JPS58127719A - Production of cationic acetone resin - Google Patents

Abstract

PURPOSE:To produce at low cost the titled resin useful, for example, in the treatment of various wastewaters and in the fixation and retention improvent of a size, by subjecting acetone, dimethylamine or diethylamine and formalin or paraformaldehyde to the Mannich reaction and a polycondensation reaction at pH>=7.5. CONSTITUTION:Acetone, formalin or paraformaldehyde and dimethylamine or diethylamine are simultaneously subjected to the Mannich reaction and a polycondensation reaction at pH>=7.5 under conditions of 0.3a<=c<=0.8a and b=c+1.0, wherein (a) is the molar number of acetone, (b) is the molar number of formalin or paraformaldehyde, and (c) is the molar number of diemthylamine or diethylamine. A cationic acetone resin can be obtained which can be applied to the treatment of various wastewaters, the fixation and retention improvement of a size, the retention improvement and fixation of a paper strengthening agent, etc. This acetone resin can be produced at low cost because of the cheapness of the materials and is comparable or superior, in effect, to the conventional dicyandiamide/formaldehyde resin, or the like. Thus, the resin is a cationic polymer which is very useful industrially.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a cationic acetone resin, and more specifically, acetone is subjected to Mannich reaction and polymerization with dimethylamine or diethylamine and formalin or paraformaldehyde at pH 7.5 or higher. The present invention relates to a method for producing a cationic acetone resin by carrying out a condensation reaction.

Polycondensation-based cationic polymers are used industrially for a wide range of purposes, including treatment of various types of wastewater, 9 paper strength agents, sizing agents, fixing agents and retention agents, ion sequestering agents, 2 dispersants, and fiber treatment agents. It's very useful. Therefore, various types of polycondensation cationic polymers have been developed.
In many cases, expensive polyamines are used as raw materials and epichlorohydrin is used as a linking agent in the polycondensation reaction, resulting in excessive chemical costs.

The cationic acetone resin of the present invention is produced by using inexpensive acetone as a raw material, dimethylamine or diethylamine, which is relatively inexpensive among amines, and formalin or paraformaldehyde as a linking agent in the pentacondensation reaction. Cationic polymers can be obtained at very low cost. It is also effective to use conventional commercially available dicyacydiamide formaldehyde resins.

Alkylamine, polyamine - equivalent to or better than epichlorohydrin resin, and industrial (
It is an extremely useful cationic polymer.

The reaction of condensing acetone with formaldehyde using an alkali catalyst is known. In addition, the above two substances and the aliphatic second
It is also known that a Mannich reaction occurs with the amine dimethylamine, and methyl vinyl ketone is produced by thermally decomposing the Mannich base produced, which is a well-known reaction for monomer synthesis.

The present inventor has focused on the Mannich reaction of acetone and has made various studies to synthesize a double condensation cationic polymer.
Double the mole of dimethylamine or diethylamine, formalin or paraformaldehyde in the molar ratio of these amines plus 1.0, for example, when the amine is 03, the aldehyde is 1.3, and when the amine is 0.8, it is 1.8. It was found that a cationic acetone resin can be produced by performing a Mannich reaction at a pH of 7.5 or higher and a polycondensation reaction at a molar ratio such that the present invention has been achieved.

The molar ratios of aldehyde and amine to acetone used in the present invention are related to each other, and when the molar ratio of one is determined, the other is automatically determined. That is, the molar ratio of aldehyde to acetone is The molar ratio of amine to acetone plus 1.0 is calculated by adding 1.0 to the molar ratio of aldehyde to acetone.
The value obtained by subtracting the value is Q. If the aldehyde deviates from this molar ratio, for example when the dialkylamine is 03,
If the aldehyde content is 2.0, a large amount of unreacted aldehyde remains in the product, which is not only uneconomical but also reduces the storage stability of the product solution. Also, if the dialkylamine has this molar ratio and the aldehyde is 1.0,
This time, unreacted dialkylamine remains.

This is also inconvenient. Therefore, the optimum molar ratio of aldehyde is when 1.0 is added to the molar ratio of dialkylamine.

Next, the molar ratio of amine to acetone used in the present invention is 0.3 to 0.8. If the molar ratio of amine is less than 0.3, the O copolymer tends to gel during the polycondensation reaction, and the resulting polymer is less effective for various uses. Moreover, if the molar ratio to acetone is greater than 0.8, not only will the polycondensation reaction be difficult to occur, but the viscosity will not increase.

The molecular weight per amine of the polymer also deviates greatly from the calculated value. In other words, the reaction rate is poor.

In addition, the Mannich reaction of acetone in the present invention is p
It must be carried out in an alkaline condition of H7.5 or higher. Preferably the pH is 7.5 to 11.0, and the most suitable pH is 8.
0 to 10. It is O. On the acidic side from pH 7.5 or below, Mannich reaction and polycondensation reaction do not occur, which is outside the scope of the present invention. Moreover, if the pH is above 0, the reaction of formaldehyde with acetone will be too vigorous and a water-insoluble condensate will be formed, which is not preferable. It is therefore necessary to partially neutralize the added amine. Inorganic and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, and acetic acid can be used as acids for partial neutralization, but considering the polycondensation reaction that occurs after the Mannich reaction, concentrated sulfuric acid and concentrated sulfuric acid can be used. , highly concentrated acids such as acetic acid are preferred.

When acetone, formalin or paraformaldehyde, dimethylamine or diethylamine are reacted at the molar ratio of the present invention under the above conditions, one of the two methyl groups in the acetone molecule is methylolated. However, it is thought that two types of acetone exist as main components: a dialkylaminomethylated derivative and a derivative in which one of the two methyl groups in the acetone molecule is methylolated.

If the Mannich reaction is carried out at a temperature of 30°C or higher, the reaction will proceed efficiently, but if the temperature is too high, the acetone will evaporate, which is undesirable. Therefore, the appropriate temperature is between 30° and 4°.
It is 5°C. In addition, it is preferable to carry out this Mannich reaction (following polycondensation reaction) at a temperature as high as possible, but if the temperature is too high, the generated Mannich base will decompose, so care must be taken.
It is as follows.

The cationic acetone resin produced in the present invention can be applied to the treatment of various wastewaters, the fixation and retention improvement of various sizing agents, the retention improvement and fixation of paper strength agents, and the like.

The present invention will be specifically explained below using examples. Note that the present invention is not limited to the following examples.

[Example 1] 90 g of acetone and 176 g of 37% formalin (1.4 mol relative to acetone) are each weighed, placed in a 500 tnt glass reaction vessel, mixed, covered with a three-necked lid, and attached to a stirrer. Attach a 50°C thermometer to one neck and a 100 ml separatory funnel containing 56 g of 50% dimethylamine (0.4 mol to acetone) to the other neck. When dimethylamine is added dropwise from the separatory funnel while stirring, the temperature of the mixture rises somewhat due to heat generation, so keep it below 45°C while cooling from the outside.

After dropping dimethylamine, 27 g of concentrated sulfuric acid (90% equivalent to the amine) is added dropwise while keeping the temperature below 45° C. in the same manner as dimethylamine. 3 from the end of sulfuric acid dropping
Acetone is converted into Mannich by holding at 40-45°C for a period of 40-45°C. Next, the reaction mixture was raised to 85° C. to continue the reaction. After 2 hours and 5 minutes, the viscosity increased, so an aqueous sulfuric acid solution was added to adjust the pH of the solution to 3.0 to stop the reaction.

The concentration of the product was determined to be 45% by measurement of the evaporated solid content, and the molecular weight per cation was determined to be 247 by colloid titration.
゜The viscosity of this solution was 874 cp (25°C).

[Example 2] In the same manner as in Example 1, a cationic acetone resin was synthesized using 1.5 mol of formalin to acetone and 90% equivalent of sulfuric acid to dimethylamine O.

After carrying out the Mannich reaction for 3 hours, the temperature of the two reactants was reduced to 85.
The temperature was raised to °C to carry out a polycondensation reaction. temperature to 85°C
After 2 hours and 40 minutes, the viscosity increased, so the pH of the product solution was adjusted to 3.2 with an aqueous sulfuric acid solution to stop the reaction. The concentration of the solution was 42%, and the molecular weight per cation was 239. The viscosity was 632 cp (25°C).

[Example 3] In the same manner as in Example 1, a cationic acetone resin was synthesized using 1.7 mol of formalin to acetone, 0.7 mol of dimethylamine, and 90% equivalent of sulfuric acid to dimethylamine. After carrying out the Mannich reaction for 3 hours, the temperature of the two reactants was raised to 85°C to carry out a polycondensation reaction. After 3 hours of JO after the temperature rose to 85°C, the viscosity increased, so the pH of the sulfuric acid aqueous solution was adjusted to 29 to stop the reaction. The concentration of the product solution was 50%, the molecular weight per cation was 227, and the viscosity was 324 cp (2
5°C).

[Example 4] Using the cationic acetone resin of the present invention, the effect of an anionic paper strength enhancer as a retention improver was observed. Anionization degree 6.7%, 10% as an anionic paper strength enhancer
The viscosity of the aqueous solution was 8.500 cp, and the order was anionic paper strength enhancer, sulfuric acid, and cationic polymer. Pulp filling was carried out using cardboard waste paper beaten to C8F = 400 ml, and the pulp was 70 jj/m in the usual manner. The specific bursting degree was calculated from the measurement number of the bursting strength.For comparison, a commercially available dicyandiamide-formaldehyde resin was also tested*.The results are shown in Table 1.

Table 1゜02% 3% Sample of Example 1 0.0
3% 1940.06' 2.08 0.06 2.05 0.06 1.97 Mono-formaldehyde resin 0.06 1.88
[Example 5] Using the cationic acetone resin of the present invention, the fixing effect of an anionic petroleum resin sizing agent was observed.

For comparison, sulfuric acid, dicyandiamide-bormaldehyde resin, and aluminum-epichlorohydrin resin were included in the test. Slurry made by beating hardwood kraft pulp (LBKP) with CS F = 400fnt & 0
．． 5%, add cationic resin (or sulfuric acid) and aporous ionic sizing agent in the order of 0 and pulp slurry 1)-1,
Paper with a basis weight of 70 g/m was made using a conventional method, and its sizing was measured using the Nutext method.

The results are shown in Table 2.

Table 2゜Sample of Example 1 005% 05%
49 seconds 0, 1
19.70, 2
24.00,
3
26.1 Sample of Example 2 0.05%
05% 700, 1
24.60, 2

27.40, 3
28.6 Sample of Example 3 0.
05% 05% 530, 1
1
4.50, 2
18.90, 3
28.40.2
12.90, 3
20.80.2
10.30.3
15.6 Liquid sulfuric acid band 3% 05%
224 [Example 6] Using the cationic acetone resin of the present invention, the color removal effect of a red direct dye was observed. For comparison, dicyandiamide-formaldehyde resin was used.

Adjust the red direct dye solution to 300 ppm, add each sample in the specified amount, and test with a jar tester to 150 ppm.
After stirring at rpm for 3 minutes, 2 ppm of a dye solution of polyacrylamide-based flocculant with a degree of anionization of 10% was added, and the mixture was stirred at 150 rpm for 2 minutes and 50 rpm for 1 minute, and left for 5 minutes. The absorbance of the two-clear liquid was measured using an absorbance meter using a wavelength of 405 nm, and the residual color rate was measured. The amount of anti-liquid added that would give each sample a residual color rate of 2% or less was determined, and the results are shown in Table 3.

Table 3゜Example 1. Sample of 70ppm Example 2. Sample 70 Sample of Example 3 80 [Example 7] Using the cationic acetone resin of the present invention, the color removal effect of kraft pulp production waste liquid was observed. At the same time, dicyandiamide-polmaldehyde resin was added to the test for comparison. Kraft pulp production waste liquid has a solid content of 1. OOpp
Adjust to make a m solution.

Add the specified amount of each sample and use a jar tester to
50 rprn After stirring for 3 minutes, the degree of anionization was 10.
% polyacrylamide-based flocculant was added to the liquid at 2 ppm, stirred at 150 rpm for 2 minutes and 50 rpm for 1 minute, and after standing for 5 minutes, the absorbance of the supernatant was measured using an absorbance meter using a wavelength of 530 nm. The amount added to the liquid that would give a residual color rate of 10% or less was determined for each sample. The results are shown in Table 4. Shown below.

Table 4゜Sample Remaining color rate 10% or less (This is the amount added to the liquid Sample of Example 1. 1.OOppm Sample of Example 2. 100 Sample of Example 3. 110 Dicyandiamide
120-formaldehyde resin

Claims (1)

[Claims] The number of moles of acetone, formalin or formaldehyde, dimethylamine or diethylamine is a, b,
A cationic acetone resin characterized in that Mannich reaction and polycondensation reaction are carried out at pH 7.5 or higher with a ratio of 0.3a≦C≦0.8 a, b=c+ 1.0, where c is 0.3a≦C≦0.8. Manufacturing method.