JPS61192734A - Production of water-soluble cationic polymer - Google Patents

Abstract

PURPOSE:To produce the title polymer excellent in coagulation effect in water, high in cationic character and useful as a coagulant, a sizing agent or the like, by reacting epichlorohydrin with a diallylamine and an alkali (alkaline earth) metal (hydr)oxide. CONSTITUTION:1mol of epichlorohydrin is added to a cooled aqueous solution of a concentration >=20wt% containing 1.00-1.05mol of a dialkylamine (e.g., dimethylamine) and kept at 15-100 deg.C. To this solution 0.00001-0.05mol of an alkali (alkaline earth) metal (hydr)oxide (e.g., MgO) is added with agitation and the resulting mixture is reacted in an inert gas atmosphere at 15-100 deg.C until the agitation becomes hard and allowed to stand at 40-80 deg.C for 5-6hr to obtain a water-soluble cationic polymer of an intrinsic viscosity >=0.1 (as measured in a 2N-aqueous KBr solution).

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for producing a water-soluble cationic polymer. More specifically, it has excellent solubility in water, high cationicity, and is highly resistant to aggregation (f) of suspended substances in aqueous media.
The present invention relates to a method for producing a water-soluble cationic polymer that can be used as a wet paper strength enhancer in the paper industry, a sizing agent in the paper industry, a retention improver for fillers, etc.

``Prior art'' A method for producing a water-soluble cationic polymer by reacting epichlorohydrin and dialkylamine was disclosed in Japanese Patent Publication No. 54
It is described in Japanese Patent Application Laid-open No. 10039-10039, Japanese Patent Application Laid-Open No. 121033-1983, and US Pat. No. 3,975,347.

However, when using the methods described in these publications, the degree of polymerization is low, and when used as a flocculant for suspended solids in an aqueous medium, the flocculation performance is poor, and it is used as a sizing agent, filler, etc. in the paper industry. When used as a retention aid, it has the disadvantage of insufficient performance.

``Problems to be Solved by the Invention'' The present invention has excellent flocculant performance when used as a flocculant for suspended solids in an aqueous medium, and is used as a retention improver for sizing agents, fillers, etc. in the paper manufacturing industry. It is an object of the present invention to provide an industrially advantageous method for producing a water-soluble cationic polymer with a high degree of polymerization that exhibits excellent performance in various cases.

"Means for Solving the Problems" The gist of the present invention is that 1.0θ to 1.0% of dialkylamine is added to 1 mole of epichlorohydrin.
5 mol and 0.00001 to 0.05 mol of a compound selected from alkali metal oxides or hydroxides and alkaline earth metal oxides or hydroxides,
The present invention relates to a method for producing a water-soluble cationic polymer, characterized in that the reaction is carried out in a temperature range of 100°C.

The present invention will be explained in detail below.

In the present invention, epichlorohydrin and dialkylamine are used as raw materials. The dialkylamine refers to one in which the alkyl group bonded to nitrogen has 3 or less carbon atoms. Specific examples include dimethylamine, diethylamine, noprobylamine, methylethylamine, methylpropylamine, dithylpropylamine, and the like. At least one or two of these
Among these, aqueous solutions of dialkylamines are industrially advantageous, although they may be mixtures of more than one species. The concentration of dialkylamine in the aqueous solution is preferably 20% by weight or more, particularly preferably 35% or more. As the number of carbon atoms in the alkyl group of dialkylamine increases, the reactivity tends to decrease, so if only the reactivity is considered, trimethylamine is particularly suitable, and furthermore, it is easy to obtain raw materials,
Also, trimethylamine is preferred in terms of increasing the nitrogen content per unit weight.

When reacting two types of raw materials, epichlorohydrin 1
The amount of dialkylamine is in the range of 1.00 to 1.05 moles. When the molar ratio of the raw materials is within the above range, it is easy to obtain a water-soluble cationic polymer with a high degree of polymerization as desired. If the molar ratio of the raw materials is outside the range of 2), the degree of polymerization of the polymer will not increase, probably because equilibrium will be lost during the reaction.

In the method of the present invention, a small amount of an alkali metal oxide or hydroxide or an alkaline earth metal oxide or hydroxide is added to the reaction system. These compounds function to increase the degree of polymerization of the polymer obtained by the reaction.

Specifically, the alkali metal oxide or hydroxide is L
i2O, Na2O, 20. Cs2O, LiOH, Na
There are OH, KOH, CsOH, etc., and specific examples of alkaline earth metal oxides or hydroxides include MgOwC&
OHB ao g S to *Mg(OH)2yca
(OH)2yS t(OH)2, etc. These compounds may be used alone or in combination of two or more.

To add these compounds to the reaction system, add 5 to 100 times as much water as an aqueous solution or dispersion. ^
J/k 1-In 1 mol of chlorhydrin is preferably selected from the range of 0.00001 to 0.05 mol per mol of chlorohydrin. If it is less than the above range, a polymer with the desired high degree of polymerization cannot be obtained, which is undesirable. If it is more than the above range, the product will decompose and gel, resulting in water insolubility or poorly soluble. I ended up
It is not possible to obtain something that achieves the object of the present invention.

The procedure for producing the desired product according to the method of the present invention is preferably as follows.

First, a closed container equipped with a stirrer is prepared, and the inside of the container is replaced with an inert gas such as nitrogen. The dialkylamine was charged into this container, and while stirring, epichlorohydrin was added while cooling to prevent the temperature inside the reaction container from rising too much.
Prepare batchwise or continuously. The internal temperature of the reaction vessel is 1
The temperature range is preferably 5 to 100°C. This temperature is 1
When the temperature is less than 5°C, the reaction time becomes too long, which is inconvenient, and it is difficult to remove and control the reaction heat during the reaction, which is not preferable. When this temperature exceeds 100° C., it is not preferable because the internal pressure of the reaction vessel becomes very high in the initial stage and the reaction product becomes sluggish or colored, degrading its quality. The time spent charging epichlorohydrin into the reaction vessel can be changed depending on whether or not the internal temperature of the reaction vessel can be controlled.

As mentioned above, it is preferable that the noalkylamine is an aqueous solution having a weight of 20 weight or more because the temperature inside the reaction vessel can be easily controlled. If the weight is less than 20 weight, it is difficult to remove the degree of polymerization, which is not preferable.

An aqueous solution or dispersion of an alkali metal oxide or hydroxide, an alkaline earth metal oxide or hydroxide is added to the reaction vessel containing the two raw materials under stirring. After adding this compound, the internal temperature of the reaction vessel was adjusted to 15-1
6. If the internal temperature of the reaction vessel is maintained within this temperature range, the degree of polymerization of the reaction product will gradually increase, making it difficult to stir the reaction solution. If stirring becomes difficult, it may be discontinued. After discontinuing stirring, the reaction vessel is preferably left at a temperature in the range of 40 to 80°C for 5 to 6 hours. Even if stirring is stopped, if the atmosphere in the reaction vessel is kept under an inert gas, the reaction to increase the degree of polymerization will proceed slowly for about 2 months at a temperature of 30°C.

During this time, if oxygen or air is introduced into the reaction vessel, the reaction that increases the degree of polymerization will not proceed.

The polymer, which is a reaction product, is determined to have a large,
It is difficult to judge small. In order to achieve the object of the present invention, [η1 is preferably 0.1 or more, more preferably 0.15 or more, and particularly preferably 0.2 or more.

The water-soluble cationic polymer obtained by the method of the present invention is in the form of an aqueous solution. This product can be used as a retention aid for flocculating suspended solids in aqueous media, as a wet paper strength enhancer in the paper industry, as a sizing agent, as a filler, etc. in the paper industry. For use, the product is diluted with water to bring the polymer concentration up to 5% by weight, preferably 2% by weight.
It is recommended to use the following.

"Effects of the Invention" The present invention has been described above, and has the following particularly remarkable effects, and its industrial utility value is extremely large.

(1) When using the method of the present invention, a water-soluble cationic polymer with a high degree of polymerization can be easily produced.

(2) The water-soluble cationic polymer with a high degree of polymerization obtained by the method of the present invention can be used to agglomerate suspended substances in an aqueous medium, as a wet paper strength enhancer in the paper industry, as a sizing agent, as a filler, etc. in the paper industry. Demonstrates excellent performance as a retention aid.

[Example 1] Hereinafter, the present invention will be explained in detail based on Examples.
The present invention is not limited to the following examples unless the scope thereof is exceeded.

Example 1 (Production of polymer) A pressure-resistant sealed reaction vessel (SU
S 3049 was prepared, and 4% of a 5% aqueous solution of dimethylamine was added to a reaction vessel whose interior was replaced with nitrogen gas.
kg (44.4 mol) was charged in this reaction vessel at 25°C.
While cooling with water, add 4 ml of epichlorohydrin to the container.
107 g (44.4 mol) at a rate of 151/min, 4
It took 30 minutes to prepare the mixture, and in the middle of the preparation, the internal temperature of the reaction vessel was lowered to a maximum of 75°C. In addition, the reaction internal pressure was 2.5 kg immediately after the start of charging epichlorohydrin.
/ Increased to C theory 2, but in the final stage it was 0.5 kg/cm
' has dropped to '.

After the addition of epichlorohydrin was completed, 170 ml of 10% NaOH aqueous solution was added to the same reaction vessel. Thereafter, the internal temperature of the reaction vessel was raised to 60° C. and maintained at this temperature for 4 hours.

5 g of the product was collected from the reaction vessel and added to 5001 acetate to precipitate the polymer.

After this polymer was filtered and dried, it was dissolved in a 2N KB aqueous solution, and its intrinsic viscosity [η1 was measured by a conventional method and found to be 0.23.

(Performance evaluation of polymer as a flocculant) Sludge is a sediment obtained by statically settling domestic wastewater with a thickener, and the natural sedimentation volume is 100%, and the solid content is 1.5 weight. % of the product obtained above (aqueous solution of polymer) was added in an amount equivalent to 2,000 pp-based on the precipitate. The precipitate to which the above polymer had been added was supplied to a super decanter (manufactured by Tomoe Kogyo Co., Ltd., P660), and dehydrated at 3000G under 10017 hours.

The resulting dehydrated cake had a moisture content of 75% by weight. This water content can be said to be extremely low compared to about 85% by weight in the conventional case.

Example 2 (g1 construction of polymer) In the example described in Example 1, 50% of dimethylamine
Instead of the aqueous solution, 3241 g of dinotylamine (44,
The procedure was the same as in the same example except that 4 mol) and 10,100 O of water were used.

The intrinsic viscosity of the resulting polymer was measured in a manner similar to that described in Example 1. The results are shown in Table 1.

(Evaluation of the performance of the polymer as a flocculant) In the same manner as described in Example 1, the performance of the polymer obtained in the above example as a flocculant was evaluated.

The results of measuring the moisture content of the obtained dehydrated cake are shown in Table 1.

Examples 3 to 7 The same procedure as in Example 1 was repeated, except that 170 liters of a 10% aqueous solution or dispersion of the compound shown in Table V41 was added instead of the 10% NaOH aqueous solution. .

The intrinsic viscosity of the resulting polymer was measured in a manner similar to that described in Example 1. The results are shown in Table 1.

(Evaluation of the performance of polymers as flocculants) In the same manner as described in Example 1, the performance of each polymer obtained in the above example as a flocculant was evaluated.

The results of measuring the moisture content of the obtained dehydrated cake are shown in Table 1.

Example 8 (Manufacture of polymer) A pressure-resistant sealed reaction vessel (made of SUS304) equipped with a stirrer and a jacket having a volume of fi2M3 was prepared, and the inside of the vessel was purged with nitrogen gas. Add 50% of dinotylamine to this reaction vessel.
% aqueous solution was charged.

While cooling the reaction vessel by passing industrial water at 25°C through the jacket of the reaction vessel, 925 kg of epichlorohydrin was charged over a period of 10 hours while maintaining the internal temperature of the reaction vessel in the temperature range of 60 to 90°C.

A dispersion was prepared by dispersing fine powder 2.8K, which is a ground product of CaO and passed through a 200 mesh sieve, in 101 water, and this was charged into the reaction vessel after the completion of the preparation of epichlorohydrin. Also, the internal temperature of the reaction vessel was set to 60℃.
This temperature was maintained for 10 hours.

10 g of the product was taken from the reaction vessel and added to 11 acetone to precipitate the polymer. After this polymer was filtered and dried, it was dissolved in a 2N KBr aqueous solution, and the intrinsic viscosity r1 was measured by a conventional method and found to be 0.28.

(Evaluation of the performance of the polymer as a flocculant) The performance of the polymer obtained in Example L as a flocculant was evaluated in the same manner as described in Example 1.

The results of measuring the moisture content of the obtained dehydrated cake are shown in Table 1.

Example 9 (Manufacture of polymer) The same procedure as in Example 8 was carried out except that 20% of 10% NaOH water W# solution was added instead of the aqueous CaO dispersion.

The intrinsic viscosity of the resulting polymer was measured in a manner similar to that described in Example 1. The results are shown in Table 1.

(Performance evaluation of polymer as a flocculant) The same procedure was used as in Example 1.

Comparative Example 1 (Production of Polymer) The same procedure as in Example 1 was carried out except that the NaOH aqueous solution was not added after the addition of epichlorohydrin was completed.

The intrinsic viscosity of the produced polymer was also measured in the same manner as in the same example. The results are shown in Table 1.

(Performance evaluation of polymer as a flocculant) The same procedure was used as in Example 1.

Comparative Example 2 (Production of Polymer) The same procedure as in Example 2 was carried out except that the NaOH aqueous solution was not added after the addition of epichlorohydrin was completed.

The intrinsic viscosity of the produced polymer was also measured in the same manner as in the same example. The results are shown in Table 1.

Comparative Example 3 In the example described in Example 1 (performance evaluation of polymer as a flocculant), a commercially available high molecular weight cationic polyacrylamide-based flocculant was used instead of the polymer obtained in the same example. agent (Nitto Kagaku Co., Ltd. 91. Trade name KP-355),
2000 ppm was added to the sediment, and the performance as a flocculant was evaluated in the same manner as described in the same example.

The moisture content of the obtained dehydrated cake was measured and the results are shown in Table 1.

From Table 1, the following becomes clear.

(1) The water-soluble cationic polymer obtained by the method of the present invention has a high intrinsic viscosity.

(2) The water-soluble cationic polymer obtained by the method of the present invention has extremely excellent performance in flocculating suspended substances in an aqueous medium.

Claims (3)

[Claims] (1) For 1 mole of epichlorohydrin, add 1.00 to 1.05 moles of dialkylamine and a compound selected from alkali metal oxides or hydroxides and alkaline earth metal oxides or hydroxides. 0.00001~0.0
A method for producing a water-soluble cationic polymer, which comprises adding 5 mol of the polymer and reacting at a temperature range of 15 to 100°C. (2) As dialkylamine, dialkylamine is 2
Using an aqueous solution containing 0% by weight or more, epichlorohydrin is added while adjusting the temperature of this aqueous solution in the range of 15 to 100°C, and then an alkali metal oxide or hydroxide, an alkaline earth metal oxide or water is added. The method for producing a water-soluble cationic polymer according to claim (1), which comprises adding a compound selected from oxides. (3) Claims (1) to (2) characterized in that the dialkylamine is dimethylamine.
A method for producing a water-soluble cationic polymer as described in Section 1.