JP2003020340A - Production method for polymer compound solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method for a polymer compound solution whereby active carbon used for purifying the solution can be removed by filtration at a high filtration rate. SOLUTION: This production method comprises mixing a polymer compound solution with active carbon of which at least 50% of the particles have sizes in the range of 149 μm to 2,380 μm, adding a filtration assistant to the resultant mixture, and removing the active carbon by filtration from the mixture containing the assistant or comprises mixing a polymer compound solution with active carbon of which at least 50% of the particles have sizes in the range of 149 μm to 2,380 μm and removing the active carbon from the resultant mixture by using a filter medium having a filtration assistant attached thereto in advance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polymer compound solution. More specifically, for example, cosmetics,
The present invention relates to a method for producing a high-purity polymer compound solution used as a raw material for hygiene products, household products, and chemical products.

[0002]

2. Description of the Related Art As one of the methods for producing a high-purity liquid,
A method is known in which powdered activated carbon and a liquid are mixed with stirring to adsorb impurities in the liquid onto the activated carbon, and then the activated carbon is removed from the solution by filtration to obtain a highly pure liquid. JP-A-5
JP-A-179246 discloses that powdered activated carbon is superior to granular activated carbon in order to increase the rate of adsorbing the platinum compound of the catalyst in the polymer liquid crystal solution onto the activated carbon. Powdered activated carbon generally has a high adsorption rate, but since the filtration rate at the time of filtering is low, in order to mitigate this, a filter aid such as silicon earth is added to the solution before filtration or the surface of the filter medium is There is a method in which a filter aid is attached to and then filtered.

However, when a high-purity polymer compound solution is produced by this method, the viscosity of the polymer compound solution is usually high. Therefore, when powdered activated carbon is used, the filtration rate is very slow and a filter aid is used. Even if it does, the improvement can be recognized to some extent, but there is a drawback that the filtration rate is still low.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a polymer compound solution having a high filtration rate when the activated carbon is removed by filtration after purifying the polymer compound solution using activated carbon. The task is to do.

[0005]

[Means for Solving the Problems] [1] A mixture of [1] a polymer compound solution and activated carbon having a particle size of 149 μm or more and less than 2380 μm of 50% or more, and A method for producing a polymer compound solution in which a filter aid is added and activated carbon is removed from the mixture after the addition by filtration, and [2] a polymer compound solution and a particle size of 149 μm or more, 2380 μm
After mixing with activated carbon whose particle size is below 50%,
The present invention relates to a method for producing a polymer compound solution, in which activated carbon is removed from a mixture obtained by filtration using a filter medium having a filter aid attached to the surface of the filter medium in advance.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer compound used in the present invention is not particularly limited as long as it can be uniformly dissolved in a solvent such as an organic solvent or water. Examples of the polymer compound include acrylic resin, epoxy resin, phenol resin, polyester, polystyrene, silicone resin, cellulose resin, saccharides and the like.

Examples of the polymer compound soluble in water include ionic polymer compounds in addition to those mentioned above.
Examples of the ionic polymer compound include polymer compounds having any of anionic, cationic or zwitterionic groups. Among them, in the production of a cationic polymer compound, an amine is used as a raw material, and a cationic monomer having an odor often remains, and the amine has an unpleasant odor even in an extremely small amount. From the viewpoint of improving the above, a cationic polymer compound is particularly preferable.
Further, since the cationic polymer compound is easily adsorbed on the activated carbon having an anionic group on the surface, the cationic polymer compound is particularly preferable from the viewpoint of adsorbing it more efficiently than the anionic polymer compound. Examples of cationic polymer compounds include polymers of one or more cationic monomers. Specifically, for example, a cationic monomer homopolymer, a cationic monomer, an aliphatic carboxylic acid vinyl ester such as vinyl acetate, a (meth) acrylic acid ester such as methyl methacrylate, an alkyl vinyl ether such as methyl vinyl ether, N- N-vinyl cyclic amide such as vinylpyrrolidone, styrene, a copolymer with a monomer having no salt-forming group such as alkyl-substituted styrene,
And mixtures of these polymers.

Examples of the cationic monomer include (meth) acrylic acid esters or (meth) acrylamides having a dialkylamino group such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylamide and dimethylaminopropyl methacrylamide. Styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene; vinylpyridines such as 4-vinylpyridine and 2-vinylpyridine; alkyl halides, benzyl halides, alkylsulfonic acids and aryls thereof Examples thereof include quaternized quaternary ammonium salts such as sulfonic acid and dialkyl sulfate.

The solvent used for the polymer compound solution may be any solvent which can dissolve the polymer compound uniformly,
There is no particular limitation. Examples of the solvent include commonly used organic solvents, water, mixed solvents thereof, and the like. Activated carbon easily adsorbs organic substances, but when the solvent is water, adsorption of organic substances is promoted, so water is preferred.

As the organic solvent, for example, ethanol,
Alcohols such as isopropyl alcohol, acetone,
Ketones such as methyl ethyl ketone, esters such as ethyl formate and ethyl acetate, aromatic hydrocarbons such as toluene and xylene, aliphatic straight chain hydrocarbons such as n-hexane and n-heptane, alicyclic rings such as cyclopentane and cyclohexane Group hydrocarbons and the like can be mentioned.

The weight average molecular weight of the polymer compound is preferably 5,000 or more from the viewpoint of suppressing adsorption of the polymer compound on activated carbon, and from the viewpoint of not increasing the viscosity of the polymer compound solution.
It is preferably 1.5 million or less. The preferred range of the weight average molecular weight of the polymer compound is 5000 to 1.5 million, more preferably 1
It is 0000 to 1,000,000, and more preferably 20,000 to 500,000.

The content of the polymer compound in the polymer compound solution is preferably 3 to 70% by weight from the viewpoint of lowering the viscosity in order to improve the filterability. From the viewpoint of improving filterability, the viscosity of the polymer compound solution is preferably 5 to 1000 mPa · s at the time of filtration.

The impurities contained in the polymer compound solution include, for example, an average of residual monomers, residual monomer-derived substances, residual polymerization catalysts, polymerization catalyst-derived substances, polymerization inhibitors contained in raw material monomers, and monomer decomposition products. Examples include compounds having a molecular weight of less than 5000. When these impurities are contained in the polymer compound solution, the polymer compound solution may be colored or have an offensive odor.

The particle size of activated carbon is 149 μm or more, preferably 177 μm or more, from the viewpoint of reducing filtration resistance and improving filtration rate. The particle size of the activated carbon is less than 2380 μm, preferably 1680 from the viewpoint of increasing the adsorption rate.
It is less than μm. The particle size of activated carbon of these particle sizes is 50
% Or more, preferably 90% or more. The particle size is measured by the method shown in Example 1 (JIS K1474 "Activated carbon test method" 5.3 Measured according to particle size, the same applies hereinafter). That is,
The particle size at 149 μm or more and below 2380 μm is 50% or more, preferably 90% or more. Furthermore, 177 μm or more, 1680
The particle size of less than μm is more preferably 50% or more, still more preferably 90% or more.

In the present specification, the particle size is A μm or more, B
Less than μm means passing through a sieve having an opening of B μm, which remains on a sieve having an opening of A μm. Also, if the particle size is
Powdered activated carbon less than 149 μm and granular activated carbon more than 149 μm.

The method of mixing the polymer compound solution and activated carbon is not particularly limited. For example, activated carbon may be added to the polymer compound solution and the resulting mixture may be stirred. In this case, it is preferable to uniformly disperse the activated carbon in the polymer compound solution. The mixing of the polymer compound solution and the activated carbon can be usually performed in a container.

Examples of the activated carbon include DIAHOPE, DIAHOPE [351-2360 μm (42-8 mesh)] manufactured by Mitsubishi Chemical Co., Ltd., and Kuraray Coal [246-16] manufactured by Kuraray Chemical Co., Ltd.
51 μm (60 to 10 mesh)] and Takeshi Yakuhin Kogyo Co., Ltd. granular Shirasagi [246 to 1651 μm (60 to 10 mesh)].

The content of the activated carbon in the mixture of the polymer compound solution and the activated carbon is not particularly limited, but may be any content as long as the mixing can be sufficiently performed and the impurity concentration can be sufficiently reduced. To reduce it as much as possible,
It is better to lower the activated carbon concentration as much as possible. Usually, its content is 0.01 to 30% by weight.

The temperature at which the activated carbon and the polymer compound solution are mixed is preferably 200 ° C. or lower from the viewpoint that adsorption of impurities on the activated carbon is not inhibited, and the mixture of the activated carbon and the polymer compound solution is preferable. From the viewpoint of lowering the viscosity and improving the filterability, it is preferably 5 ° C or higher. From this viewpoint, the temperature is preferably 5 to 200 ° C.

In the present invention, it is preferable to use a filter aid from the viewpoint of improving the filtration rate.

Examples of the filter aid include inorganic compounds such as diatomaceous earth, perlite, acid clay, bentonite, silica and zeolite. The average particle size of the filter aid is
From the viewpoint of increasing the filtration rate and also filtering the fine powder of activated carbon, the particle size is preferably 1 to 100 μm, and more preferably 5 to 50 μm. The average particle size is measured with a laser diffraction / scattering particle size distribution measuring device (manufactured by Horiba, Ltd.).

The filter aid may be added to the polymer compound solution in advance (body feed method) or may be attached to the surface of the filter medium in advance (precoating method).

In the case of adopting the body feed method, the time for adding the filter aid may be the time of introducing activated carbon or the time of mixing activated carbon and the polymer compound solution. It may be during the filtration of the mixture.

The amount of the filter aid cannot be unconditionally determined because it varies depending on the particle size and shape of the activated carbon, the type and particle size of the filter aid, etc. However, when the body feed method is adopted, the activated carbon is used. It is desirable that the amount is 0.1 to 50 parts by weight, preferably 1 to 10 parts by weight, relative to 100 parts by weight. It is preferable to form a cake layer of the agent.

As a method for removing the activated carbon from the mixture of the activated carbon and the polymer compound solution, filtration can be usually adopted. At the time of filtration, a filter paper, filter cloth, filter board or the like can be used.

Specific filtration methods include vacuum filtration,
Examples include pressure filtration and centrifugal filtration.

The liquid temperature of the mixture at the time of filtration is 5 to 200 from the viewpoint that adsorption of impurities on activated carbon is not hindered and the filterability of the mixture of activated carbon and polymer compound solution is enhanced. C., preferably below the boiling point of the solvent.

Thus, the impurities in the polymer compound solution can be removed from the polymer compound solution.

[0029]

Example 1 400 g of 30% by weight polymethacryloyloxyethyldimethylammonium sulfate (weight average molecular weight 100,000) aqueous solution (residual monomer amount 1500 mg / kg solid content) was added to 351 μm.
As described above, 12 g of granular activated carbon having a particle size of 92% and having a particle size of less than 701 μm (trade name: DIAHOPE S80S manufactured by Mitsubishi Chemical Co., Ltd.) was added and mixed and stirred for 2 hours with a stirrer to reduce the amount of residual monomer ( Hereinafter referred to as "Mixture 1")
Got The amount of residual monomer in the mixture 1 was 100 mg / kg solid or less when examined by the following measuring method.

[Measurement Method of Amount of Residual Monomer] Liquid Chromatography Method Detector: Ultraviolet absorptiometer (measurement wavelength: 220 nm) Column: Shiseido, trade name: Capcellpak 18, type SG120, length 250 mm Column temperature: 25 ° C. Mobile phase: sodium monohydrogen phosphate 0.0063 mol /
L, sodium dihydrogenphosphate 0.0328 mol / L and sodium 1-heptanesulfonate 0.0105 mol / L
Water containing L and 2-propanol in a weight ratio of 19: 1 mixed solution injection amount: 0.20 mL Flow rate: 1.0 mL / min Measurement lower limit: 100 mg / kg solid content

The particle size of activated carbon is measured according to JIS K1474.
Based on the sieving method of "Activated carbon test method". A standard sieve (JIS) is used for the sieve. Sieves (Tyler mesh) may be used for products purchased by other companies.

1.0 g of diatomaceous earth [manufactured by Showa Kagaku Co., Ltd., trade name: Radiolite # 500] was added to the mixture 1, and the mixture was further stirred and mixed for 10 minutes, and then the mixture was put into a pressure filtration container [filtration area 50 cm. ² , pressure 0.25MPa, filter cloth [Shikishima Spinning Co., Ltd.
Product, trade name: FT400S], air permeability 800 mL / cm ² · min]. The time required for complete filtration was 12 minutes.

Example 2 Filtration was carried out in the same manner as in Example 1 except that the amount of diatomaceous earth was changed from 1.0 g to 6.0 g, but the time required for complete filtration was 6 minutes. .

Example 3 To 50 g of purified water, 1.0 g of the same diatomaceous earth as in Example 1 was added, dispersed in purified water, and passed through the same pressure filter as in Example 1,
Diatomaceous earth was attached to the surface of a filter cloth, which is a filter medium. afterwards,
Mixture 1 of Example 1 was filtered. The time required for complete filtration was 20 minutes.

Comparative Example 1 The mixture 1 obtained in Example 1 was filtered using the same pressure filtration container as in Example 1. The time required for complete filtration was 65 minutes.

Comparative Example 2 In Example 1, 105 μm was used instead of 12 g of granular activated carbon.
Powdered activated carbon with a particle size of less than 99% [manufactured by Mitsubishi Chemical Corporation,
Trade name: Diahope 6D] 12 g was used, and a mixture having a residual monomer amount of 100 mg / kg solid or less was obtained in the same manner as in Comparative Example 1 except that the mixing and stirring time was changed from 2 hours to 1 hour.

This mixture was filtered using the same pressure filtration container as in Example 1. As a result, the time required for total filtration was 9 hours.

Comparative Example 3 The same procedure as in Comparative Example 2 was repeated except that the amount of powdered activated carbon was changed from 12 g to 6 g and the mixing and stirring time was changed from 1 hour to 3 hours. A mixture of less than kg solids was obtained.

6 g of the same diatomaceous earth as used in Example 2 was added to this mixture, the mixture was stirred and mixed for 10 minutes, and then the mixture was filtered using the same pressure filtration container as in Example 1. The time required for complete filtration was 4 hours and 50 minutes.

From the above results, according to Examples 1 to 3,
Since the filtration time is extremely shortened, it can be seen that the filtration rate is high as compared with Comparative Examples 1 to 3.

[0041]

According to the method for purifying a polymer compound solution of the present invention, after the activated carbon and the polymer compound solution are stirred and mixed to purify the polymer compound solution, the activated carbon has a high filtration rate and is activated. It can be filtered efficiently.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01D 37/02 C08J 3/03 CEP C08J 3/075 CEP CEZ CER CEZ // C08L 101: 00 (72) Invention Person Hideaki Kubo 1334 Minato Minato, Wakayama City Kao Corporation Research Laboratory F-term (reference) 4D017 AA03 BA04 BA12 CA03 CB01 DA07 4D066 BA01 CA01 CA02 CA03 CB12 4F070 AA32 AC04 AC12 AC22 BB05 CA20

Claims (4)

[Claims] 1. A polymer compound solution and a particle size of 149 μm or more,
A method for producing a polymer compound solution, comprising: mixing with activated carbon having a particle size of 50% or more at a particle size of less than 2380 μm, adding a filter aid to the obtained mixture, and removing the activated carbon from the mixture after the addition by filtration. 2. A polymer compound solution and a particle size of 149 μm or more,
A polymer compound solution for removing activated carbon from a mixture obtained by mixing the activated carbon having a particle size of less than 2380 μm and having a particle size of 50% or more with a filter aid previously attached to the surface of the filter medium by filtration. Manufacturing method. 3. The production method according to claim 1, wherein the solvent of the polymer compound solution is water. 4. The purification method according to claim 1, wherein the polymer compound is a cationic polymer compound.