JP2012214723A - Poly (branched-chain alkylene) carbonate diol and poly (branched-chain alkylene) carbonate diol copolymer, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate diol useful as a raw material of polyurethane and a thermoplastic elastomer or the like, and excellent in thermal stability and hydrolysis resistance.SOLUTION: The novel poly (branched-chain alkylene) carbonate diol uses a branched-chain alkylene diol in which at least one hydroxyl group (OH group) bonds to a secondary or tertiary carbon atom, and a specific carbonate as raw materials; a poly (branched-chain alkylene) carbonate diol copolymer uses at least two kinds of different branched-chain alkylene diols, and a specific carbonate as raw materials; and methods of manufacturing the same are disclosed. The obtained novel poly (branched-chain alkylene) carbonate diol and poly (branched-chain alkylene) carbonate diol copolymer can be used industrially and widely for instance as a coating, a coating agent or the like for the appearance in an automotive field and an OA equipment field.

Description

  The present invention provides a poly (branched alkylene) carbonate diol and a poly (branched alkylene) carbonate diol copolymer having excellent hydrolysis resistance and handling property at room temperature using a branched alkylene diol. The present invention relates to coalescence and methods for producing them.

  In general, polyalkylene carbonate diol is expected as a material excellent in, for example, excellent transparency, impact resistance, heat resistance and the like, and is useful as a raw material for soft segments such as polyurethane and thermoplastic elastomer.

In the production of polyalkylene carbonate diols, alkylene diols are used as one component of raw materials, and so far, for example, linear alkylene diols such as 1,6-hexanediol, cyclohexanedimethanol, tricycloalkanedimethanol and the like. Alkylene diols having an alicyclic skeleton and alkylene diols such as aromatic dimethanol such as benzene dimethanol have been widely used (see, for example, Patent Documents 1 to 3). For the purpose of lowering the melting point of the polyalkylene carbonate diol, for example, in the middle of the alkylene main chain such as 2,2-dialkyl-1,3-propanediol and 2,4-dialkyl-1,5-pentanediol. A production example of a polyalkylene carbonate diol using an alkylene diol having a branched chain has already been reported (for example, see Patent Document 4). However, for example, when the polyalkylene carbonate diol having a branched alkylene group is used as a raw material for polyurethane, since the raw material polyalkylene carbonate diol has a low melting point, handling during production is improved. However, in exchange, the manufactured polyurethane has a problem that material properties such as light resistance and oxidation deterioration resistance may be deteriorated.
Furthermore, conventional polyalkylene carbonate diols have a hydroxymethyl skeleton (HO) in which a hydroxyl group (OH group) as mentioned above is bonded to a primary carbon atom because of the restrictions on the synthesis thereof. Those having —CH ₂ —) have been mainly used.

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

  On the other hand, no polyalkylene carbonate diol using a branched alkylene diol in which at least one hydroxyl group (OH group) is bonded to a secondary or tertiary carbon atom has not been known so far. As one of the reasons, for example, when the diol compound is used as a raw material, it is considered that interester transesterification polymerization reaction hardly occurs and a desired polyalkylene carbonate diol is hardly obtained.

  Therefore, the present invention is excellent in hydrolysis resistance, has a good balance with heat resistance stability, and, for example, a polyalkylene carbonate diol that can exhibit good physical properties even when used as a raw material for polyurethane, or An object is to provide a polyalkylene carbonate diol copolymer. More specifically, a novel poly (branched alkylene) carbonate diol using an alkylene diol having a branched alkylene group in which at least one hydroxyl group (OH) group is bonded to a secondary or tertiary carbon atom, and It is to provide a poly (branched alkylene) carbonate diol copolymer and a method for producing them.

  Specifically, an object of the present invention is to use an alkylene diol containing at least one kind of branched alkylene diol, which is shown by the following inventions [1] to [12]. It is solved by (alkylene) carbonate diol, poly (branched alkylene) carbonate diol copolymer, and their production method.

  [1] A poly (branched alkylene) carbonate diol represented by the formula (1).

(In the formula (1),
R ¹ to R ⁴ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a fluorine atom, or an alkyl group having 1 to 6 carbon atoms that may be substituted with an alkyloxy group having 1 to 4 carbon atoms. It is an alkyl group. However, R ¹ to R ⁴ are not all hydrogen atoms.
Z represents a Z ¹ group represented by may be substituted with a fluorine atom alkylene group having 2 to 12 carbon atoms, or the following formula (2).

[In the formula (2), L represents an oxygen atom; a sulfur atom; a carbonyl group; a thiocarbonyl group; an amide group (—CONH—, —NHCO—); a sulfonyl group; a phosphonyl group; a halogen atom, having 1 to 4 carbon atoms. A phenylene group which may have an alkyl group or an alkyloxy group having 1 to 4 carbon atoms; a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms; Biphenylene group; one linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group optionally having an alkyloxy group having 1 to 4 carbon atoms. N and m represent the number of methylene groups and represent an integer of 1 to 6. ]
X represents the number of repeating units of the alkylene carbonate structure having Z, and is an arbitrary real number of 1 or more. )
[2] A poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by two or more different formulas (A).

(In the formula (A),
R ¹ to R ⁴ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a fluorine atom, or an alkyl group having 1 to 6 carbon atoms that may be substituted with an alkyloxy group having 1 to 4 carbon atoms. It is an alkyl group. However, R ¹ to R ⁴ are not all hydrogen atoms.
Z represents a Z ¹ group represented by may be substituted with a fluorine atom alkylene group having 2 to 12 carbon atoms, or the following formula (2).

[In the formula (2), L represents an oxygen atom; a sulfur atom; a carbonyl group; a thiocarbonyl group; an amide group (—CONH—, —NHCO—); a sulfonyl group; a phosphonyl group; a halogen atom, having 1 to 4 carbon atoms. A phenylene group which may have an alkyl group or an alkyloxy group having 1 to 4 carbon atoms; a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms; Biphenylene group; one linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group optionally having an alkyloxy group having 1 to 4 carbon atoms. N and m represent the number of methylene groups and represent an integer of 1 to 6. ]
X represents the number of repeating units of the alkylene carbonate structure having Z, and is an arbitrary real number of 1 or more. )
[3] A poly (branched alkylene) carbonate diol copolymer having at least one molecular structure represented by the formula (A) and at least one molecular structure represented by the formula (B).

(In formula (A), R ¹ to R ⁴ and X are the same as those in formula (A)).

(In the formula (B), Y represents the number of repeating units of the methylene carbonate structure represented by the formula (B) and is an arbitrary real number of 1 or more, and k represents the number of methylene groups. To an integer from 12 to 12.)
[4] A formula in which a branched alkylene diol represented by the formula (3) is reacted with at least one carbonate selected from the group consisting of the formula (4) and the formula (5) in the presence of an alkali metal compound. A method for producing a poly (branched alkylene) carbonate diol represented by (1).

(In the formula (1),
R ¹ to R ⁴ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a fluorine atom, or an alkyl group having 1 to 6 carbon atoms that may be substituted with an alkyloxy group having 1 to 4 carbon atoms. It is an alkyl group. However, R ¹ to R ⁴ are not all hydrogen atoms.
Z is an alkylene group having 2 to 12 carbon atoms which may be substituted by a fluorine atom, or an Z ¹ group represented by the formula (2).

[In the formula (2), L represents an oxygen atom; a sulfur atom; a carbonyl group; a thiocarbonyl group; an amide group (—CONH—, —NHCO—); a sulfonyl group; a phosphonyl group; a halogen atom, having 1 to 4 carbon atoms. A phenylene group which may have an alkyl group or an alkyloxy group having 1 to 4 carbon atoms; a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms; Biphenylene group; one linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group optionally having an alkyloxy group having 1 to 4 carbon atoms. N and m represent the number of methylene groups and represent an integer of 1 to 6. ]
X represents the number of repeating units of the alkylene carbonate structure having Z, and is an arbitrary real number of 1 or more. )

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (1)).

(In the formula (4), R ⁵ and R ⁶ are alkyl groups of a fluorine atom or an alkyl group carbon atoms which may be substituted with 1-6 of 1 to 4 carbon atoms; a halogen atom, a nitro group, a cyano group , A phenyl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, wherein R ⁵ and R ⁶ are the same as each other, or Each may be different.)

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (1)).
[5] A method for producing a poly (branched alkylene) carbonate diol represented by the formula (1) according to the above [4], wherein at least one carbonate represented by the formula (4) is used as the carbonate.

  [6] Two or more different branched alkylene diols represented by formula (3) in the presence of an alkali metal compound, and at least one carbonate selected from the group consisting of formula (4) and formula (5) A process for producing a poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by two or more different formulas (A).

(In formula (A), R ¹ to R ⁴ , and Z and X are the same as those described in formula (A).)

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (3)).

(In Formula (4), R ⁵ and R ⁶ are the same as those described in Formula (4)).

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (5)).
[7] Poly (branched chain) having a molecular structure represented by two or more different formulas (A) according to [6], wherein at least one carbonate represented by the formula (4) is used as the carbonate. A process for producing an alkylene) carbonate diol copolymer.

  [8] In the presence of an alkali metal compound, at least one branched alkylene diol represented by formula (3), at least one linear alkylene diol having 2 to 12 carbon atoms, and formula (4) and formula (5) and at least one carbonate selected from the group consisting of carbonates represented by formula (8) are reacted with at least one molecular structure represented by the following formula (A) and at least one following formula (B The manufacturing method of the poly (branched alkylene) carbonate diol copolymer which has the molecular structure shown by this.

(In the formula (A), R ¹ to R ⁴ and X are the same as those in the above (1).)

(In the formula (B), Y represents the number of repeating units of the methylene carbonate structure represented by the formula (B) and is an arbitrary real number of 1 or more, and k represents the number of methylene groups. To an integer from 12 to 12.)

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (3)).

(In Formula (4), R ⁵ and R ⁶ are the same as those described in Formula (4)).

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (5)).
[9] As the carbonate, at least one carbonate represented by the formula (4) is used, and at least one molecular structure represented by the formula (A) according to the above [8] and at least one kind of the above A method for producing a poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by the formula (B).

  [10] Selected from the group consisting of alcohols represented by formula (6) and formula (7), which are by-produced by reaction at atmospheric pressure (101.133 kPa or less) and at a reaction solution temperature of 150 ° C. or less. 70% by mass or more of at least one alcohol is first distilled off with respect to the theoretical production amount (mass), and then the reaction pressure is reduced to the atmospheric pressure or less, and the remaining by-product alcohol is removed. The manufacturing method of the poly (branched alkylene) carbonate diol shown by said Formula (1) as described in said [5] distilled off.

(In Formula (6), R ⁵ is the same as that described in Formula (4).)

(In Formula (7), R ⁵ is the same as that described in Formula (4).)
[11] From the group consisting of alcohols represented by the above formula (6) and the above formula (7), which are by-produced by reaction at atmospheric pressure (101.133 kPa or less) and at a reaction solution temperature of 150 ° C. or less. At least one selected alcohol is first distilled off at least 70% by mass with respect to the theoretical production amount (mass), then the reaction pressure is reduced to atmospheric pressure or less, and the remaining by-produced alcohol is removed. A method for producing a poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by two or more different formulas (A) according to [7], which is distilled off.

  [12] From the group consisting of alcohols represented by the above formula (6) and the above formula (7), which are by-produced by reaction at atmospheric pressure (101.133 kPa or less) and at a reaction solution temperature of 150 ° C. or less. At least one selected alcohol is first distilled off at least 70% by mass with respect to the theoretical production amount (mass), then the reaction pressure is reduced to atmospheric pressure or less, and the remaining by-produced alcohol is removed. The poly (branched alkylene) having at least one molecular structure represented by the formula (A) and at least one molecular structure represented by the formula (B) as described in [9] A method for producing a carbonate diol copolymer.

From the alkylene diol having a branched alkylene group in which at least one hydroxyl group (OH group) is bonded to a secondary or tertiary carbon atom by the production method of the present invention, a novel poly (branched alkylene) carbonate diol Alternatively, a poly (branched alkylene) carbonate diol copolymer can be obtained.
The novel poly (branched alkylene) carbonate diol or poly (branched alkylene) carbonate diol copolymer of the present invention has at least one branched alkylene group in the main chain structure of the polyalkylene carbonate. Due to the structural factors, it has a low melting point. Therefore, since the poly (branched alkylene) carbonate diol or the poly (branched alkylene) carbonate diol copolymer of the present invention is in a liquid state even at room temperature (30 ° C. or lower), the handling is good. In addition, since it has heat stability derived from a carbonate bond, it is a compound that can be suitably used industrially.
Furthermore, the poly (branched alkylene) carbonate diol copolymer obtained by the production method of the present invention has a novel alkylene main chain structure in which at least one carbon atom adjacent to the carbonate bond is composed of a carbon atom having a branched chain. A good polymer. Therefore, it is a compound exhibiting better hydrolysis resistance due to inhibition of hydrolysis by external degradation promoting factors, particularly moisture and water, due to the influence of the three-dimensional structure by the branched chain.
From the above characteristics, the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer of the present invention are, for example, exterior paints, coating agents in the automotive field and OA equipment field, It can be used as a constituent material such as an adhesive.
Further, when the poly (branched alkylene) carbonate diol of the present invention and the poly (branched alkylene) carbonate diol copolymer are used as raw materials for producing polyurethane, the obtained novel polyurethane is, for example, It is expected to improve the low weather resistance and low deterioration resistance as seen in the polyurethane of Patent Document 4, and therefore, it can be expected to be widely used in various material fields.

The present invention uses at least one alkylene diol containing a branched alkylene diol represented by the following formula (3), poly (branched alkylene) carbonate diol, and poly (branched chain) The present invention relates to a method for producing an alkylene) carbonate diol copolymer.
≪Production raw materials≫
Next, the raw materials for producing the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer of the present invention will be described.

<Alkylene diol used in the present invention>
As the alkylene diol used in the present invention, an alkylene diol containing at least one branched alkylene diol represented by the following formula (3) is used.
Furthermore, since this invention also includes the method of manufacturing the poly (branched alkylene) carbonate diol copolymer (II) of this invention mentioned later, as alkylene diol used by this invention, at least 1 sort (s) of the following An alkylene diol comprising a branched alkylene diol represented by the formula (3) and at least one linear alkylene diol having 2 to 12 carbon atoms is also used.

(Branched alkylene diol represented by the formula (3))
The branched alkylene diol represented by the formula (3) used in the present invention is an alkylene having 4 to 36 carbon atoms in which at least one hydroxyl group of two hydroxyl groups is bonded to a secondary or tertiary carbon atom. Diol. In addition, the branched alkylene diol represented by the formula (3) of the present invention may be used alone or in combination.

In Formula (3), R ¹ to R ⁴ are substituted with a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, or an alkyloxy group having 1 to 4 carbon atoms. It may be an alkyl group having 1 to 6 carbon atoms. However, R ¹ to R ⁴ are not all hydrogen atoms. The alkyl group in R ¹ to R ⁴ is a linear or branched alkyl group, and further includes a positional isomer in the case of a branched chain.

Z represents a C 1-12 alkylene group which may be substituted with a fluorine atom, or a Z ¹ group represented by the following formula (2).

In Z ¹ of formula (2), L represents an oxygen atom; a sulfur atom; a carbonyl group; a thiocarbonyl group; an amide group (—CONH—, —NHCO—); a sulfonyl group; a phosphonyl group; A phenylene group optionally having 4 alkyl groups or an alkyloxy group having 1 to 4 carbon atoms; a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms; A linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group that may have an alkyloxy group having 1 to 4 carbon atoms. N and m represent the number of methylene groups and represent an integer of 1 to 6.

From the above, as the branched alkylene diol represented by the formula (3),
Branched alkylene diols having 3 to 36 carbon atoms, such as 2,7-octanediol, 2,6-heptanediol, 2,5-hexanediol, 2,4-pentanediol, 1,4-pentanediol; , 2-cyclopropanediol, 1,3-cyclopentanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, etc., alicyclic alkylene diols having 3 to 36 carbon atoms; di (propylene glycol), di A hetero atom-containing alkylene diol having 3 to 36 carbon atoms and having an ether bond or a thioether bond such as (propylene thioglycol) is preferably used.
2,7-octanediol, 2,6-heptanediol, 2,5-hexanediol, 2,4-pentanediol, 1,4-pentanediol, 1,4-cyclohexanediol, di (propylene glycol), di ( Propylenethioglycol) is more preferably used.

(Linear alkylene diol)
Examples of the linear alkylene diol used in the present invention include 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentamethylene glycol, 1,6-hexa A linear alkylene diol having 1 to 12 carbon atoms having a hydroxyl group at both molecular ends such as methylene glycol is shown.

(how to get)
If there is a commercially available product, the alkylene diol used in the present invention may be used as it is. Those not commercially available are synthesized separately by a known method such as hydride reduction of the corresponding ketone compound or carboxylic acid compound. 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.

<Carbonates used in the present invention>
As the carbonate used in the present invention, at least one carbonate containing a carbonate represented by formula (4) or formula (5) is used.
Furthermore, since the present invention includes a method for producing the poly (branched alkylene) carbonate diol copolymer (II) of the present invention described later, the carbonate used in the present invention is represented by formula (4) or formula A carbonate comprising at least one carbonate including the carbonate represented by (5) and at least one carbonate represented by the formula (8) is also used.

(Carbonate represented by formula (4))
First, the carbonate represented by the following formula (4) used in the present invention will be described.

In the carbonate represented by the formula (4), R ⁵ and R ⁶ are each an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom; an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms An aryl group having 6 to 18 carbon atoms which may be substituted with an alkoxy group; a benzyl group or an allyl group; The carbon number of the carbonate represented by the formula (4) is 3 to 37. The alkyl group is a linear or branched alkyl group, and further includes a positional isomer in the case of a branched chain. In addition, the carbonate shown by Formula (4) of this invention may be used independently, or may be used multiple types.

From the above, as the carbonate represented by the formula (4) used in the present invention,
Symmetric carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and diisopropyl carbonate; at least one carbonate selected from the group consisting of asymmetric carbonates such as methyl ethyl carbonate, diphenyl carbonate, dibenzyl carbonate, and diallyl carbonate are preferably used. ;
More preferably at least one carbonate selected from the group consisting of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and diphenyl carbonate;
Dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate is particularly preferably used.

  In the production method of the present invention, the temperature of the reaction solution is lowered under the influence of the boiling point of the carbonate used, and the reaction may not proceed. Therefore, in order to avoid such a low reactivity state, a plurality of carbonates represented by the formula (4) may be used.

(Carbonate represented by formula (5))
Next, the carbonate represented by the following formula (5) used in the present invention will be described.

In carbonate represented by the formula (5), ^{R 1 to R 4} and Z are the same as each of ^{R 1} and ^{R 4} and Z in the formula (1). In addition, you may use together the carbonate shown by Formula (5) of this invention with the carbonate shown by the said Formula (4). In the present invention, when a carbonate represented by the formula (5) is used, a branched alkylene diol represented by the formula (3) is produced after the reaction. Therefore, for example, this may be used in the reaction of the present invention to produce the poly (branched alkylene) carbonate diol or the poly (branched alkylene) carbonate diol copolymer of the present invention.

  Examples of the carbonate represented by the formula (5) include 1-methylethylene carbonate (4-methyl-1,3-dioxolan-2-one), 1,1-dimethylethylene carbonate (4,4-dimethyl-1, 3-dioxolan-2-one), 1,2-dimethylethylene carbonate (4,5-dimethyl-1,3-dioxolan-2-one), 1-ethylethylene carbonate (4-ethyl-1,3-dioxolan- 2-one), 1-ethyl-2-methylethylene carbonate (4-ethyl-5-methyl-1,3-dioxolan-2-one), 1,1-diethylethylene carbonate (4,4-diethyl-1, 3-dioxolan-2-one), 1,2-diethylethylene carbonate (4,5-diethyl-1,3-dioxolan-2-one), 1-methylpropylene carbonate (4-methyl-1,3-dioxan- 2-one), 1,1-dimethylpropylene carbonate (4,4-dimethyl-1,3-dioxan-2-one), 1,2-dimethylpropylene carbonate (4,5-dimethyl-1,3-dioxan- 2-one), 1,3- Methyl propylene carbonate (4,6-dimethyl-1,3-dioxan-2-one), 1,1,3,3-tetramethyl propylene carbonate (4,4,6,6-tetramethyl-1,3-dioxan- 2-one), 1-ethylpropylene carbonate (4-ethyl-1,3-dioxan-2-one), 1,1-dimethylpropylene carbonate (4,4-dimethyl-1,3-dioxan-2-one) 1-ethyl-2-methylpropylene carbonate (4-ethyl-5-methyl-1,3-dioxan-2-one), 1-ethyl-3-methylpropylene carbonate (4-ethyl-6-methyl-1, 3-dioxan-2-one), 1-methyl-2-ethylpropylene carbonate (4-methyl-5-ethyl-1,3-dioxan-2-one), 1-ethyl-2-ethylpropylene carbonate (4, 5-diethyl-1,3-dioxan-2-one) or 1-ethyl-3-ethylpropylene carbonate (4,6-diethyl-1,3-dioxan-2-one) or the like is used.

(Carbonate represented by the formula (8))
Furthermore, the carbonate represented by the following formula (8), which can be used for producing the poly (branched alkylene) carbonate diol copolymer (II) of the present invention described later, will be described.

  In the carbonate represented by the formula (8) used in the present invention, k represents the number of methylene groups and represents an integer of 1 to 12.

  Examples of the carbonate represented by the formula (8) include linear carbonates having 3 to 13 carbon atoms such as ethylene carbonate, propylene carbonate, butylene carbonate, pentamethylene carbonate, hexamethylene carbonate, and the like.

(how to get)
If there exists a commercial item, the carbonate shown by Formula (4), Formula (5), or Formula (8) used by this invention may be used 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.

(Amount of carbonate used in the present invention)
In the production method of the present invention, the carbonate represented by the formula (4) may be used alone or in combination. Moreover, you may use it, mixing the carbonate shown by Formula (4), and the carbonate shown by Formula (5).
Furthermore, since this invention also includes the method of manufacturing the poly (branched alkylene) carbonate diol copolymer (II) of this invention mentioned later, the group which consists of carbonate shown by Formula (4) and Formula (5) A carbonate comprising at least one carbonate selected from the above and at least one carbonate represented by the formula (8) may be used as the carbonate used in the present invention.
In addition, the (total) usage amount of the carbonate of the present invention containing the carbonate represented by the formula (4), formula (5) and / or formula (8) is 1 (total) usage amount of the alkylene diol of the present invention. In the case of mol, 0.5 to 2 mol is preferably used, 0.8 to 2 mol is more preferably used, and 1 to 1.5 mol is particularly preferably used.

<Alkali metal compound used in the present invention>
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 salt, etc.).

As the alkali metal compound used in the present invention, an alkali metal alkoxide having 1 to 6 carbon atoms is preferably used,
Lithium methoxide, lithium ethoxide, lithium isopropoxide, lithium t-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, and More preferably, at least one alkali metal alkoxide selected from the group consisting of sodium t-butoxide is used,
At least one alkali metal alkoxide selected from the group consisting of potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, and sodium t-butoxide; More preferably used,
More preferably, at least one alkali metal alkoxide selected from the group consisting of potassium methoxide, potassium ethoxide, sodium methoxide, and sodium ethoxide,
Sodium methoxide or sodium ethoxide is particularly preferably used.

(Acquisition method or manufacturing method)
The alkali metal compound used in the present invention may be a commercially available product. For example, in the case of a metal alkoxide, it may be prepared separately from the corresponding alkali metal and alcohol.

(Amount of alkali metal compound used)
In the production method of the present invention, the alkali metal compound may be used alone or in combination.

Moreover, the (total) usage-amount of the said alkali metal compound should use the quantity used as 0.001-0.5 mass% (10-5000 ppm) with respect to the (total) usage-amount of the alkylene diol of this invention. Is preferred,
More preferably, an amount of 0.005 to 0.1% by mass (50 to 1000 ppm) is used,
It is particularly preferable to use an amount of 0.01 to 0.05% by mass (100 to 500 ppm).

  According to the production method of the present invention, by performing the reaction using the kind and amount of the alkali metal compound, the production of the olefin compound can be suppressed and the polymerization reaction can be favorably progressed. As a result, a poly (branched alkylene) carbonate diol represented by the formula (1) and a poly (branched alkylene) carbonate diol copolymer having a sufficient degree of polymerization (number average molecular weight) are obtained for the first time. Became.

<Reaction solvent used in the present invention>
The reaction of the present invention may be performed separately in the presence of a reaction solvent or in the absence.
Separately, when a reaction solvent is used, the reaction solvent that can be used is not particularly limited as long as it does not inhibit the reaction. For example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; dimethyl ether, diisopropyl ether, Ethers such as dimethoxyethane, cyclopentyl methyl ether and tetrahydrofuran; Nitriles such as acetonitrile and propionitrile; Aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons such as methylene chloride and chloroform; Dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone. As the reaction solvent, ethers, nitriles, and / or amides are preferably used. In addition, you may use these solvents individually or in mixture of 2 or more types, The usage-amount is adjusted suitably. 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 as much solvent as possible.

≪Manufacturing method≫
Next, the manufacturing method of the poly (branched alkylene) carbonate diol of this invention and a poly (branched alkylene) carbonate diol copolymer is demonstrated.

<Method for producing poly (branched alkylene) carbonate diol represented by the formula (1)>
The poly (branched alkylene) carbonate diol represented by the formula (1) of the present invention, the branched alkylene diol represented by the formula (3), the formula (4) or the formula (5) in the presence of an alkali metal compound. And at least one kind of carbonate represented by

(In formula (1), R ^{1 to} R ⁴ , Z and X are the same as those described in formula (1)).

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (1)).

(In Formula (4), R ⁵ and R ⁶ are the same as those described in Formula (4)).

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (1)).

<Method for producing poly (branched alkylene) carbonate diol copolymer of the present invention>
As a method for producing the poly (branched alkylene) carbonate diol copolymer of the present invention, for example, when two or more kinds of branched alkylene diols represented by the formula (3) are used, two or more different kinds of the above-mentioned A poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by the formula (A) (hereinafter, sometimes referred to as poly (branched alkylene) carbonate diol copolymer (I)) is obtained. .
Further, for example, when at least one branched alkylene diol represented by the formula (3) and at least one linear alkylene diol are used, at least one molecular structure represented by the formula (A) And a poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by at least one formula (B) (hereinafter referred to as poly (branched alkylene) carbonate diol copolymer (II)). Is obtained).

  In formula (B), Y represents the number of repeating units of the methylene carbonate structure represented by formula (B), and is an arbitrary real number of 1 or more. K represents the number of methylene groups and represents an integer of 1 to 12.

(Method for producing poly (branched alkylene) carbonate diol copolymer (I))
The poly (branched alkylene) carbonate diol copolymer (I) having two or more different molecular structures represented by the formula (A) of the present invention is represented by the formula (3) in the presence of an alkali metal compound. It is produced by a method in which the branched alkylene diol is reacted with at least one carbonate selected from the group consisting of formula (4) and formula (5).

(In formula (A), R ¹ to R ⁴ , and Z and X are the same as those described in formula (1)).

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (3)).

(In Formula (4), R ⁵ and R ⁶ are the same as those described in Formula (4)).

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (5)).

(Method for producing poly (branched alkylene) carbonate diol copolymer (II))
The poly (branched alkylene) carbonate diol copolymer (II) having at least one molecular structure represented by the formula (A) and at least one molecular structure represented by the formula (B) of the present invention is an alkali. In the presence of a metal compound, at least one selected from the group consisting of at least one branched alkylene diol represented by the formula (3) and a carbonate represented by the formula (4), the formula (5) and the formula (8). Produced by a method of reacting a seed carbonate.

(In the formula (A), R ¹ to R ⁴ and X are the same as those described in the above (1).)

(In formula (B), Y and k are respectively the same as those described in (B).)

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (3)).

(In Formula (4), R ⁵ and R ⁶ are the same as those described in Formula (4)).

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (5)).

<Reaction method, reaction equipment>
The method for producing the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer of the present invention is used in the present invention and the alkylene diol used in the present invention in the presence of an alkali metal compound. In a polymerization reaction by transesterification, which is carried out by mixing with carbonates under heating in the presence or absence of a reaction solvent, atmospheric pressure or reduced pressure, and / or in an inert gas stream. is there.
In addition, the production method of the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer of the present invention may be any method such as a batch method or a continuous method.
Therefore, as reaction equipment to be used, specifically, a stirred tank reactor, a thin film reactor, a centrifugal thin film evaporation reactor, a surface renewal type biaxial kneading reactor, a biaxial horizontal stirring reactor, a wet wall type Examples thereof include, but are not particularly limited to, a reactor, a perforated plate reactor that polymerizes while being dropped freely, and a perforated plate reactor with a wire that polymerizes while dropping along a wire. These polymerization devices may be used alone or in combination. Furthermore, there is no restriction | limiting in particular also about the material of these superposition | polymerization apparatuses, For example, it selects and uses suitably from stainless steel, nickel, or glass lining etc., for example.

<Reaction conditions>
(Reaction temperature and reaction pressure)
The reaction temperature of the reaction of the present invention is preferably 90 ° C to 150 ° C, more preferably 100 ° C to 140 ° C. The reaction pressure is preferably 0.01 kPa to 102 kPa (absolute pressure), more preferably 0.01 kPa to 20 kPa (absolute pressure). It is desirable that the reaction system (reaction environment) is under non-aqueous conditions.
The polymerization reaction of the present invention is an equilibrium reaction, and the polymerization reaction can be promoted by biasing the reaction equilibrium toward the product side by heating or reduced pressure.
Then, as one of the suitable manufacturing methods of this invention, when using at least 1 sort (s) of carbonate shown by said Formula (4) as a carbonate, for example, the formula (as a by-product as needed during reaction) ( 6) and at least one alcohol selected from the group consisting of alcohols represented by the formula (7) is extracted from the reaction system while the reaction is carried out until a desired molecular weight (for example, number average molecular weight) is reached. Examples thereof include a method of obtaining a (branched alkylene) carbonate diol or a poly (branched alkylene) carbonate diol copolymer.

(In Formula (6), R ⁵ is the same as that described in Formula (4)).

(In Formula (7), R ⁵ is the same as that described in Formula (4)).

  More specific operation methods include, for example, at least one branched chain alkylene diol of the present invention (and under reaction conditions of atmospheric pressure (101.133 kPa or less) and a reaction liquid temperature of 150 ° C. or less). At least one linear alkylene diol) and at least one carbonate represented by the formula (4), and a group consisting of alcohols represented by the formula (6) and the formula (7) produced as a by-product. 70% by mass or more of the at least one alcohol selected from the theoretically generated amount (mass) is first distilled off, and then the reaction pressure is reduced to the atmospheric pressure or less, and the remaining by-produced alcohol By a method for producing poly (branched alkylene) carbonate diol or poly (branched alkylene) carbonate diol copolymer It is.

<< Poly (branched alkylene) carbonate diol of the present invention >>
As mentioned above, according to the manufacturing method of this invention, the novel poly (branched alkylene) carbonate diol shown by following formula (1) is obtained.

In the poly (branched alkylene) carbonate diol represented by the formula (1) of the present invention,
R ¹ to R ⁴ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a fluorine atom, or an alkyl group having 1 to 6 carbon atoms that may be substituted with an alkyloxy group having 1 to 4 carbon atoms. It is an alkyl group. However, R ¹ to R ⁴ are not all hydrogen atoms.
X represents the number of repeating units of the alkylene carbonate structure, and is an arbitrary real number of 1 or more.
Z represents a Z ¹ group represented by may be substituted with a fluorine atom alkylene group having 2 to 12 carbon atoms, or the following formula (2).

  In the formula (2), L represents an oxygen atom; a sulfur atom; a carbonyl group; a thiocarbonyl group; an amide group (—CONH—, —NHCO—); a sulfonyl group; a phosphonyl group; a halogen atom, an alkyl having 1 to 4 carbon atoms. Group or a phenylene group optionally having an alkyloxy group having 1 to 4 carbon atoms; a biphenylene optionally having a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms Group; one linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group which may have an alkyloxy group having 1 to 4 carbon atoms. N and m represent the number of methylene groups and represent an integer of 1 to 6.

<< Poly (branched alkylene) carbonate diol copolymer of the present invention >>
Further, according to the production method of the present invention, for example, the poly (branched alkylene) carbonate diol copolymer (I) having two or more different molecular structures represented by the formula (A), at least one kind, The poly (branched alkylene) carbonate diol copolymer (II) having a molecular structure represented by the formula (A) and at least one molecular structure represented by the formula (B) is obtained.

<Poly (branched alkylene) carbonate diol copolymer (I)>
As the poly (branched alkylene) carbonate diol copolymer (I) of the present invention, for example, when two types of branched alkylene diols represented by the above formula (3) are used, from the production method of the present invention, A poly (branched alkylene) carbonate diol copolymer (I) having a molecular structure represented by the following formulas (Aa) and (Ab) is obtained.

Here, in Formula (Aa) and Formula (Ab),
R ^1a to R ^4a and R ^1b to R ^4b are the same as R ¹ to R ^{4 in} the formula (A), respectively. However, Formula (Aa) and Formula (Ab) show the molecular structures of different repeating units.
^Xa and ^Xb represent the number of repeating units of the alkylene carbonate structure represented by the formulas (Aa) and (Ab), and are any real number of 1 or more.
Z ^a and Z ^b are each represented by a single bond, an alkylene group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, or the following formula (2a) and formula (2b).

Here, ^{L a} and ^{L b} represents an oxygen atom; a sulfur atom; carbonyl group; a thiocarbonyl group; amide group (-CONH -, - NHCO-); a sulfonyl group; a phosphonyl group; a halogen atom, 1 to 4 carbon atoms A phenylene group which may have an alkyl group or an alkyloxy group having 1 to 4 carbon atoms; a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms; Biphenylene group; one linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group optionally having an alkyloxy group having 1 to 4 carbon atoms. Further, _{n a} and m _a, sequence _{n b} and _{m b} each represent the number of methylene group, an integer of 1 to 6.

  Further, as described above, when three or more kinds of branched alkylene diols of the formula (3) are used, a poly (branched chain) having three or more kinds of molecular structures represented by the formula (A) as described above. -Like alkylene) carbonate diol copolymer is obtained.

<Poly (branched alkylene) carbonate diol copolymer (II)>
On the other hand, as the poly (branched alkylene) carbonate diol copolymer (II) of the present invention, for example, at least one branched alkylene diol represented by the formula (3) and at least one linear chain When alkylene diol is used, poly (branched alkylene) carbonate diol copolymer having at least one molecular structure represented by the following formula (A) and at least one molecular structure represented by the following formula (B) Combined (II) is obtained.

(In the formula (A), R ¹ to R ⁴ and X are the same as those in the above (1)).

  In formula (B), Y represents the number of repeating units of the methylene carbonate structure represented by formula (B), and is an arbitrary real number of 1 or more. K represents the number of methylene groups and represents an integer of 1 to 12.

(Number average molecular weight of poly (branched alkylene) carbonate diol or poly (branched alkylene) carbonate diol copolymer)
The novel poly (branched alkylene) carbonate diol represented by the formula (1) of the present invention, or the poly (branched alkylene) carbonate diol copolymer (I) or the poly (branched alkylene) carbonate The number average molecular weight of the diol copolymer (II) is preferably 300 to 5,000, more preferably 500 to 3,000, and particularly preferably 500 to 2,000. Here, the number average molecular weight may be, for example, a number average molecular weight calculated from a ¹ H-NMR spectrum by a known method, or a number average molecular weight calculated from a hydroxyl value measurement. The number average molecular weight calculated from (GPC: standard substance; polystyrene) may be calculated from either case.
Further, the number of repeating units Xa and Xb of the novel poly (branched alkylene) carbonate diol copolymer (I) represented by the formula (1), and the poly (branched alkylene) carbonate diol copolymer (II) The number of repeating units Xa and Y are real numbers satisfying the number average molecular weight calculated above.

  Since the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer of the present invention have at least one branched alkylene group in the polyalkylene carbonate main chain, Because of the factors, it has the property of having a lower melting point than conventional polyalkylene carbonate diols. Therefore, the novel poly (branched alkylene) carbonate diol of the present invention has heat resistance stability derived from a carbonate bond, and also has good handling (operability and workability) because it is liquid even at room temperature, for example. Therefore, it can be used without problems even in a confined environment or in a fine part where it has been difficult to use.

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

≪Analysis method≫
<Calculation method of number average molecular weight of poly (branched alkylene) carbonate diol and poly (branched alkylene) carbonate diol copolymer of the present invention>
(Measurement of ¹ H-NMR)
The poly (branched alkylene) carbonate diol or poly (branched alkylene) carbonate diol copolymer represented by the formula (1) obtained in the present invention is dissolved in deuterated chloroform or deuterated acetonitrile, respectively. A sample for measurement was prepared, and ¹ H-NMR spectrum was measured by non-decoupling using NMR (“AVANCE 500 type”, manufactured by Bruker Biospin).

(Calculation method of the number of molecular structures of repeating units)
The number of molecular structures of the repeating unit was calculated with reference to “Nuclear Magnetic Resonance of Polymers (Edited Committee for Polymer Experimental Studies, Society of Polymer Science, Kyoritsu Shuppan, pages 282 to 285)”.

More specifically, from the ¹ H-NMR spectrum data obtained above, a methine moiety adjacent to the hydroxyl group at the molecular end or a hydrogen atom in the methylene moiety (value of chemical shift in 1H-NMR: 3.50 3. The value of chemical shift in ¹ H-NMR: 4.50 to 4.4 at a hydrogen atom in a methine site or a methylene site adjacent to the carbonate group in the polycarbonate main chain when the integrated value of 1.80 ppm is 1. The ratio of the integral values of 80 ppm or 4.00 to 4.20 ppm is shown as X, which is the number of molecular structures of the repeating units shown in the formula (3) and the formula (A), and is compared in the same manner. and from the integrated value of the formula (a-a), formula (a-b) number molecular structure of the repeating unit represented in _the, X a, indicated as _{X b.}

(Calculation method of number average molecular weight)
The number average molecular weight of the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer represented by the formula (1) obtained in the present invention is the number of repeating units calculated above. It is calculated by adding the molecular weight of the molecular structure of the terminal portion to the product of the number of molecular structures (X, _Xa or _Xb ) and the molecular weight of the molecular structure of the repeating unit. For example, when two or more kinds of branched alkylene diols represented by the formula (3) are used, the number average molecular weight of the obtained poly (branched alkylene) carbonate diol copolymer is the above ¹ H-NMR spectrum. The composition ratio was calculated from the analysis and the amount of raw material charged and recovered.

<Method of measuring thermal behavior of poly (branched alkylene) carbonate diol and poly (branched alkylene) carbonate diol copolymer of the present invention>
The melting point and the glass transition point of the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer obtained in the present invention are measured with a differential scanning calorimeter (DSC) in the range of- Measurement was performed at 100 to 150 ° C.

<Method for Measuring Viscosity of Poly (Branched Alkylene) Carbonate Diol and Poly (Branched Alkylene) Carbonate Diol Copolymer of the Present Invention>
The viscosity of the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer obtained in the present invention was measured using an E-type rotational viscometer ("Programmable Digital Viscometer DV-II +", Brookfield). ).

<Calculation method of terminal hydroxyl group purity of poly (branched alkylene) carbonate diol and poly (branched alkylene) carbonate diol copolymer of the present invention>
In the present invention, the ratio of the terminal group of the obtained poly (branched alkylene) carbonate diol and poly (branched alkylene) carbonate diol copolymer to a hydroxyl group was calculated as the terminal hydroxyl group purity. The terminal hydroxyl group purity is determined from the obtained ¹ H-NMR spectrum data by a hydrogen atom at the methine moiety or methylene moiety adjacent to the terminal hydroxyl group (value of chemical shift in ¹ H-NMR: 3.50 to 3.80 ppm). The integral value of A is A (in the case of methylene, A / 2), the integral value of one proton of the hydrogen atom of the olefin site (value of chemical shift in 1H-NMR: 5.20 to 6.00 ppm) is B, numerator When the integrated value of the hydrogen atom of the methyl group portion of the terminal methyl carbonate group (value of chemical shift in ¹ H-NMR: 3.65 to 3.85 ppm) is C, A / (A + B + [C / 3 ]) Is a value further expressed as a percentage (%).

Example 1 (Synthesis of poly (branched alkylene) carbonate diol)
In a glass flask having an internal volume of 200 ml equipped with a stirrer, a heating device, a distillation device, and a thermometer, 62.77 g (0.53 mol) of 2,5-hexanediol, 47.85 g (0.53 mol) and 28 of dimethyl carbonate were added. A 20 mg% sodium methoxide-methanol solution was added, and the mixture was stirred with heating at an internal temperature of 105 ° C. to 110 ° C. for 1.5 hours under an atmospheric pressure and an argon stream. Subsequently, the low-boiling liquid containing methanol produced by the reaction was heated and stirred at an internal temperature of 100 to 140 ° C. for 6.5 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 stirred with heating at an internal pressure of 13.3 kPa for 12.5 hours, and methanol was completely distilled off. Subsequently, the internal temperature was 130 to 140 ° C., and the internal pressure was 0.4. The mixture was heated and stirred for 22 hours at -0.6 kPa, and unreacted 2,5-hexanediol was distilled off by distillation. After completion of the reaction, 30 mg of acetic acid and 55 g of toluene were added to the resulting reaction solution, and the mixture was stirred for 30 minutes, and then the organic layer washed with pure water was concentrated to obtain poly (branched butylene) carbonate as a pale yellow viscous liquid. 50.12 g of diol was obtained (the following reaction formula <1>).

The obtained poly (branched butylene) carbonate diol was determined for number average molecular weight and terminal hydroxyl group purity from ¹ H-NMR spectrum analysis, and measured for melting point and glass transition point 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 below.

Number average molecular weight: 1300
Terminal hydroxyl group purity: 99.7%
Melting point: cannot be confirmed by DSC measurement Glass transition point: -18 ° C
Viscosity (75 ° C.): 2840 mPa · sec

Example 2 (Synthesis of poly (branched alkylene) carbonate diol)
194.38 g (1.64 mol) of 2,5-hexanediol, 162.99 g (1.81 mol) of dimethyl carbonate and sodium were added to a 500 ml glass flask equipped with a stirrer, a heating device, a distillation device, and a thermometer. 70 mg of a 28% methanol solution of methoxide was added, and the mixture was heated and stirred at atmospheric pressure and an internal temperature of 100 ° C. for 5.5 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 100 to 140 ° C. for 7 hours while distilling off by distillation at a distillate temperature of 65 ° C. or lower. Furthermore, while maintaining the internal temperature at 140 ° C., the internal pressure was heated and stirred at 13.3 kPa for 10 hours, and methanol was completely distilled off. Then, the internal temperature was 135 to 140 ° C., and the internal pressure was 0.3 to 0. The reaction mixture was heated and stirred for 20 hours, and unreacted 2,5-hexanediol was distilled off by distillation. 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, and then the organic layer washed with pure water was concentrated to obtain poly (branched butylene) carbonate as a pale yellow viscous liquid. 183.42 g of diol was obtained (the following reaction formula <2>).

The obtained poly (branched butylene) carbonate diol was determined for the number average molecular weight and terminal hydroxyl group purity from ¹ H-NMR spectrum analysis, and measured for melting point and glass transition point 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 below.

Number average molecular weight: 1120
Terminal hydroxyl group purity: 99.9% or more Melting point: Cannot be confirmed from DSC measurement Glass transition point: -21 ° C
Viscosity (75 ° C): 1800 mPa · sec

Example 3 (Synthesis of poly (branched alkylene) carbonate diol)
Di (propylene glycol) 75.18 g (0.56 mol), dimethyl carbonate 50.47 g (0.56 mol), and sodium methoxy were added to a 200 ml glass flask equipped with a stirrer, a heating device, a distillation device, and a thermometer. 30 mg of a 28% methanol solution was added, and the mixture was heated and stirred at an internal temperature of 100 ° C. for 1 hour under an atmospheric pressure and an argon stream. Next, the low-boiling liquid containing methanol produced in the reaction was heated and stirred at an internal temperature of 100 to 140 ° C. for 4.5 hours while distilling off by distillation at a distillate temperature of 65 ° C. or lower. Furthermore, while maintaining the internal temperature at 140 ° C., the mixture was heated and stirred at an internal pressure of 13.3 kPa to 2.0 kPa for 10 hours, and methanol was completely distilled off. Subsequently, the internal temperature was 135 to 140 ° C. and the internal pressure was 0. The mixture was heated and stirred at 4 to 0.6 kPa for 6 hours, and unreacted di (propylene glycol) was distilled off by distillation. After completion of the reaction, 50 mg of acetic acid and 70 g of toluene were added to the resulting reaction solution, and the mixture was stirred for 1 hour, and then the organic layer washed with pure water was concentrated to give a poly (ether-linked branched chain having an ether bond). 61.13 g of (butylene) carbonate diol was obtained (the following reaction formula <3>).

The resulting polycarbonate diol (branched butylene having an ether bond), number average molecular weight from ¹ hydroxyl value measurement, determine the terminal hydroxyl groups purity from the hydroxyl value measurement and ¹ H-NMR spectrum analysis and differential scanning calorimetry The melting point and glass transition point were measured by (DSC) analysis, and the viscosity at a temperature of 75 ° C. was further measured using an E-type rotational viscometer. The results are shown below.

Number average molecular weight: 1600
Terminal hydroxyl group purity: 99.9% or more Melting point: Cannot be confirmed by DSC measurement Glass transition point: -32 ° C
Viscosity (75 ° C.): 730 mPa · sec

Example 4 (Synthesis of poly (branched alkylene) carbonate diol)
1,4-pentanediol 48.91 (0.470 mol), dimethyl carbonate 42.30 g (0.470 mol), and sodium were added to a 200 mL glass flask equipped with a stirrer, heating device, distillation device, and thermometer. 20 mg of a 28% methanol solution of methoxide was added, and the mixture was heated and stirred at an internal temperature of 96.6 to 98 ° C. for 1 hour under atmospheric pressure and argon flow. Subsequently, the low boiling liquid containing methanol produced by the reaction was distilled off at a distillate temperature of 65 ° C. or lower by distillation, and the internal temperature was heated and stirred at 96.6 to 140 ° C. for 4 hours. Further, while maintaining the internal temperature at 140 ° C., the mixture was heated and stirred at an internal pressure of 13.3 kPa for 10.5 hours, methanol was completed and heated and stirred for 15.5 hours, and unreacted 1,4-pentanediol was distilled. After distilling out by distillation, the internal temperature was 125 to 140 ° C. and the internal pressure was 0.1 to 0.5 kPa. After completion of the reaction, 50 mg of acetic acid and 50 g of toluene were added to the resulting reaction solution, and the mixture was stirred for 1 hour, and then the organic layer washed with pure water was concentrated to obtain poly (branched butylene) carbonate as a pale yellow viscous liquid. 32.45 g of diol was obtained (the following reaction formula <4>).

The obtained poly (branched butylene) carbonate diol was determined for number average molecular weight and terminal hydroxyl group purity from ¹ H-NMR spectrum analysis, and measured for melting point and glass transition point 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 below.

Number average molecular weight: 1200
Terminal hydroxyl group purity: 99.9% or more Melting point: Cannot be confirmed from DSC measurement Glass transition point: -35 ° C
Viscosity (75 ° C): 1120 mPa · sec

Example 5 (Synthesis of poly (branched alkylene) carbonate diol copolymer (II))
In a glass flask having an internal volume of 200 ml equipped with a stirrer, a heating device, a distillation device, and a thermometer, 30.65 g (0.294 mol) of 1,4-pentanediol and 29.92 g (0. 287 mol), 47.81 g (0.53 mol) of dimethyl carbonate and 20 mg of a 28% methanol solution of sodium methoxide were added, and the mixture was heated and stirred for 30 minutes at an internal temperature of 94 ° C. under an argon stream under atmospheric pressure. Next, the low-boiling liquid containing methanol produced by the reaction was heated and stirred at an internal temperature of 94 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 methanol was completely distilled off, followed by an internal temperature of 130 ° C. (internal pressure of 0.20 kPa) for 4 hours. The mixture was heated and stirred for 3 hours at an internal temperature of 140 to 150 ° C. and an internal pressure of 0.25 to 0.28 kPa, and unreacted 1,4-pentanediol and 1,5-pentanediol were distilled off by distillation. After completion of the reaction, 50 mg of acetic acid and 50 g of toluene were added to the resulting reaction solution, and the mixture was stirred for 1 hour, and then the organic layer washed with pure water was concentrated to obtain a poly (branched butylene-pentapentane as a pale yellow viscous liquid. 48.22 g of methylene) carbonate diol copolymer was obtained (the following reaction formula <5>).

The obtained poly (branched butylene) carbonate diol copolymer was determined for number average molecular weight and terminal hydroxyl group purity from ¹ H-NMR spectrum analysis, and was also analyzed for melting point and glass transition point 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 below.

Number average molecular weight: 1290
Terminal hydroxyl group purity:> 99.9%
Melting point: cannot be confirmed by DSC measurement Glass transition point: -47 ° C
Viscosity (75 ° C.): 810 mPa · sec

Example 6 (Synthesis of poly (branched alkylene) carbonate diol copolymer (II))
In a glass flask having an internal volume of 200 ml equipped with a stirrer, a heating device, a distillation device, and a thermometer, 35.00 g (0.296 mol) of 2,5-hexanediol and 35.04 g (0. 296 mol), 53.40 g (0.593 mol) of dimethyl carbonate and 10 mg of a 28% methanol solution of sodium methoxide were added, and the mixture was heated and stirred at an internal temperature of 99 to 100 ° C. for 1 hour under atmospheric pressure and argon flow. Subsequently, the low-boiling liquid containing methanol produced by the reaction was heated and stirred at an internal temperature of 100 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 6 hours, and methanol was completely distilled off. Subsequently, the internal temperature was 129 ° C. to 140 ° C., and the internal pressure was 0.40 to 0.00. The mixture was heated to 27 kPa and stirred for 3 hours, and unreacted 2,5-hexanediol and 1,6-hexanediol were distilled off by distillation. After completion of the reaction, 50 mg of acetic acid and 50 g of toluene were added to the resulting reaction solution, and the mixture was stirred for 1 hour, and then the organic layer washed with pure water was concentrated to give poly (branched butylene-directly as a pale yellow viscous liquid. 62.5 g of a linear hexamethylene) carbonate diol copolymer was obtained (the following reaction formula <6>).

The obtained poly (branched butylene) carbonate diol copolymer was determined for number average molecular weight and terminal hydroxyl group purity from ¹ H-NMR spectrum analysis, and was also analyzed for melting point and glass transition point 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 below.

Number average molecular weight: 1310
Terminal hydroxyl group purity:> 99.9%
Melting point: cannot be confirmed by DSC measurement Glass transition point: -46 ° C
Viscosity (75 ° C.): 900 mPa · sec

  From Examples 1 to 6, the poly (branched alkylene) carbonate diol or poly (branched alkylene) carbonate diol copolymer obtained in the present invention is a compound having a high terminal hydroxyl group purity. Was confirmed. This means that the molecular end of the obtained product is not a carbonate group, but has a structure in which the molecular end is a hydroxyl group, such as poly (branched alkylene) carbonate diol represented by the formula (1). It shows that it is a polyalkylene carbonate diol having.

  Furthermore, both the poly (branched alkylene) carbonate diol and the poly (branched alkylene) carbonate diol copolymer obtained by the production method of the present invention have a glass transition point of room temperature (25 ° C.) or less. Therefore, it can be handled well in a normal working environment.

<(Alkali resistance) hydrolysis test>
Example 7
Poly (branched butylene) carbonate diol obtained in the same manner as in Example 1 using 2,5-hexanediol in a glass flask having an internal volume of 20 ml equipped with a stirrer, a heating device, and a thermometer (Number average molecular weight 1740) 0.90 g, 4.50 g of t-butyl alcohol, and 0.45 g of 0.01 mol / L sodium hydroxide aqueous solution were added, and the mixture was heated and stirred at an internal temperature of 75 to 80 ° C. for 72 hours under atmospheric pressure. did. At that time, in order to measure the change with time of the ratio of hydrolysis of poly (branched butylene) carbonate diol, ¹ H-NMR spectrum analysis was performed by sampling as appropriate, and the number average molecular weight was calculated. The results are shown in Table 1.

* 1: Number average molecular weight of poly (branched butylene) carbonate diol used in Example 7 * 2: Molecular weight reduction = [Number average molecular weight at start (1740)]-[Number average molecular weight after each lapse of time]

Comparative Example 1
A stirrer, a heating device, and a thermometer were obtained in the same manner as in Example 1, except that 1,4-butanediol was used instead of 2,5-hexanediol in a glass flask having an internal volume of 20 ml. 0.90 g of poly (linear butylene) carbonate diol (number average molecular weight 1770), 4.50 g of t-butyl alcohol, and 0.45 g of 0.01 mol / L sodium hydroxide aqueous solution were added, and the internal temperature was changed under atmospheric pressure. The mixture was heated and stirred at 75 to 80 ° C. for 72 hours. At that time, in order to measure the change with time of the ratio of hydrolysis of the poly (linear butylene) carbonate diol, the sample was appropriately sampled and subjected to ¹ H-NMR spectrum analysis to calculate the number average molecular weight. The results are shown in Table 2.

* 1: Number average molecular weight of poly (linear butylene) carbonate diol used in Comparative Example 1 * 2: Molecular weight reduction = [Number average molecular weight at start (1770)]-[Number average molecular weight after each lapse of time]

<(Acid resistance) hydrolysis resistance test>
Example 8
The same poly (branched butylene) carbonate diol (number average molecular weight 1740) 1.00 g as used in Example 7 in a glass flask having an internal volume of 20 ml equipped with a stirrer, a heating device, and a thermometer, t -5.00 g of butyl alcohol and 0.50 g of a 0.1 mol / L sulfuric acid aqueous solution were added, and the mixture was heated and stirred at an internal temperature of 75 to 80 ° C for 72 hours under atmospheric pressure. At that time, in order to measure the change with time of the ratio of hydrolysis of poly (branched butylene) carbonate diol, ¹ H-NMR spectrum analysis was performed by sampling as appropriate, and the number average molecular weight was calculated. The results are shown in Table 3.

＊１：実施例７で使用したものと同じポリ(分岐鎖状ブチレン)カーボネートジオールの数平均分子量
＊２：分子量減少＝〔開始時の数平均分子量（１７４０）〕−〔各時間経過後の数平均分子量〕

* 1: Number average molecular weight of the same poly (branched butylene) carbonate diol as used in Example 7 * 2: Molecular weight reduction = [Number average molecular weight at start (1740)]-[Number after each lapse of time] (Average molecular weight)

Comparative Example 2
The same poly (linear butylene) carbonate diol (number average molecular weight 1770) as used in Comparative Example 1 was added to a glass flask having an internal volume of 20 ml equipped with a stirrer, a heating device and a thermometer, t. -The butyl alcohol 5.50g and the 0.15 mol / L sulfuric acid aqueous solution 0.55g were put, and it heated and stirred at internal temperature 75-80 degreeC under atmospheric pressure for 72 hours. At that time, in order to measure the change with time of the ratio of hydrolysis of the poly (linear butylene) carbonate diol, the sample was appropriately sampled and subjected to ¹ H-NMR spectrum analysis to calculate the number average molecular weight. The results are shown in Table 4.

* 1: Number average molecular weight of the same poly (linear butylene) carbonate diol used in Comparative Example 1 * 2: Molecular weight reduction = [Number average molecular weight at the start (1770)]-[Number after each lapse of time] (Average molecular weight)

  From the results of Examples (Tables 1 and 3) and Comparative Examples (Tables 2 and 4), the novel poly (branched alkylene) carbonate diol of the present invention and two or more different formulas (A) are shown. The poly (branched alkylene) carbonate diol copolymer has a smaller number average molecular weight reduction (molecular weight reduction) after a certain heating time than the conventional linear poly (branched alkylene) carbonate diol, That is, it has the feature which is excellent in hydrolysis resistance (acid resistance, alkali resistance). Therefore, from the above characteristics, when the poly (branched alkylene) carbonate diol or the poly (branched alkylene) carbonate diol copolymer of the present invention is used as a raw material for producing polyurethane, for example, (Branched alkylene) A novel polyurethane expected to be improved in low weather resistance and low deterioration resistance as seen in carbonate diol can be obtained.

  The novel poly (branched alkylene) carbonate diol and poly (branched alkylene) carbonate diol copolymer of the present invention are both polyalkylene carbonate diols having excellent heat stability and hydrolysis resistance. Therefore, for example, it can be widely used industrially as a constituent material for exterior paints, coating agents, adhesives and the like in the automotive field and OA equipment field. In addition, the poly (branched alkylene) carbonate diol or the poly (branched alkylene) carbonate diol copolymer of the present invention can be used as a raw material for, for example, polyurethane or thermoplastic elastomer. .

Claims (12)

A poly (branched alkylene) carbonate diol represented by the formula (1).

(In the formula (1),
R ¹ to R ⁴ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a fluorine atom, or an alkyl group having 1 to 6 carbon atoms that may be substituted with an alkyloxy group having 1 to 4 carbon atoms. It is an alkyl group. However, R ¹ to R ⁴ are not all hydrogen atoms.
Z represents a Z ¹ group represented by may be substituted with a fluorine atom alkylene group having 2 to 12 carbon atoms, or the following formula (2).

[In the formula (2), L represents an oxygen atom; a sulfur atom; a carbonyl group; a thiocarbonyl group; an amide group (—CONH—, —NHCO—); a sulfonyl group; a phosphonyl group; a halogen atom, having 1 to 4 carbon atoms. A phenylene group which may have an alkyl group or an alkyloxy group having 1 to 4 carbon atoms; a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms; Biphenylene group; one linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group optionally having an alkyloxy group having 1 to 4 carbon atoms. N and m represent the number of methylene groups and represent an integer of 1 to 6. ]
X represents the number of repeating units of the alkylene carbonate structure having Z, and is an arbitrary real number of 1 or more. ) A poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by two or more different formulas (A).

(In the formula (A),
R ¹ to R ⁴ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a fluorine atom, or an alkyl group having 1 to 6 carbon atoms that may be substituted with an alkyloxy group having 1 to 4 carbon atoms. It is an alkyl group. However, R ¹ to R ⁴ are not all hydrogen atoms.
Z represents a Z ¹ group represented by may be substituted with a fluorine atom alkylene group having 2 to 12 carbon atoms, or the following formula (2).

[In the formula (2), L represents an oxygen atom; a sulfur atom; a carbonyl group; a thiocarbonyl group; an amide group (—CONH—, —NHCO—); a sulfonyl group; a phosphonyl group; a halogen atom, having 1 to 4 carbon atoms. A phenylene group which may have an alkyl group or an alkyloxy group having 1 to 4 carbon atoms; a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms; Biphenylene group; one linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group optionally having an alkyloxy group having 1 to 4 carbon atoms. N and m represent the number of methylene groups and represent an integer of 1 to 6. ]
X represents the number of repeating units of the alkylene carbonate structure having Z, and is an arbitrary real number of 1 or more. ) A poly (branched chain alkylene) carbonate diol copolymer having at least one molecular structure represented by the formula (A) and at least one molecular structure represented by the formula (B).

(In formula (A), R ¹ to R ⁴ and X have the same meanings as those in formula (1)).

(In the formula (B), Y represents the number of repeating units of the methylene carbonate structure represented by the formula (B) and is an arbitrary real number of 1 or more, and k represents the number of methylene groups. To an integer from 12 to 12.) [4] In the presence of an alkali metal compound, the branched alkylene diol represented by the formula (3) is reacted with at least one carbonate selected from the group consisting of the formula (4) and the following formula (5). A method for producing a poly (branched alkylene) carbonate diol represented by the formula (1).

(In the formula (1),
R ¹ to R ⁴ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a fluorine atom, or an alkyl group having 1 to 6 carbon atoms that may be substituted with an alkyloxy group having 1 to 4 carbon atoms. It is an alkyl group. However, R ¹ to R ⁴ are not all hydrogen atoms.
Z represents a Z ¹ group represented by may be substituted with a fluorine atom alkylene group having 2 to 12 carbon atoms, or the following formula (2).

[In the formula (2), L represents an oxygen atom; a sulfur atom; a carbonyl group; a thiocarbonyl group; an amide group (—CONH—, —NHCO—); a sulfonyl group; a phosphonyl group; a halogen atom, having 1 to 4 carbon atoms. A phenylene group which may have an alkyl group or an alkyloxy group having 1 to 4 carbon atoms; a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms; Biphenylene group; one linking group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a naphthylene group optionally having an alkyloxy group having 1 to 4 carbon atoms. N and m represent the number of methylene groups and represent an integer of 1 to 6. ]
X represents the number of repeating units of the alkylene carbonate structure having Z, and is an arbitrary real number of 1 or more. )

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (1)).

(In the formula (4), R ⁵ and R ⁶ are alkyl groups of a fluorine atom or an alkyl group carbon atoms which may be substituted with 1-6 of 1 to 4 carbon atoms; a halogen atom, a nitro group, a cyano group , A phenyl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, wherein R ⁵ and R ⁶ are the same as each other, or Each may be different.)

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (1)).   The method for producing a poly (branched alkylene) carbonate diol represented by the formula (1) according to claim 4, wherein at least one carbonate represented by the formula (4) is used as the carbonate. In the presence of an alkali metal compound, at least one selected from the group consisting of two or more different branched alkylene diols represented by the formula (3) and carbonates represented by the formula (4) and the following formula (5): A method for producing a poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by two or more different formulas (A), which is reacted with carbonate.

(In formula (A), R ¹ to R ⁴ , and Z and X are the same as those described in formula (A).)

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (3)).

(In Formula (4), R ⁵ and R ⁶ are the same as those described in Formula (4)).

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (5)).   The poly (branched alkylene) carbonate having a molecular structure represented by two or more different formulas (A) according to claim 6, wherein at least one carbonate represented by the formula (4) is used as the carbonate. A method for producing a diol copolymer. In the presence of an alkali metal compound, at least one branched alkylene diol represented by the formula (3), at least one linear alkylene diol having 2 to 12 carbon atoms, and the formulas (4) and (5) And at least one molecular structure represented by the formula (A) and at least one molecule represented by the formula (B), which are reacted with at least one carbonate selected from the group consisting of the carbonate represented by the formula (8). A method for producing a poly (branched alkylene) carbonate diol copolymer having a structure.

(In the formula (A), R ¹ to R ⁴ and X are the same as those in the above (1).)

(In the formula (B), Y represents the number of repeating units of the methylene carbonate structure represented by the formula (B) and is an arbitrary real number of 1 or more, and k represents the number of methylene groups. To an integer from 12 to 12.)

(In Formula (3), R ¹ to R ⁴ and Z are the same as those described in Formula (3)).

(In Formula (4), R ⁵ and R ⁶ are the same as those described in Formula (4)).

(In Formula (5), R ¹ to R ⁴ and Z are the same as those described in Formula (5)).   The at least one molecular structure represented by the formula (A) and at least one kind of the formula (B) according to claim 8, wherein at least one carbonate represented by the formula (4) is used as the carbonate. The manufacturing method of the poly (branched alkylene) carbonate diol copolymer which has the molecular structure shown by these. The theory of at least one alcohol selected from the group consisting of alcohols represented by formula (6) and formula (7), which is by-produced by reaction at atmospheric pressure and at a liquid temperature of 150 ° C. or lower, is the theory. 70% by mass or more is first distilled off with respect to the production amount (mass), and then the reaction pressure is reduced to atmospheric pressure or less to distill off the remaining by-produced alcohol. A process for producing a poly (branched alkylene) carbonate diol represented by the formula (1):

(In Formula (6), R ⁵ is the same as that described in Formula (4).)

(In Formula (7), R ⁵ is the same as that described in Formula (4).)   At least one alcohol selected from the group consisting of the alcohol represented by the formula (6) and the formula (7), which is produced as a by-product by reaction at atmospheric pressure and at a liquid temperature of 150 ° C. or lower, The 70 mass% or more is first distilled off with respect to the theoretical production amount (mass), then the reaction pressure is reduced to atmospheric pressure or less, and the remaining by-produced alcohol is distilled off. A method for producing a poly (branched alkylene) carbonate diol copolymer having a molecular structure represented by the formula (A) of two or more different types.   At least one alcohol selected from the group consisting of the alcohol represented by the formula (6) and the formula (7), which is produced as a by-product by reaction at atmospheric pressure and at a liquid temperature of 150 ° C. or lower, The 70 mass% or more is first distilled off with respect to the theoretical production amount (mass), then the reaction pressure is reduced to atmospheric pressure or less, and the remaining by-produced alcohol is distilled off. A process for producing a poly (branched alkylene) carbonate diol copolymer having at least one molecular structure represented by the formula (A) and at least one molecular structure represented by the formula (B).