be substituted with a halogen atom or may have an oxygen atom, and is substituted with a halogen atom. It may be a monovalent hydrocarbon group having 1 to 7 carbon atoms or a halogen atom, which may have an oxygen atom, to facilitate interaction with the metal (M) in the catalyst composition. It is more preferred from the viewpoints of solubility in the sheath organic solvent and raw material monomers, acid-base strength, low colorability, and the like. Moreover, when R ₁ to R ₃ are the above-mentioned suitable functional groups, the resulting PEPCD has high solubility and low coloration, so a low-coloration PEPCD with no turbidity can be obtained.

R ₁ and R ₃ are specifically methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, phenyl group, benzyl group, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, monochloromethyl group, dichloromethyl group, trichloromethyl group and the like, and among these, methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, phenyl group, benzyl group, trifluoromethyl group and trichloromethyl group are preferred. Although R ₁ and R ₃ may be the same or different, they are preferably the same from the viewpoint of ease of synthesis and availability.

Further, R ₂ specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group and a hexyl group. group, cyclohexyl group, phenyl group, benzyl group, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, monochloromethyl group, dichloromethyl group, trichloromethyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. among these, especially methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, phenyl group, benzyl group, trifluoromethyl group , a trichloromethyl group, a fluorine atom and a chlorine atom are preferred.

As the metal (M) selected from zinc and Group 2 metals of the periodic table, zinc, magnesium, calcium and barium are particularly preferred from the viewpoint of reactivity, zinc and magnesium are more preferred, and magnesium is most preferred.

The amount of such a catalyst to be used is usually 10 μmol or more and 1500 μmol per 1 mol of the total of the starting polyether polyol compound and the diol compound having 7 to 50 carbon atoms and other dihydroxy compounds that are optionally used. The following are preferable, and the lower limit is more preferably 20 μmol, still more preferably 30 μmol, and particularly preferably 50 μmol. 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 distillate of the 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. Moreover, in order to reduce the 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, the diol compound having 7 to 50 carbon atoms, or other dihydroxy compound for the production of PEPCD is n moles of the carbonate compound per n moles of the polyether polyol compound. Ether polyol compounds, diol compounds having 7 to 50 carbon atoms or other dihydroxy compounds (n+1) moles are preferably 1.1 to 1.3 times the theoretical molar ratio in consideration of losses. The polyether polyol compound, the diol compound having 7 to 50 carbon atoms, or other dihydroxy compound may be charged at the initial stage of the reaction, or may be added during the reaction.

<Deactivation of catalyst>
As described above, when a catalyst is used in the transesterification reaction, the catalyst usually remains in the obtained PEPCD composition, and the residual metal catalyst may make it impossible to control the reaction during the polyurethane formation reaction. There is In order to suppress the effect of this residual catalyst, a catalyst deactivator, such as an acidic or decomposed to acidic compound such as a phosphorus-based or sulfur-based compound, may be added in approximately the same molar amount as the catalyst used. Furthermore, after the addition, the transesterification catalyst can be efficiently inactivated by heat treatment as described later.

Examples of the compound used for deactivating the transesterification catalyst (hereinafter sometimes referred to as a catalyst deactivator) include inorganic phosphoric acid such as phosphoric acid and phosphorous acid, dibutyl phosphate, and tributyl phosphate. , trioctyl phosphate, triphenyl phosphate, triphenyl phosphite and other organic phosphates, sulfonic acids, sulfonate esters, and the like. These may be used individually by 1 type, and may use 2 or more types together.

The amount of the catalyst deactivator used is not particularly limited, but as described above, it may be approximately equimolar to the used ester exchange catalyst, specifically, per 1 mol of the used ester exchange catalyst The upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.8 mol, more preferably 1.0 mol. When the catalyst deactivator is used in an amount less than this, the deactivation of the transesterification catalyst in the reaction product is insufficient, and when the obtained PEPCD composition is used as a raw material for producing polyurethane, for example, the PEPCD In some cases, the reactivity of the composition to isocyanate groups cannot be sufficiently reduced. Also, if a catalyst deactivator exceeding this range is used, the obtained PEPCD composition may be colored.

Deactivation of the transesterification catalyst by adding a catalyst deactivator can be carried out at room temperature, but is more efficient if treated with heat. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 150°C, more preferably 120°C, and still more preferably 100°C, and the lower limit is preferably 50°C, more preferably 60°C, and still more preferably. is 70°C. If the temperature is lower than this, deactivation of the transesterification catalyst takes a long time and is not efficient, and the degree of deactivation may be insufficient. On the other hand, at temperatures above 150° C., the resulting PEPCD composition may become colored.
Although the reaction time with the catalyst deactivator is not particularly limited, it is usually 1 to 5 hours.

<Refinement>
After the polycondensation reaction, impurities whose terminal structure is an alkoxy group in the PEPCD composition, impurities whose terminal structure is an aryloxy group, monohydroxy compounds or dihydroxy compounds such as phenols, alcohols and diols, carbonate compounds, by-produced light Purification can be carried out for the purpose of removing the cyclic carbonate of the boiling point, the added catalyst, and the like. For purification at that time, a method of distilling off light boiling compounds by distillation can be adopted. Specific methods of distillation include reduced-pressure distillation, steam distillation, thin-film distillation, and the like, but the thin-film distillation is particularly effective. In addition, in order to remove water-soluble impurities, washing may be performed with water, alkaline water, acidic water, a chelating agent-dissolved solution, or the like. In that case, the compound to be dissolved in water can be arbitrarily selected.

The conditions for thin film distillation are not particularly limited, but the upper limit of the temperature during thin film distillation is preferably 250°C, more preferably 200°C. Also, the lower limit is preferably 120°C, more preferably 150°C.
By setting the lower limit of the temperature during thin-film distillation to the above value, the effect of removing light-boiling components becomes sufficient. Further, by setting the upper limit to 250° C., it is possible to prevent the PEPCD composition obtained after thin-film distillation from being colored.

The upper limit of the pressure during thin film distillation is preferably 500 Pa, more preferably 150 Pa, and even more preferably 50 Pa. By setting the pressure during thin-film distillation to the above upper limit or less, a sufficient effect of removing light-boiling components can be obtained.

In addition, the upper limit of the temperature for keeping the PEPCD composition just before the thin film distillation is preferably 250°C, more preferably 150°C. Also, the lower limit is preferably 80°C, more preferably 120°C.
By setting the temperature at which the PEPCD composition is kept warm immediately before thin film distillation to the lower limit or higher, it is possible to prevent the fluidity of the PEPCD composition immediately before thin film distillation from being lowered. On the other hand, by making it equal to or less than the above upper limit, it is possible to prevent the PEPCD composition obtained after thin-film distillation from being colored.

<Metal content of PEPCD composition>
As described above, when a catalyst is used to produce PEPCD, the catalyst used remains as a metal in the resulting PEPCD. That is, PEPCD is obtained as a PEPCD composition containing a metal. The metal content in the PEPCD composition is preferably 1 ppm by mass or more and 500 ppm by mass or less.
If the metal content exceeds the above upper limit, the metal derived from the catalyst will adversely affect the polyurethane-forming reaction, making it difficult to control the polyurethane-forming reaction. On the other hand, in order to make the metal content less than the above lower limit, deactivation of the catalyst and purification of PEPCD are excessively burdened, which is not industrially preferable. The metal content in the PEPCD composition is more preferably 3 to 300 mass ppm, more preferably 5 to 100 mass ppm.
Here, the PEPCD composition is generally referred to as "PEPCD", which is obtained by producing PEPCD by the method described above, and subjecting it to deactivation treatment and purification of the catalyst as necessary.
In the present invention, in order to indicate the amount of residual metal in PEPCD, a composition containing a metal, rather than a composition consisting only of PEPCD, is referred to as a "PEPCD composition" for convenience. , PEPCD and residual catalytic metals.

The metal in this PEPCD composition is the above-mentioned suitable catalytic metal, preferably at least one selected from the group consisting of zinc and Group 2 metals of the periodic table.

[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 water-based 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 producing an aqueous polyurethane emulsion using the PEPCD of the present invention, at least one hydrophilic functional group and at least A compound having two isocyanate-reactive groups is mixed to form a prepolymer, and a water-based polyurethane emulsion is formed through a process of neutralization and chlorination of hydrophilic functional groups, an emulsification process by adding water, and a chain extension reaction process. can be done.

As used herein, the hydrophilic functional group of compounds 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, neutralized with an alkaline group. is a possible 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. It doesn't matter if you are.

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 '-dimethylol valeric 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 are neutralized with amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine and triethanolamine, and alkaline compounds such as sodium hydroxide, potassium hydroxide and ammonia. be able to.

When producing a water-based polyurethane emulsion, the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is limited to the lower limit of is preferably 1% by mass, more preferably 5% by mass, and still more preferably 10% by mass, based on the total weight of PEPCD and other polyols. On the other hand, the upper limit is preferably 50% by mass, more preferably 40% by mass, still more preferably 30% by mass.

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 an aqueous polyurethane emulsion without a solvent, the upper limit of the number average molecular weight obtained from the hydroxyl value of the PEPCD to be used is preferably 5000, more preferably 4500, and still more preferably 4000. . 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 water-based polyurethane emulsions, anionic interfaces represented by higher fatty acids, resin acids, acidic fatty alcohols, sulfate esters, higher alkyl sulfonates, alkylaryl sulfonates, sulfonated castor oil, sulfosuccinates, etc. active agents, cationic surfactants such as primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, pyridinium salts, or mixtures of ethylene oxide and long-chain fatty alcohols or phenols A nonionic surfactant represented by a known reaction product may be used in combination to maintain emulsion stability.

Further, when making a water-based polyurethane emulsion, water is mechanically mixed with high shear in the presence of an emulsifier to the organic solvent solution of the prepolymer, if necessary, without the neutralization and chlorination step, to produce the emulsion. can also

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 less 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 has high flexibility and hydrolysis resistance because the PEPCD contains the structural unit B derived from a diol compound having 7 to 50 carbon atoms. It can be used more effectively than conventional water-based polyurethane emulsions using polycarbonate diol or PTMG as agents. In particular, compared to conventional water-based polyurethane emulsions using PTMG, since it has a hydrophilic carbonate group, it has a good affinity for water and can use the PEPCD of the present invention with a higher molecular weight. A soft feel and transparency can be imparted by a film, synthetic leather, artificial leather, or the like. In addition, since the water-based polyurethane emulsion is excellent in dispersibility in water, the degree of freedom in molecular design of the water-based polyurethane emulsion is increased.

The storage stability of the polyurethane solution and water-based polyurethane emulsion produced using the PEPCD of the present invention using an organic solvent and/or water depends on the concentration of polyurethane in the solution or emulsion (hereinafter referred to as "solid content concentration"). ) is adjusted to 1 to 80% by mass, stored under specific temperature conditions, and the presence or absence of change in the solution or emulsion can be visually measured. For example, a polyurethane solution (N,N-dimethylformamide/toluene mixed solution, solid content concentration 30 mass %), 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.

[Polyurethane]
The polyurethane of the present invention is produced using the PEPCD of the present invention and contains structural units derived from the PEPCD of the present invention.
The polyurethane of the present invention is produced by an addition polymerization reaction of raw materials containing the PEPCD of the present invention and a compound having a plurality of isocyanate groups (hereinafter sometimes referred to as "polyisocyanate compound" or "polyisocyanate"). be done.
Generally, the polyurethane of the present invention can be produced by a normal polyurethane-forming 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.
Alternatively, the PEPCD of the present invention and an excess polyisocyanate compound are first reacted to produce a prepolymer having terminal isocyanate groups, and a chain extender is used to increase the degree of polymerization to produce the polyurethane of the present invention. be able to.

<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, 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. Aliphatic diisocyanate compounds; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and 1,3- Alicyclic diisocyanate compounds such as bis(isocyanatomethyl)cyclohexane; xylylene diisocyanate, 4,4'-diphenyl diisocyanate, toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate), m-phenylene diisocyanate, p -phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3, aromatic diisocyanate compounds such as 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 from the viewpoint of reactivity with PEPCD and high curability of the resulting polyurethane, and 4,4'-diphenylmethane diisocyanate is particularly preferred because it is industrially available in large quantities at low cost. (hereinafter sometimes referred to as "MDI"), toluene diisocyanate (TDI), and xylylene diisocyanate are preferred.

<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 include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,9-nonanediol. , 1,10-decanediol, 1,12-dodecanediol, and other linear diols; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-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, dimer diol, and other branched diols 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; xylylene glycol; diols having aromatic groups such as 1,4-dihydroxyethylbenzene and 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane and pentaerythritol; N-methylethanolamine and N-ethylethanol hydroxyamines such as amine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxy ethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4′-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tri polyamines such as diamine, 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, has excellent flexibility and elastic recovery due to excellent phase separation between the soft segment and the hard segment of the polyurethane obtained, and is industrially available in large quantities at low cost. -Butanediol, 1,6-hexanediol are preferred.

<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.
These chain terminators include aliphatic monools having one hydroxyl group such as methanol, ethanol, propanol, butanol and hexanol, diethylamine, dibutylamine, n-butylamine, monoethanolamine and diethanolamine having one amino group. , and morphopholine.
These may be used individually by 1 type, and may use 2 or more types together.

<Catalyst>
In the polyurethane-forming reaction for producing the polyurethane of the present invention, an amine-based catalyst such as triethylamine, N-ethylmorpholine and triethylenediamine, or an acid-based catalyst such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid and sulfonic acid, and trimethyltin laurate. , dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate, and other tin-based compounds, and furthermore, known urethane polymerization catalysts typified by organic metal salts such as titanium-based compounds can also be used. 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. It is also possible to mix PEPCD different from the present invention. Among these, polyether polyol and PEPCD are preferable, and polytetramethylene ether glycol is particularly preferable because it can obtain urethane physical properties close to those of PEPCD. Here, the mass ratio of the PEPCD of the present invention to the combined mass 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. If the mass 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 obtained polyurethane will be good.

<Method for producing polyurethane>
As a method for producing the polyurethane of the present invention using the above-mentioned reaction agent, production methods generally used experimentally or industrially can be used.
An example thereof is a method of mixing and reacting the PEPCD of the present invention, other polyols, polyisocyanate compounds and chain extenders used as necessary (hereinafter sometimes referred to as "one-step method"). Or, first, the PEPCD of the present invention, other polyols and polyisocyanate compounds used as necessary are reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer and a chain extender are reacted. (hereinafter sometimes referred to as the “two-stage method”), etc.

In the two-step method, the PEPCD of the present invention and other polyols are preliminarily reacted with 1 equivalent or more of a polyisocyanate compound to prepare an isocyanate intermediate at both ends corresponding to the soft segment of the polyurethane. It is. 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. is useful.

(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 the sum of the total number of hydroxyl groups of the PEPCD of the present invention and other polyols, the number of hydroxyl groups and the number of amino groups of the chain extender was set to 1 equivalent. When the is 2.0 equivalents, more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents.

If the amount of the polyisocyanate compound used is less than the above upper limit, unreacted isocyanate groups may cause side reactions, resulting in the resulting polyurethane becoming too viscous, making handling difficult and flexibility impaired. If it is at least the above lower limit, the molecular weight of the polyurethane tends to be sufficiently large and sufficient strength can be obtained.

In addition, 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 1 equivalent, the lower limit is preferably is 0.7 equivalents, more preferably 0.8 equivalents, 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 further Preferably 1.5 equivalents, 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 be easily soluble in a solvent and easy to process. Hardness, elasticity recovery performance and elasticity retention performance are obtained, and heat resistance is also improved.

(two-step method)
The two-step method, also called a prepolymer method, mainly includes the following methods.
(a) The PEPCD of the present invention, other polyols, and an excess polyisocyanate compound are added in advance to an amount in which the reaction equivalent ratio of polyisocyanate compound/(PEPCD of the present invention and other polyols) exceeds 1 to 10. A method for producing a polyurethane by reacting at 0 or less to produce a prepolymer having an isocyanate group at the molecular chain end and then adding a chain extender thereto.
(b) A polyisocyanate compound and an excess of the PEPCD of the present invention and other polyols are added in advance to a reaction equivalent ratio of polyisocyanate compound/(PEPCD of the present invention and other polyols) of 0.1 or more to 1.5. A method of producing a prepolymer having a hydroxyl group at the molecular chain end by reacting at less than 0, and then reacting this with a polyisocyanate compound having an isocyanate group at the 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) First, a polyisocyanate compound, the PEPCD of the present invention, and other polyols are directly reacted without using a solvent 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 elongation reaction, the chain elongating agent is dissolved in the solvent, or the prepolymer and the chain elongating agent are dissolved in the solvent at the same time. It is important to obtain
The amount of the polyisocyanate compound used in the two-step method (a) is not particularly limited, but 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 is 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, still more preferably It is in the range of 3.0 equivalents.

If the amount of the polyisocyanate compound used is less than 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. can be sufficiently increased to increase strength and thermal stability.
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 equivalents per equivalent of the number of isocyanate groups contained in the prepolymer. 8 equivalents, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, and still more preferably 2.0 equivalents.

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 used in preparing the prepolymer having a hydroxyl group at the end is not particularly limited, but the amount of the total hydroxyl groups of the PEPCD of the present invention and the other polyols is As the number of isocyanate groups when the number is 1 equivalent, 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 equivalents, still more preferably 0.97 equivalents.

If the amount of the polyisocyanate compound used is at least the above lower limit, the process to obtain the desired molecular weight in the subsequent chain extension reaction tends to be not too long and the production efficiency tends to be good. It is possible to prevent the flexibility of the resulting polyurethane from being too high and the productivity from being poor due to poor handling.
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 and other polyols used in the prepolymer is 1 equivalent, the equivalent of the isocyanate group used in the prepolymer is added. As the total equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, and the upper limit is preferably less than 1.0 equivalents, more preferably 0.99 equivalents, More preferably, it is in the range of 0.98 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 rapidly, 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. They may be used together. Examples of stabilizers include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N,N'-di-2-naphthyl-1,4-phenylenediamine, tris(dinonylphenyl)phosphite, and the like. and may be used singly or in combination of two or more. 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 to the polyurethane of the present invention. Agents can be added and mixed 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, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl Phosphorus compounds such as pentaerythritol diphosphite and dialkylbisphenol A diphosphite; phenol derivatives, especially hindered phenol compounds; Compounds containing sulfur; tin-based compounds such as tin malate, dibutyltin monoxide, and the like can be used.

Specific examples of hindered phenol compounds include "Irganox1010" (trade name: manufactured by BASF Japan Ltd.), "Irganox1520" (trade name: manufactured by BASF Japan Ltd.), "Irganox245" (trade name: manufactured by BASF Japan Ltd.). ) and the like.
Phosphorus compounds include "PEP-36", "PEP-24G", "HP-10" (all trade names: manufactured by ADEKA Corporation), "Irgafos 168" (manufactured by BASF Japan Ltd.), etc. is mentioned.

Specific examples of sulfur-containing compounds include thioether compounds such as dilaurylthiopropionate (DLTP) and distearylthiopropionate (DSTP).
Examples of light stabilizers include benzotriazole-based compounds and benzophenone-based compounds. ”, “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.).

Colorants 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; Organic pigments such as anthraquinone-based, thioindigo-based, dioxazone-based, and phthalocyanine-based pigments can be used.

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.

As for the amount of these additives added, the lower limit is preferably 0.01% by mass, more preferably 0.05% by mass, and still more preferably 0.1% by mass, and the upper limit is preferably 10% by mass, based on the polyurethane. % by mass, more preferably 5% by mass, still more preferably 1% by mass. 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. It is more preferably 10,000 to 300,000, further preferably 120,000 to 300,000. 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 solvent resistance and good flexibility and mechanical strength, it can be used for foams, elastomers, elastic fibers, paints, fibers, pressure-sensitive adhesives, adhesives, flooring materials, sealants, medical materials, It can be widely used for artificial leather, synthetic leather, coating agents, water-based polyurethane coatings, active energy ray-curable polymer compositions, and the like.

In particular, when the polyurethane of the present invention is used for applications such as artificial leather, synthetic leather, moisture-permeable waterproof fabric, waterproof fabric, water-based polyurethane, adhesives, elastic fibers, medical materials, flooring materials, paints, coating agents, etc. It has a good balance of solvent resistance, flexibility, and mechanical strength, so it is highly durable and flexible enough in areas where it comes in contact with human skin, or where cosmetic chemicals or alcohol for disinfection are used. In addition, it is possible to impart good properties such as being strong against physical impacts and the like. 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 applications include rolling rolls, paper manufacturing rolls, office equipment, rolls such as pretension rolls, solid tires for forklifts, automobile vehicle nutrams, trolleys, trucks, casters, etc. Industrial products include conveyor belt idlers and guides. Rolls, pulleys, steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, etc. 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. The method of foaming or forming a polyurethane elastomer may be, for example, chemical foaming using water or mechanical foaming such as mechanical flossing. Similarly, slabs, flexible foams obtained by molding, and the like can be mentioned.
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. mentioned.

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-pack paints, blocked isocyanate-based solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, ultraviolet-curable paints, water-based urethane paints, and the like. Paints for plastic bumpers, strippable paints, coating agents for magnetic tapes, overprint varnishes for floor tiles, flooring materials, paper, wood grain printing films, etc., varnishes for wood, coil coats for high processing, optical fiber protective coatings, solder resists, metals It can be applied to printing top coats, vapor deposition base coats, white coats for food cans, and the like.

The polyurethane of the present invention can also be applied as a pressure-sensitive adhesive or adhesive to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, and the like. can also be used.
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 pesticides, polymer cement mortar, resin mortar, rubber chip binders, recycled foams, glass fiber sizing, and the like. Available.

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 and caulking for concrete rammed walls, induced joints, around sashes, wall-type PC (Precast Concrete) joints, ALC (Autoclaved Light-weight Concrete) joints, board joints, composite glass sealants, It can be used for insulating sash sealants, automotive sealants, roof tarpaulins, etc.

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

By modifying the terminal of the polyurethane of the present invention, it 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. can.

[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 permeation 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, although a moisture-permeable waterproof fabric using polycarbonate diol can exhibit moisture permeability by forming micropores by a wet manufacturing method, it cannot have sufficient moisture permeability when made into a film. 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, a water pressure resistance of 10,000 mm or more, and further 20,000 mm or more can be achieved. 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 for the non-porous type, for example, release paper is coated with a polyurethane solution for the skin layer to which an antiblocking agent or pigment is added to prevent the films from sticking together, and then 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 provides 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. Obtained by processing. The features of CNF are light (specific gravity 1.3 to 1.5 g/cm ³ , about 1/5 that of steel), strength (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 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 a reinforcing effect efficiently, 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 automotive interiors are usually painted for the purpose of concealing and protecting molding defects and imparting design properties. Because they are used in environments where they are touched by human hands and exposed to strong direct sunlight, high light resistance, heat resistance, chemical resistance, and scratch resistance are required, as well as good touch and advanced design. be done. 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. is possible. 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, coating films must have chemical resistance to acids, alkalis, oils and fats, spray paintability, low-temperature drying properties, and scratch resistance during transportation due to packaging materials. be done.
Polyurethanes using the PEPCD of the present invention have excellent resistance by controlling the concentration of carbonate bonds/ether bonds, adjusting the molecular weight and number of functional groups, selecting diisocyanate and chain extender, adjusting hard segment content and molecular weight. It can be used as a main agent for paints for housings of home appliances because of its chemical resistance, adhesiveness, and scratch resistance.

<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 produce 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, and by controlling the number of functional groups and optimizing the concentration of ether bonds, the re-solubility is improved, and it is introduced by urethane bonds and a diamine-based chain extender. By controlling the concentration of the urea bond, blocking on the back surface of the film can be suppressed, and it can be used as a binder resin for gravure inks 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 less irritating, weak solvent-based, and more eco-friendly aqueous solutions are 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 it is used as a water-based paint, the surface of the coating film has less unevenness. A high gloss appearance is 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, the adhesion of lipophilic contaminants is weakened to form a low-staining coating film that 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 a prepolymer obtained from polypropylene glycol and diisocyanate with an aromatic diamine 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.
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. It can be used as a base agent for coating film waterproofing materials.

<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 sealants are required to have barrier properties, heat resistance, hydrolysis resistance, transparency, light resistance, adhesiveness, flexibility, mechanical strength and the like.
The polyurethane using the 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 improved. By adjusting the content, other required performances can be adjusted in a well-balanced manner, and it can be used as a sealing agent resin for light-emitting elements of flat panel displays, solar cell panels, and the like.

<Ultra-low hardness, low compression set, non-foam resin>
Polyurethanes with the PEPCD of the present invention can be used in ultra-low hardness, low compression set non-foam resins. In order to lower 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 be polyfunctionalized, and PPG has low reactivity due to the terminal OH group being bound to a secondary carbon and is olefinized at a certain rate by dehydration. unusable for
As long as the PEPCD of the present invention uses a polyfunctional alcohol having an OH group bonded to a primary carbon as a raw material, an OH group bonded to a highly reactive primary carbon always remains at the end, so complete cross-linking is achieved while increasing the molecular weight between cross-links. Structured polyurethane is obtained, and because it has high weather resistance derived from polycarbonate, it is a material for various special rolls used in printers and copiers as a non-foam molded product with high durability, flexibility comparable to foam, and compression set. is valid as

<Polyurethane flexible foam>
Polyurethanes using the PEPCD of the present invention can be used in flexible polyurethane foams. In order to lower 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 be polyfunctionalized, and PPG has low reactivity due to the terminal OH group being bound to a secondary carbon and is olefinized at a certain rate by dehydration. unusable for
As long as the PEPCD of the present invention uses a polyfunctional alcohol having an OH group bonded to a primary carbon as a raw material, an OH group bonded to a highly reactive primary carbon always remains at the end, so complete cross-linking is achieved while increasing the molecular weight between cross-links. Polyurethane with a structure is obtained, and since it has high weather resistance derived from polycarbonate, various special rolls used in printers and copiers as foam moldings with high durability, flexibility, low compression set, and high impact resilience, It is effective as a material for shoe soles, urethane bats, sleepers for railway rails, and anti-vibration materials. This characteristic is particularly noticeable in high-density foams having a foaming density of 0.1 g/cc or more.

[Urethane (meth)acrylate resin]
The PEPCD of the present invention is subjected to an addition reaction with a polyisocyanate and a hydroxyalkyl (meth)acrylate to obtain a urethane (meth)acrylate oligomer (hereinafter sometimes referred to as "the urethane (meth)acrylate oligomer of the present invention"). can be manufactured. When other raw material compounds such as a polyol and a chain extender are used in combination, the urethane (meth)acrylate oligomer can be produced by subjecting the polyisocyanate to an addition reaction with 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. It can be used as a raw material for mold coatings, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating compositions, and the like.

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, usable hydroxyalkyl (meth)acrylates are compounds having both one or more hydroxyl groups and one or more (meth)acryloyl groups, as typified by 2-hydroxyethyl (meth)acrylate. There is no particular limitation, if any. 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 includes an active energy ray-reactive monomer other than the urethane (meth)acrylate-based oligomer of the present invention, an active energy ray-curable oligomer, and polymerization. Initiators and photomultipliers as well as other additives and the like may be mixed.

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 that is excellent in stain resistance and protection against general household contaminants such as ink and ethanol. be.
Laminates obtained by using the cured film as a film on various substrates have excellent design and surface protection properties, and can be used as a paint substitute film. And it can be effectively applied to various members such as home appliances.

[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 with known polycarbonate polyols, the polyether carbonate ester 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. It becomes an elastomer and can be suitably used for various molding materials such as fibers, films and sheets, such as elastic yarns, 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 period of time when exposed to an active energy ray such as ultraviolet rays. It is possible to impart excellent properties such as 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 method〕
Evaluation methods for PEPCD and polyurethane obtained in the following examples and comparative examples are as follows.

[Hydroxyl value and number average molecular weight of PEPCD]
The hydroxyl value of PEPCD was measured by a method using an isocyanating reagent according to 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]
The mass ratio of structural unit A and structural unit B in PEPCD was 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 structural unit A and structural unit B was determined. This molar ratio was converted into a mass ratio using the molecular weight of each structural unit.
If 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. 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. Let the mass ratio of the structural unit A and the structural unit B hydrolyzate obtained here be the mass ratio of the structural unit A and the structural unit B. When PEPCD is composed only of structural unit A and structural unit B, the mass ratio of structural unit A is calculated by subtracting the mass ratio of structural unit B from the total.

[Terminal alkoxy/aryloxy ratio of PEPCD]
PEPCD was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (ECZ-400 manufactured by JEOL Ltd.) was measured, and calculated 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 ratio of terminal alkoxy/aryloxy in this ¹ H-NMR measurement method is 0.01%.

[Metal content in PEPCD]
When a metal catalyst that does not volatilize or decompose under the PEPCD reaction conditions is used, the metal content concentration (ppm) corresponds to the ratio of the metal catalyst amount (g) used in the charge to the PEPCD yield (g).
As an analysis method, the following method (ICP-MS) was used.
0.2 g of the PEPCD composition was precisely weighed into a Kjeldahl flask and subjected to wet decomposition using concentrated sulfuric acid and concentrated nitric acid. After cooling to room temperature, the solution was made to a constant volume using pure water and measured with ICP-MSELEMENT2 (manufactured by Thermo Fisher Scientific) to calculate the metal concentration (mass ppm) in the PEPCD composition.

[Glass transition temperature (Tg) of PEPCD]
About 10 mg of PEPCD was sealed in an aluminum pan, and using DSC7 (manufactured by PerkinElmer Japan), in a helium atmosphere, at a rate of 10 ° C. per minute from 30 ° C. to 100 ° C., at a rate of 10 ° C. per minute from 100 ° C. to - The temperature was increased and decreased from −130° C. to 100° C. at a rate of 20° C. per minute at 130° C., and the inflection point during the second temperature increase was taken as the glass transition temperature (Tg).

[Melt viscosity of PEPCD]
After about 1 g of PEPCD was heated to 40° C. to melt, the melt viscosity was measured at 40° C. using an E-type viscometer (DV-II+Pro manufactured by BROOKFIELD, cone: CPE-52).

[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 is injected, and the weight average molecular weight (Mw) of the polyurethane is calculated in terms of standard polystyrene. and the number average molecular weight (Mn) were measured.

[Polyurethane Room Temperature Tensile Test]
The polyurethane solutions produced in Examples and Comparative Examples were applied to a fluororesin sheet (fluororesin tape Nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) with a 9.5 mil applicator, and the solution was applied at 50° C. for 5 hours. , and vacuum conditions of 80° C. for 15 hours to produce a polyurethane film (thickness: 50 to 100 μm). A test piece of 1 cm x 15 cm is cut out from this polyurethane film (thickness 50 to 100 μm), and this test piece is subjected to a tensile tester (manufactured by Orientec, product name “Tensilon UTM-III-100”) according to JIS K6301 (2010). ”), a tensile test was performed at a chuck distance of 50 mm, a tensile speed of 500 mm / min, a temperature of 23 ° C., and a relative humidity of 55%. % modulus (hereinafter sometimes referred to as "100% M") was measured. The flexibility is excellent when the 100% modulus (100% M) is 10 MPa or less, more preferably 8 MPa or less, and even more preferably 6 MPa or less. In addition, elongation (elongation at break) and stress (strength at break) when the test piece was broken were also measured. The greater the elongation at break and the higher the strength at break, the better the flexibility and mechanical strength. For use as a high-strength elastomer, the breaking elongation is preferably 300% or more, particularly 400% or more, especially 500% or more, and the breaking strength is preferably 25 MPa or more, more preferably 30 MPa or more, and further preferably 34 MPa or more. , 36 MPa or more are particularly preferred.

[Polyurethane low temperature tensile test]
The above-described polyurethane test piece was placed in a constant temperature bath [manufactured by Shimadzu Corporation, product name "THERMOSTATIC CHAMBER TCR2W-200T"] set at -10 ° C. so that the distance between chucks was 50 mm, and the temperature was set at -10 ° C. After standing for 3 minutes, a tensile test was performed at a tensile speed of 500 mm / min using a tensile tester [manufactured by Shimadzu Corporation, product name "Autograph AG-X 5 kN"]. 100% modulus (100% M) and stress and elongation at break were measured.
The 100% modulus (100M) at −10° C. is preferably 20 MPa or less, more preferably 15 MPa or less, still more preferably 10 MPa or less from the viewpoint of low-temperature flexibility. If the 100% modulus at −10° C. exceeds the above upper limit, the flexibility, impact resistance, and flex resistance at low temperatures may be insufficient, or handling properties such as workability may be impaired. In addition, the elongation at break at -10°C is preferably 350% or more, particularly 400% or more, particularly preferably 450% or more, and the breaking strength is preferably 40 MPa or more, more preferably 50 MPa or more, and further preferably 60 MPa or more. .
Polyurethanes using the PEPCD of the present invention have good low-temperature properties. Low-temperature properties are flexibility, impact resistance, flex resistance, and durability at low temperatures, which are measured by the above-mentioned low-temperature tensile test. It can be evaluated by measured tensile elongation at break, breaking strength and 100% modulus.

[Polyurethane wet heat condition test]
A polyurethane test piece (10 mm wide, 100 mm long, and approximately 50 μm thick strip) manufactured in the same manner as the polyurethane tensile test was placed in a thermo-hygrostat (Yamato Scientific IH401) at a temperature of 70° C. It was stored at a relative humidity of 95% for 7 days, and a room temperature tensile test was performed on the polyurethane test piece before and after this storage to measure the elongation at break and the strength at break.
It can be evaluated that the higher the breaking strength after the moist heat test, the higher the moist heat resistance of the polyurethane, that is, the better the hydrolysis resistance. For use as an elastomer with high resistance to heat and humidity, the breaking strength after a heat and humidity test for 7 days is preferably 40 MPa or higher, more preferably 42 MPa or higher, even more preferably 44 MPa or higher, and particularly preferably 46 MPa or higher. In addition, the ratio of the strength after the 7-day wet heat test to the strength before the wet heat test is preferably high, and the ratio is preferably 400% or more, more preferably 500% or more, and even more preferably 600% or more. In addition, it is preferable that the ratio of the strength after the wet heat test for 7 days to the strength before the wet heat test is higher from the viewpoint of durability under wet heat conditions, and the ratio is preferably 80% or more, more preferably 85% or more. 90% or more is even more preferable.

[Compound abbreviation]
Abbreviations of compounds in Examples and Comparative Examples are as follows.
PTMG-1: hydroxyl value 510.0 mg-KOH / g, number average molecular weight 220
Polyoxytetramethylene ether glycol EC: Ethylene carbonate Mitsubishi Chemical Co., Ltd. Mg (acac) ₂ : Magnesium (II) acetylacetonate Tokyo Chemical Industry Co., Ltd. BEPD: 2-butyl-2-ethyl-1,3-propanediol Tokyo Chemical Industry Co., Ltd. 1,10DD: 1,10-decanediol Tokyo Chemical Industry Co., Ltd. (derived from plants)
DMD: Dimer Diol Croda Japan Product name: PRIPOL2033 (derived from plants)
1,3PD: 1,3-propanediol manufactured by DuPont Product name: Susterra (derived from plants)
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 1-1]
PTMG-1: 683 g, BEPD: 124 g, EC: 393 g, Mg (acac) in a 2 L glass separable flask equipped with a stirrer, distillate trap, pressure regulator, 30 mmφ regular packed distillation column, fractionator ₂ : 345 mg was added, and nitrogen gas was substituted. While stirring, the internal temperature was raised to 150° C. to heat and dissolve the contents. Thereafter, while removing ethylene glycol and EC from the system by reducing the pressure, polymerization was carried out at a reaction temperature of 150° C. to 160° C. and a pressure of 6 kPa to 1 kPa for 20 hours. During the polymerization, 153 g of EC was further added to obtain a polymer.
Then, 1.5 g of 8.5% by mass phosphoric acid/BG solution was added to the obtained polymer to deactivate the catalyst. After that, the distillation column was removed and residual monomers were removed at 0.5 kPa and 170° C. to obtain a crude PEPCD-containing composition.

The resulting crude PEPCD-containing composition was fed 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. 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 2 shows analytical values and physical property values of the obtained PEPCD (hereinafter referred to as "PEPCD-1").

[Examples 1-2 to 3, Comparative Examples 1-1 and 2]
PEPCD-2 to 3, PEPCD-R1 and R2 were produced in the same manner as in Example 1 except that the types and/or amounts of the polyalkylene ether glycol, diol compound and carbonate compound were changed as shown in Table 1.
Table 2 shows the analytical values and physical property values of the obtained PEPCD.

[Comparative Example 1-3]
Beneviol NL2010DB manufactured by Mitsubishi Chemical Corporation, which is a commercially available polycarbonate diol (PCD) (polycarbonate diol having a molecular weight of 2000 using 1,4-butanediol and 1,10-decanediol as diol compounds) (hereinafter referred to as PCD-R3) ) are shown in Table 2.

[Production and Evaluation of Polyurethane]
[Examples 2-1 to 3, Comparative Examples 2-1 to 3]
Polyurethanes were produced using the PEPCD or PCD obtained in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3, respectively, and their physical properties were measured.

<Production of Polyurethane>
Using the PEPCD-1 obtained in Example 1-1 as a raw material, a polyurethane was produced by the following procedure.
A separable flask equipped with a thermocouple, a condenser tube and a stirrer was placed on an oil bath at 60° C., and 50.6 g of PEPCD-1 preheated to 80° C., 4.9 g of BG, dehydrated N, 177 g of N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, then 14.6 g of MDI was added, and the temperature was raised to 80°C in about 1 hour while stirring at 60 rpm in a separable flask under a nitrogen atmosphere. did. After reaching 80°C, 0.0136 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. Thereafter, MDI was added in portions so that the equivalent amount of NCO to OH was around 1.0 to obtain a polyurethane. The properties and physical properties of this polyurethane are shown in Tables 3A and 3B.
PEPCD or PCD obtained in Examples 1-2 to 1-3 and Comparative Examples 1-1 to 1-3 were also used as starting materials to synthesize polyurethanes. The properties and physical properties of the resulting polyurethanes were evaluated in Tables 3A and 3B. It was shown to.

The polyurethanes of Examples 2-1 to 2-3 synthesized using the PEPCD-1 to 3 obtained in Examples 1-1 to 1-3 as raw materials had a low 100% modulus (100% M) and a large breaking elongation. The polyurethane had excellent flexibility and was hard to break when stretched. Similarly, since the 100% modulus (100% M) at low temperature was low and the elongation at break was large, the flexibility and extensibility could be maintained even at low temperatures. In addition, the polyurethane had a high breaking strength retention rate after the wet heat test and was also excellent in hydrolysis resistance.
The polyurethanes of Comparative Examples 2-1 and 2-2, which were synthesized using the PEPCD-R1 and PEPCD-R2 obtained in Comparative Examples 1-1 and 1-2 as raw materials, were exposed to moist heat conditions for 7 days, resulting in The breaking strength decreased from the state of 1 to 80% or less. That is, the wet heat resistance and hydrolysis resistance were low.
The polyurethane of Comparative Example 2-3 synthesized from PCD-R3 of Comparative Example 1-3 had a large 100% modulus (100% M), a low elongation at break, and low flexibility. Furthermore, in the measurement at low temperature, the 100% modulus (100% M) was extremely large and the elongation at break was also low.

Claims (14)

Polyether polycarbonate containing a structural unit derived from polyalkylene ether glycol (hereinafter referred to as "structural unit A") and a structural unit derived from a diol compound having 7 to 50 carbon atoms (hereinafter referred to as "structural unit B") Diol. 2. The polyether polycarbonate diol according to claim 1, which has a hydroxyl value of 20 mg-KOH/g or more and 450 mg-KOH/g or less. 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 0.01% or more and 7.0% or less. 4. The polyether polycarbonate diol according to any one of claims 1 to 3, wherein the structural unit A contains a structural unit derived from polytetramethylene glycol. 5. The ratio of the mass of the structural unit B to the sum of the mass of the structural unit A and the mass of the structural unit B is 0.5% or more and 50% or less according to any one of claims 1 to 4. Polyether polycarbonate diol. 6. The polyether polycarbonate diol of any one of claims 3-5, wherein said alkoxy end groups comprise methoxy end groups. 7. The polyether polycarbonate diol of any one of claims 3-6, wherein the alkoxy end groups comprise butoxy end groups. A polyether polycarbonate diol composition comprising the polyether polycarbonate diol according to any one of claims 1 to 7 and a metal,
The polyether polycarbonate diol composition, wherein the metal is at least one selected from the group consisting of zinc and Group 2 metals of the long-period periodic table. 9. The polyether polycarbonate diol composition according to claim 8, wherein the metal content is 1 mass ppm or more and 500 mass ppm or less. A method for producing the polyether polycarbonate diol according to any one of claims 1 to 7,
A method for producing a polyether polycarbonate diol comprising a step of reacting a polyalkylene ether glycol having a hydroxyl value of 220 mg-KOH/g or more and 750 mg-KOH/g or less, a diol compound having 7 to 50 carbon atoms and a carbonate compound in the presence of a catalyst. . 11. The method for producing a polyether polycarbonate diol according to claim 10, wherein the carbonate compound is an alkylene carbonate. The catalyst is a composition containing at least one metal (M) selected from zinc and Group 2 metals of the long-period periodic table and at least one compound represented by the following formula (1), or 12. The method for producing a polyether polycarbonate diol according to claim 10 or 11, which is at least one salt represented by the formula (2) and a composition containing them as a precursor.

(In the formula, R ₁ and R ₃ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom and has an oxygen atom. may
R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, and the hydrocarbon group may be substituted with a halogen atom or may have an oxygen atom.
M represents zinc or a metal of group 2 of the long period periodic table, and n=2. ) A polyurethane comprising a structural unit derived from the polyether polycarbonate diol according to any one of claims 1 to 7. 8. A method for producing polyurethane, wherein raw materials containing the polyether polycarbonate diol according to any one of claims 1 to 7 and a compound having a plurality of isocyanate groups are subjected to an addition polymerization reaction.