JPH0710944A - Water-soluble polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a water-sol. polymer which does not give off the odor of sulfur dioxide gas, has a high quality and a low cost, and is useful for a dispersant, etc., by selecting a water-sol. polymer having two kinds of specific repeating units. CONSTITUTION:A water-sol. polymer having repeating units of formulas I and II [wherein R<1> is H or methyl; X is H or an alkali metal; and (m/n) is (1/1)-(19/1)] is selected. The polymer can be produced pref. by jointly using NaOH when a poly(meth)acrolein (co)polymer is reacted with NaHSO3 or Na2S2O5.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel water-soluble polymer having a sulfonic acid group and a method for producing the water-soluble polymer by using (meth) acrolein as a starting material.

[0002]

2. Description of the Related Art Sodium bisulfite (NaHS) is added to poly (meth) acrolein obtained by radical polymerization.
It is known that a water-soluble polymer can be obtained by addition reaction of O ₃ ) or sodium pyrosulfite (Na ₂ S ₂ O ₅ ). For example, ENCYCLOPEDIA OF POLYMER S published by John Wiley & Sons.
CIENCE AND ENGINEERING, 2nd
Edition, Vol. 1, pp. 162-165, Kunstoffee P
plastics, 1957, Vol. 6, pages 303-312, and West German Patent No. 1076372, etc., but a water-soluble polymer obtained by adding sodium bisulfite to poly (meth) acrolein obtained by ionic polymerization. Is not yet known.

Further, when producing a water-soluble polymer by this addition reaction, according to the description of the above-mentioned document, sodium bisulfite is used excessively with respect to poly (meth) acrolein, and after the reaction, it is dialyzed to produce an excess amount. Sodium bisulfite is removed.

For example, West German Patent No. 1076372
No., column 3, Example 1 10 g (0.178 mol) of polyacrolein obtained by redox polymerization
To 10 ml of a 10% aqueous solution of sulfite (0.328 mol)
After the polyacrolein is dissolved, the excess sulfite is removed by dialysis. Here, sodium bisulfite, sodium pyrosulfite, and sulfurous acid are all considered to be equivalent compounds because the reactions proceed in the same manner.

[0005] When (meth) acrolein is polymerized by radical polymerization, vinyl polymerization occurs, so that the obtained poly (meth) acrolein does not have a vinyl group or an isopropenyl group as a functional group. Therefore, it is impossible to stably introduce the sulfonic acid group into the polymer by the reaction with sodium bisulfite or sodium pyrosulfite.

For example, J. Am. Chem. Soc., 19
As described in 1986, vol. 86, pages 4791-4795, the reaction between an aldehyde group and sodium bisulfite is an equilibrium reaction, so that it is impossible to stably introduce a sulfonic acid group into a polymer.

Further, since the above-mentioned method for producing a water-soluble polymer uses an excess amount of sodium bisulfite, the solution after the reaction contains unreacted sodium bisulfite, and the excess sodium bisulfite is obtained by dialysis. Need to be removed,
There were problems in terms of economy and quality.

[0008]

The object of the present invention is to use a novel water-soluble polymer having a sulfonic acid group and an excess of sodium bisulfite, and to eliminate the need for a treatment step such as dialysis. An object of the present invention is to provide an odorless, economical and high-quality production method of the water-soluble polymer.

[0009]

DISCLOSURE OF THE INVENTION The inventors of the present invention firstly found that poly (meth) acrolein obtained by ionic polymerization has a vinyl group or an isopropenyl group as a functional group, and sodium bisulfite or sodium pyrosulfite is used. It was found that a sulfonic acid group can be stably introduced into the polymer by the reaction with.

The sulfonic acid group-containing water-soluble polymer obtained here is (A) or (B) of the following general formula (I).

[0011]

[Chemical 2]

(Wherein R ¹ represents hydrogen or a methyl group,
X represents hydrogen or an alkali metal.

However, it is a water-soluble polymer having a repeating unit represented by m / n = 1/1 to 19/1).

The molecular weight of this water-soluble polymer is not particularly limited, but is usually between 500 and 50,000,
The ratio of m to n in the general formula (I) is generally m / n = 1/1 to 19/1.

In the present invention, poly (meth) acrolein obtained by polymerizing (meth) acrolein by ionic polymerization can be used. Particularly, poly (meth) acrolein obtained by anionic polymerization has a high polymerization yield. , Further in the reaction of poly (meth) acrolein with sodium bisulfite or sodium pyrosulfite,
It is economically advantageous because a water-soluble polymer having a sulfonic acid group can be quantitatively obtained. Further, there is no problem even if it is copolymerized with another monomer.

The method of anionic polymerization is not particularly limited, and a conventionally known method can be used as it is. As an initiator, a hydroxide, nitrate, acetate or carbonate of an alkali metal or alkaline earth metal is used. Salt, or 1,
8-diazabicyclo [5.4.0] unde-7-sen,
Use of organic amines such as triethylenediamine, pyridine, pyrazole, pyrazine, pyrimidine, benzimidazole, 1,2,4-triazole, and imidazole is easier to handle than the case of using an organic metal or the like, and economically preferable. .

In the present invention, sodium bisulfite or sodium pyrosulfite is used in an amount of 50 to 100 mol% and sodium hydroxide is used in an amount of 5 to 50 mol% based on the (meth) acrolein monomer in the poly (meth) acrolein, preferably. Sodium bisulfite or sodium pyrosulfite is used at 60 to 90 mol% and sodium hydroxide is used at 10 to 40 mol%.

In this addition reaction, the reaction temperature is 10 to 12
The temperature is preferably 0 ° C. If the temperature is lower than this range, the reaction is slow, and if the temperature is higher than this range, a pressurized reactor is required due to the water vapor pressure, which is economically disadvantageous.

Further, when producing this water-soluble polymer, sodium bisulfite or sodium pyrosulfite and sodium hydroxide are used in combination, but if sodium bisulfite or sodium pyrosulfite and sodium hydroxide are added at the same time, a neutralization reaction occurs. In some cases, it proceeds and the capture of sulfurous acid gas by sodium hydroxide does not proceed efficiently. Therefore, in this case, after the reaction between sodium bisulfite or sodium pyrosulfite and poly (meth) acrolein sufficiently progresses, sodium hydroxide is added to capture sulfurous acid gas and recycle it as sodium bisulfite.
As a method of adding sodium bisulfite or sodium pyrosulfite and sodium hydroxide, for example, if sodium bisulfite or sodium pyrosulfite is added all at once in the initial stage, the generated sulfurous acid gas may increase out of the system and the exhaust gas treatment Therefore, it is preferable to divide into several times, and it is suitable to divide into several times according to this also for sodium hydroxide.

[0020]

The method for producing a water-soluble polymer provided by the present invention is a method such as dialysis because sodium bisulfite or sodium pyrosulfite used as a water-solubilizing agent (sulfonating agent) does not remain in the system after the reaction. No process is required. In addition, since the sulfurous acid gas generated during the reaction is converted to sodium bisulfite with sodium hydroxide and recycled in the system, it is not necessary to use excess sodium bisulfite or sodium pyrosulfite, and a processing device for the byproduct sulfurous acid gas is also unnecessary. Becomes

Since the novel water-soluble polymer provided in the present invention has a sulfonic acid group in the molecule,
For example, dispersants, surfactants, detergent builders, oil drilling additives, scale inhibitors, flocculants, cooling water additives,
It can be suitably used in the fields in which water-soluble polymer compounds containing a sulfonic acid group have hitherto been used such as boiler additives and anticorrosion agents.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(A) The following TOS is used for the measurement of gel permeation chromatography (hereinafter abbreviated as GPC).
It was carried out using an OH device and a solvent.

Pump: CCPM Detector: RI-8010 Column: G5000PW, G4000PW, G3000
PW and G2500PW are connected Column temperature: 40 ° C. Data processor: SC-8020 Developing solvent: 50 mmol / l sodium chloride aqueous solution and 80:20 by volume ratio of acetonitrile The molecular weight is polyethylene glycol of known molecular weight as a standard sample. A calibration curve was prepared using the above and calculated based on this.

(B) The fluorescent X-ray spectrum was measured by using a System 3080 apparatus manufactured by Rigaku Co., Ltd., and dehydrating the reaction solution to obtain a solid, which was powdered.

(C) The infrared absorption spectrum is BIO R
An FTS-45 type FT-IR apparatus manufactured by AD was used, and the solid obtained by dehydrating the reaction solution was used as a KBr tablet plate for measurement.

(D) Quantification of aldehyde groups in poly (meth) acrolein was carried out by using the Junalof Polymer.
r Science, Polymer Chemist
ryEdition, 1984, Vol. 22, 145-158
It was carried out by the method using hydroxylamine hydrochloride described on page. The measuring method is shown below.

50 mg of poly (meth) acrolein was added to 5
Suspend in ml of deionized water, add 500 mg of hydroxylamine hydrochloride to the suspension, and stir at room temperature for 24 hours.
Stir. The polymer is separated by filtration, washed several times with ion-exchanged water, and then dried under reduced pressure at room temperature. The nitrogen content in the obtained dried product is quantified by elemental analysis, and the aldehyde group content is calculated based on this.

(Production Example-1) 50 with cooling pipe and stirring device
In a 0 ml flask, 280 ml of ion-exchanged water and a surfactant (Dowfax-2A-1 manufactured by Nippon Emulsifier Co., Ltd.)
After charging 2 g and purging with nitrogen, 70 g of acrolein was added and the mixture was cooled to 5 ° C. with ice water. After cooling, 2N aqueous sodium hydroxide solution was added until the pH of the reaction solution reached 11 or higher, and then the mixture was stirred at a temperature range of 5 to 40 ° C for 2 hours.
The reaction liquid after the reaction was a suspension solution containing a white solid. Collect a part of this suspension solution and add dioxane,
When acrolein in the solution as a homogeneous solution was quantified by gas chromatography, the conversion of acrolein was 99 mol% or more.

(Production Example-2) The same operation as in Production Example-1 was carried out except that the initiator was changed from sodium hydroxide to calcium hydroxide and the amount used was 1 mol% of acrolein. After completion of the reaction, the conversion of acrolein was measured in the same manner as in Production Example 1, and it was 99 mol% or more.

(Production Example 3) 1,8-diazabicyclo [5.4.0] unde-7 was used as an initiator from sodium hydroxide.
-The same operation as in Production Example 1 was carried out except that cerene was used and the amount used was 1 mol% of acrolein. After the reaction,
When the conversion of acrolein was measured in the same manner as in Production Example 1, it was 99 mol% or more.

(Production Example-4) The procedure of Production Example-1 was repeated except that acrolein was changed to methacrolein. The solution after completion of the reaction was separated into two layers, and unreacted methacrolein floated in the upper layer. In addition, when unreacted methacrolein was quantified by gas chromatography,
The conversion of methacrolein was 15 mol%.

(Analysis of Aldehyde Group in Poly (meth) acrolein) The aldehyde groups in the poly (meth) acrolein obtained in Production Examples 1 to 4 were quantified by the above method and the structure was analyzed. Results were obtained.

Structural formula of poly (meth) acrolein

[0035]

[Chemical 3]

(In the formula, R ¹ represents hydrogen in the case of acrolein and a methyl group in the case of methacrolein.) Production Example-1 m: n = 80: 20 Production Example-2 m: n = 90: 10 Production Example-3 m: n = 65: 35 Production Example-4 m: n = 70: 30 (Example-1) 100 g of the suspension containing 20 g of the polyacrolein obtained in Production Example-1 was cooled to an internal volume of 200 ml. It was put in a flask equipped with a tube and a stirrer, and heated to 50 ° C. in an oil bath. After reaching 50 ° C., 285 mmol of sodium bisulfite (29.6 g) was added every 30 minutes in 5 portions, and a 40 wt% sodium hydroxide aqueous solution (7
1 mmol) was added in 5 portions and added 25 minutes after the addition of sodium bisulfite. After the last sodium bisulfite was added, stirring was continued at 50 ° C. for 1 hour and then cooled to room temperature. The obtained aqueous solution was a substantially colorless and homogeneous solution containing no sulfurous acid gas odor. Further, when the obtained solution was dried and the solid content was analyzed by fluorescent X-ray, sodium bisulfite did not remain. In addition, sodium sulfite produced by the reaction between sodium bisulfite and sodium hydroxide was not present. The number average molecular weight of the obtained water-soluble polymer was 3,000.

Example 2 Using the polyacrolein suspension obtained in Production Example-2, sodium bisulfite was added to 3 times.
20 mmol, and sodium hydroxide aqueous solution 35 mm
The same operation as in Example-1 was carried out except that it was ol.
When the precipitated calcium sulfite was filtered off from the obtained aqueous solution, an almost colorless homogeneous solution was obtained. Also in this case, sodium bisulfite and sodium sulfite did not remain in the solid content, and the number average molecular weight of the obtained water-soluble polymer was 3,000.

(Example-3) Using the polyacrolein suspension obtained in Production Example-3, 2 parts of sodium bisulfite was added.
30 mmol, sodium hydroxide aqueous solution 125m
The same operation as in Example-1 was performed except that the amount was mol. The obtained aqueous solution was a substantially colorless homogeneous solution.
Also in this case, sodium bisulfite and sodium sulfite did not remain, and the number average molecular weight of the obtained water-soluble polymer was 3,500.

(Example-4) From the reaction solution obtained in Production Example-4, unreacted methacrolein was distilled off together with water under reduced pressure to obtain a polymethacrolein suspension having a solid content of 20% by weight. It was Using 50 g of this suspension, the same operation as in Example 1 was performed except that sodium bisulfite was adjusted to 100 mmol and the sodium hydroxide aqueous solution was changed to 40 mmol. The obtained aqueous solution was a substantially colorless homogeneous solution. Also in this case, sodium bisulfite and sodium sulfite did not remain, and the number average molecular weight of the obtained water-soluble polymer was 3,000.

(Structure of sodium bisulfite adduct of poly (meth) acrolein) From the structure of poly (meth) acrolein, the structure of sodium bisulfite adduct is estimated as follows.

[0041]

[Chemical 4]

(In the formula, R ¹ represents hydrogen or a methyl group, and X represents hydrogen or sodium.) Example-1 m: n = 80: 20 Example-2 m: n = 90: 10 Example -3 m: n = 65: 35 Example-4 m: n = 70: 30

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum of the substance obtained in Example-1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsuto Matsuda 5-8 Nishiomitabicho Suita City Osaka

Claims (2)

[Claims] 1. A molecule represented by the following general formula (I):
(B) [Chemical formula 1] (In the formula, R ¹ represents hydrogen or a methyl group, X represents hydrogen or an alkali metal, and m / n = 1/1 to 19/1). 2. A poly (meth) acrolein (co) polymer is reacted with sodium bisulfite or sodium pyrosulfite to produce a water-soluble polymer according to claim 1, which is combined with sodium hydroxide. A method for producing a water-soluble polymer characterized by the above.