JPS5827702A - Preparation of water-soluble high polymer having high polymerization degree - Google Patents

Abstract

PURPOSE:To obtain the titled substance suitable for flocculants, yield increasing agents, viscosity increasing agents, etc., by reacting an acrylaminde water- soluble high polymer with an aliphatic dialdehyde, and joining them in a specific range. CONSTITUTION:One or more aliphatic dialdehydes, e.g. malonaldehyde, of the formula OHC-R-CHO (R is alkylene or alkenyl), are reacted with an aqueous solution of an acrylamide water-soluble high polymer, e.g. polyacrylamide, in a concentration of preferably 0.5-10%, and the raw material high polymer is mutually joined in such a range as to keep the formed high polymer water soluble.

Description

Detailed Description of the Invention Water-soluble polymeric substances include flocculants, retention improvers in paper mills, paper speed enhancers, thickeners, and fluidity regulators for oil recovery by press-injecting high-viscosity aqueous solutions. It is widely used as It is generally known that the higher the polymerization degree of water-soluble polymer substances used for such purposes, the more effective they are. , improvements in polymerization methods such as suspension polymerization, and redox initiators 1. Improvements in polymerization initiation methods, such as initiation of polymerization using radiation or the like, are being studied for azo-based initiators.

Conditions for obtaining water-soluble polymeric/molecular substances with a high degree of polymerization include the polymerization method, polymerization initiation method, type of raw material monomer, and its quality.Currently, polyacrylamide with a degree of polymerization of about 200,000 is known; The degree of polymerization of the water-soluble polymeric substance obtained is limited to this degree of purity. The raw material monomers OaI vary depending on the use of the polymeric substance, but the degree of polymerization of water-soluble polymeric substances obtained using O monomers other than acrylamide is 200,000 or less. Therefore, in order to make water-soluble polymer substances more effective for each purpose,
It has been desired to develop water-soluble polymeric substances with a higher degree of polymerization than ever before.

The present inventors further conducted research on a method for obtaining a water-soluble polymer substance with a high degree of polymerization, and as a result, they arrived at the present invention. That is, the present invention provides formula one for acrylamide-based water-soluble polymeric substances.
-R-ago (In the formula, R represents an alkylene group or an alkenylene group.) One or several aliphatic dialdehydes are added and reacted, and the resulting polymer substance is water-soluble. A method for producing a water-soluble polymer substance with a high degree of polymerization, characterized by bonding raw polymer substances with each other within a certain range, the water-soluble polymer substance obtained by the present invention It has a high degree of polymerization of 0%.

The water-soluble polymeric substance with a high degree of polymerization obtained by the present invention is used as a flocculant for use in water/waste water treatment, water/sewage sensitive layers, and treatment of suspensions generated in various production processes, and as a papermaking process K> It is effectively used for various purposes such as a yield increaser, a paper speed enhancer, a thickener, and a thickener for rounding the injection of high viscosity water in the oil extraction industry.

The raw material acrylamide-based water-soluble polymer materials used in the present invention include polyacrylamide, polymethacrylamide, polyacrylamide t, partial hydrolysates of polymethacrylamide, and other copolymerizable monomers with acrylamide and methacrylamide. A water-soluble copolymer with is used. Other copolymerizable monomers include acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfate, fonic acid and salts thereof, dimethylaminoethyl methacrylate and its tertiary salts, and quaternary salts thereof.
Salts, lower alkyl acrylates, vinylpyrrolidone, vinylpyridine-1-acetate vinyl esters, etc. can be used. In the case of a copolymer, it is desirable that one unit of the amide-containing monomer contained in the polymer is 10 moles or more in terms of zero monomer before polymerization. The aliphatic dialdehydes used in the present invention include malonaldehyde,
Alkylene dialdehydes such as succinic aldehyde, glutaraldehyde, and adipaldehyde, and alkenyl dialdehydes such as maleic dialdehyde and fumardialdehyde can be used, and can be used alone or in combination. These aliphatic dialdehydes are generally used as an aqueous solution, but they can also be used as a solution in an organic solvent such as methanol, ethanol, or acetone.

The method for producing a water-soluble polymer substance with a high degree of polymerization according to the present invention K is as follows:
This can be carried out by mixing the raw material powder or water-soluble acrylamide-based water-soluble polymer with a solution of aliphatic dialdehydes in a tank or during transportation in a 7-inch tube, trough, or the like.

When reacting a water-soluble polymer material as a raw material in the form of an aqueous solution, the concentration of the aqueous solution varies depending on the type and molecular weight of the water-soluble polymer material as a raw material, but is generally 1s~1@Is@
A concentration of 0.5°C is preferred.

If the concentration is 10 or more, it becomes difficult to adjust the reaction to achieve an appropriately high degree of polymerization, or a water-insoluble polymer substance is produced during the reaction. Furthermore, if the concentration is less than 5% (L), the reaction will be slow and a sufficient degree of polymerization will not be achieved.

When reacting an acrylamide-based water-soluble polymer substance as an aqueous solution, the reaction solution may be p) Ifi or alkaline, but since the reaction is faster in alkaline, pIIa
The above is desirable. However, when reacting a water-soluble polymer substance that is unstable in alkaline conditions, it is necessary to carry out the reaction in acidic conditions even if the reaction with aliphatic dialdehyde is slow.

The reaction in an aqueous solution can be carried out at temperatures above the freezing point and below the boiling point, but since the reaction is slow at low temperatures, temperatures higher than 20 to 100°C are preferred.

The amount of aliphatic dialdehyde to be used for the water-soluble polymeric material used as the raw material varies depending on the single layer or heptadhesion of the raw material polymeric material, the 4 degree Celsius and liquid properties of the aqueous solution, the reaction temperature, etc., but in general, The number of aldehyde groups per one amide group of the molecular substance is one or less; when the reaction is carried out in acidic conditions, the number of aldehyde groups is 1 to 1 per 1 amide group; in the case of alkaline conditions, the number of aldehyde groups is 1 to 1 per amide group; Aldehyde group is 1/2-1
/s,. It is preferable to use an amount that is limited to 100%. If an excess of aliphatic dialdehyde is used, the reaction proceeds excessively in a short period of time, making it difficult to adjust t1 of the reaction to achieve an appropriately high degree of polymerization, and the resulting polymer becomes insoluble in water. If the amount of aliphatic dialdehyde used is small, a water-soluble polymer substance with a sufficiently high degree of polymerization may not be obtained.

The mechanism of increasing the degree of polymerization by the method of the present invention is basically considered to be due to the reactions of formulas (1) to (3) (wherein, OR has the same meaning as above, - □ [Indicates a polymer base.] −・・・・・ ■ −・・・・ ■ In other words, the amide group of the water-soluble polymer substance of the W material undergoes an addition reaction with the aldehyde group of the aliphatic dialdehyde, condensation reaction,
By causing a polycondensation reaction, the raw material polymer i is dimerized or multimerized and further changed into a polymer substance with a high degree of polymerization.6 Under alkalinity, which is the preferred reaction condition of the present invention, the formula (1 ) is considered to be a book that takes precedence in reactions.

The progress of the reaction of the raw material water-soluble polymer substance and aliphatic dialdehyde in an aqueous solution can be determined by measuring the viscosity of the reaction solution. The water-soluble polymer substance with a high degree of polymerization produced by this reaction is rounded to maintain its water solubility.
The reaction may be stopped at a point where the viscosity of the reaction solution has increased to an appropriate level, or the system may be stabilized so as to sufficiently slow down the reaction. There are several methods to stabilize this reaction system, such as diluting the reaction solution, neutralizing the liquid, and rapidly lowering the reaction temperature. In general, cities are better because the diluted solution can be used for various purposes.

When reacting the raw material O water-soluble polymer substance in powder form, add the O powder to a solution of aliphatic dialdehyde in the amount used above in an alcohol such as methanol or ethanol or an organic solvent such as acetone. It may be suspended or the solution may be sprayed onto the powder.

When comparing the reactivity of aliphatic dialdehydes used in the present invention with acrylamide-based water-soluble polymer substances with formaldehyde, acetaldehyde, and glyoxal, the reactivity of acetaldehyde in formaldehyde is small, and the degree of polymerization with acetaldehyde is particularly low. It's difficult and difficult. Glyoxal exhibits a wide range of reactivity, ranging from 0 to 0, and 9, but it is found that it is inferior in achieving a high degree of polymerization compared to the aliphatic dialdehydes used in the present invention. This is because the aliphatic dialdehydes used in the present invention (different from glyoxal), having aldehyde groups at both ends of the alkylene group or alkenylene group, react particularly with the water-soluble polymeric material of the raw material shown in the above formula (1)K. It is easy to do (,
This is thought to be because a water-soluble polymer substance with a high degree of polymerization having a linear shape close to a linear shape is produced.

According to the IJll method of the present invention, non-ionic polymer substances such as polyacrylamide and polymethacrylamide, acrylamide, methacrylamide, etc., and acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and their Anionic polymer substances such as copolymers with O salts, partial hydrolysates of polyacrylamide, and acrylamide are combined with dimethylaminoethyl methacrylate and its tertiary or quaternary salts, etc. It is possible to increase the degree of polymerization of various acrylamide-based water-soluble polymer substances, such as polymers and cationic polymer substances such as polyacrylamide zero-partial Mannich-formed products with secondary amines and formaldehyde.

A water-soluble polymer substance with a high degree of polymerization produced by an aqueous solution reaction according to method O of the present invention can be used as an aqueous solution by diluting the reaction solution, but the reaction solution can be frozen while being concentrated under reduced pressure. By drying it, you can turn it into a powder in a concentrated solution.

The water-soluble polymeric substance produced by method (O) of the present invention has an unprecedentedly high degree of polymerization obtained by the reactions of formulas (1) and (2) above, and contains a new substance with an increased content of flocculant. O exhibits a remarkable effect even when used in small amounts as a viscous agent, and can be used not only to simply reduce the amount of chemicals used, but also to use the polymeric substance of the present invention as a flocculant to clarify and concentrate suspensions. The present invention can be used to improve the efficiency of a suspension treatment facility, and when used for dewatering sludge, it has been found to be effective in improving the combustion efficiency of the dehydrated cake by reducing the water content of the dehydrated cake. The value is huge.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example t Sampo 17-1i-5ol (Polyacrylamide manufactured by Sankyo Kasei Kogyo Co., Ltd., average degree of polymerization 210,000) After adjusting the O'1-aqueous solution r1a t to pH 10 with to9g of caustic soda solution, glutaraldehyde II! 6 aqueous solution (adjusted to pH 7 with sodium carbonate) 5F was added and reacted at 60°C. During the reaction, a portion of the reaction solution was sampled over time, diluted with water to a concentration of 12%, and the viscosity of the diluted solution was measured using a Bffi rotational viscometer at 25°C.

For comparison, instead of glutaraldehyde, glyoxal 1s aqueous solution 0135 f and #i device sr"1jlt3
The same reaction as above was carried out using 7'1g formalin and 1F, respectively, and the viscosity of each reaction dilution was measured in the same manner.

Table 1 shows the maximum viscosity of the reaction diluted solution obtained by this reaction.

Table 1 From Table 1, it can be seen that by the method of the present invention Sunpoly Summer-$1) I
It can be seen that the viscosity of the water-soluble polymer obtained by reacting K-glutaraldehyde is higher than that obtained by reacting formaldehyde with formaldehyde.

Example λ A 00.2% diluted reaction solution obtained over time by the reaction of Sunpoly-N-500 and glutaraldehyde in Example 1 was added to a bentonite suspension, and its sedimentation rate was measured.

The bentonite particles were added in an amount equivalent to s ppm as quality, and the measuring cylinder was shaken well by inverting, and after standing still, the rate at which the aggregated bentonite particles settled was measured.

For comparison, the sedimentation rate using a 0.12% diluted solution of the reaction solution obtained by reacting glutaraldehyde (10s) with formalin and glyoxal in Example 1 was also measured in the same manner.

Table 2 shows the maximum sedimentation rate depending on the reaction diluted solution for each reaction.

'Table 2 From Table 2, it can be seen that the water-soluble polymeric substance obtained by reacting siglutaraldehyde according to the method of the present invention has better flocculation performance than those obtained by reacting formaldehyde and glyoxal, respectively.

Example λ Acrylamide-sodium acrylate copolymer (molar ratio 9
: 1) 150t of 05chi aqueous solution with 11g of caustic soda water S solution: pl! After IK adjustment, up-alahide 1 chronic aqueous solutions T and SF were added and reacted at 111°C for 3 minutes. After the reaction, the reaction solution was diluted to a concentration of L1 by adding water, and further stabilized by adding 16-thiosulfuric acid to adjust the concentration to px6.

The viscosity of each aqueous solution of the raw material copolymer and the water-soluble polymer substance obtained by reacting it with adipaldehyde was measured in the same manner as in Example 1.
Furthermore, the sedimentation rates of the bentonite suspensions with each 111% aqueous solution measured in the same manner as in Example 2 were StS and 66 ca/rnin.

Example 4 Acrylamide-sodium acrylate copolymer (molar ratio T
: 250 ml of the 296 aqueous solution of 3) was adjusted to pH to 10% with a 10% caustic soda aqueous solution, and then 1 ml of maleic dialdehyde was added.
2 g of an aqueous solution was added and reacted at 0° C. for S minutes. After the reaction, water was added to dilute the reaction solution to a Kame 19G concentration, and 11 g of sulfuric acid was further added to adjust the pH to stabilize it.

When measured in the same manner as in Example 1, each rL1-aqueous solution of the additive O copolymer and the water-soluble polymer substance obtained by reacting it with maleic dialdehyde had 110 and 1115 op.
and each 61% measured in the same manner as in Example 2.
The sedimentation rate of an aqueous solution is 1411Th! 5tL57/
It was mln.

Example 4 IL of acrylamide-methacryloyloxyethyl-methylammonium chloride copolymer (molar ratio A: 3)
Add 1 ton of s@CH aqueous solution of 1110 fK glutaraldehyde, and then add 1.
Adjust it to This mixed solution with a viscosity of t 2 a o ep was reacted at le°C for 70 minutes, and the viscosity of the reaction solution was
e When Oop is reached, immediately add water to bring the reaction solution to α.
It was stabilized by diluting it to a concentration of 2.

Coagulation performance when 2% aqueous solutions of water-soluble polymer substances obtained by reacting copolymer 1 and glutaraldehyde with each other are added to excess sludge from a sewage treatment plant and the excess sludge is separated into the same liquid. compared. The results are shown in Table 3.

Table 3 Surplus sludge oil turbidity concentration/SIG, pad
L @ mourning.

The optimum addition amount is the optimum addition amount of the water-soluble polymer substance in the diluent to the sludge, and can be determined from the aSte (cavity suction time) measured using a Triton 1111i device.

In addition, according to the water content of the sludge cake, # & 9 sludge was mixed with the optimal addition amount using 120 mesh nylon P cloth to 460 (
It was centrifuged at I rpm for @O seconds and measured as the water content of the sludge cake separated on the furnace cloth.

From Table 3, it can be seen that the water-soluble polymer substance obtained by the method of the present invention can reduce the water content of sludge cake with a small amount of use, and is extremely effective for solid-liquid separation of sludge, etc. Recognize.

Patent Applicant Sankyo Kasei Kogyo Co., Ltd. Agent Patent Attorney Shoji Kashi Procedural Amendment (Voluntary) 1980 9 To 1 Commissioner of the Patent Office Kazuo Wakasugi Shun 1, Incident O Displayed 1988 Patent Application No. 124977λ Issuing VSO name Process for producing water-soluble polymeric substances with high degree of polymerization Person making the amendment Sankyo Co., Ltd. A, Amendment O Contents (1) V4 specification page 2 line 4 Or "retention improver, speed per second enhancer" Corrected to "step 19 improver and speed per second enhancer."

Q) "Temperature station higher than 100℃" on page 6, line 17 of the same page is r.
amended as "loOcO temperature".

(3) Formula in the bottom two lines of page 7 I am corrected.

(4) On page 9, line 11 to line 1.2, "with the above usage amount" was replaced with "with the above usage amount, that is, one aldehyde group per 1 72-do group, preferably **0 The number of aldehyde groups is 1/! Soo − for 77211 of the polymer substance
The usage amount is 1/Zoo, 000 pieces,'' he corrected.

(5) No. 11] [Insert the following sentences in lines 12 and 13.

When using this water-soluble polymeric substance as a flocculant or thickening agent, it is preferable to prepare it immediately before use and use it as is.'' (6) Comparison of Table 1 on page 13 of the same. For the aldehyde in the example, the word ``glyochidage'' should be corrected to ``glyoxol.''

(7) Insert the following O sentence after the 2nd line on page 19.

Example 6 Acrylamide-acrylic acid-L copolymer (J!-L ratio 95:5) particle size 1.W or less OS car 87 FKS glutar, aldehyde in 0.003-methanol solution @87-
was added and heated at 50° C. for 1 hour, and the resulting product was filtered and dried at 80°C for 1 hour to obtain powder 84).

Each 0.1-aqueous solution of the raw material copolymer powder and the copolymer powder obtained by treating it with daltaraldehyde was determined in the same manner as in Example 1, and had a viscosity of 32 and 47 cp. When the sedimentation velocity of -1 was measured in the same manner as described in Example 2, it was found to be 41.5 and 6Q, Oca/wi
It was n. "that's all

Claims (1)

[Claims] (!) Acrylamide-based water-soluble polymer substance with the formula 0
HO-RC! One or more aliphatic dialdehydes represented by HO (in the formula, R represents an alkylene group or an alkenylene group) are added and reacted, and the raw material is reacted within a range in which the resulting polymer substance maintains water solubility. A txom method for water-soluble polymers with a high degree of polymerization, which is characterized by mutually bonding polymeric substances. , (2) 10% of the raw material acrylamide-based water-soluble polymer substance
The method according to claim 1, characterized in that the reaction is carried out as a low concentration aqueous solution of % or less. (2) The method according to claim 1, wherein the aliphatic dialdehyde is malonaldehyde, succinaldehyde, maleic dialdehyde, fumardialdehyde, glutaraldehyde, or adipaldehyde.