JP2001040073A - Polyester having hydroxymethyl group on side chain and production of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polyester having hydroxymethyl group on side chain exhibiting excellent hydrophilic property, dye-affinity, adhesive property, etc., useful for paints, coating agent, adhesive, etc., by carrying out a polyaddition reaction of a specific dioxetane compound and a specific dicarboxylic acid. SOLUTION: This polyester having hydroxymethyl group on side chain expressed by formula II (n is an integer >=2) is obtained by carrying out a polyaddition reaction of (A) a dioxetane compound of formula I (k is 0-30; X is an alkylene, ethylene, etc., R1 and R2 are each H or a 1-4C alkyl), and (B) a dicarboxylic acid of formula HOOC-Ym-COOH (Y is an arylene or an alkylene; m is 0 or 1), in the presence of an onium salt. The R1 and R2 of the polyester are preferably methyl or ethyl. The even mole of the component A and B are preferably used. A single or plural onium salts are used, and <=20 mol.%., especially 5-15% of the salt is preferably used to the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester having a hydroxymethyl group in a side chain obtained by a polyaddition reaction between a dioxetane compound and a dicarboxylic acid. Polyester having a hydroxymethyl group in the side chain has excellent hydrophilicity, dyeability, adhesion, organic solvent solubility,
It shows reactivity and can be used for paints, coatings, adhesives, films as soluble polyesters, and the like.

[0002]

2. Description of the Related Art As a polyester obtained by a polyaddition reaction of a dioxetane compound, a polyester having a chloromethyl group in a side chain obtained by a polyaddition reaction of a dioxetane compound and a bisacyl halide [J. Polym. S
ci. , Part A: Polym. Chem. , 3
1, 1639 (1993)] and polyesters having a hydroxymethyl group in the side chain obtained by a polyaddition reaction between a dioxetane compound and a dicarboxylic acid (Japanese Patent Application Laid-Open No.
No. 0-139866) is known.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a novel functional compound having excellent hydrophilicity, dyeability, adhesion, solubility in organic solvents and reactivity by having a hydroxymethyl group in the side chain. It is an object of the present invention to provide a novel polyester which can be used as an excellent raw material for producing a molecule, and a method for producing the same.

[0004]

The object of the present invention is solved by a polyester represented by the general formula (1) and having a hydroxymethyl group in a side chain.

[0005]

Embedded image (Where k represents an integer of 0 to 30. When k = 1, X
Is an alkylene group (which may contain an unsaturated bond, an aliphatic hydrocarbon ring, or an aromatic ring in the carbon chain), -CO
Represents an -NH-Z-NH-CO- group or a -CO- group,
When k is an integer of 2 to 30, X represents an ethylene group. Z
Represents an arylene group (an aromatic ring may be bonded via an alkylene group) or an alkylene group. Also, Y
Represents an arylene group (an aromatic ring may be bonded via an alkylene group) or an alkylene group, and m represents 0 or 1. R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n represents an integer of 2 or more. )

[0006]

DETAILED DESCRIPTION OF THE INVENTION The novel polyester of the present invention is:
It is produced by subjecting a dioxetane compound represented by the general formula (2) and a dicarboxylic acid represented by the general formula (3) to a polyaddition reaction in the presence of an onium salt.

[0007]

Embedded image (In the formula, X, k, R ¹ and R ² are the same as described above.)

[0008]

Embedded image (In the formula, Y and m are the same as described above.)

In the polyester having a hydroxyl group on the side chain of the present invention represented by the general formula (1), n is 2
Above, preferably an integer of 2 to 200. The polyester of the present invention has a number average molecular weight (Mn) of 500 or more, preferably 1,000 to 50,000, and a ratio of weight average molecular weight (Mw) to number average molecular weight (Mw / Mn) of 1.0 to 10.0. , Preferably from 1.0 to 5.0. Among the polyesters of the present invention, those in which both R ¹ and R ² are a methyl group or an ethyl group are preferred. The molecular weight is measured by the GPC method (in terms of polystyrene).

As the dioxetane compound represented by the general formula (2), (A) k = 1 and X is an alkylene group (an unsaturated bond, an aliphatic hydrocarbon ring, or an aromatic ring in the carbon chain). (B) k = 1 and X is -CO-NH-Z-N
A diurethane dioxetane, wherein Z is an arylene group (an aromatic ring may be bonded via an alkylene group) or an alkylene group in the H-CO- group, (C) k = 1,
X is a -CO- group, carbonate dioxetanes,
(D) k = an integer of 2 to 30 (preferably 2 to 25),
A polyether dioxetane wherein X is an ethylene group,
(E) monoether dioxetanes wherein k = 0.

In the dioxetane compound represented by the general formula (2), R ¹ and R ^{2 each} represent a hydrogen atom or an alkyl group (particularly, an alkyl group having 1 to 4 carbon atoms). You may. Among the dioxetane compounds, those in which R ¹ and R ² are the same are preferable,
Among them, those in which R ¹ and R ² are the same and are each a hydrogen atom, a methyl group or an ethyl group are more preferable, and among them, R ¹ and R ² are the same and any one of a methyl group and an ethyl group is preferable. Are particularly preferred.

In the above (A) diether dioxetanes, the alkylene group (X) contains an unsaturated bond, an aliphatic hydrocarbon ring, or an aromatic ring inside the carbon chain (carbon chain excluding both terminals). May be available. That is, examples of the alkylene group include an alkylene group having 2 to 20 carbon atoms such as an ethylene group, a tetramethylene group, and a hexamethylene group, and further include an unsaturated group in the carbon chain such as a group represented by the formula (4). The number of carbon atoms having an aliphatic hydrocarbon ring (such as a cyclohexane ring) inside a carbon chain such as an alkylene group having 4 to 20 carbon atoms containing a bond (such as a carbon-carbon double bond) or a group represented by the formula (5) 8 to 20 (including an aromatic ring (benzene ring or the like) in the carbon chain such as an alkylene group of 8 to 20 (including a carbon atom constituting a ring), a xylylene group and a group represented by the formula (6). And alkylene groups (including carbon atoms constituting the ring) (including isomers such as o-, m- and p-).

[0013]

Embedded image

Examples of the diether dioxetanes include 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane and 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] Butane, 1,6
-Bis [(3-ethyl-3-oxetanylmethoxy) methyl] hexane, 1,4-bis (3-ethyl-3-oxetanylmethoxy) -2-butene, and 1,4-bis [(3-ethyl- 3-oxetanylmethoxy) methyl]
Cyclohexane, 1,4-bis [(3-ethyl-3-
Oxetanylmethoxy) methyl] benzene, 4,4'-
Bis [(3-ethyl-3-oxetanylmethoxy) methyl] biphenyl, 4,4'-bis [(3-methyl-3-
Oxetanylmethoxy) methyl] biphenyl and the like.

The diether dioxetanes are:
For example, it is synthesized by reacting the corresponding dibromide (xylylene dibromide, ethylene dibromide, etc.) with 3-alkyl-3-hydroxymethyloxetane.

In the above (B) diurethane dioxetanes, the arylene group (Z) may have an aromatic ring bonded via an alkylene group. That is, as the arylene group, an arylene group having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group (o-, m-, p-, 1,
5-isomer, etc.), and further include an arylene group in which an aromatic ring such as a group represented by the formula (7) is bonded via an alkylene group. Further, as the alkylene group (Z), an ethylene group,
2-2 carbon atoms such as a tetramethylene group and a hexamethylene group
And an alkylene group of 0.

[0017]

Embedded image

The diurethane dioxetanes include, for example, 4,4'-methylenebis (3-ethyl-3-oxetanylmethyl N-phenylcarbamate), 1,3-
Phenylenebis (3-ethyl-3-oxetanylmethyl carbamate), 1,5-naphthylenebis (3-ethyl-3-oxetanylmethylcarbamate), 1,6-
Hexamethylene bis (3-ethyl-3-oxetanylmethyl carbamate) and the like.

As the diurethane dioxetanes, Z is an arylene group, R ¹ and R ² are the same, and a hydrogen atom,
Compounds that are either methyl or ethyl are preferred. Incidentally, the diurethane dioxetane, for example,
The corresponding diisocyanate (e.g., 4,4'-diphenylmethane diisocyanate, 1,3-benzene diisocyanate, 1,6-hexane diisocyanate, etc.) is reacted with 3-alkyl-3-hydroxymethyloxetane Are synthesized.

Examples of the carbonate dioxetanes (C) include bis (3-ethyl-3-hydroxymethyloxetanyl) carbonate and bis (3-methyl-3-hydroxymethyloxetanyl) carbonate. Note that carbonate dioxetanes are, for example, dimethyl carbonate and 3-alkyl-3
Synthesized by reacting -hydroxymethyloxetane.

The polyether dioxetane (D) includes, for example, triethylene glycol bis (3-
Ethyl-3-hydroxymethyloxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-
3-hydroxymethyloxetanylmethyl) ether and the like. In addition, polyether dioxetanes are, for example, polyethylene glycol (such as triethylene glycol and tetraethylene glycol) and 3
Synthesized by reacting p-toluenesulfonyl chloride of -alkyl-3-hydroxymethyloxetane.

The (E) monoether dioxetanes include, for example, bis (3-ethyl-3-hydroxymethyloxetanylmethyl) ether, bis (3-methyl-3-hydroxymethyloxetanylmethyl) ether and the like. . In addition, monoether dioxetanes are 3-alkyl-3-hydroxymethyloxetanes and p-alkyl-3-hydroxymethyloxetanes.
-Synthesized by reacting toluenesulfonyl chloride.

The dicarboxylic acid represented by the general formula (3) includes (F) an aromatic dicarboxylic acid wherein m = 1, Y is an arylene group, and (G) Y is an aromatic dicarboxylic acid having 1 to 18 carbon atoms. Aliphatic dicarboxylic acids wherein m = 0 or 1 in the alkylene group;

In the aromatic dicarboxylic acid (F), the arylene group may have an aromatic ring bonded through an alkylene group. That is, examples of the arylene group include a phenylene group and a naphthylene group having 6 to 2 carbon atoms.
0 arylene group (including each isomer such as o-, m-, p-, 1,5- etc.), and further, an aromatic ring such as a group represented by the formula (7) is an alkylene group. And an arylene group bonded through the intermediary. Further, the arylene group may have an alkyl group having 1 to 4 carbon atoms at an arbitrary position of the aromatic ring.

[0025]

Embedded image

Examples of the aromatic dicarboxylic acid (F) include an alkyl group having 1 to 4 carbon atoms such as phthalic acid, 3-methylphthalic acid, 3-ethylphthalic acid, 4-methylphthalic acid and 4-ethylphthalic acid. Phthalic acid, isophthalic acid, 2-methylisophthalic acid,
Isophthalic acid which may have an alkyl group having 1 to 4 carbon atoms, such as ethyl isophthalic acid, 4-methyl isophthalic acid, 4-ethyl isophthalic acid, 5-methyl isophthalic acid, and 5-ethyl isophthalic acid, and terephthalic acid And terephthalic acid which may have an alkyl group having 1 to 4 carbon atoms, such as methyl terephthalic acid and ethyl terephthalic acid. Also, 2,2-bis (p-carboxyphenyl) hexafluoropropane and the like can be mentioned.

Examples of the aliphatic dicarboxylic acid (G) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, dodecane diacid, eicosane diacid and the like.

Among the dicarboxylic acids, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, dodecandioic acid,
2,2-bis (p-carboxyphenyl) hexafluoropropane is preferred.

The onium salts used in the present invention include:
An ammonium salt, a phosphonium salt, an arsonium salt, a stibonium salt, an oxonium salt, a sulfonium salt, a selenonium salt, wherein any one of N, P, As, Sb, O, S, Se, Sn, and I is a central atom; Stannonium salts, iodonium salts and the like can be mentioned. As the central atom, N and P are preferable.

The group or atom which forms the cation portion by bonding to the central atom of the onium salt is a hydrogen atom, having 1 to 3 carbon atoms.
It is an alkyl group having 0, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may be the same or different. The alkyl group, the aralkyl group, and the aryl group include various isomers and may have a substituent. As a group having a substituent, a hydroxyalkyl group having a hydroxyl group at the terminal of an alkyl group is preferably exemplified. Examples of the anion constituting the anion portion of the onium salt include a halogen ion, a hydroxide ion, an alkoxide ion, a carbonate ion, a bicarbonate ion, a dihydrogen phosphate ion, a bisulfate ion, and the like. Among the anions, halogen ions are preferred in the order of Br ⁻ ≧ I ⁻ > Cl ⁻ .

As the ammonium salt, tetra-n-
Butyl ammonium chloride (TBAC), tetra n
And tetraalkylammonium halides such as -butylammonium bromide (TBAB) and tetra n-butylammonium iodide (TBAI).
Examples of the phosphonium salt include tetraalkylphosphonium halides such as tetra-n-butylphosphonium chloride (TBPC), tetra-n-butylphosphonium bromide (TBPB) and tetra-n-butylphosphonium iodide (TBPI), and tetraphenylphosphonium chloride (TPPC). ), Tetraphenylphosphonium halides such as tetraphenylphosphonium bromide (TPPB) and tetraphenylphosphonium iodide (TPPI).

As the arsonium salt, tetra-n-
Examples of the stibonium salts such as tetraalkylarsonium halides such as butylarsonium bromide (TBAsB) include tetraalkylstibonium halides such as tetra-n-butylstibonium bromide (TBSbB). Examples of the sulfonium salt include tetraalkyloxonium halides such as n-butyloxonium bromide (TBOB). Examples of the sulfonium salt include tetraalkylsulfonium halides such as tetra-n-butylsulfonium bromide (TBSB). Examples of the stanonium salts such as tetraalkylsulfonium halides such as butylselenonium bromide (TBSeB) include tetra-n-butylstanonium bromide (T
Examples of the iodonium salt such as tetraalkylstannonium halides such as BSnB) include tetraalkyliodonium halides such as tetra-n-butyliodonium bromide (TBIB).

Among the onium salts, ammonium salts and phosphonium salts are preferred, and ammonium halides and phosphonium halides are particularly preferred. Among them, tetraalkylammonium halide, tetraalkylphosphonium halide and tetraarylphosphonium halide are preferable, but tetraalkylphosphonium halide,
Tetraaryl phosphonium halides are more preferred.
In the tetraalkylammonium halide,
TBAC, TBAB and TBAI are preferred, and among tetraalkylphosphonium halides, TBPC, TBP
B and TBPI are preferred, and among tetraarylphosphonium halides, TPPC, TPPB and TPPI are preferred.

In the polyaddition reaction between the dioxetane compound and the dicarboxylic acid, the dioxetane compound and the dicarboxylic acid are preferably used in an equimolar amount. The onium salt can be used alone or in combination of two or more, but is preferably 20 mol% or less, more preferably about 5 to 15 mol%, based on the dicarboxylic acid.

The polyaddition reaction between the dioxetane compound and the dicarboxylic acid is carried out in a homogeneous system in the presence or absence of a reaction solvent. Therefore, when performing the reaction in the presence of a reaction solvent,
The reaction temperature is set so that the reaction system is in a homogeneous solution in which the dioxetane compound or dicarboxylic acid is dissolved in the reaction solvent.
The temperature is preferably 50 ° C or higher, more preferably 50 to 300 ° C. When the reaction is performed in the absence of a solvent, the reaction temperature is at least the lower temperature of the melting point of the dioxetane compound or dicarboxylic acid, so that the reaction system becomes a homogeneous solution in which the dioxetane compound or dicarboxylic acid is melted, and furthermore, Preferably, it is in the range of low temperature to 300 ° C.

In the polyaddition reaction, the reaction pressure is not particularly limited as long as the reaction system is maintained in a homogeneous solution state as described above, and may be any of normal pressure, increased pressure, or reduced pressure. Usually, the reaction is preferably performed at normal pressure, but when the reaction is performed in the presence of a reaction solvent, the reaction pressure may be such that a homogeneous solution state can be maintained. The reaction time varies depending on the reaction conditions, but is preferably about 1 to 50 hours, more preferably about 2 to 30 hours. The reaction atmosphere is preferably under an inert gas atmosphere such as nitrogen, argon, and helium.

It is preferable that the reaction solvent has a function of dissolving a dioxetane compound or a dicarboxylic acid and is inactive against these. Examples of such a reaction solvent include formamide, N, N-dimethylformamide, N, N-dimethylacetamide (DMAC), hexamethylphosphoric triamide (HMP) such as tetrahydrofuran (THF), anisole, and diglyme.
A) and solvents such as dimethylsulfoxide (DMSO), sulfolane, tetramethylurea, and N-methyl-2-pyrrolidone (NMP), such as toluene, o-dichlorobenzene, and nitrobenzene. Among these solvents, THF, DMSO, DMAC, HMPA, NMP
Is preferred.

The amount of the reaction solvent to be used may be any range as long as the reaction system is maintained in a homogeneous solution state as described above, that is, an amount sufficient to dissolve the dioxetane compound or dicarboxylic acid. For example, DMSO, DMAC, HMPA, NM
When a polar solvent such as P is used, the amount is preferably about 1 to 10 ml per 1 g of the dioxetane compound. The reaction solvent can be used alone or in combination.

In the present invention, in addition to the reaction solvent, an organic solvent which forms a homogeneous phase with the reaction solvent and which is inert to the dioxetane compound or dicarboxylic acid can be used alone or in combination. As such an organic solvent,
Aliphatic hydrocarbons such as n-hexane and n-octane; aromatic hydrocarbons such as benzene and xylene (excluding toluene); ketones such as acetone, methyl ethyl ketone and methyl propyl ketone; halogenated fats such as dichloromethane and dichloroethane Group hydrocarbons, dioxane and the like. The ratio of these organic solvents to the reaction solvent is not particularly limited as long as the reaction system is maintained in a homogeneous solution state as described above.

The above polyaddition reaction is carried out in a batch or continuous manner according to a conventional method. For example, a predetermined amount of a dioxetane compound and a dicarboxylic acid, as they are or after dissolving in a reaction solvent, are supplied to a reactor equipped with a stirrer and a heating device,
Further, a predetermined amount of an onium salt can be added, and the reaction can be carried out in a batch system while heating and stirring under predetermined conditions. The dicarboxylic acid and the onium salt can be separately supplied. The reactor is not particularly limited as long as it can be mechanically stirred by a stirrer. For example, a batch reactor, a single-tank or multi-tank continuous reactor, a tubular reactor, or the like is used.

Polyester formed after completion of the polyaddition reaction (polyester having hydroxymethyl group in side chain)
When a reaction solvent is used, is obtained as a precipitate by adding the reaction solution to a precipitation solvent and allowing to stand (for example, at room temperature for about 24 hours), and is separated by filtration, centrifugation or the like. At this time, if necessary, it is preferable to remove insoluble matters such as gel-like substances by filtration, centrifugation or the like before adding the precipitation solvent, if necessary. In addition,
The amount of the separation solvent used is preferably 1 to 20 times the volume of the reaction solution. If no reaction solvent is used, the resulting polyester is obtained as a uniform solid.

The precipitation solvent may be a poor solvent for the polyester, and may be used alone or in combination. Examples of such a solvent include water, aliphatic alcohols having 1 to 4 carbon atoms (methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, etc.), ketones (acetone) , Methyl ethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, etc.), aliphatic hydrocarbons (n-hexane,
n-octane, etc.), aromatic hydrocarbons (benzene, xylene; excluding toluene), diethyl ether, diisopropyl ether, diisobutyl ether, phenetole, diphenyl ether, dioxane and the like. Among these precipitation solvents, water, methanol, ethanol, diethyl ether, diisobutyl ether, acetone, methyl ethyl ketone, and methyl isobutyl ketone are preferred. Among them, water, methanol, ethanol,
Diethyl ether is more preferred.

The precipitate (solid matter) separated as described above is purified by dissolving it in a solvent, then reprecipitating and separating. This operation may be repeated as necessary, and is preferably repeated at least once or more, more preferably two to three times. The solvent for dissolving the solid may have a dissolving action on the solid and be inert.
For example, a reaction solvent (may be a mixture with the organic solvent) in the polyaddition reaction can be suitably used. The amount of the solvent used may be any amount that is sufficient to dissolve the solid, and is preferably about 1 to 60 ml per 1 g of the separated solid. The reprecipitation is performed by adding a solid solution to the precipitation solvent and leaving it to stand, as in the case of the reaction solution described above. The type of the precipitating solvent, the amount of the precipitating solvent used, the leaving conditions and the like are the same as described above.

As described above, a corresponding polyester is obtained from the dioxetane compound and the dicarboxylic acid by a polyaddition reaction. Finally, the obtained polyester is dried at 100 ° C. or lower by hot air drying, vacuum drying, or the like.

[0045]

Next, the present invention will be described in more detail by way of examples. Example 1 3.34 g of 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (manufactured by Toa Gosei), 1.46 g of adipic acid, and 0.42 g of tetraphenylphosphonium bromide were placed in a 30 ml sample tube. After weighing and mixing well, a degassing operation was performed to bring the sample tube to 150 ° C.
Immersed in an oil bath. While stirring at this temperature, 20
The reaction was carried out for a period of time to obtain 5.22 g of a pale ocher soft solid reaction product.

When the physical properties of the white solid obtained by purifying the reaction product were measured, the glass transition point was −23.2 ° C. by DSC analysis, and the number average molecular weight (Mn) was by GPC analysis (polystyrene conversion). 6400, weight average molecular weight (M
w) was 16,800, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mw / Mn) was 2.6. And ¹ H-
NMR, ¹³ C-NMR, FT-IR analysis (980 cm ^-1
Reduction of characteristic absorption of oxetane ring near 1700 cm ^-1
Disappearance of characteristic absorption of carboxylic acid near, appearance of characteristic absorption of carboxylic ester near 1740 cm ⁻¹ , 3450c
(Appearance of characteristic absorption of a hydroxyl group near m ^-1 ), this polymer is a polyester of the general formula (1) in which k = 1, m = 1, X is a p-xylylene group, and Y is a hexamethylene group. I found it.

Example 2 Adipic acid was replaced with 1.66 g of phthalic acid, and the reaction time was 4
The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 8 hours, to obtain 5.42 g of a pale ocher hard solid reaction product. The physical properties of the white solid obtained by purification in the same manner as in Example 1 were measured. The glass transition point was 30.5 ° C., the number average molecular weight (Mn) was 8,800, the weight average molecular weight (Mw) was 18,800, and Mw. / Mn was 2.1. Then, ¹ H
According to -NMR, ¹³ C-NMR and FT-IR analyses, this polymer is represented by the general formula (1) where k = 1 and m = 1,
It was a polyester in which X was a p-xylylene group and Y was an o-phenylene group.

Example 3 bis [4- (3-ethyl-3-oxetanylmethoxycarbonylamino) phenyl] methane (4,4'-
Methylene bis (3-ethyl N-phenylcarbamate-
2.41 g, 0.73 g of adipic acid, and 0.21 g of tetraphenylphosphonium bromide were weighed into a 30 ml sample tube, mixed well, and then degassed. C. in an oil bath. The reaction was carried out for 20 hours with stirring at this temperature, and the reaction product was 3.35 as a brown hard solid.
g was obtained. The dioxetane compound (T
g: 20.8 ° C.) was synthesized from 4,4′-diphenylmethane diisocyanate and 3-ethyl-3-hydroxymethyloxetane.

When the physical properties of the white solid obtained by purification in the same manner as in Example 1 were measured, the glass transition point was 6.0 ° C.
Having a melting point of 56.6 ° C. and a number average molecular weight (Mn) of 130.
00, weight average molecular weight (Mw) 34,000, Mw / Mn
Was 2.6. And ¹ H-NMR, ¹³ C-NM
According to R and FT-IR analyses, this polymer is represented by the general formula (1) where k = 1 and m = 1 and X is -CONH-
A Z-NHCO- group, a group in which Z is represented by the above formula (6), Y
Is a polyester having a hexamethylene group.

Example 4 The reaction time was changed to 4 by replacing adipic acid with 0.83 g of phthalic acid.
The reaction was carried out in the same manner as in Example 3 except that the reaction time was changed to 8 hours, to obtain 3.45 g of a brown hard solid reaction product. When the physical properties of the white solid obtained by purification in the same manner as in Example 1 were measured, the glass transition point was 56.5 ° C., the number average molecular weight (Mn) was 15,200, and the weight average molecular weight (Mw) was 38.
500, Mw / Mn was 2.5. And ¹ H-N
According to MR, ¹³ C-NMR and FT-IR analyses, this polymer is represented by the general formula (1) where k = 1 and m = 1, X is a —CONH—Z—NHCO— group, and Z is the above formula (6) ), Wherein Y is an o-phenylene group.

Example 5 The reaction was carried out in the same manner as in Example 1 except that the dioxetane compound was replaced with 2.42 g of bis (3-ethyl-3-hydroxymethyloxetanyl) carbonate. 4.30 g of product were obtained. When the physical properties of the white solid obtained by purification in the same manner as in Example 1 were measured, the glass transition point of the solid was -55.8 ° C, and the number average molecular weight (M
n) is 6,800, the weight average molecular weight (Mw) is 15,900,
Mw / Mn was 2.3. And ¹ H-NMR, ¹³
According to C-NMR and FT-IR analyses, this polymer was represented by the general formula (1) where k = 1 and m = 1 and X was -CO-
The polyester in which the group, Y, was a hexamethylene group. The dioxetane compound used here (mp: 5
3 ° C.) was synthesized from dimethyl carbonate and 3-ethyl-3-hydroxymethyloxetane.

Example 6 Adipic acid was replaced with 1.66 g of phthalic acid, and the reaction time was 3
The reaction was carried out in the same manner as in Example 5, except that the time was changed to 0 hour.
To obtain 4.50 g of a reaction product as a pale ocher hard solid.
Was. Physical properties of white solid obtained by purification in the same manner as in Example 1.
Measured, the glass transition point was -10.3 ° C.
Average molecular weight (Mn) is 8600, weight average molecular weight (Mw)
Was 19500 and Mw / Mn was 2.3. And¹
H-NMR, ¹³From C-NMR and FT-IR analyses,
In the general formula (1), k = 1 and m = 1
Wherein X is a —CO— group and Y is an o-phenylene group.
It was an ester.

Example 7 The reaction was carried out in the same manner as in Example 1 except that the dioxetane compound was replaced with 2.14 g of bis (3-methyl-3-hydroxymethyloxetanylmethyl) ether, to give a reaction of a soft ocher solid. 4.02 g of the product was obtained. Example 1
When the physical properties of the white solid obtained by purification in the same manner as described above were measured, the glass transition point was 22.2 ° C., and the number average molecular weight (M
n) is 5400, and the weight average molecular weight (Mw) is 24600
And Mw / Mn was 4.6. And ¹ H-NM
From R, ¹³ C-NMR and FT-IR analyses, this polymer was a polyester in the general formula (1) where k = 0 and m = 1 and Y was a hexamethylene group. The dioxetane compound used here was synthesized from 3-ethyl-3-hydroxymethyloxetane and p-toluenesulfonyl chloride of 3-ethyl-3-hydroxymethyloxetane.

Example 8 A reaction was carried out in the same manner as in Example 7 except that adipic acid was replaced by 1.66 g of phthalic acid, to obtain 4.22 g of a reaction product as a hard ocher solid. When the physical properties of the white solid obtained by purification in the same manner as in Example 1 were measured, the glass transition point was 73.8 ° C., the number average molecular weight (Mn) was 6,400, the weight average molecular weight (Mw) was 29100, and Mw. / Mn was 4.7. And, ¹ H-NMR, ¹³ C-NMR, FT-
According to IR analysis, this polymer was a polyester in the general formula (1) where k = 0 and m = 1 and Y was an o-phenylene group.

[0055]

According to the present invention, by having a hydroxymethyl group in the side chain, excellent hydrophilicity, dyeability, adhesion, solubility in organic solvents and reactivity are exhibited, and a new functional polymer is obtained. A novel polyester that can be used as a raw material for synthesis can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08G 65/26 C08G 65/26 F term (Reference) 4J005 AA04 AA07 AA11 BD02 4J029 AA01 AA07 AA08 AB01 AC01 AC02 AD01 AD07 AE03 AE11 AE13 BF30 CA01 CA02 CA03 CA04 CA05 CA06 CB04A CB04B CB05A CB05B CB06A CB06B CG09Y GA02 JC091 JC631 JF461 KB02 KB05 KE05 KE09

Claims (4)

[Claims] 1. A polyester represented by the general formula (1) having a hydroxymethyl group in a side chain. Embedded image (Where k represents an integer of 0 to 30. When k = 1, X
Is an alkylene group (which may contain an unsaturated bond, an aliphatic hydrocarbon ring, or an aromatic ring in the carbon chain), -CO
Represents an -NH-Z-NH-CO- group or a -CO- group,
When k is an integer of 2 to 30, X represents an ethylene group. Z
Represents an arylene group (an aromatic ring may be bonded via an alkylene group) or an alkylene group. Also, Y
Represents an arylene group (an aromatic ring may be bonded via an alkylene group) or an alkylene group, and m represents 0 or 1. R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n represents an integer of 2 or more. ) 2. The polyester according to claim ¹ , wherein R ¹ and R ² are methyl groups. 3. The polyester having a hydroxymethyl group in the side chain according to claim ¹ , wherein R ¹ and R ² are ethyl groups. 4. A dioxetane compound represented by the general formula (2): (In the formula, X, k, R ¹ and R ² are the same as described above.) The dicarboxylic acid represented by the general formula (3) is converted into (Wherein, Y and m are the same as described above.) The method for producing a polyester having a hydroxymethyl group in a side chain according to claim 1, wherein the polyaddition reaction is carried out in the presence of an onium salt.