JP2013108074A - Polyalkylene carbonate diol having cyclic alkylene group, copolymer there of, and method for producing them - Google Patents

Abstract

【選択図】なし[PROBLEMS] A novel polyalkylene carbonate diol and a copolymer thereof using a cyclic alkylene diol having a hydroxyl group bonded to a secondary or tertiary carbon atom, and a simple cyclic control of the composition of the copolymer. A method for producing a polyalkylene carbonate diol having an alkylene group and a copolymer thereof is provided.
A cyclic alkylene group: a polyalkylene carbonate diol copolymer having a molecular structure of a repeating unit represented by the following formulas (A) and (B) containing Z and having a hydroxyl group at the molecular end. .

[Selection figure] None

Description

  The present invention relates to a polyalkylene carbonate diol having a cyclic alkylene group, a copolymer thereof, and a production method thereof.

Polyalkylene carbonate diol is generally known as a material excellent in transparency, impact resistance, heat resistance, and the like, and is useful as a raw material for producing, for example, polyurethane resins and thermoplastic elastomers.
By the way, as an alkylene diol which is a monomer of this polyalkylene carbonate diol, for example, in addition to linear alkylene diols such as 1,5-pentanediol and 1,6-hexanediol, Alkylene diols having a branched chain such as 2,2-dialkyl-1,3-propanediol and 2,4-dialkyl-1,5-pentanediol; alicyclic skeletons such as cyclohexanedimethanol and tricycloalkanedimethanol In general, branched alkylene diols having a hydroxyl group bonded to a primary carbon atom such as aromatic dimethanol such as benzene dimethanol have been widely used (for example, Patent Documents 1 to 4). reference).

From the above patent documents, in particular, branched alkylene having a hydroxyl group bonded to a primary carbon atom such as 2,2-dimethyl-1,3-propanediol and 2,4-dialkyl-1,5-pentanediol. Polyalkylene carbonate diols and copolymers thereof using diols are known to have a significant decrease in viscosity, and have been studied for the purpose of improving fluidity (liquidity).
In addition, through the above examination, a method for producing a polyalkylene carbonate diol and a copolymer thereof using a branched alkylene diol having a “hydroxyl group bonded to a primary carbon atom” is well known in the art using a linear alkylene diol. Similar to the production method, it is also known that not only the homopolymer but also copolymers (copolymers) of various composition ratios can be produced relatively easily only by adjusting the blending ratio of the raw materials used.

JP 2000-290342 A JP 2000-336140 A JP 60-195117 A JP 2003-183376 A

The polyalkylene carbonate diol having a branched chain or cyclic alkylene group, which has been studied so far from the above-mentioned patent documents, is mainly used for lowering the viscosity of polyurethane resin as a soft segment raw material. On the other hand, the possibility of so-called polyalkylene carbonate diol as a raw material for a hard segment, which is oriented toward high solidity such as high viscosity, has not been studied so far.
As one of the reasons, for example, as described in Patent Document 4 [0004], a cyclic alkylene diol and a linear chain in which a hydroxyl group is bonded to a secondary carbon atom such as 1,4-cyclohexanediol. When a polyalkylene carbonate diol copolymer is produced using a linear alkylene diol, the reaction site is a “hydroxy group bonded to a secondary or tertiary carbon atom” of the cyclic alkylene diol and a linear alkylene diol. The “hydroxyl group bonded to the primary carbon atom” in FIG. 1 has a large reactivity with the carbonate compound (for example, presence or absence of side reaction) and reaction rate (for example, contribution to the reaction of steric hindrance of the adjacent alkyl group). Therefore, it is not easy to produce a copolymer having a desired composition ratio by controlling the reactivity and reaction rate. This is because there was a problem.

  Then, an object of this invention is to provide the polyalkylene carbonate diol useful as a raw material for hard segments of a polyurethane resin, etc., and its manufacturing method, for example.

Accordingly, as a result of intensive studies to achieve the above-mentioned object, the present inventors have found that an alkylene diol (hereinafter referred to as “the hydroxyl group is bonded to a secondary or tertiary carbon atom”) containing a cyclic structure. In the present invention, a novel polyalkylene carbonate diol using a “cyclic alkylene group-containing diol” (hereinafter sometimes referred to as “cyclic alkylene group-containing polyalkylene diol” in the present invention). And a copolymer thereof (hereinafter referred to as “cyclic alkylene group-containing polyalkylenediol copolymer” in the present invention).
Further, under specific reaction conditions, a cyclic alkylene group-containing diol, an alkylene diol having a hydroxyl group bonded to a primary carbon atom, and a carbonate can be reacted while controlling the composition ratio of the resulting copolymer. An industrially suitable method for producing a polyalkylene carbonate diol and a copolymer thereof has been found, and the present invention has been achieved.

That is, the present invention includes the following items [1] to [7].
[1] A polyalkylene carbonate diol having a molecular structure of a repeating unit represented by the following formula (A) and having a hydroxyl group at the molecular end.

［式（Ａ）中、Ｚは、下記式（Ｚ^１）〜（Ｚ^４）で示される基を示す。］

[In the formula (A), Z represents a group represented by the following formulas (Z ¹ ) to (Z ⁴ ). ]

（式（Ｚ^１）〜（Ｚ^４）中、Ｘ及びＹは、単結合、酸素原子、硫黄原子、スルホニル基、カルボニル基、フッ素原子もしくは炭素原子数１〜４のアルキル基で置換されたメチレン基又は炭素原子数１〜４のアルキルアミノ基をそれぞれ示し、ＸとＹは互いに同一であっても、又は異なっていてもよい。また、ｐ及びｑは、それぞれメチレン基の数を示し、ｐは１又は２の整数を示し、ｑは０、１又は２の整数を示す。ここで、ｐとｑは互いに同一であっても、又は異なっていてもよい。Ｌ^１は、単結合、酸素原子、硫黄原子、スルホニル基、カルボニル基、フッ素原子もしくは炭素原子数１〜４のアルキル基で置換されたメチレン基又は炭素原子数１〜４のアルキルアミノ基のいずれかを示す。なお、式（Ｚ^１）〜（Ｚ^４）中、波線を付した結合は、カーボネート基（−Ｏ−ＣＯ−Ｏ−）の酸素原子と環状分子骨格上の任意の炭素原子との結合を示す。）
［２］ 下記式（Ａ）と一種以上の式（Ｂ）で示される繰り返し単位の分子構造を有し、かつ分子末端が水酸基である、ポリアルキレンカーボネートジオール共重合体。

(In the formulas (Z ¹ ) to (Z ⁴ ), X and Y are methylenes substituted with a single bond, oxygen atom, sulfur atom, sulfonyl group, carbonyl group, fluorine atom or alkyl group having 1 to 4 carbon atoms. Each represents a group or an alkylamino group having 1 to 4 carbon atoms, and X and Y may be the same as or different from each other, and p and q each represent the number of methylene groups; Represents an integer of 1 or 2, q represents an integer of 0, 1 or 2. Here, p and q may be the same or different from each other, L ¹ represents a single bond, oxygen One of an atom, a sulfur atom, a sulfonyl group, a carbonyl group, a fluorine atom, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms is shown. in ^{Z 1) ~ (Z 4)} , the wavy line Bonds and indicates the binding of carbonate groups (-O-CO-O-) oxygen atoms and cyclic molecules any carbon atom on the backbone of.)
[2] A polyalkylene carbonate diol copolymer having a molecular structure of a repeating unit represented by the following formula (A) and one or more formulas (B) and having a molecular terminal hydroxyl group.

(In the formula (A), Z represents a cyclic alkylene group represented by the following formulas (Z ¹ ) to (Z ⁴ ).)

(In the formulas (Z ¹ ) to (Z ⁴ ), X and Y are methylenes substituted with a single bond, oxygen atom, sulfur atom, sulfonyl group, carbonyl group, fluorine atom or alkyl group having 1 to 4 carbon atoms. Each represents a group or an alkylamino group having 1 to 4 carbon atoms, and X and Y may be the same as or different from each other, and p and q each represent the number of methylene groups; Represents an integer of 1 or 2, q represents an integer of 0, 1 or 2. Here, p and q may be the same or different from each other, L ¹ represents a single bond, oxygen One of an atom, a sulfur atom, a sulfonyl group, a carbonyl group, a fluorine atom, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms is shown. in ^{Z 1) ~ (Z 4)} , the wavy line Binding indicates the bond between the oxygen atom and the cyclic molecule any carbon atom on the backbone of carbonate groups (-O-CO-O-). However, in the formula ^{(Z 3), p = 1} , q = 0 (Single bond) and X and Y are both oxygen atoms are excluded.)

(In the formula (B), n and m each represent an integer of 1 to 6, and n and m may be the same or different from each other. L ² represents a single bond, an oxygen atom, or sulfur. An methylene group substituted with an atom, a methylene group, a sulfonyl group, a carbonyl group, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms).
[3] The content ratio of the molecular structure of the repeating unit represented by the formula (A) in one molecule and the molecular structure of one or more repeating units represented by the formula (B) (of the molecular structure of the formula (B) The polyalkylene carbonate diol copolymer according to the above [2], wherein the total number: the number of molecular structures of the formula (A) is 80:20 to 20:80.
[4] The polyalkylene carbonate diol according to the above [1], wherein the number average molecular weight calculated from ¹ H-NMR spectrum analysis is 500 to 3000.
[5] The polyalkylene carbonate diol copolymer according to [2] or [3], wherein the number average molecular weight calculated from ¹ H-NMR spectrum analysis is 500 to 3000.
[6] In the presence of an alkali metal compound, the cyclic alkylene diol represented by the following formula (1) and one or more carbonates represented by the following formula (3) are reacted at a reaction temperature of 80 to 150 ° C. The manufacturing method of the polyalkylene carbonate diol as described in said [1].

(In formula (1), Z represents a group represented by the following formulas (Z ¹ ) to (Z ⁴ ).)

(In the formulas (Z ¹ ) to (Z ⁴ ), X and Y are a single bond, an oxygen atom, a sulfur atom, a methylene group (—CH ₂ —), a sulfonyl group, a carbonyl group, or a carbon atom having 1 to 4 carbon atoms. Each represents an alkylamino group, and X and Y may be the same or different from each other, p and q represent the number of methylene groups, p represents an integer of 1 or 2, and q represents Represents an integer of 0, 1 or 2. Here, p and q may be the same or different from each other, L ¹ is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, Or a methylene group substituted with an alkylamino group having 1 to 4 carbon atoms, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and a wavy line in the formulas (Z ¹ ) to (Z ⁴ ). The bond is an oxygen atom of the hydroxyl group and any It shows the binding of atom. However, the formula in ^{(Z 3), p = 1} , q = 0 ( single bond), and X and Y are excluding both those is an oxygen atom.)

(In Formula (3), R ¹ and R ² may have a fluorine atom and may have a C 1-6 alkyl group; a benzyl group; an allyl group; a halogen atom or a fluorine atom. An alkyl group having 1 to 6 carbon atoms, and a phenyl group having 6 to 18 carbon atoms that may have an alkyloxy group having 1 to 6 carbon atoms which may have a fluorine atom, and R ¹ and R ² are They may be the same as or different from each other, provided that the carbon number of the carbonate represented by the formula (3) is 3 to 37.)
[7] In the presence of an alkali metal compound, it is represented by a cyclic alkylene diol represented by the following formula (1), one or more linear alkylene diols represented by the following formula (2), and one or more formulas (3) below. The method for producing a polyalkylene carbonate diol copolymer according to [2] or [3], wherein the carbonate is reacted at a reaction temperature of 80 to 150 ° C.

（式（１）中、Ｚは、下記式（Ｚ^１）〜（Ｚ^４）で示される基を示す。）

(In formula (1), Z represents a group represented by the following formulas (Z ¹ ) to (Z ⁴ ).)

(In the formulas (Z ¹ ) to (Z ⁴ ), X and Y are a single bond, an oxygen atom, a sulfur atom, a methylene group (—CH ₂ —), a sulfonyl group, a carbonyl group, or a carbon atom having 1 to 4 carbon atoms. Each represents an alkylamino group, and X and Y may be the same or different from each other, p and q represent the number of methylene groups, p represents an integer of 1 or 2, and q represents Represents an integer of 0, 1 or 2. Here, p and q may be the same or different from each other, L ¹ is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, Or a methylene group substituted with an alkylamino group having 1 to 4 carbon atoms, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and a wavy line in the formulas (Z ¹ ) to (Z ⁴ ). The bond is an oxygen atom of the hydroxyl group and any It shows the binding of atom. However, the formula in ^{(Z 3), p = 1} , q = 0 ( single bond), and X and Y are excluding both those is an oxygen atom.)

(In formula (2), n and m each represent an integer of 1 to 6, and n and m may be the same or different from each other. L ² represents a single bond, an oxygen atom, or sulfur. Any one of an atom, a sulfonyl group, a carbonyl group, a fluorine atom, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms is shown.)

(In Formula (3), R ¹ and R ² may have a fluorine atom and may have a C 1-6 alkyl group; a benzyl group; an allyl group; a halogen atom or a fluorine atom. An alkyl group having 1 to 6 carbon atoms, and a phenyl group having 6 to 18 carbon atoms that may have an alkyloxy group having 1 to 6 carbon atoms which may have a fluorine atom, and R ¹ and R ² are They may be the same as or different from each other, provided that the carbon number of the carbonate represented by the formula (3) is 3 to 37.)
[8] The alkali metal compound is lithium methoxide, lithium ethoxide, lithium isopropoxide, lithium t-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium t-butoxide, sodium methoxide, sodium ethoxy. Of polyalkylene carbonate diol or a copolymer thereof according to [6] or [7] above, which is one or more alkali metal alkoxides selected from the group consisting of sodium, sodium isopropoxide, and sodium t-butoxide Method.
[9] The linear alkylene diol represented by the formula (2) is 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane. Selected from the group consisting of diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, or 1,12-dodecanediol The method for producing a polyalkylene carbonate copolymer according to [7] above, which is one or more linear alkylene diols.
[10] A polyalkylene carbonate for producing a polyurethane resin, wherein the molecular end according to [1] is a hydroxyl group.
[11] A polyalkylene carbonate copolymer for producing a polyurethane resin, wherein the molecular end described in [2] or [3] is a hydroxyl group.

  The polyalkylene carbonate diol and the copolymer thereof according to the present invention are characterized in that the main chain structure of the polymer has one or more skeleton-strength cyclic alkylene groups, and therefore the copolymer and However, the viscosity is high. For example, when used as a monomer for polyurethane resin, a new soft-feel type polyurethane resin with high transparency is provided by using linear alkylene diisocyanate such as hexamethylene diisocyanate as a soft segment. In addition, for example, an aromatic diisocyanate such as toluene diisocyanate can be used to provide a polyurethane resin that can be expected to have higher mechanical strength.

  In addition, since the polyalkylene carbonate diol and the copolymer thereof according to the present invention have a carbonate bond formed with a secondary or tertiary carbon atom in the cyclic structure, weather resistance (light stability, moisture resistance) Property and hydrolysis resistance).

  Furthermore, in the production method of the present invention, the polymerization reaction is carried out under specific reaction conditions using an inexpensive alkali metal compound as a reaction catalyst, so that even if a cyclic alkylene group-containing diol is used, A simple and industrial process that can produce polyalkylene carbonate diol and / or a copolymer thereof, in which both ends of the molecule are hydroxyl groups, without producing a large amount of an alkylene carbonate diol oligomer with insufficient organism or molecular weight. A suitable manufacturing method is also provided.

<< Polyalkylene carbonate diol and copolymer thereof of the present invention >>
The polyalkylene carbonate diol according to the present invention is a polyalkylene carbonate diol (cyclic alkylene group-containing diol) having a molecular structure of the repeating unit represented by the formula (A) and having a hydroxyl group at the molecular end. The polyalkylene carbonate diol copolymer according to the present invention comprises a polyalkylene carbonate diol copolymer having a molecular structure of a repeating unit represented by the formula (A) and one or more formulas (B) and having a hydroxyl group at the molecular end. It is a polymer (cyclic alkylene group-containing polyalkylene diol copolymer). In the polyalkylene carbonate diol copolymer of the present invention, the content ratio of the molecular structure of the formula (A) and one or more formulas (B) is usually that of the target polyalkylene carbonate diol copolymer. It is adjusted appropriately according to the intended use. Therefore, the content ratio of the molecular structure of the repeating unit represented by the formula (A) in one molecule and the molecular structure of one or more repeating units represented by the formula (B) (the sum of the molecular structures of the formula (B) As specific examples of the number: the number of molecular structures of the formula (A), it is usually 99: 1 to 1:99, preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and more preferably. Is 80: 20-30: 70, particularly preferably 80: 20-40: 60.

The number average molecular weight of the polyalkylene carbonate diol and the copolymer thereof according to the present invention is preferably 300 to 5000, more preferably 500 to 3000, more preferably 500 to 2000, and particularly preferably 500 to 1500. Here, the number average molecular weight is, for example, a number average molecular weight calculated from a ¹ H-NMR spectrum measurement by a known method (for example, refer to Examples of the present application), or a known hydroxyl value measurement (for example, , JIS K 1557 or JIS K 0070), and the number average molecular weight calculated from gel filtration chromatography (GPC: standard substance; polystyrene). It may be calculated from the measurement method.

  The polyalkylene carbonate diol and the copolymer thereof according to the present invention can be produced by adjusting the composition ratio with high reliability within the range of the number average molecular weight shown above. Furthermore, since the polyalkylene carbonate diol and its copolymer obtained in the present invention have a skeleton-strength cyclic alkylene moiety, it has higher mechanics than the polyalkylene carbonate diol and its copolymer known so far. Therefore, it can be used as a constituent or raw material for various industrial materials that take advantage of the characteristics.

≪Method for producing polyalkylene carbonate diol of the present invention or polyalkylene carbonate diol copolymer of the present invention≫
The polyalkylene carbonate diol according to the present invention or the polyalkylene carbonate diol copolymer of the present invention is a kind in the case of synthesizing a cyclic alkylene group-containing diol represented by the above formula (1) in the presence of an alkali metal compound. It is produced by reacting the linear alkylene diol represented by the above formula (2) and one or more carbonates represented by the above formula (3).

<Cyclic alkylene diol represented by the formula (1)>
The cyclic alkylene group-containing diol represented by the formula (1) used as a raw material for producing the polyalkylene carbonate diol and the copolymer thereof according to the present invention is preferably a carbon number of the above formulas (Z ¹ ) to (Z ⁴ ). Is a cyclic alkylene group-containing diol having 4 to 18 carbon atoms, more preferably a cyclic alkylene group-containing diol having 4 to 12 carbon atoms in the above formulas (Z ¹ ) to (Z ⁴ ), particularly preferably 1,3-cyclohexanediol. 1,2-cyclohexanediol, 2,2-bis (4-hydroxycyclohexyl) propane (perhydrobisphenol A), 2,2-bis (4-hydroxycyclohexyl) hexafluoropropane, and isosorbide.

  The cyclic alkylene diol represented by the formula (1) of the present invention may be used as it is if there is a commercially available product. On the other hand, for those that do not have a commercially available product, for example, the corresponding ketone compound is subjected to hydride reduction. It is separately synthesized and used by a known method. Further, a commercially available product or a synthesized product may be used after being purified by, for example, distillation, crystallization, and / or column chromatography.

<Linear alkylene diol represented by the formula (2)>
In the method for producing a polyalkylene carbonate diol copolymer according to the present invention, the linear alkylene diol represented by the formula (2) used as a production raw material is specifically 1,2-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- A linear alkylene diol having 2 to 12 carbon atoms such as decanediol, 1,11-undecanediol, or 1,12-dodecanediol; diethylene glycol, dipropylene glycol, dibutylene glycol, 2,2′-thiodiethanol, Such as 3,3′-thiodipropanol or 2,2′-sulfonyldiethanol C2-C12 heteroatom-containing linear alkylene diol having a tellurium bond, thioether bond or sulfonyl bond, C2-C6 linear alkylene diol, or C2-C6 heteroatom-containing A linear alkylene diol, more preferably a linear alkylene diol having 4 to 6 carbon atoms, may be mentioned, but 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, , 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, or 1 One or more linear alkylene diols selected from the group consisting of, 12-dodecanediol are used.

  As long as there is a commercial product, the linear alkylene diol represented by the formula (2) may be used as it is. On the other hand, for a product without a commercial product, for example, the corresponding carboxylic acid compound or carboxylic acid The ester compound is separately synthesized and used by a known method such as hydride reduction. Further, a commercially available product or a synthesized product may be used after being purified by, for example, distillation, crystallization, column chromatography or the like. Further, in the production of the polyalkylene carbonate diol copolymer of the present invention, the linear alkylene diol represented by the formula (2) may be used alone or in combination, and the total amount used. Is preferably 0.1 to 9.0 moles, more preferably 0.25 to 6.0 moles, and more preferably 0.5 to 4. moles per mole of the cyclic alkylene diol represented by the formula (1). 0 mol, particularly preferably 0.8 to 4.0 mol, particularly preferably 1.0 to 3.0 mol.

<Carbonate represented by formula (3)>
In the production method according to the present invention, R ¹ and R ² of the carbonate represented by the formula (3) used as a production raw material have 1 to 1 carbon atoms in which R ¹ and R ² may have a fluorine atom. An alkyl group having 6 carbon atoms; a benzyl group; an allyl group; an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a fluorine atom; an alkyloxy group having 1 to 6 carbon atoms which may have a fluorine atom It is a C6-C18 phenyl group which may have. R ¹ and R ² may be the same or different from each other. The number of the substituents is not particularly limited, but the carbon number of the carbonate represented by the formula (3) is 3 to 37. The alkyl group may be linear, branched or cyclic, and further includes a positional isomer in the case of a branched chain. Furthermore, in this invention, the carbonate shown by Formula (3) may be used individually or may be used in multiple types.

  From the above, the carbonate represented by the formula (3) used in the present invention is preferably a symmetric carbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisopropyl carbonate; an asymmetric carbonate such as methyl ethyl carbonate; One or more carbonates selected from the group consisting of carbonate, dibenzyl carbonate, and diallyl carbonate, more preferably one or more carbonates selected from the group consisting of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and diphenyl carbonate, especially Preferably dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate is used.

  Moreover, in the manufacturing method of the polyalkylene carbonate diol and its copolymer which concern on this invention, you may use multiple types of carbonate shown by Formula (3). For example, in the reaction of the present invention, under the influence of alcohol by-produced from the carbonate to be used, the liquid temperature of the reaction solution is lowered and cannot be set to a desired reaction temperature, or the reaction mixture In some cases, precipitates are generated due to a decrease in the solubility of the polymer, and the polymerization reaction for obtaining a polyalkylene carbonate diol having a target molecular weight and a copolymer thereof may not proceed. Therefore, in order to avoid such a low reactivity state, a high boiling point or highly soluble carbonate may be added as appropriate to improve the reaction state.

  If there exists a commercial item, you may use the carbonate shown by Formula (3) of this invention as it is. Moreover, about what has no commercial item, you may synthesize | combine separately, for example, referring to Unexamined-Japanese-Patent No. 2006-104095 etc. Further, a commercially available product or a synthesized product may be used after being purified by, for example, distillation, crystallization, column chromatography or the like.

  The carbonate represented by the formula (3) may be used alone or in combination, and the total amount used is 1 mol of the cyclic alkylene diol represented by the formula (1). On the other hand, it is preferably 0.5 to 2 mol, more preferably 0.8 to 2 mol, and particularly preferably 1 to 1.5 mol.

<Alkali metal compound>
Examples of the alkali metal compound used in the present invention include alkali metal hydroxides (for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), metal alkoxides (for example, lithium of alcohol having 1 to 6 carbon atoms, Potassium, sodium salts, etc.) and mixtures thereof.

  The alkali metal compound used in the present invention is preferably an alkali metal alkoxide having 1 to 6 carbon atoms; more preferably lithium methoxide, lithium ethoxide, lithium isopropoxide, lithium t-butoxide, potassium methoxide, One or more alkali metal alkoxides selected from the group consisting of potassium ethoxide, potassium isopropoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, and sodium t-butoxide; The group consisting of potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, and sodium t-butoxide One or more alkali metal alkoxides selected from the group consisting of potassium methoxide, potassium ethoxide, sodium methoxide, and sodium ethoxide; particularly preferably, Sodium methoxide or sodium ethoxide.

  If the alkali metal compound used by this invention has a commercial item, you may use it as it is. Moreover, if it is a metal alkoxide, you may use separately prepared from the corresponding alkali metal and alcohol, for example.

Further, the alkali metal compounds may be used alone or in combination, and the total amount used is a linear alkylene diol represented by the formula (1) and a linear chain represented by the formula (2). Preferably, it is 0.001-1.0 mass% (10-10000 ppm), More preferably, it is 0.005-0.1 mass% (50-1000 ppm) with respect to the total usage-amount with a linear alkylene diol, More preferably It is used so that it may become 0.005-0.05 mass% (50-500 ppm), Most preferably 0.005-0.02 mass% (50-200 ppm).

  In the method for producing a polyalkylene carbonate diol and a copolymer thereof according to the present invention, the reaction is allowed to proceed satisfactorily while suppressing the reaction temperature by performing a polymerization reaction using the type and amount of the alkali metal compound. Succeeded. That is, in the methods known so far, an olefin compound by a decarboxylation reaction of a reaction intermediate that occurs in parallel during the polymerization reaction or a polyalkylene carbonate diol copolymer having an insufficient polymerization degree due to a low reaction temperature condition. In contrast to the formation of a large amount of coal, according to the method of the present invention, the polyalkylene of the present invention has a sufficient molecular weight (degree of polymerization) and has a desired composition ratio without being affected by these side reactions. A carbonate diol copolymer can be obtained.

<Reaction solvent>
The reaction of the present invention may be performed separately in the presence of a reaction solvent or in the absence.
In addition, when using a reaction solvent separately, as a reaction solvent which can be used, if it does not inhibit reaction, it will not specifically limit, For example, aliphatic hydrocarbons, such as hexane, heptane, a cyclohexane, diethyl ether, Ethers such as diisopropyl ether, t-butyl methyl ether, dimethoxyethane, cyclopentyl methyl ether and tetrahydrofuran; Nitriles such as acetonitrile and propionitrile; Aromatic hydrocarbons such as toluene and xylene; Halogens such as methylene chloride and chloroform Hydrocarbons; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be mentioned, but ethers, nitriles and / or amides are preferably used. Moreover, these reaction solvents may be used alone or in admixture of two or more, and the amount used is not particularly limited because it is appropriately adjusted. However, in the reaction of the present invention, for example, when the solubility of the starting material used is low, a reaction solvent may be used separately. However, in general, the reaction after completion of the reaction is considered in view of the complexity of the treatment. It is desirable to carry out the reaction without using a solvent as much as possible.

<Reaction conditions>
In the method for producing the polyalkylene carbonate diol and the copolymer thereof according to the present invention, in the presence of an alkali metal compound, the cyclic alkylene diol represented by the formula (1) and one or more linear chains represented by the formula (2) are used. An alkylene diol and one or more carbonates represented by formula (3) in the presence or absence of a reaction solvent, under atmospheric pressure or reduced pressure, and / or under an inert gas stream such as argon, helium, nitrogen, etc. In the transesterification polymerization reaction, the mixture is mixed by stirring or the like while being heated. Therefore, it is desirable that the reaction system (reaction environment) is under non-aqueous conditions.
In addition, the manufacturing method may be any method such as a batch method or a continuous method, and is not particularly limited. It is desirable that the reaction system (reaction environment) is under non-aqueous conditions.

  Specifically, the reaction equipment used is a stirred tank reactor, a thin film reactor, a centrifugal thin film evaporation reactor, a surface renewal biaxial kneading reactor, a biaxial horizontal stirring reactor, a wet wall reactor A perforated plate type reactor that polymerizes while freely falling, a perforated plate type reactor with wire that polymerizes while dropping along a wire, and the like are exemplified, but are not particularly limited. These polymerization devices may be used alone or in combination. Moreover, there is no restriction | limiting in particular also about the material of these superposition | polymerization apparatuses, For example, it selects from stainless steel, nickel, glass lining etc. suitably, and is used.

In the reaction of the present invention, the reaction temperature (temperature of the reaction solution) is usually 65 ° C. or higher and lower than 180 ° C., preferably 65 to 160 ° C., more preferably 80 to 150 ° C., more preferably 90 to 145 ° C., particularly preferably. Is 100-140 ° C. When the reaction temperature (temperature of the reaction solution) is lower than 65 ° C, the reaction may be affected by alcohol produced as a by-product of the reaction, which is not preferable from the viewpoint of an industrial production cycle. In the case of exceeding the ratio of the terminal group of the copolymer of the present invention to the olefin terminal group within 5 hours within 16 hours, for example, such as polyurethane resin or thermoplastic elastomer When used as a monomer, it adversely affects the polymerization degree and molecular weight dispersion of the resulting polymer, which is not preferable.
In the production method of the present invention, the reaction time depends on the reaction temperature, but is preferably 30 hours or less, more preferably 24 hours or less, more preferably 20 hours or less, particularly preferably 18 hours or less, particularly Preferably it is 16 hours or less.

The polyalkylene carbonate diol and its copolymer according to the present invention are produced by a transesterification polymerization reaction with chemical equilibrium. Therefore, by appropriately adjusting the reaction pressure within the above temperature range, this chemical equilibrium can be biased toward the direction of promoting the polymerization reaction. An alkylene carbonate diol copolymer can be obtained.
Therefore, as one embodiment of the production method of the present invention that is also industrially suitable, for example, the alcohol produced as a by-product during the reaction may be distilled off at atmospheric pressure or under reduced pressure as desired. A method of obtaining this after reacting until the molecular weight (for example, number average molecular weight, etc.) is reached can be mentioned. As a specific example of the production method of the present invention including this operation, under the reaction conditions of atmospheric pressure and the reaction solution temperature of 160 ° C. or lower (particularly preferably 140 ° C.), the formula ( In the case of synthesizing a cyclic alkylene diol represented by 1), a linear alkylene diol represented by one or more formulas (2) and one or more carbonates represented by formula (3) are reacted, First, 70 mass% or more of the alcohol or phenol produced as a by-product is distilled off with respect to the theoretical production amount, and then the reaction pressure is gradually reduced to remove the remaining by-produced alcohol. Examples include a method for producing an alkylene carbonate diol and a copolymer thereof. Here, the final pressure (internal pressure) of the reaction pressure gradually reduced is preferably less than atmospheric pressure to 0.01 kPa (absolute pressure), more preferably 50 to 0.01 kPa (absolute pressure), more preferably 10 to 10. 0.01 kPa (absolute pressure), particularly preferably 5 to 0.01 kPa (absolute pressure).

  As a feature of the method for producing a polyalkylene carbonate diol and a copolymer thereof according to the present invention, even when a cyclic alkylene group-containing diol is used, a reaction by-product or an alkylene carbonate diol oligomer with insufficient molecular weight is used. It can be mentioned that the polyalkylene carbonate diol copolymer in which both ends of the molecule are hydroxyl groups can be produced by a simple method without producing a large amount.

Furthermore, another feature of the production method according to the present invention is that the amount of the cyclic alkylene diol represented by the formula (1) and the linear alkylene diol represented by the formula (2) (mixing ratio) is as it is, It is mentioned that it is a manufacturing method reflected in the composition ratio of the molecular structure of the repeating unit shown by said Formula (A) and Formula (B) of the polyalkylene carbonate diol copolymer of this invention. That is, according to the production method of the present invention, by using an alkylene diol in proportion to the composition ratio of the target polyalkylene carbonate diol copolymer of the present invention, the resulting polyalkylene carbonate diol copolymer This is an industrially suitable production method in which the composition ratio can be easily controlled. Moreover, it is not necessary to carry out a composition ratio control method that uses a large excess amount of one diol or more of the target composition ratio among the two diols that have a difference in reactivity. Is also a suitable manufacturing method.

  EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

<Calculation method of number average molecular weight of polyalkylene carbonate diol and its copolymer>
(Measurement of ¹ H-NMR spectrum)
The ¹ H-NMR spectrum measurement of the polyalkylene carbonate diol obtained in this example and its copolymer was prepared by dissolving the obtained polymer in deuterated chloroform or deuterated acetonitrile to prepare a sample for NMR measurement. Using a measuring device (“AVANCE 500 type”, manufactured by Bruker Biospin), the measurement was performed with non-decoupling.

(Calculation method of the number of molecular structures of repeating units)
In the polyalkylene carbonate diol copolymer obtained in this example, the content ratio of the molecular structure of the formula (A) and the formula (B) is expressed as “polymer nuclear magnetic resonance (edited by Polymer Society of Polymer Experiments”). It was calculated from the number of molecular structures of the repeating units of the formula (A) and the formula (B) with reference to “Committee edition Kyoritsu publication page 283)”.

More specifically, from the ¹ H-NMR spectrum data of the polyalkylene carbonate diol copolymer obtained in this example, the number of molecular structures represented by the formula (A): a is the hydroxyl group at the molecular end. The methine site adjacent to the carbonate group in the polycarbonate main chain when the integrated value of the adjacent methine site (the value of chemical shift in ¹ H-NMR (δ / ppm: 3.50 to 3.80) is 1) The integrated value of hydrogen atoms (chemical shift value in ¹ H-NMR (δ / ppm): calculated at a ratio of 4.50 to 4.80.
Similarly, from the ¹ H-NMR spectrum data obtained above, the number of molecular structures represented by the formula (B): b is the integral value ( ¹ H-NMR of the methylene moiety adjacent to the hydroxyl group at the molecular end. When the value of chemical shift in (δ / ppm: 3.50 to 3.80) is 1, the integrated value of hydrogen atoms in the methylene site adjacent to the carbonate group in the polycarbonate main chain (in ¹ H-NMR The chemical shift value (δ / ppm: 4.00 to 4.30) is calculated.

(Calculation method of composition ratio of polyalkylene carbonate diol copolymer)
In the polyalkylene carbonate diol copolymer obtained in this example, the composition ratio of the molecular structure of the repeating unit represented by formula (A) or formula (B, respectively) is calculated from the formulas a and b calculated above. The composition ratio (%) of (A) is a / (a + b) * 100 (%), and the composition ratio (%) of formula (B) is b / (a + b) * 100 (%). Calculated.

(Calculation method of number average molecular weight)
The number average molecular weight of the polyalkylene carbonate diol copolymer obtained in this example is the value of a and b, which is the number of molecular structures of each repeating unit calculated above, and the molecule of each repeating unit. The calculation was performed by adding the molecular weight of the molecular structure of the terminal portion to the product of the molecular weight of the structure. More specifically, the composition ratio was calculated from the ¹ H-NMR spectrum analysis of the obtained polyalkylene carbonate diol copolymer, and the charged amount and recovered amount of raw materials.

<Measuring method of thermal behavior of polyalkylene carbonate diol copolymer>
The glass transition point of the polyalkylene carbonate diol copolymer obtained in this example was measured with a differential scanning calorimeter (DSC) at a measurement temperature range of −100 to 150 ° C.

<Measurement method of viscosity of polyalkylene carbonate diol copolymer>
The viscosity of the polyalkylene carbonate diol copolymer obtained in this example was measured with an E-type rotational viscometer (“Programmable Digital Viscometer DV-II +”, manufactured by Brookfield).

<Calculation method of terminal hydroxyl group purity of polyalkylene carbonate diol copolymer>
In this example, the ratio of the terminal group of the obtained polyalkylene carbonate diol copolymer being a hydroxyl group was calculated as “terminal hydroxyl group purity”. The terminal hydroxyl purity than ¹ H-NMR spectrum data obtained, methine site adjacent to the terminal hydroxyl group (or methylene site) chemical shift of a hydrogen atom ⁽¹ H-NMR value: 3.50 to 3. 80 ppm) of the integrated value of A (or A / 2 in the case of the methylene moiety), the hydrogen atom of the olefin moiety (value of chemical shift in ¹ H-NMR (δ: ppm): 5.20 to 6.00 ppm) The integral value of 1 proton is B, and the integral value of the hydrogen atom in the methyl group part of the methyl carbonate group at the molecular end (chemical shift value in ¹ H-NMR (δ: ppm): 3.65 to 3.85 ppm). When A is C, A / (A + B + C / 3) is a value further expressed as a percentage (%).

Example 1 (polyalkylene carbonate diol copolymer comprising 1,4-cyclohexanediol and 1,6-hexanediol)
In a 200 mL glass flask equipped with a stirrer, a heating device, a distillation device, and a thermometer, 33.08 g (0.28 mol) of 1,4-cyclohexanediol and 41.06 g of 1,6-hexanediol (0 .35 mol), 56.91 g (0.63 mol) of dimethyl carbonate and 30 mg of 28% sodium methoxide-methanol solution (sodium methoxide: 8.4 mg, 113 ppm), and at an internal temperature of 98- The mixture was heated and stirred at 99 ° C. for 1 hour. Next, the low-boiling liquid containing methanol produced in the reaction was heated and stirred at an internal temperature of 99 to 140 ° C. for 4 hours while distilling off by distillation at a distillate temperature of 65 ° C. or lower. Further, while maintaining the internal temperature at 140 ° C., the mixture was heated and stirred at an internal pressure of 13.3 kPa for 3 hours, and after the methanol was distilled off by distillation, the internal temperature was continuously maintained at an internal temperature of 140 ° C. and an internal pressure of 1.6 kPa for 7 hours. Heating and stirring were performed for 2 hours at 140 ° C. and an internal pressure of 0.6 kPa. After completion of the reaction, 100 mg of acetic acid and 85 g of toluene were added to the resulting reaction solution, and the mixture was stirred at an internal temperature of 45 to 80 ° C. for 1 hour, and then the organic layer washed with pure water was concentrated. After adding 1 g and stirring, this was filtered and the toluene solution containing the target object was obtained. Finally, this toluene solution was dried and concentrated to obtain 84.46 g of a polyalkylene carbonate diol copolymer composed of 1,4-cyclohexanediol and 1,6-hexanediol as a colorless viscous liquid.

The obtained polycarbonate diol copolymer was obtained from the analysis value of ¹ H-NMR spectrum to determine the number average molecular weight, composition ratio and terminal hydroxyl group purity, and the glass transition point was measured by differential scanning calorimetry (DSC) analysis. Furthermore, the viscosity at a temperature of 75 ° C. was measured using an E-type rotational viscometer. The results are shown in Table 1.

Example 2 (polyalkylene carbonate diol copolymer comprising 1,4-cyclohexanediol and 1,6-hexanediol)
In a 500 mL glass flask equipped with a stirrer, heating device, distillation device, and thermometer, 80.23 g (0.69 mol) of 1,4-cyclohexanediol and 75.38 g of 1,6-hexanediol (0 .64 mol), 125.63 g (1.40 mol) of dimethyl carbonate and 60 mg of a 28% sodium methoxide-methanol solution (sodium methoxide: 16.8 mg, 108 ppm) were added. The mixture was heated and stirred at 97 ° C. for 1 hour. Next, the low-boiling liquid containing methanol produced by the reaction was heated and stirred at an internal temperature of 97 to 140 ° C. for 3 hours while distilling off by distillation at a distillate temperature of 65 ° C. or lower. Further, while maintaining the internal temperature at 140 ° C., the mixture was heated and stirred at an internal pressure of 13.3 kPa for 2 hours, and the methanol was distilled off. Subsequently, the internal temperature was 140 ° C. and the internal pressure was 1.3 kPa for 7 hours. Heating and stirring were performed at 140 ° C. and an internal pressure of 0.7 kPa for 4 hours. After completion of the reaction, 100 mg of acetic acid and 180 g of toluene were added to the resulting reaction solution, and the mixture was stirred at an internal temperature of 50 to 60 ° C. for 1 hour, and then the organic layer washed with pure water was concentrated. After adding 1 g and stirring, this was filtered and the toluene solution containing the target object was obtained. Finally, this toluene solution was dried and concentrated to obtain 146.21 g of a polyalkylene carbonate diol copolymer composed of 1,4-cyclohexanediol and 1,6-hexanediol as a colorless viscous liquid.

The obtained polycarbonate diol copolymer was obtained from the analysis value of ¹ H-NMR spectrum to determine the number average molecular weight, composition ratio and terminal hydroxyl group purity, and the glass transition point was measured by differential scanning calorimetry (DSC) analysis. Furthermore, the viscosity at a temperature of 75 ° C. was measured using an E-type rotational viscometer. The results are shown in Table 1.

Example 3 (polyalkylene carbonate diol copolymer comprising 1,4-cyclohexanediol and 1,6-hexanediol)
A glass flask having an internal volume of 500 mL equipped with a stirrer, a heating device, a distillation device, and a thermometer was charged with 100.05 g (0.86 mol) of 1,4-cyclohexanediol and 86.79 g of 1,6-hexanediol (0). .73 mol), 155.17 g (1.72 mol) of dimethyl carbonate and 60 mg of 28% sodium methoxide-methanol solution (sodium methoxide: 16.8 mg, 90 ppm) were added, and the internal temperature was 94 to 80 at atmospheric pressure under an argon stream. The mixture was heated and stirred at 97 ° C. for 1 hour. Next, the low-boiling liquid containing methanol produced by the reaction was heated and stirred at an internal temperature of 97 to 140 ° C. for 4 hours while distilling off by distillation at a distillate temperature of 65 ° C. or lower. Further, while maintaining the internal temperature at 140 ° C., the mixture was heated and stirred at an internal pressure of 13.3 kPa for 3 hours, and after the methanol was distilled off by distillation, the internal temperature was continuously maintained at an internal temperature of 140 ° C. and an internal pressure of 1.3 kPa for 7 hours. Heating and stirring were performed at 140 ° C. and an internal pressure of 0.7 kPa for 3 hours. After completion of the reaction, 100 mg of acetic acid and 200 g of toluene were added to the obtained reaction solution, and the mixture was stirred for 1 hour at an internal temperature of 40 to 70 ° C., and then the organic layer washed with pure water was concentrated. After adding 1 g and stirring, this was filtered and the toluene solution containing the target object was obtained. Finally, this toluene solution was dried and concentrated to obtain 169.80 g of a polyalkylene carbonate diol copolymer composed of 1,4-cyclohexanediol and 1,6-hexanediol as a colorless viscous liquid.

The obtained polycarbonate diol copolymer was obtained from the analysis value of ¹ H-NMR spectrum to determine the number average molecular weight, composition ratio and terminal hydroxyl group purity, and the glass transition point was measured by differential scanning calorimetry (DSC) analysis. Furthermore, the viscosity at a temperature of 75 ° C. was measured using an E-type rotational viscometer. The results are shown in Table 1.

Example 4 (polyalkylene carbonate diol copolymer comprising 1,4-cyclohexanediol and 1,6-hexanediol)
In a 200 mL internal volume glass flask equipped with a stirrer, a heating device, a distillation device, and a thermometer, 35.07 g (0.30 mol) of 1,4-cyclohexanediol and 29.17 g of 1,6-hexanediol (0 .25 mol), 59.34 g (0.66 mol) of dimethyl carbonate, and 30 mg of 28% sodium methoxide-methanol solution (sodium methoxide: 8.4 mg, 131 ppm) were added. The mixture was heated and stirred at 97 ° C. for 1 hour. Next, the low-boiling liquid containing methanol produced by the reaction was heated and stirred at an internal temperature of 97 to 140 ° C. for 4 hours while distilling off by distillation at a distillate temperature of 65 ° C. or lower. Further, while maintaining the internal temperature at 140 ° C., the mixture was heated and stirred at an internal pressure of 13.3 kPa for 2 hours, and the methanol was distilled off. Subsequently, the internal temperature was 140 ° C. and the internal pressure was 1.3 kPa for 7 hours. Heating and stirring were performed at 140 ° C. and an internal pressure of 0.4 kPa for 3 hours. After completion of the reaction, 50 mg of acetic acid and 75 g of toluene were added to the resulting reaction solution, and the mixture was stirred at an internal temperature of 50 to 70 ° C. for 1 hour, and then the organic layer washed with pure water was concentrated. After adding 1 g and stirring, this was filtered and the toluene solution containing the target object was obtained. Finally, this toluene solution was dried and concentrated to obtain 50.58 g of a polyalkylene carbonate diol copolymer composed of 1,4-cyclohexanediol and 1,6-hexanediol as a colorless viscous liquid.

The obtained polycarbonate diol copolymer was obtained from the analysis value of ¹ H-NMR spectrum to determine the number average molecular weight, composition ratio and terminal hydroxyl group purity, and the glass transition point was measured by differential scanning calorimetry (DSC) analysis. Furthermore, the viscosity at a temperature of 75 ° C. was measured using an E-type rotational viscometer. The results are shown in Table 1.

Example 5 (polyalkylene carbonate diol copolymer comprising isosorbide and 1,6-hexanediol)
In a 200 mL glass flask equipped with a stirrer, heating device, distillation device, and thermometer, 37.39 g (0.26 mol) isosorbide, 30.05 g (0.25 mol) 1,6-hexanediol, dimethyl 45.95 g (0.51 mol) of carbonate and 30 mg of a 28% sodium methoxide-methanol solution (sodium methoxide: 8.4 mg, 125 ppm) were added. The mixture was heated and stirred for 5 hours. Subsequently, the low-boiling liquid containing methanol produced by the reaction was heated and stirred at an internal temperature of 94 to 140 ° C. for 5 hours while distilling off by distillation at a distillate temperature of 65 ° C. or lower. Further, while maintaining the internal temperature at 140 ° C., the mixture was heated and stirred at an internal pressure of 13.3 kPa for 2.5 hours, and methanol was distilled off, followed by heating at an internal temperature of 140 ° C. and an internal pressure of 0.2 kPa for 8 hours. Stirring was performed. After completion of the reaction, 30 mg of acetic acid and 80 g of toluene were added to the obtained reaction solution, and the mixture was stirred at an internal temperature of 45 to 60 ° C. for 1 hour, and then the organic layer containing toluene washed with pure water was concentrated. After adding 80 mL of toluene and 1 g of activated carbon and stirring, this was filtered to obtain a toluene solution containing the target product. Finally, this toluene solution was concentrated and dried to obtain 18.72 g of a polyalkylene carbonate diol copolymer composed of isosorbide and 1,6-hexanediol as a pale yellow viscous liquid.

Example 6 (polyalkylene carbonate diol copolymer comprising 2,2-bis (4-hydroxycyclohexyl) propane and 1,6-hexanediol)
In a 200 mL internal volume glass flask equipped with a stirrer, heating device, distillation device, and thermometer, 50.23 g (0.21 mol) of 2,2-bis (4-hydroxycyclohexyl) propane, 1,6 -24.71 g (0.21 mol) of hexanediol, 37.67 g (0.42 mol) of dimethyl carbonate and 30 mg of 28% sodium methoxide-methanol solution (sodium methoxide: 8.4 mg, 112 ppm) were added under atmospheric pressure. The mixture was heated and stirred at an internal temperature of 100 to 105 ° C. for 2 hours under an argon stream. Subsequently, the low-boiling liquid containing methanol produced by the reaction was heated and stirred at an internal temperature of 105 to 140 ° C. for 6 hours while distilling off by distillation at a distillate temperature of 65 ° C. or lower. Further, while maintaining the internal temperature at 140 ° C., the mixture was stirred with heating at an internal pressure of 13.3 kPa for 2 hours, and after the methanol was distilled off by distillation, subsequently, the internal temperature was 140 ° C. and the internal pressure was 0.23 to 0.28 kPa. Stirring was performed for hours. After completion of the reaction, 100 mg of acetic acid and 80 g of toluene were added to the resulting reaction solution, and the mixture was stirred at an internal temperature of 35 to 60 ° C. for 1 hour, and then the organic layer washed with pure water was concentrated. After adding 1 g and stirring, this was filtered and the toluene solution containing the target object was obtained. Finally, the toluene solution was dried and concentrated to obtain a polyalkylene carbonate diol copolymer composed of 2,2-bis (4-hydroxycyclohexyl) propane and 1,6-hexanediol as a pale yellow viscous liquid. Obtained .73 g.

The obtained polycarbonate diol copolymer was obtained from the analysis value of ¹ H-NMR spectrum to determine the number average molecular weight, composition ratio and terminal hydroxyl group purity, and the glass transition point was measured by differential scanning calorimetry (DSC) analysis. Furthermore, the viscosity at a temperature of 75 ° C. was measured using an E-type rotational viscometer. The results are shown in Table 1.

Comparative Example 1 (polyhexamethylene carbonate diol: “UH-100”)
For the purpose of comparing the physical properties of the polyalkylene carbonate diol copolymer of the present invention, a commercially available polyhexapolymer having a number average molecular weight of about 1000, produced using only hexanediol (1,6-HDL) as an alkylene diol component. The glass transition point was measured by differential scanning calorimetry (DSC) analysis in the same manner as in the above example using methylene carbonate diol (manufactured by Ube Industries, “UH-100” (trade name), and E The viscosity at a temperature of 75 ° C. was measured using a mold rotational viscometer, and the results are shown in Table 1.

＊１：数平均分子量：１Ｈ−ＮＭＲ測定により算出。
＊２：１，６−ＨＤＬ：１，６−ヘキサンジオール
１，４−ｃＨＤＬ：１，４−シクロヘキサンジオール
Ｈ−ＢＰＡ：２，２−ビス（４−ヒドロキシシクロへキシル）プロパン
組成比は、前記（ポリアルキレンカーボネートジオール共重合体の組成比の算出方法）の記載に従って算出。
＊３：前記＜ポリアルキレンカーボネートジオール共重合体の末端水酸基純度の算出方法＞の記載に従って算出。
＊４：ＤＳＣ測定データ。
＊５：７５℃における測定値（Ｅ型粘度計）。Ｎ．Ｄは高い固化状態により、粘度測定が不能であったことを示す。
＊６：ＵＨ−１００（宇部興産（株）製）。
＊７：ＪＩＳ Ｋ１５５７−１記載の水酸基価測定により算出。

* 1: Number average molecular weight: Calculated by 1H-NMR measurement.
* 2: 1,6-HDL: 1,6-hexanediol 1,4-cHDL: 1,4-cyclohexanediol H-BPA: 2,2-bis (4-hydroxycyclohexyl) propane Calculated as described in (Calculation method of composition ratio of polyalkylene carbonate diol copolymer).
* 3: Calculated according to the description in <Method for calculating terminal hydroxyl group purity of polyalkylene carbonate diol copolymer>.
* 4: DSC measurement data.
* 5: Measured value at 75 ° C. (E-type viscometer). N. D indicates that viscosity measurement was impossible due to a high solidified state.
* 6: UH-100 (manufactured by Ube Industries).
* 7: Calculated by hydroxyl value measurement described in JIS K1557-1.

  From the above, it was confirmed that the polyalkylene carbonate diol copolymer having a cyclic alkylene group according to this example has a higher viscosity (75 ° C.) as the introduction rate of the cyclic alkylene group is higher. Furthermore, it was confirmed that the viscosity (75 ° C.) of these copolymers is higher than that of polyhexamethylene carbonate diol (UH-100), which is one of the homopolymers.

Example 7 (Polyalkylene carbonate diol using 1,4-cyclohexanediol: POL)
In a 200 mL glass flask equipped with a stirrer / distiller, 65.27 g (0.56 mol) of 1,4-cyclohexanediol, 59.98 g (0.28 mol) of diphenyl carbonate and lead acetate trihydrate 6 0.5 mg (100 ppm) was added, and the temperature of the reaction solution was gradually raised to 140 ° C. while stirring in an argon stream under atmospheric pressure. Subsequently, the reaction solution was gradually reduced in pressure from 3 kPa to 0.45 kPa over 12 hours to distill off phenol produced as a by-product in the reaction. Thereafter, 16.94 g (0.079 mol) of diphenyl carbonate was added, and the internal pressure was gradually reduced from 3 kPa to 0.1 kPa over 12 hours at an internal temperature of 140 ° C. to distill off the phenol. After completion of the reaction, the resulting reaction solution was post-treated in the same manner as in Example 1 to obtain 56.61 g of polyalkylene carbonate diol (POL) using 1,4-cyclohexanediol as a colorless solid. .

  Next, 200 mL of t-butyl methyl ether was added to the obtained POL, and sonication was performed. The insoluble matter after ultrasonic treatment was obtained by filtration, and this was dried to obtain 26.43 g of a polyalkylene carbonate diol high molecular weight product (POL-1) using 1,4-cyclohexanediol as a white solid. On the other hand, about the filtrate obtained after the said filtration, the solvent etc. were distilled off and 22.24g of polyalkylene carbonate diol low molecular weight substance (POL-2) using 1, 4- cyclohexanediol was obtained as a colorless viscous substance. .

The obtained product (POL-1, POL-2) is obtained by replacing the integral value of the hydrogen atom at the methyl group site of the methyl carbonate group at the molecular end with hydrogen at the phenyl group site of the phenyl carbonate group at the molecular end instead of C. Description of <Method for calculating terminal hydroxyl group purity of polyalkylene carbonate diol copolymer> except that the integral value of atoms (value of chemical shift in ¹ H-NMR: 7.2 to 7.5 ppm) is D Using the same method, the terminal olefin group content (%) was calculated as B / (A + B + D / 5) × 100 from ¹ H-NMR spectrum data. As a result, as for POL-1, the terminal olefin group content was 0% (terminal hydroxyl group purity: 100%), and the number average molecular weight was 720 from the analysis value of the ¹ H-NMR spectrum. POL-1 was soluble in solvents such as chloroform, tetrahydrofuran (THF) and dimethylformamide (DMF). Further, with respect to POL-2, the terminal olefin group content was 0% (terminal hydroxyl group purity: 100%), and the number average molecular weight was 511 from the analysis value of the ¹ H-NMR spectrum.

Comparative Example 2 (polyalkylene carbonate diol using 1,4-cyclohexanediol)
1,4-cyclohexanediol 50.0 g (0.43 mol), diphenyl carbonate 85.8 g (0.40 mol) and zinc acetate 7.5 mg (150 ppm) in a 300 mL glass flask equipped with a stirrer / distillation device Was added, and the temperature of the reaction solution was gradually raised to 180 ° C. while stirring in an argon stream under atmospheric pressure. Subsequently, the reaction solution was gradually reduced in pressure from 20 kPa to 0.1 Kpa over 12 hours to distill off phenol produced as a by-product in the reaction. After completion of the reaction, the resulting reaction solution was post-treated in the same manner as in Example 1 to obtain 169.80 g of a colorless viscous liquid.

  When the terminal olefin group content of the obtained product was calculated by the method described in Example 7, it was 5.4%. The terminal hydroxyl group purity was 0.4%.

  From the above, according to this reference example, when the reaction was carried out by raising the temperature of the reaction solution to 180 ° C., not only the terminal olefin group content was 5.4%, Since the transition metal organic acid salt is used instead of the alkali metal compound of the invention, the terminal hydroxyl group purity becomes 0.4%, and the polyalkylene carbonate diol has hydroxyl groups at both ends of the molecule, which is one of the features of the object of the present invention. It has been confirmed that even no results have been obtained.

Reference Example 1 (Production example of polyurethane resin)
Next, an example of a method for producing a polyurethane resin is shown.
For example, in a glass reactor having an internal volume of 200 mL equipped with a stirrer, a thermometer, and a reflux condenser, 1 mol of POL obtained in Example 6 (molecular weight is number average molecular weight (GPC: gel filtration chromatography, or ¹ H -Calculated from NMR spectrum analysis), 2 mol equivalent of 1,4-butanediol with respect to 1 mol of POL and about 40 g of dimethylacetamide were added, and the internal temperature was adjusted to about 60 ° C. while stirring the solution under a nitrogen stream. , 4,4'-diphenylmethane diisocyanate (MDI) is added in an amount of about 3.5 molar equivalents relative to 1 mol of POL (at this time, the amount of water in the POL mixture is measured by the Karl Fischer method, and can be consumed by hydrolysis) The amount of MDI is calculated and MDI is added in excess (here, about 3.5 mol is used as an example). When set, the internal temperature was set to about 80 ° C., and stirring was further continued at about 80 ° C. During that time, the content of free isocyanate groups in the reaction solution was appropriately measured, and when all the isocyanate groups were consumed. The desired polyurethane resin can be obtained by stopping the reaction with (and completing the reaction) and purifying by a known purification method.

  According to the production method of the present invention, a novel polyalkylene carbonate diol copolymer in which an inexpensive alkali metal compound is used as a reaction catalyst and the composition of the diol component is controlled without using an excessive amount of alkylene diol. A polymer can be obtained.

  The polyalkylene carbonate diol and its copolymer obtained by the method of the present invention can be used as, for example, a paint, an adhesive, a paper processing agent, a thickener for an aqueous lubricant, an additive thereof, and the like. It can also be used as a so-called rheology control agent that controls and adjusts physical properties such as viscosity and fluidity of solutions and substances according to the purpose and purpose of the material used. Accordingly, the cured resin product obtained by using the polyalkylene carbonate diol and / or copolymer thereof of the present invention as, for example, a raw material compound for producing a thermoplastic polymer or a polyalkylene carbonate diol material for producing a polyurethane resin. There is also an advantage that the mechanical strength of polyurethane resin can be improved, and it can be expected to be widely used in various material fields.

Claims (11)

A polyalkylene carbonate diol having a molecular structure of a repeating unit represented by the following formula (A) and having a hydroxyl group at the molecular end.

[In the formula (A), Z represents a group represented by the following formulas (Z ¹ ) to (Z ⁴ ). ]

(In the formulas (Z ¹ ) to (Z ⁴ ), X and Y are substituted with a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. Each represents a methylene group or an alkylamino group having 1 to 4 carbon atoms, X and Y may be the same or different from each other, and p and q each represent the number of methylene groups, p represents an integer of 1 or 2, q represents an integer of 0, 1 or 2. Here, p and q may be the same or different from each other, L ¹ is a single bond, One of an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a fluorine atom, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms is shown. ^(Z 1) in ~ ^{(Z 4),} wavy line Bond denoted shows the binding of carbonate groups (-O-CO-O-) oxygen atoms and cyclic molecules any carbon atom on the backbone of.) The polyalkylene carbonate diol copolymer which has the molecular structure of the repeating unit shown by following formula (A) and 1 or more types of formula (B), and a molecular terminal is a hydroxyl group.

(In the formula (A), Z represents a cyclic alkylene group represented by the following formulas (Z ¹ ) to (Z ⁴ ).)

(In the formulas (Z ¹ ) to (Z ⁴ ), X and Y are methylenes substituted with a single bond, oxygen atom, sulfur atom, sulfonyl group, carbonyl group, fluorine atom or alkyl group having 1 to 4 carbon atoms. Each represents a group or an alkylamino group having 1 to 4 carbon atoms, and X and Y may be the same as or different from each other, and p and q each represent the number of methylene groups; Represents an integer of 1 or 2, q represents an integer of 0, 1 or 2. Here, p and q may be the same or different from each other, L ¹ represents a single bond, oxygen One of an atom, a sulfur atom, a sulfonyl group, a carbonyl group, a fluorine atom, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms is shown. in ^{Z 1) ~ (Z 4)} , the wavy line Binding indicates the bond between the oxygen atom and the cyclic molecule any carbon atom on the backbone of carbonate groups (-O-CO-O-). However, in the formula ^{(Z 3), p = 1} , q = 0 (Single bond) and X and Y are both oxygen atoms are excluded.)

(In formula (2), n and m each represent an integer of 1 to 6, and n and m may be the same or different from each other. L ² represents a single bond, an oxygen atom, or sulfur. Any one of an atom, a sulfonyl group, a carbonyl group, a fluorine atom, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms is shown.)   Content ratio of the molecular structure of the repeating unit represented by the formula (A) in one molecule and the molecular structure of the repeating unit represented by one or more formulas (B) (total number of molecular structures of the formula (B): The polyalkylene carbonate diol copolymer according to claim 2, wherein the number of molecular structures A) is from 80:20 to 20:80. ^The polyalkylene carbonate diol according to claim 1, wherein the number average molecular weight calculated from ¹ H-NMR spectrum analysis is 500 to 3,000. ^The polyalkylene carbonate diol copolymer according to claim 2 or 3, wherein the number average molecular weight calculated by ¹ H-NMR spectrum analysis is 500 to 3000. The cyclic alkylene diol represented by the following formula (1) and one or more carbonates represented by the following formula (3) are reacted at a reaction temperature of 80 to 150 ° C in the presence of an alkali metal compound. A process for producing a polyalkylene carbonate diol as described in 1 above.

(In the formula (1), Z represents a group represented by the following formulas (Z ¹ ) to (Z ⁴ ).]

(In the formulas (Z ¹ ) to (Z ⁴ ), X and Y are a single bond, an oxygen atom, a sulfur atom, a methylene group (—CH ₂ —), a sulfonyl group, a carbonyl group, or a carbon atom having 1 to 4 carbon atoms. Each represents an alkylamino group, and X and Y may be the same or different from each other, p and q represent the number of methylene groups, p represents an integer of 1 or 2, and q represents Represents an integer of 0, 1 or 2. Here, p and q may be the same or different from each other, L ¹ is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, Or a methylene group substituted with an alkylamino group having 1 to 4 carbon atoms, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and a wavy line in the formulas (Z ¹ ) to (Z ⁴ ). The bond is an oxygen atom of the hydroxyl group and any Shows the binding of atom. However, the formula in ^{(Z 3), p = 1} , q = 0, and that of X and Y are both oxygen atoms are excluded.)

(In Formula (3), R ¹ and R ² may have a fluorine atom and may have a C 1-6 alkyl group; a benzyl group; an allyl group; a halogen atom or a fluorine atom. An alkyl group having 1 to 6 carbon atoms, and a phenyl group having 6 to 18 carbon atoms that may have an alkyloxy group having 1 to 6 carbon atoms which may have a fluorine atom, and R ¹ and R ² are They may be the same as or different from each other, provided that the carbon number of the carbonate represented by the formula (3) is 3 to 37.) In the presence of an alkali metal compound, a cyclic alkylene diol represented by the following formula (1), one or more linear alkylene diols represented by the following formula (2), and one or more carbonates represented by the following formula (3): The method for producing a polyalkylene carbonate diol copolymer according to claim 2 or 3, wherein the reaction is performed at a reaction temperature of 80 to 150 ° C.

(In the formula (1), Z represents a group represented by the following formulas (Z ¹ ) to (Z ⁴ ).]

(In the formulas (Z ¹ ) to (Z ⁴ ), X and Y are a single bond, an oxygen atom, a sulfur atom, a methylene group (—CH ₂ —), a sulfonyl group, a carbonyl group, or a carbon atom having 1 to 4 carbon atoms. Each represents an alkylamino group, and X and Y may be the same or different from each other, p and q represent the number of methylene groups, p represents an integer of 1 or 2, and q represents Represents an integer of 0, 1 or 2. Here, p and q may be the same or different from each other, L ¹ is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, Or a methylene group substituted with an alkylamino group having 1 to 4 carbon atoms, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and a wavy line in the formulas (Z ¹ ) to (Z ⁴ ). The bond is an oxygen atom of the hydroxyl group and any Shows the binding of atom. However, the formula in ^{(Z 3), p = 1} , q = 0, and that of X and Y are both oxygen atoms are excluded.)

(In formula (2), n and m each represent an integer of 1 to 6, and n and m may be the same or different from each other. L ² represents a single bond, an oxygen atom, or sulfur. Any one of an atom, a sulfonyl group, a carbonyl group, a fluorine atom, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms is shown.)

(In Formula (3), R ¹ and R ² may have a fluorine atom and may have a C 1-6 alkyl group; a benzyl group; an allyl group; a halogen atom or a fluorine atom. An alkyl group having 1 to 6 carbon atoms, and a phenyl group having 6 to 18 carbon atoms that may have an alkyloxy group having 1 to 6 carbon atoms which may have a fluorine atom, and R ¹ and R ² are They may be the same as or different from each other, provided that the carbon number of the carbonate represented by the formula (3) is 3 to 37.)   The alkali metal compound is lithium methoxide, lithium ethoxide, lithium isopropoxide, lithium t-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium The method for producing a polyalkylene carbonate diol or a copolymer thereof according to claim 6 or 7, which is at least one alkali metal alkoxide selected from the group consisting of isopropoxide and sodium t-butoxide.   The linear alkylene diol represented by the formula (2) is 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 One or more selected from the group consisting of 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, or 1,12-dodecanediol. The method for producing a polyalkylene carbonate copolymer according to claim 7, which is a linear alkylene diol.   A polyalkylene carbonate for producing polyurethane, wherein the molecular end according to claim 1 is a hydroxyl group.   The polyalkylene carbonate diol copolymer for polyurethane resin manufacture whose molecular terminal of Claim 2 or Claim 3 is a hydroxyl group.