JP2000313721A - New hydroxy group-containing copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer which has a diol structural unit and a vinyl alcoholic structural unit, in which the decrease of properties is suppressed by regulating a molecular weight and a hydroxy value so as to be within specific ranges, and which is useful for a resin molded product, a coating material or the like. SOLUTION: This copolymer comprises (A) a diol structural unit of formula I, preferably of 0.1-50 mol%, and (B) a vinyl alcoholic structural unit of formula II (R1 to R6 are each H or an alkyl), preferably of 99.9-50 mol%, and has >=10,000 weight average molecular weight and >=1,000 mgKOH/g hydroxy value. The copolymer can be obtained by a method or the like for copolymerizing a vinylethylene carbonate-based monomer (e.g. vinylethylene carbonate) with a vinyl ester-based monomer (e.g. vinyl acetate) to provide a copolymer, and hydrolyzing the obtained copolymer. The copolymer exhibits properties such as thermoplasticity and hydrophilicity, and is excellent in properties such as toughness, flexibility and softness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel hydroxyl group-containing copolymer used for resin molded articles, paints, adhesives, resin additives, packaging materials, films and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Hydroxyl group-containing (co) polymers include, for example, polyvinyl alcohol and copolymers thereof.
Hydroxyethyl poly (meth) acrylate and copolymers thereof are known. No. 2,518,4.
No. 40 discloses a hydroxyl group-containing (co) polymer obtained by hydrolyzing a homopolymer of vinylethylene carbonate or a copolymer of vinylethylene carbonate and various other vinyl compounds. I have. These hydroxyl group-containing (co) polymers are used in resin moldings, paints, adhesives, resin additives, packaging materials, films, etc. by utilizing their properties such as thermoplasticity and water solubility. .

[0003]

An object of the present invention is to provide a novel hydroxyl group-containing copolymer and a method for producing the same.

[0004]

Means for Solving the Problems To solve the above problems, the present inventors have made various studies. In the process, attention was paid to a hydroxyl group-containing copolymer obtained by hydrolyzing a copolymer of vinyl ethylene carbonate and vinyl acetate. However, the present inventors have found that the hydroxyl group-containing copolymer has a problem that its physical properties are reduced depending on the molecular weight and the hydroxyl value. Thus, the present inventors have conducted further studies, and as a result,
When the molecular weight and the hydroxyl value of the above-mentioned hydroxyl group-containing copolymer are in the following specific ranges, it has been found that deterioration in physical properties can be suppressed, and the present invention has been completed.

That is, the novel hydroxyl group-containing copolymer according to the present invention comprises a diol structural unit (A) represented by the following general formula (i) and a vinyl alcohol structural unit (B) represented by the following general formula (ii): Having a weight average molecular weight of 1
000 or more and a hydroxyl value of 1,000 mg KO
H / g or more.

[0006]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ each independently represents a hydrogen atom or an alkyl group. Further, the method for producing a hydroxyl group-containing copolymer according to the present invention comprises a vinyl ethylene carbonate monomer (a) represented by the following general formula (iii) and a vinyl ester monomer represented by the following general formula (iv): A novel hydroxyl group-containing compound of the present invention by subjecting the vinyl ethylene carbonate-based copolymer obtained in the copolymerization step to a copolymerization step of copolymerizing a monomer component containing the compound (b) And a hydrolysis step of obtaining a copolymer.

[0008]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group. In addition, the novel hydroxyl group-containing copolymer of the present invention may be one obtained by the production method of the present invention.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the hydroxyl group-containing copolymer of the present invention and a method for producing the same will be sequentially described in detail. [Hydroxyl Group-Containing Copolymer] In the general formula (i) representing the diol structural unit (A) of the hydroxyl group-containing copolymer of the present invention, R ¹ , R ² and R ³ are each independently a hydrogen atom or It is an alkyl group. R ¹ , R ² , R ³
Examples of the alkyl group include, but are not particularly limited to, for example, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, ter
An alkyl group having 1 to 4 carbon atoms such as a t-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 hydroxyl group-containing copolymer of the present invention comprises:
In addition to enhancing the performance derived from the diol structural unit (A) of the copolymer or adding other performances to the copolymer, the proportion of the diol structural unit (A) in the copolymer For the purpose of obtaining a wide range of the above, the vinyl alcohol-based structural unit (B) represented by the general formula (ii)
Has further. The structural unit (B) is appropriately selected depending on the purpose.

In the general formula (ii) representing the vinyl alcohol structural unit (B), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group. R ⁴ , R ⁵ , R
Specific examples of the alkyl group as the example of ⁶ are not particularly limited, but those described above as specific examples of the alkyl group as examples of R ¹ , R ² and R ^{3 in} the general formula (i) are given. be able to.

In the hydroxyl group-containing copolymer of the present invention,
The content of the diol structural unit (A) and the vinyl alcohol-based structural unit (B) is not particularly limited, but is preferably (A) 0.1 to 0.1 based on the total amount of these structural units.
50 mol%, (B) 99.9-50 mol%, more preferably (A) 0.5-30 mol%, (B) 99.5-70
Mol%, more preferably (A) 1.0 to 15 mol%,
(B) 99.0 to 85 mol%. When the content of the diol structural unit (A) is less than 0.1 mol%, the crystallinity of the hydroxyl group-containing copolymer becomes too high, and the copolymer tends to have poor water solubility at low temperatures. There are 50
If it exceeds mol%, the crystallinity of the copolymer is greatly reduced, and the copolymer tends to have reduced physical properties such as toughness, flexibility, and flexibility.

The weight average molecular weight of the hydroxyl group-containing copolymer of the present invention can be determined, for example, by gel permeation chromatography (hereinafter referred to as "GPC") under the following measurement conditions.
Is usually 10,000 in terms of polyethylene glycol
0 or more, preferably 10,000 to 1,000,000
0, more preferably 10,000 to 500,000, and still more preferably 10,000 to 200,000.

<Weight average molecular weight measurement conditions of hydroxyl group-containing 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: Type TSK-GEL G4000SWXL x 3 + GUAR manufactured by Tosoh Corporation
D COLUMN Calibration Curve: Weight average molecular weight of a hydroxyl group-containing copolymer based on polyethylene glycol was 10,
If it is less than 000, the toughness, flexibility, flexibility,
Physical properties such as adhesiveness, dispersibility, oil resistance, weather resistance, and heat resistance are reduced.

The hydroxyl value of the hydroxyl group-containing copolymer of the present invention is usually 1,000 mg KOH / g, as measured by, for example, JIS-K0070-7.1 neutralization titration or ¹ H-NMR. (The maximum value is theoretically 1,275), preferably 1,075 mg KO
H / g or more, more preferably 1,100 mgKOH / g
That is all. If the hydroxyl value is less than 1,000 mgKOH / g, the water solubility of the hydroxyl group-containing copolymer at 40 ° C. or higher will be poor.

The hydroxyl group-containing copolymer of the present invention comprises:
For example, resin moldings, paints, adhesives, resin additives,
Used for packaging materials, films, etc.

The hydroxyl group-containing copolymer of the present invention comprises:
For example, it can be obtained by the production method of the present invention described below, but the production method of the copolymer is not limited thereto. [Production Method of Hydroxyl Group-Containing Copolymer] The production method of the present invention comprises a copolymerization step of producing a vinylethylene carbonate-based copolymer described below, and hydrolysis of the copolymer to form a hydroxyl group-containing copolymer of the present invention. And obtaining a hydrolysis step.

(Copolymerization step): In the copolymerization step, a vinylethylene carbonate monomer (a) represented by the general formula (iii) and a vinyl ester monomer (b) represented by the general formula (iv) Are copolymerized.

In the above general formula (iii) representing the vinyl ethylene carbonate monomer (a), R ¹ , R ² , R
³ is the same as that in the general formula (i).

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.

The vinyl ester monomer (b)
In the general formula (iv), R^Four, R^Five, R ⁶Is the aforementioned general formula (i
i) is the same as that in⁷Is R^Four, R^Five, R⁶When
Independently represents a hydrogen atom or an alkyl group. R⁷In the example
Specific examples of a certain alkyl group are not particularly limited.
Is a group represented by R in the general formula (i)¹, R^Two, R^ThreeIs an example of
Specific examples of the alkyl group include those described above.
it can.

Specific examples of the vinyl ester monomer (b) are not particularly limited, but include vinyl acetate, vinyl propionate, vinyl lactate, vinyl butyrate, vinyl caproate, vinyl pivalate, vinyl laurate, and stearin. Vinyl acid and the like can be mentioned. Among these, vinyl acetate and vinyl propionate are preferred from the viewpoint of copolymerizability with the vinyl ethylene carbonate monomer (a).

The vinyl ester monomer (b) may be used alone or in combination of two or more.

In the monomer components to be copolymerized, the ratio of the vinyl ethylene carbonate monomer (a) and the vinyl ester monomer (b) is not particularly limited, but the total amount of these monomers is On the other hand, preferably (a) 0.1 to 5
0 mol%, (b) 99.9 to 50 mol%, more preferably (a) 0.5 to 30 mol%, (b) 99.5 to 70 mol%, further preferably (a) 1.0 to 15 mol%,
(B) 99.0 to 85 mol%. If the proportion of the vinylethylene carbonate-based monomer (a) is less than 0.1 mol%, the crystallinity of the hydroxyl group-containing copolymer as the final target product becomes too high. When the content exceeds 50 mol%, the crystallinity of the copolymer is significantly reduced, and the physical properties of the copolymer such as toughness, flexibility, and flexibility are reduced. It tends to happen.

As the copolymerization method, a known copolymerization method,
For example, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like can be used, and there is no particular limitation.

The copolymerization temperature is not particularly limited, but is preferably 0 to 300 ° C., more preferably 10 to 200 ° C.
° C, more preferably 25 to 150 ° C. 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,
(5), (6), (9), (10), (11), (1
Those selected from 4) and (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 is preferably 1%.
-100% by weight, more preferably 5-95% by weight, even more preferably 10-90% by weight. If this ratio is less than 1% by weight, the productivity tends to be poor, which is not preferable.

[0032] 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 carried out in an atmosphere of an inert gas such as nitrogen or argon.

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

(Hydrolysis step): In the hydrolysis step, the vinylethylene carbonate-based copolymer obtained in the copolymerization step is subjected to a hydrolysis reaction.

The above-mentioned vinylethylene carbonate-based copolymer is a copolymer having a vinylethylene carbonate-based structural unit (C) represented by the following general formula (v) and a vinyl ester-based structural unit (D) represented by the following general formula (vi). It is united.

[0039]

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(Wherein R ¹ , R ² , and R ³ are the same as those in the general formula (iii), and R ⁴ , R ⁵ , R ⁶ ,
R ⁷ is the same as that in the general formula (iv). In the hydrolysis reaction, the ethylene carbonate ring in the side chain of the vinyl ethylene carbonate-based structural unit (C) of the vinyl ethylene carbonate-based copolymer undergoes a hydrolysis reaction to open the ring, whereby the diol structural unit (A) is formed. In addition, the ester group of the side chain of the vinyl ester-based structural unit (D) is hydrolyzed and cleaved to form the vinyl alcohol-based structural unit (B). A polymer is obtained.

The content of the vinyl ethylene carbonate structural unit (C) and the vinyl ester structural unit (D) in the vinyl ethylene carbonate copolymer is not particularly limited, but is preferably based on the total amount of these structural units. Are (C) 0.1 to 50 mol%, (D) 99.9 to
50 mol%, more preferably (C) 0.5 to 30 mol%, (D) 99.5 to 70 mol%, still more preferably (C) 1.0 to 15 mol%, (D) 99.0 to 90 mol%. 85 mol%. If the content of the vinylethylene carbonate-based structural unit (C) is less than 0.1 mol%, the crystallinity of the hydroxyl group-containing copolymer, which is the target product, becomes too high. Water solubility tends to deteriorate, and if it exceeds 50 mol%, the crystallinity of the copolymer is drastically reduced, and physical properties such as toughness, flexibility, and flexibility of the copolymer are reduced. And so on.

The weight-average molecular weight of the vinylethylene carbonate-based copolymer is not particularly limited.
Usually 10,000 or more, preferably 10,000 to 1,
1,000,000, more preferably 10,000-50
0000, more preferably 10,000 to 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 piece, α-6000 × 1 piece + GUARD COLUMN Calibration curve: polystyrene standard If the weight average molecular weight of the vinyl ethylene carbonate copolymer is less than 10,000, the toughness and flexibility of the hydroxyl group-containing copolymer, which is the target product, , Physical properties such as flexibility, adhesiveness, dispersibility, oil resistance, weather resistance, heat resistance, etc. are reduced.

When the vinylethylene carbonate copolymer is subjected to a hydrolysis reaction, the reaction temperature is not particularly limited, but is preferably 0 to 300 ° C., more preferably 10 to 300 ° C.
To 200 ° C, more preferably 25 to 150 ° C.
If the reaction temperature is lower than 0 ° C., the progress of the reaction tends to be very slow, and if it exceeds 300 ° C., the side reaction such as thermal decomposition of the copolymer tends to increase, which is not preferable.

In the hydrolysis reaction, the reaction pressure may be, for example, normal pressure to about 100 kg / cm ² , and is not particularly limited.

The reaction solvent used in the hydrolysis reaction is not particularly limited, but, for example, the solvent groups (1) to (1) exemplified above as the solvent used in the copolymerization reaction for obtaining the vinyl ethylene carbonate copolymer. 1
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 hydrolysis reaction, the concentration of the vinylethylene carbonate copolymer in the raw material mixture is not particularly limited, but is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and further preferably 20 to 80% by weight. ~ 6
0% by weight. If this ratio is less than 5% by weight, the productivity tends to be poor, and if it exceeds 90% by weight, the viscosity of the raw material mixture tends to be extremely high, and handling tends to be difficult. .

The hydrolysis 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 for purifying the hydroxyl group-containing copolymer produced by the hydrolysis reaction includes, for example, a method of removing the solvent by reprecipitation, dialysis, centrifugal separation, drying under reduced pressure, etc., but is not particularly limited. Not done.

[0050]

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 “Mw”) of the vinyl ethylene carbonate copolymer is a value in terms of polystyrene determined by GPC under the above-described measurement conditions, and The Mw of the union is a value in terms of polyethylene glycol obtained by GPC under the measurement conditions described above. The hydroxyl value in the following examples is a value obtained by measuring ¹ H-NMR and analyzing the composition. <Example 1> In a reactor equipped with a thermometer, a reflux cooling pipe, a nitrogen gas introduction pipe, and a stirrer, 57 parts of vinylethylene carbonate (hereinafter, referred to as "VEC") and vinyl acetate (hereinafter, "VAc") were used. After charging 43 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 was used as a polymerization initiator.
2′-azobis (isobutyric acid) dimethyl (hereinafter referred to as “MAI
B), and a copolymerization reaction was carried out. During this copolymerization reaction, the viscosity of the reaction solution increases, and finally the
After an hour, stirring became difficult, so 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-VAc) was obtained as a vinylethylene carbonate copolymer in a yield of about 50%. In addition, this copolymer was identified by ¹ H-NMR. The Mw of this copolymer was 60,000, the VEC structural unit content was 50 mol%, and the VAc structural unit content was 50 mol%.

Next, 20 parts of the copolymer obtained above and 80 parts of a 20% aqueous sodium hydroxide solution were mixed at room temperature, and the resulting mixture was subjected to a hydrolysis reaction at 80 ° C. for 5 hours while 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. 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. 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. The solid after drying was analyzed by ¹ H-NMR, ¹³ C-NMR and IR. The results are shown in FIGS. 1, 2 and 3, respectively.
From these figures, the obtained solid was poly (3-butene-
1,2-diol-vinyl alcohol) (a hydroxyl group-containing copolymer; hereinafter, referred to as “P (BDL-VAL)”). In addition, this P (BDL-VA
The yield of L) was about 95%, the Mw was 33,000, the hydroxyl value was 1,275 mgKOH / g, the BDL structural unit content was 50 mol%, and the VAL structural unit content was 50 mol%. <Example 2> A reactor equipped with a thermometer, a reflux cooling pipe, a nitrogen gas introducing pipe and a stirrer was charged with 18 parts of VEC and VAc32.
And 50 parts of acetone, the inside of the reactor was purged with nitrogen gas. Next, the mixture in the reactor was heated to 70 ° C. while stirring, and 1 part of MAIB was added as a polymerization initiator, and after another 3 hours, another part of MAIB was added and the copolymerization reaction was performed for 7 hours. After confirming disappearance of VEC and VAc by gas chromatography (hereinafter referred to as “GC”), the mixture was cooled to room temperature.

Thereafter, the reaction solution was dissolved in DMF, and the resulting solution was poured into a 5-fold volume (by volume) of 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-VAc) was obtained as a vinylethylene carbonate-based copolymer with a yield of about 98%. The identification of this copolymer was performed by ¹ H-NMR, and it was confirmed that the copolymer was copolymerized according to the charged ratio. The Mw of the copolymer was 30,000, the VEC structural unit content was 30 mol%, and the VAc structural unit content was 70 mol%.

Thereafter, the hydrolysis reaction of poly (VEC-VAc) and the purification of the reaction product were carried out in the same manner as in Example 1, and as a result, a hydroxyl group-containing copolymer was obtained in a yield of about 95%. P (BDL-VAL) was obtained as a polymer.
The copolymer was identified by ¹ H-NMR, ¹³ C-
Performed by NMR and IR. In addition, this P (BDL-V
AL) has a Mw of 18,000 and a hydroxyl value of 1,250 m.
gKOH / g, BDL structural unit content is 30 mol%, V
The AL structural unit content was 68 mol%, and the VAc structural unit content was 2 mol%. <Example 3> In Example 2, the charged amounts of VEC and VAc were changed to 6 parts and 44 parts, respectively, and a methanol-water mixed solvent (methanol / water weight ratio = By performing the same operation as in Example 2 except that 8/2) was used, poly (VEC-VAc) was obtained as a vinylethylene carbonate-based copolymer in a yield of about 98%. The identification of this copolymer was performed by ¹ H-NMR, and it was confirmed that the copolymer was copolymerized according to the charged ratio. The Mw of the copolymer was 35,000, the VEC structural unit content was 10 mol%, and the VAc structural unit content was 90 mol%.

Thereafter, the hydrolysis reaction of poly (VEC-VAc) and the purification of the reaction product were carried out in the same manner as in Example 1, and as a result, the hydroxyl group-containing copolymer was obtained in a yield of about 95%. P (BDL-VAL) was obtained as a polymer.
The copolymer was identified by ¹ H-NMR, ¹³ C-
Performed by NMR and IR. In addition, this P (BDL-V
AL) has a Mw of 20,000 and a hydroxyl value of 1,220 m
gKOH / g, BDL structural unit content is 15 mol%, V
The AL structural unit content was 81 mol%, and the VAc structural unit content was 4 mol%. <Example 4> In Example 2, the charged amounts of VEC and VAc were changed to 6 parts and 44 parts, respectively, and the acetone initially charged into the reactor was replaced with methanol, and instead of methanol during the reprecipitation operation. By performing the same operation as in Example 2 except that a methanol-water mixed solvent (methanol / water weight ratio = 8/2) was used, a poly (ethylene carbonate) -based copolymer was obtained in a yield of about 98%. VEC-VAc) was obtained. The identification of this copolymer was performed by ¹ H-NMR, and it was confirmed that the copolymer was copolymerized according to the charged ratio. The Mw of the copolymer was 35,000, the VEC structural unit content was 10 mol%, and the VAc structural unit content was 90 mol%.

Thereafter, a hydrolysis reaction of poly (VEC-VAc) and purification of the reaction product were carried out in the same manner as in Example 1, and as a result, a hydroxyl group-containing copolymer was obtained in a yield of about 95%. P (BDL-VAL) was obtained as a polymer.
The copolymer was identified by ¹ H-NMR, ¹³ C-
Performed by NMR and IR. In addition, this P (BDL-V
AL) has a Mw of 20,000 and a hydroxyl value of 1,270 m.
gKOH / g, BDL structural unit content is 10 mol%, V
The AL structural unit content was 90 mol%. <Example 5> In Example 2, the charged amounts of VEC and VAc were changed to 6 parts and 44 parts, respectively. The acetone initially charged into the reactor was replaced with ethyl acetate, and methanol was replaced with methanol during the reprecipitation operation. The same operation as in Example 2 was carried out except that a methanol-water mixed solvent (methanol / water weight ratio = 8/2) was used as the vinyl ethylene carbonate copolymer in a yield of about 98%. (VEC-VAc) was obtained. The identification of this copolymer was performed by ¹ H-NMR, and it was confirmed that the copolymer was copolymerized according to the charged ratio. The Mw of the copolymer was 35,000, the VEC structural unit content was 10 mol%, and the VAc structural unit content was 90 mol%.

Thereafter, the hydrolysis reaction of poly (VEC-VAc) and the purification of the reaction product were carried out in the same manner as in Example 1, and as a result, a hydroxyl group-containing copolymer was obtained in a yield of about 95%. P (BDL-VAL) was obtained as a polymer.
The copolymer was identified by ¹ H-NMR, ¹³ C-
Performed by NMR and IR. In addition, this P (BDL-V
AL) has a Mw of 20,000 and a hydroxyl value of 1,260 m
gKOH / g, BDL structural unit content is 10 mol%, V
The AL structural unit content was 89 mol%, and the VAc structural unit content was 1 mol%. <Comparative Example 1> The procedure of Example 2 was repeated, except that the copolymerization reaction was carried out using 4 parts of lauryl mercaptan as a chain transfer agent.
%, Yielding poly (VEC-VAc) as a vinylethylene carbonate-based copolymer. The identification of this copolymer was performed by ¹ H-NMR, and it was confirmed that the copolymer was copolymerized according to the charged ratio. The copolymer had an Mw of 8,000 and a VEC structural unit content of 30.
Mol%, VAc structural unit content was 70 mol%.

Thereafter, the hydrolysis reaction of poly (VEC-VAc) and the purification of the reaction product were carried out in the same manner as in Example 1, and as a result, a hydroxyl group-containing copolymer was obtained in a yield of about 95%. P (BDL-VAL) was obtained as a polymer.
The copolymer was identified by ¹ H-NMR, ¹³ C-
Performed by NMR and IR. In addition, this P (BDL-V
AL) has a Mw of 4,500 and a hydroxyl value of 1,220 mg.
KOH / g, BDL structural unit content is 35 mol%, VA
The L structural unit content was 61 mol%, and the VAc structural unit content was 4 mol%. <Comparative Example 2> The poly (VEC-VA) obtained in Example 2
The hydrolysis reaction of c) and purification of the reaction product were performed in the same manner as in Example 1. However, the concentration of the aqueous sodium hydroxide solution used for the hydrolysis reaction was changed to 5%. As a result, P (BDL / VEC-VAL / VAc) was obtained as a hydroxyl group-containing copolymer in a yield of about 95%.
I got This copolymer was identified by ¹ H-NM
Performed by R, ¹³ C-NMR and IR. Also, this P
Mw of (BDL / VEC-VAL / VAc) is 20,0
00, hydroxyl value is 950 mg KOH / g, BDL structural unit content is about 22.5 mol%, VEC structural unit content is about 7.5 mol%, VAL structural unit content is about 52.5 mol%, VAc structure The unit content was about 17.5 mol%. <Evaluation of Physical Properties of Hydroxyl Group-Containing Copolymer> The physical properties of the hydroxyl group-containing copolymers obtained in the above Examples and Comparative Examples were evaluated by the following methods. (1) Mechanical strength: A 30% aqueous solution of each hydroxyl group-containing copolymer was prepared, applied to a PET film with a bar coater, dried in a reduced pressure oven at 100 ° C. for 30 minutes, and then peeled off from the PET film. Thereby, a film having a thickness of 20 μm was obtained. About this film,
According to JIS-K7127, the tensile strength and the tensile elongation were measured under the conditions of a humidity of 50% and a test speed E of 20 mm / min.
In addition, according to JIS-K7127, each was measured under the conditions of a humidity of 20% and a test speed E = 20 mm / min. (2) Water solubility at 40 ° C. and 60 ° C .: The water solubility of each copolymer when a 20% aqueous solution of each hydroxyl group-containing copolymer was prepared was examined. The water solubility was visually evaluated at a liquid temperature of 40 ° C. and 60 ° C. according to the following criteria.

○: Dissolves in water.

Δ: Cloudy in water.

×: Does not dissolve in water.

Table 1 shows the evaluation results.

[0064]

[Table 1]

[0065]

The novel hydroxyl group-containing copolymer of the present invention comprises a diol structural unit (A) represented by the above general formula (i).
And the vinyl alcohol-based structural unit (B) represented by the general formula (ii), and exhibits properties such as thermoplasticity and hydrophilicity derived from these structural units. Further, since this copolymer has a weight average molecular weight of 10,000 or more, it has higher toughness, flexibility, flexibility, adhesiveness, dispersibility, and oil resistance than those having a weight average molecular weight of less than 10,000. sex,
Excellent physical properties such as weather resistance and heat resistance. Further, the above-mentioned novel hydroxyl group-containing copolymer is 1,000 mgKOH /
g or more, the hydroxyl value is 1,000 or more.
It is more excellent in water solubility at 40 ° C. or higher than that of less than mgKOH / g.

Since the method for producing a hydroxyl group-containing copolymer of the present invention includes the above-mentioned copolymerization step and the above-mentioned hydrolysis step, the above-mentioned novel hydroxyl group-containing 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-vinyl alcohol) ¹ H-NMR chart (solvent: D ₂ O, ppm on the horizontal axis is the chemical shift δ value from the reference substance).

FIG. 2 shows the poly (3-butene-1,2) obtained in Example 1.
^13C -NMR chart of -diol-vinyl alcohol) (solvent: D ₂ O, ppm on the horizontal axis is the chemical shift δ value from the reference substance).

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

Claims (4)

[Claims] A diol structural unit (A) represented by the following general formula (i) and a vinyl alcohol structural unit (B) represented by the following general formula (ii) having a weight average molecular weight of 10,000.
A novel hydroxyl group-containing copolymer having a hydroxyl value of 0 or more and 1,000 mgKOH / g or more. Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or an alkyl group.) 2. A monomer component containing a vinyl ethylene carbonate monomer (a) represented by the following general formula (iii) and a vinyl ester monomer (b) represented by the following general formula (iv): The novel hydroxyl group-containing copolymer according to claim 1, wherein the copolymer is obtained by a production method comprising a copolymerization step of performing a polymerization reaction, and a hydrolysis step of performing a hydrolysis reaction of the vinylethylene carbonate-based copolymer obtained in the copolymerization step. Polymer. Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or an alkyl group.) 3. The composition according to claim 1, wherein the content of the diol structural unit (A) is 0.1 to 50 mol% based on the total amount of the structural unit and the vinyl alcohol structural unit (B). The novel hydroxyl group-containing copolymer according to the above. 4. A monomer component containing a vinyl ethylene carbonate monomer (a) represented by the following general formula (iii) and a vinyl ester monomer (b) represented by the following general formula (iv): A novel hydroxyl group-containing copolymer according to any one of claims 1 to 3, wherein a copolymerization step of performing a polymerization reaction and a vinylethylene carbonate-based copolymer obtained in the copolymerization step are subjected to a hydrolysis reaction. A method for producing a hydroxyl group-containing copolymer, comprising: a hydrolysis step. Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or an alkyl group.)