CN117164839A - Transesterification catalyst, method for producing polycarbonate diol, and polycarbonate diol - Google Patents

Transesterification catalyst, method for producing polycarbonate diol, and polycarbonate diol Download PDF

Info

Publication number
CN117164839A
CN117164839A CN202310642484.9A CN202310642484A CN117164839A CN 117164839 A CN117164839 A CN 117164839A CN 202310642484 A CN202310642484 A CN 202310642484A CN 117164839 A CN117164839 A CN 117164839A
Authority
CN
China
Prior art keywords
group
metal
polycarbonate diol
transesterification catalyst
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310642484.9A
Other languages
Chinese (zh)
Inventor
增渕徹夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Original Assignee
Asahi Kasei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Corp filed Critical Asahi Kasei Corp
Publication of CN117164839A publication Critical patent/CN117164839A/en
Pending legal-status Critical Current

Links

Abstract

Provided are a transesterification catalyst capable of efficiently producing a polycarbonate diol or a polyester under mild conditions, a method for producing a polycarbonate diol, and a polycarbonate diol. A transesterification catalyst comprising at least two transesterification catalysts of transesterification catalyst A1 and transesterification catalyst A2, the transesterification catalyst A1 containing at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long periodic table of elements, and the transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long periodic table of elements.

Description

Transesterification catalyst, method for producing polycarbonate diol, and polycarbonate diol
Technical Field
The present invention relates to a transesterification catalyst, a method for producing a polycarbonate diol, and a polycarbonate diol.
Background
Conventionally, polyurethane resins and polyurea resins have been used in a wide variety of fields such as synthetic leather, artificial leather, adhesives, furniture coatings, and automobile coatings.
In the production of the polyurethane resin and the polyurea resin, polyether and polyester are used as the polyol component that reacts with isocyanate (for example, refer to patent document 1 and non-patent document 1).
However, in recent years, the demands for resin resistance such as heat resistance, weather resistance, hydrolysis resistance, mold resistance, and oil resistance have been increasing for the polyurethane resin and polyurea resin.
In order to cope with such high-demand properties, various polycarbonate diols have been proposed as soft segments excellent in hydrolysis resistance, light resistance, oxidation degradation resistance, heat resistance, and the like (for example, see patent documents 2 to 5).
In the production of polycarbonate diols and polyesters, transesterification catalysts have been generally used in the past.
For example, in the production of copolymerized polycarbonate diol of diethyl carbonate, 1, 6-hexanediol and 1, 5-pentanediol, sodium metal is used as a catalyst (for example, refer to patent document 6); in a combination of diethyl carbonate and diols such as 1, 3-propanediol, 2-methyl-1, 3-propanediol, and 1, 3-butanediol, sodium ethoxide and magnesium acetate are used as catalysts (for example, refer to patent document 7).
In addition, lead acetate and tetra-n-butyl titanate are used as catalysts in the production of copolymerized polycarbonate diols of ethylene carbonate and diols such as 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and 2-methyl-1, 3-propanediol, and in the production of polycarbonate diols of ethylene carbonate and various alkylene glycols and oxyalkylene glycols such as diethylene glycol and dibutylene glycol, tetra-n-butyl titanate is used as a catalyst (for example, refer to patent document 8).
In addition, in the case of producing a copolymerized polycarbonate diol by using a combination of ethylene carbonate and 1, 6-hexanediol, dibutyltin dilaurate, sodium acetate, lithium hydroxide, tin powder, or the like is used as a catalyst in addition to tetra-n-butyl titanate (for example, refer to patent document 9).
Further, in the case of producing a copolymerized polycarbonate diol of diphenyl carbonate, 1, 6-hexanediol and neopentyl glycol, magnesium acetate is used favorably as a catalyst (for example, refer to patent document 10).
In recent years, as a method for improving the color tone of a polycarbonate diol under milder conditions, a method for producing a polycarbonate diol using an ester interchange catalyst, characterized in that zinc and a salt of acetylacetone (or a salt of acetylacetone derivative) with at least 1 metal selected from the group consisting of group 2 metals of the long-period periodic table are present as the catalyst (for example, refer to patent document 11).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2000-95836
Patent document 2: japanese patent laid-open No. 2001-123112
Patent document 3: japanese patent laid-open No. 5-51428
Patent document 4: japanese patent laid-open No. 6-49166
Patent document 5: international publication No. 2002/070584
Patent document 6: japanese patent laid-open No. 2-289616
Patent document 7: japanese patent application laid-open No. 2012-46659
Patent document 8: international publication No. 2006/088152
Patent document 9: japanese patent laid-open No. 51-144492
Patent document 10: japanese patent laid-open publication No. 2013-010950
Patent document 11: japanese patent laid-open No. 2020-125467
Non-patent literature
Non-patent document 1: basic and application of polyurethane (Japanese, use of coating of polyethylene base ), pages 96 to 106, song Yongsheng Ji, CMC company publication, release 11 in 2006)
Disclosure of Invention
Problems to be solved by the invention
The above prior art has the following problems: in order to cause polycondensation of various dihydroxy compounds having different reactivity, it is necessary to set the reaction temperature to be high or to add a large amount of catalyst, which may cause coloration and thermal degradation of polycarbonate diol and polyester. Therefore, the transesterification catalyst known in the art has room for improvement in terms of fashion in the production of various polycarbonate diols and polyesters.
For example, when alkali metal, alkaline earth metal, alkoxide thereof, or other strong base is used as a catalyst, coloring of polycarbonate diol or polyester is likely to occur.
In addition, when a titanium compound is used as a catalyst, the activity of the catalyst is insufficient, and thus a long time is required for producing a polycarbonate diol or a polyester. If the reaction time is long, formation of an undesirable ether group or vinyl group is promoted. These groups may cause deterioration of weather resistance and heat resistance of the polyurethane obtained when polycarbonate diol or polyester is used as a polyurethane raw material, and therefore are not preferable as a polyurethane raw material.
On the other hand, in recent years, it has been clarified that lead compounds and organotin compounds are harmful to the human body and adversely affect the ecological system. Therefore, these compounds are not preferable as components remaining in the polycarbonate diol and the polyester.
In addition, when magnesium acetate, magnesium alkoxide, or magnesium acetylacetonate is used as a catalyst, the polymerization activity is high and improvement in productivity is observed as compared with titanium compounds, but the polymerization activity is insufficient, and therefore there is room for improvement in terms of coloration of the obtained polycarbonate diol or polyester and improvement in productivity.
Accordingly, an object of the present invention is to provide a transesterification catalyst with high activity which can efficiently produce a polycarbonate diol or a polyester (specifically, under milder reaction conditions and in a short period of time). The present invention also aims to provide a method for producing a polycarbonate diol or a polyester with high efficiency (specifically, under milder reaction conditions and in a short time). Further, it is a preferred object to provide a polycarbonate diol having excellent color tone, few ether linkages and high purity of terminal primary hydroxyl groups (OH); and a polyurethane having excellent chemical resistance, heat resistance and hydrolysis resistance, which is obtained by using the polycarbonate diol.
Solution for solving the problem
The present inventors have conducted intensive studies to solve the problems of the prior art, and as a result, found that: when a polycarbonate diol or a polyester is produced by polycondensation by transesterification, the use of a transesterification catalyst containing at least two transesterification catalysts containing specific metals enables the polycarbonate diol or the polyester to be produced efficiently, and the above problems can be solved. Further, it has been found that a polycarbonate diol which is excellent in color tone, has few ether linkages and has a high purity of terminal primary hydroxyl groups (OH); and a polyurethane excellent in chemical resistance, heat resistance and hydrolysis resistance, which is obtained by using the polycarbonate diol. Namely, the gist of the present invention is as follows.
[1]
A transesterification catalyst comprising at least two transesterification catalysts of transesterification catalyst A1 and transesterification catalyst A2, the transesterification catalyst A1 containing at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long periodic table of elements, and the transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long periodic table of elements.
[2] The transesterification catalyst according to [1], wherein the transesterification catalyst A1 is at least 1 metal complex represented by the following formula (1) and/or a hydrate thereof,
(in the formula (1), R 1 And R is 3 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 1 And R is 3 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; r is R 2 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 2 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; m1 represents at least 1 metal selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements; n is 1, 2 or 3. In addition, a metal represented by formula (1)The complex is optionally a plurality of associates. )
[3] The transesterification catalyst according to [1], wherein the transesterification catalyst A1 is a salt of at least 1 carboxylic acid represented by the following formula (2) with at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long periodic Table of elements and/or a hydrate thereof.
(in the formula (2), R 4 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 4 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms. )
[4] The transesterification catalyst according to any one of [1] to [3], wherein the transesterification catalyst A2 is at least 1 metal complex represented by the following formula (3) and/or a hydrate thereof.
(in the formula (3), R 5 And R is 7 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 5 And R is 7 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; r is R 6 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 6 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; m2 represents at least 1 metal selected from the group consisting of group 2 metals of the long periodic table of elements; n is 1, 2 or 3. The metal complex represented by the formula (3) is optionally a plurality of associates. )
[5] The transesterification catalyst according to any one of [1] to [3], wherein the transesterification catalyst A2 is a salt of at least 1 carboxylic acid represented by the following formula (4) with at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic Table of elements and/or a hydrate thereof.
(in the formula (4), R 8 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 8 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms. )
[6] The transesterification catalyst according to any one of [1] to [3], wherein the transesterification catalyst A2 is an alkoxide formed of at least 1 alcohol represented by the following formula (5) and at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic Table.
R 9 -OH (5)
(in the formula (5), R 9 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 9 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms. )
[7] A method for producing a polycarbonate diol, comprising: a step of polycondensing a dihydroxy compound and a carbonate ester as raw material monomers in the presence of a transesterification catalyst to obtain a polycarbonate diol,
the transesterification catalyst comprises a transesterification catalyst A1 and a transesterification catalyst A2, wherein the transesterification catalyst A1 contains at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long periodic Table of elements, and the transesterification catalyst A2 contains at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long periodic Table of elements.
[8] The method for producing a polycarbonate diol according to [7], wherein the transesterification catalyst A1 is at least 1 metal complex represented by the following formula (1) and/or a hydrate thereof.
(wherein R is 1 And R is 3 Each independently represents the number of carbon atoms1 to 10 monovalent hydrocarbon groups, R 1 And R is 3 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; r is R 2 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 2 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; m1 represents at least 1 metal selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long period periodic table of elements, and n is 1, 2 or 3. The metal complex represented by the formula (1) is optionally a plurality of associates. )
[9] The method for producing a polycarbonate diol according to [7], wherein the transesterification catalyst A1 is a salt of at least 1 carboxylic acid represented by the following formula (2) with at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic Table of elements and/or a hydrate thereof.
(wherein R is 4 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 4 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms. )
[10] The method for producing a polycarbonate diol according to any one of [7] to [9], wherein the metal (M1) is at least 1 metal selected from the group consisting of molybdenum, manganese, iron, cobalt, nickel and copper.
[11] The method for producing a polycarbonate diol according to any one of [7] to [10], wherein the transesterification catalyst A2 is at least 1 metal complex represented by the following formula (3) and/or a hydrate thereof.
(wherein R is 5 And R is 7 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 5 And R is 7 Is optionally hydrocarbon-basedSubstituted with halogen atoms and, in addition, optionally with oxygen atoms; r is R 6 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 6 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; m2 represents at least 1 metal selected from the group consisting of group 2 metals of the long periodic table of elements; n is 1, 2 or 3. The metal complex represented by the formula (3) is optionally a plurality of associates. )
[12] The method for producing a polycarbonate diol according to any one of [7] to [10], wherein the transesterification catalyst A2 is a salt of at least 1 carboxylic acid represented by the following formula (4) with at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic Table of elements and/or a hydrate thereof.
(wherein R is 8 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 8 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms. )
[13] The method for producing a polycarbonate diol according to any one of [7] to [10], wherein the transesterification catalyst A2 is an alkoxide of at least 1 alcohol represented by the following formula (5) and at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic Table.
R 9 -OH (5)
(wherein R is 9 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 9 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms. )
[14] The method for producing a polycarbonate diol according to any one of [7] to [13], wherein the metal (M2) is at least 1 metal selected from the group consisting of magnesium and calcium.
[15] The method for producing a polycarbonate diol according to any one of [7] to [14], wherein,
the amount of the transesterification catalyst A1 is 0.5ppm or more and 20ppm or less relative to the total amount of all the dihydroxy compounds and the carbonate based on the total amount of the metal (M1),
the amount of the transesterification catalyst A2 is 0.25ppm to 10ppm based on the total amount of the metal (M2) and the total amount of the dihydroxy compound and the carbonate.
[16] The method for producing a polycarbonate diol according to any one of [7] to [15], wherein the dihydroxy compound comprises at least 1 selected from the group consisting of aliphatic dihydroxy compounds and alicyclic dihydroxy compounds having a structure represented by the following formula (6).
HO-R 10 -OH (6)
(wherein R is 10 Represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms. )
[17] A polycarbonate diol which is a polycondensate obtained by transesterification of a dihydroxy compound with a carbonate,
a number average molecular weight of 250 to 100000,
at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements is present in the polycarbonate diol in an amount of 1ppm or more and 25ppm or less based on the total amount thereof, and at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long-period periodic table of elements is present in the polycarbonate diol in an amount of 0.5ppm or more and 12.5ppm or less based on the total amount thereof,
the polycarbonate diol has a Harsen color number measured in accordance with JIS-K0071-1 (1998) of 50 or less,
the amount of ether bond is 5 mol% or less,
the purity of the terminal primary hydroxyl (OH) is more than 97%.
[18] The polycarbonate diol according to [17], wherein the metal (M1) is at least 1 metal selected from the group consisting of molybdenum, manganese, iron, cobalt, nickel and copper, and the metal (M2) is at least 1 metal selected from the group consisting of magnesium and calcium.
[19] A polyurethane comprising structural units derived from the polycarbonate diol of [17] or [18 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a transesterification catalyst capable of efficiently producing a polycarbonate diol or polyester under milder conditions than in the prior art can be provided.
Further, by using the transesterification catalyst of the present invention, a polycarbonate diol or polyester having excellent color tone, few ether bonds and high purity of terminal primary hydroxyl groups (OH) can be provided; and a polyurethane having excellent chemical resistance, heat resistance and hydrolysis resistance, which is obtained by using the polycarbonate diol or the polyester.
Detailed Description
Hereinafter, embodiments for carrying out the present invention (hereinafter, abbreviated as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiments, and may be implemented by various modifications within the scope of the present invention.
<1 transesterification catalyst >
The transesterification catalyst of the present embodiment is composed of at least two transesterification catalysts, namely, a transesterification catalyst A1 and a transesterification catalyst A2, wherein the transesterification catalyst A1 contains at least 1 metal (M1) selected from the group consisting of metals of group 6, 7, 8, 9, 10 and 11 of the long period periodic table, and the transesterification catalyst A2 contains at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long period periodic table.
<1-1 transesterification catalyst A1:1 containing at least 1 metal (M1) selected from the group consisting of metals of group 6, group 7, group 8, group 9, group 10 and group 11 of the long periodic Table of elements
As one embodiment of the transesterification catalyst A1 containing at least 1 metal (M1) selected from the group consisting of metals of group 6, group 7, group 8, group 9, group 10 and group 11 of the long period periodic table, at least 1 metal complex represented by the following formula (1) and/or a hydrate thereof is preferable.
In the formula (1), R 1 And R is 3 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 1 And R is 3 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; r is R 2 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 2 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; m1 represents at least 1 metal selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements; n is 1, 2 or 3. The metal complex represented by the formula (1) is optionally a plurality of associates.
The ligand on the metal of the metal complex represented by formula (1) is an acetylacetonate analogue, and may be represented by the non-localized form of the anion as represented by formula (I) below, or may be represented by the equilibrium state of 3 organic anions as represented by formula (II) below.
In the formula (I) and the formula (II), R 1 And R is 3 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 1 And R is 3 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; r is R 2 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 2 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms.
As a method for producing the transesterification catalyst represented by the above formula (1), for example, the following methods are mentioned: a method for producing a transesterification catalyst represented by the above formula (1) by reacting a metal halide salt with an acetylacetone analogue in the presence of a base as represented by the following formula (III); the method for producing the transesterification catalyst represented by the above formula (1) by exchanging the metal alkoxide with the acetylacetone analogue is not limited to this, as shown by the following formula (IV).
M1(OR 6 ) n +R 1 COCHR 2 COR 3 →M1(R 1 COCR 2 CPR 3 ) n +nR 6 OH (IV)
In the formulas (III), (IV), R 1 、R 2 、R 3 M1 and n are as defined in formula (1), X is any halogen atom, R 6 Is an arbitrary hydrocarbon group.
In addition, the transesterification catalyst represented by the above formula (1) may be used in combination with an auxiliary basic compound such as a transition metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound.
R in the formula (1) 1 、R 3 Examples of the group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, phenyl, benzyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl and the like. Among these, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, benzyl, trifluoromethyl and trichloromethyl are particularly preferred. R is as follows 1 And R is R 3 May be the same or different.
In addition, as R 2 Examples of the group include, but are not limited to, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, phenyl, benzyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, fluorine atom, chlorine atom, bromine atom, iodine atom and the like. Among these, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl are preferred, and hydrogen is more preferred.
The metal (M1) selected from the group consisting of group 6, group 7, group 8, group 9, group 10 and group 11 of the long-period periodic table is not limited to the following metal, and molybdenum, manganese, iron, cobalt, nickel and copper are preferable from the viewpoint of catalytic activity, and manganese is more preferable.
In the present embodiment, the organometallic complex formed with the acetylacetone analog used as the transesterification catalyst may be used in the form of a hydrate.
As another embodiment of the transesterification catalyst A1 containing at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements, salts of at least 1 carboxylic acid represented by the following formula (2) with at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements and/or hydrates thereof are preferable.
In the formula (2), R 4 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 4 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms.
Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, palmitic acid, heptadecanoic acid, and stearic acid. Among these, acetic acid, propionic acid, and butyric acid are preferable, and acetic acid is more preferable.
The metal (M1) selected from the group consisting of group 6, group 7, group 8, group 9, group 10 and group 11 of the long-period periodic table in the above formula (2) is not limited to the following metal, but molybdenum, manganese, iron, cobalt, nickel and copper are preferable from the viewpoint of catalytic activity, and manganese is more preferable.
In the present embodiment, the salts of these carboxylic acids used as transesterification catalysts may be used in the form of hydrates.
<1-2 transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of group 2 metals of the long periodic Table of elements
In the transesterification catalyst of the present embodiment, the transesterification catalyst A1 is used in combination with a transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of group 2 metals of the long periodic table.
The group 2 metal of the long-period periodic table is not limited to the following metals, and examples thereof include beryllium, magnesium, calcium, strontium, barium, and radium. Among these, magnesium and calcium are preferable because they have high catalytic activity. In particular, calcium having high activity and having a small amount of ether bonds in the produced polycarbonate diol is more preferable.
The form of the transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic table is not particularly limited, and examples thereof include salts with inorganic acids, salts with organic acids, alkoxides and hydroxides of various alcohols.
As one form of the transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of group 2 metals of the long periodic table, at least 1 metal complex represented by the following formula (3) and/or a hydrate thereof is preferable.
In the formula (3), R 5 And R is 7 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 5 And R is 7 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; r is R 6 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 6 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms; m2 represents at least 1 metal selected from the group consisting of group 2 metals of the long periodic table of elements; n is 1, 2 or 3. In addition, a metal complex represented by formula (3)The polymer is optionally a plurality of associates.
R in the formula (3) 5 、R 7 Examples of the group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, phenyl, benzyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl and the like. Among these, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, benzyl, trifluoromethyl and trichloromethyl are particularly preferred. R is as follows 5 And R is R 7 May be the same or different.
In addition, as R 6 Examples of the group include, but are not limited to, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, phenyl, benzyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, fluorine atom, chlorine atom, bromine atom, iodine atom and the like. Among these, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl are preferred, and hydrogen is more preferred.
The metal (M2) selected from the group consisting of group 2 of the long-period periodic table in the above formula (3) is not limited to the following metal, but magnesium and calcium are preferable from the viewpoint of catalytic activity, and among these, calcium is particularly preferable.
As another form of the transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of group 2 metals of the long periodic table, a salt of at least 1 carboxylic acid represented by the following formula (4) with at least 1 metal (M2) selected from the group consisting of group 2 metals of the long periodic table and/or a hydrate thereof is preferable.
In the formula (4), R 8 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 8 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms.
Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, palmitic acid, heptadecanoic acid, and stearic acid, and among these, acetic acid, propionic acid, and butyric acid are preferable, and acetic acid is more preferable.
The metal (M2) selected from the group consisting of group 2 of the long periodic table is not limited to the following metal, but magnesium and calcium are preferable from the viewpoint of catalytic activity, and calcium is more preferable.
In another embodiment of the transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic table, an alkoxide formed from at least 1 alcohol represented by the following formula (5) and at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic table is preferable because of high catalytic activity and little coloration.
R 9 -OH (5)
In the formula (5), R 9 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 9 Optionally substituted with halogen atoms and, in addition, optionally having oxygen atoms.
The alkoxide formed by at least 1 alcohol represented by the above formula (5) and the group 2 metal of the long periodic table of elements is not limited to the following alkoxide, and examples thereof include beryllium alkoxide, magnesium alkoxide, calcium alkoxide, strontium alkoxide, barium alkoxide, radium alkoxide, and the like. Among these alkoxides, magnesium alkoxides and calcium alkoxides having high catalytic activity and less ether bond amount and coloration of the produced polycarbonate diol are preferable, and calcium alkoxides are more preferable.
The alkoxide with the group 2 metal of the long-period periodic table is not limited to the following alkoxide, and examples thereof include magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutanoate, calcium dimethoxide, calcium diethoxide, calcium dipropoxide, and calcium dibutanoxide. Of these, calcium dimethoxide, calcium diethoxide, calcium dipropoxide, and calcium dibutanoate are more preferable.
The transesterification catalyst of the present embodiment is a transesterification catalyst comprising at least two transesterification catalysts, namely, a transesterification catalyst A1 and a transesterification catalyst A2, the transesterification catalyst A1 containing at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long periodic table of elements, and the transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long periodic table of elements.
By using the transesterification catalyst A1 and the transesterification catalyst A2 in combination, a higher catalytic activity can be obtained than by using the transesterification catalyst A1 or the transesterification catalyst A2 alone, and polycarbonate diol and polyester can be produced efficiently.
The mechanism for exhibiting such an effect is not clear, but the present inventors speculate that it is based on the reaction mechanism represented by the following formula (V). It can be considered that: first, the transesterification catalyst A1 containing at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements is a carbonyl oxygen coordinated to a carbonate group or an ester group as a lewis acid. As a result, the cationicity of the carbonyl carbon is improved, and the transesterification reaction is activated. On the other hand, the transesterification catalyst A2 containing at least 1 metal M1 selected from the group consisting of metals of groups 1 and 4 of the long period periodic table anionizes the oxygen of the alcohol to promote its reaction with the activated carbonyl carbon.
In the formula (V), M1 represents at least 1 metal selected from the group consisting of metals of group 6, group 7, group 8, group 9, group 10 and group 11 of the long periodic table of elements; m2 represents at least 1 metal selected from the group consisting of group 2 metals of the long periodic table of elements; r is R 10 、R 11 、R 12 Represents any hydrocarbon; l (L) 1 、L 2 Represents an arbitrary ligand (there are also pluralLigand).
<2 > method of Using catalyst >
As a method for using the transesterification catalyst of the present embodiment, for example, in the case of producing a polycarbonate diol, the following method is generally used: the dihydroxy compound and the carbonate are used as raw material monomers, and the transesterification catalyst of the present embodiment is added to polycondense the raw material monomers by transesterification. In addition, when used for producing polyesters, the following methods are generally exemplified: as the raw material monomer, a dihydroxy compound is used, and a dibasic acid such as adipic acid and phthalic acid and/or a methyl ester and ethyl ester compound thereof is used, and the transesterification catalyst of the present embodiment is added to polycondense the mixture by transesterification.
By using the transesterification catalyst of the present embodiment, a polycarbonate diol or a polyester can be produced efficiently (for example, under milder reaction conditions and in a short period of time).
Hereinafter, a specific method of using the catalyst will be described by taking a method of producing polycarbonate diol as an example.
<2-1 raw material monomer >
In the case of producing a polycarbonate diol using the transesterification catalyst of the present embodiment, a dihydroxy compound and a carbonate ester are generally used as raw material monomers.
<2-1-1 dihydroxy Compound >
Examples of the dihydroxy compound as a raw material monomer include, but are not limited to, linear terminal dihydroxy compounds such as 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, 11-undecanediol, 1, 12-dodecanediol, and 1, 20-eicosanediol; dihydroxy compounds having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol and polytetramethylene glycol; thioether glycols such as dihydroxyethyl sulfide; 2, 2-dialkyl-substituted 1, 3-propanediol (hereinafter sometimes referred to as 2, 2-dialkyl-1, 3-propanediol) such as 2-ethyl-1, 6-hexanediol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 8-octanediol and 2, 4-diethyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol (hereinafter sometimes abbreviated as neopentyl glycol), 2-ethyl-2-butyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol and 2-pentyl-2-propyl-1, 3-propanediol; tetraalkyl-substituted alkylene glycols such as 2, 4-tetramethyl-1, 5-pentanediol and 2, 9-tetramethyl-1, 10-decanediol; dihydroxy compounds containing a cyclic group such as 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane; dihydroxy compounds having a branched chain such as 2, 2-diphenyl-1, 3-propanediol, 2-divinyl-1, 3-propanediol, 2-diacetyl-1, 3-propanediol, 2-dimethoxy-1, 3-propanediol, bis (2-hydroxy-1, 1-dimethylethyl) ether, bis (2-hydroxy-1, 1-dimethylethyl) sulfide, and 2, 4-tetramethyl-3-cyano-1, 5-pentanediol; dihydroxy compounds having a cyclic group in the molecule such as 1, 3-cyclohexanediol, 1, 4-cyclohexanedimethanol, 4-dicyclohexyldimethylmethane glycol, 2 '-bis (4-hydroxycyclohexyl) propane, 1, 4-dihydroxyethylcyclohexane, isosorbide, spiroglycol, 2, 5-bis (hydroxymethyl) tetrahydrofuran, 4' -isopropylidenediohexanol, and 4,4 '-isopropylidenedio (2, 2' -hydroxyethoxycyclohexane); dihydroxy compounds having an aromatic ring such as 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 9, 9-bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene; nitrogen-containing dihydroxy compounds such as diethanolamine and N-methyl-diethanolamine; sulfur-containing dihydroxy compounds such as bis (hydroxyethyl) sulfide; 2, 2-bis (4-hydroxyphenyl) propane [ =bisphenol a ], 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-diethylphenyl) propane, 2-bis (4-hydroxy- (3, 5-diphenyl) phenyl) propane, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2-bis (4-hydroxyphenyl) pentane, 2,4' -dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane aromatic bisphenols such as 1, 1-bis (4-hydroxyphenyl) ethane, 3-bis (4-hydroxyphenyl) pentane, 1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4' -dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) sulfide, 4' -dihydroxydiphenyl ether, 4' -dihydroxy-3, 3' -dichlorodiphenyl ether, 9-bis (4-hydroxyphenyl) fluorene, and 9, 9-bis (4-hydroxy-2-methylphenyl) fluorene.
Among them, from the viewpoint of weather resistance of the polyurethane obtained using the polycarbonate diol produced using the transesterification catalyst of the present embodiment, the dihydroxy compound is preferably at least 1 compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound, and preferably at least 1 compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound represented by the following formula (6).
HO-R 10 -OH (6)
(wherein R is 10 Represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms. )
Among these dihydroxy compounds, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, 1, 10-decanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 8-octanediol are particularly preferred, and 1, 4-cyclohexanedimethanol and tricyclodecanedimethanol are particularly preferred as alicyclic dihydroxy compounds.
These dihydroxy compounds may be used alone or in combination of 2 or more, preferably in combination of two or more, depending on the properties required for the resulting polycarbonate diol. The copolymerized polycarbonate diol is generally hindered from crystallization, has higher flowability than the homopolymerized polycarbonate diol, is excellent in handling properties when processed into polyurethane, and imparts flexibility and texture to polyurethane.
In the case of using two types of dihydroxy compounds, for example, the composition ratio of the copolymerization is preferably, relative to all of the dihydroxy compounds: the dihydroxy compounds are used in an amount of 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more.
In general, when a dihydroxy compound having a different molecular structure is copolymerized, polymerization may be unevenly or inhibited due to a difference in reactivity, and thus a copolymerized polycarbonate diol can be easily obtained according to the present embodiment using a specific transesterification catalyst described later.
<2-1-2. Carbonate >
In the production of a polycarbonate diol using the transesterification catalyst of the present embodiment, examples of the carbonate ester that can be used as a raw material monomer include dialkyl carbonate, diaryl carbonate, and alkylene carbonate.
Among the carbonates usable in the production of the polycarbonate diol of the present embodiment, examples of the dialkyl carbonate include, but are not limited to, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, and ethyl-isobutyl carbonate.
The diaryl carbonates are not limited to the following, and examples thereof include diphenyl carbonate, xylene carbonate, bis (chlorophenyl) carbonate, and xylene carbonate.
The alkylene carbonate is not limited to the following, and examples thereof include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1, 2-propylene carbonate, 1, 2-butylene carbonate, 1, 3-butylene carbonate, 2, 3-butylene carbonate, 1, 2-pentylene carbonate, 1, 3-pentylene carbonate, 1, 4-pentylene carbonate, 1, 5-pentylene carbonate, 2, 3-pentylene carbonate, 2, 4-pentylene carbonate, and neopentylene carbonate.
The number of these may be 1 alone or 2 or more.
Among these carbonates, dimethyl carbonate, diethyl carbonate, ethylene carbonate and diphenyl carbonate which can be obtained at low cost as industrial raw materials, have good reactivity and have a small amount of by-produced alcohol are particularly preferred.
<2-1-3 ratio of raw material monomers used >
In the production of a polycarbonate diol using the transesterification catalyst of the present embodiment, the amount of the carbonate to be used is required to be appropriately changed depending on the target molecular weight of the polycarbonate diol, and is not particularly limited, but the lower limit is usually preferably 0.5, more preferably 0.7, still more preferably 0.8, and the upper limit is usually 1.5, preferably 1.3, still more preferably 1.2, in terms of a molar ratio relative to 1 mol of the total of the dihydroxy compounds. If the amount of the carbonic acid diester is not more than the upper limit, the following tends to be present: the proportion of the material in which the terminal group of the obtained polycarbonate diol is not a hydroxyl group can be suppressed, or a polycarbonate diol having a molecular weight in a predetermined range can be produced, and if the molecular weight is not less than the lower limit, polymerization tends to proceed to the predetermined molecular weight.
<2-2. Process for producing polycarbonate diol Using transesterification catalyst >
In the method for producing a polycarbonate diol using the transesterification catalyst of the present embodiment, a polycarbonate diol is produced by transesterifying 1 or more of the dihydroxy compounds with 1 or more of the carbonates in the presence of the at least two transesterification catalysts A1 and A2.
<2-2-1. Amount of catalyst used >
The amount of the transesterification catalyst A1 used in the present embodiment in the production of the polycarbonate diol is preferably 0.5ppm or more and 20ppm or less, more preferably 1ppm or more and 10ppm or less, still more preferably 2ppm or more and 7ppm or less, based on the total amount of the metal (M1), and the amount of the transesterification catalyst A2 is preferably 0.25ppm or more and 10ppm or less, more preferably 0.5ppm or more and 5ppm or less, still more preferably 1ppm or more and 3ppm or less, based on the total amount of the metal (M2).
If the amount of the transesterification catalyst A1 is 0.5ppm or more based on the total amount of the metal (M1), the rate of transesterification tends to be high. In addition, if the amount of the transesterification catalyst is 20ppm or less based on the total amount of the metal (M1), the following tends to occur: the coloring of the obtained polycarbonate diol or polyester can be suppressed, and when the polycarbonate diol or polyester is used as a raw material for a urethane, the urethanization reaction is stable, and the color tone of the obtained urethane tends to be good and the heat resistance tends to be improved.
If the amount of the transesterification catalyst A2 is 0.25ppm or more based on the total amount of the metal (M2), the rate of transesterification tends to be high. In addition, if the amount of the transesterification catalyst is 10ppm or less based on the total amount of the metal (M2), the following tends to occur: the coloring of the obtained polycarbonate diol and polyester can be suppressed, the number of ether bonds becomes small, and in the case of using as a raw material for a urethane, the urethanization reaction is stable, and the color tone of the obtained urethane tends to be good and the heat resistance tends to be improved.
<2-2-2. Reaction conditions, etc.)
The method of charging the reaction raw materials is not particularly limited, and examples thereof include the following methods: a method in which 1 or more dihydroxy compounds and carbonate or dibasic acid and transesterification catalyst are all fed simultaneously and supplied to the reaction; in the case where the carbonate or the dibasic acid is solid, a method comprising first charging the carbonate or the dibasic acid and heating and melting the carbonate or the dibasic acid, and then adding the dihydroxy compound and the transesterification catalyst; on the other hand, when the dihydroxy compound is solid, the dihydroxy compound is first charged and melted, and a method of charging the carbonate or the dibasic acid and the transesterification catalyst thereto, and the like, can be freely selected.
The reaction temperature in the transesterification reaction may be any temperature as long as the reaction rate in practical use can be obtained. The temperature is not particularly limited, but the lower limit is preferably 80 ℃, more preferably 110 ℃, and further preferably 130 ℃. The upper limit of the reaction temperature is preferably 220 ℃, more preferably 200 ℃, further preferably 180 ℃, further preferably 170 ℃. If the reaction temperature is not less than the lower limit, the transesterification reaction tends to proceed at a practically useful rate. In addition, when the reaction temperature is not higher than the upper limit, the coloring of the obtained polycarbonate diol can be suppressed, and the formation of ether bonds or improvement in quality such as improvement in haze can be suppressed.
In particular, by using the transesterification catalyst of the present embodiment, a polycarbonate diol or a polyester can be efficiently obtained in a short period of time even under mild reaction conditions, for example, at a low temperature of 160 ℃ or lower (preferably 150 ℃ or lower).
The reaction may be carried out under normal pressure, and the transesterification reaction is an equilibrium reaction, and the resulting monohydroxy compound or dihydroxy compound is distilled out of the system, whereby the reaction can be shifted to the resulting system. Therefore, it is generally preferable to carry out the reaction while distilling off the monohydroxy compound or the dihydroxy compound under reduced pressure in the latter half of the reaction. Alternatively, the pressure may be gradually reduced from the middle of the reaction, and the produced monohydroxy compound or dihydroxy compound may be distilled off and reacted. If the pressure is gradually reduced from the reaction, the following tends to occur: the volatilization of the unreacted monomer having a low boiling point can be suppressed, and the yield can be improved, and a polycarbonate diol or polyester having a predetermined molecular weight or, in the case of copolymerization, a polycarbonate diol or polyester having a predetermined copolymerization composition ratio can be obtained.
The pressure at the time of the reaction is appropriately selected depending on the kind of the alcohol derived from the carbonate or the dibasic acid to be distilled off (water or alcohol in the case of the dibasic acid), and for example, in the case where the alcohol to be distilled off is an alcohol having a relatively low boiling point such as methanol, the preferable pressure in the reactor is 5kPa to normal pressure, more preferably 7kPa to 15kPa. In the case where the alcohol to be distilled off is an alcohol having a relatively high boiling point such as ethylene glycol, the pressure in the reactor is preferably 1 to 10kPa, more preferably 3 to 7kPa.
Further, from the viewpoint of preventing the distillation of the raw materials at the initial stage of the reaction, it is also possible to: a rectifying column having a theoretical plate number of 10 or more, preferably 15 or more, more preferably 20 or more is installed in the reactor, and water, a monohydroxy compound or a dihydroxy compound produced by the reaction of the carbonate is azeotroped while the carbonate and the dihydroxy compound as raw materials are refluxed and separated, whereby the water, the monohydroxy compound or the dihydroxy compound produced by the reaction of the carbonate is efficiently separated and distilled off. In this case, the amount ratio of the reagents can be accurately integrated without losing the raw material monomer to be charged, which is preferable.
In addition, in the final stage of the reaction, the reaction is usually switched to single distillation, and if the reaction is carried out at an elevated pressure, by-produced alcohols, diols, monohydroxy compounds such as phenols, residual monomers such as dihydroxy compounds and carbonates, and cyclic carbonates (cyclic oligomers) which may cause turbidity can be distilled off with high efficiency.
The reaction pressure at the end of the reaction at this time is not particularly limited, but the upper limit is usually preferably 5kPa, more preferably 2kPa, and still more preferably 1kPa. In order to effectively distill off these low boiling components, the reaction may be carried out while introducing a small amount of inert gas such as nitrogen, argon, helium or the like into the reaction system.
In the case of using a carbonate or a dihydroxy compound having a low boiling point in the transesterification reaction, the following method may be employed: in the initial stage of the reaction, the reaction proceeds near the boiling point of the carbonate or the dihydroxy compound, and the temperature is gradually increased as the reaction proceeds, thereby further advancing the reaction. In this case, the unreacted carbonate and the dihydroxy compound can be prevented from being distilled off at the initial stage of the reaction, which is preferable.
<2-3. Polymerization reactor >
The polymerization (polycondensation) may be carried out either batchwise or continuously, and continuous is preferable from the viewpoint of stability of quality such as molecular weight of the product. The device may be any of a tank type, a pipe type and a tower type, and a known polymerization tank having various stirring blades may be used. The atmosphere during the heating of the apparatus is not particularly limited, and is preferably performed under normal pressure or reduced pressure in an inert gas such as nitrogen from the viewpoint of product quality.
<2-4. Reaction time >
In the production of a polycarbonate diol or a polyester using the transesterification catalyst of the present embodiment, the time required for the transesterification reaction (polymerization reaction or polycondensation reaction) is significantly different depending on the types and amounts of the dihydroxy compound, the carbonate, and the transesterification catalyst used, and thus, the reaction time required to achieve a predetermined molecular weight is preferably 20 hours or less, more preferably 10 hours or less, and even more preferably 5 hours or less, not all in all.
<2-5. Deactivation of catalyst >
As described above, when the transesterification catalyst of the present embodiment is used in the transesterification reaction, the transesterification catalyst of the present embodiment or the residue thereof may remain in the polycarbonate diol or polyester which is usually obtained, and the reaction may not be controlled in the urethanization reaction. In order to suppress the influence of the residual catalyst, a catalyst deactivator, for example, an acidic compound or a compound such as a phosphorus-based compound or a sulfur-based compound which is decomposed to form an acidic compound may be added in an amount substantially equal to the amount of the transesterification catalyst to be used. Further, if the heat treatment is performed as described later after the addition, the transesterification catalyst can be deactivated efficiently. Further, the deactivation can reduce the color development of the transesterification catalyst, and a polycarbonate diol having a Harsen color number of preferably 50 or less, more preferably 30 or less, as measured in accordance with JIS-K0071-1 (1998) can be obtained.
Further, the addition of the catalyst deactivator can suppress the discoloration and physical property changes of the obtained polycarbonate diol or polyester due to the change of the terminal structure and skeleton of the residual catalyst during storage at high temperature and long time and during handling.
The compound for inactivating the transesterification catalyst (hereinafter, sometimes referred to as a catalyst inactivating agent) is not limited to the following compound, and examples thereof include inorganic phosphoric acid such as phosphoric acid and phosphorous acid; organic phosphates such as monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and triphenyl phosphite; sulfonic acids, sulfonic esters, and the like. The number of these may be 1 alone or 2 or more.
The amount of the catalyst deactivator is not particularly limited, and as described above, it is only required to be approximately equal to the amount of the transesterification catalyst to be used, and specifically, the upper limit is preferably 5 moles, more preferably 2 moles, and the lower limit is preferably 0.8 moles, more preferably 1.0 mole, relative to 1 mole of the transesterification catalyst to be used. When the catalyst deactivator is used in an amount of not less than the lower limit, the following tends to be used: when the transesterification catalyst in the reaction product is sufficiently deactivated and the obtained polycarbonate diol is used as a raw material for producing polyurethane, for example, the reactivity of the polycarbonate diol with respect to isocyanate groups can be sufficiently reduced. In addition, when the catalyst deactivator is used in an amount not higher than the upper limit, the following tends to be used: the coloring of the obtained polycarbonate diol or polyester can be suppressed, and in the case of being used as a raw material for urethane, the polymerization of urethane can be performed well.
Deactivation of the transesterification catalyst by the addition of the catalyst deactivator may be performed at room temperature, and the heat treatment may be more efficient. The temperature of the heat treatment is not particularly limited, but the upper limit is preferably 140 ℃, more preferably 130 ℃, further preferably 120 ℃, and the lower limit is preferably 80 ℃, more preferably 100 ℃, further preferably 110 ℃. When the temperature is not less than the lower limit, the time for deactivating the transesterification catalyst becomes short and efficient, and the degree of deactivation becomes sufficient. On the other hand, when the phosphorus compound is used as the inactivating agent at a temperature of 140 ℃ or lower, decomposition of the phosphorus compound is suppressed and inactivation is likely to be performed stably. Therefore, coloring of the obtained polycarbonate diol can be suppressed, and in the case of using the polycarbonate diol as a urethane raw material, the urethanization reaction tends to be stable.
The reaction time with the catalyst deactivator is not particularly limited, and is, for example, 1 to 5 hours.
<3 > characteristics of polycarbonate diol or polyester produced by using the transesterification catalyst of the present embodiment >
The polycarbonate diol or polyester produced by using the transesterification catalyst of the present embodiment is excellent in mechanical properties and durability, and therefore can be used for various applications.
Can be widely used for foams, elastomers, paints, fibers, adhesives, flooring materials, sealants, medical materials, artificial leather, coating agents, aqueous polyurethane paints, and the like. In particular, when the polycarbonate diol produced by using the transesterification catalyst of the present embodiment is used as a raw material in applications such as artificial leather, synthetic leather, aqueous polyurethane, adhesives, medical materials, flooring materials, and coating agents, it is excellent in weather resistance, heat resistance, moist heat resistance, and abrasion resistance, and therefore, it is possible to impart good surface characteristics such as less coloration, less susceptibility to damage due to scratches and less deterioration due to friction, and thus, it is suitable as a raw material for various paints.
Hereinafter, suitable physical properties of the polycarbonate diol of the present embodiment will be described.
<3-1. Molecular weight/molecular weight distribution >
The lower limit of the number average molecular weight (Mn) of the polycarbonate diol of the present embodiment is 250, preferably 500, more preferably 750, and still more preferably 1000. On the other hand, the upper limit of the number average molecular weight (Mn) of the polycarbonate diol of the present embodiment is 100000, preferably 50000, more preferably 10000, particularly preferably 3000. When the number average molecular weight of the polycarbonate diol is not less than the lower limit, flexibility and the like tend to be good when the polyurethane is produced. On the other hand, when the number average molecular weight of the polycarbonate diol is not more than the upper limit, the viscosity of the polycarbonate diol tends to be lowered, and handling during urethanization tends to be easy.
The number average molecular weight of the polycarbonate diol is determined from the hydroxyl value (average hydroxyl value number) of the polycarbonate diol as shown in examples described below.
The method for controlling the number average molecular weight (Mn) of the polycarbonate diol to the above range is not particularly limited, and the following methods are exemplified: the number average molecular weight (Mn) of the polycarbonate diol is controlled to the above range by adjusting the polycondensation reaction time of the polycarbonate diol and adjusting the amount of the dihydroxy compound which is the raw material monomer to be taken out.
<3-2.APHA value >
The color of the polycarbonate diol of the present embodiment is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, particularly preferably 20 or less, in terms of the value expressed in Harsen color number (expressed as "APHA value" hereinafter based on JIS K0071-1:1998). The lower limit of the APHA value is not particularly limited, and is, for example, 0 or more. If the APHA value is 50 or less, the following tends to occur: the polyurethane obtained from the polycarbonate diol as a raw material has a good color tone, and has an improved commercial value and good thermal stability.
The method for controlling the APHA value of the polycarbonate diol to the above range is not particularly limited, and examples thereof include the following methods: a method carried out under conditions such that the reaction temperature at the time of transesterification is within the aforementioned preferred temperature range; a method in which the time required for the transesterification reaction (polymerization reaction or polycondensation reaction) is within the aforementioned preferred range, and the like.
In the present embodiment, the APHA value of the polycarbonate diol can be measured by the method described in examples described later.
<3-3. Metal-containing in polycarbonate diol >
The polycarbonate diol of the present embodiment preferably contains, as the metal contained therein, at least 1 metal (M1) selected from the group consisting of metals of group 6, group 7, group 8, group 9, group 10 and group 11 of the long-period periodic table of elements; and at least 1 metal (M2) selected from the group consisting of group 2 metals of the long period periodic table of elements.
In the polycarbonate diol of the present embodiment, at least 1 metal (M1) selected from the group consisting of metals of group 6, group 7, group 8, group 9, group 10 and group 11 of the long-period periodic table is preferably present in an amount of 1ppm to 25ppm, more preferably 2ppm to 15ppm, still more preferably 5ppm to 10ppm, based on the total amount thereof.
In the polycarbonate diol of the present embodiment, if the content of the metal (M1) is 1ppm or more based on the total amount thereof, the following tends to occur: the APHA value becomes low, and when the catalyst is used as a raw material for carbamates, the reaction rate of carbamation increases. In the polycarbonate diol of the present embodiment, if the content of the metal (M1) is 25ppm or less based on the total amount, the following tends to occur: the coloring of the polycarbonate diol caused by heating can be suppressed, and the urethanization reaction is stable when the polycarbonate diol is used as a raw material for urethane.
The metal (M1) contained in the polycarbonate diol of the present embodiment is preferably at least 1 metal selected from molybdenum, manganese, iron, cobalt, nickel and copper. Among them, manganese is more preferable as the metal.
The metal-containing component in these polycarbonate diols may be present as a residue of the polymerization catalyst, or may be actively added in a predetermined amount after production.
In the polycarbonate diol of the present embodiment, at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic table is preferably present in an amount of 0.5ppm or more and 12.5ppm or less, more preferably 0.7ppm or more and 7.5ppm or less, still more preferably 1ppm or more and 3ppm or less, based on the total amount thereof.
In the polycarbonate diol of the present embodiment, if the content of the metal (M2) is 0.5ppm or more based on the total amount thereof, the following tends to occur: the APHA value becomes low, and when the catalyst is used as a raw material for carbamates, the reaction rate of carbamation increases. In the polycarbonate diol of the present embodiment, if the content of the metal (M2) is 12.5ppm or less based on the total amount, the following tends to occur: the amount of ether bonds becomes small, and the coloring of the polycarbonate diol caused by heating can be suppressed, and in the case of using as a urethane raw material, the urethanization reaction is stable.
The metal (M2) contained in the polycarbonate diol of the present embodiment is preferably at least 1 metal selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, and radium. Of these, at least 1 metal selected from the group consisting of magnesium and calcium is more preferable, and calcium is particularly preferable.
The metal-containing component in these polycarbonate diols may be present as a residue of the polymerization catalyst, or may be actively added in a predetermined amount after production.
<3-4 ether bond >
In the polycarbonate diol of the present embodiment, the structure obtained by polymerizing a dihydroxy compound via a carbonate group is based. However, depending on the production method, a substance forming an ether bond by a side reaction such as dehydration reaction of a part of the dihydroxy compound or decarbonation reaction of the carbonate may be mixed, and if the amount of the substance is increased, weather resistance and heat resistance may be reduced, so that it is preferable to produce the resin composition so that the ratio of the ether bond does not become excessive. The amount of the ether bond contained in the molecular chain of the polycarbonate diol of the present embodiment is usually 5 mol% or less, preferably 3 mol% or less, more preferably 2 mol% or less in terms of a molar ratio, from the viewpoint of reducing the ether bond in the polycarbonate diol and securing the characteristics such as weather resistance and heat resistance. The lower limit of the amount of the ether bond is not particularly limited, and is, for example, 0 mol%. These values can be determined by performing alkaline hydrolysis and measuring gas chromatography. Specifically, the measurement can be performed by the method described in examples described below.
The method for controlling the amount of the ether bond contained in the polycarbonate diol to the above range is not particularly limited, and examples thereof include a method for producing the polycarbonate diol under milder reaction conditions and in a short time using the transesterification catalyst of the present application.
<3-5. Terminal primary hydroxyl (OH) ratio >
The terminal primary hydroxyl (OH) purity of the polycarbonate diol of the present embodiment is preferably 97% or more, more preferably 98% or more, and still more preferably 99% or more. The upper limit of the purity of the terminal primary hydroxyl group (OH) is not particularly limited, and is, for example, 100%. By setting the purity of the terminal primary hydroxyl group (OH) to 97% or more, the reaction rate tends to be high when a polyurethane (particularly a thermoplastic polyurethane) is produced (synthesized) using the polycarbonate diol of the present embodiment as a raw material compound, and the strength of the obtained polyurethane tends to be high.
In the present embodiment, the use of the transesterification catalysts A1 and A2 can shorten the reaction time and can produce polycarbonate diol under mild reaction conditions, so that a high terminal primary hydroxyl (OH) purity can be achieved.
In the present embodiment, the purity of the terminal primary hydroxyl (OH) group of the polycarbonate diol can be measured by the method described in examples described later.
<4 > polyurethane >
The polyurethane of the present embodiment contains structural units derived from the polycarbonate diol described above. The polyurethane of the present embodiment contains the structural unit derived from the polycarbonate diol, and thus is excellent in chemical resistance, heat resistance, and hydrolysis resistance.
Examples
Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples at all.
The parts in the examples are parts by mass unless otherwise specified.
Further, the performances of the transesterification catalysts obtained in the following examples and comparative examples, the polycarbonate diol produced using the transesterification catalysts, and the physical properties of the polyurethane film obtained using the polycarbonate diol were tested according to the following test methods.
[ test method ]
[ evaluation of transesterification catalyst Performance ]
In the production of polycarbonate diol (PCD) from a dihydroxy compound and a carbonate, for example, as shown in the following formula (9), in the esterification step, the carbonate (for example, ethylene Carbonate (EC)) and the dihydroxy compound (raw material diol) as monomer raw materials are reduced to produce polycarbonate diol (PCD), and a hydroxyl compound derived from the carbonate (a monohydroxy compound when the carbonate as raw material is a dialkyl carbonate, a dihydroxy compound when the carbonate as raw material is an alkylene carbonate, for example, ethylene Glycol (EG)) is produced as a by-product.
( Here, an example using Ethylene Carbonate (EC) as the carbonate is shown. In this case, ethylene Glycol (EG) is produced as a byproduct by the reaction. )
In the reaction of a dihydroxy compound and a carbonate to form a polycarbonate diol (PCD), the amount of a hydroxy compound distilled off 1 hour and 2 hours after the start of the reaction (a monohydroxy compound when the carbonate as a raw material is a dialkyl carbonate, a dihydroxy compound when the carbonate as a raw material is an alkylene carbonate, for example, ethylene Glycol (EG)) was determined by gas chromatography, and the carbonate conversion was determined according to the following formula (10), (11) or (12).
(calculation method of carbonate conversion when alkylene carbonate is used)
Carbonate conversion (%) = (moles of dihydroxy compound distilled)/(moles of carbonate charged) ×100 (10)
(calculation method of carbonate conversion when dialkyl carbonate is used)
Carbonate conversion (%) = (moles of hydroxy compound distilled/2)/(moles of carbonate charged) ×100 (11)
(calculation method of carbonate conversion when diphenyl carbonate is used)
Carbonate conversion (%) = (moles of phenol distilled/2)/(moles of carbonate charged) ×100 (12)
The conditions for the gas chromatography are shown below.
A gas chromatograph GC-14B (manufactured by Shimadzu corporation) equipped with DB-WAX (manufactured by J & W corporation) as a column was used, 1, 3-propanediol was used as an internal standard, and a detector was set as FID. The temperature rise curve of the column was set as: after 5 minutes at 100 ℃, the temperature was raised to a profile of 200 ℃ at 5 ℃/min.
[ determination of hydroxyl (OH) value of polycarbonate diol ]
An acetylation reagent was prepared by diluting 12.5g of acetic anhydride with 50mL of pyridine to a constant volume (Japanese mountain ash). 2.5 to 5.0g of a polycarbonate diol sample was precisely weighed into a 100mL eggplant type flask. After adding 5mL of an acetylating reagent and 10mL of toluene to the eggplant-type flask by using a full-capacity pipette, a condenser was attached, and the solution in the eggplant-type flask was heated with stirring at 100℃for 1 hour. 2.5mL of distilled water was added to the above-mentioned eggplant-type flask by means of a full-capacity pipette, and the solution in the above-mentioned eggplant-type flask was further heated and stirred for 10 minutes. After cooling the solution in the above-mentioned eggplant-type flask for 2 to 3 minutes, 12.5mL of ethanol was added. 2 to 3 drops of phenolphthalein were added dropwise as an indicator to the above-mentioned eggplant-type flask, and then the solution in the above-mentioned eggplant-type flask was titrated with 0.5mol/L ethanol potassium hydroxide.
As a blank test, 5mL of an acetylation reagent, 10mL of toluene, and 2.5mL of distilled water were put into a 100mL eggplant-type flask, and after heating and stirring for 10 minutes, titration was performed in the same manner as described above. From the result, the OH value is calculated by the following formula (13).
OH value (mg-KOH/g) = { (b-a) × 28.05 ×f }/e (13)
a: titration amount of sample (mL)
b: titration amount (mL) of blank test
e: sample mass (g)
f: factor of titration solution
[ number average molecular weight (Mn) of polycarbonate diol ]
The number average molecular weight of the polycarbonate diol was determined by the following formula (14).
Number average molecular weight=2/(OH number×10) -3 /56.11)(14)
[ determination of APHA number of polycarbonate diol ]
The Harsen color number (APHA) was measured according to JIS K0071-1, compared with the standard liquid contained in the cuvette. Regarding the polycarbonate diol which is solid at ordinary temperature, it was dissolved by heating to 70℃and the Harsen color number (APHA number) was measured.
[ method of analyzing the amount of ether bond in polycarbonate diol ]
1g of polycarbonate diol was placed in a 100mL eggplant-type flask, and 30g of methanol and 8g of 28% sodium methoxide in methanol were introduced and reacted at 100℃for 1 hour. After the reaction solution was cooled to room temperature, 2 to 3 drops of phenolphthalein was added as an indicator, and neutralization was performed with hydrochloric acid. The neutralized reaction solution was cooled in a refrigerator for 1 hour, and then filtered. Thereafter, the obtained filtrate was analyzed using a Gas Chromatograph (GC). GC analysis was performed as follows: quantitative analysis of each component was performed using a gas chromatograph GC-14B (manufactured by Shimadzu corporation, japan) having DB-WAX (manufactured by J & W corporation) as a column, using 1, 3-propanediol as an internal standard, and using a hydrogen Flame Ionization Detector (FID) as a detector. The temperature rise curve of the column was set as: after 5 minutes at 110 ℃, the temperature was raised to a profile of 200 ℃ at 5 ℃/min.
It can be considered that: the ether bond is formed by dehydration reaction of a hydroxyl group and decomposition (decarbonation) of a carbonate, and in the case of producing a polycarbonate diol using ethylene carbonate and hexanediol as raw materials, for example, diethylene glycol and 6- (2-hydroxyethoxy) hexane-1-ol are detected as compounds having an ether bond.
[ analytical method of terminal primary hydroxyl (OH) ratio of polycarbonate diol ]
70g to 100g of a polycarbonate diol was weighed into a 300ml eggplant-type flask, and heated and stirred in a heating bath at about 180℃under a pressure of 0.1kPa or less using a rotary evaporator to which a collecting ball for collecting the fraction was connected, whereby a fraction equivalent to about 1 to 2% by mass of the polycarbonate diol, that is, a fraction of about 1g (0.7 to 2 g) was obtained in the collecting ball. About 100g (95-105 g) of ethanol was used as a solvent and recovered. The recovered solution was subjected to gas chromatography (hereinafter referred to as GC analysis), and the terminal primary hydroxyl (OH) ratio (%) of the polycarbonate diol was calculated from the peak area value of the obtained chromatogram by the following formula (15). The GC analysis was performed as follows: a gas chromatograph 6890 (manufactured by Hewlett-packard Co., ltd.) equipped with a DB-WAX (manufactured by J & W Co., ltd.) having a film thickness of 0.25 μm as a column was used, and a hydrogen Flame Ionization Detector (FID) was used as the detector. The temperature rise curve of the column was set as: after heating from 60 ℃ to 250 ℃ at 10 ℃/min, the curve was maintained at that temperature for 15 minutes.
The identification of each peak in the GC analysis was performed using the following GC-MS apparatus. The GC apparatus used 6890 (manufactured by Hewlett-packard Co., ltd.) equipped with DB-WAX (manufactured by J & W Co., ltd.) as a column. In the GC apparatus, the temperature was increased from the initial temperature of 40 ℃ to 220 ℃ at a heating rate of 10 ℃/min. An Auto-mass SUN (manufactured by JEOL Co., ltd.) was used for the MS device. In the MS apparatus, the ionization voltage was 70eV, the scanning range m/z=10 to 500, and the photomultiplier gain was 450V.
Terminal primary OH ratio (%) =b ++a×100 (15)
A: sum of peak areas of glycol-containing alcohols (excluding ethanol)
B: sum of peak areas of diols having primary OH groups at both ends
[ amount of catalyst remaining in polycarbonate diol (amount of metal remaining) ]
About 0.1g of polycarbonate diol was measured and dissolved in 4mL of acetonitrile to obtain a solution. Thereafter, 20mL of pure water was added to the obtained solution to precipitate polycarbonate diol, and the precipitated polycarbonate diol was removed by filtration. The filtered solution was diluted with pure water to a predetermined concentration to obtain a diluted solution. The concentration of metal ions in the diluted solution was analyzed by ion chromatography. The metal ion concentration of acetonitrile used as a solvent was measured as a blank value, and the value obtained by subtracting the metal ion concentration of the solvent amount from the metal ion concentration of the diluted solution was used as the metal ion concentration of the polycarbonate diol product. The measurement conditions are as follows.
The concentrations (ppm) of the various metals (M1, M2) remaining in the polycarbonate diol were determined using a standard curve of the various metals prepared in advance, and the amounts of the remaining metals (M1, M2) were obtained.
The amount of the residual metal was evaluated as the amount of the residual catalyst.
High performance liquid chromatography (HPCL) measurement conditions
The device comprises: waters2690
Column: ionPac CS12A
Flow rate: 1.0mL/min
Injection amount: 1.5mL
Pressure: 950-980 psi
Column temperature: 35 DEG C
Detector sensitivity: RANGE 200 mus
An eliminator: CSRS 60mA
Eluent: 20mmol/L aqueous methanesulfonic acid solution
[ determination of number average molecular weight of polyurethane ]
A portion of the polyurethane film was cut, and an N, N-Dimethylacetamide (DMF) solution was prepared so that the concentration of polyurethane became 0.1 mass%. Using the prepared DMF solution, the number average molecular weight of polyurethane was determined as follows.
For the measurement, a GPC apparatus (manufactured by Tosoh Co., ltd., product name "HLC-8320" (column: tskgel SuperHM-H.4 roots) was used.
The eluting solution was prepared by dissolving 2.6g of lithium bromide in 1L of dimethylacetamide.
Based on the measurement results obtained, the number average molecular weight (Mn) of the polyurethane calculated according to the standard polystyrene conversion was calculated.
[ room temperature tensile test of polyurethane film ]
A strip-shaped test piece having a width of 10mm, a length of 100mm and a thickness of about 0.5mm was produced from a polyurethane film in accordance with JIS K6301 (2010). The tensile test was performed on the produced test piece at a temperature of 23℃and a tensile speed of 100 mm/min using a tensile tester (model "TENSILON, RTE-1210" manufactured by ORIENTEC Co.).
In the tensile test, the stress (100% modulus) and the breaking point strength and the breaking point elongation at 100% elongation of the test piece were measured.
[ evaluation of oil acidity (chemical resistance) of polyurethane ]
Test pieces of 3 cm. Times.3 cm were cut from the polyurethane film. The mass of the test piece was measured using a precision balance. Thereafter, a test piece was put into a 250mL glass bottle containing 50mL of oleic acid as a test solvent, and the test piece was allowed to stand in a constant temperature bath at 80℃under a nitrogen atmosphere for 16 hours, whereby a chemical resistance test was performed.
After the test, the test piece was taken out and the front and back were gently rubbed with a paper towel. Thereafter, the mass of the test piece was measured by a precision balance. The mass change rate (increase rate) compared with that before the test was calculated by the following equation. The mass change rate of approximately 0% indicates good oil acidity (chemical resistance).
Mass change rate (%)
= (mass of test piece after test-mass of test piece before test)/mass of test piece before test x 100
[ evaluation of Heat resistance of polyurethane ]
A strip-shaped test piece having a width of 10mm, a length of 100mm and a thickness of about 50 μm was produced from the polyurethane film. The test pieces were heated in a Gill oven at a temperature of 120℃for 1000 hours. The breaking strength of the heated test piece was measured in the same manner as in the above-mentioned [ room temperature tensile test ]. The retention (%) of the fracture strength was obtained by the following formula.
Retention of breaking Strength (%)
Breaking strength of test piece after heating/breaking strength of test piece before test x 100
[ evaluation of hydrolysis resistance of polyurethane ]
A strip-shaped test piece having a width of 10mm, a length of 100mm and a thickness of about 50 μm was produced from the polyurethane film. The test piece was heated in a constant temperature and humidity tank at a temperature of 85℃and a relative humidity of 85% for 200 hours. The breaking strength of the heated test piece was measured in the same manner as in the above-mentioned [ room temperature tensile test ]. The retention (%) of the fracture strength was obtained by the following formula.
Retention of breaking Strength (%)
Breaking strength of test piece after heating/breaking strength of test piece before test x 100
[ abbreviation for Compounds ]
The abbreviations of the compounds in the following examples and comparative examples are as follows.
Mn(acac) 2 ·2H 2 O: manganese (II) acetylacetonate dihydrate
Mn(acac) 3 : manganese acetylacetonate (III)
Mn(OAc) 2 ·4H 2 O: manganese (II) acetate tetrahydrate
Mn(tBuCOCH 2 COtBu) 2 ·2H 2 O:2, 6-tetramethyl-3, 5-heptanedione manganese (II) dihydrate
Mn(CF 3 COCH 2 COCF 3 ) 2 ·2H 2 O: manganese hexafluoroacetylacetonate dihydrate
[Mo(acac)] 2 : molybdenum (II) acetylacetonate dimer
Fe(acac) 3 : iron acetylacetonate (III)
Co(acac) 2 ·2H 2 O: cobalt acetylacetonate(II) dihydrate
Ni(acac) 2 ·2H 2 O: nickel (II) acetylacetonate dihydrate
Cu(acac) 2 : copper acetylacetonate (II)
Ti(OBu) 4 : tetra-n-butyl titanate
Ti(acac) 2 (OiPr) 2 : bis (acetylacetonate) titanium (IV) diisopropoxide
Li-OMe: lithium methoxide
Mg(acac) 2 ·2H 2 O: magnesium (II) acetylacetonate dihydrate
Mg(OAc) 2 ·4H 2 O: magnesium acetate tetrahydrate
Ca(acac) 2 ·2H 2 O: calcium acetylacetonate (II) dihydrate
Ca(OAc) 2 H2O: calcium acetate monohydrate
Ca(OMe) 2 : calcium dimethoxide
Ba(OAc) 2 : barium acetate
EC: ethylene carbonate
EG: ethylene glycol
DMC: dimethyl carbonate
DEC: diethyl carbonate
DPC: diphenyl carbonate
13PDO:1, 3-propanediol
14BDO:1, 4-butanediol
15PDO:1, 5-pentanediol
16HDO:1, 6-hexanediol
110DDO:1, 10-decanediol
3M15PDO: 3-methyl-1, 5-pentanediol
In the following examples and comparative examples, polycarbonate diols were produced using transesterification catalysts shown in the following tables.
Example 1
Into a 1L separable flask equipped with a stirrer, a thermometer, an Oldershaw (theoretical plate number: 15 plates) having a reflux head on top and a vacuum jacket were charged 355g (3.00 mol) of 1, 6-hexanediol and 264g (3.00 mol) of ethylene carbonate as raw material monomersAnd Mn (acac) is added 2 ·2H 2 O16.3 mg and Ca (OAc) 2 ·H 2 O6.8 mg as catalyst.
The raw material in the flask was heated with an oil bath set to 170℃and the raw material monomer was polycondensed by transesterification for 2 hours while taking out a part of the fraction from the reflux head under the conditions that the internal temperature of the flask was 150℃and the vacuum was 4kPa, to obtain a polycarbonate diol.
The carbonate conversion after 1 hour and after 2 hours from the start of the reaction was analyzed by gas chromatography. In addition, the amount of ether bond after 2 hours from the start of the reaction was measured.
The measurement results are shown in Table 1.
Examples 2 to 15 and comparative examples 1 to 5
Except that the types and amounts of the catalysts to be added were set to those described in table 1, the raw material monomers were polycondensed by transesterification in the same manner as in example 1 to obtain polycarbonate diol. The carbonate conversion after 1 hour and after 2 hours from the start of the reaction was analyzed by gas chromatography in the same manner as in example 1.
In addition, the amount of ether bond after 2 hours from the start of the reaction was measured.
The measurement results are shown in Table 1.
TABLE 1
Examples 16 to 26
A polycarbonate diol was obtained by polycondensing a raw material monomer by the transesterification reaction in the same manner as in example 1 except that the kind and amount of the catalyst to be added were set to those described in table 2 below and the reaction temperature was set to those described in table 2 below. The carbonate conversion after 1 hour and after 2 hours from the start of the reaction was analyzed by gas chromatography in the same manner as in example 1.
In addition, the amount of ether bond and APHA value after 2 hours from the start of the reaction were measured.
The measurement results are shown in Table 2.
TABLE 2
Examples 27 to 30 and comparative examples 6 and 7
Except that the types and amounts of the catalyst to be added and the types of the carbonates to be used were as shown in table 3 below, the raw material monomers were polycondensed by transesterification in the same manner as in example 1 to obtain polycarbonate diol.
The carbonate conversion after 1 hour and after 2 hours from the start of the reaction was analyzed by gas chromatography in the same manner as in example 1.
The measurement results are shown in Table 3.
TABLE 3
Examples 31 to 38
In the same manner as in example 1 except that the types and amounts of the catalyst to be added and the dihydroxy compound to be used were set to the types and amounts shown in table 4 below, the raw material monomers were polycondensed by transesterification to obtain polycarbonate diol.
The carbonate conversion after 1 hour and after 2 hours from the start of the reaction was analyzed by gas chromatography in the same manner as in example 1.
The measurement results are shown in Table 4.
TABLE 4
Example 39
To Oldershaw (theoretical plate number: theoretical plate number) equipped with a stirrer, a thermometer, a reflux head on top and a vacuum jacket15 trays) in a 1L separable flask, 355g (3.00 mol) of 1, 6-hexanediol and 264g (3.00 mol) of ethylene carbonate were charged, and Mn (OAc) was added 2 ·4H 2 O 13.8mg、Ca(OAc) 2 ·H 2 O6.8 mg as catalyst. The raw material in the flask was heated with an oil bath set to 170℃and the raw material monomer was polycondensed by transesterification for 2 hours while taking out a part of the fraction from the reflux head under the conditions that the internal temperature of the flask was 150℃and the vacuum was 4kPa, to obtain a polycarbonate diol. The carbonate conversion at this time (after 2 hours from the start of the reaction) was measured. The measurement results are shown in Table 5.
Thereafter, the reaction was switched to single distillation, the pressure was gradually reduced to 0.5kPa, the temperature of the oil bath was set to 175℃and the reaction was carried out for 1 hour under the condition that the internal temperature of the flask was 160℃to obtain a polycarbonate diol by distilling off the monomers. After nitrogen gas was introduced to prepare a normal pressure, the temperature of the oil bath was set to 125℃and the internal temperature of the flask was set to 110 to 120 ℃. As a catalyst deactivator, monobutyl phosphate was added in an equimolar amount to the amount of the catalyst to be charged, and stirred at a temperature of 110 to 120℃for 3 hours. The analysis results of the obtained polycarbonate diol are shown in Table 5. This polycarbonate diol is referred to as PC1.
Examples 40 to 42
In the same manner as in example 39 except that the types and amounts of the dihydroxy compounds used were set as shown in table 5, the raw material monomers were polycondensed by transesterification to obtain polycarbonate diol. The carbonate conversion after 2 hours from the start of the reaction and the properties of the obtained polycarbonate diol are shown in Table 5. The obtained polycarbonate diols are referred to as PC2, PC3 and PC4, respectively.
Example 43
In the same manner as in example 42 except that the types and amounts of the dihydroxy compounds used were set as shown in table 5, and the reaction time after the single distillation was set to 0.5 hour, polycondensation of the raw material monomers was performed by transesterification to obtain polycarbonate diol. The carbonate conversion after 2 hours from the start of the reaction and the properties of the obtained polycarbonate diol are shown in Table 5. The resulting polycarbonate diol was designated as PC5.
Example 44
In the same manner as in example 42 except that the types and amounts of the dihydroxy compounds used were set as shown in table 5, and the reaction time after the single distillation was set to 2 hours, polycondensation of the raw material monomers was performed by transesterification to obtain polycarbonate diol. The carbonate conversion after 2 hours from the start of the reaction and the properties of the obtained polycarbonate diol are shown in Table 5. The resulting polycarbonate diol was designated as PC6.
Comparative example 8
To a 1L separable flask equipped with a stirrer, a thermometer, an Oldershaw (theoretical plate number: 15 plates) having a reflux head on top and a vacuum jacket were charged 156g of 1, 5-pentanediol, 177g of 1, 6-hexanediol and 264g (3.00 mol) of ethylene carbonate as raw material monomers, and Mn (OAc) was added 2 ·4H 2 O20.4 mg as catalyst. The raw materials in the flask were heated in an oil bath set to 170℃and reacted for 7 hours while taking out a part of the distillate from the reflux head under the condition that the internal temperature of the flask was 150℃and the vacuum was 4kPa (after 2 hours from the start of the reaction, a part of the reaction solution was taken out, and the carbonate conversion after 2 hours was obtained). Thereafter, the reaction was carried out for 4 hours at a temperature of 160 to 170℃in the flask while gradually reducing the pressure to 0.5kPa, and the temperature of the oil bath was set to 180℃to obtain a polycarbonate diol by distilling off the monomer. After nitrogen gas was introduced to prepare a normal pressure, the temperature of the oil bath was set to 125℃and the internal temperature of the flask was set to 110 to 120 ℃. As a catalyst deactivator, monobutyl phosphate was added in an equimolar amount to the amount of the catalyst to be charged, and stirred at a temperature of 110 to 120℃for 3 hours. The analysis results of the obtained polycarbonate diol are shown in Table 5. This polycarbonate diol is referred to as PC7.
Comparative example 9
Into a 1L separable flask equipped with a stirrer, a thermometer, an Oldershaw (theoretical plate number: 15 plates) having a reflux head on top and a vacuum jacket were charged 156g of 1, 5-pentanediol, 177g of 1, 6-hexanediol and 264g (3.00 mol) of ethylene carbonate as raw material monomers, and Ca (OAc) was added 2 ·H 2 O20.4 mg as catalystAnd (3) an agent. The raw materials in the flask were heated in an oil bath set to 170℃and reacted for 7 hours while taking out a part of the distillate from the reflux head under the condition that the internal temperature of the flask was 150℃and the vacuum was 4kPa (after 2 hours from the start of the reaction, a part of the reaction solution was taken out, and the carbonate addition rate after 2 hours was determined). Thereafter, the reaction was carried out for 4 hours at a temperature of 160 to 170℃in the flask while gradually reducing the pressure to 0.5kPa, and the temperature of the oil bath was set to 180℃to obtain a polycarbonate diol by distilling off the monomer. After nitrogen gas was introduced to prepare a normal pressure, the temperature of the oil bath was set to 125℃and the internal temperature of the flask was set to 110 to 120 ℃. As a catalyst deactivator, monobutyl phosphate was added in an equimolar amount to the amount of the catalyst to be charged, and stirred at a temperature of 110 to 120℃for 3 hours. The analysis results of the obtained polycarbonate diol are shown in Table 5. This polycarbonate diol is referred to as PC8.
TABLE 5
Example 45
To a 200mL separable flask equipped with a stirring blade, which was heated in an oil bath at 60℃and nitrogen-sealed, was charged 15.7g of diphenylmethane-4, 4' -diisocyanate (hereinafter also referred to as "MDI"), 180mL of N, N-dimethylformamide (hereinafter also referred to as "DMF") as a solvent, and 0.003g of dibutyltin dilaurate as a catalyst, and a solution of polycarbonate diol PC1 42g and DMF 60g, which had been preheated to 60℃was added dropwise thereto using a dropping funnel over about 1 hour, was obtained. After the resulting solution was stirred for 1 hour, 3.2g of 1, 4-butanediol (hereinafter also referred to as "14 BDO") was added. After the solution was further stirred at 60℃for 3 hours, 1g of ethanol was added to stop the reaction. The resulting polyurethane solution was applied to a polypropylene resin sheet (width 100mm, length 1200mm, thickness 1 mm) with a width 80mm, length 100mm, thickness 0.6mm using an applicator to obtain a coating film. The resulting coating film was dried on a hot plate having a surface temperature of 60℃for 2 hours, and then dried in an oven having a temperature of 100℃for 12 hours. Further, the mixture was allowed to stand at a constant temperature and humidity of 23℃and 55% RH for 48 hours or more to obtain a polyurethane film. The obtained polyurethane film was subjected to evaluation of various physical properties. The evaluation results are shown in table 6.
Examples 46 to 50 and comparative examples 10 and 11
Polyurethane films were obtained in the same manner as in example 45, except that PC2 to PC8 were used as the polycarbonate diol and the amounts of MDI and 14BDO were set to the amounts shown in table 6. The obtained polyurethane film was subjected to evaluation of various physical properties. The evaluation results are shown in table 6.
TABLE 6
Industrial applicability
The transesterification catalyst of the present embodiment is industrially applicable as a catalyst capable of producing a polycarbonate diol under milder conditions than those of the prior art. The transesterification catalyst of the present embodiment is industrially applicable as a catalyst for producing a polycarbonate diol having excellent color tone, few ether bonds and a high terminal primary hydroxyl group ratio.

Claims (19)

1. A transesterification catalyst comprising at least two transesterification catalysts of transesterification catalyst A1 and transesterification catalyst A2, the transesterification catalyst A1 containing at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long periodic table of elements, and the transesterification catalyst A2 containing at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long periodic table of elements.
2. The transesterification catalyst according to claim 1, wherein the transesterification catalyst A1 is at least 1 metal complex represented by the following formula (1) and/or a hydrate thereof,
in the formula (1), R 1 And R is 3 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 1 And R is 3 Optionally substituted with halogen atoms, and optionally having oxygen atoms; r is R 2 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 2 Optionally substituted with halogen atoms, and optionally having oxygen atoms; m1 represents at least 1 metal selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements; n is 1, 2 or 3; and the metal complex represented by the formula (1) is optionally plural in association.
3. The transesterification catalyst according to claim 1, wherein the transesterification catalyst A1 is a salt of at least 1 carboxylic acid represented by the following formula (2) with at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long periodic Table of elements and/or a hydrate thereof,
in the formula (2), R 4 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 4 Optionally substituted with halogen atoms, and optionally with oxygen atoms.
4. A transesterification catalyst according to any one of claims 1 to 3, wherein the transesterification catalyst A2 is at least 1 metal complex represented by the following formula (3) and/or a hydrate thereof,
in the formula (3), R 5 And R is 7 Each of which is a single pieceIndependently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R 5 And R is 7 Optionally substituted with halogen atoms, and optionally having oxygen atoms; r is R 6 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 6 Optionally substituted with halogen atoms, and optionally having oxygen atoms; m2 represents at least 1 metal selected from the group consisting of metals of group 2 of the long periodic table of elements; n is 1, 2 or 3; and the metal complex represented by the formula (3) is optionally plural in association.
5. A transesterification catalyst according to any one of claims 1 to 3, wherein the transesterification catalyst A2 is a salt of at least 1 carboxylic acid represented by the following formula (4) with at least 1 metal (M2) selected from the group consisting of group 2 metals of the long periodic Table of elements and/or a hydrate thereof,
in the formula (4), R 8 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 8 Optionally substituted with halogen atoms, and optionally with oxygen atoms.
6. The transesterification catalyst according to any one of claims 1 to 3, wherein the transesterification catalyst A2 is an alkoxide of at least 1 alcohol represented by the following formula (5) and at least 1 metal (M2) selected from the group consisting of group 2 metals of the long periodic Table of elements,
R 9 -OH (5)
in the formula (5), R 9 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 9 Optionally substituted with halogen atoms, and optionally with oxygen atoms.
7. A method for producing a polycarbonate diol, comprising: a step of polycondensing a dihydroxy compound and a carbonate ester as raw material monomers in the presence of a transesterification catalyst to obtain a polycarbonate diol,
the transesterification catalyst comprises a transesterification catalyst A1 and a transesterification catalyst A2, wherein the transesterification catalyst A1 contains at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long periodic Table of elements, and the transesterification catalyst A2 contains at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long periodic Table of elements.
8. The method for producing a polycarbonate diol according to claim 7, wherein the transesterification catalyst A1 is at least 1 metal complex represented by the following formula (1) and/or a hydrate thereof,
in the formula (1), R 1 And R is 3 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 1 And R is 3 Optionally substituted with halogen atoms, and optionally having oxygen atoms; r is R 2 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 2 Optionally substituted with halogen atoms, and optionally having oxygen atoms; m1 represents at least 1 metal selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements; n is 1, 2 or 3; and the metal complex represented by the formula (1) is optionally plural in association.
9. The method for producing a polycarbonate diol according to claim 7, wherein the transesterification catalyst A1 is a salt of at least 1 carboxylic acid represented by the following formula (2) with at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic Table of elements and/or a hydrate thereof,
in the formula (2), R 4 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 4 Optionally substituted with halogen atoms, and optionally with oxygen atoms.
10. The method for producing a polycarbonate diol according to any one of claims 7 to 9, wherein the metal (M1) is at least 1 metal selected from the group consisting of molybdenum, manganese, iron, cobalt, nickel, and copper.
11. The method for producing a polycarbonate diol according to any one of claims 7 to 10, wherein the transesterification catalyst A2 is at least 1 metal complex represented by the following formula (3) and/or a hydrate thereof,
in the formula (3), R 5 And R is 7 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and each independently represents 5 And R is 7 Optionally substituted with halogen atoms, and optionally having oxygen atoms; r is R 6 R represents hydrogen, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms 6 Optionally substituted with halogen atoms, and optionally having oxygen atoms; m2 represents at least 1 metal selected from the group consisting of group 2 metals of the long periodic table of elements; n is 1, 2 or 3; and the metal complex represented by the formula (3) is optionally plural in association.
12. The method for producing a polycarbonate diol according to any one of claims 7 to 10, wherein the transesterification catalyst A2 is a salt of at least 1 carboxylic acid represented by the following formula (4) with at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic Table of elements and/or a hydrate thereof,
In the formula (4), R 8 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 8 Optionally substituted with halogen atoms, and optionally with oxygen atoms.
13. The method for producing a polycarbonate diol according to any one of claims 7 to 10, wherein the transesterification catalyst A2 is an alkoxide of at least 1 alcohol represented by the following formula (5) and at least 1 metal (M2) selected from the group consisting of group 2 metals of the long-period periodic Table of elements,
R 9 -OH (5)
in the formula (5), R 9 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms 9 Optionally substituted with halogen atoms, and optionally with oxygen atoms.
14. The method for producing a polycarbonate diol according to any one of claims 7 to 13, wherein the metal (M2) is at least 1 metal selected from the group consisting of magnesium and calcium.
15. The method for producing a polycarbonate diol according to any one of claims 7 to 14, wherein,
the amount of the transesterification catalyst A1 is 0.5ppm or more and 20ppm or less relative to the total amount of all the dihydroxy compound and the carbonate based on the total amount of the metal (M1),
the amount of the transesterification catalyst A2 is 0.25ppm or more and 10ppm or less relative to the total amount of all the dihydroxy compound and the carbonate based on the total amount of the metal (M2).
16. The method for producing a polycarbonate diol according to any one of claims 7 to 15, wherein the dihydroxy compound comprises at least 1 selected from the group consisting of aliphatic dihydroxy compounds and alicyclic dihydroxy compounds having a structure represented by formula (6) below,
HO-R 10 -OH (6)
in the formula (6), R 10 Represents a divalent aliphatic hydrocarbon or alicyclic hydrocarbon having 2 to 20 carbon atoms.
17. A polycarbonate diol which is a polycondensate obtained by transesterification of a dihydroxy compound with a carbonate,
a number average molecular weight of 250 to 100000,
at least 1 metal (M1) selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long-period periodic table of elements is present in the polycarbonate diol in an amount of 1ppm or more and 25ppm or less based on the total amount thereof, and at least 1 metal (M2) selected from the group consisting of metals of group 2 of the long-period periodic table of elements is present in the polycarbonate diol in an amount of 0.5ppm or more and 12.5ppm or less based on the total amount thereof,
the polycarbonate diol has a Harsen color number measured in accordance with JIS-K0071-1 (1998) of 50 or less,
the amount of ether bond is 5 mol% or less,
the purity of the terminal primary hydroxyl (OH) is more than 97%.
18. The polycarbonate diol of claim 17, wherein the metal (M1) is at least 1 metal selected from the group consisting of molybdenum, manganese, iron, cobalt, nickel, and copper, and the metal (M2) is at least 1 metal selected from the group consisting of magnesium and calcium.
19. A polyurethane comprising structural units derived from the polycarbonate diol of claim 17 or 18.
CN202310642484.9A 2022-06-03 2023-06-01 Transesterification catalyst, method for producing polycarbonate diol, and polycarbonate diol Pending CN117164839A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2022-090624 2022-06-03
JP2022109939A JP2024008235A (en) 2022-07-07 2022-07-07 Transesterification catalysts
JP2022-109939 2022-07-07

Publications (1)

Publication Number Publication Date
CN117164839A true CN117164839A (en) 2023-12-05

Family

ID=88932500

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310642484.9A Pending CN117164839A (en) 2022-06-03 2023-06-01 Transesterification catalyst, method for producing polycarbonate diol, and polycarbonate diol

Country Status (2)

Country Link
JP (1) JP2024008235A (en)
CN (1) CN117164839A (en)

Also Published As

Publication number Publication date
JP2024008235A (en) 2024-01-19

Similar Documents

Publication Publication Date Title
JP4302781B2 (en) Process for producing branched-chain polycarbonate
WO2020068796A1 (en) Polycarbonate block copolymers and methods thereof
JP2007277507A (en) Polycarbonate polyol and its manufacturing process
US9499661B2 (en) Process for producing highly polymerized aromatic polycarbonate resin
JP6229250B2 (en) Polycarbonate diol-containing composition and method for producing polycarbonate diol-containing composition
JP5532592B2 (en) Method for producing polycarbonate diol
US20060004176A1 (en) Oligocarbonate polyols having terminal secondary hydroxyl groups
EP2921517B1 (en) Production method for aromatic polycarbonate resin having increased molecular weight
JP2009051887A (en) Polycarbonate diol whose reaction control is easy
JP2017036463A (en) Polycarbonate diol and manufacturing method therefor
US9428608B2 (en) Aromatic polycarbonate resin composition
CN110392710B (en) Polycarbonate diol composition and method for producing same
JP6135264B2 (en) Method for producing polycarbonate diol having excellent thermal stability
EP3872112B1 (en) Highly bio-based polycarbonate ester and method for producing same
JP2018080346A (en) Polycarbonate diol with excellent heat stability and method for producing the same
JP6696546B2 (en) Method for producing polycarbonate diol
CN117164839A (en) Transesterification catalyst, method for producing polycarbonate diol, and polycarbonate diol
JP2023177771A (en) Method for producing polycarbonate diol and polycarbonate diol
EP3165552B1 (en) Polycarbonates, polyurethanes, elastomers, processes for manufacturing polycarbonates, and processes for manufacturing polyurethanes
CN114729178A (en) Polycarbonate diol composition and coating composition using same
JP2023106848A (en) Method for producing polycarbonate diol and polycarbonate diol
CN112119108B (en) Polycarbonate diol
WO2023140247A1 (en) Method for producing polycarbonate diol, polycarbonate diol, and transesterification catalyst
JP2023086513A (en) Method for producing polycarbonate diol and polycarbonate diol
JP2023106850A (en) Method for producing polycarbonate diol and polycarbonate diol

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination