JP2000219705A - New diol copolymer and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new diol copolymer which has diol units derived from vinylethylene carbonate and units derived from a monomer selected from among N-vinyl compounds, acrylic acid or its esters, (meth)acrylamides and vinyl ethers and/or units derived from maleic acid compounds and is useful for moldings, coating materials, hardenable pressure-sensitive adhesives, resin additives, etc. SOLUTION: The diol unit derived from vinylethylene carbonate is represented by formula I, and the unit derived from a maleic acid compound, by formula II. In the formulas, R1 to R5 are each H or alkyl; and M1 and M2 are each H, a metal atom, ammonium, an organic amine group or a hydrocarbon group, Here, the oxygen atom bonded to M1 may combine with a carbon atom bonded to M2 or a carbon atom bonded to M1 may combine with the oxygen atom bonded to M2, thus forming an acid anhydride group (-CO-O-CO-); in this case, M1 and OM2 are not present or OM1 and M2 are not.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel diol-based copolymer used for resin moldings, paints, adhesives, resin additives and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Known hydroxyl group-containing (co) polymers include, for example, polyvinyl alcohol and copolymers thereof, and hydroxyethyl poly (meth) acrylate and copolymers thereof. These hydroxyl group-containing (co) polymers are used in resin molded articles, paints, adhesives, resin additives, etc., utilizing their properties such as thermoplasticity and water solubility.

[0003]

An object of the present invention is to provide a novel diol-based copolymer and a method for producing the same.

[0004]

The novel diol copolymer according to the present invention comprises a diol structural unit (A) represented by the following general formula (i), an N-vinyl compound, acrylic acid, acrylic acid esters, At least one selected from the group consisting of (meth) acrylamides and vinyl ethers
And a structural unit (B) derived from a kind of monomer and / or a structural unit (C) represented by the following general formula (ii).

[0005]

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(Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group)

[0007]

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(Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, and M ¹ and M ² each independently represent a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. represented. However, if the carbon to oxygen and M ² which M ¹ is bonded is bonded to bind, or bonded with oxygen atoms and M ² which M ¹ is bonded is bonded (In this case, M ¹ and OM ² or OM ¹ and M ² do not exist.) The copolymer is obtained by removing a vinylethylene carbonate-based copolymer having a vinylethylene carbonate-based structural unit (D) represented by the following general formula (iii) and the structural unit (B) and / or the structural unit (C). Obtained by carbonic acid reaction May be used.

[0009]

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(In the formula, R ¹ , R ² and R ³ are the same as those in the general formula (i).) The method for producing the diol copolymer according to the present invention is represented by the following general formula (v) ) And at least one monomer selected from the group consisting of N-vinyl compounds, acrylic acid, acrylic esters, (meth) acrylic amides and vinyl ethers A copolymerization step of copolymerizing a monomer component containing a monomer (b) and / or a monomer (c) represented by the following general formula (vi), and the vinylethylene carbonate obtained in the copolymerization step A decarboxylation step of decarboxylation of the copolymer.

[0011]

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(In the formula, R ¹ , R ² and R ³ are the same as those in the general formula (i).)

[0013]

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(Wherein R ⁴ , R ⁵ , M ¹ and M ² are the same as those in the general formula (ii))

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the diol copolymer of the present invention and a method for producing the same will be sequentially described in detail. [Diol-based copolymer] The above-mentioned general formula (i) representing the diol structural unit (A) of the diol-based copolymer of the present invention.
Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group. Examples of the alkyl group which is an example of R ¹ , R ² and R ³ include, but are not particularly limited to, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n
An alkyl group having 1 to 4 carbon atoms such as -butyl group, isobutyl group and tert-butyl group is preferred. The alkyl group may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, and a sulfonic acid group, if necessary.

The diol-based copolymer of the present invention not only enhances the performance derived from the diol structural unit (A) of the copolymer, additionally imparts other properties to the copolymer, but also enhances the copolymer. Diol structural unit (A) occupying in polymer
Has the following structural units (B) and / or (C) for the purpose of widening the ratio of
These structural units (B) and (C) are appropriately selected depending on the purpose.

The structural unit (B) is at least one monomer (b) selected from the group consisting of N-vinyl compounds, acrylic acid, acrylic esters, (meth) acrylic amides and vinyl ethers. Is a structural unit derived from In particular, when the structural unit (B) is a structural unit derived from an N-vinyl compound, the copolymerizability between the N-vinyl compound and a vinyl ethylene carbonate-based monomer (a) described below is good, It is preferable because a diol-based copolymer having a structural unit derived from a monomer is easily obtained. From the same viewpoint, among the structural units derived from the N-vinyl compound, a structural unit represented by the following general formula (iv) is preferable.

[0018]

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(Wherein, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group, and X and Y each independently represent a hydrogen atom or an organic group; provided that X and Y
Are bonded to form a heterocyclic structure including a nitrogen atom. In the general formula (iv), specific examples of the alkyl group that is an example of R ⁶ , R ⁷ , and R ⁸ are not particularly limited, but R ¹ , R ² , and R in the general formula (i) are not particularly limited. Specific examples of the alkyl group in the ^third example include those described above.

In the above general formula (iv), examples of the organic group which is an example of X and Y include, but are not particularly limited to, a methyl group, an ethyl group, a phenyl group and the like. Also,
X and Y may combine to form a heterocyclic structure including a nitrogen atom. Such a heterocyclic structure is not particularly limited. For example, among the monomers described below used in the production method of the present invention, cyclic N-
The heterocyclic structure of the vinyl compound is exemplified. The organic group may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, and a sulfonic acid group, if necessary. Among the hydrogen atoms represented by X and Y and the above-mentioned organic groups, a hydrogen atom and a methyl group are preferable from the viewpoint of the copolymerizability described above.

The structural unit represented by the general formula (iv) is
It is derived from an N-vinyl compound represented by the following general formula (vii). The structural unit (C) is represented by the general formula (ii). In the general formula (ii), specific examples of the alkyl group which is an example of R ⁴ and R ⁵ are not particularly limited, but are examples of R ¹ , R ² and R ^{3 in} the general formula (i). Specific examples of the alkyl group include those described above.

In the general formula (ii), the metal atom which is an example of M ¹ and M ² is not particularly limited.
Sodium, calcium, potassium, lithium, barium and the like can be mentioned. Among these metal atoms, sodium, potassium and lithium are preferable from the viewpoint of improving the solubility of the diol copolymer in water. The organic amine group which is another example of M ¹ and M ² is not particularly limited, and examples thereof include a methylamine group, an ethylamine group, a dimethylamine group, a butylamine group, an octylamine group, a pyrrolidine group, and a morpholine group. No. Among these organic amine groups, a methylamine group and a dimethylamine group are preferable from the viewpoint of improving the solubility of the diol-based copolymer in water.

The hydrocarbon group which is another example of M ¹ and M ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a t-butyl group, a cyclohexyl group, a phenyl group and the like. No. The hydrocarbon group may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, and a sulfonic acid group, if necessary. The structural unit (C) is derived from a monomer (c) represented by the general formula (vi) described below. Among such structural units,
Structural units derived from at least one maleic monomer selected from the group consisting of maleic acid, maleic anhydride, a metal salt of maleic acid, and maleic acid esters, are combined with the maleic acid monomer as described below. It is preferable because it has good copolymerizability with the vinylethylene carbonate-based monomer (a) and is easy to obtain a diol-based copolymer having a structural unit derived from these monomers.

More specific examples of the monomer units (b) and (c) from which the structural units (B) and (C) are derived include monomer units copolymerized with a vinylethylene carbonate-based monomer (a) described below. Specific examples of the monomers (b) and (c) will be described later. In the diol-based copolymer of the present invention, the content of the diol structural unit (A) is not particularly limited, but is preferably 0.1 to 99.9% by weight, more preferably, based on the whole diol-based copolymer. Is 5 to 95% by weight, more preferably 10 to 90% by weight.

The weight-average molecular weight of the diol-based copolymer of the present invention is not particularly limited. For example, gel permeation chromatography (hereinafter referred to as “G
PC ") in terms of polyethylene glycol.
It is preferably 500 to 1,000,000, more preferably 3,000 to 500,000, and still more preferably 1 to 500,000.
It is between 000 and 200,000.

<Measurement Conditions of Weight Average Molecular Weight of Diol Copolymer> Model: Waters LCM1 (manufactured by Waters) Detector: Waters 410 (manufactured by Waters) Eluent: Type Acetonitrile / water = 40/60 Vol% pH 6.0 Flow rate: 0.6 ml / min Column: Kind TSK-GEL G4000SWXL x 3 + GUARD COLUMN Calibration curve: polyethylene glycol standard If the weight average molecular weight of the diol-based copolymer is less than 500, the copolymer is manufactured by Tosoh Corporation. Physical properties such as heat resistance tend to decrease, and when the weight average molecular weight exceeds 1,000,000, workability such as processing and handling of the copolymer tends to decrease, which is not preferable. .

The diol-based copolymer of the present invention is used, for example, in resin molded articles, paints, adhesives, resin additives and the like. The diol copolymer of the present invention can be obtained, for example, by the production method of the present invention described below, but the production method of the copolymer is not limited thereto. [Production method of diol-based copolymer] The production method of the present invention includes a copolymerization step and a decarboxylation step described below.

(Copolymerization step): In the copolymerization step, a vinylethylene carbonate monomer (a) represented by the above general formula (v), an N-vinyl compound, acrylic acid, acrylic acid esters, (meth) A monomer component containing at least one monomer (b) selected from the group consisting of acrylic acid amides and vinyl ethers and / or the monomer (c) represented by the general formula (vi). The polymerization reaction is performed.

Specific examples of the vinyl ethylene carbonate monomer (a) include, but are not particularly limited to, vinyl ethylene carbonate, 2-methyl-vinyl ethylene carbonate, 3-methyl-vinyl ethylene carbonate, and the like. Among these monomers (a), vinyl ethylene carbonate is preferred in that it is easily available and has good copolymerization reactivity. The monomer (a) is 1
Only one kind may be used, or two or more kinds may be used in combination.

In the copolymerization step, either one of the monomers (b) and (c) may be used, or both may be used. Among the monomers (b), as the N-vinyl compound,
Although not particularly limited, for example, the following general formula (vi
and i).

[0031]

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(In the formula, R ⁶ , R ⁷ , R ⁸ , X and Y are the same as those in the general formula (iv).) Specific examples of the N-vinyl compound represented by the general formula (vii) Although it does not specifically limit, N-vinylformamide, N-vinylacetamide, etc. are mentioned. Also,
Examples of those in which X and Y combine to form a heterocyclic structure including a nitrogen atom include N-vinylpyrrolidone, N-vinylpyrrolidone,
And cyclic N-vinyl compounds such as vinyl oxazolidone and N-vinyl caprolactam.

The N-vinyl compound is not limited to the above. For example, it may be N-vinylimidazole, N-vinyloxazoline, or the like. Further, the acrylates are not particularly limited, for example,
Methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, etc., which are synthesized by an esterification reaction between acrylic acid and an alcohol having 1 to 18 carbon atoms; hydroxyethyl acrylate, hydroxypropyl acrylate And sulfonic acid group-containing acrylates such as ethyl acrylate 2-ethyl sulphonate and derivatives thereof.

[0034] The (meth) acrylamides are not particularly restricted but include, for example, (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) amide. Acrylamide and the like can be mentioned. Although it does not specifically limit as a vinyl ether, For example, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, etc. are mentioned.

From the viewpoint of copolymerizability with the vinyl ethylene carbonate monomer (a), an N-vinyl compound is preferable among the above monomers (b), and among the N-vinyl compounds, the above-mentioned general formula Those shown in (vii) are preferred. Specific examples of the monomer (c) include, but are not particularly limited to, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and citraconic acid; unsaturated acid anhydrides such as maleic anhydride and citraconic anhydride; A half ester or diester of the above unsaturated dicarboxylic acid and an alcohol having 1 to 8 carbon atoms, such as monomethyl maleate, dimethyl maleate, diethyl maleate, monomethyl fumarate and dimethyl fumarate; Examples thereof include a monovalent metal salt, a divalent metal salt, an ammonium salt and an organic amine salt.

Among the monomers (c), at least one maleic acid monomer selected from the group consisting of maleic acid, maleic anhydride, metal salts of maleic acid and maleic esters is vinyl ethylene carbonate. It is preferable from the viewpoint of copolymerizability with the system monomer (a). Monomer (c)
May be used alone or in combination of two or more.

The proportion of the vinyl ethylene carbonate monomer (a) in the monomer components to be copolymerized is not particularly limited, but is preferably 0.1 to 9 relative to all monomer components.
It is 9.9% by weight, more preferably 5 to 95% by weight, and still more preferably 10 to 90% by weight. As the copolymerization method, known copolymerization methods, for example, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like can be used, and there is no particular limitation.

[0038] The copolymerization temperature is not particularly limited, but is preferably from 0 to 300 ° C, more preferably from 25 to 150 ° C.
It is. If the copolymerization temperature is lower than 0 ° C., the copolymerization reactivity tends to decrease, and if it exceeds 300 ° C., side reactions increase and the reaction control becomes difficult, which is not preferable. The solvent for the copolymerization reaction is not particularly limited. For example, a single solvent or a mixed solvent selected from the following solvent groups can be used.

(1) Aliphatic hydrocarbons such as hexane and octane; (2) Alicyclic saturated hydrocarbons such as cyclohexane; (3) Alicyclic unsaturated hydrocarbons such as cyclohexene; (4) Benzene (5) ketones such as acetone and methyl ethyl ketone; (6) esters such as methyl acetate, ethyl acetate, butyl acetate, and γ-butyrolactone; (7) dichloroethane, chloroform; Halogenated hydrocarbons such as carbon tetrachloride; (8) ethers such as diethyl ether, dioxane, dioxolane; (9) alkylene glycol ethers such as propylene glycol monomethyl ether acetate and diethylene glycol monomethyl ether acetate; (10) methyl Alcohol, ethyl alcohol, butyl Alcohols such as alcohol, isopropyl alcohol, ethylene glycol and propylene glycol monomethyl ether; (11) amides such as dimethylformamide and N-methylpyrrolidone; (12) sulfonic acid esters such as dimethyl sulfoxide; (13) dimethyl carbonate; (14) Alicyclic carbonates such as ethylene carbonate and propylene carbonate; (15) Water.

Among these solvents, solvent groups (4) to (6), from the viewpoint of easiness of purification and recovery of the produced copolymer,
Those selected from (8) to (15) are preferable,
Those selected from (8) to (15) are more preferable. When performing the copolymerization reaction, the concentration of the monomer component in the raw material mixture is not particularly limited, but preferably 1 to 100
%, More preferably from 5 to 95% by weight, even more preferably from 10 to 90% by weight. If this ratio is less than 1% by weight, the productivity tends to be poor, which is not preferable.

The copolymerization reaction is usually carried out using a polymerization initiator. The polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile, azobis (2-methyl) butyronitrile, 2,2 ′
Azo compounds such as dimethyl azobis (isobutyrate); peroxides such as benzoyl peroxide and di-tert-butyl peroxide. One type of polymerization initiator may be used alone, or two or more types may be used in combination.

The amount of the polymerization initiator is not particularly limited, but is preferably from 0.001 to
It is 10% by weight, more preferably 0.01 to 5% by weight, still more preferably 0.1 to 3% by weight. If the amount of the polymerization initiator is less than 0.001% by weight, the copolymerization reaction tends to be extremely slow, and if it exceeds 10% by weight, the side reaction tends to increase, which is not preferable.

At the time of the copolymerization reaction, a chain transfer agent such as lauryl mercaptan or mercaptoethanol or a regulator may be used. The copolymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. Examples of a method for purifying the vinylethylene carbonate-based copolymer produced by the copolymerization reaction include a method for removing the solvent by reprecipitation, dialysis, centrifugation, drying under reduced pressure, and the like, but are not particularly limited.

(Decarboxylation step): In the decarboxylation step, the vinylethylene carbonate copolymer obtained in the above copolymerization step is subjected to a decarboxylation reaction. The vinylethylene carbonate-based copolymer is a copolymer having a vinylethylene carbonate-based structural unit (D) represented by the general formula (iii) and the structural unit (B) and / or the structural unit (C). .

In the decarboxylation reaction, a diol structure is formed by decarboxylation of the ethylene carbonate ring on the side chain of the vinylethylene carbonate structural unit (D) of the vinylethylene carbonate copolymer to open the ring. The content of the vinylethylene carbonate-based structural unit (D) in the vinylethylene carbonate-based copolymer is not particularly limited, but is preferably 0.1 to 99.
It is 9% by weight, more preferably 5 to 95% by weight, still more preferably 10 to 90% by weight.

The weight-average molecular weight of the vinylethylene carbonate-based copolymer is not particularly limited.
It is preferably 500 to 1,000,000, more preferably 3,000 to 500,000, and still more preferably 1 to 500,000.
It is between 000 and 200,000. <Measurement conditions of weight average molecular weight of vinyl ethylene carbonate copolymer> Model: LC10A series (manufactured by Shimadzu) Detector: RID6A (manufactured by Shimadzu) Eluent: Type DMF (dimethylformamide) + 0.1 wt% LiBr Flow rate 0.8 ml / min Column: Type TSK GEL manufactured by Tosoh Corporation α-2500 × 2, α-3000 × 1, α-6000 × 1 + GUARD COLUMN Calibration curve: Weight average molecular weight of polystyrene-based vinyl ethylene carbonate copolymer is less than 500 And the physical properties such as heat resistance of the copolymer tend to decrease, and the weight average molecular weight is
If it exceeds 000, workability such as processing and handling of the copolymer tends to decrease, which is not preferable.

When the vinylethylene carbonate copolymer is subjected to a decarboxylation reaction, the reaction temperature is not particularly limited, but is preferably 0 to 300 ° C, more preferably 10 to 300 ° C.
The temperature is 150 ° C, more preferably 25 to 120 ° C. If the reaction temperature is lower than 0 ° C., the progress of the reaction tends to be slow, and if it exceeds 300 ° C., the copolymer tends to undergo thermal decomposition, which is not preferable.

In the decarboxylation reaction, the reaction pressure is, for example,
The pressure may be about normal pressure to about 100 kg / cm ² and is not particularly limited. The reaction solvent used in the decarboxylation reaction is not particularly limited. For example, the solvent groups (1) to (1) exemplified above as the solvent used in the copolymerization reaction for obtaining the vinylethylene carbonate-based copolymer
A single solvent or a mixed solvent selected from 5) can be used. In order to allow the homogeneous reaction to proceed to the end without generating a precipitate, the reaction solvent is selected from the polar solvent groups (5), (6), (9) to (15) among the above reaction solvents. It is preferable to use one selected from the group consisting of alcohols (10) and water (15).

When performing the decarboxylation reaction, the concentration of the vinylethylene carbonate copolymer in the raw material mixture is not particularly limited, but is preferably 1 to 99% by weight, more preferably 5 to 80% by weight, and further preferably 10 to 80% by weight. ６０60% by weight. If this ratio is less than 1% by weight, productivity tends to be poor, and if it exceeds 99% by weight, the viscosity of the raw material mixture tends to be very high, and handling tends to be difficult, which is not preferable. .

The decarboxylation reaction may be carried out using a reaction catalyst to accelerate the reaction. The reaction catalyst is not particularly restricted but includes, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methylate, lithium methylate, sodium ethylate, tertiary amine compounds, quaternary ammonium salts, anion exchange resins And basic catalysts such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, zeolite and cation exchange resin. The reaction catalyst may be used alone or in combination of two or more.

The method of purifying the diol-based copolymer produced by the decarboxylation reaction includes, for example, a method of removing the solvent by reprecipitation, dialysis, centrifugation, drying under reduced pressure, etc., but is not particularly limited. .

[0052]

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" indicating units are "parts by weight" and "% by weight", respectively, unless otherwise specified.
Shall be expressed. In the following examples, the weight average molecular weight (hereinafter referred to as "M
w ") is a value in terms of polystyrene determined by GPC under the above-described measurement conditions, and Mw of the diol-based copolymer is a value in terms of polyethylene glycol determined by GPC under the above-described measurement conditions. <Example 1> In a reactor equipped with a thermometer, a reflux cooling pipe, a nitrogen gas introduction pipe, and a stirrer, 50 parts of vinylethylene carbonate (hereinafter, referred to as "VEC") and vinylpyrrolidone (hereinafter, referred to as "VP"). After charging 50 parts,
The inside of the reactor was replaced with nitrogen gas. Next, the temperature of the mixture in the reactor was raised to 70 ° C. while stirring, and then 2,2′-azobis (isobutyric acid) dimethyl (hereinafter “M”) was used as a polymerization initiator.
AIB "), and a polymerization reaction was carried out. During this polymerization reaction, the viscosity of the reaction solution increased, and finally, after 5 hours, stirring became difficult. Therefore, the reaction was stopped and cooled to room temperature.

Thereafter, the reaction solution was dissolved in dimethylformamide (hereinafter referred to as "DMF"), and the resulting solution was poured into a 5-fold (by volume) methanol with stirring. This resulted in a white solid. This solid was separated by filtration and sufficiently washed with methanol. Next, the solid is dissolved in DMF, and the obtained solution is poured into a five-fold volume (by volume) of methanol with stirring to reprecipitate the solid, followed by filtration and washing with methanol. The solid was purified by repeating the reprecipitation operation 2 to 3 times, and then dried under reduced pressure. As a result, poly (VEC-VP) was obtained as a vinylethylene carbonate-based copolymer in a yield of about 50%. In addition, this copolymer was identified by ¹ H-NMR. The copolymer had Mw of 80,000 and a VEC structural unit content of 4
It was 5% by weight.

Next, 20 parts of the copolymer obtained above and 80 parts of a 2% aqueous sodium hydroxide solution were mixed at room temperature, and the resulting mixture was reacted at 40 ° C. for 3 hours with stirring. The mixed solution was cloudy at the beginning of mixing, but became a uniform solution after the reaction. Thereafter, the cation exchange resin was added to the reaction solution, and after confirming that the pH of the reaction solution was around 7, the cation exchange resin was separated by filtration. afterwards,
The reaction solution was poured into a 5-fold (by volume) acetone with stirring. As a result, a white fibrous solid was obtained. This solid was separated by filtration and sufficiently washed with acetone. Next, the solid is dissolved in water, and the obtained solution is poured into a 5-fold volume (by volume) of acetone with stirring to reprecipitate the solid, followed by filtration and washing with acetone. The solid was purified by repeating the reprecipitation operation 2 to 3 times, and then dried under reduced pressure. Dried solid by ¹ H
-Analyzed by NMR and IR. The results are shown in FIGS. 1 and 2, respectively. From these figures, the obtained solid was poly (3-butene-1,2-diol-vinylpyrrolidone) (diol-based copolymer; hereinafter, referred to as “P (BDL-V
P) "). In addition, this P (B
DL-VP) yield is about 95%, Mw is 60,000,
The BDL structural unit content was 30% by weight. <Example 2> A reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube and a stirrer was charged with 50 parts of VEC and 50 parts of maleic anhydride (hereinafter referred to as "MAn"), and then charged in the reactor. Was replaced with nitrogen gas. Next, the temperature of the mixture in the reactor was raised to 70 ° C. while stirring, and then 1 part of MAIB was added as a polymerization initiator to carry out a polymerization reaction for 5 hours. During this polymerization reaction, the viscosity of the reaction solution increased. After the completion of the reaction, the resultant was cooled to room temperature.

Thereafter, the reaction solution is dissolved in dimethyl sulfoxide (hereinafter, referred to as “DMSO”), and the obtained solution is dissolved in a 5-fold (by volume) tetrahydrofuran (hereinafter, referred to as “THF”). Poured in with stirring.
This resulted in a white solid. This solid was filtered off and washed thoroughly with THF. The solid was then added to DMSO
And the resulting solution is diluted 5 times (by volume) with TH.
After re-precipitating the solid by pouring into F while stirring, the solid is purified by repeating the re-precipitation operation of filtering and washing sufficiently with THF two to three times, and then dried under reduced pressure. I let it. As a result, poly (VEC-M) was obtained as a vinylethylene carbonate-based copolymer in a yield of about 35%.
An) was obtained. The identification of this copolymer was ¹ H-
Performed by NMR. The Mw of the copolymer was 5,000, and the VEC structural unit content was 55% by weight.

Next, 20 parts of the copolymer obtained above and 80 parts of a 10% aqueous solution of sodium hydroxide were mixed at room temperature, and the resulting mixture was reacted at 40 ° C. for 3 hours with stirring. The above mixture was cloudy at the beginning of mixing,
After the reaction, a homogeneous solution was obtained. Thereafter, the cation exchange resin was added to the reaction solution, and after confirming that the pH of the reaction solution was around 7, the cation exchange resin was separated by filtration. Thereafter, the reaction solution was poured into a 5-fold (by volume) acetone with stirring. As a result, a white fibrous solid was obtained. This solid was separated by filtration and sufficiently washed with acetone. The solid is then dissolved in water and the resulting solution is
The solid is re-precipitated by pouring it into a double volume (by volume) of acetone with stirring, and then the solid is purified by repeating a re-precipitation operation of filtering and washing sufficiently with acetone 2-3 times. After that, it was dried under reduced pressure. After drying the solid
^It was analyzed by ¹ H-NMR and IR. The results are shown in FIGS. 3 and 4, respectively. From these figures, the obtained solid was poly (3-butene-1,2-diol-maleic acid) (diol-based copolymer; hereinafter, referred to as “P (BDL-M
A) "). In addition, this P (B
DL-MA) yield is about 95%, Mw is 3,000, B
The DL structural unit content was 35% by weight.

[0057]

The novel diol-based copolymer of the present invention has a diol structural unit (A) represented by the above general formula (i), and therefore exhibits properties such as thermoplasticity and hydrophilicity derived from the structural unit. I do. Since the method for producing a diol copolymer of the present invention includes the copolymerization step and the decarboxylation step, the novel diol copolymer of the present invention can be easily obtained.

[Brief description of the drawings]

FIG. 1 shows the poly (3-butene-1,2) obtained in Example 1.
- diol - vinylpyrrolidone) of the ¹ H-NMR chart (solvent: D ₂ O, ppm of abscissa chemical shift δ values of the reference substance).

FIG. 2 shows the poly (3-butene-1,2) obtained in Example 1.
-Diol-vinylpyrrolidone) (Wavenumbers on the horizontal axis are wave numbers (cm ^-1 ) and T on the vertical axis)
(transmittance is transmittance (%)).

FIG. 3 shows poly (3-butene-1,2) obtained in Example 2.
- diol - ¹ H-NMR chart of maleic acid) (solvent: D ₂ O, ppm of abscissa chemical shift δ values of the reference substance).

FIG. 4 shows the poly (3-butene-1,2) obtained in Example 2.
-Diol-maleic acid) IR chart (horizontal axis Wa)
“venumbers” is wave number (cm ⁻¹ ), and Tran on the vertical axis is
Smittance is transmittance (%).

Front page of the continued F-term (reference) 4J100 AD11P AE02Q AE03Q AE04Q AJ08Q AJ08R AJ09Q AJ09R AK19Q AK19R AK20Q AK20R AK21Q AK21R AK31Q AK31R AK32Q AK32R AL03Q AL08Q AL09Q AL34Q AL34R AL36Q AL36R AM15Q AM17Q AM19Q AN04Q AN06Q AQ01P AQ06Q AQ08Q AQ15Q AQ19Q BA56Q BC04Q CA04 CA05 CA31 DA01 HA55 HB25 HB39 HB44 HB52 HC12 HC42 HC45 HC71 HE41 JA01 JA03 JA05

Claims (5)

[Claims] 1. A diol structural unit (A) represented by the following general formula (i), and selected from the group consisting of N-vinyl compounds, acrylic acid, acrylic esters, (meth) acrylic amides and vinyl ethers. And / or a structural unit (B) derived from at least one monomer and / or the following general formula (i)
A novel diol-based copolymer having the structural unit (C) represented by i). Embedded image (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group.) (In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, and M ¹ and M ² each independently represent a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. , M ¹ is bound to oxygen and M ²
Is bonded to the carbon to which M ¹ is bonded, or the carbon to which M ¹ is bonded and the oxygen to which M ² is bonded to form an acid anhydride group (—CO—O—CO—). Includes what constitutes it. In this case, M ¹ and OM ² or OM ¹
And M ² does not exist. ) 2. A decarboxylation of a vinyl ethylene carbonate copolymer having a vinyl ethylene carbonate structural unit (D) represented by the following general formula (iii) and the structural unit (B) and / or the structural unit (C): The novel diol-based copolymer according to claim 1, which is obtained by reacting. Embedded image (In the formula, R ¹ , R ² , and R ³ are the same as those in the general formula (i).) 3. The structural unit (B) is a structural unit derived from the N-vinyl compound, and the structural unit derived from the N-vinyl compound is a structural unit represented by the following general formula (iv). Item 3. The novel diol copolymer according to Item 1 or 2. Embedded image (Wherein, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group, X and Y each independently represent a hydrogen atom or an organic group, provided that X and Y are combined to form a nitrogen atom And those which form a heterocyclic structure including.) 4. A structural unit wherein said structural unit (C) is derived from at least one maleic monomer selected from the group consisting of maleic acid, maleic anhydride, maleic acid metal salts and maleic esters. The novel diol-based copolymer according to any one of claims 1 to 3, wherein 5. A composition comprising a vinylethylene carbonate monomer (a) represented by the following general formula (v), an N-vinyl compound, acrylic acid, acrylic esters, (meth) acrylamide and vinyl ethers. A copolymerization step of copolymerizing a monomer component containing at least one monomer (b) selected from the group and / or a monomer (c) represented by the following general formula (vi); A decarboxylation step of decarboxylation of the vinylethylene carbonate-based copolymer obtained in the copolymerization step, and a method for producing a diol-based copolymer. Embedded image (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group.) (In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, and M ¹ and M ² each independently represent a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. , M ¹ is bound to oxygen and M ²
Is bonded to the carbon to which M ¹ is bonded, or the carbon to which M ¹ is bonded and the oxygen to which M ² is bonded to form an acid anhydride group (—CO—O—CO—). Includes what constitutes it. In this case, M ¹ and OM ² or OM ¹
And M ² does not exist. )