JP2678759B2 - Method for producing ammonium salt of solid polymer compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an ammonium salt of a solid polymer compound.

[Prior Art] Ammonium salts of carboxyl group-containing polymer compounds such as ammonium salts of acrylic acid / acrylic acid ester copolymers and ammonium salts of acrylic acid / vinyl acetate copolymers include fiber sizing agents and coating agents. It is used for various purposes.

However, since the ammonium salt is usually obtained only in the form of an aqueous solution, it is inevitable to handle the ammonium salt in an aqueous solution in each of such applications. Therefore, in the storage and transportation of the ammonium salt aqueous solution, it is indispensable to use a very bulky container such as a drum can or a gallon can, and it is hard to say that the handling is not always efficient.

[Problems to be Solved by the Invention] Therefore, if the present inventors can obtain an ammonium salt of a solid polymer compound instead of such an ammonium salt in an aqueous solution that is difficult to handle, it is associated with various uses. Therefore, various studies were carried out, considering that it was extremely useful in industry.

As a method for producing a solid ammonium salt of a carboxyl group-containing polymer compound, a method of once obtaining a solid product from an ammonium salt in an aqueous solution is considered first, but the aqueous solution is dried by air or at low temperature under reduced pressure. It has become clear that a special method must be adopted in order to prevent the scattering of ammonia and to remove the aqueous medium, such as drying or using a precipitant.

Moreover, each of these methods requires two steps of first forming an ammonium salt of a polymer compound and then removing the solvent, and even if such a special method is carried out, the polymer compound is caused by the disappearance of ammonia and the like. It is unavoidable that the water solubility of the ammonium salt is deteriorated, and it is very difficult to obtain a satisfactory product on an industrial scale in view of reproducibility.

Therefore, there is a technical limit inevitably in obtaining a solid ammonium salt of a high molecular compound from an ammonium salt of a high molecular compound once made into an aqueous solution. He continued his earnest research.

[Means for Solving the Problems] In producing the ammonium salt of a solid polymer compound, the present inventor added a solid carboxyl group-containing polymer compound that can be dissolved in water when converted to an ammonium salt, The inventors have found that the object can be achieved by catalytically reacting ammonia gas and / or lower amine gas, and have completed the present invention.

The feature of the present invention resides in that the solid carboxyl group-containing polymer compound is catalytically reacted with ammonia gas and / or lower amine gas as described above. When the method of the present invention is used, it becomes possible to produce an ammonium salt of a solid polymer compound containing a desired ammonium component in one step.

In carrying out the method of the present invention, a typical method is to bring ammonia gas or amine gas into contact with a solid carboxyl group-containing polymer compound under normal pressure, elevated pressure or in some cases reduced pressure system.

Any form is possible for carrying out the catalytic reaction.For example, a packed column or a tube is filled with particles of a solid carboxyl group-containing polymer compound, and an ammonia gas or an amine gas is blown from the bottom of the column, or the reaction is carried out. Examples include a method of blowing ammonia or amine gas while flowing the particles of the solid carboxyl group-containing polymer compound stored in the container in the container.

As another method, a solid carboxyl group-containing polymer compound and a solid ammonium salt of a low molecular weight compound are mixed, and ammonia gas is generated by utilizing decomposability by thermal decomposition of the salt, It is also possible to react this with a polymer compound.

In this case, if the product form is produced as a simple mixture of a solid carboxyl group-containing high molecular compound and an ammonium salt of a low molecular compound, ammonium chloride will progress during storage and transportation, resulting in the desired water solubility. It is also possible to obtain an ammonium salt of the polymer compound, which is very advantageous.

As described above in the present invention, as the source of the ammonia gas and / or amine gas, not only ammonia gas and amine gas but also ammonium salts of solid low-molecular compounds such as ammonium carbonate and ammonium bicarbonate are used. It is also possible to spray liquid ammonia, an aqueous solution of ammonia, an aqueous solution of ammonium salt or the like or an amine solution and bring them into contact with the solid carboxyl group-containing polymer compound for reaction.

The solid carboxyl group-containing polymer compound to be the subject of the present invention is one that maintains a solid state at room temperature, and may be any as long as it can be dissolved in water when it is converted into an ammonium salt. Examples thereof include vinyl acetate-based resins, acrylic resins, polyester-based resins and the like containing a carboxyl group, but there is no particular limitation as long as they are solid polymer compounds containing a carboxyl group and dissolved in water when forming an ammonium salt.

For example, the carboxyl group-containing vinyl acetate resin may be any random copolymer, block copolymer, graft copolymer or the like of vinyl acetate and a carboxyl group-containing unsaturated monomer. The polymerization method can be any of solution polymerization, emulsion polymerization and suspension polymerization. Examples of the carboxyl group-containing unsaturated monomer include polycarboxylic acids such as maleic acid, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, and allylmalonic acid, and anhydrides, partially esterified products, acrylic acid, and methacrylic acid thereof. And monocarboxylic acids such as crotonic acid. A typical copolymer is a vinyl acetate-maleic anhydride copolymer or the like.

Examples of the carboxyl group-containing acrylic resin include a copolymer of an acrylate monomer and a carboxyl group-containing unsaturated monomer as described above. A typical copolymer is an acrylic acid ester-acrylic acid copolymer. The acrylate ester may be any of methyl, ethyl, propyl, butyl, hexyl, etc., and two or more different acrylate esters may be used in combination. The polymerization method is the same as that of the vinyl acetate resin.

The carboxyl group-containing polyester resin is obtained by increasing the acid value of a polyester containing a dicarboxylic acid component and a glycol component as main condensing components. Examples of a method for producing a polyester having a high acid value include polycondensation for reducing the ratio of a glycol component to a dicarboxylic acid component, polycondensation in which a carboxylic acid having a valency of 3 or more is added during the reaction, and depolymerization using a carboxylic acid having a valency of 2 or more. is there. Phthalic acid, terephthalic acid, isophthalic acid, adipic acid,
Oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, maleic acid (anhydrous), fumaric acid, itaconic acid,
Examples include citraconic acid, and glycol components include ethylene glycol, neopentyl glycol, diethylene glycol, propylene glycol, dipropylene glycol, cyclohexane dimethal, pentaerythritol, and bisphenol A.

The shape of the solid carboxyl group-containing polymer compound is not particularly limited, but is preferably spherical, for example, having an average particle size of 0.5 to 3000 μ, in view of reactivity with ammonia gas and amine gas. Therefore, the polymer compound obtained by carrying out the suspension polymerization method is practical.

The content of the carboxyl group in the carboxyl group-containing polymer compound, its purpose, use, the difference in water solubility of the resin, etc. can not be unconditionally specified, but the present invention is ultimately a water-soluble polymer compound. As the ammonium salt is obtained, consideration should be given to making the hydrate water soluble. Practically acid value 10-200mgKOH / g, preferably 30-150mgKOH / g
It is about.

The solid ammonium salt used as the generation source of ammonia gas is not particularly limited as long as it can easily generate ammonia gas by thermal decomposition or the like.

For example, ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium chloride, ammonium acetate, ammonium oxalate, etc. and ammonium salts with organic or inorganic compounds such as zinc ammonium carbonate and zirconyl ammonium carbonate can be used as complex salts. Particularly, ammonium carbonate and ammonium bicarbonate are practically preferable.

Examples of the lower amine that can be used in the present invention include methylamine, ethylamine, triethylamine, etc.
It is an amine of about 8.

The ammonium salt of the solid carboxyl group-containing polymer thus obtained can be used as a film, a sheet, a molded article such as a fiber, an adhesive, a paint, a coating agent, a temporary protective film, a fiber paste (especially for water jet), etc. It can be used for.

[Action] A solid polymer compound ammonium salt can be easily produced by contacting a solid carboxyl group-containing polymer compound with an ammonia gas and / or a lower amine gas.

[Examples and Controls] The present invention will be described in more detail with reference to the following examples.

Example 1 The following acrylic resin was obtained by suspension polymerization.

○ Composition Methyl methacrylate 39% by weight Ethyl acrylate 50% by weight Acrylic acid 3% by weight Methacrylic acid 8% by weight ○ Acid value 75 mg KOH / g ○ Average particle size 1000 μm ○ Volatile content 3% by weight Carboxyl group-containing acrylic copolymer Coalescing powder 10
0 part by weight was left standing at 30 ° C. in an ammonia gas atmosphere for 2 hours. The degree of neutralization was 90%.

When 100 g of the ammonium salt of the resin was dissolved in 400 g of water at a temperature of 60 ° C. with stirring, it was completely dissolved.

Control Example 1 The resin bulk powder used in Example 1 was dissolved under the same conditions as in Example 1, but it was not dissolved at all.

Example 2 The following vinyl acetate resin was obtained by suspension polymerization.

○ Composition Vinyl acetate 92% by weight Crotonic acid 8% by weight ○ Acid value 52mgKOH / g ○ Average particle size 700μm ○ Volatile content 3% by weight Carboxyl group-containing vinyl acetate copolymer powder
100 parts by weight was left standing at 30 ° C. in an ammonia gas atmosphere for 2 hours. The degree of neutralization was 85%.

When 100 g of the ammonium salt of the resin was dissolved in 900 g of water at a temperature of 80 ° C. with stirring, it was completely dissolved.

Example 3 The following polyester resin was obtained.

○ Composition terephthalic acid 21% by weight Isophthalic acid 21% by weight Ethylene glycol 18% by weight Diethylene glycol 34% by weight Trimellitic anhydride 6% by weight ○ Acid value 30 mg KOH / g ○ Pellet 3 mm × 3 mm ○ Volatile content 3% by weight Containing the above carboxyl groups 100 parts by weight of the polyester-based polycondensate powder was allowed to stand at 30 ° C. in an ammonia gas atmosphere for 2 hours. The degree of neutralization was 95%.

When 100 g of the ammonium salt of the resin was dissolved in 250 g of water at a temperature of 90 ° C. with stirring, it was completely dissolved.

Example 4 100 parts by weight of the same carboxyl group-containing acrylic copolymer powder used in Example 1 was mixed with 10 parts by weight of ammonium bicarbonate powder, and the mixture was allowed to stand in a reaction vessel at 65 ° C. for 3 hours. When the amount of generated carbon dioxide was measured, the decomposition rate was 80%
The degree of neutralization was 70%.

When the same dissolution test as in Example 1 was performed, it was completely dissolved.

Example 5 The same operation as in Example 4 was performed using 6 parts by weight of ammonium carbonate instead of ammonium bicarbonate. The degree of neutralization was 80%.

 The same dissolution test result as in Example 1 was completely dissolved.

Example 6 The same operation as in Example 1 was performed using methylamine gas instead of ammonia gas. The degree of neutralization was 85%.

 As a result of the same dissolution test as in Example 1, complete dissolution was obtained.

Example 7 The same operation as in Example 2 was performed using ethylamine gas instead of ammonia gas. The degree of neutralization was 75%.

 As a result of the same dissolution test as in Example 2, the product was completely dissolved.

Example 8 The same operation as in Example 3 was performed using triethylamine gas instead of ammonia gas. Neutralization degree is 70
%Met.

 As a result of the same dissolution test as in Example 3, complete dissolution was obtained.

[Effect] As described above, in the production method of the present invention, a solid carboxyl group-containing polymer compound is contacted with ammonia gas and / or lower amine gas to easily produce an ammonium salt of a solid polymer compound. It is possible, and is very useful industrially. 4

Claims (2)

(57) [Claims] 1. An ammonium salt of a solid polymer compound, which comprises reacting a solid carboxyl group-containing polymer compound, which is soluble in water when converted to an ammonium salt, with ammonia gas and / or lower amine gas. Manufacturing method. 2. A patent characterized in that a solid carboxyl group-containing polymer compound that is soluble in water when it is made into an ammonium salt is an acrylic polymer compound that is soluble in water when it is made into an ammonium salt. A method for producing an ammonium salt of a solid polymer compound according to claim 1.