NL8003782A - POLYACRYLAMIDE AND POLYACRYLIC ACID POLYMERS. - Google Patents

Description

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Polyacrylamide and polyacrylic acid polymers.

The invention relates to water-soluble high-molecular-weight synthetic polymers as well as processes for their preparation, in particular when the monomers contain an unacceptably high impurity content, resulting in a poor polymer product, e.g. excessive amounts of insoluble material and / or unacceptably low viscosities and / or low polymerization degree. More particularly, the invention relates to the use of a cyclic compound containing the formula I unit of the formula sheet, wherein polymers of acrylic-10 amide and / or acrylic acid and / or 2-acrylamido-2-methylpropanesulfonic acid and salts essentially the same as the polymers prepared from the pure monomers.

Acrylamide is usually prepared by the hydration of acrylonitrile as is known in the art. This material generally comes out of the reactor in the form of a concentrated solution (1 * 0 - 60% by weight). Acrylic acid is usually prepared by oxidation of propylene as known in the art. This material is usually available in the form of concentrated solutions, i.e., 60% in glacial acetic acid. 2-Acrylamido-2-methylpropanesulfonic acid 20 is usually prepared from acrylonitrile and sulfuric acid via the Ritter reaction. This material is available as a solid powder that often has to be purified by recrystallization. For economic reasons, it is essential that these products are directly polymerized into water-soluble high molecular products. These monomer solutions or powders apparently contain unknown parts per million impurities, the exact amount or type of which is hitherto unknown. When the monomers are polymerized, even at these very low impurity levels, completely unacceptable polymers often arise.

In solution polymerizations, to solve such problems, the following measures, individually or in combination, must be applied: (a] very low drying temperatures; (b) intensive and expensive purification of the monomer solution; (c) very long polymerization times (d) addition of very large amounts of urea to 8003782 2 the monomer and / or (e) polymerization in very dilute solution.

However, these measures appear to be unsatisfactory for large-scale commercial use due to high energy consumption or excessive cost because the production capacity of the polymers is severely limited or the percentage of desired polymer is reduced to an unacceptably low level.

In water-in-oil emulsion polymerizations, attempts to solve these problems lead to: (a) monomer purification; (b) polymerization of very dilute solutions; (c) application of different initiators; (d) adding urea to the monomer; and (e) application of chain transfer agents. However, these measures all appear to be unsatisfactory for the same or similar reasons as mentioned above.

Thus, it is a primary object of the invention to overcome this problem and allow the polymerization of a concentrated monomer solution to proceed without the need for intensive purification, i.e., crystallization.

It is a further object of the invention to reduce the insolubles content in dry, solution polymerized poly-acrylamide and polyacrylic acid polymers to a commercially acceptable level, i.e. below about 2 wt%.

It is a still further object of the invention to raise the standard viscosity of emulsion-polymerized polyacrylamide and polyacrylic acid polymers to an acceptable level, i.e.

25 resp. above about U, 5 and 5 centipoise. It is a still further object of the invention to avoid the amount of cross-linked polymer which forms during polymerization and / or during drying or grinding an acrylamide or acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid polymer. Finally, it is an object of the invention to increase the polymerization rate of acrylic acid and 2-acrylic amido-2-methylpropane sulfonic acid type monomers.

According to the invention, an acrylamide and / or acrylic acid and / or 2-acrylamido-2-methylpropanesulfonic acid monomer solution is provided in which a cyclic organic compound containing a unit of the formula 1 is present. Preferably, the cyclic compound further designated 1,3-dione is present in an amount of 8003782 L · 3 such that after polymerization of the monomer an improved product, preferably a commercially acceptable product, is formed and / or the degree of polymerization is increased. For solution polymerization, this generally means a percentage of insoluble material below about 2 wt.%. For acrylamide or acrylic acid homopolymer emulsion polymerizations, this means a percentage of insoluble material that is low enough not to lower the standard viscosity below about 1.5 cps. If a lower viscosity emulsion polymerization product is deliberately desired, the 1,3-dione can be used to increase the reaction rate. For homopolymers. of aeryl acid or 2-acrylamido-2-methylpropanesulfonic acid and its salts, this means increasing the degree of polymerization.

Furthermore, a method for preparing a water-soluble, high molecular weight polyacrylamide or polyacrylic acid polymer, in which the percentage of insoluble material is reduced to below about 2%, polymerizing acrylamide or acrylic acid monomer, optionally with others, is provided ethylenically unsaturated monomers, and the resulting polymer is dried, with at least drying performed in the presence of a 1,3-dione.

Furthermore, a method for preparing a water-soluble, high molecular polymer comprising an emulsion polymerization of an acrylamide or aeric acid or 2-aerylamido-2-methylpropanesulfonic acid monomer, optionally with another ethylenically unsaturated monomer, in the presence of a 1,3- is provided. dion.

Furthermore, a method of increasing the polymerization degree of homopolymers of 2-aerylamido-2-methyl-propanesulfonic acids and salts thereof is provided, the polymerization being carried out in the presence of a 1,3-dione. These and other purposes will become apparent from the description that follows.

The compounds used to prepare the improved polymers are those cyclic organic compounds containing a unit of formula 1.

These compounds are referred to as 1,3-diones, although the unit may also be present elsewhere in the compound.

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Examples of such 1,3-diones include, but are not "limited to, as many substituted as unsubstituted derivatives of 1,3-cyclopentanedione, 1,3-cyclohexanedione, 1,3-cycloheptanedione; 1,3-cyclooctanedione ; 1,3-cyclodecanedione; 5s5-dimethyl-5-1,3-cyclohexanedione; 5,5-diethyl-1,3-cyclohexanedione; 1,3,5-cyclohexanedione and the phloroglucinol automatic (1,3,5- trihydroxybenzene), tetrahydronaphthalene-1,3-dione, barbituric acid and other such compounds.

The tautomers of these compounds of the group according to formula 1a are defined by the meaning of 1,3-dione as used in the invention as do the metal enolates including carb-alkoxydimedone metal enolates, such as carbometboxydimedone sodium enolate, carbetboxydimedon potassium enolate, etc.

Most preferred as 1,3-dione trophies 5> 5-dimethyl-1,3-15 cyclobexanedione, also known as metbon or dimedone.

When the 1,3-dione is added to the monomer and the monomer is subsequently polymerized, the 1,3-dione must not also be a polymerization inhibitor. If it is an inhibitor, then it must be removed (or which vessel removes it) from the monomer before polymerization. One such method of removing this compound is to pass the monomer solution through a bed of activated carbon. Her choice can be added to the polymer gel in a solution polymerization to dry 1,3-dione for drying.

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

In some cases as indicated below, it has been found to be desirable to include urea or a urea derivative together with the 1,3-dione up to 20% by weight (based on the monomer content). Preferably, 5-10 Suitable ureas themselves Suitable compounds of this type are described in U.S. Pat. No. 3,622,333 The urea can be added before, after or simultaneously with the 1,3-dione.

The monomers to be polymerized are acrylamide, acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid and its salts. Copolymers of these said monomers or one or more of said 8003782 # 5 monomers with other ethylenically unsaturated monomers suitable for forming vateroproshare products can also be prepared. Such other monomers include, but are not limited to, methacrylamide, acrylic acid salts, methacrylic acid, and salts thereof, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl acrylate, methyl ethyl acrylate, methyl ethyl acrylate, methyl ethyl acrylate, methyl ethyl acrylate, methyl acrylate acrylonitrile, 3- (methyl acrylamido) propyl trimethyl ammonium chloride, vinyl methyl ether, vinyl ethyl ether, alkali or ammonium salts of vinyl sulfonic acid and the like. All or part of the acrylamide part of the polymers can be hydrolyzed »

The polymerization method used. is a common method for such monomers. This includes in particular solution and emulsion polymerizations as well as other techniques such as grain and suspension dispersion polymerizations. The particular polymerization system of each of these is the system that is commonly used.

For solution polymerization, this generally involves the use of one or more azo initiators, with or without a redox system, and optionally such conventional additives as sequestrants, alcohols, and diluents as necessary for the polymerization. For emulsion polymerization, which is a water-in-oil emulsion, this means. the use of a water-in-oil emulsifier, an oil phase such as toluene, xylene or a paraffinic oil and a free radical initiator.

The invention is independent of the particular polymerization method used, so that reference is made to the literature for further details. The amounts and individual components will depend on the polymerized monomers and the process conditions under which the polymerization will take place.

The amount of 1,3-dione used according to the invention appears to depend, at least in part, on the type of polymerization, the type of purification of the monomer, the degree of aging of the monomer / 1,3- dion composition, for solution polymerization, the temperatures at which the product is prepared and / or dried, the presence or absence of urea and the amount thereof, the amount of impurities in the concentrated monomer solution as well as the residence time of the polymer in the maximum temperature. As such, an accurate "polymer improving amount" cannot be defined. Generally, this amount is in the range of 0.001 - 2 wt.% (Although more may be used) based on the monomer, and more in especially for emulsion polymerizations, the larger amounts and for solution polymerizations, the smaller amounts are used For emulsion polymerizations, the preferred amount for solutions which are not aged or aged at room temperature is about 0.3 - 1%, most preferably 0.1+ -0 .7 wt.% In accelerated aging (above about 50 ° C for more than about 2 hours), the preferred amount is 0.005 - 0.2%, most preferably 0.007 - 0.1 / Voor. For solution polymerizations, 15 the preferred amount about 0.03-0.k%, most preferably about 0.05-0.25 wt%.

For solution polymerizations of acrylamide and acrylic acid, it has been found advantageous to (a) purify the concentrated monomer solution by contacting it with a cation exchange resin and / or activated carbon - it is not known what these steps involve removed but improved results have been observed; (b) also to use urea when the drying temperature is above about 80 ° C, especially above 85 ° C and more especially above 90 ° C or higher; and (c) using the monomer / 1,3-dione solution as quickly as possible, i.e. without intensive aging. The advantages of the invention can also be realized by adding the 1,3-dione, not to the monomer, but to the obtained polymeric gel before drying. This is not so desirable because it can be difficult to mix the 1,3-dione uniformly in the gel. However, this shows that the 1,3-dione is apparently active during the drying step of a solution polymerization.

For emulsion polymerizations, it has proven advantageous to a) age the monomer / 1,3-dione composition for about 5 days before use or (b) use the composition at elevated temperature for several hours (60 - 80 ° C, for about 5 hours) to age before use. This aging appears to improve the efficiency of the 8003782 τ 1,3-dione. However, beneficial effects have also been achieved without aging by using larger amounts of the 1,3-dione, i.e., about 0.9-2 # based on the monomer.

For the preparation of the acrylamide or acrylic acid / 1,3-dione-5 solutions according to the invention, it has proved advantageous to dissolve the 1,3-dione in the concentrated solution of the monomer before any dilution is used for polymerization purposes. This is due to the longer time that appears to be necessary to dissolve the 1,3-dione in a dilute solution, although essentially no difference in effectiveness has been noted. To prepare the 2-acrylamido-2-methylpropanesulfonic acid / 1,3-dione solutions, the two components can be simply mixed with water.

As desired, the 1,3-dione can be incorporated into the acrylonitrile or propylene from which the monomers are prepared.

The following specific examples illustrate certain aspects of the invention and detail the advantages attainable thereby.

These examples are for illustrative purposes only and are not intended to be limiting. All parts and percentages are by weight unless otherwise indicated.

Example I

Preparation of acrylamide / 1,3-dione solutions (a) To a polyethylene lined vessel, preferably a vessel in which subsequent polymerization will take place if it is a solution polymerization, 810.9 g of a 51.3% aqueous solution acrylamide "as is" and 0.83 g of methon added. This mass was stirred magnetically in air for about 5 min to dissolve the methon. The solution contained 0.2% methon based on the acrylamide monomer.

(B) The procedure of (aj was repeated except that before the addition of the methon, the aqueous acrylamide was passed through a bed of cation exchange resin (Amberlite IR-120 from Rohm & Haas).

(c) The procedure of (a) was repeated except that before the addition of the methon, the aqueous acrylamide (i) was passed through a bed of a cation exchange resin (Amberlite IR-120) and 8003782 then (ii) was passed through a bed of activated carbon (Huchar WV-L 8 x 30 mesh, 0.59 - 2.38 mm).

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

Example II

Solution polymerization of monomer of Example I (c)

The monomer solution of Example 1 (c) was subjected to solution polymerization as follows: This was placed in a 3.8 liter polyetre reactor and stirred magnetically. The following materials were then added with continued stirring.

2311.2 g dexonized water k, 2 ml 2% 1s aqueous ethylenediamine tetra-acetic acid 15 3.2 ml 10 # aqueous isopropanol 16.6 g dry sodium sulfate k, 2 g <dry ammonium sulfate 20.8 g urea

After complete solution, the pH of the reaction mass was adjusted to 3.0 with sulfuric acid. Nitrogen was purged at about 1000 ml / hr for 30 min warming the reaction mass to about 35 ° C. With continued nitrogen blowing, the polymerization was started within minutes after the introduction of the catalysts: 13.3 ml 0.0078 g / ml 2,2'-azobis (2,1 * dimethyl-h-methoxyvaleronitrile) and 15, 6 ml 0.02 g / ml 2,2'-azobis (cyanovaleric acid)

The polymerization was allowed to proceed almost adiabatically by isolating the reactor. The polymerisate was allowed to reach a temperature of 29.8 ° C for 2 hours by exothermic heat development before being transferred to a curing oven at about 70 ° C where it was cured for an additional 18 hours to form 3,200 g of a rigid gel product.

The gel was subsequently cut into strips and parts thereof dried in a convection oven to 7-10% residual volatile with temperatures of 90, 100 and 113 + 2 ° C. The dry product was made up to 8003782

• V

9 particles milled in a Waring mixer and sieved to obtain a product with a particle size greater than 0.8b mm (-20 U.S. mesh).

Example III

Evaluation of the product of Example II

To evaluate the product prepared in Example II, the following was performed: 0.3 g of the product dried at any temperature was dissolved in deionized water to give 300 g of a 0.1% aqueous polymer solution. The solution was passed through a 0.15 mm (100 mesb U.S.) aperture screen for insoluble material filtration. The sieve was washed with about 500 ml of deionized water at room temperature and dried at 100 ° C overnight to determine the amount of insolubles indicated as% insoluble.

The percent volatile residue was determined by measuring the weight loss of a 1 g sample after drying for 2 hours at 100-110 ° C.

The degree of hydrolysis (% carboxyl) was determined by conductometric titration of the carboxyl content in the polymer.

The lower the number, the better the product obtained for non-ionic polymers.

The viscosity "as is" was determined by dissolving 0.3 g of product in deionized water for 2 hours until a 300 g of aqueous solution was obtained, filtering the insoluble material through a 0.15 mm mesh sieve and then add sufficient sodium chloride to form a 1 molar MaCl solution and determine the Brookfield viscosity thereof with a UI adapter.

This is an indication of the effectiveness of the product obtained, the higher the number, the more desirable the final product.

The results together with those of a comparative sample prepared according to the same procedure using no methon. are shown in Table A. This clearly demonstrates that by adding 0.2% methone to the monomer, the viscosity counts ("as is" i is greatly increased and the percentage insoluble is reduced from about βθ to less than 0.9%.

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Example IV

The procedure of Examples II and UI was repeated except that the amount of methon was reduced to resp.

0.10 and 0.05 $ · The results were as follows:

5 Drying temperature, ° C

0.10 $ Methon 90. 100 "As Is" Viscosity 3 »3 3.3 $ Volatiles 8.25 7.08 $ Insoluble 0.9 0.7 10 $ Carboxyl - 0.15 0.05 $ Methon" As is "viscosity 3.3 3.1 $ Volatiles · 8.21 6.67 $ Insoluble 1.6 13.1 15 $ Carboxyl 0.15 0.075

These data demonstrate that as the amount of methon is reduced, the percentage of insoluble increases; and that when the amount of $ 0.05 and the drying temperature was $ 100, there was not enough methone present to make it $ 2 insoluble. 20 Examples V - X

The procedure of Examples II and III was repeated except that (in the purification procedure and (2) the amount of methone was changed. The results are shown in Table B. As can be seen from this, an improved product was obtained when the amount of methone was increased. (demonstrated by the increased viscosity and the reduced insolubility}.

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Examples XI - XX

The basic procedure of Examples II and III was repeated except that the treatment of the monomer, the presence and amount of urea and methon, the catalyst system and the pH, the percentage of solids, the maximum temperature and the time of the maximum temperature were modified as detailed in Table C1.

Regarding the treatment of the monomer, f'JA, r means that it was treated with a cation exchange resin as in Example Ib and "GEEW" that it was prepared as in Example Ia. The percentage (HEj ^ SOj ^ in Example II was 1/2, the percentage Wa ^ O ^ k% and the percentage urea $ 5

The data of the dry product are given in Table C2.

15 To demonstrate that it. 1,3-dione and / or urea can be omitted from the monomer and added to the gel, so that it is only present during the drying step, various post-treatments were carried out as follows:

Example XV - 0.1% methon and 10% urea added afterwards

Example XVI- 0.1 $ methon added afterwards only Example XIX

and XX- only 10 $ urea added afterwards.

The dry product data for these variants is also shown in Table C2.

As can be seen from the data in Tables C1 and C2, the influence of methon is independent of the catalyst system or polymerization conditions and it is advantageous to use a combination of methon and urea.

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Examples XXI - XXVIII

The basic procedure of Examples II and II was repeated except that the following compounds were used: Another untreated monomer, $ 27 solid, diethylene triamine-5-pentaacetic acid as sequestrant, 2,2'-azobis (2-amidinopropane) hydrochloride as catalyst with an ammonium persulfate / ferrous ammonium sulfate redox system, pH 6.0, initiation of the reaction at 0 ° C and residence time U hours.

The amounts of methyl ether and urea as well as the data of the dry product for the product dried at about 60 DEG-90 DEG C. to 12 volatiles are shown in Table D.

As can be seen, under these polymerization conditions, ethnone produced only an acceptable product (high viscosity and percent insolubility below 2%), while urea alone did not.

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Examples XXIX - XXXVIII Emulsion polymerization of acrylamide Methon was added with stirring for 5 min to aqueous acrylamide solutions as in Example Ia. The following procedure was applied except that when the pH was 9 sodium hydroxide was added.

To a suitable reaction vessel were added 2100.0 parts of acrylamide, as a 50% strength aqueous solution, and 850.0 parts of deionized water. To this solution were added 2.12 parts of the disodium salt of ethylenediamine tetraacetic acid and 1.15 parts of hydrated ferric sulfate (J2% PegiSO4) used as 1.5 parts / 1000 parts HgO). The pH of the resulting solution was adjusted to 5.0.

This represents the aqueous monomer phase. The oil phase 15 was prepared by dissolving 90.0 parts of sorbitan monooleate in 10 ^ 0.0 parts of AMSC0 01 ©, a commercially available clear oily liquid from Union Oil Co. Calif.

The entire oil phase was added to a suitable high speed homogenizer. The homogenizer was started and the aqueous monomer phase slowly added to form an emulsion with a viscosity of 990 cps. The dispersed phase of the obtained emulsion had a particle size of about 2.5 microns or less.

The entire emulsion system was added with stirring to a suitable reaction vessel. 70.0 parts per million (based on monomer) t-butyl hydroperoxide were added. The resulting medium was purged with nitrogen gas to remove oxygen from the system. Stirring was continued and the sodium metabisulfite was slowly pumped into the vessel over a 6 hour period, maintaining the vessel at about 10 ° C, after which about 100 parts per million (based on monomer) was added. The viscous emulsion obtained showed an acrylamide conversion of 99.9%

Stabilization of the polymer solution was accomplished by adding 78.28 parts of a 30 # aqueous sodium metabisulfite-35 solution. The emulsion was maintained under polymerization conditions (60 min at 50 ° C) to substantially convert the residual acrylamide 8003782 19. 0.1% of the emulsion included bisulfite which stabilized the polymer system. To the polymer emulsion obtained, as an inverting agent mixture, 5.5 # of a 70 # 's solution of sodium bis (2-ethylhexyl) sulfo-5 succinate in AMSCO OMS and 2.0 # of a 70 #' s solution was added over a 30 min period. the reaction product of 1 mole of octyl phenol and 7 * 5 moles of ethylene oxide was added. The resulting emulsion was kept at 0 ° C for an additional hour after which time the product was smooth and free of particles. The dispersed polymer phase had a particle size of 2.5 microns or less. The standard viscosity 10 was as shown in Table E.

The standard viscosity of the product obtained, as well as that of the other products with changes in the amount of methon and the degree of aging are shown in Table E.

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Examples XXXIX-XLII Preparation of conolymers

The basic procedure of Example II was repeated except that 10 wt.% Acrylamide was replaced by an equivalent weight of each of the following monomers (a) acrylic acid (b) 2-ar »Tylamiflo-g-methyl propane-ammonium sulfonate (c) dimethylamnoethyl methacrylate methyl sulfate

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

Similar improved results over those of the same copolymers without methone were observed.

Example ILIII

Preparation of 95/5 acrylic acid / acrylamide copolymer 15 To a stainless steel beaker were added 2 g g of ice acrylic acid (Rohm & Haas Production quality). While stirring with a magnetic stirrer, 29% aqueous ammonia (technical) was added and the temperature maintained at ^35 ° C until the pH became 7.5 (about 1.5 hours). Distilled water was added to bring the total weight to g. The solution was transferred to a 1 liter glass beaker and 1.07 g of methone was added (0.5% based on acrylic acid) with stirring. This dissolved within about 10 minutes, then 23 g of 50% acrylamide was added and the procedure of Examples XXIX - XXXVIII followed by the emulsion polymerization of the monomers.

The standard viscosity was 5> 7 centipoise. Repeating the aforementioned test without methon, the standard viscosity was less than 2.9 cps.

Example XI.IV

- Preparation of Acrylic Acid Homopolymer The procedure of Example XLIII was repeated to homopolymerize acrylic acid. This had a standard viscosity of 5.2 cps. Without the addition of methon, the standard viscosity was 2.5 cps.

Examples XLV - L

The procedure of Example II was repeated except that the methone was replaced by the additives ranked 8003782 22 in Table F in the amounts indicated therein. The results of drying the polyacrylamide at 90 ° C are also shown in that table.

As can be seen, the carbethoxydimedone sodium enolate, which may be an intermediate in the preparation of methone, gave the best results of the additives tested.

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Example Dl 1.3— Indaandion

The procedure of Example II was repeated except that the methone was replaced with 0.05 wt.% 1,3-indanedione 5 of formula 3 of the formula sheet.

The monomer would not polymerize since the 1,3-indanedione acted as an inhibitor.

The procedure of Example XV was repeated but 1,3-indanedione (0.2 $) and urea (5.0 $) were added afterwards. Thus, the polymer, prepared without additives, was dried in the presence of the additives. The results of drying at 90 ° C were as follows:

Ash is viscosity 2.9% volatiles 7% 15 insolubles 0.13

Thus, the insolubility level was below about $ 2.

Example Lil Meldrums Acid The procedure of Example II was repeated except that the pH was changed and the methon was replaced with 0.103 $ Meldrums acid according to formula k of the formula sheet. Two polymerizations were performed, one at pH h-, 5 and one at 8.0. As can be seen from the data below, an improved product resulted at a higher pH. must be to be effective.

The results of products dried at 90 ° C were as follows: pH k, 5 pa 8.0

Ash is viscosity 1, h 2.1 $ volatiles 9.9 9.2 $ Insolubles 60.0 38.5

35 Examples LIII-LXVI

Following the basic procedure of Example II, co-8003782 polymers and homopolymers as indicated in Table G were prepared. Blancos without methon were also prepared.

In the table, AMD is acrylamide; AMPS 2-acrylamido-2-methylpropanesulfonic acid; M acrylonitrile and MAPTAC 3- (methylacrylamido) propyl trimethyl ammonium chloride. TCHF means that the product could not be filtered and thus the determination of the insoluble percentage could not be made.

Examples LVII and LVIII included 5% urea and were run with 10.3% solid.

10 Examples LIX-LXII were performed in the absence of urea and at 13% solids.

Examples LXUI and LXIV were performed in the absence of urea and a redox system but with sodium hydroxide to adjust the pH.

For the 100% AMPS examples, LXIII and LXIV, the average polymerization rates expressed as degrees C exo-therm / min / adiabatic were determined as follows:

Example Methon Grade LXIII no Q, 07% / min 20 LXIV, yes

Thus, the use of methon doubled the degree of polymerization.

In Examples LUI-LXU, the effect of using methon to reduce the percentage of insolubles is demonstrated.

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Example LXV

The procedure of Example 1 (a) was repeated to prepare a solution of acrylamide containing 0.2% by weight. The solution was left overnight and passed over a bed of activated charcoal (Huehar WV-L 0.59-2.38mm).

The monomer obtained, with no methone present, was polymerized according to Example IX. The polymeric product was dried at 90 ° C and had an "as is" viscosity greater than 2.8 and less than 2 insoluble.

* 8003782

Claims (25)

A composition comprising a monomer selected from acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and its salts, or mixtures thereof, and a cyclic organic compound containing a 1,3-dione unit of formula 1. Composition according to claim 1, characterized in that the 1,3-dione is present in an amount which improves the product obtained in the polymerization of the monomer. 3- Composition according to claim 1, characterized in that the 1,3-dione is present in an amount of 0.001 - 2 based on the monomer. k. Composition according to claim 1, characterized in that it further contains at least one additional ethylenically unsaturated monomer which can be polymerized to form a water solution. bar copolymer. Composition according to claim 1, characterized in that the 1,3-dione is not a polymerization inhibitor. The composition according to claims 1 to 5, characterized in that the 1,3-dione is 5,5-dimethyl-1,3-cyclohexanedione or the tautomer is 5,5-dimethyl-tetrahydro-m-resorcinol. J. A composition according to claims 1-5, characterized in that the 1,3-dione is selected from 1,3-eyclohexanedione, floro-glucinol, harbituric acid, methoxydimedonenolate, and arbethoxydimedone enolate. 8. Process for improving a monomer selected from acylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, or a mixture thereof, characterized in that a cyclic organic compound containing a 1.3 is added to the monomer. -dione unit of formula 1. 9. Process according to claim 8, characterized in that the 1,3-dione is present in an amount of 0.001 - 2% by weight, based on the monomer. Process according to claims 8-9, characterized in that the 1,3-dione is 5,5-dimethyl-1,3-cyclohexanedione or its tautomer is 5,5-dimethyltetrahydro-m-resorcinol. 8003782 11. Process according to claims 8-9, characterized in that the 1,3-dione is selected from 1,3-cyclohexane clion, phloroglucinol, barbituric acid, carbmethoxydimedonenolate and carbethoxy-dimedonenolate. 12. Process according to claims 8-11, characterized in that the 1,3-dione is removed before the polymerization. Process according to claims 8-11, characterized in that the 1,3-dione is present during polymerization and is not a polymerization inhibitor. 1U. Method for preparing a. water-soluble high molecular polymer by polymerizing a monomer selected from acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and its salts, or mixtures thereof, characterized in that a cyclic organic compound is used for the polymerization on the monomer which is not a polymerization inhibitor and which contains a 1,3-dione unit of formula III. 15. A method according to claim 1, characterized in that the monomer is an aqueous solution containing about 50-60 wt.% Acrylamide monomer when the 1,3-dione is added thereto. 16. Process according to claim 15, characterized in that the acrylamide solution is diluted to about 10-35% by weight of acrylamide before the polymerization. 1T. Process according to claims 1U-16, characterized in that the polymerization is a solution polymerization. 18. Process according to claim 17, characterized in that the 1,3-dione is present in an amount of about 0.03-0.4% by weight, based on the monomer. 19. Process according to claim 17, characterized in that the product is dried after the polymerization. 20. Process according to claim 19, characterized in that 30. is the monomer acrylamide and drying is carried out at a temperature above about 8 ° C and urea is also added to the acrylamide before polymerization. Process according to claim 1U, characterized in that the polymerization is a water-in-oil emulsion polymerization. A method according to claim 21, characterized in that the 1,3-dione is present in an amount of about 0.3-1% by weight, based on the monomer. 8003782 i ___ ____ ............. .... __ 23. Process according to claim 21, characterized in that the 1,3-dione is used in an amount of about 0.005-0.2% by weight, based on the monomer, and the mixture is aged at a temperature of about 50 ° C for more than about 2 hours. 2h. Process for preparing a water-soluble high molecular polymer by polymerizing a monomer selected from acrylamide, acrylic acid, 2-acrylamido-2-methane-propanesulfonic acid and its salts, or mixtures thereof, and drying the resulting polymer, characterized in that to the polymer, after the polymerization but before drying, a cyclic organic compound containing a 1,3-dione unit of formula 1 is added. Process according to claims 1U-2k, characterized in that the 1,3-dione is present in an amount of about 0.01 - 15. wt.% Based on the monomer. 26. Process according to claims 1U-25, characterized in that the 1,3-dione 5,5-dimethyl-1,3-cyclohexanedione or its tautomer 5,5-dimethyl-tetrahydro-m-resorcinol. 2J. Process according to claims 1U-25, characterized in that the 1,3-dione is selected from the group consisting of 1,3-cyclohexanedione, phloroglucinol, barbituric acid, carbmethoxydimedone olate, and carbethoxydimedone olate. 28. Process according to claims 1-27, characterized in that at least one additional ethylenically unsaturated monomer is copolymerized with the monomer to form a water-soluble polymer. 29. Process according to claims 1U-28, characterized in that urea is added to the monomer before the polymerization. 30. Process according to claims 1U-28, characterized in that urea is added after the polymerization but before drying. 8003782 * 1a O o -C-CH = C- I! 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