FI68065B - PROCEDURE FOR FRAMSTATING WITH ENVIRONMENTAL POLYMER IN HOUSE MOLEKYLVIKT - Google Patents

Description

1 68065

A process for preparing a high molecular weight water-soluble polymer

The present invention relates to a process for preparing a high molecular weight water-soluble polymer by polymerizing a monomer which is acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, or a mixture thereof.

This method can be applied in particular when the monomers contain unacceptable amounts of impurities, resulting in a poor polymer product with, for example, excessive amounts of insoluble substances and / or too low viscosity values and / or low polymerization rates. In the process of the invention, it is essential to use a cyclic compound containing a 1,3-dione moiety

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- C - CH2 - c - 20 polymers of acrylamide and / or acrylic acid and / or 2-acrylamido-2-methylpropanesulfonic acid and their salts are obtained which are substantially similar to those polymers obtained from particularly pure monomers.

Acrylamide is conventionally prepared by hydrating 25 acrylonitrile, as is well known in the art. This material usually leaves the reactor as a concentrated (40-60% by weight) solution. Acrylic acid is conventionally prepared by oxidizing propylene, as is well known in the art. This substance is usually available in concentrated solutions, i.e. i.e. 60% of the solution all the way to glacial acrylic acid. 2-Acrylamido-2-methylpropanesulfonic acid is usually prepared from acrylonitrile and sulfuric acid by the Ritter reaction. This material is available as a solid powder, which often needs to be purified by recrystallization. For economic reasons, it is essential that these products be polymerized directly into a high molecular weight water-soluble product. However, these 2,68065 monomer solutions or powders contain apparently unknown impurities in parts per million, the exact amount and type of which have not yet been established. When monomers are polymerized to contain this very low concentration of impurities, quite unacceptable polymers are quite often obtained.

In solution polymerization, attempts to solve these problems required one or all of the following: (a) very low drying temperatures; (b) extensive and expensive purification of the monomer solution; (c) very long polymerization times; (d) adding very large amounts of urea to the monomers; and / or (e) polymerization in very dilute solutions. However, all of these have proven unsatisfactory for commercial use on a large scale, either because they are energy consuming or expensive because the polymer production rate drops sharply or because the yield of the desired polymer decreases to an unacceptable level.

In water-in-oil emulsion polymerizations, attempts to solve these problems included: (a) purification of the monomer; (b) polymerization of very dilute solutions; (c) use of different initiators; (d) adding urea to the monomer; and (e) using chain transfer agents. However, these too have proved unsatisfactory for the same and similar reasons set out above.

It is therefore an object of the present invention to overcome this problem and to state that the polymerization of a concentrated monomer solution can take place without the need for extensive purification, i.e. crystallization.

Another object is to reduce the content of insoluble substances in dry solution polymerized polyacrylamide and polyacrylic acid polymers to a commercially acceptable level, i.e. less than about 2% by weight.

It is a further object of the invention to raise the standard viscosity for emulsion polymerized polyacrylamide and polyacrylic acid polymers to an acceptable level, i.e., greater than about 4.5 centipoise or 5.0 centipoise.

Yet another object is to reduce the amount of crosslinked polymer formed during polymerization and / or during the drying or grinding of an acrylamide or acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid polymer.

In addition, one object is to increase the polymerization rate of acrylic acid-10 and 2-acrylamido-2-methylpropanesulfonic acid type monomers.

These objects are achieved by the process according to the invention, which is characterized in that a cyclic organic compound which is not a polymerization inhibitor and which contains a 1,3-dione moiety is added to the monomer or its polymer, and which cyclic organic compound is 1,3-cyclohexane. dione, phloroglucinol, barbituric acid, carbmethoxydimedon enolate or carbethoxydimedon enolate.

In this method, a cyclic organic compound containing a 1,3-dione moiety is preferably used in an amount sufficient to polymerize the monomer to give an improved product, preferably a commercially acceptable product, and / or an increased polymerization rate. By solution polymerization, this usually means less than about 2% by weight of insoluble matter. For acrylamide or acrylic acid homopolymer emulsion polymerization, this means a content of insoluble substances that is sufficiently low that it does not intentionally reduce the standard viscosity to less than about 4.5 by 30 centipoise. If an emulsion polymerization product with a lower viscosity is intentionally desired, 1,3-dione can be used to increase the reaction rate. For homopolymers of acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid and its salts, this means an increase in the rate of knee formation.

4 68065

The process of the invention for preparing a water-soluble polyacrylamide or polyacrylic acid polymer having a high molecular weight and an insoluble matter content of less than about 2% can be carried out by polymerizing an acrylamide or acrylic acid monomer in aqueous solution, optionally with other ethylene solutions. with unsaturated monomers and the resulting polymer is dried, at least in the presence of 1,3-dione.

The process according to the invention for the preparation of a high molecular weight water-soluble polymer can also be carried out by emulsion polymerization of acrylamide or acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid monomers, optionally with other ethylenically unsaturated monomers in the presence of 1,3-dione.

The process of the invention can increase the rate of polymerization of homopolymers of 2-acrylamido-2-methylpropanesulfonic acid and its salts, the polymerization being carried out in the presence of 1,3-dione.

Suitable 1,3-diones include, for example, substituted and unsubstituted 1,3-cyclohexanedione; 5,5-di-methyl-1,3-cyclohexanedione, 5,5-diethyl-l, 3-cyclohexanedione; 1,3,5-cyclohexanedione and its tautomer phloroglucinol (1,3,5-trihydroxybenzene); tetrahydro-naphthalene-1,3-dione; derivatives of barbituric acid and other such compounds.

The tautomers of these compounds having the group -C-CH = C— are included in the meaning of 1,3-dione, which is used herein.

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The invention uses carbalkoxy dimedone metal enolates in the same manner.

The 1,3-dione is preferably 5,5-dimethyl-1,3-cyclohexanedione, also known as methone or dimedone.

Any polymerization inhibitor present in the monomer must be removed from the monomer prior to polymerization. One way to do this is to pass the monomer solution through an activated carbon mattress. Alternatively, in solution polymerization, 1,3-dione can be added to the polymer gel prior to drying.

If the 1,3-dione is not stable under the polymerization conditions, the polymerization conditions must be changed to avoid destabilization or the 1,3-dione must be added to the polymer gel before drying.

In certain cases, as described in detail below, it has been found desirable for 1,3-dione to mean up to about 20% by weight (based on the monomer content) of urea or a urea derivative. Preferably 5-10% urea is used. Suitable such compounds are described in U.S. Patent No. 3,622,533. Urea may be added before, after or simultaneously with 1,3-dione.

The monomers polymerized herein are acrylamide, acrylic acid and 2-acrylamido-2-methylpropane-20-sulfonic acid and their salts. Copolymers of these administered monomers or of one or more administered monomers with other ethylenically unsaturated monomers suitable for the preparation of water-soluble products may also be prepared. Such other monomers 25 are, for example, methacrylamide, acrylic acid salts, methacrylic acid and its salts, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl-acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, dimethylaminoethyl acrylate, di-30 metyyliaminometyylimetakrylaatti, dietyyliaminoetyyliakry-methacrylate, diethylaminoethyl methacrylate, hydroxyethyl -acrylate, hydroxyethyl methacrylate, diethylaminoethyl acrylate methyl sulfate, styrene, acrylonitrile, 3- (methylacrylamido) propyltrimethylammonium ethanidone aliquinate; .

The polymerization process used may be any of those conventionally used to polymerize such monomers. This includes, in particular, solution and emulsion polymerizations, although other procedures such as bead and suspension dispersion polymerizations may be used. The specific polymerization system for each of these 10 is that conventionally used. For solution polymerization, this usually involves the use of one or more azo initiators, with or without an oxidation reduction system, and possibly the use of conventional additives such as sequestering agents, alcohols and diluents necessary for the polymerization.

For emulsion polymerization, which is a water-in-oil emulsion, this involves the use of a water-in-oil emulsifier, an oil phase such as toluene, xylene or paraffin oil, and a free radical initiator.

Since the present invention is independent of a particular polymerization process, further details in this regard can be readily found in the literature. In addition, the amounts and individual components will vary according to the monomers being polymerized and the process conditions under which the polymerization takes place.

The amount of 1,3-dione used in accordance with this invention has been shown to depend at least in part on the type of polymerization, the method of monomer purification, the degree of aging of the monomer / 1,3-dione combination, the temperature at which the product is prepared and / or described , the possible presence and amount of urea, the amount of impurities in the concentrated monomer solution and the retention time of the polymer at maximum temperature. The exact "polymer curing amount" cannot be determined as such. However, it usually ranges from about 0.001 to 2% by weight (although more can be used) based on the monomer, and in particular higher amounts are used in emulsion polymerization and smaller amounts are used in solution polymerization.

For emulsion polymerizations, the preferred amount for non-aged or room temperature aged solutions is about 0.3 to 1% and the preferred amount is about 0.4 to 0.7% by weight. When using accelerated aging (more than approx.

50 ° C for more than about two hours), an amount of about 0.005 to 0.2% is preferred, and an amount of 0.007 to 0.1% is preferred. For solution polymerization, an amount of about 0.03 to 0.4% is preferred, and an amount of about 0.05 to 0.25% by weight is preferred.

For solution polymerizations of acrylamide and acrylic acid, it has proven advantageous to (a) purify the concentrated monomer-15 solution by contacting it with a cation exchange resin and / or activated carbon - it is not known what is removed by these steps, but improved results have been observed; (b) more urea is used when the drying temperature is above about 80 ° C, in particular above 85 ° C and in particular 90 ° C 20 or higher, and (c) a monomer / 1,3-dione solution is used as soon as possible, i.e. without significant obsolescence. In addition, the advantages of the present invention can also be obtained by adding 1,3-dione, not to the monomer, but instead to the resulting polymer gel before drying. This is less desirable in that there may be great difficulty in uniformly mixing the 1,3-dione with the gel. This indicates that 1,3-dione nevertheless acts and appears to act during the drying step in solution polymerization.

In emulsion polymerization, it has proven advantageous to (a) age the monomer / 1,3-dione combination for about five days before use, or (b) age the combination at elevated temperature for a few hours (60-80 ° C for about five hours) before use. This aging has been shown to increase the effect of 1,3-dione. However, advantageous effects have been obtained without aging by using 8,68065 higher amounts of 1,3-dione, i.e. about 0.9-2% based on the monomer.

For the preparation of acrylamide or acrylic acid / 1,3-dione solutions according to the present invention, it has proved advantageous to dissolve the 1,3-dione in a concentrated monomer solution before each dilution for polymerization purposes. This is due to the prolonged time that has been shown to be necessary to dissolve the 1,3-dione in the dilute solution, although essentially no difference in performance has been observed. To prepare 2-acrylamido-2-methylpropanesulfonic acid / 1,3-dione solutions, the two can be mixed with water quite simply.

Alternatively, the 1,3-dione can be combined with the acrylonitrile or propylene from which the monomers are prepared.

The invention can be further illustrated by the following examples in which all parts and percentages are by weight unless otherwise indicated.

Example 1

Preparation of Acrylamide / 1,3-Dione Solutions 20 (a) 810.9 g of 51.3% aqueous acrylamide "as is" was placed in a polyethylene-coated vessel, preferably a vessel in which the subsequent polymerization will take place if it is a solvent polymerization, and 0.83 g of methone This mass was stirred with a magnet in air for about five to 25 minutes to cause the methone to dissolve and contained 0.2% methone based on the acrylamide monomer.

(b) The procedure in (a) was repeated with the difference that prior to the addition of methone, the aqueous acrylamide (R) was passed through a cation exchange resin pad (Amberlite IR-120 30 from Rohm and Haas).

(c) The procedure in (a) was repeated except that prior to the addition of methone, the aqueous acrylamide was passed (i) through a cation exchange resin mattress (Amberlite 'IR-120) and (ii) then passed through an activated carbon pad 35 (Nuchar WV-L 8 x 30 mesh).

(d) Other such solutions were prepared with varying amounts of methone, as shown in the following examples.

Il 68065 9

Example 2

Solution polymerization of the monomer from Example 1 (c)

The solution of the monomer from Example 1 (c) was polymerized as follows: the solution was placed in a 3.75 L polyethylene reactor and stirred with a magnet. The following substances were then added with constant stirring: 2,311.2 g of deionized water 4.2 ml of 2% aqueous ethylenediaminetetraacetic acid 10 3.2 ml of 10% aqueous isopropanol 16.6 g of anhydrous sodium sulphate 4.2 g of anhydrous ammonium sulphate 20.8 g urea

When the solution was completed, the pH was adjusted to 15 for reaction mass 3, Ora with sulfuric acid. The nitrogen purge was started at about 1000 ml per hour for 30 minutes, heating the reaction mass to about 35 ° C. During the continuous nitrogen purge, the polymerization started within a few minutes after the addition of the catalysts: 13.3 ml of 0.0078 g / ml of 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and 15.6 ml of 0.02 g / ml of ml 2,2'-azobis (cyanovaleric acid)

The polymerization was allowed to proceed mainly adiabatically by isolating the reactor. The polymer was subjected to an exotherm of 29.8 ° C for a period of about two hours before being transferred to a curing oven at about 70 ° C where it was cured for a further 18 hours to give 3,200 g of a rigid gel product.

The gel was then cut into strips and portions of them were dried in a conventional oven to a residual concentration of 7-10% volatiles at 90, 100 and 113 ± 2 ° C. The particle size of the dried product was reduced in a Waring mixer and screened to give a product having a sieve number of -20 U.S. Pat. mesh particle size.

10 68065

Example 3

Evaluation of the product of Example 2

The following procedure was used to evaluate the product prepared in Example 2: 0.3 g of the product dried at said temperatures was dissolved in deionized water to prepare 300 g of a 0.1% aqueous polymer solution. The solution was derived from a 100 U.S. sieve. mesh through a weighed sieve to filter out insoluble matter. The sieve was rinsed with about 500 ml of deionized water at room temperature and dried at 100 ° C overnight before determining the amount of insolubles, expressed as a percentage of insolubles.

The percentage of volatiles remaining was determined by measuring the weight loss on a 1 g sample after drying for two hours at 100-110 ° C. The degree of hydrolysis (% carboxyl) was determined by conductometric titration of the carboxyl content of the polymer. The lower the value, the better the product obtained for non-ionic substances.

The viscosity "as is" was determined by dissolving 0.3 g of product in deionized water over two hours to give 300 g of an aqueous solution, filtering insolubles out through a 100 mesh sieve and then adding sufficient sodium chloride to make a 1 M NaCl solution and Brookfield to determine the viscosity for it using a UL accessory, which indicates the performance values for the product obtained, the higher the value, the more suitable the product.

The results, together with a comparative test prepared by the same method but without the use of methone, are shown in Table I below. The results clearly show that the addition of 0.2% methone to the monomer increases the viscosity "as such" in large quantities and the percentage of insolubles. decreases from about 60 to less than 0.4.

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The procedure of Examples 2 and 3 was repeated with the exception that the amount of methone was reduced to 0.10 and 0.05%, respectively.

5 The following results were obtained:

Drying temperature ° C

0.10% methone 90 100 viscosity "as such" 3.3 3.3% volatile substances 8.25 7.08 10% insoluble matter 0.9 0.7% carboxyl - 0.15 0.05% methone viscosity "as such" 3.3 3.1% volatiles 8.21 6.67 15% insolubles 1.6 13.1% carboxyl 0.15 0.075

The results show that when the amount of methone is reduced, the percentage of insolubles increases, while at 0.05% and when the drying temperature was 100 ° C, an insufficient amount of methone was present to bring the content of insolubles to less than 2%.

Examples 5-10

The procedure of Examples 2 and 3 was repeated with the exception that (1) the purification method and (2) the amount of methone were varied. The results are shown in Table II. As can be seen, when the amount of methone was increased, an improved product was obtained (as indicated by the increased viscosity in the "as is" column and the reduced amount of insoluble matter).

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Examples 11-20

The basic procedure of Examples 2 and 3 was repeated with the exception that the monomer treatment, presence and amount of urea and methone, catalyst system and pH, 5% solids, maximum temperature and time at maximum temperature were varied as detailed in Table lila below. As for the treatment of the monomer, "AND" means that it was treated with a cation exchanger as in Example Ib and "NEJ" means that it was prepared as in Example 1a. (The percentage of NH 2 SO 4 in Example 2 was 1; the percentage of Na 2 SO 4 was 4 and the percentage of urea was 5.

The numerical values for the dry product are shown in the table

IIIb.

In order to show that 1,3-dione and / or urea can be omitted from the monomer and added to the gel, as a result of which they are only present during the drying step, various additions were made as follows:

Example 15 - 0.1% methone and 10% urea were added afterwards.

Example 16 - only 0.1% methone was added afterwards.

Examples 19 and 20 - only 10% urea was added afterwards.

25 The numerical values for the dry product for these are also shown in Table IIIb.

As can be seen from the values in Tables lilac and IIIb, the effect of methone is independent of the catalyst system or the polymerization conditions, and by using a combination of methone and urea, an advantage is obtained.

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Examples 21-28

The basic procedure in Examples 2 and 3 was repeated with the exception of the following: monomer treated differently, 27% solids, diethylene-5-triaminepentaacetic acid as sequestering agent, 2,2'-azobis- (2-amidinopropane) hydrochloride as catalyst ammonium persulfate / ferroammonium with an oxidation reduction system, pH 6.0, initiation of the reaction at 0 ° C and a retention time of four hours.

The amount of methone and urea used, as well as the numerical values for the dry product, the product dried at about 60-70 ° C to a volatile matter content of about 12%, are shown in Table IV below.

As can be seen, methone alone gave an acceptable product under these polymerization conditions (high viscosity as such and insoluble content less than about 2%), while urea alone did not give this.

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Examples 29-38

Emulsion polymerization of acrylamide

Methone was added to the aqueous acrylamide solutions in the same manner as in Example 1a with stirring for about 5 to 5 minutes. The following procedure was used with the exception that when the pH was 9, sodium hydroxide was added.

2,100.0 parts of acrylamide as a 50.47% aqueous solution and 850.0 parts of deionized water are placed in a suitable reaction vessel. To this solution are added 2.12 parts of the disodium salt of ethylenediamine-10 tetraacetic acid and 1.15 parts of hydrated ferric sulfate (72% Fe 2 SO 4 -j) used in 4.5 parts / 100 parts of H 2 O). The pH of the resulting solution is adjusted to 5.0.

This forms the aqueous monomer phase.

the oil phase is prepared by dissolving 90.0 parts of sorbium 15 monane oleate in 1,040.0 parts of AMSCO OMS, a commercially available, clear oily liquid sold by Union Oil Co. of California.

A complete high phase homogenizer is fitted with a complete oil phase system. The homogenizer is started and the aqueous monomer phase is slowly added here to form an emulsion having a viscosity of 990 cP. The resulting emulsion has a particle size of about 2.5 or less in the dispersed phase.

This complete emulsion system is placed in a suitable reaction vessel with stirring. 70.0 parts per million (based on monomer) of t-butyl hydroperoxide are added. The resulting medium is purged with nitrogen gas to remove oxygen from the system. Stirring is continued and sodium bisulfite is slowly pumped into the vessel for six hours at about 30 ° C while the vessel is maintained at about 40 ° C, after which n.

100 parts per million (based on monomer) have been added. In the resulting viscous emulsion, the conversion of acrylamide is 99.49%.

Stabilization of the polymer emulsion is performed by adding 78 78.28 parts of a 30% aqueous sodium metabisulfite solution.

The emulsion is maintained under polymerization conditions (60 minutes at 40 ° C for the complete reaction of the remaining acrylamide, mainly 20 6 80 6 5. 0.4% of the emulsion is bisulphite, which causes the polymer system to stabilize.

To the resulting polymer emulsion, 1.5% of a 70% solution of sodium bis (2-ethylhexyl) -5 sulfosuccinate in AMSCO OMS and 2.0% of one mole of octylphenol and 7.5 moles of ethylene oxide of the reaction product are added as a modifier mixture over 30 minutes. The resulting emulsion is kept at 40 ° C for another hour, after which the product is smooth and free of particles. The dispersed polymers have a particle size of 2.5 μm or less. The standard viscosity is shown in Table V.

The standard viscosity for the resulting product, as well as for other products with varying amounts of methone and degree of aging, is shown in Table V below.

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22 68065

Examples 39-42

Manufacture of copolymers

The basic procedure in Example 2 is repeated with the exception that 10% by weight of acrylamide is replaced by an equivalent weight of each of the following monomers: (a) acrylic acid (b) 2-acrylamido-2-methylpropanammonium sulfonate (c) dimethylaminoethyl methacrylate.

For 10 (a) and (b), the pH is adjusted with sodium hydroxide.

Comparable improved results compared to the results of the same copolymers without methone are taken into account.

Example 43 Preparation of 95/5 acrylic acid / acrylamide copolymer

214 g of glacial acrylic acid (Rohm and Haas production grade) was placed in a stainless steel cup. With stirring with a magnetic stirrer, 29% aqueous ammonia (technical) was added and the temperature was kept below 35 ° C until the pH became 7.5 (about 1.5 hours). Distilled water was added to bring the total weight to 428 g. The solution was transferred to a 1 L glass beaker and 1.07 g of methone (0.5% based on acrylic acid) was added with stirring.

25 It dissolved in about 10 minutes. Then 25 g of 50% acrylamide was added and the procedure in Examples 29-38 was repeated for emulsion polymerization of monomers.

The standard viscosity was 5.7 centipoise.

When the above procedure was repeated without metho-30, the standard viscosity was less than 2.9 centipoise.

Example 44

Preparation of acrylic acid homopolymer

The procedure of Example 43 was repeated to homo-polymerize acrylic acid. Its standard viscosity was 5.2 cP.

When no methone was added, the standard viscosity was 2.5 cp.

23 6 8 0 6 5

Examples 45-50

The procedure of Example 2 was repeated with the exception that the methone was replaced by the additives given in the amounts shown in Table VI below. The results of drying the polyacrylamide at 90 ° C are also shown in the table. As can be seen, carbethoxydimedon sodium sodium enate, which may be an intermediate in the preparation of methone, gave the best results of the additives tested.

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Example 51 1,3-Indanedione

The procedure of Example 2 was repeated with the exception that the methone was replaced by 0.05% by weight of 1,3-indanedione: 50? o

The monomer did not polymerize because 1,3-indanedione is an inhibitor of polymerization.

The procedure of Example 15 was repeated to add 1,3-indanedione (0.2%) and urea (5.0%). The polymer prepared without any additives was thus dried in the presence of additives. The results of drying at 90 ° C were as follows: viscosity as such 2.9% volatiles 7.4% insolubles 0.13

The content of insoluble matter was thus less than about 2%.

25 Example 52

Meldrum's acid

The procedure of Example 2 was repeated with the exception that the pH was varied and the methone was replaced with 0.103% Meldrum's acid:

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Two polymerizations were performed, one at pH 4.5 and the other at pH 8.0. As can be seen from the following figures, an improved product was obtained at a higher pH. Thus, it is apparent that 1,3-dione, if present during polymerization and not only as a post-additive, must be stable under the polymerization conditions in order to be effective.

The result for products dried at 90 ° C was as follows: pH 4.5 pH 8.0

Viscosity as such 1.4 2.1 10% volatiles 9.9 9.2% insolubles 60.0 38.5

Examples 53-64 Using the basic procedure of Example 2, the copolymers and homopolymers shown in Table VII were prepared. Control samples without methone were also prepared.

The table shows AMD acrylamide; AMPS 2-acrylamido-2-methylpropanesulfonic acid; AN is acrylonitrile; and MAPTAC is 3- (methylacrylamido) propyltrimethylammonium chloride. WNF means that the product could not be filtered non-20 and thus the percentage of insoluble matter could be determined.

Examples 57 and 58 comprised 5% urea and were performed on 10.3% solids. Examples 59-62 were performed without urea and 13% solids. Pre-25 characters 63-64 were performed without urea and an oxidation reduction system, but with sodium hydroxide to adjust the pH.

For 100% AMPS Examples 63 and 64, average rates for polymerization, expressed as exothermic as-30 degrees Celsius / minute, were determined adiabatically as follows:

Example Methone Speed 63 no 0.07% / min 64 yes 0.14% / min

The use of methone thus doubled the polymerization rate.

Examples 53-62 show the effect of using methone to reduce insoluble matter.

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Example 65

The procedure of Example 1 (a) is repeated to prepare a solution of acrylamide containing 0.2% methone. The solution is allowed to stand overnight and then passed through an activated-5 carbon mattress (Nuchar WV-L 8 x 30 mesh).

The resulting monomer, without the methone present, is polymerized according to Example two. The polymer product is dried at 90 ° C and has a viscosity as such of more than 2.8 and an insoluble matter content of less than 2%.

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Claims (14)

29 6 80 6 5 A process for producing a high molecular weight water-soluble polymer by polymerizing a monomer which is acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, or a mixture thereof, characterized in that a cyclic organic compound is added to the monomer or its polymer. is not a polymerization inhibitor and contains a 1,3-dione moiety, and which cyclic organic compound is 1,3-cyclohexanedione, floroglucinol, barbituric acid, carbmethoxydimedonienolate or carbethoxydimedonienolate. Process according to Claim 1, characterized in that the 1,3-dione is 5,5-dimethyl-1,3-cyclohexanedione or its tautomer 5,5-dimethyltetrahydro-m-resorcinol. Process according to Claim 1 or 2, characterized in that 1,3-dione is present in an amount of about 0.001 to 2% by weight of the monomer. Process according to one of Claims 1 to 3, characterized in that the 1,3-dione is added to the monomer before the polymerization and in that the monomer is an aqueous solution containing about 40 to 60% by weight of acrylamide monomer when the 1,3-dione added to it. Process according to Claim 4, characterized in that the acrylamide solution is diluted to contain about 10 to 35% by weight of acrylamide before polymerization. Process according to one of Claims 1 to 5, characterized in that the polymerization is a solution polymerization. Process according to Claim 6, characterized in that 1,3-dione is present in an amount of about 0.03 to 0.4% by weight of monomer. Process according to Claim 6, characterized in that the product is dried after polymerization. 68065 Process according to Claim 8, characterized in that the monorera are acrylamide and the drying takes place at a temperature above about 80 ° C, and urea is also added to the acrylamide before polymerization. Process according to one of Claims 1 to 3, characterized in that the 1,3-dione is added to the monomer before the polymerization, and in that the polymerization is a water-in-oil emulsion polymerization. Process according to Claim 10, characterized in that 1,3-dione is present in an amount of about 0.3 to 1% by weight of the monomer. Process according to Claim 10, characterized in that 1,3-dione is used in an amount of about 0.005 to 0.2% by weight of the monomer and the mixture is aged at a temperature of more than about 50 ° C for longer than about two hours . Process according to one of Claims 1 to 8 and 10 to 12, characterized in that urea is added to the monomer before polymerization. Process according to one of Claims 1 to 12, characterized in that the urea is added after the polymerization and before drying. Il 680 6 5