JPH0368895B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a method for dissolving a polyethylene oxide high polymer in water, and more specifically, a dissolution method that can quickly produce an aqueous solution of a polyethylene oxide high polymer. The polyethylene oxide polymer to be dissolved in the present invention has a main chain mainly of -CH ₂ -
A polymer composed of repeating structural units of CH ₂ -O- and having a weight average molecular weight of 50,000 or more, preferably 500,000 or more as determined by gel permeation chromatography, and is a polymer composed of repeating structural units of CH 2 -O-. In addition to coalescence, when ethylene oxide is subjected to open reduction polymerization using a suitable catalyst, compounds containing small amounts of epoxy groups, such as propylene oxide, isobutylene oxide, styrene oxide, butadiene monoxide, allyl glycidyl ether, glycidyl acrylate, Vinylcyclohexene monoxide, 2-methyl-5,6-
Copolymers obtained by coexisting epoxyhexene-1 and other compounds having carbon-carbon double bonds, such as ethylene, propylene, vinyl chloride, etc., can also be applied to the present invention as long as they are water-soluble. . These water-soluble polyethylene oxide polymers are usually produced by introducing a monomer into a system containing an organometallic compound as a catalyst in a suitable medium, and are usually in powder form. Often taken out. Polyethylene oxide high polymer is used as adhesive for paper making,
It is an extremely useful polymer used in various applications such as flocculants, dispersants, and sedimentation promoters, and in these fields, it is generally used as an aqueous solution of about 1 ppm to 15%. However, when polyethylene oxide high polymer is dissolved in water, it tends to form poorly soluble lumps, so-called "mamako", due to its high degree of polymerization, even though its solubility is quite high, and it is difficult to dissolve it in a short period of time. It is very difficult to obtain a homogeneous aqueous solution, and it takes a considerable amount of time to dissolve the produced "mamako" and causes various troubles in operation and equipment. As a method to prevent the formation of such "mamako",
Conventionally, a method has been known in which polyethylene oxide high polymers are first dispersed in an organic solvent and then added to water, but this method not only requires a large amount of organic solvent but also increases the number of manufacturing steps. However, in many cases, it becomes an obstacle when using an aqueous solution. The present inventors have conducted extensive research on a method for dissolving polyethylene oxide high polymers that can eliminate the above-mentioned drawbacks, and have found that at least one member selected from the group consisting of polysiloxane and polyalkyl glycol is added to polyethylene oxide high polymers. The present invention was completed based on the discovery that the addition of a compound shown in the figure shows an excellent effect on solubility in water. That is, the present invention provides a polyethylene oxide high polymer having a weight average molecular weight of 50,000 or more.
polysiloxane and fatty acid per 100 parts by weight,
A compound having 3 or more carbon atoms selected from acid amide, sulfonic acid, alcohol, primary amine and secondary amine, phenol, sulfuric acid and phosphoric acid, and at least one selected from the group consisting of ethylene oxide and/or A high-density polyethylene oxide, characterized in that it is soluble in water in the presence of 0.0001 to 50% by weight of at least one compound selected from the group consisting of polyalkylene glycols having a structure produced by reacting propylene oxide. This provides a method for dissolving coalescence. The polysiloxane used in the present invention is an organosilicon polymer having a siloxane bond (-Si-O-Si-) as a backbone and an organic group mainly consisting of carbon and hydrogen attached thereto. These polysiloxanes exist in various forms such as oils, rubbers, varnishes, and resins, and any form can be used by adding and mixing with polyethylene oxide high polymer. Mix directly or
Alternatively, it is convenient to add polysiloxane to a polyethylene oxide polymer suspended in an organic solvent such as alcohol or aromatic hydrocarbon, stir and mix, remove the solvent, and use the powdered form. The polysiloxane used in the present invention is dimethylpolysiloxane, or a polysiloxane in which part or all of the methyl groups of dimethylpolysiloxane are replaced with an organic group such as an ethyl group, a propyl group, a vinyl group, a phenyl group, and hydrogen. Compounds substituted with one species or two or more species, and compounds having structures in which halogen, hydroxyl group, amino group, cyano group, carboxyl group, carbonyl group, etc. are introduced into the substituted organic group of the compound are mentioned. The polyalkylene glycols used in the present invention are selected from the group consisting of fatty acids having three or more carbon atoms, acid amides, sulfonic acids, alcohols, primary amines, secondary amines and phenols, as well as sulfuric and phosphoric acids. It is a compound having a structure produced by reacting at least one type of active hydrogen compound (hereinafter abbreviated as an active hydrogen compound) with ethylene oxide and/or propylene oxide. Examples of alcohols having three or more carbon atoms as representative active hydrogenated compounds include propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol,
Octyl alcohol, caprylic alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol , mericyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, oleyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, furfuryl alcohol, propylene glycol, trimethylene glycol, α-butylene glycol, β- Butylene glycol, tetramethylene glycol, 2,3-butadienediol, hexamethylene glycol, cyclohexanediol, 2,2-bis(4'-oxyphenyl)propane, 4,4-dihydroxydylphenyl sulfone, glycerin, trimethylolethane, Trimethylolpropane, pentaerythritol, mannitol, sorbitol, etc., and monosaccharides and sugars relatively similar to monosaccharides, glucose,
It is a polysaccharide such as sucrose. It is also possible to use mixtures of these, such as so-called Ziegler alcohol, oxo alcohol, secondary alcohol, Matsukou alcohol, and the like. Among these polyalkylene glycols, it is industrially advantageous to use those that are used as raw materials for polymers such as polyurethane, polyester, and alkyd resins, and are more easily dispersed in water than those that are highly soluble in water. Moderate cases often show good results. The method of adding polyalkylene glycol to polyethylene oxide polymer is as follows:
The same method as in the case of adding polysiloxane may be employed. In the present invention, the amount of polysiloxane and polyalkylene glycol added to the polyethylene oxide high polymer varies somewhat depending on the concentration of the polyethylene oxide aqueous solution to be prepared, the type of these additives, the addition method, etc. Usually, the amount is preferably in the range of 0.001 to 50 parts by weight per 100 parts by weight of polyethylene oxide. If the amount of the additive is too small than the above range, no improvement in the solubility of the polyethylene oxide polymer can be expected, and even if it is added beyond the above range, the solubility cannot be further improved, so it is not economical. isn't it. When dissolving the polyethylene oxide high polymer by the method of the present invention, the polyethylene oxide high polymer is dispersed in water, then the additives are added and stirred, or the additives are dissolved or dispersed in water and then the polyethylene oxide high polymer is dissolved or dispersed in water. The dissolution operation can be carried out by adding the ethylene oxide high polymer and stirring, or by adding the polyethylene oxide high polymer and additives to water at the same time and stirring, but usually the most effective aqueous solution is The preparation method is a method in which additives are added to a polyethylene oxide high polymer in advance and the polyethylene oxide high polymer is uniformly mixed, and then the polyethylene oxide high polymer is dispersed and dissolved in stirring sewage water. The aqueous solution obtained in the present invention may exhibit some cloudiness depending on the type and amount of additives used, but this does not pose a problem when using this aqueous solution for various purposes. According to the present invention, the polyethylene oxide high polymer becomes a homogeneous aqueous solution in a short time, and the viscosity of the aqueous solution is almost the same as when no additive is added, and there are no defects such as a decrease in viscosity of the prepared aqueous solution. It has the following excellent advantages. Next, the present invention will be explained with reference to examples. Example 1 Polyethylene nitride with a weight average molecular weight of 4.25 million
After suspending 100 g in 100 g of hexane and adding 0.1 g of silicone oil WM100 (manufactured by Watzker, dimethyl polysiloxane) and stirring, the hexane was distilled off to obtain powdered polyethylene oxide mixed with dimethyl polysiloxane. Ta. 5 g of this mixture was dissolved in stirred water (stirrer rotation speed 200 rpm) at a water temperature of 20°C, and an aqueous solution of 300 centipoise was obtained in 2 hours. At this time, the formation of "mamako" was not observed. In addition, when dimethylpolysiloxane was not used, about 2 days were required for complete dissolution. Example 2 While stirring 100 g of polyethylene oxide powder with a weight average molecular weight of 2 million, silicone oil was added.
10 g of WM100 (manufactured by Watzker, dimethylpolysiloxane) was added dropwise to the mixture. 5 g of this mixture was dissolved in stirred water (stirrer rotation speed: 200 rpm) at a water temperature of 20° C. to obtain a 40 centipoise aqueous solution in 2 hours. With this solution operation, ``Mamako'' could not be made to blink. Example 3 Pronone 201 (manufactured by NOF Corporation, ethylene oxide propylene oxide block copolymer type surfactant) 2 instead of 0.1 g of dimethylpolysiloxane
A 10 centipoise aqueous solution was obtained in 2 hours by carrying out the same method as in Example 1, except that polyethylene oxide having a weight average molecular weight of 1 million was used. Example 4 The same method as in Example 1 was carried out, except that 2 g of Nonion NS-202 (manufactured by NOF Corporation, nonylphenol ethylene oxide adduct) was used instead of 0.1 g of dimethylpolysiloxane, and the same results were obtained. Example 5 Except that 2 g of a reaction product of 1 mole of oleyl alcohol and 2 moles of ethylene oxide was used instead of 0.1 g of dimethylpolysiloxane.
The same method as in Example 1 was carried out and similar results were obtained. Example 6 A mixture of polyethylene oxide mixed with dimethylpolysiloxane prepared by the method of Example 1 and an equal amount of raw material polyethylene oxide was dissolved in water in the same manner as in Example 1, and it was dissolved in water at 300 centipoise in 5 hours. An aqueous solution was obtained. Example 7 Polyethylene oxide with a weight average molecular weight of 4.25 million
Suspend 100g in 100g of hexane, add various types of Aqua Seal 190-S (manufactured by Seitetsu Kagaku, aromatic hydrocarbon solution of polysiloxane) and stir, then distill off the organic solvent and mix the polysiloxane. A powdered polyethylene oxide was obtained. A water solubility test was conducted on this mixture according to the method of Example 1, and the first
Obtained the results in the table.

[Table] Example 8 The same test as in Example 6 was conducted using 0.5 g or 5 g of a propylene oxide adduct of 2,2-bis(4'-oxyphenyl)propane with a molecular weight of 360 or 900 instead of Aqua Seal 190-S. and obtained similar results. Example 9 The same test as in Example 7 was conducted, except that polyoxypropylene glycol having a molecular weight of 1000 was used in addition to Aqua Seal 190-S, and the results shown in Table 2 were obtained.

【table】

Claims (1)

[Scope of Claims] 1. A polyethylene oxide high polymer having a weight average molecular weight of 50,000 or more, based on 100 parts by weight of the high polymer, polysiloxane, fatty acids, acid amides, sulfonic acids, alcohols, and primary amines. A structure produced by reacting ethylene oxide and/or propylene oxide with at least one selected from the group consisting of compounds having three or more carbon atoms selected from and secondary amines, phenol, sulfuric acid, and phosphoric acid. At least one compound selected from the group consisting of polyalkylylene glycols having
A method for dissolving a polyethylene oxide high polymer, the method comprising dissolving it in water in the presence of 0.0001 to 50 parts by weight. 2 Polysiloxane is dimethylpolysiloxane, a compound in which part or all of the methyl groups of dimethylpolysiloxane are substituted with one or more types selected from the group consisting of ethyl group, propyl group, vinyl group, phenyl group, and hydrogen. , and a halogen, hydroxyl group, amino group in the substituted organic group of the compound,
The method according to claim 1, wherein the compound is selected from compounds having a structure into which a cyano group, a carboxyl group, and a carbonyl group are introduced.