JP2000178328A - Production of high-molecular-weight polyacetals - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high-molecular-weight polyacetal industrially, and inexpensively at good efficiency by chain-extending a polymer prepared by polymerizing a monomer composition containing a glyoxylic ester with a compound having at least two functional groups reactive with the terminals of the polymer chain. SOLUTION: The compound reactive with the terminals of the polymer main chain is exemplified by a compound having at least two reactive groups selected from among isocyanate groups, glycidyl groups, vinyl ether groups, vinyl groups, and cyclic ether groups. The terminals of the polymer skeleton and the reactive compound may be reacted with each other during or after the polymerization of the monomer composition. The amount of the compound reactive with the terminals of the polymer skeleton is desirably 0.001-50 mol% based on the glyoxylic ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing high molecular weight polyacetals. More specifically, the present invention relates to a method for producing a high molecular weight polyacetal obtained by polymerizing a monomer composition containing a glyoxylate.

[0002] High molecular weight polyacetals include ceramic binders, coal and cement dispersants, pigment dispersants, ceramic dispersants, drilling additives, water treatment chemicals, thickeners, water retention agents, flocculants, and adhesives. It is useful for applications such as tackifiers.

[0003]

2. Description of the Related Art As means for polymerizing glyoxylate to obtain a polyacetal having a relatively high molecular weight, it has been proposed to carry out polymerization of glyoxylate at a polymerization initiation temperature of -20.degree. C. to -70.degree. It is known from Japanese Patent No. 37,044.

However, there has been a problem that setting the polymerization temperature to a low temperature is not industrially suitable from the viewpoint of cost. In addition, a polymer having a sufficiently high molecular weight was not obtained.

On the other hand, Japanese Patent Application Laid-Open No. 8-500618 discloses that glyoxylate and cyclic acetal are copolymerized, and other comonomers include glycidyl acrylate and glycidyl methacrylate.

Japanese Patent Application Laid-Open No. 9-124754 describes a method of reacting a compound having at least two epoxy groups in a carboxyl group as a side chain of a polyacetal carboxylate to crosslink.

However, there is no disclosure that these substances are used as a polymer chain extender to obtain a high molecular weight polyacetal, and there is no disclosure of how to use these substances as a chain extender or the effect of using them. Further, the molecular weight of the obtained polymer was not sufficiently high.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a polymer having a high molecular weight obtained by polymerizing a monomer composition containing glyoxylate, and It is an object of the present invention to provide a method for efficiently producing a molecular weight polymer at low cost on an industrial scale.

[0009]

According to the present invention, a polymer (hereinafter, sometimes referred to as polymer (P)) obtained by polymerizing a monomer composition containing a glyoxylate is added to a polymer main chain terminal. The present invention relates to a method for producing high molecular weight polyacetals, which comprises a step of reacting a compound containing two or more functional groups capable of reacting with a compound (hereinafter, compound (A)).

The high molecular weight polyacetals referred to in the present invention refer to high molecular weight polyacetals and derivatives thereof.
Examples of the derivative include an amidated product of a part or all of the ester group of the polyacetal, and a hydrolyzed product of a part or all of the ester group of the polyacetal.

The reactive functional group is, for example, at least one functional group selected from the group consisting of a vinyl ether group, a glycidyl group and an isocyanate group.

Another invention of the present invention relates to a polyacetal (hereinafter referred to as polyacetal (PA)) produced by the above method.
).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As the glyoxylate used in the production method of the present invention, those having 1 to 20 carbon atoms in the ester group are used. Examples include glyoxylic acid methyl ester, glyoxylic acid ethyl ester, glyoxylic acid n-propyl ester, glyoxylic acid isopropyl ester, glyoxylic acid n-butyl ester, glyoxylic acid isobutyl ester, and the like. These are used alone or in combination of two or more.
Among them, glyoxylic acid methyl ester and glyoxylic acid ethyl ester are preferred for use. The glyoxylate used preferably has a low content of impurities such as water and alcohol. If the content of impurities is large, a high molecular weight compound may not be obtained. Water, alcohol and the like can be removed by, for example, distillation.

Further, a part of the glyoxylate used may be replaced with a general copolymerizable monomer. Examples of copolymerizable monomers include aldehydes such as formaldehyde and acetaldehyde; cyclic acetals such as 1,3-dioxolane and trioxane; epoxy compounds such as ethylene oxide and propylene oxide; vinyl monomers such as ethylene and N-vinyl-2-pyrrolidone; Examples thereof include carbon dioxide, a divinyl ether compound, and a diglycidyl compound.

[0015] The glyoxylate in the monomer composition is preferably used in an amount of 20 mol% to 100 mol%.

The method of polymerizing the monomer composition containing the glyoxylate is not particularly limited, and a general method is used. For example, anionic polymerization, cationic polymerization, coordination anionic polymerization and the like are used. Therefore, the polymerization initiator is not particularly limited, and a general initiator is used. For example,
Protic acids such as sulfuric acid and phosphoric acid; Lewis acids such as boron trifluoride and aluminum trichloride; organometallic compounds such as alkylalumnium halide and trialkylalumnium;
Heteropoly acids such as phosphotungstic acid and phosphomolybdic acid; water, ethylene glycol, 1,2-hydroxy-3
Hydroxyl-containing compounds such as butene, glycidol and 2-hydroxyethyl vinyl ether; alkali salts such as sodium hydroxide and potassium hydroxide; pyridine, 1,4-
Tertiary amines such as diazabicyclo [2,2,2] octane; alkali metals such as sodium and potassium; aluminum;
Examples include zinc oxide and alkoxide. These are used alone or in combination of two or more.

The compound containing two or more reactive functional groups (compound (A)) includes, for example, a reactive group selected from the group consisting of isocyanate groups, glycidyl groups, vinyl ether groups, vinyl groups and cyclic ether groups. 2
Or more compounds.

Examples of the divinyl ether compound having two vinyl ether groups include diethylene glycol divinyl ether and triethylene glycol divinyl ether. Examples of the divinyl compound having two vinyl groups include, for example, divinylbenzene, and examples of the diisocyanate compound having two or more isocyanate groups include hexamethylene diisocyanate, and 2,6-diisocyanate toluene. Examples of the diglycidyl compound having two glycidyl groups include ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether. Examples of the compound having a vinyl group and a glycidyl group include epoxy butene, and examples of the compound having a vinyl group and a cyclic ether include vinyl dioxolane and vinyl oxazoline. These compounds are used alone or in combination of two or more.

When polymerizing the monomer composition containing glyoxylate, the compound (A) may be reacted with a polymer terminal with or without a known catalyst, or may be reacted after the polymerization is completed. Alternatively, the reaction may be carried out after isolating the polymer.

Known catalysts are not limited, and include, for example, amines and inorganic alkali substances as base catalysts; protonic acids such as hydrochloric acid, trifluoroacetic acid and methanesulfonic acid as acid catalysts; Lewis acids such as aluminum chloride and titanium chloride; Examples thereof include organometallic compounds such as alkylaluminum halides and trialkylaluminums; heteropolyacids such as phosphotungstic acid and phosphomolybdic acid; and halogens such as I ₂ and ICl.

In addition, in the reaction between the compound (A) and the terminal of the polymer (P) in the present invention, the addition order of the reaction catalyst of the compound (A), the compound (A) and the polymer (P) to the reaction system. May be added, and each of them may be partially added several times.

In the present invention, if necessary, a chemically stable group may be introduced into the terminal of the polymer (P) in order to stabilize the polymer. The group is introduced before the reaction with the compound (A),
The reaction may be performed during or after the reaction, or may not be performed. The group to be introduced is not limited, and examples thereof include an alkyl group such as a methyl group and an ethyl group; a cyclic alkyl group such as a cyclohexyl group; an alkoxy group such as a methoxy group and an ethoxy group; a cyclic alkyl group containing oxygen; In order to introduce a stable group, for example, epoxides such as ethylene oxide and propylene oxide;
Cyclic ethers such as 3-dioxolan and 1,4-butanediol formal; alkyl vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; substituted olefins such as propylene and n-vinyl-2-pyrrolidone; alcohols such as methanol and butanol; Methyl,
A method of reacting a compound such as an alkyl halide such as tert-butyl chloride; an allyl halide such as allyl chloride; an acetal such as acetaldehyde dimethyl acetal; an alkyl sulfate such as dimethyl sulfate or diethyl sulfate; a benzyl halide such as benzyl chloride. No. One or more of these can be used.

In the present invention, the reaction temperature of the reaction between the compound (A) and the terminal of the polymer (P) is not particularly limited, but is in the range of -20 ° C to 120 ° C in view of the reaction rate and the polymer. Is preferred in that it does not decompose.

In the present invention, the reaction between the compound (A) and the terminal of the polymer is usually carried out without solvent or in an inert solvent.

In the present invention, the amount of the compound (A) to be added is not particularly limited, but is preferably 0.001 mol% to 50 mol%, more preferably 0.01 mol% to 10 mol%, based on glyoxylate. When the amount of addition increases, a plurality of compounds (A) may be added to the terminal of the polymer to form a gel. If the amount is less than the above range, a polymer having a sufficiently high molecular weight may not be obtained.

When an acidic catalyst is used for the reaction between the polymer (P) and the polymerization initiator or the compound (A), it is preferable to neutralize the catalyst after the reaction. For neutralization of the catalyst, for example, a basic substance such as a tertiary amine is used.

The polyacetal (PA) obtained by the production method of the present invention can be used, for example, at the main chain terminal of a polymer obtained by polymerizing a monomer composition containing glyoxylate.
It is a polymer obtained by reacting the compound (A).
The structure of the polyacetal (PA) varies depending on the type of the compound (A) used. Specifically, for example, the following general formula (1)

[0028]

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(Wherein M represents any of hydrogen, an alkyl group having 1 to 10 carbon atoms, a monovalent metal, a divalent metal, an ammonium group, and an organic amine group, and R represents a divalent organic residue Wherein X and Y are each independently the following general formula (2):

[0030]

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The following general formula (3):

[0032]

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The following general formula (4):

[0034]

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Alternatively, the following general formula (5):

[0036]

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Wherein m and n are 1
A polyacetal having a structural unit represented by the following integer: The general formulas (2) to (5)
(R) in the above indicates that it is bonded to R in the general formula (1).

The molecular weight of the polyacetal (PA) obtained by the production method of the present invention is usually from 5,000 to 500,000.
0, especially in the range of 10,000 to 500,000.

The resulting polyacetal (PA) can be partially or entirely amidated with a known amidating agent (polyacetal (PA)).
A-Am)).

The ratio of amidation is appropriately adjusted according to the charging ratio of the amidating agent. One or more amidating agents are used.

Examples of the amidating agent used include ammonia; various amines such as alkylamine, alkanolamine, mercaptoamine, amino acid, amino acid anhydride, cyclic amine, and polyamine.

When an alkylamine is reacted, the hydrophobicity of the polymer can be adjusted according to the length of the alkyl group. Examples of the alkylamine include methylamine and n-amine.
Primary amines such as propylamine and amylamine, and secondary amines such as diethylamine and dibutylamine are exemplified.

By reacting an amine having a functional group, a functional group other than an ester can be introduced. For example, alkanolamines include monoethanolamine, diethanolamine and the like. Examples of the mercaptoamine include 2-aminoethylmercaptan and dimercaptoethylamine.

Examples of the amino acid include glycine, glutamic acid and taurine, and examples of the amino acid anhydride include glycine anhydride.

In order to impart rigidity to the main chain, it is effective to introduce a cyclic amine such as pyrrolidine or morpholine. To crosslink the polymer, polyvalent amines such as ethylenediamine, hexamethylenediamine and the like can be used.

The amidation reaction is usually carried out without solvent or in water or an organic solvent. The solvent is preferably an inert solvent. The reaction temperature is preferably from -10 to 150C. If the temperature is lower than −10 ° C., the reaction rate may decrease, or the solidification or the viscosity may increase, which may make handling difficult. The amidation of the polymer (PA) may be performed after isolating the polymer, or directly after or during the polymerization.

The molecular weight of the polyacetal (PA-Am) obtained by the above amidation is usually 5,000 to 5,000.
000, especially 10,000 to 500,000.

By amidating the ester group of the polyglyoxylate, the hydrophilicity is improved, the solubility in a solvent is improved, the compatibility with a known polymer is improved, and the adhesion at the interface with an additive or a mixture is improved. Can be imparted with physical properties such as improvement of the temperature, and further reaction points can be introduced.
For example, the polymer can be made water-soluble by amidation with methylamine, dimethylamine, ethylamine, monoethanolamine, diethanolamine, pyrrolidine, or the like, and the solvent can be dried safely. If desired, the raw material polymer can be further modified according to the required physical properties, which is beneficial.

In the polymer (PA) obtained by the production method of the present invention, part or all of the ester groups can be hydrolyzed in the presence of a base.

Examples of the base include alkali metal bases such as sodium hydroxide and potassium hydroxide, alkaline earth metal bases such as calcium hydroxide, ammonia, and amines.

The hydrolysis of the polymer may be carried out after isolating the polymer or directly after the polymerization.

By hydrolyzing the ester group of polyglyoxylate (PA), it is possible to improve the hydrophilicity, the compatibility with known polymers, and the adhesion at the interface with additives or mixtures. Physical properties can be imparted and further reaction sites can be introduced.

[0053]

EXAMPLES The present invention will be described below in detail with reference to examples, but the scope of the present invention is not limited by these examples.

Example 1 55 g of dimethylformamide, 12 μl of pyridine, and 66 μl of ethylene glycol were previously added to a 100 ml reaction vessel, and the mixture was distilled and purified to obtain 32 g of methyl glyoxylate.
1 was added over about 30 minutes to polymerize at room temperature. After aging for 1 hour, 0.95 g of diethylene glycol divinyl ether was added to the polymerization reaction product. Reaction temperature of 10
After cooling to about ° C, 32 μl of methanesulfonic acid was added to the polymerization reaction product. The internal temperature was raised to 35 ° C, and 3.0 g of 1,3-dioxolane was further added to the polymerization reaction product over about 30 minutes, followed by aging at 35 ° C for 2 hours. After 1.4 g of triethylamine was added to the polymerization reaction product to neutralize methanesulfonic acid, the reaction solution was poured into ethanol. After removing the ethanol, the resultant was dried under reduced pressure at 50 ° C. for 10 hours. The yield of the obtained polymer was 38.5 g, and the apex molecular weight in terms of polystyrene measured by gel permeation chromatography was 48,000.

Example 2 55 g of acetonitrile, 12 μl of pyridine and 66 μl of ethylene glycol were previously added to a 100 ml reaction vessel, and 32 ml of distilled and purified methyl glyoxylate was added to the mixture over about 30 minutes. The polymerization was carried out at room temperature. After aging for 1 hour, 0.95 g of diethylene glycol divinyl ether was added to the polymerization reaction solution. The reaction temperature was cooled to about 10 ° C., and 126 μl of phosphoric acid was added to the polymerization reaction solution. The internal temperature was raised to 35 ° C, and after 1 hour of reaction, the reaction temperature was raised to 1 ° C.
After cooling to about 0 ° C., 63 μl of boron trifluoride diethyl ether complex was added. After adding 3.0 g of propylene oxide to the polymerization reaction solution over about 30 minutes, it was aged at 35 ° C. for 2 hours. After 1.4 g of triethylamine was added to the polymerization reaction product to neutralize the boron trifluoride diethyl ether complex, the reaction solution was poured into ethanol. After removing the ethanol, the resultant was dried under reduced pressure at 50 ° C. for 10 hours. The yield of the obtained polymer was 39.2 g, and the apex molecular weight in terms of polystyrene measured by gel permeation chromatography was 53,000.

Example 3 55 g of acetonitrile, 12 μl of pyridine and 100 μl of 3-butene-1,2-diol were previously added to a 100 ml reaction vessel, and 32 ml of distilled and purified methyl glyoxylate was added to the mixture. Polymerization was carried out at room temperature while adding over about 30 minutes. After aging for 1 hour, the reaction temperature was cooled to about 10 ° C., 63 μl of boron trifluoride diethyl ether complex was added to the polymerization reaction solution, and 0.95 g of diethylene glycol divinyl ether was added. Raise the internal temperature to 35 ° C,
3.0 g of propylene oxide was added to the polymerization reaction solution in an amount of about 30.
After the addition, the mixture was aged at 35 ° C. for 2 hours. After 1.4 g of triethylamine was added to the polymerization reaction product to neutralize the boron trifluoride diethyl ether complex, the reaction solution was poured into ethanol. After removing the ethanol, the resultant was dried under reduced pressure at 50 ° C. for 10 hours. The yield of the obtained polymer was 39.
2 g, and the apex molecular weight in terms of polystyrene measured by gel permeation chromatography was 50,000.
It was 0.

Comparative Example 1 55 g of acetonitrile, 12 μl of pyridine and 66 μl of ethylene glycol were previously added to a 100 ml reaction vessel, and 32 ml of distilled and purified methyl glyoxylate was added to the mixture over about 30 minutes. The polymerization was carried out at room temperature. After aging for 1 hour, 0.63 g of propylene oxide was added to the polymerization reaction product.
Was added. The reaction temperature was cooled to about 10 ° C., and 63 μl of boron trifluoride diethyl ether complex was added to the polymerization reaction product. The internal temperature was raised to 35 ° C, 3.0 g of propylene oxide was added over about 30 minutes, and the mixture was aged at 35 ° C for 2 hours. After 1.4 g of triethylamine was added to the polymerization reaction product to neutralize the boron trifluoride diethyl ether complex, the polymerization reaction product was added to ethanol. After removing the ethanol, the polymer was dried under reduced pressure at 50 ° C. for 10 hours to obtain a polymer. The yield of the obtained polymer was 32.0 g, and the apex molecular weight in terms of polystyrene measured by gel permeation chromatography was 11,000.

Example 4 55 g of 1,4-dioxane, 12 μl of triethylamine and 66 μl of ethylene glycol were previously added to a 100 ml reaction vessel, and 32 ml of distilled and purified methyl glyoxylate was added to the mixture for about 30 minutes. The polymerization was carried out at room temperature while adding over time. After aging for 1 hour, 0.95 g of ethylene glycol diglycidyl ether was added to the polymerization reaction product. Cool the reaction temperature to about 10 ° C and add 126 μl
Of boron trifluoride diethyl etherate was added. The internal temperature was raised to 30 ° C., and 3.9 g of ethylene oxide was added to about 3
After adding over 0 minutes, the mixture was aged at 30 ° C. for 2 hours. After 1.4 g of triethylamine was added to the polymerization reaction product to neutralize the boron trifluoride diethyl ether complex, the polymerization reaction product was added to ethanol. After removing methanol, 50 ° C
And dried under reduced pressure for 10 hours to obtain a polymer. The yield of the obtained polymer was 35.2 g, and the apex molecular weight in terms of polystyrene measured by gel permeation chromatography was 37,000.

Example 5 55 g of ethyl acetate, 12 μl of pyridine and 66 μl of ethylene glycol were previously added to a 100 ml reaction vessel, and 32 ml of distilled and purified methyl glyoxylate was added to about 30 ml of the mixture.
The polymerization was carried out while adding over minutes. After aging for 1 hour, 126 μl of boron trifluoride diethyl ether complex was added to the polymerization reaction product, and 5.2 g of 1,3-dioxolane was added. The reaction was carried out for 3.5 hours while maintaining the internal temperature at 35 ° C. After adding 1.4 g of triethylamine to neutralize the boron trifluoride diethyl ether complex, the polymerization reaction product was added to methanol. After removing methanol, the polymer was dried under reduced pressure at 50 ° C. for 10 hours to obtain a polymer. The yield of the obtained polymer was 28.8 g, and the apex molecular weight measured by gel permeation chromatography was 11,000.

28.8 g of the obtained polymer was
C., dried at 1 mmHg for 1 hour, and the polymer was added with 0.83 g of 2,4-diisocyanate toluene and 25 μl of di-n-butyltin dilaurate as a catalyst, and reacted at 100 ° C. for 2 hours. A polymer was obtained. The yield of the obtained polymer was 28.4 g, and the apex molecular weight measured by gel permeation chromatography was 38.0.
00.

(Example 6) 10 g of the polymer obtained in Example 1 was dissolved in 40 g of 1,3-dioxolane, and 8.0 g of a 70% ethylamine aqueous solution was slowly added dropwise with stirring. After stirring at room temperature for 3 hours,
It was added dropwise to a large excess of diethyl ether and dried under reduced pressure at 50 ° C. for 10 hours to obtain an amidated product of the polymer. The apex molecular weight in terms of polystyrene measured by gel permeation chromatography was 51,000.

As a result of measuring the proton nuclear magnetic resonance spectrum (solvent: heavy DMSO, standard substance: TMS, δ value), a broad peak of 8.1 to 8.9 ppm (attributable to the glyoxylic acid amide unit in the polymer) was obtained. NH,
1H), 5.1-5.9 ppm (CH, 1H resulting from glyoxylic amide units in the polymer), 3.1
around ppm (CH ₂ , 2H derived from glyoxylic amide units in the polymer), 0.8 to 1.1 ppm
(CH ₃ , 3H attributable to glyoxylic acid amide units in the polymer).

[0063]

According to the production method of the present invention, a polymer polyacetal containing a glyoxylate ester structural unit and a derivative thereof can be obtained industrially at low cost and efficiently, as compared with the conventional production method.

The high molecular weight polyacetals obtained by the process of the present invention include ceramic binder, coal, cement dispersant, pigment dispersant, ceramic dispersant, excavating additive, water treatment chemical, scale inhibitor, It is effectively used for thickeners, water retention agents, anticorrosives, adhesives and the like.

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Claims (3)

[Claims] 1. A step of subjecting a polymer obtained by polymerizing a monomer composition containing a glyoxylate to a chain extension reaction using a compound having two or more functional groups capable of reacting with the main chain terminal of the polymer. A method for producing a high molecular weight polyacetal, comprising: 2. The method for producing a high-molecular-weight polyacetal according to claim 1, wherein the reactive functional group is at least one functional group selected from the group consisting of a vinyl ether group, a glycidyl group, and an isocyanate group. 3. A high molecular weight polyacetal produced by the method according to claim 1.