JP7226042B2 - Polyether polycarbonate diol composition and method for producing the same - Google Patents

Description

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

Polyurethanes are used in a wide range of applications such as urethane foams, paints, adhesives, sealants and elastomers. Polyurethane is composed of a hard segment composed of isocyanate and a chain extender and a soft segment composed mainly of polyol. Polyol, one of the main raw materials of polyurethane, is classified into polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, acrylic polyol, polyether polycarbonate diol, etc. according to the difference in molecular chain structure. polyols are selected.

Among the above, polyurethanes in which the polyol is a polyether polycarbonate diol are liquid at room temperature and have good flexibility, so they are useful.
Conventionally, various investigations have been made on catalysts used in the production of polyether polycarbonate diols. Patent Document 1 describes the use of a sodium-based catalyst in the first step and the use of a titanium or tin-based catalyst in the second step in the production of a polycarbonate copolyetherdiol, which consists of two steps. Patent Document 2 describes the production of polyether-polycarbonate polyol using a titanium-based catalyst.

JP-A-10-45678 JP 2015-17183 A

However, the conventionally known techniques have problems of poor efficiency in the production of polyether polycarbonate diols and large amounts of by-products produced. Moreover, the produced polyether polycarbonate diol has the disadvantage that it tends to be colored, and is deteriorated particularly by heating or the like. Furthermore, when polyurethane is produced using polyether polycarbonate diol as a raw material, impurities contained in polyether polycarbonate diol make it difficult to control the reaction, and there are cases where polyurethane having desired physical properties cannot be obtained.

The present invention has been made in view of the above problems, and is a polyether polycarbonate diol composition that is less colored even when heated, and is easy to control the reaction even when used as a raw material for producing polyurethane. It is an object of the present invention to provide a polyether polycarbonate diol composition from which the produced polyurethane is less likely to be colored, and a method for producing the same.

The present inventors have made intensive studies to solve the above problems, and found that a polyether polycarbonate diol composition containing a metal and a polyether polycarbonate diol, wherein the metal is zinc and a metal of Group 2 of the long period periodic table The polyether polycarbonate diol composition is at least one selected from the group consisting of, and the polyether polycarbonate diol is a polyether polycarbonate diol containing a specific structural unit. Further, the present inventors have also found that even when used as a raw material for the production of urethane, the reaction can be easily controlled and a polyurethane which is less likely to be colored can be produced, leading to the completion of the present invention.

That is, the present invention is as follows.
[1] A polyether polycarbonate diol composition containing a metal and a polyether polycarbonate diol,
the metal is magnesium ,
The polyether polycarbonate diol contains a structural unit (A) derived from polyoxytetramethylene glycol and a structural unit (B) derived from a compound represented by the following formula (1), and the structural unit (A) and the structural unit (B ) in a molar ratio of 100:0 to 50:50.

(Wherein, R represents a divalent hydrocarbon group having 2 to 12 carbon atoms.)
[2] The metal content according to [1], wherein the content of the metal is 1 ppm by mass or more and 200 ppm by mass or less
A polyether polycarbonate diol composition.
[3] The polyether polycarbonate diol composition according to [1] or [2], wherein the polyether polycarbonate diol composition has a number average molecular weight of 250 or more and 5000 or less.

[4] Using a dihydroxy compound containing polyoxytetramethylene glycol and a carbonic acid diester as raw material monomers, polycondensation is carried out by transesterification reaction in the presence of a transesterification catalyst to produce poly with a number average molecular weight of 250 or more and 5000 or less. A method of making an ether polycarbonate diol composition comprising:
A method for producing a polyether polycarbonate diol composition, wherein the transesterification catalyst is a composition containing magnesium .

[5] The amount of the transesterification catalyst used is 10 μmol/mol or more and 1500 μmol/m with respect to the amount of the dihydroxy compound containing the polyoxytetramethylene glycol.
ol or less, the method for producing a polyether polycarbonate diol composition according to [4].
[6] A composition in which the transesterification catalyst contains the magnesium and at least one compound represented by the following formula (2), or a set containing at least one salt represented by the following formula (3): /> A method for producing the polyether polycarbonate diol composition according to [4] or [5].

(Wherein, R1 and R3 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms,
It may be substituted with a halogen atom and may have an oxygen atom.
R2 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, and the hydrocarbon group may be substituted with a halogen atom or may have an oxygen atom.
M represents magnesium and n=2. )
[7] A method for producing polyurethane using the polyether polycarbonate diol composition according to any one of [1] to [3].

INDUSTRIAL APPLICABILITY The polyether polycarbonate diol composition of the present invention is a polyether polycarbonate diol composition with little coloration even when heated, and even when used as a raw material for producing polyurethane, reaction control is easy, and it is produced. It is a polyether polycarbonate diol composition that makes it difficult for polyurethane to color. Furthermore, since a specific transesterification catalyst is used in the method for producing the polyether polycarbonate diol composition of the present invention, it is possible to reduce the amount of by-products produced.

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

[Polyether polycarbonate diol composition]
The polyether polycarbonate diol composition of the present invention (hereinafter referred to as "PEPCD composition"
may be abbreviated as ) contains metal and polyether polycarbonate diols.
The metal is at least one selected from the group consisting of zinc and metals of Group 2 of the long period periodic table
preferably at least one of zinc, calcium and magnesium, more preferably zinc and/or magnesium, and even more preferably magnesium. The metal is preferably contained in the form of a metal compound. The metal compound may be an ester exchange catalyst used in producing a polyether polycarbonate diol using a dihydroxy compound and a diester carbonate as raw materials, or may be added to the polyether polycarbonate diol.

The content of the metal in the PEPCD composition is preferably 1 ppm by mass or more and 200 ppm by mass. The upper limit is more preferably 100 mass ppm, more preferably 50 mass ppm, particularly preferably 30 mass ppm, and most preferably 20 mass ppm. The lower limit is more preferably 2 ppm by mass, more preferably 5 ppm by mass, and particularly preferably 10 ppm by mass. By setting the content of the metal within the above range, there is a possibility that the PEPCD composition will be less colored and that reaction control will become easier when the PEPCD composition is used to produce polyurethane.
In addition, the content of the metal in the PEPCD composition is determined by an inductively coupled plasma coupled analysis method (ICP-M
S).

The polyether polycarbonate diol of the PEPCD composition of the present invention contains a structural unit (A) derived from polyoxytetramethylene glycol and a structural unit (B) derived from a compound represented by the following formula (1), and has the structure The molar ratio of the unit (A) and the structural unit (B) is 100:
0 to 50:50.

(Wherein, R represents a divalent hydrocarbon group having 2 to 12 carbon atoms.)
The compound of formula (1) is preferably 2-methyl-1,3-propanediol, 2,2-
Dimethyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 3-methyl-1
,5-pentanediol, 2-methyl-1,8-octanediol, etc., more preferably 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propane. diol, 2-butyl-2-ethyl-1,3-propanediol. Further, the molar ratio of structural unit (A) and structural unit (B) is preferably 100:0 to 70
:30, more preferably 100:0 to 80:20, still more preferably 100:0
~90:10. Within the above range, when the PEPCD composition is used to produce a polyurethane, there is a possibility that the flexibility of the polyurethane will be high.
The structural unit of polytetramethylene ether glycol can be analyzed by NMR.

(Number average molecular weight)
The number average molecular weight of the PEPCD composition of the present invention is preferably 250 or more and 5000 or less. The upper limit is more preferably 4,000, more preferably 3,000, and particularly preferably 2,500. The lower limit is more preferably 500, more preferably 700, and particularly preferably 900.
If the number average molecular weight is too high, the viscosity of the PEPCD composition increases, which can impair handling when the PEPCD composition is used to produce polyurethanes. If the number average molecular weight is too small, the polyurethane produced using the PEPCD composition may not have sufficient flexibility.
The number average molecular weight in the PEPCD composition can be measured by the acetylation method according to JIS K1557-1.

(Percentage of number of molecular chain ends with alkyloxy group or aryloxy group/hydroxyl value)
The PEPCD composition of the present invention basically has a hydroxyl group as the terminal structure of the polymer. However, in the polyether polycarbonate diol obtained by the reaction of the dihydroxy compound and the carbonic acid diester, there may be some impurities having a structure in which the terminal end of the polymer is not a hydroxyl group. As a specific example of the structure, the terminal of the molecular chain is an alkyloxy group or an aryloxy group, and most of them are structures derived from diester carbonate.

For example, when diphenyl carbonate is used as the carbonate diester, the aryloxy group is the phenoxy group (PhO-), when dimethyl carbonate is used, the alkyloxy group is the methoxy group (MeO-), and when diethyl carbonate is used, the ethoxy group. (EtO-), hydroxyethoxy group (HO
CH ₂ CH ₂ O—) may remain as terminal groups (where Ph represents a phenyl group, Me represents a methyl group and Et represents an ethyl group).

In the polyether polycarbonate diol produced in the present invention, the ratio of the structure having an alkyloxy group or an aryloxy group at the end of the molecular chain contained in the polyether polycarbonate diol produced in the present invention is 5 mol % or less of the total number of terminal groups, especially It is preferably 3 mol % or less, more preferably 1 mol % or less. The lower limit of the ratio of the number of molecular chain terminals having an alkyloxy group or an aryloxy group is not particularly limited, and is usually 0.01 mol %, preferably 0.001 mol %, most preferably 0 mol %. If the proportion of alkyloxy or aryloxy terminal groups is large, problems such as a failure to increase the degree of polymerization may occur during the polyurethane formation reaction.

In the polyether polycarbonate diol contained in the PEPCD composition of the present invention, the ratio of the number of molecular chain terminals having alkyloxy groups or aryloxy groups is 5% as described above.
In the following, both terminal groups of the molecular chain are basically hydroxyl groups, and it is preferable that these hydroxyl groups have a structure capable of reacting with isocyanate during the polyurethane formation reaction.
The hydroxyl value of the polyether polycarbonate diol contained in the PEPCD composition of the present invention is not particularly limited, but the lower limit is usually 10 mg-KOH/g, preferably 20 mg-KO.
H/g, more preferably 35 mg-KOH/g, even more preferably 80 mg-KOH/g. Also, the upper limit is usually 230 mg-KOH/g, preferably 160 mg-KOH/g,
More preferably 140 mg-KOH/g. If the hydroxyl value is less than the above lower limit, the viscosity may be too high and handling may become difficult during polyurethane formation. If the above upper limit is exceeded, the polyurethane may lack strength and hardness.
The method for measuring the hydroxyl value of the polyether polycarbonate diol is as described in Examples below.

[Method for producing polyether polycarbonate diol composition]
In the method for producing the PEPCD composition of the present invention, a dihydroxy compound containing polyoxytetramethylene glycol and a carbonic acid diester are used as raw material monomers, and polycondensation is performed by transesterification reaction in the presence of an ester exchange catalyst to obtain a number average Molecular weight 250-5000
The following is a method of making a polyether polycarbonate diol composition.

(Diol compound)
The dihydroxy compound may further contain a diol compound in addition to the polyalkylene ether glycol. As the diol compound, ethylene glycol, 1
,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6
-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-
nonanediol, 1,10-decanediol, 1,12-dodecanediol and other chain alkyl diols, 2-methyl-1,3-propanediol, neopentyl glycol, 2
-Branched alkyl such as butyl-2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol Cyclic alkyldiols such as diols, cyclohexanedimethanol, and isosorbide can be mentioned. These other diol compounds may be used singly or in combination of two or more.

(carbonic acid diester)
Usable carbonic acid diesters are not limited as long as the effects of the present invention are not lost, and include dialkyl carbonates, diaryl carbonates, and alkylene carbonates. Among these, the use of diaryl carbonate has the advantage that the reaction proceeds rapidly. However, on the other hand, when diaryl carbonate is used as a raw material, phenols with high boiling points are by-produced, and since the by-produced phenols are monofunctional compounds, they can become polymerization inhibitors during polyurethane formation. There is also a risk of causing the problem of becoming a coloring causative substance. From this point of view, the smaller the residual amount of phenols in the PEPCD composition of the present invention, the better.

(Transesterification catalyst)
As transesterification catalysts, zinc and group 2 in the long-period periodic table (hereinafter simply "
Sometimes referred to as "family 2". ) at least one metal selected from the group consisting of metals (M
), wherein the transesterification catalyst is a composition containing the metal (M) and at least one compound represented by the following formula (2) (hereinafter referred to as “catalyst composition (2)” Sometimes.
) or at least one salt represented by the following formula (3) and a composition using them as a precursor (hereinafter referred to as “catalyst composition (3)”, catalyst composition (2) and catalyst composition (3 ) may be referred to as the “catalyst of the present invention”) is preferably used as the transesterification catalyst (hereinafter, sometimes simply referred to as the “catalyst”).

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

The stable form of zinc or a Group 2 metal compound usually includes the form of a salt represented by the above formula (3). Therefore, it is effective to use the catalyst composition (3), When it is difficult to obtain a salt or when it is desired to arbitrarily adjust the composition ratio of zinc or a Group 2 metal and the compound represented by the above formula (2), the metal compound and the formula (2) A catalyst composition (2) with a compound having a structure may also be used.

Moreover, the catalyst composition (2) and the catalyst composition (3) may be used in combination.
As a method for preparing the catalyst composition (3), for example, as shown in the following formula (4), using a method similar to the method for synthesizing a metal acetylacetone salt, a metal halide salt and A method of preparing the catalyst composition (3) by reacting with an acetylacetone analogue, or preparing a catalyst composition (3) by exchanging a metal alkoxide with an acetylacetone analogue as shown in the following formula (5) However, it is not limited to this.

(In formulas (4) and (5) above, R ₁ , R ₂ , R ₃ , M and n are as defined in formula (3) above, and R ₅ is an arbitrary hydrocarbon group.)
The catalyst compositions (2) and (3) may be prepared in advance and mixed with a dihydroxy compound and a diester carbonate as raw material monomers, or each component may be mixed with the raw material monomers in any order.

In addition to these catalyst compositions (2) and (3), a basic compound such as a transition metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound is used in combination. is also possible.
In the above formulas (2) and (3), each of R ₁ and R ₃ is independently substituted with a halogen atom, optionally having an oxygen atom, and having 1 to 12 carbon atoms. is preferably a hydrocarbon group, which may be substituted with a halogen atom or may have an oxygen atom, and may be a monovalent hydrocarbon group having 1 to 7 carbon atoms. It is more preferable from the viewpoints of easiness of interaction with the metal (M) inside, solubility as a catalyst composition, thermal stability and low coloration. R ₂ may be substituted with a halogen atom or may have an oxygen atom;
It is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms or a halogen atom, optionally substituted with a halogen atom, optionally having an oxygen atom, and having 1 to 7 carbon atoms. A hydrocarbon group or a halogen atom is preferred from the viewpoint of ease of interaction with the metal (M) in the catalyst composition, solubility in organic solvents and raw material monomers, acid-base strength and low coloring. preferable. Further, when R ₁ to R ₃ are the above preferred functional groups, the solubility in the resulting polycarbonate is high and the coloration is low, so that a PEPCD composition with no turbidity and low coloration can be obtained.

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

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

As the metal (M) selected from zinc and Group 2 metals, zinc, magnesium, calcium and barium are particularly preferred from the viewpoint of reactivity, zinc and magnesium are more preferred, and magnesium is most preferred.
The amount of the transesterification catalyst used is generally preferably 10 μmol/mol or more and 1500 μmol/mol or less, and the lower limit is more preferably 20 μmol/mol, and further preferably 30 μmol/mol, relative to the dihydroxy compound containing the polyalkylene ether glycol. 50 μmol/mol is particularly preferred. The upper limit is more preferably 1000 μmol/mol, still more preferably 500 μmol/mol, particularly preferably 300 μmol/mol, most preferably 200 μmol/mol. If the amount of the transesterification catalyst used is less than the lower limit, the reactivity may be poor when synthesizing the PEPCD composition, and the desired product may not be obtained. Moreover, when the amount of the transesterification catalyst used is larger than the upper limit, problems such as difficulty in controlling the reaction and generation of by-products other than the target product may occur.

(Auxiliary catalyst)
In the present invention, a basic compound such as a transition metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used as an auxiliary catalyst together with the transesterification catalyst. It is possible.
Examples of transition metal compounds include titanium alkoxides such as tetraethyl titanate, tetraisopropyl titanate and tetra-n-butyl titanate; titanium halides such as titanium tetrachloride; tin (II) chloride, tin (IV) chloride, tin acetate ( II), tin acetate (IV)
), dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide; zirconium compounds such as zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide; lead (II) acetate, lead (IV) acetate, lead (IV) chloride and lead compounds such as

Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, and tributylbenzylboron. boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron,
Sodium salts, potassium salts, lithium salts, calcium salts such as butyltriphenylboron,
Barium salts, magnesium salts, strontium salts and the like can be mentioned.

Examples of basic phosphorus compounds include tertiary phosphines such as triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, tri(ethylhexyl)phosphine, diethyl Phosphine, di-n-propylphosphine, diisopropylphosphine, di-n-butylphosphine, diphenylphosphine, dibutylphosphine, di(ethylhexyl)phosphine and other secondary phosphines and quaternary phosphonium salts, phosphoric acid, phosphorous acid, etc. Inorganic phosphoric acid, organic phosphates such as dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, di(ethylhexyl) phosphate, and triphenyl phosphite, and the like can be mentioned.

Examples of basic ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
tetrabutylammonium hydroxide, trimethylethylammonium hydroxide,
trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltri phenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide and the like.

Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N, N
-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole,
2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.
These co-catalysts may be used alone or in combination of two or more.

When these co-catalysts are used, the upper limit of the amount used is preferably 100 times or less, particularly 10 times or less in terms of molar ratio, relative to the metal (M) in the catalyst composition. 0 as lower bound
. 01 times or more, particularly preferably 0.1 times or more. The combined use of these co-catalysts may have the effect of improving catalytic activity and selectivity, or suppressing the deterioration of catalytic activity due to impurities in the raw materials and reaction by-products. If it is too much, not only the color tone, transparency, light resistance, heat stability, etc. of the obtained PEPCD composition may be deteriorated, but also an abnormal reaction may be caused during the polyurethane formation reaction. If it is too small, the effect may not be sufficiently obtained.

(Method for producing polyether polycarbonate diol composition)
In the present invention, the dihydroxy compound containing the polyalkylene ether glycol (hereinafter sometimes simply referred to as "dihydroxy compound") and the carbonic acid diester are
In the presence of the transesterification catalyst, the number average molecular weight is 2 by polycondensation by transesterification reaction
A PEPCD composition of 50 to 5000 is produced.

(Reaction conditions, etc.)
The method of charging the reaction raw materials is not particularly limited, and a method of simultaneously charging the dihydroxy compound, the carbonic acid diester, and the catalyst in all amounts and subjecting them to the reaction, or when the carbonic acid diester is solid, first charging the carbonic acid diester, heating and melting it, and then adding the carbonic acid diester. a method of adding a dihydroxy compound and a catalyst;
Conversely, the method can be freely selected, such as a method in which the dihydroxy compound is charged first, melted, and then the diester carbonate and the catalyst are introduced. Adopting a method of adding a part of the dihydroxy compound used at the end of the reaction in order to reduce the ratio of the number of molecular chain terminals of the obtained polyether polycarbonate diol having an alkyloxy group or an aryloxy group. is also possible.

The reaction temperature for the transesterification reaction can be arbitrarily adopted as long as it is a temperature at which a practical reaction rate can be obtained. The temperature is not particularly limited, but the lower limit is usually 70°C, preferably 100°C, more preferably 130°C. The upper limit of the reaction temperature is usually 250°C, preferably 200°C, more preferably 190°C, even more preferably 180°C, particularly preferably 170°C. If the reaction temperature is below the above lower limit, the transesterification reaction may not proceed at a practical rate. Moreover, if the reaction temperature exceeds the above upper limit, quality problems such as coloration of the resulting PEPCD composition, generation of an ether structure, and deterioration of turbidity may occur.

Although the reaction can be carried out under normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the production system by distilling off the produced monohydroxy compound or dihydroxy compound out of the system. Therefore, in the latter half of the reaction, it is usually preferable to adopt reduced pressure conditions and carry out the reaction while distilling off the monohydroxy compound or dihydroxy compound. Alternatively, the reaction can be continued while the monohydroxy compound or dihydroxy compound produced by gradually lowering the pressure during the reaction is distilled off. If the pressure is lowered too much at the initial stage of the reaction, volatilization of low-boiling unreacted monomers is facilitated, making it impossible to obtain a PEPCD composition having a predetermined number-average molecular weight. A composition may not be obtained.

On the other hand, if the reaction is carried out at a reduced pressure at the end of the reaction, monohydroxy compounds or dihydroxy compounds such as phenols, alcohols and diols produced as by-products, residual monomers such as diester carbonate, and turbidity may be caused. A possible cyclic carbonate (
cyclic oligomers) can be distilled off, which is preferable.
In this case, the reaction pressure at the end of the reaction is not particularly limited, but the upper limit is usually 10 kPa, preferably 5 kPa, more preferably 1 kPa. In order to effectively distill these light-boiling components, the reaction may be carried out while passing a small amount of an inert gas such as nitrogen, argon or helium into the reaction system.

When using a carbonic acid diester or a dihydroxy compound with a low boiling point in the transesterification reaction, the reaction should be carried out at around the boiling point of the carbonic acid diester or dihydroxy compound at the beginning of the reaction. A method of allowing the reaction to proceed can also be employed. In this case, it is possible to prevent unreacted diester carbonate and dihydroxy compound from distilling off in the initial stage of the reaction, which is preferable. Furthermore, in order to prevent the raw materials from being distilled off in the initial stage of the reaction, a reflux tube is attached to the reactor, and the monohydroxy compound or dihydroxy compound produced as a by-product is distilled off while the diester carbonate and the dihydroxy compound are refluxed to carry out the transesterification reaction. is also possible. In this case, the raw material monomer charged is not lost, and the quantitative ratio of the reagents can be adjusted accurately, which is preferable.

(Polycondensation reactor)
The polycondensation reaction can be carried out either batchwise or continuously, but the continuous method is superior in terms of quality stability such as the molecular weight of the product. The apparatus to be used may be of any type of tank type, tubular type or tower type, and known polymerization tanks equipped with various stirring blades and the like can be used. The atmosphere during heating of the apparatus is not particularly limited, but from the viewpoint of product quality, it is preferably carried out in an inert gas such as nitrogen gas under normal pressure or reduced pressure.

(reaction time)
The time required for the transesterification reaction to obtain the PEPCD composition by the method of the present invention varies greatly depending on the type and amount of the dihydroxy compound, carbonic acid diester, and catalyst used, and therefore cannot be generally defined, but is usually used. The reaction time required to reach the desired number average molecular weight is 50 hours or less, preferably 20 hours or less, more preferably 10 hours or less.

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

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

The amount of the catalyst deactivator to be used is not particularly limited. 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 less than this amount of catalyst deactivator is used, the deactivation of the transesterification catalyst in the reaction product is not sufficient and the resulting PEPCD
When the composition is used, for example, as a raw material for polyurethane production, the reactivity of the PEPCD composition to isocyanate groups may not be sufficiently reduced. Also, if a catalyst deactivator exceeding this range is used, the obtained PEPCD composition may be colored.

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

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

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

The upper limit of the pressure during thin film distillation is preferably 500 Pa, more preferably 150 Pa, and even more preferably 50 Pa. By setting the pressure at the time of thin-film distillation to the above upper limit or less, a sufficient effect of removing light-boiling components can be obtained.
The upper limit of the temperature for keeping the PEPCD composition just before the thin film distillation is preferably 250°C, more preferably 150°C. Also, the lower limit is preferably 80°C, more preferably 120°C.
By setting the temperature at which the PEPCD composition is kept warm immediately before thin film distillation to the lower limit or higher, it is possible to prevent the fluidity of the PEPCD composition immediately before thin film distillation from being lowered. On the other hand, by making it equal to or less than the above upper limit, it is possible to prevent the PEPCD composition obtained after thin-film distillation from being colored.

[Physical Properties of Polyether Polycarbonate Diol Composition]
Preferred physical properties of the PEPCD composition produced by the method for producing a PEPCD composition of the present invention are described below.

(Molecular weight/molecular weight distribution)
The lower limit of the number average molecular weight (Mn) of the PEPCD composition produced by the method for producing a PEPCD composition of the present invention is 250, preferably 500, more preferably 700, still more preferably 900. On the other hand, the upper limit is 5,000, preferably 3,000, more preferably 2,000. If the number average molecular weight of the PEPCD composition is less than the above lower limit, flexibility and the like may be impaired when made into polyurethane. On the other hand, if the above upper limit is exceeded, the viscosity of the PEPCD composition increases, which may hinder handling during polyurethane formation.
Here, the number average molecular weight of the PEPCD composition is determined by gel permeation chromatography (GPC) as shown in the examples below.

The molecular weight distribution (Mw/Mn) of the PEPCD composition of the present invention is not particularly limited, but the lower limit is usually 1.5, preferably 1.7, more preferably 2.0. The upper limit is usually 3.5, preferably 3.0.
If the molecular weight distribution exceeds the above range, the physical properties of the polyurethane produced using this PEPCD composition tend to deteriorate, such as hardening at low temperatures and poor elongation. If you try to produce , it may be necessary to perform advanced purification operations such as removing oligomers.
Here, Mw is a weight-average molecular weight, and Mn is a number-average molecular weight, which can usually be determined by GPC measurement.

(APHA value)
The color of the PEPCD composition of the present invention is Hazen color number (JIS K0071-1: 1998
(hereinafter referred to as "APHA value") is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less. APHA value of 50
If it exceeds , the color tone of the polyurethane obtained using the PEPCD composition as a raw material may be deteriorated, the commercial value may be lowered, or the heat stability may be deteriorated.

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

[Method for producing polyurethane]
The method for producing the polyurethane of the present invention uses the PEPCD composition of the present invention,
Normally, except for using the PEPCD composition of the present invention, a polyisocyanate compound and a chain extender as starting materials, it can be produced by a normal polyurethane-forming reaction.
For example, the polyurethane of the present invention can be produced by reacting the PEPCD composition of the present invention with a polyisocyanate compound and a chain extender at a temperature ranging from room temperature to 200°C.
Alternatively, the PEPCD of the present invention and an excess polyisocyanate compound are first reacted to produce a prepolymer having terminal isocyanate groups, and a chain extender is used to increase the degree of polymerization to produce the polyurethane of the present invention. be able to.

(Polyisocyanate compound)
The polyisocyanate compound used as a raw material for producing polyurethane may have two or more isocyanate groups, and includes various known aliphatic, alicyclic or aromatic polyisocyanate compounds.

For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2
,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer diisocyanate in which the carboxyl group of dimer acid is converted to an isocyanate group.
1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-
Alicyclic diisocyanate compounds such as 2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane; xylylene diisocyanate, 4 ,4'-diphenyl diisocyanate, toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethyl methane diisocyanate, 4,4'
- dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3
,3′-dimethyl-4,4′-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and aromatic diisocyanate compounds such as m-tetramethylxylylene diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

Among these, aromatic polyisocyanate compounds are preferred because of their high reactivity with polyether polycarbonate diols and the curability of the resulting polyurethane. - diphenylmethane diisocyanate (hereinafter, "
MDI"), toluene diisocyanate (TDI), and xylylene diisocyanate are preferred.

(chain extender)
The chain extender used as a raw material for producing the polyurethane of the present invention is a low-molecular-weight compound having at least two active hydrogens that react with isocyanate groups, and is selected from polyols and polyamines.
Specific examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,9-nonanediol. , 1,10-decanediol, 1,12-dodecanediol, and other linear diols; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl -1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2
- diols having a branched chain such as ethyl-1,3-propanediol and dimer diol; diols having an ether group such as diethylene glycol and propylene glycol;
,4-cyclohexanediol, 1,4-cyclohexanedimethanol, diols having an alicyclic structure such as 1,4-dihydroxyethylcyclohexane, xylylene glycol,
Diols having aromatic groups such as 1,4-dihydroxyethylbenzene and 4,4′-methylenebis(hydroxyethylbenzene); Polyols such as glycerin, trimethylolpropane and pentaerythritol; N-methylethanolamine and N-ethylethanol hydroxyamines such as amine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxy ethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4′-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tri polyamines such as diamine, hydrazine, piperazine, N,N'-diaminopiperazine;

One of these chain extenders may be used alone, or two or more thereof may be used in combination.
Among these, ethylene glycol, 1, 4, has excellent flexibility and elastic recovery due to excellent phase separation between the soft segment and the hard segment of the polyurethane obtained, and is industrially available in large quantities at low cost. -Butanediol, 1,6-hexanediol are preferred.

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

(catalyst)
In the polyurethane-forming reaction when producing the polyurethane of the present invention, an amine-based catalyst such as triethylamine, N-ethylmorpholine and triethylenediamine, or an acid-based catalyst such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid and sulfonic acid, trimethyltin laurate. , dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate, and other tin-based compounds, and furthermore, known urethane polymerization catalysts typified by organic metal salts such as titanium-based compounds can also be used. A urethane polymerization catalyst may be used individually by 1 type, and may use 2 or more types together.

(Polyol other than PEPCD composition)
In the method for producing the polyurethane of the present invention, a polyol other than the PEPCD composition of the present invention may be used in combination, if desired. Here, the polyol other than the PEPCD composition of the present invention is not particularly limited as long as it is used in ordinary polyurethane production, and examples thereof include polyester polyol, polycaprolactone polyol and polycarbonate polyol. Here, the weight ratio of the PEPCD composition of the present invention to the combined weight of the PEPCD composition of the present invention and other polyols is preferably 70% or more, more preferably 90% or more. If the weight ratio of the PEPCD composition of the present invention is small, the controllability and flexibility of the urethane polymerization reaction may be impaired.

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

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

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

If the amount of the polyisocyanate compound used is too large, the unreacted isocyanate groups will cause side reactions, and the viscosity of the resulting polyurethane will become too high, making handling difficult and flexibility likely to be impaired. If it is too small, the molecular weight of the polyurethane will not be sufficiently large, and there will be a tendency that sufficient strength will not be obtained.
The amount of the chain extender used is not particularly limited, but when the number obtained by subtracting the total number of hydroxyl groups of the PEPCD composition of the present invention and other polyols from the number of isocyanate groups of the polyisocyanate compound is 1 equivalent, the lower limit is , preferably 0.7 equivalents, more preferably 0.8 equivalents,
More preferably 0.9 equivalents, particularly preferably 0.95 equivalents, the upper limit is preferably 3
. 0 equivalents, more preferably 2.0 equivalents, still more preferably 1.5 equivalents, particularly preferably 1
. 1 equivalent. If the amount of chain extender used is too large, the resulting polyurethane tends to be difficult to dissolve in the solvent and processing becomes difficult. In some cases, retention performance cannot be obtained, and in some cases, heat resistance deteriorates.

(two-step method)
The two-step method, also called a prepolymer method, mainly includes the following methods.
(a) The PEPCD composition of the present invention, other polyols, and an excess polyisocyanate compound are mixed in advance so that the reaction equivalent ratio of polyisocyanate compound/(PEPCD composition of the present invention and other polyols) exceeds 1 A method for producing a polyurethane by reacting the amount to 10.0 or less to produce a prepolymer having an isocyanate group at the molecular chain end, and then adding a chain extender thereto.
(b) a polyisocyanate compound and an excess amount of the PEPCD composition of the present invention and other polyols are added in advance so that the reaction equivalent ratio of polyisocyanate compound/(the PEPCD composition of the present invention and other polyols) is 0.1; From the above, a method of producing a prepolymer having a molecular chain end with a hydroxyl group by reacting at less than 1.0, and then reacting this with a polyisocyanate compound having an isocyanate group end as a chain extender to produce a polyurethane.

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

In the case of method (1), in the chain elongation reaction, the chain elongating agent is dissolved in the solvent, or the prepolymer and the chain elongating agent are dissolved in the solvent at the same time. It is important to obtain
The amount of the polyisocyanate compound used in the two-step method (a) is not particularly limited, but the number of isocyanate groups when the total number of hydroxyl groups of the PEPCD composition of the present invention and other polyols is 1 equivalent As, the lower limit is preferably an amount exceeding 1.0 equivalents, more preferably 1.2 equivalents, more preferably 1.5 equivalents, and the upper limit is preferably 10.0 equivalents, more preferably 5.0 equivalents, and further It is preferably in the range of 3.0 equivalents.

If the amount of the polyisocyanate compound used is too large, the excess isocyanate groups tend to cause side reactions, making it difficult to achieve the desired physical properties of the polyurethane. Thermal stability may be reduced.
The amount of the chain extender used is not particularly limited, but the lower limit is preferably 0.1 equivalents, more preferably 0.5 equivalents, and still more preferably 0 equivalents per equivalent of the number of isocyanate groups contained in the prepolymer. .8 equivalents, and the upper limit is preferably 5.0 equivalents, more preferably 3
. It is in the range of 0 equivalents, more preferably 2.0 equivalents.

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

If the amount of this polyisocyanate compound used is too small, the subsequent chain elongation reaction will take a long time to obtain the desired molecular weight, and production efficiency tends to decrease. In some cases, the performance may be lowered, and the handling may be poor, resulting in poor productivity.
The amount of the chain extender used is not particularly limited, but the P of the present invention used in the prepolymer
When the total number of hydroxyl groups in the EPCD composition and other polyols is 1 equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.7 equivalents, as the total equivalents including the isocyanate group equivalents used in the prepolymer. It is 8 equivalents, more preferably 0.9 equivalents, and the upper limit is preferably less than 1.0 equivalents, more preferably 0.99 equivalents, and still more preferably 0.98 equivalents.

For the purpose of adjusting the molecular weight, monofunctional organic amines and alcohols may coexist during the chain extension reaction.
The chain extension reaction is usually carried out at 0° C. to 250° C., but this temperature varies depending on the amount of solvent, reactivity of raw materials used, reaction equipment, etc., and is not particularly limited. If the temperature is too low, the progress of the reaction will be slowed down, and the production time will be lengthened due to the low solubility of the raw materials and polymer. . The chain extension reaction may be performed under reduced pressure while defoaming.

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

(Additive)
Various additives such as heat stabilizers, light stabilizers, colorants, fillers, stabilizers, ultraviolet absorbers, antioxidants, anti-adhesives, flame retardants, anti-aging agents, and inorganic fillers can be added to the polyurethane of the present invention. Agents can be added and mixed as long as the properties of the polyurethane of the present invention are not impaired.
Compounds that can be used as heat stabilizers include phosphoric acid, aliphatic, aromatic or alkyl-substituted aromatic esters of phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl Phosphorus compounds such as pentaerythritol diphosphite and dialkylbisphenol A diphosphite; phenol derivatives, especially hindered phenol compounds; Compounds containing sulfur; tin-based compounds such as tin malate, dibutyltin monoxide, and the like can be used.

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

Specific examples of compounds containing sulfur include dilaurylthiopropionate (DLTP),
Thioether compounds such as distearyl thiopropionate (DSTP) are included.
Examples of light stabilizers include benzotriazole-based and benzophenone-based compounds. Specifically, "TINUVIN622LD" and "TINUVIN765"
Specialty Chemicals Co., Ltd.), “SANOL LS-2626”, “SA
NOL LS-765" (manufactured by Sankyo Co., Ltd.) and the like can be used.

Examples of UV absorbers include "TINUVIN328", "TINUVIN234" (
(manufactured by Chiba Specialty Chemicals Co., Ltd.) and the like.
Colorants include dyes such as direct dyes, acid dyes, basic dyes and metal complex dyes; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide and mica; Organic pigments such as anthraquinone-based, thioindigo-based, dioxazone-based, and phthalocyanine-based pigments can be used.

Examples of inorganic fillers include short glass fibers, carbon fibers, alumina, talc,
Graphite, melamine, white clay, and the like.
Examples of flame retardants include additive and reactive flame retardants such as phosphorous and halogen containing organic compounds, bromine or chlorine containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide and the like.

These additives may be used alone, or two or more of them may be used in any combination and ratio.
As for the amount of these additives added, the lower limit is preferably 0.01% by mass, more preferably 0.05% by mass, still more preferably 0.1% by mass, and the upper limit is preferably 10% by mass, as a weight ratio to polyurethane. % by mass, more preferably 5% by mass, and even more preferably 1% by mass. If the amount of the additive added is too small, the effect of the addition cannot be sufficiently obtained, and if it is too large, the polyurethane may precipitate or become turbid.

(molecular weight)
The molecular weight of the polyurethane of the present invention is appropriately adjusted according to its use, and is not particularly limited.
10,000 is preferable, and 100,000 to 300,000 is more preferable. If Mw is less than the above lower limit, sufficient strength and hardness may not be obtained, and if it exceeds the above upper limit, there is a tendency to impair handling properties such as workability.

(Application)
The polyurethane produced by the polyurethane production method of the present invention has transparency, flexibility,
It has excellent durability, good heat resistance and wear resistance, and is also excellent in workability, so it can be used for various purposes.
For example, it can be used in cast polyurethane elastomers. Specific applications include rolling rolls, paper manufacturing rolls, office equipment, rolls such as pretension rolls, solid tires for forklifts, automobile vehicle nutrams, trolleys, trucks, casters, etc. Industrial products include conveyor belt idlers and guides. Rolls, pulleys, steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, etc. It can also be used for OA equipment belts, paper feed rolls, copying cleaning blades, snow plows, toothed belts, surf rollers and the like.

It is also applicable for use as a thermoplastic elastomer. That is, by molding a thermoplastic polyurethane elastomer comprising the polyurethane of the present invention, a molded product having excellent stretchability can be obtained. The molding method of the thermoplastic polyurethane elastomer comprising the polyurethane of the present invention is not particularly limited, and various molding methods commonly used for thermoplastic polymers can be used. For example, any molding method such as injection molding, extrusion molding, press molding, blow molding, calender molding, casting molding, roll processing, etc. can be employed, and resin plates, films, sheets, tubes, hoses, belts, rolls, etc. can be used. , synthetic leather, shoe soles, automobile parts, escalator handrails, road sign members, textiles, etc.

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

The polyurethane elastomer can also be a foamed polyurethane elastomer or polyurethane foam. Examples of methods for foaming or forming a polyurethane elastomer include chemical foaming using water and mechanical foaming such as mechanical flossing. Similarly, slabs, flexible foams obtained by molding, and the like can be mentioned.
Specific uses of foamed polyurethane elastomers or polyurethane foams include thermal insulation and vibration-proof materials for electronic devices and construction, automobile seats, automobile ceiling cushions, bedding such as mattresses, insoles, midsoles, shoe soles, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically 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 results〕
Methods for evaluating various physical properties, performance, etc. in the following examples and comparative examples are as follows.

[Evaluation of catalyst performance]
In the production of polyether polycarbonate diols from PTMG and carbonic acid diesters, the raw materials PTMG and carbonic acid diesters are reduced in the esterification process, and monohydroxy compounds derived from carbonic acid diesters (dihydroxy compounds in the case of alkylene carbonate) are added as secondary compounds in the transesterification process. live. As an index of the performance as a catalyst for the production of polyether polycarbonate diol, together with the reduction rate (conversion rate) of PTMG and diester carbonate,
The production rate of by-product monohydroxy compounds (dihydroxy compounds in the case of alkylene carbonate) is important. More specifically, for example, as shown in the following formula (A), PTMG
In the production of polyether polycarbonate diol from and ethylene carbonate (EC), the high conversion rate of PTMG and EC together with the high production rate of ethylene glycol (EG), which is a by-product, contributes to the production of polyether polycarbonate diol. This indicates that the ratio is high, and it is an index of the excellent transesterification catalyst for the production of polyether polycarbonate diol. Furthermore, in the production of polyether polycarbonate diol using PTMG, tetrahydrofuran (THF) is produced as a by-product due to undesired etherification. It is an indicator that the catalyst is producible.
Therefore, the conversion rate of raw materials PTMG and carbonic acid diester (carbonates), the production rate of monohydroxy compounds or dihydroxy compounds produced as by-products, and the production rate of undesired ether by-products are measured and used for the production of polyether polycarbonate diols. The transesterification catalyst performance was evaluated.

<Structural unit>
The product was dissolved in CDCl ₃ and analyzed by 400 MHz ¹ H-NMR (EC manufactured by JEOL Ltd.).
Z-400) was measured, and the ratio of each structural unit was obtained from the integrated value of the signal of each component.

<APHA value>
In accordance with JIS K0071-1, it was measured by comparing with a standard solution placed in a colorimetric tube.

<Hydroxyl value>
The hydroxyl value of the polyether polycarbonate diol was measured according to JIS K1557-1 by a titration method using an acetylation reagent.

<Number average molecular weight>
From the hydroxyl value obtained by titration using an acetylation reagent, the number average molecular weight was determined according to the following formula (II).
Number average molecular weight = 2 × 56.1 / (hydroxyl value × 10 ^-3 ) (II)

<Concentration of catalyst metal content>
When using a metal catalyst that does not volatilize or decompose under the reaction conditions of the polyether polycarbonate diol, the metal concentration (ppm) is the yield of the polyether polycarbonate diol (g
) to the amount (g) of the metal catalyst used for charging.
As an analysis method, the following method (ICP-MS) was used.
0.2 g of the polyether polycarbonate diol composition was accurately weighed into a Kjeldahl flask and subjected to wet decomposition using concentrated sulfuric acid and concentrated nitric acid. After cooling to room temperature, the solution was made to a constant volume using pure water and measured with ICP-MSELEMENT2 (manufactured by Thermo Fisher Scientific) to determine the metal content concentration (mass p
pm) was calculated.

[Compound abbreviation]
Abbreviations of compounds in Examples and Comparative Examples are as follows.
EC: ethylene carbonate BG: 1,4-butanediol EG: ethylene glycol THF: tetrahydrofuran EtOH: ethanol NPG: neopentyl glycol PTMG: polyoxytetramethylene glycol PTMG#250: polyoxytetramethylene glycol (number average molecular weight 250)
Mg(acac) ₂ : magnesium (II) acetylacetonate Ti(OBu) ₄ : tetra-n-butyl titanate

[Production and Evaluation of Polyether Polycarbonate Diol Composition]
[Example 1-1]
PTMG #250 (Mitsubishi Chemical Co., Ltd.) 2 in a glass test tube reactor with a diameter of 30 mm
1.2 g and 8.8 g of EC (Tokyo Chemical Industry Co., Ltd.) were charged, heated with an aluminum block heater under a nitrogen atmosphere, and stirred at 300 rpm with a magnetic stirrer. After the internal temperature reached 140° C., a toluene diluted solution containing 1.42 mg of Mg(acac) ₂ (Tokyo Chemical Industry Co., Ltd.) was added as a catalyst to initiate transesterification reaction, followed by heating and stirring.
Sampling was performed at 1 hour and 3 hours after the start of the reaction, and the weights of the monomer compositions EC, EG and THF in the reactor were quantified by gas chromatography by the following method,
The number of moles in each reactor was determined.

<Gas chromatography analysis>
About 100 mg of the reaction solution and about 50 mg of N-methyl-2-pyrrolidone as an internal standard were accurately weighed and diluted with about 5 mL of acetonitrile. Analyze this liquid as it is, or collect 1 mL of this liquid, add 0.2 mL of N-trimethylsilylimidazole (Wako Pure Chemical Industries, for gas chromatography), shake well, let stand for 10 minutes or more, and then pass through a syringe filter. Analyzed what was done.
(Gas chromatography analysis conditions)
Column: DB-WAX 30 m×0.250 mm×0.25 μm, I.D. D. (Agilent Technologies) or equivalent Carrier gas: helium, 1.23 mL/min Column temperature: 50°C (hold for 5 minutes) → temperature rise at 10°C/min → 250°C (hold for 5 minutes)
Inlet temperature: 250°C, injection volume: 1 µL, split ratio: 1:50
Detector temperature: 250°C, detector: FID

(Calculation formula for conversion rate/production rate)
EC conversion rate = (number of EC moles charged - number of EC moles in the reactor) / theoretical number of EC moles charged (*
) x 100 (mol%)
EG production rate = number of moles of EG in reactor/number of moles of theoretically produced EG (**) x 100 (mol%)
THF production rate = number of moles of THF in reactor/number of moles of EG in reactor x 100 (mol%)
*Theoretical number of moles of EC charged = number of moles of theoretically produced EG (**) is the number of moles of EC theoretically required for PTMG in order to obtain a polyether polycarbonate diol composition having a number average molecular weight of 2000. and corresponds to the number of moles of EG produced when reacted stoichiometrically.
The THF production rate is the percentage of the number of THF moles (
mol%).

[Example 1-2]
A transesterification reaction was carried out in the same manner as in Example 1-1, except that the amount of catalyst was changed. Table 1 shows the results.

[Example 1-3]
A transesterification reaction was carried out in the same manner as in Example 1-1, except that the type and amount of the dihydroxy compound were changed and the amount of the catalyst was changed. Table 1 shows the results.

[Comparative Example 1-1]
A transesterification reaction was carried out in the same manner as in Example 1-1, except that the catalyst species and amount were changed. Table 1 shows the results.

[Example 2-1]
PTMG #250: 2453 g (10.1 mol), EC: 1022 g (11. 6 mol) and Mg(acac) ₂ : 360 mg (1.6 mmol) were added, and the mixture was replaced with nitrogen gas. While stirring, the internal temperature was raised to 150° C. to heat and dissolve the contents. Then, after reacting at normal pressure for 3 hours, the pressure was lowered to 6 kPa, and reaction was carried out for 12 hours while removing ethylene glycol and ethylene carbonate out of the system. Then, the pressure was lowered to 1 kPa over 20 hours and the reaction was carried out at 150-170°C. Ethylene carbonate (EC): 667 g (7.6 mol) was added during the above process. Further 0.5kPa
After the reaction was continued for 8 hours, the number average molecular weight was 190 by ¹ H-NMR (measurement method 2).
After confirming that it was equivalent to 0, a polyether polycarbonate diol-containing composition was obtained.
Then add 8.5% aqueous phosphoric acid to the polyether polycarbonate diol-containing composition:
1.6 mL (1.4 mmol) was added to deactivate the catalyst. Then remove the distillation column and
A polyether polycarbonate diol-containing composition was obtained by removing residual monomers at 0.5 kPa and 170°C.

The resulting polyether polycarbonate diol-containing composition was fed to a thin film distillation apparatus at a flow rate of 20 g/min, and subjected to thin film distillation (temperature: 210°C, pressure: 53 Pa) to obtain a polyether polycarbonate diol composition. As a thin film distillation apparatus, a diameter of 50 mm and a height of 2
00 mm, an area of 0.0314 m ² , and a jacketed molecular distillation apparatus MS-300 special model manufactured by Shibata Scientific Co., Ltd. was used. Table 2 shows analytical values and physical property values of the resulting polyether polycarbonate diol composition.

[Example 2-2]
A polyether polycarbonate diol composition was obtained in the same manner as in Example 2-1, except that the amount of the dihydroxy compound, the type and amount of the diester carbonate, and the amount of the catalyst were changed. Table 2 shows analytical values and physical property values of the resulting polyether polycarbonate diol composition.

[Example 2-3]
PTMG#250: 393 g (1.6 mol), N
98 g of PG and 259 g (2.94 mol) of EC were added, and the atmosphere was replaced with nitrogen gas. The internal temperature was raised to 80°C in an oil bath to heat and dissolve the contents, and under stirring, Mg(acac) ₂ : 10 was added.
4 mg (0.47 mmol) was added. After raising the temperature of the oil bath and reacting at an internal temperature of 135 to 150° C. at normal pressure for 2 hours, the pressure is lowered to 6 kPa and the internal temperature is 150 to 170° C. while removing ethylene glycol and ethylene carbonate from the system for 20 hours. reacted. The reaction was interrupted, ethylene carbonate (EC): 34 g (0.38 mol) was added, and the internal temperature was 145-15.
After heating at 5 ° C. normal pressure for 1 hour, the internal temperature is 150 ° C. to 17 while lowering the pressure to 6 to 3 kPa.
The reaction was carried out at 5°C for 15 hours. Furthermore, ethylene carbonate (EC): 34 g (0.38 mol) was added, and after heating at an internal temperature of 160 to 167°C and normal pressure for 2 hours, the pressure was lowered to 3 kPa, and the reaction was performed at an internal temperature of 170 to 175°C for 6 hours. . Then Mg(acac) ₂ : 51 mg (0.
23 mmol) was added, and the reaction was carried out at an internal temperature of 170° C. for 6 hours while lowering the pressure to 4 to 3.5 kPa. It was confirmed by ¹ H-NMR (measurement method 2) that the number average molecular weight was equivalent to 2500, and a polyether polycarbonate diol-containing composition was obtained.
8.5% aqueous phosphoric acid in polyether polycarbonate diol-containing composition: 0.68
mL (0.59 mmol) was added to deactivate the catalyst, then the Vigreux tube was removed and 1
A polyether polycarbonate diol-containing composition was obtained by removing residual monomers at 165-185° C. kPa.

The obtained polyether polycarbonate diol-containing composition was fed 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 a polyether polycarbonate diol composition. As a thin film distillation apparatus, a diameter of 50 mm and a height of 2
00 mm, an area of 0.0314 m ² , and a jacketed molecular distillation apparatus MS-300 special model manufactured by Shibata Scientific Co., Ltd. was used. Table 2 shows analytical values and physical property values of the resulting polyether polycarbonate diol composition.

[Comparative Example 2-1]
A polyether polycarbonate diol composition was obtained in the same manner as in Example 2-1, except that the amount of the dihydroxy compound and the amount of the diester carbonate were changed, and the type and amount of the catalyst were changed. Table 2 shows analytical values and physical property values of the resulting polyether polycarbonate diol composition.

The methods for producing the polyether polycarbonate diol compositions of Examples 1-1 to 1-3 had good reaction efficiency, whereas the method for producing the polyether polycarbonate diol composition of Comparative Example 1-1 had poor reaction efficiency. , the EG conversion remains low even after the reaction time elapses.
All of the polyether polycarbonate diol compositions of Examples 2-1 to 2-3 have little coloration and low APHA values. On the other hand, the polyether polycarbonate diol composition of Comparative Example 2-1 exhibits a high APHA.

Claims (7)

A polyether polycarbonate diol composition comprising a metal and a polyether polycarbonate diol,
the metal is magnesium ,
The polyether polycarbonate diol contains a structural unit (A) derived from polyoxytetramethylene glycol and a structural unit (B) derived from a compound represented by the following formula (1), and the structural unit (A) and the structural unit (B ) in a molar ratio of 100:0 to 50:50.

(Wherein, R represents a divalent hydrocarbon group having 2 to 12 carbon atoms.) 2. The polyether polycarbonate diol composition according to claim 1, wherein the metal content is 1 mass ppm or more and 200 mass ppm or less. The polyether polycarbonate diol composition has a number average molecular weight of 250 to 500
3. The polyether polycarbonate diol composition according to claim 1, wherein the polyether polycarbonate diol composition is 0 or less. A polyether polycarbonate diol having a number average molecular weight of 250 or more and 5000 or less by polycondensing a dihydroxy compound containing polyoxytetramethylene glycol and a carbonic acid diester as raw material monomers through a transesterification reaction in the presence of a transesterification catalyst. A method of manufacturing a composition comprising:
A method for producing a polyether polycarbonate diol composition, wherein the transesterification catalyst is a composition containing magnesium . 5. The method for producing a polyether polycarbonate diol composition according to claim 4, wherein the amount of the transesterification catalyst used is 10 μmol/mol or more and 1500 μmol/mol or less with respect to the amount of the dihydroxy compound containing the polyoxytetramethylene glycol. . The transesterification catalyst is a composition containing magnesium and at least one compound represented by the following formula (2), or a composition containing at least one salt represented by the following formula (3): 6. A method for producing a polyether polycarbonate diol composition according to 4 or 5.

(wherein R ₁ and R ₃ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms,
It may be substituted with a halogen atom and may have an oxygen atom.
R ₂ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, and the hydrocarbon group may be substituted with a halogen atom or may have an oxygen atom.
M represents magnesium and n=2. ) A method for producing polyurethane using the polyether polycarbonate diol composition according to any one of claims 1 to 3.