JP2022078712A - Polyether polycarbonate diol and method for producing the same - Google Patents

Abstract

To provide a polyether polycarbonate diol that has balanced physical properties such as mechanical strength, hydrolytic resistance, chemical resistance, adhesion and serves as the raw material for polyurethane.SOLUTION: A polyether polycarbonate diol contains a structural unit derived from polyalkylene ether glycol and a structural unit derived from a C3-6 diol compound. Relative to the total number of end groups, the number of alkoxy end groups and the number of aryloxy end groups are 0.01% or more and 7.0% or less in total.SELECTED DRAWING: None

Description

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

Polyurethane is 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 containing a polyol as a main component. Polyols, which are one of the main raw materials for polyurethane, are classified into polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, acrylic polyols, etc. according to the difference in molecular chain structure, and polyols according to the required performance of polyurethane are selected. To. Among the polyether polyols, polytetramethylene ether glycol (hereinafter, may be abbreviated as PTMG) has high crystallinity, so polyurethane obtained by reaction with isocyanates has excellent wear resistance and hydrolysis resistance. It develops sex and tear resistance. The main uses of such polyurethanes are spandex, thermoplastic elastomers, thermosetting elastomers, artificial leathers, synthetic leathers and the like.

Due to these excellent properties, polyurethane obtained from polytetramethylene ether glycol is used for various purposes, but polytetramethylene ether glycol has a high melting point and viscosity, and has problems in handling, and some of them have problems. In the application, there was room for improvement in the durability such as chemical resistance of the obtained polyurethane.

As a method for improving the physical characteristics of polytetramethylene glycol, a method of linking with a carbonate bond is known. For example, a polyether polycarbonate diol (hereinafter, may be abbreviated as PEPCD) produced from polytetramethylene ether glycol having a small molecular weight is known as a room temperature liquid polyol (Patent Document 1).

Japanese Patent Application Laid-Open No. 2002-25669

According to Patent Document 1, a polyol that is liquid at room temperature can be obtained, but in this PEPCD, a polyurethane that sufficiently satisfies hydrolysis resistance, mechanical strength, chemical resistance, etc. can be obtained as a polyurethane used for synthetic leather and the like. I couldn't. In particular, since it is difficult to introduce hydroxyl groups at the ends of PEPCD in a sufficient proportion, such PEPCD can obtain polyurethane having a weight average molecular weight of about 200,000, which is used for high-strength synthetic leather, urethane resin, and the like. I couldn't.

INDUSTRIAL APPLICABILITY The present invention has been made in view of the above problems, and provides a polyether polycarbonate diol as a raw material for polyurethane having an excellent balance of physical properties such as mechanical strength, hydrolysis resistance, chemical resistance, and adhesiveness. The purpose.

As a result of diligent studies to solve the above problems, the present inventors have a structure derived from a structural unit derived from polyalkylene ether glycol (hereinafter referred to as "structural unit A") and a diol compound having 3 to 6 carbon atoms. A polyether polycarbonate diol containing a unit (hereinafter referred to as "structural unit B"), wherein the ratio of the total number of alkoxy-terminated groups and aryloxy-terminal groups to the total number of terminal groups is in a suitable range as a raw material. By using it, it is possible to achieve both good solvent resistance when made into polyurethane, mechanical strength and hydrolysis resistance, and by using the polyether polycarbonate diol, it becomes easy to control the urethane polymerization reaction. It has been found that it is possible to obtain a polyurethane having an excellent balance of physical properties such as mechanical strength, hydrolysis resistance, chemical resistance and adhesiveness at a desired molecular weight by suppressing a rapid polymerization reaction.
The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] Includes 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 3 to 6 carbon atoms (hereinafter referred to as "structural unit B"). A polyether polycarbonate diol in which the ratio of the total number of alkoxy-terminated groups and the number of allyloxy-terminal groups to the total number of terminal groups is 0.01% or more and 7.0% or less.

[2] The polyether polycarbonate diol according to [1], wherein the structural unit B is a structural unit derived from 1,3-propanediol and / or a structural unit derived from 1,4-butanediol.

[3] The polyether polycarbonate diol according to [1] or [2], which has a hydroxyl value of 20 mg-KOH / g or more and 450 mg-KOH / g or less.

[4] Any of [1] to [3], wherein the ratio of the mass of the structural unit B to the total 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. The polyether polycarbonate diol according to.

[5] The polyether polycarbonate diol according to any one of [1] to [4], wherein the alkoxy-terminated group contains a methoxy-terminated group.

[6] The polyether polycarbonate diol according to any one of [1] to [5], wherein the alkoxy-terminated group contains a butoxy-terminated group.

[7] A polyether polycarbonate diol composition containing the polyether polycarbonate diol according to any one of [1] to [6] and a metal, wherein the metal is zinc and Group 2 of the Long Periodic Table. A polyether polycarbonate diol composition which is at least one selected from the group consisting of metals.

[8] The polyether polycarbonate diol composition according to [7], wherein the content of the metal is 1 mass ppm or more and 500 mass ppm or less.

[9] The method for producing a polyether polycarbonate diol according to any one of [1] to [6], wherein the hydroxyl value is 220 mg-KOH / g or more and 750 mg-KOH / g or less in the presence of a catalyst. A method for producing a polyether polycarbonate diol, which comprises a step of reacting an alkylene ether glycol, a diol compound having 3 to 6 carbon atoms and a carbonate compound.

[10] The method for producing a polyether polycarbonate diol according to claim 9, wherein the carbonate compound is an alkylene carbonate.

[11] A composition in which the catalyst contains at least one metal (M) selected from zinc and a metal of Group 2 of the long-periodic table, and at least one compound represented by the following formula (1). Or the method for producing a polyether polycarbonate diol according to claim 9 or 10, which is a composition having 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. May be.
R ₂ represents a monovalent hydrocarbon group or a halogen atom having 1 to 20 carbon atoms, 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-periodic table, and n = 2. )

[12] Polyurethane containing a structural unit derived from the polyether polycarbonate diol according to any one of [1] to [6].

[13] A method for producing a polyurethane in which a raw material containing the polyether polycarbonate diol according to any one of [1] to [6] and a compound having a plurality of isocyanate groups is subjected to an addition polymerization reaction.

According to the polyether polycarbonate diol of the present invention, it is possible to produce polyurethane having an excellent balance of physical properties such as mechanical strength, hydrolysis resistance, chemical resistance and adhesiveness.

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.

[Polyester Polycarbonate Diol]
The polyether carbonate diol of the present invention (hereinafter, may be abbreviated as "PEPCD") contains a structural unit A derived from a polyalkylene ether glycol and a structural unit B derived from a diol compound having 3 to 6 carbon atoms. It is a polyether polycarbonate diol, and the ratio of the total number of alkoxy-terminated groups and the number of allyloxy-terminal groups to the total number of terminal groups (hereinafter, may be referred to as "terminal alkoxy / allyloxy ratio") is 0.01% or more and 7.0. It is characterized by being less than%.
The PEPCD of the present invention has the same meaning as the PEPCD composition described in the description of the metal content (residual amount of catalytic metal of PEPCD) described later.

In the present invention, the polyether polycarbonate diol means "a compound having a repeating unit of a polyether polycarbonate", and the polyether polycarbonate diol of the present invention usually has a repeating unit of a polyether polycarbonate and has different terminal groups. It is composed as a mixture of a plurality of kinds of compounds having.

PEPCD is produced by reacting a carbonate compound such as an alkylene carbonate, a dialkyl carbonate, or a diallyl carbonate with a polyether polyol compound and a diol compound different from the polyether polyol compound used as needed. In this reaction, the target product, PEPCD having hydroxyl groups at both ends, as a by-product, an alkoxy-terminated group by a reaction between a dialkyl carbonate and a polyether polyol compound, and an allyloxy terminal by a reaction between a diaryl carbonate and a polyether polyol compound. Groups are formed (hereinafter, these alkoxy-terminated groups and allyloxy-terminated groups may be collectively referred to as "alkoxy / allyloxy-terminated").
Further, these alkoxy / allyloxy terminals may be brought into the reaction system as impurities in a polyether polyol compound such as PTMG used as a raw material for producing PEPCD, and may be mixed in the obtained PEPCD.
In addition, the alkoxy / allyloxy terminal will be mixed into PEPCD by heating in the purification step of PEPCD.
The present inventor determines the amount of the alkoxy / allyloxy terminal produced as this reaction by-product and the amount of the alkoxy / allyloxy terminal mixed in the product as a result of being mixed in the raw material compound and brought into the reaction system. By controlling the allyloxy ratio to be 0.01% or more and 7.0% or less, the urethane polymerization reaction can be easily controlled, the rapid polymerization reaction can be suppressed, and it is desired to be suitable for various uses as polyurethane. We have found that it is possible to produce polyurethane with a molecular weight.

<Terminal alkoxy / allyloxy ratio>
In the PEPCD of the present invention, the ratio of the total number of alkoxy terminal groups and allyloxy terminal groups (terminal alkoxy / allyloxy ratio) to the total number of terminal groups is 0.01% to 7.0%. If the terminal alkoxy / allyloxy ratio exceeds 7.0%, the urethane polymerization reaction does not proceed sufficiently, and a polyurethane having a sufficient molecular weight and high mechanical strength cannot be obtained. The value of the terminal alkoxy / allyloxy ratio is preferably 5.0% or less, more preferably 3.0% or less, further preferably 2.0% or less, and 1.0% or less, the obtained polyurethane machine. Most preferable from the viewpoint of physical properties and solvent resistance.
On the other hand, if the terminal alkoxy / allyloxy ratio is less than 0.1%, the urethane polymerization reaction rate becomes too fast and reaction control is difficult. In either case, polyurethane having a desired molecular weight may not be obtained. If it is less than 01%, the tendency is even more remarkable. That is, the lower limit of the terminal is 0.01% or more, preferably 0.1% or more, and more preferably 0.2% or more.

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

<Alkoxy / allyloxy terminal>
As described above, the alkoxy / allyloxy terminal contained in the PEPCD of the present invention is mainly derived from the polyether polyol compound or the carbonate compound which is the raw material for producing PEPCD.

Examples of the alkoxy-terminated group include a methoxy-terminated group, an ethoxy-terminated group, a propoxy-terminated group, a butoxy-terminated group, and the like, but from the viewpoint of PEPCD quality, a methoxy-terminated group or a butoxy-terminated group is preferable.

Specific examples of allyloxy terminal groups include substituted or unsubstituted phenoxy terminal groups.

The PEPCD of the present invention may contain only one of these alkoxy / allyloxy terminals, or may contain two or more of them. If two or more alkoxy / allyloxy terminals are included, the total content of these should be within the above range.

<Method of controlling terminal alkoxy / allyloxy ratio>
The method for controlling the terminal alkoxy / allyloxy ratio of PEPCD of the present invention is not particularly limited.
(1) Method of mixing PEPCD containing an alkoxy / allyloxy terminal with PEPCD not containing an alkoxy / allyloxy terminal (2) Adjusting the alkoxy / allyloxy terminal concentration in PEPCD containing an alkoxy / allyloxy terminal by operations such as distillation and extraction. (3) Method for controlling the content of alkoxy / aryloxy terminals in polyether polyol compounds, carbonate compounds, and diol compounds that are the raw materials for PEPCD (4) Alkoxy / as a by-product produced by the reaction during the production of PEPCD Examples thereof include a method of controlling the amount of aryloxy terminal by adjusting the pH of the solution.

<Structure of PEPCD>
The PEPCD of the present invention contains a structural unit A derived from polyalkylene ether glycol and a structural unit B derived from a diol compound having 3 to 6 carbon atoms, and has good solvent resistance, mechanical strength and hydrolysis resistance when made into polyurethane. Both degradability can be achieved.

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, but the low temperature characteristics and flexibility are good. Therefore, it is preferably a copolymer. Further, in the case of a copolymer, a block copolymer or a random copolymer may be used, but PEPCD of the random copolymer is preferable because it has good low temperature characteristics and flexibility.

The mass ratio of the structural unit A and the structural unit B to the total structural units of the PEPCD of the present invention can be obtained by analyzing each dihydroxy compound obtained by hydrolyzing the PEPCD with an alkali by gas chromatography.
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 at the time of polymerization to the mass of the obtained polyether polycarbonate diol. It is also possible to calculate the mass ratio of the structural unit A and the structural unit B introduced into the PEPCD from the weight, the amount of by-biomass and the amount of distillate of the diol used for charging the PEPCD.

The content of the structural unit A of the PEPCD of the present invention is not particularly limited, but if the content of the structural unit A is too small, the flexibility of polyurethane is insufficient, and if it is too large, the ether skeleton increases. If it is made of polyurethane too much, the hydrophilicity may increase and the hydrolysis resistance may not be sufficient, or the mechanical strength may decrease. The content of the structural unit A of the PEPCD of the present invention is preferably 15% by mass or more, more preferably 30% by mass or more, still 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 even more preferably 90% by mass or less.
Further, if the content ratio of the structural unit B of PEPCD of the present invention is too small, the hydrolysis resistance may not be sufficient, and if it is too large, the flexibility of polyurethane may not be sufficient. The ratio of the mass of the structural unit B to the total of the mass of the structural unit A and the mass of the structural unit B contained in the PEPCD of the present invention in order to obtain the effect of including the structural unit A and the structural unit B in a well-balanced manner. Is preferably 0.5 to 50% by mass, more preferably 1 to 45% by mass, further preferably 2 to 40% by mass, still more preferably 3 to 35% by mass, and further preferably 3 to 35% by mass. Most preferably, it is 5 to 35%.

The PEPCD of the present invention is a structural unit other than the structural unit A and the structural unit B as long as it contains the structural unit A and the structural unit B, that is, a polyalkylene ether glycol and a diol compound having 3 to 6 carbon atoms. It may contain a structural unit derived from other dihydroxy compounds other than the above. In this case, the content of the other structural units is preferably 50% by mass or less, more preferably 60% by mass or less, still more preferably 20% by mass or less, and most preferably 10% by mass or less with respect to all the structural units of PEPCD. .. If the ratio of other structural units is large, the balance of chemical resistance, flexibility, etc. may be impaired.

The compounds constituting the structural unit A, the structural unit B, and other structural units will be described later.

<Hydroxy group value, number average molecular weight, molecular weight distribution of PEPCD>
The hydroxyl value of 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, still more preferable. Is 28.1 mg-KOH / g, particularly preferably 37.4 mg-KOH / g, with an upper limit of 450 mg-KOH / g, preferably 320 mg-KOH / g, more preferably 187.0 mg-KOH / g, even more preferably. Is 140.3 mg-KOH / g, particularly preferably 112.2 mg-KOH / g. If the hydroxyl value is at least the above lower limit, the viscosity does not become too high, and handling when using the PEPCD as a raw material tends to be easy, and if it is at least the above upper limit, the flexibility of the obtained polyurethane is high. Tends to be good.

Further, in the PEPCD of the present invention, hydrolysates 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 the 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 have suppressed increase in 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 an appropriate viscosity and may be excellent in handleability. The hydroxyl value of the hydrolyzate of the structural unit A is more preferably 280 mg-KOH / g or more, further preferably 370 mg-KOH / g or more, and even more preferably 700 mg-KOH / g or less. It is more preferably 660 mg-KOH / g or less.
The method for hydrolyzing PEPCD is as described in the Examples section.

The molecular weight of PEPCD of the present invention is not particularly limited, but is preferably a number average molecular weight (Mn) obtained from a hydroxyl group, the lower limit is usually 600, preferably 800, more preferably 1000, and the upper limit is usually 5000, preferably. It is 4000, more preferably 3000. When the number average molecular weight (Mn) of PEPCD is 600 or more, the flexibility of the obtained polyurethane is sufficient, 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 by, for example, the following method.

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

The molecular weight distribution (Mw / Mn) of 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. It is preferably 2.2 or less.
When the molecular weight distribution is 3 or less, the increase in the high molecular weight body and the increase in the viscosity are suppressed, the handling property is excellent, and the physical properties of various polyurethanes such as the tensile strength tend to be good. On the other hand, the lower limit of the 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)>
Weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) [manufactured by Toso, product name "HLC-8220", column: TskgelSuperHZM-N (4 pieces)] after preparing a tetrahydrofuran solution of PEPCD. Was divided by the number average molecular weight (Mn) (Mw / Mn) and used as the molecular weight distribution of PEPCD. The POLYTETRAHYDROFURAN calibration kit from POLYMER LABORATORIES in the United Kingdom was used for GPC calibration.

<APHA value>
The color of PEPCD of the present invention is preferably 50 or less in terms of the number of Hazen colors (based on JIS K0071-1: 1998) (hereinafter referred to as "APHA value"), preferably 40 or less. More preferably, it is more preferably 30 or less. If the APHA value exceeds 50, the color tone of the obtained polyurethane may be deteriorated, the commercial value may be lowered, or the thermal stability may be deteriorated.

In order to reduce the APHA value to 50 or less, the selection of the type and amount of the catalyst at the time of PEPCD production, the thermal history, the concentration of the monohydroxy compound during and after the polymerization, and the concentration of the unreacted monomer are comprehensively controlled. There is a need. Further, shading during polycondensation and after polycondensation is completed is also effective. It is also important to set the number average molecular weight of PEPCD and select the dihydroxy compound species that is the monomer. In particular, PEPCD made from an aliphatic dihydroxy compound having an alcoholic hydroxyl group exhibits various excellent performances such as flexibility, water resistance, and light resistance when processed into polyurethane, but the aromatic dihydroxy compound is used as a raw material. It is not easy to set the APHA value to 60 or less because the heat history and the coloring by the catalyst tend to be more remarkable than in the case of the above.

[Manufacturing method of polyether polycarbonate diol]
The PEPCD of the present invention is not particularly specified as long as the desired PEPCD can be obtained while controlling the terminal alkoxy / allyloxy ratio as described above, but it is usually composed of a polyether polyol compound and a diol compound having 3 to 6 carbon atoms. It is produced by reacting a carbonate compound. At the time of the reaction, if necessary, a diol compound different from the polyether polyol compound and the diol compound having 3 to 6 carbon atoms may be copolymerized. Further, in the manufacturing process, a catalyst, an additive or the like may be added as needed.
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 3 to 6 carbon atoms and a carbonate compound in the presence of a catalyst. It is produced by the method for producing a polyether polycarbonate diol of the present invention, which comprises.

<Carbonate compound>
As the carbonate compound, alkylene carbonate, dialkyl carbonate and diaryl carbonate can be used.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate and the like.
Examples of the dialkyl carbonate include a symmetric dialkyl carbonate such as dimethyl carbonate, diethyl carbonate and dibutyl carbonate, and an asymmetric dialkyl carbonate such as methyl ethyl carbonate.
Examples of the diaryl carbonate include symmetric diaryl carbonates such as diphenyl carbonate and dinaphthyl carbonate, and asymmetric diaryl carbonates such as phenylnaphthyl carbonate.
Further, chlorocarbonic acid esters such as methyl chlorocarbonate and phenylchlorocarbonate, phosgene and its equivalents, and carbon dioxide gas can also be used as carbonic acid sources.

Among these, from the viewpoint of ease of control of the ratio of the total number of alkoxy-terminal groups to the total number of terminal groups, alkylene carbonate or dialkyl carbonate is preferable, ethylene carbonate or dimethyl carbonate is more preferable, and further. It is preferably an alkylene carbonate such as ethylene carbonate.
The above-mentioned carbonate compound may be used alone or in combination of two or more.

<Polyether polyol compound>
The polyether polyol compound can be produced by ring-opening polymerization of cyclic ether.

The number of carbon atoms constituting the cyclic ether is usually 2 to 10, preferably 3 to 7.
Specific examples of the cyclic ether include tetrahydrofuran (THF), ethylene oxide, propylene oxide, oxetane, tetrahydropyran, oxepane, 1,4-dioxane and the like. Further, 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 thereof include 3-methyl-tetrahydrofurfurn and 2-methyltetrahydrofurne. One of these cyclic ethers may be used alone, or two or more of them may be mixed and used, but it is preferable to use one of them.

Specific polyether polyol compounds include low molecular weight polymer polyols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and dipropylene glycol, polyethylene glycol having a number average molecular weight of 100 or more and 3000 or less obtained from hydroxyl groups, polypropylene glycol, and oxidation. Examples thereof include a copolymer of ethylene and propylene oxide, polyalkylene ether glycol such as polytetramethylene ether glycol (PTMG), a copolymer of THF and 3-methyl-tetrachloride, dipropylene glycol polyethylene glycol and the like.

Among these, polyalkylenes 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 the tensile properties and durability of the obtained polyurethane. If the hydroxyl value is 750 mg-KOH / g or less, the polyalkylene ether glycol can suppress an increase in the crystallinity and melting point of the obtained PEPCD. Further, when the hydroxyl value of the polyalkylene ether glycol is 220 mg-KOH / g or more, the viscosity of the obtained PEPCD does not become too high and the handleability is excellent.
Further, this polyalkylene ether glycol has a number average molecular weight (Mn) of 100 or more and 3000 or less, particularly 150 or more and 2000 or less, and particularly 200 or more and 850 or less, that is, the tensile properties and durability of the obtained polyurethane. It is preferable from the viewpoint of. When the polyalkylene ether glycol having a number average molecular weight of 100 or more is used, the obtained PEPCD can suppress an increase in crystallinity and melting point. Further, when the number average molecular weight of the polyalkylene ether glycol is 3000 or less, the viscosity of the obtained PEPCD does not become too high, and the handleability is excellent.

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 the number average molecular weight (Mn) of PEPCD of the present invention described above.

As the polyalkylene ether glycol, PTMG is particularly preferable because it has an excellent balance of flexibility, low temperature flexibility, mechanical strength, hydrophilicity, 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 subjecting diacetoxybutene, which is an intermediate obtained by performing an acetoxylation reaction using raw materials butadiene, acetic acid and oxygen, and hydrogenating and hydrolyzing the diacetoxybutene. A method obtained by cyclization dehydration; a method obtained by cyclizing and dehydrating 1,4-butanediol obtained by hydrogenating maleic acid, succinic acid, maleic anhydride and / or fumaric acid as raw materials; A method of cyclizing and dehydrating 1,4-butanediol obtained by hydrogenating butinediol obtained by contacting with an aqueous formaldehyde solution using the above; 1,4-butanediol obtained via oxidation of propylene. Method obtained by cyclization dehydration; Method obtained by cyclization dehydration of 1,4-butanediol obtained by hydrogenating succinic acid obtained by the fermentation method; 1,4 obtained by direct fermentation from biomass such as sugar -A method for obtaining butanediol by cyclization and dehydration; a method for decarbonylating and reducing furfural obtained from biomass; and the like.

<Glycol compound with 3 to 6 carbon atoms>
The diol compound having 3 to 6 carbon atoms from which the structural unit B is derived is not particularly limited as a structure, and examples thereof include the following compounds.
Examples of the linear diols include 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Side chain diols include 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methyl-1,4-butanediol, and 3-methyl-pentane. Examples include diol. Examples of the cyclic diols include 1,3-cyclopentanediol, 1,4-cyclohexanediol, and erythritan. Only one kind of these diol compounds may be used, or two or more kinds thereof may be used in combination. In addition, these diols may be contained as impurities in raw materials such as other diol compounds.
Among these diol compounds, linear diols are preferable because they have an excellent balance of chemical resistance and flexibility when polyurethane is used. The carbon number of the diol compound is more preferably 3 to 5 from the viewpoint of solvent resistance, and further preferably 3 to 4. As the diol compound, 1,3-propanediol and 1,4-butanediol are particularly preferable, the carbonate groups are appropriately densely packed, the balance between crystallinity and hydrophobicity is good, and both hydrolysis resistance and solvent resistance are good. In terms of good points, 1,4-butanediol is most preferable. Further, by combining diol compounds having different carbon atoms, crystallinity may be lowered and flexibility may be improved.

When the carbon number of the diol compound used is 7 or more, the density of the carbonate group decreases, and sufficient solvent resistance cannot be obtained, or the crystallinity decreases, so that the hydrolysis resistance decreases. On the other hand, when the carbon number of the diol compound used is 2 or less, the density of the carbonate group becomes too high, the flexibility of the polyurethane is impaired, and the hydrolysis resistance is lowered.
Therefore, in the present invention, a diol compound having 3 to 6 carbon atoms is used.

It is preferable that the structural unit A and the structural unit B contained in the PEPCD of the present invention are derived from plants from the viewpoint of reducing the environmental load. Compounds from which structural unit B applicable as plant origin is derived include 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, and 2-methyl-1. , 3-Propanediol, 2,2-dimethyl-1,3-propanediol and the like.

<Other dihydroxy compounds>
In the production of PEPCD of the present invention, other than the compounds from which structural unit A and structural unit B are derived, as long as the effects of the present invention are not impaired, that is, within the range of the upper limit of the content of other structural units described above or less. Other dihydroxy compounds (hereinafter, may be referred to as "other dihydroxy compounds") may be used. Examples of other dihydroxy compounds 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, other than diol compounds having 3 to 6 carbon atoms. Can be mentioned. More specifically, chain alkyl diols such as ethylene glycol, 1,7-heptane diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, and 1,12-dodecane diol. Cyclic alkyl diols such as cyclohexanedimethanol and isosorbide can be mentioned.
One of these other dihydroxy compounds may be used alone, or two or more thereof may be mixed and used.
One of these other dihydroxy compounds may be used alone, or two or more thereof may be mixed and used.

<Halogen component>
If a halogen component such as chloride ion or bromide ion is contained in the raw material compound used as a raw material for producing PEPCD, it may affect the reaction during the polycarbonate formation reaction and further during the polyurethane conversion of the obtained PEPCD. Since it may cause coloring, it is preferable that the content is small. Usually, the upper limit of the content of the halogen component in the polyether polyol compound, the diol compound or the carbonate compound used in the production of the PEPCD of the present invention is 10 ppm, preferably 5 ppm, more preferably 1 ppm as the halogen mass with respect to these masses. Is.

<Ratio of raw materials used>
In the production of PEPCD, the amount of the carbonate compound used is not particularly limited, but is usually a molar ratio to 1 mol of the total of the polyether polyol compound and the diol compound, and the lower limit is preferably 0.35, more preferably 0.50, and further. It is preferably 0.60, and the upper limit is preferably 1.00, more preferably 0.98, and even more preferably 0.97. When the amount of the carbonate compound used is not more than the above upper limit, the proportion of the obtained PEPCD whose terminal group is not a hydroxyl group is suppressed, and the number average molecular weight can be easily set within a predetermined range. When the amount of the carbonate compound used is at least the above lower limit, it is easy to proceed with the polymerization to a predetermined number average molecular weight.

<Transesterification catalyst>
In the PEPCD of the present invention, a polyether polyol compound, which is a compound from which structural unit A is derived, a diol compound having 3 to 6 carbon atoms from which structural unit B is derived, and a carbonate compound are polycondensed by an ester exchange reaction. Can be manufactured by

In the case of producing PEPCD of the present invention, a transesterification catalyst (hereinafter, may be 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 ester exchange catalysts include long-periodic periodic tables such as lithium, sodium, potassium, rubidium, and cesium (hereinafter simply referred to as "periodic table"), compounds of Group 1 metals; magnesium, calcium, strontium, etc. Periodic Table Group 2 metal compounds such as barium; Periodic Table Group 4 metal compounds such as titanium and zirconium; Periodic Table Group 5 metal compounds such as hafnium; Periodic Table Group 9 metal compounds such as cobalt; Periodic Table Group 12 Metal Compounds such as Zinc; Periodic Table Group 13 Metal Compounds such as Aluminum; Periodic Table Group 14 Metal Compounds such as Germanium, Tin, Lead; Periodic Table Group 15 such as Antimon and Rubidium Metal compounds; Examples thereof include compounds of lanthanide-based metals such as lanthanum, cesium, europium, and itterbium. Among these, from the viewpoint of increasing the ester exchange reaction rate, a compound of the Group 1 metal of the Periodic Table, a compound of the Metal of Group 2 of the Periodic Table, a compound of the Metal of Group 4 of the Periodic Table, and a compound of the Metal of Group 5 of the Periodic Table. Periodic Table Group 9 metal compounds, Periodic Table Group 12 metal compounds, Periodic Table Group 13 metal compounds, Periodic Table Group 14 metal compounds are preferred, Periodic Table Group 1 metal compounds, Periodic Table No. 1 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 the Group 1 metal in the periodic table, compounds of lithium, potassium and sodium are preferable, compounds of lithium and sodium are more preferable, and compounds of sodium are even more preferable. Among the compounds of the Group 2 metal in the periodic table, magnesium, calcium and barium compounds are preferable, calcium and magnesium compounds are more preferable, and magnesium compounds are even more preferable. 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, iodides; carboxylates such as acetates, formates, benzoates; methanesulphonic acid, toluenessulfonic acids, trifluo. Sulfonates such as lomethane sulfonic acid; phosphorus-containing salts such as phosphates, hydrogen phosphates, dihydrogen phosphates; acetylacetonate salts; and the like can be mentioned. The catalyst metal can also be used as an alkoxide such as methoxide or ethoxide.

Of these, preferably, acetates, nitrates, sulfates, carbonates, phosphates, hydroxides, halides, acetylacetonate salts, etc. of at least one metal selected from Group 2 metals in the periodic table. An alkoxide is used, more preferably an acetate or acetylacetone salt of Group 2 metal of the periodic table is used, and more preferably an acetate or carbonate of magnesium or calcium, a carbonate or an acetylacetonate salt is used, from the viewpoint of reactivity. Most preferably magnesium acetylacetonate is used.

The catalyst used in the production of PEPCD of the present invention contains at least one metal (M) selected from zinc and a metal of Group 2 of the periodic table, and at least one compound represented by the following formula (1). A composition (hereinafter, may be referred to as "catalyst composition (1)"), or at least one salt represented by the following formula (2) and a composition using them as a precursor (hereinafter, "catalyst"). The composition (2) ”may be referred to as“ composition (2) ”).

(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 be.
R ₂ represents a monovalent hydrocarbon group or a halogen atom having 1 to 20 carbon atoms, 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 present form of zinc or the Group 2 metal compound of the periodic table usually includes the form of the salt represented by the above formula (2), and therefore it is effective to use the catalyst composition (2). However, if it is difficult to obtain it as a salt, or if the composition ratio of zinc or the Group 2 metal of the periodic table and the compound represented by the above formula (1) is to be arbitrarily adjusted, the metal compound and the above are desired. A catalyst composition (1) with a compound having a structure represented by the formula (1) may be used.
Further, 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), a method similar to the method for synthesizing a metal acetylacetone salt is used to combine a halogenated salt of a metal in the presence of a base. A method for preparing a catalyst composition (2) by reacting with an acetylacetone analog, or as shown in the following formula (4), a catalyst composition (2) is prepared by exchanging a metal alkoxide with an acetylacetone analog. There are ways to do this, but it is not limited to this.

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

The catalyst compositions (1) and (2) may be mixed with a polyether polyol compound as a raw material monomer, a diol compound having 3 to 6 carbon atoms, and a carbonate compound, each of which is an arbitrary component. It may be mixed with the raw material monomer in order.

Further, together with these catalyst compositions (1) and (2), a transition metal compound and a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound and an amine compound are used in combination. It is also possible.

In the above formulas (1) and (2), R ₁ and R ₃ are independently substituted with a halogen atom or may have an oxygen atom, and are monovalent with 1 to 12 carbon atoms. The catalyst composition is preferably a monovalent hydrocarbon group having 1 to 7 carbon atoms, which may be substituted with a halogen atom or may have an oxygen atom. It is more preferable from the viewpoint of ease of interaction with the metal (M) inside, solubility as a catalyst composition, thermal stability and low colorability. _R2 is preferably a monovalent hydrocarbon group or a halogen atom having 1 to 12 carbon atoms, 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, so that it is easy to interact with the metal (M) in the catalyst composition. It is more preferable from the viewpoint of solubility in pods and organic solvents and raw material monomers, strength of acid bases, low colorability and the like. Further, when R ₁ to R ₃ are the above-mentioned suitable functional groups, the obtained PEPCD has high solubility and low coloring, so that PEPCD having no turbidity and low coloring can be obtained.

Specific examples of R ₁ and R ₃ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, and the like. Hexyl group, cyclohexyl group, phenyl group, benzyl group, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, monochloromethyl group, dichloromethyl group, trichloromethyl group and the like can be mentioned, and among these, the methyl group, in particular, 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 preferable. 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.

Specific examples of R ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group and hexyl. 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, particularly methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, phenyl group, benzyl group and trifluoromethyl group. , Trichloromethyl group, fluorine atom, chlorine atom are preferable.

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

The amount of such a catalyst used is usually 10 μmol or more and 1500 μmol with respect to 1 mol of the total of the starting material polyether polyol compound, the diol compound having 3 to 6 carbon atoms and other dihydroxy compounds used as needed. The following is preferable, the lower limit is more preferably 20 μmol, further preferably 30 μmol, and particularly preferably 50 μmol. The upper limit is more preferably 1000 μmol, further preferably 500 μmol, particularly preferably 300 μmol, and most preferably 200 μmol. When the amount of the catalyst is not less than the above lower limit, the reaction time can be shortened, the production efficiency can be improved, and the coloring of the obtained PEPCD can be suppressed. Further, when the amount of the catalyst is not more than the above upper limit, the coloring of PEPCD and the coloring at the time of producing polyurethane are suppressed, the urethane polymerization reaction rate does not become too fast, and the reaction control tends to be easy.

<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, it is preferable to set the temperature near the boiling point of the raw material carbonate compound, specifically 100 to 150 ° C., and gradually raise the temperature as the reaction progresses to further proceed the reaction. Alcohol, phenol, etc., which are reaction by-products, are separated by distillation. At this time, when the raw material carbonate compound is distilled together with the distilled alcohol and the like and the loss is large, it is preferable to suppress the loss amount by using a reactor equipped with a shelf column or a packed column. Further, in order to reduce the loss, the distillate raw material carbonate compound may be recovered and recycled into a 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 diol compound having 3 to 6 carbon atoms or other dihydroxy compounds for the production of PEPCD is the polyether with respect to n mol of the carbonate compound. Although it is a polyol compound, a diol compound having 3 to 6 carbon atoms or another dihydroxy compound (n + 1) mol, it is preferably 1.1 to 1.3 times the theoretical molar ratio in consideration of loss. The polyether polyol compound, the diol compound having 3 to 6 carbon atoms or another dihydroxy compound may be charged at the initial stage of the reaction, or may be added from the middle.

<Catalyst deactivation>
As described above, when a catalyst is used in the transesterification reaction, the catalyst remains in the normally obtained PEPCD composition, and the residual metal catalyst makes it impossible to control the reaction when the polyurethane reaction is carried out. There is. In order to suppress the influence of this residual catalyst, a catalyst deactivating agent having a molar amount approximately equal to that of the catalyst used, for example, a phosphorus-based or sulfur-based compound that is acidic or decomposes into an acidic compound may be added. Further, after the addition, the transesterification catalyst can be efficiently inactivated by heat treatment as described later.

Examples of the compound used for inactivating the ester exchange catalyst (hereinafter, may be referred to as a catalyst deactivating agent) include inorganic phosphoric acid such as phosphoric acid and phosphite, dibutyl phosphate, and tributyl phosphate. , Organic phosphate esters such as trioctyl phosphate, triphenyl phosphate, triphenyl phosphite, sulfonic acid, sulfonic acid ester and the like. These may be used alone or in combination of two or more.

The amount of the catalyst deactivating agent used is not particularly limited, but as described above, it may be approximately the same mol as the ester exchange catalyst used, and specifically, with respect to 1 mol of the ester exchange catalyst used. 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 a smaller amount of the catalyst deactivating agent is used, the ester exchange catalyst in the reaction product is not sufficiently deactivated, and when the obtained PEPCD composition is used as a raw material for producing polyurethane, for example, the PEPCD is used. It may not be possible to sufficiently reduce the reactivity of the composition with the isocyanate group. Further, if a catalyst deactivating agent exceeding this range is used, the obtained PEPCD composition may be colored.

The inactivation of the transesterification catalyst by adding the catalyst deactivating agent can be carried out even at room temperature, but it is more efficient when the heating treatment is performed. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 150 ° C, more preferably 120 ° C, still more preferably 100 ° C, and the lower limit is preferably 50 ° C, more preferably 60 ° C, still more preferable. Is 70 ° C. If the temperature is lower than this, the deactivation of the transesterification catalyst takes time and is not efficient, and the degree of deactivation may be insufficient. On the other hand, at a temperature exceeding 150 ° C., the obtained PEPCD composition may be colored.
The time for reacting with the catalyst deactivating agent is not particularly limited, but is usually 1 to 5 hours.

<Purification>
After the polycondensation reaction, the terminal structure in the PEPCD composition is an impurity having an alkoxy group, an impurity having an allyloxy group, a monohydroxy compound such as phenols, alcohols and diols, or a dihydroxy compound, a carbonate compound, and a light by-product. Purification can be performed for the purpose of removing the boiling cyclic carbonate and the added catalyst and the like. For purification at that time, a method of distilling off the light boiling compound by distillation can be adopted. The specific method of distillation is not particularly limited in its form such as vacuum distillation, steam distillation, and thin film distillation, but thin film distillation is particularly effective. Further, in order to remove water-soluble impurities, it may be washed with water, alkaline water, acidic water, a chelating agent dissolving 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. Further, the lower limit is preferably 120 ° C, more preferably 150 ° C.
By setting the lower limit of the temperature at the time of thin film distillation to the above value, the effect of removing the light boiling component 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, the effect of removing the light boiling component can be sufficiently obtained.

Further, the temperature of the heat retention of the PEPCD composition immediately before the thin film distillation is preferably 250 ° C., more preferably 150 ° C. Further, the lower limit is preferably 80 ° C, more preferably 120 ° C.
By setting the heat retention temperature of the PEPCD composition immediately before the thin film distillation to the above lower limit or higher, it is possible to prevent the fluidity of the PEPCD composition immediately before the thin film distillation from decreasing. On the other hand, when the content is not more 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 PEPCD is produced using a catalyst, the catalyst used in the obtained PEPCD remains as a metal. That is, PEPCD is obtained as a PEPCD composition containing a metal. The metal content in this PEPCD composition is preferably 1 mass ppm or more and 500 mass ppm or less.
If this metal content exceeds the above upper limit, the metal derived from the catalyst adversely affects the polyurethane-forming reaction, and it becomes difficult to control the polyurethane-forming reaction. On the other hand, in order to reduce the metal content below the above lower limit, deactivation of the catalyst and excessive load on the purification of PEPCD are applied, which is industrially unfavorable. The content of the metal in the PEPCD composition is more preferably 3 to 300 mass ppm, still more preferably 5 to 100 mass ppm.
Here, the PEPCD composition is usually referred to as "PEPCD", which is obtained by producing PEPCD by the above-mentioned method and, if necessary, inactivating or purifying the catalyst.
In the present invention, in order to indicate the amount of residual metal in PEPCD, the composition is not composed of PEPCD alone, but is referred to as a "PEPCD composition" for convenience as a composition containing a metal. , PEPCD and residual catalytic metal.

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

[Use of PEPCD]
The PEPCD of the present invention is useful as a raw material for polyurethane 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 an aqueous polyurethane emulsion can be produced and used from PEPCD of the present invention.
The use of PEPCD of the present invention will be further described later.
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 and the like, sealants, adhesives and the like 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.

[Use of PEPCD]
The PEPCD of the present invention is useful as a raw material for polyurethane 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 an aqueous polyurethane emulsion can be produced and used from PEPCD of the present invention.
The use of PEPCD of the present invention will be further described later.
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 and the like, sealants, adhesives and the like 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 an aqueous polyurethane emulsion is produced using the PEPCD of the present invention, at least one hydrophilic functional group and at least one hydrophilic functional group are used when the polyol containing the PEPCD of the present invention is reacted with an excess of polyisocyanate to produce a prepolymer. A compound having two isocyanate-reactive groups is mixed to form a prepolymer, and a water-based polyurethane emulsion is obtained through a neutralization chloride step of a hydrophilic functional group, an emulsification step by adding water, and a chain extension reaction step. Can be done.

The hydrophilic functional group of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups used here is, for example, a carboxyl group or a sulfonic acid group, and is neutralized with an alkaline group. It is a possible group. The isocyanate-reactive group is a group that generally reacts with isocyanate to form a urethane bond or a urea bond, such as a hydroxyl group, a primary amino group, or a secondary amino group, and these are mixed in the same molecule. It doesn't matter if you have it.

Specific examples of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups include 2,2'-dimethylol propionic acid, 2,2-methylol butyric acid, and 2,2. '-Dimethylol valeric acid and the like can be mentioned. In addition, diaminocarboxylic acids such as lysine, cystine, 3,5-diaminocarboxylic acid and the like can also be mentioned. These may be used alone or in combination of two or more. 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 an aqueous polyurethane emulsion, the lower limit of the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is the present invention in order to improve the dispersion performance in water. It is preferably 1% by mass, more preferably 5% by mass, and further preferably 10% by mass with respect to the total weight of the PEPCD and the other polyols. On the other hand, in order to maintain the characteristics of the polycarbonate diol, the upper limit thereof is preferably 50% by mass, more preferably 40% by mass, and further preferably 30% by mass.

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

When a solvent-free aqueous polyurethane emulsion is produced using PEPCD of the present invention as a raw material, the upper limit of the number average molecular weight obtained from the hydroxyl value of PEPCD used is preferably 5000, more preferably 4500, and further 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 obtained from the hydroxyl value is within the above range, emulsification tends to be easy.

Anionic surfactants typified by higher fatty acids, resin acids, acidic fatty alcohols, sulfate esters, higher alkyl sulfonic acids, alkylaryl sulfonates, sulfonated castor oil, sulfosuccinic acid esters, etc. for the synthesis or storage of aqueous polyurethane emulsions. Cationic surfactants such as activators, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, pyridinium salts, or ethylene oxide with long-chain fatty alcohols or phenols. A nonionic surfactant typified by a known reaction product may be used in combination to maintain emulsion stability.

Further, when preparing an aqueous polyurethane emulsion, water is mechanically mixed with a prepolymer organic solvent solution in the presence of an emulsifier in the presence of an emulsifier without a neutralizing chloride step, if necessary, to produce an emulsion. You can also do it.

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

Specific uses of the water-based polyurethane emulsion include, for example, coating agents, water-based paints, adhesives, synthetic leather, and artificial leather. In particular, the water-based polyurethane emulsion produced using PEPCD of the present invention contains an alkoxy / allyloxy terminal so that PEPCD has a predetermined terminal alkoxy / allyloxy terminal, and therefore has flexibility and is a conventional polycarbonate diol as a coating agent or the like. It can be effectively used as compared with the water-based polyurethane emulsion using or PTMG. In particular, since it has a hydrophilic group as compared with the conventional water-based polyurethane emulsion using PTMG, it has a good affinity for water, and a higher molecular weight PEPCD of the present invention can be used, so that it can be used as a coating film or synthetic. Softness and transparency can be imparted by leather, artificial leather, etc. In addition, since it is excellent in dispersibility in water, the degree of freedom in molecular design of the water-based polyurethane emulsion is increased, and it is possible to obtain a matte property by adjusting the composition.

The storage stability of a polyurethane solution and an aqueous polyurethane emulsion produced using the PEPCD of the present invention using an organic solvent and / or water is defined as the concentration of polyurethane in the solution or the emulsion (hereinafter referred to as "solid content concentration"). (Sometimes referred to as) can be adjusted to 1 to 80% by mass, stored under specific temperature conditions, and then visually measured for changes in the solution or emulsion. For example, a polyurethane solution (N, N-dimethylformamide / toluene mixed solution, solid content concentration of 30 mass) produced by the above-mentioned two-step method using PEPCD, 4,4'-dicyclohexylmethanediisocyanate and isophoronediamine of the present invention. %), The period in which no change is visually observed in the polyurethane solution when stored at 10 ° C. is preferably 1 month, more preferably 3 months or longer, still more preferably 6 months or longer.

[Polyurethane]
The polyurethane of the present invention is manufactured using the PEPCD of the present invention, and contains a structural unit derived from the PEPCD of the present invention.
The polyurethane of the present invention is produced by subjecting a raw material containing the PEPCD of the present invention and a compound having a plurality of isocyanate groups (hereinafter, may be referred to as "polyisocyanate compound" or "polyisocyanate") to an addition polymerization reaction. Will be done.
Usually, the polyurethane of the present invention can produce the polyurethane of the present invention by a usual 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 PEPCD of the present invention with a polyisocyanate compound and a chain extender in the range of room temperature to 200 ° C.
Further, the PEPCD of the present invention is first reacted with an excess polyisocyanate compound to produce a prepolymer having an isocyanate group at the terminal, and then 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 be any compound having two or more isocyanate groups, and examples thereof include various known polyisocyanate compounds of aliphatic, alicyclic or aromatic.

For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimerized isocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group, etc. 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 (isocyanisocyanmyl) cyclohexane; xylylene diisocyanate, 4,4'-diphenyl diisocyanate, toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate), m-phenylene diisocyanate, p. -Pholuene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyldiisocyanide, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3, Examples thereof include aromatic diisocyanate compounds such as 3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more.

Among these, aromatic polyisocyanate compounds are preferable because of their reactivity with PEPCD and the high curability of the obtained polyurethane, and 4,4'-diphenylmethane diisocyanate is particularly industrially inexpensive and can be obtained in large quantities. (Hereinafter, it may be referred to as "MDI"), toluene diisocyanate (TDI), and xylylene diisocyanate are preferable.

<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 an isocyanate group, and is selected from polyols and polyamines.

Specific examples thereof 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, dimerdiol and other diols having branched chains. 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 amines; 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), xylylene diamine, diphenyldiamine, tri Polyamines such as rangeamine, hydrazine, piperazine, N, N'-diaminopiperazine; and the like can be mentioned.

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 is excellent in flexibility and elastic recovery due to excellent phase separation between the soft segment and hard segment of polyurethane obtained, and in that it can be obtained in large quantities at low cost industrially. -Butandiol and 1,6-hexanediol are preferred.

<Chain terminator>
When producing the polyurethane of the present invention, a chain terminator having one active hydrogen group can be used, if necessary, for the purpose of controlling the molecular weight of the obtained polyurethane.
Examples of these chain terminators include aliphatic monools such as methanol, ethanol, propanol, butanol and hexanol having one hydroxyl group, diethylamine having one amino group, dibutylamine, n-butylamine, monoethanolamine and diethanolamine. , Morphophorin and other aliphatic monoamines are exemplified.
These may be used alone or in combination of two or more.

<Catalyst>
In the polyurethane forming reaction when producing the polyurethane of the present invention, an amine-based catalyst such as triethylamine, N-ethylmorpholine, or triethylenediamine, an acid-based catalyst such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, or sulfonic acid, or trimethyltinlaurate. , A tin-based compound such as dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecaneate, and a known urethane polymerization catalyst typified by an organic metal salt such as a titanium-based compound can also be used. One type of urethane polymerization catalyst may be used alone, or two or more types may be used in combination.

<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 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 the production of ordinary polyurethane, and examples thereof include polyester polyols, polycaprolactone polyols, polycarbonate polyols, and polyether polyols. Among these, a polyether polyol is preferable, and a polytetramethylene ether glycol capable of obtaining urethane physical properties similar to that of PEPCD is particularly preferable. Here, the weight ratio of the PEPCD of the present invention to the total weight of the PEPCD of the present invention and other polyols is preferably 30% or more, more preferably 50% or more, still more preferably 90% or more. When the weight ratio of 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 are good.

<Polyurethane manufacturing method>
As a method for producing the polyurethane of the present invention using the above-mentioned reaction reagent, a production method generally used experimentally or industrially can be used.
As an example, a method in which the PEPCD of the present invention, other polyols used as necessary, a polyisocyanate compound and a chain extender are collectively mixed and reacted (hereinafter, may be referred to as a "one-step method"). A method of first reacting the PEPCD of the present invention, other polyols and polyisocyanate compounds used as necessary to prepare a prepolymer having an isocyanate group at both ends, and then reacting the prepolymer with a chain extender. (Hereinafter, it may be referred to as "two-step method").

The two-step method goes through a step of preparing a two-terminal isocyanate intermediate of a portion corresponding to a soft segment of polyurethane by reacting PEPCD of the present invention with a polyol other than the above in advance with one equivalent or more of a polyisocyanate compound. It is a thing. As described above, when the prepolymer is once prepared and then reacted with the chain extender, it may be easy to adjust the molecular weight of the soft segment portion, and when it is necessary to reliably perform phase separation between the soft segment and the hard segment. Is useful.

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

If the amount of the polyisocyanate compound used is not more than the above upper limit, unreacted isocyanate groups may cause a side reaction, and the viscosity of the obtained polyurethane may become too high, making it difficult to handle or impairing flexibility. If it is not more than the above lower limit, the molecular weight of polyurethane becomes sufficiently large, and a sufficient strength tends to be obtained.

The amount of the chain extender used is not particularly limited, but the lower limit is preferably 1 equivalent when the total number of hydroxyl groups of PEPCD and other polyols of the present invention is subtracted from the number of isocyanate groups of the polyisocyanate compound. Is 0.7 equivalents, more preferably 0.8 equivalents, even more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, with an upper limit of preferably 3.0 equivalents, more preferably 2.0 equivalents, and further. It is preferably 1.5 equivalents, particularly preferably 1.1 equivalents. If the amount of the chain extender used is not more than the above upper limit, the obtained polyurethane tends to be easily dissolved in the solvent and processed easily, and if it is more than the above lower limit, the obtained polyurethane is not too soft and has sufficient strength. Hardness, elastic recovery performance and elastic holding performance can be obtained, and heat resistance is also good.

(Two-step method)
The two-step method is also called a prepolymer method, and there are mainly the following methods.
(A) From the amount in which the reaction equivalent ratio of the polyisocyanate compound / (PEPCD of the present invention and other polyols) exceeds 1 in advance with the PEPCD of the present invention, other polyols, and the excess polyisocyanate compound. A method for producing a polyurethane by reacting at 0 or less to produce a prepolymer having an isocyanate group at the end of the molecular chain, and then adding a chain extender to the prepolymer.
(B) The reaction equivalent ratio of the polyisocyanate compound and the excess PEPCD of the present invention and other polyols to the polyisocyanate compound / (PEPCD of the present invention and other polyols) is 0.1 or more. A method for producing a polyurethane by reacting it with less than 0 to produce a prepolymer having a hydroxyl group at the end of the molecular chain, and then reacting it with a polyisocyanate compound having an isocyanate group at the end as a chain extender.

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 performed by any of the methods (1) to (3) described below.
(1) A prepolymer is synthesized by directly reacting the polyisocyanate compound with the PEPCD of the present invention and other polyols without using a solvent, and is used as it is for the chain extension reaction.
(2) The prepolymer is synthesized by the method of (1), then dissolved in a solvent, and used for the subsequent chain extension reaction.
(3) A solvent is used from the beginning to react the polyisocyanate compound with PEPCD of the present invention and other polyols, and then a chain extension reaction is carried out.

In the case of the method (1), in the chain extension reaction, polyurethane coexists with the solvent by a method such as dissolving the chain extender in a solvent or dissolving the prepolymer and the chain extender in the solvent at the same time. It is important to get in.
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 PEPCD and other polyols of the present invention is 1 equivalent is used. The lower limit is preferably an amount exceeding 1.0 equivalent, more preferably 1.2 equivalent, still more preferably 1.5 equivalent, and the upper limit is preferably 10.0 equivalent, more preferably 5.0 equivalent, still more preferably. It is in the range of 3.0 equivalents.

If the amount of the polyisocyanate compound used is not more than the above upper limit, there is a tendency to suppress side reactions due to excess isocyanate groups to easily reach the desired physical properties of polyurethane, and if it is more than the above lower limit, the molecular weight of the obtained polyurethane is Can be sufficiently raised 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 equivalent, more preferably 0.5 equivalent, still more preferably 0 equivalent, relative to 1 equivalent of the isocyanate groups contained in the prepolymer. It is 8.8 equivalents, with an upper limit preferably in the range of 5.0 equivalents, more preferably 3.0 equivalents, and even more preferably 2.0 equivalents.

When the chain extension reaction is carried out, monofunctional organic amines and alcohols may coexist for the purpose of adjusting the molecular weight.
Further, the amount of the polyisocyanate compound used in producing a prepolymer having a hydroxyl group at the end in the two-step method (b) is not particularly limited, but the total hydroxyl groups of PEPCD and other polyols of the present invention are not particularly limited. 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. It is more preferably 0.98 equivalent, still more preferably 0.97 equivalent.

If the amount of the polyisocyanate compound used is not less than the above lower limit, the process until the desired molecular weight is obtained 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 obtained polyurethane from becoming too high and the poor handling and the inferior productivity.
The amount of the chain extender used is not particularly limited, but when the total number of hydroxyl groups of the PEPCD of the present invention used for the prepolymer and other polyols is 1 equivalent, the equivalent of the isocyanate group used for the prepolymer is added. 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.

When the chain extension reaction is carried out, monofunctional organic amines and alcohols may coexist for the purpose of adjusting the molecular weight.
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 and the like, and is not particularly limited. If the temperature is equal to or higher than the above lower limit, the reaction proceeds quickly and the solubility of the raw material or the polymer is high, so that the production time is shortened. If the temperature is below the above upper limit, side reactions and decomposition of the obtained polyurethane can be suppressed. The chain extension reaction may be carried out while defoaming under reduced pressure.

Further, a catalyst, a stabilizer, or the like can be added to the chain extension reaction, if necessary.
Examples of the catalyst include compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid, and one type may be used alone or two or more types may be used. It may be used together. Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, disstearylthiodipropionate, N, N'-di-2-naphthyl-1,4-phenylenediamine, tris (dinonylphenyl) phosphite and the like. The above compounds may be mentioned, and one kind may be used alone, or two or more kinds may be used in combination. If the chain extender is highly reactive, such as a short-chain aliphatic amine, it may be carried out without adding a catalyst.
Further, a reaction inhibitor such as tris phosphite (2-ethylhexyl) can also be used.

<Additives>
Various additions of heat stabilizers, light stabilizers, colorants, fillers, stabilizers, ultraviolet absorbers, antioxidants, anti-adhesive agents, flame retardants, anti-aging agents, inorganic fillers, etc. to the polyurethane of the present invention. The agent can be added and mixed as long as the characteristics 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 group-substituted aromatic esters of phosphoric acid, hypophosphite derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, and dialkyl. Phosphorus compounds such as Pentaerythritol diphosphite and dialkylbisphenol A diphosphite; phenolic derivatives, especially hindered phenolic compounds; thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, thiodipropionic acid esters, etc. Compounds containing sulfur; tin-based compounds such as summalate and dibutyltin monooxide can be used.

Specific examples of the hindered phenol compound include "Irganox 1010" (trade name: manufactured by BASF Japan Ltd.), "Irganox 1520" (trade name: manufactured by BASF Japan Ltd.), and "Irganox 245" (trade name: manufactured by BASF Japan Ltd.). ) Etc. can be mentioned.
Examples of the phosphorus compound include "PEP-36", "PEP-24G", "HP-10" (trade name: manufactured by ADEKA Corporation), "Irgafos 168" (trade name: manufactured by BASF Japan Ltd.), etc. Can be mentioned.

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

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

Coloring agents include direct dyes, acidic dyes, basic dyes, metal complex salt dyes and other dyes; carbon black, titanium oxide, zinc oxide, iron oxide, mica and other inorganic pigments; and coupling azo and condensed azo, Examples thereof include organic pigments such as anthraquinone-based, thioindigo-based, dioxazone-based, and phthalocyanine-based.

Examples of the inorganic filler include glass staple fibers, carbon fibers, alumina, talc, graphite, melamine, white clay and the like.

Examples of flame retardants include addition of phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide and the like, and reactive flame retardants.

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

The lower limit of the amount of these additives added to the polyurethane is preferably 0.01% by mass, more preferably 0.05% by mass, still more preferably 0.1% by mass, and the upper limit is preferably 10. It is by mass, more preferably 5% by mass, and even more preferably 1% by mass. If the amount of the additive added is not less than the above lower limit, the effect of addition can be sufficiently obtained, and if it is not more than the above upper limit, there is no possibility of precipitation or turbidity in polyurethane.

<Molecular weight of polyurethane>
The molecular weight of the polyurethane of the present invention is appropriately adjusted according to its use and is not particularly limited, but is preferably 50,000 to 400,000 as the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC. It is more preferably 10,000 to 300,000, and even more preferably 120,000 to 300,000. When Mw is not less than the above lower limit, sufficient strength and hardness can be obtained, and when it is not more than the above upper limit, handleability such as workability tends to be excellent.

<Use of polyurethane>
Since the polyurethane of the present invention has excellent solvent resistance, good flexibility and mechanical strength, foams, elastomers, elastic fibers, paints, fibers, adhesives, adhesives, flooring materials, sealants, medical materials, etc. It can be widely used in artificial leathers, synthetic leathers, coating agents, water-based polyurethane paints, 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 cloth, waterproof cloth, water-based polyurethane, adhesive, elastic fiber, medical material, flooring material, paint, coating agent, etc., it is resistant to use. It has a good balance of solventiness, flexibility and mechanical strength, so it is highly durable and flexible in areas that come into contact with human skin or where cosmetic chemicals or disinfectant alcohol are used. Moreover, it is possible to impart good characteristics such as resistance to physical impact. Further, it can be suitably used for automobile applications where heat resistance is required and outdoor applications where weather resistance is required.

The polyurethane of the present invention can be used for polyurethane elastomers such as cast polyurethane elastomers. Specific applications include rolling rolls, paper rolls, office equipment, rolls such as pretension rolls, forklifts, automobile vehicle nut trams, trolleys, solid tires such as transport vehicles, casters, etc., as industrial products such as conveyor belt idlers and guides. Rolls, pulleys, steel pipe linings, rubber screens for ore, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, etc. It can also be used for belts of office automation equipment, paper feed rolls, cleaning blades for copying, snow plows, toothed belts, surflorers and the like.

The polyurethane of the present invention is also applied to applications as a thermoplastic elastomer. For example, it can be used for tubes and hoses, spiral tubes, fire hoses and the like in pneumatic equipment, painting equipment, analytical equipment, physics and chemistry equipment, metering pumps, water treatment equipment, industrial robots and the like used in the food and medical fields. Further, as a belt such as a round belt, a V-belt, a flat belt, etc., it is used in various transmission mechanisms, spinning machines, packing machines, printing machines and the like. It can also be used for footwear heel tops, soles, couplings, packing, pole joints, bushes, gears, rolls and other equipment parts, sports equipment, leisure equipment, watch belts and the like. Further, examples of automobile parts include oil stoppers, gearboxes, spacers, chassis parts, interior parts, tire chain substitutes and the like. It can also be used for keyboard films, films such as automobile films, curl cords, cable sheaths, bellows, conveyor belts, flexible containers, binders, synthetic leather, depinning products, adhesives and the like.

The polyurethane elastomer made of polyurethane of the present invention can be further made into a foamed polyurethane elastomer or a polyurethane foam. As a method of foaming or foaming the polyurethane elastomer, for example, chemical foaming using water or mechanical foaming such as mechanical floss may be used, and other rigid foams obtained by spray foaming, slab, injection, or molding may be used. Similarly, slabs, soft foams obtained by molding, and the like can be mentioned.
Specific applications for polyurethane foam elastomers or polyurethane foams include electronic devices, railway rails and building insulation and vibration isolation materials, automobile seats, automobile ceiling cushions, bedding such as mattresses, insoles, midsole and soles. Can be mentioned.

The polyurethane of the present invention can also be applied to applications 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 a moisture-curable one-component paint, a blocked isocyanate-based solvent paint, an alkyd resin paint, a urethane-modified synthetic resin paint, an ultraviolet curable paint, a water-based urethane paint, and the like. Overprint varnishes for plastic bumper paints, strippable paints, magnetic tape coatings, floor tiles, flooring materials, paper, wood grain printing films, wood varnishes, coil coats for high processing, optical fiber protective coatings, solder resists, metals It can be applied to top coats for printing, base coats for vapor deposition, white coats for food cans, and the like.

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

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

When the polyurethane of the present invention is used as an elastic fiber, the method for fiberizing the polyurethane can be carried out without particular limitation as long as it can be spun. For example, a melt spinning method can be adopted in which pellets are once pelletized, melted, and then directly spun through a spinneret. When elastic fibers are 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 fiber made of polyurethane of the present invention can be used as it is as a bare yarn, or it can be coated with another fiber and used as a coating yarn. Examples of other fibers include conventionally known fibers such as polyamide fiber, wool, cotton, and polyester fiber, and polyester fiber is preferably used. Further, the elastic fiber made of polyurethane of the present invention may contain a dyeing type disperse dye.

The polyurethane of the present invention can be used as a sealant coking, such as concrete casting walls, induced joints, sash circumferences, wall-type PC (Precast Concrete) joints, ALC (Autoclaved Light-weight Concrete) joints, board joints, and sealants for composite glass. It can be used for heat insulating sash sealants, automobile sealants, roof waterproof sheets, etc.

The polyurethane of the present invention can be used as a medical material, and as a blood compatible material, a tube, a catheter, an artificial heart, an artificial blood vessel, an artificial valve, etc., and as a disposable material, a catheter, a tube, a bag, a surgical glove, etc. , Can be used as an artificial kidney potting material, etc.

The polyurethane of the present invention can be used as a raw material for UV curable paints, electron beam curable paints, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating material compositions, etc. by modifying the ends. can.

[Use of polyurethane]
The uses of the polyurethane of the present invention will be described in detail below for each use.

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

Since PEPCD consists of an ether bond and a carbonate bond, it has a high oxygen content and can exhibit sufficient moisture permeability even in a non-porous type. That is, it is a single polyol that has both the moisture permeability of PEG and the durability of PCD. Therefore, the water pressure resistance can be 10,000 mm or more, and further 20,000 mm or more can be achieved. Moreover, with respect to moisture permeability, it is possible to exhibit a performance of 10,000 g / ^m 2-24 hrs or more, and further 15,000 g / ^m 2-24 hrs or more.

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

Any method can be used to form the moisture-permeable and waterproof coating film. As a non-porous type manufacturing method, for example, a release paper is coated with a polyurethane solution for an epidermis layer to which an antiblocking agent or a pigment is added to prevent the films from sticking to each other, and dried to form a film. .. A polyurethane solution for an adhesive layer composed of polyurethane, a cross-linking agent, a solvent, a catalyst, etc. is coated on the surface, and the polyurethane solution is pressure-bonded to the base material. The solvent of the adhesive layer is volatilized in a dryer, and the curing reaction is completed by aging. When the release paper is peeled off, a non-porous film type moisture permeable waterproof cloth can be obtained.

The polyurethane using PEPCD of the present invention can also be applied to the coating of a porous type moisture permeable waterproof cloth. As a method for producing a porous type, for example, a polyurethane solution for an epidermis layer is coated on a base material which has been pretreated so that the solution does not enter more than necessary, and the solution is immersed in a coagulation bath. During the immersion, the solvent in the polyurethane solution is extracted, the resin is precipitated and solidified, and a polyurethane layer having a porous structure having many voids is formed. After that, when it is dried, a microporous membrane type moisture permeable waterproof cloth is obtained. PEPCD has appropriate hydrophilicity and flexibility due to the balance between carbonate bond and ether bond, and provides excellent moisture permeable and waterproof cloth not only in terms of moisture permeable and waterproof performance but also in terms of comfort when wearing clothes.

The breathable waterproof cloth produced by using PEPCD of the present invention is suitably used for outdoor rainwear, windbreakers, cold protection wear, shoes, tents, rucksacks, bags, shoes and the like.

<Cellulose nanofiber treatment agent>
The polyurethane using PEPCD of the present invention can be used as a cellulose nanofiber treatment agent. Cellulose nanofibers (CNF) are ultra-fine 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 of steel), strong (strength 3 GPa, about 5 times that of steel), and large specific surface area (250 m ² / g or more). High adsorption characteristics, hard (tensile elastic modulus of about 140 GPa, equivalent to aramid fiber), small expansion and contraction due to heat (linear expansion coefficient 0.1 to 0.2 ppm / K, about 1/50 of glass), heat comparable to glass It is an extremely promising material as a filler for reinforcing various plastics because it is easy to convey and has excellent biocompatibility. However, it is difficult to knead a strongly hydrophilic CNF into a normally hydrophobic plastic, which has been a big issue for its widespread use.
The polyurethane using PEPCD of the present invention becomes a polymer having appropriate hydrophilicity by controlling the ether bond concentration in the polyol, 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, and it becomes possible to knead the hydrophobic general-purpose resin such as polypropylene, polyethylene, PET, PBT, polycarbonate, polyamide and the like. The CNF finely and uniformly dispersed in the resin forms a strong network, efficiently exerts a reinforcing effect, increases the strength and elastic modulus, and can significantly reduce the linear expansion coefficient.

<Paints for automobile interiors>
The polyurethane using PEPCD of the present invention can be used as an interior paint for automobiles. Large plastic parts used for automobile interiors are usually painted for the purpose of concealing molding defects and at the same time protecting them while giving them a design. Since the usage environment is touched by human hands or exposed to strong direct sunlight, high light resistance, heat resistance, chemical resistance, and scratch resistance are required, and good tactile sensation and high design are required. Will be done. Further, in order to improve productivity and save energy, dry curability at low temperature in a short time is required.
Polyurethane using PEPCD of the present invention has high durability and excellent tactile sensation by controlling the concentration, molecular weight and number of functional groups of carbonate bond and ether bond, and has low tack free time and low temperature curing due to low adhesiveness. Is possible. In addition, since the compression set is small, the self-healing coating film is naturally repaired from scratches caused by nails and the like. Therefore, it can be used as a main agent for paints for automobile interior parts such as instrumental panels and center consoles.

<Paint for home appliance housing>
The polyurethane using PEPCD of the present invention can be used as a paint for a home appliance housing. The plastic housing of home appliances may be painted for the purpose of anti-glare, anti-fouling, protection, tactile sensation, and design. The coating film needs to have adhesiveness to substrates such as polystyrene, ABS, and polycarbonate, chemical resistance to acids, alkalis, oils and fats, spray coating, low temperature drying, and scratch resistance during transportation by packaging materials. Will be done.
The polyurethane using PEPCD of the present invention has excellent resistance by controlling the carbonate bond / ether bond concentration, adjusting the molecular weight and the number of functional groups, selecting the diisocyanate and the chain extender, and adjusting the hard segment content and the molecular weight. It has chemical properties, adhesiveness, and scratch resistance, and can be used as the main agent of paints for home appliance housings.

<Gravure ink>
The polyurethane using PEPCD of the present invention can be used for gravure ink. Since gravure ink can print long films and papers at high speed and obtain multicolored high-definition printed matter, it is widely used for food packaging material films, building material wallpaper, decorative sheets, and the like. Gravure ink for packaging is required to have a high degree of printability, and in particular, the resolubility of the ink, acid resistance after printing, alkali resistance, and oil resistance are strict.
The 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, the gravure ink for building materials is 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 is introduced by a urethane bond and a diamine-based chain extender to improve resolubility by controlling the number of functional groups and optimizing the ether bond concentration. By controlling the concentration of urea bond, blocking on the back surface of the film can be suppressed, and it can be used as a binder resin for gravure ink for printing various films for building materials.

<Paint for building exterior>
The polyurethane using PEPCD of the present invention can be used as a paint for building exteriors. Architectural exterior paints are required to have a high gloss appearance, stain resistance, long-term wind and rain, and high weather resistance to withstand sunlight. On the other hand, the conventional solvent system has been shifted to a weak solvent system with less irritation, and more environmentally friendly water-based treatment is in progress. It is becoming difficult to maintain the required performance due to the water system.
The polyurethane using PEPCD of the present invention can reduce the particle size of the emulsion by controlling the carbonate bond / ether bond concentration and optimizing the hydrophilicity, and the surface of the coating film has less unevenness when it is used as a water-based paint. A high-gloss appearance can be obtained. In addition, since it has high weather resistance derived from polycarbonate, it is most suitable as a resin for paints for building exteriors. Further, by maximizing the hydrophilicity of the coating film surface, a low-contamination coating film that weakens the adhesive force of lipophilic contaminants and facilitates cleaning is formed.

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

<Seal for information electronic materials>
The polyurethane using PEPCD of the present invention can be used as a sealing agent for information and electronic materials. In each field of information and electronic materials, various encapsulants are used to protect various functional elements from the environment. These encapsulants are required to have barrier properties, heat resistance, hydrolysis resistance, transparency, light resistance, adhesiveness, flexibility, mechanical strength and the like.
Polyurethane using PEPCD of the present invention has high weather resistance derived from polycarbonate, enhances oxygen and water vapor barrier properties by controlling the polyether bond concentration and the number of functional groups, and diisocyanates, types of chain extenders, and hard segments. By adjusting the content, other required performance can be adjusted in a well-balanced manner, and it can be used as a resin for a sealing agent for a light emitting element of a flat panel display, a solar cell panel, or the like.

<Ultra-low hardness, low compression, permanent strain non-foam resin>
The polyurethane using PEPCD of the present invention can be used as an ultra-low hardness, low compression, permanent strain non-form resin. In order to reduce the hardness, it is necessary to increase the molecular weight between crosslinks and introduce a flexible ether structure in order to increase the flexibility of the molecular chain. Further, in order to achieve low compression strain, it is necessary to increase the number of functional groups and minimize the loss of the crosslinked structure. PEG lacks mechanical properties, PTMG is difficult to polyfunctionalize, and PPG has low reactivity because the terminal OH group binds to secondary carbon and is olefinized by dehydration at a constant ratio. Not durable for use.
In the PEPCD of the present invention, as long as a polyfunctional alcohol having an OH group bonded to a primary carbon is used as a raw material, an OH group bonded to a highly reactive primary carbon always remains at the terminal, so that complete cross-linking while increasing the molecular weight between cross-links is completed. Polyurethane with a structure is obtained, and since it has high weather resistance derived from polycarbonate, it is a material for various special rolls used in printing machines and copying machines as a non-form molded product with high durability, flexibility comparable to foam, and compression set. It is effective as.

<Polyurethane soft foam>
The polyurethane using PEPCD of the present invention can be used for flexible polyurethane foam. In order to reduce the hardness, it is necessary to increase the molecular weight between crosslinks and introduce a flexible ether structure in order to increase the flexibility of the molecular chain. Further, in order to achieve low compression strain, it is necessary to increase the number of functional groups and minimize the loss of the crosslinked structure. PEG lacks mechanical properties, PTMG is difficult to polyfunctionalize, and PPG has low reactivity because the terminal OH group binds to secondary carbon and is olefinized by dehydration at a constant ratio. Not durable for use.
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 terminal, so that complete cross-linking while increasing the molecular weight between cross-links is completed. Various special rolls used in printing machines and copying machines as foam moldings with high durability, flexibility, low compression set, and high repulsion elasticity because polyurethane with a structure is obtained and has high weather resistance derived from polycarbonate. It is effective as a material for shoe soles, urethane bats, pillows for railway rails, and anti-vibration materials. This characteristic is particularly remarkable in a high-density foam 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 between polyisocyanate and hydroxyalkyl (meth) acrylate to form a urethane (meth) acrylate-based oligomer (hereinafter, may be referred to as “urethane (meth) acrylate-based oligomer of the present invention”). Can be manufactured. When a polyol, which is another raw material compound, a chain extender, or the like is used in combination, the urethane (meth) acrylate-based oligomer can be produced by subjecting polyisocyanate to an addition reaction of these other raw material compounds. .. The urethane (meth) acrylate of the present invention gives an active energy ray-curable resin composition by blending with other raw materials. This active energy ray-curable resin composition can be widely used in various surface processing fields and cast-molded products. This active energy ray-curable resin composition has features of excellent balance between hardness and elongation, solvent resistance, and handleability when cured to form a cured film, and is characterized by being a UV curable paint and electron beam curing. It can be used as a raw material for mold paints, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating material compositions, and the like.

The urethane (meth) acrylate-based oligomer of the present invention can be produced by adding polyisocyanate, hydroxyalkyl (meth) acrylate, and other compounds as necessary, in addition to PEPCD of the present invention. Examples of the polyisocyanate that can be used in producing a urethane (meth) acrylate-based oligomer include polyisocyanates such as tris (isocyanatohexyl) isocyanurate, in addition to the above-mentioned organic diisocyanate.
The hydroxyalkyl (meth) acrylate that can be used is a compound having one or more hydroxyl groups and one or more (meth) acryloyl groups, as typified by 2-hydroxyethyl (meth) acrylate. If there is, it is not particularly limited. Further, 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, and these may be used in any combination.

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 photointegrators as well as other additives 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 having excellent stain resistance and protection against general household contaminants such as ink and ethanol. be.
The laminate using the cured film as a film on various substrates is excellent in design and surface protection, and can be used as a coating substitute film. For example, building materials for interior or exterior and automobiles. It can also be effectively applied to various parts such as home appliances.

[Use of polyester elastomer]
The PEPCD of the present invention can be used as a polyester-based elastomer. The polyester-based elastomer is a copolymer composed of a hard segment mainly composed of aromatic polyester and a soft segment mainly composed of aliphatic polyether, aliphatic polyester or aliphatic polycarbonate. When PEPCD of the present invention is used as a constituent component of a soft segment of a polyester-based elastomer, physical properties such as heat resistance and water resistance are excellent as compared with the case of using an aliphatic polyether or an aliphatic polyester. Further, even when compared with known polycarbonate polyols, a polyether carbonate ester having fluidity at the time of melting, that is, a melt flow rate suitable for blow molding and extrusion molding, and having 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, for example, elastic threads and molding materials such as boots, gears, tubes and packings. Specifically, it can be effectively applied to joint boots for automobiles, home appliance parts, etc., which require heat resistance and durability, and electric wire covering materials.

[Use of (meth) acrylic resin]
The PEPCD of the present invention can be derived into a novel (meth) acrylate by converting one or both of the terminal hydroxyl groups into (meth) acrylate. As the method for producing the (meth) acrylate, any of the corresponding (methacrylate) anhydrate, halide, and ester can be used.
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 a property of being cured by polymerization in a short time by active energy rays such as ultraviolet rays, and generally has excellent transparency, and the cured product has toughness, flexibility, scratch resistance, and scratch resistance. It is possible to have excellent properties such as chemical properties. 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.

Hereinafter, the present invention will be described in more detail 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〕
The evaluation methods of PEPCD and polyurethane obtained in the following Examples and Comparative Examples are as follows.

[Hydroxy group value / number average molecular weight of PEPCD]
The hydroxyl value of PEPCD was measured by a method using an isocyanateing reagent according to the method of ASTM E1899-16.
Further, 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)

[PEPCD composition analysis]
The mass ratio of the structural unit A and the structural unit B in PEPCD was determined by analyzing the mass of each dihydroxy compound obtained by hydrolyzing PEPCD with an alkali by gas chromatography. Specifically, the analysis was performed by the following method.
0.5 g of PEPCD was precisely weighed into a 100 mL flask, dissolved in 5 mL of THF, and 45 mL of methanol was added. Then, after adding 5 mL of a 25 mass% NaOH aqueous solution, a condenser was set in a 100 mL flask, and methanol was refluxed at 70 to 75 ° C. for 30 minutes for hydrolysis. 6N-HCl was added to the obtained reaction solution until it became neutral. The concentration of each dihydroxy compound was determined by GC analysis of the solution after the solution was finally made up to 100 mL with THF. A calibration curve of each dihydroxy compound with respect to the internal standard was prepared, and the mass ratio of each dihydroxy compound in PEPCD was calculated from the concentration. The mass ratio of the hydrolyzate of the structural unit A and the structural unit B obtained here was defined as the mass ratio of the structural unit A and the structural unit B. When the PEPCD is composed of only the structural unit A and the structural unit B, the mass ratio of the structural unit A is calculated by subtracting the mass ratio of the structural unit B from the whole.

[PEPCD terminal alkoxy / allyloxy ratio]
PEPCD was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (ECZ-400 manufactured by JEOL Ltd.) was measured and calculated from the integrated value of the signal of each component.
-OCH ₃ end group: δ3.33 (s, 3H)
-OCH ₂ CH ₂ CH ₂ CH ₃ Terminal group: δ0.91 (t, 3H)
It should be noted that the above-mentioned signal values may deviate due to the difference in the structure of PEPCD. The detection limit of the terminal alkoxy / allyloxy ratio 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 reaction conditions of PEPCD is used, the metal content concentration (ppm) corresponds to the ratio of the amount of metal catalyst (g) used for charging to the yield (g) of PEPCD.
The following method (ICP-MS) was used as the analysis method.
0.2 g of the PEPCD composition was precisely weighed in a Kjeldahl flask and wet-decomposed with concentrated sulfuric acid and concentrated nitric acid. After cooling to room temperature, a solution prepared with pure water was measured by ICP-MSELEMENT2 (manufactured by Thermo Fisher Scientific), and the metal content concentration (mass ppm) in the PEPCD composition was calculated.

[Molecular weight of polyurethane]
Polyurethane was dissolved in dimethylacetamide to prepare a dimethylacetamide solution so that the concentration was 0.14% by mass. Using a GPC device [manufactured by Tosoh Corporation, product name "HLC-8220" (column: TskgelGMH-XL, 2 pieces)], the dimethylacetamide solution was injected, and the weight average molecular weight (Mw) of polyurethane was converted into standard polystyrene. And the number average molecular weight (Mn) was measured.

[Polyurethane resistance to olein acidity]
The polyurethane solution produced in Examples and Comparative Examples was applied on a fluororesin sheet (fluorine tape Nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) with a 9.5 mil applicator, and at 50 ° C. for 5 hours. , The polyurethane film (thickness 50 to 100 μm) was produced by drying at 80 ° C. in the order of 15 hours under vacuum conditions. A 3 cm × 3 cm test piece was cut out from this polyurethane film. The test piece was put into a glass bottle having a capacity of 250 mL containing 50 mL of oleic acid as a test solvent, and allowed to stand at 80 ° C. for 16 hours. After the test, the test piece was taken out and lightly wiped with a paper wiper, and then the mass was measured with a precision balance to calculate the mass change rate (increase rate, hereinafter referred to as "wet rate") from before the test. .. A wet ratio close to 0% indicates that the olefin acid resistance is good. In order to impart sufficient olein acidity and solvent resistance to polyurethane, the swelling rate is preferably 14% or less, more preferably 13% or less, further preferably 12% or less, and particularly preferably 11% or less. preferable.

[Polyurethane tensile test]
A 1 cm × 15 cm test piece was cut out from a polyurethane film (thickness 50 to 100 μm) manufactured in the same manner as in the evaluation of polyurethane olein acid resistance, and the test piece was subjected to a tensile tester (Oriente) according to JIS K6301 (2010). A tensile test was carried out using a product name "Tencilon UTM-III-100" manufactured by Ku Co., Ltd. at a chuck distance of 50 mm, a tensile speed of 500 mm / min, a temperature condition of 23 ° C., and a relative humidity of 55%. The stress at the time when the test piece was 100% stretched: 100% modulus (hereinafter, may be referred to as "100% M") was measured. The 100% modulus (100% M) is excellent in flexibility at 10 MPa or less, more preferably 8 MPa or less, still more preferably 6 MPa or less. In addition, the elongation and strength when the test piece broke were also measured. The higher the elongation and the higher the strength, the better the flexibility and mechanical strength. The breaking strength for use as a high-strength elastomer is preferably 37 MPa or more, more preferably 39 MPa or more, further preferably 42 MPa or more, and particularly preferably 45 MPa or more.

[Polyurethane wet and heat condition test]
A polyurethane test piece (a strip having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm) manufactured in the same manner as in the tensile test of polyurethane is placed in a constant temperature and humidity chamber (IH401 manufactured by Yamato Scientific Co., Ltd.) at a temperature of 70 ° C., relative to each other. After storing at 95% humidity for 14 days, the polyurethane test pieces before and after the storage were subjected to a room temperature tensile test, and the breaking elongation and breaking strength were measured. It can be said that the higher the breaking strength after the moist heat test, the higher the moist heat resistance of polyurethane. In order to use it as an elastomer having high moist heat durability, the breaking strength after the moist heat test is preferably 34 MPa or more, more preferably 36 MPa or more, further preferably 38 MPa or more, and particularly preferably 40 MPa or more. Further, it is preferable that the ratio of the strength after the moist heat test to the strength before the moist heat test is high, and the ratio is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more.

[Compound abbreviation]
The abbreviations of the compounds in Examples and Comparative Examples are as follows.
PTMG: Polyoxytetramethylene ether glycol
PTMG-1: Hydroxyl value 510.0 mg-KOH / g, number average molecular weight 220
Polyoxytetramethylene ether glycol
PTMG-2: Hydroxyl value 461.5 mg-KOH / g, number average molecular weight 243
Polyoxytetramethylene ether glycol EC: ethylene carbonate Mg (acac) ₂ : magnesium (II) acetylacetonate PD: 1,3-propanediol BG: 1,4-butanediol NPG: neopentyl glycol MDI: 4,4' -Diphenylmethane diisocyanate

[Manufacturing and evaluation of PEPCD]
[Example 1-1]
PTMG-1: 472g, BG: 193g, EC: 450g, Mg (acac) in a 2L glass separable flask equipped with a stirrer, distillate trap, pressure regulator, distillation column with 30 mmφ regular filling, and fractionator. ₂ : 345 mg was added and replaced with nitrogen gas. Under stirring, the internal temperature was raised to 150 ° C. to heat and dissolve the contents. Then, while reducing the pressure and removing ethylene glycol and EC to the outside of the system, 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. Further, 153 g of EC was further added during the polymerization to obtain a polymer.
Then, 8.5 mass% phosphoric acid / BG solution: 1.5 g was added to the obtained polymer to inactivate the catalyst. Then, the distillation column was removed, and the residual monomer was removed at 0.5 kPa and 170 ° C. to obtain a crude PEPCD-containing composition.

The obtained crude PEPCD-containing composition was sent to a thin-film distillation apparatus at a flow rate of 20 g / min, and thin-film distillation (temperature: 210 ° C., pressure: 53 Pa) was performed to obtain PEPCD. As the thin film distillation apparatus, a molecular distillation apparatus MS-300 special type manufactured by Shibata Kagaku Co., Ltd. with a diameter of 50 mm, a height of 200 mm, an area of 0.0314 m ² and a jacket was used. Table 2 shows the analytical values and physical property values of the obtained PEPCD (hereinafter referred to as “PEPCD-1”).

[Examples 1-2 to 4, Comparative Examples 1-1 and 2]
PEPCD-2 to 4 and 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, the diol compound and the carbonate compound were changed to those shown in Table 1.
The analytical values and physical property values of the obtained PEPCD are shown in Table 2.

[Manufacturing and evaluation of polyurethane]
[Examples 2-1 to 4, Comparative Examples 2-1 to 2]
Polyurethane was produced using PEPCD obtained in each of Examples 1-1 to 4 and Comparative Examples 1-1 to 2, and the physical property values were measured.

<Manufacturing of polyurethane>
Using PEPCD-1 obtained in Example 1-1 as a raw material, polyurethane was produced by the following operation.
A separable flask equipped with a thermocouple, a cooling tube and a stirrer was installed on an oil bath at 60 ° C., and 50.6 g of PEPCD-1 preheated to 80 ° C., 4.9 g of BG, and dehydration N, Add 177 g of N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.), then add 14.6 g of MDI, and raise the temperature to 80 ° C in about 1 hour while stirring the inside of the separable flask at 60 rpm under a nitrogen atmosphere. did. After the temperature reached 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. Then, MDI was added in portions so that the equal amount of NCO with respect to OH was around 1.0 to obtain polyurethane. Table 3 shows the properties of this polyurethane and the evaluation results of the physical properties.
The PEPCDs obtained in Examples 1-2 to 4 and Comparative Examples 1-1 and 2 were also used as raw materials to synthesize polyurethane, and the properties of the obtained polyurethane and the evaluation results of the physical properties are shown in Table 3.

The polyurethanes of Examples 2-1 to 4 synthesized from PEPCD-1 to 4 obtained in Examples 1-1 to 4 have any of olein acid resistance, breaking strength, and breaking strength retention rate after moist heat test. Was also an excellent polyurethane.
The polyurethane of Comparative Example 2-1 synthesized from PEPCD-R1 obtained in Comparative Example 1-1 had a large swelling rate in the olein acidity resistance evaluation and a low solvent resistance. Further, when exposed to moist heat conditions for 14 days, the breaking strength decreased to 80% or less from the state before the test. That is, the moisture and heat resistance was low.
The polyurethane of Comparative Example 2-2 synthesized from PEPCD-R2 obtained in Comparative Example 1-2 had a low weight average molecular weight and a number average molecular weight. In addition, the breaking strength and the breaking strength after the wet heat test for 14 days were low.

Claims (13)

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 3 to 6 carbon atoms (hereinafter referred to as "structural unit B"). It ’s a diol,
A polyether polycarbonate diol in which the ratio of the total number of alkoxy-terminal groups to the total number of allyloxy-terminal groups is 0.01% or more and 7.0% or less. The polyether polycarbonate diol according to claim 1, wherein the structural unit B is a structural unit derived from 1,3-propanediol and / or a structural unit derived from 1,4-butanediol. The polyether polycarbonate diol according to claim 1 or 2, wherein the hydroxyl value is 20 mg-KOH / g or more and 450 mg-KOH / g or less. The invention according to any one of claims 1 to 3, wherein the ratio of the mass of the structural unit B to the total 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. Polyether polycarbonate diol. The polyether polycarbonate diol according to any one of claims 1 to 4, wherein the alkoxy-terminated group contains a methoxy-terminated group. The polyether polycarbonate diol according to any one of claims 1 to 5, wherein the alkoxy-terminated group contains a butoxy-terminated group. A polyether polycarbonate diol composition comprising the polyether polycarbonate diol according to any one of claims 1 to 6 and a metal.
A polyether polycarbonate diol composition in which the metal is at least one selected from the group consisting of zinc and a metal of Group 2 of the Long Periodic Table. The polyether polycarbonate diol composition according to claim 7, wherein the metal content is 1 mass ppm or more and 500 mass ppm or less. The method for producing a polyether polycarbonate diol according to any one of claims 1 to 6.
A method for producing a polyether polycarbonate diol, which comprises 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 3 to 6 carbon atoms and a carbonate compound in the presence of a catalyst. .. The method for producing a polyether polycarbonate diol according to claim 9, wherein the carbonate compound is an alkylene carbonate. The catalyst is a composition containing at least one metal (M) selected from zinc and a metal of Group 2 of the long-periodic table, and at least one compound represented by the following formula (1), or the following. The method for producing a polyether polycarbonate diol according to claim 9 or 10, which is a composition having at least one salt represented by the 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. May be.
R ₂ represents a monovalent hydrocarbon group or a halogen atom having 1 to 20 carbon atoms, 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-periodic table, and n = 2. ) Polyurethane containing a structural unit derived from the polyether polycarbonate diol according to any one of claims 1 to 6. A method for producing a polyurethane in which a raw material containing the polyether polycarbonate diol according to any one of claims 1 to 6 and a compound having a plurality of isocyanate groups is subjected to an addition polymerization reaction.