United States Patent 0

l
3,264} W8 POLYMERHZATION 0i? ARYlLAMlDE MQNGMER
IN THE PRESENQE @lii FREE AMMUNIA AND THE RESULTKNG FELYAQRYLAMIDE PRGDUCT

pr.

ICC

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Patented Aug. ld, i965
2

process must comprise at least two steps, i.e., the polym erization step and the detoxi?cation step. Although Harry H. Dittmar in US. Patent 2,120,933
discloses that ammonia acts as an inhibitor to the polym

Mayer B. Goren, Denver, Quid, assignor to Kerr-McGee

Oil industries, End, a corporation of Delaware No Drawing. Filed Feb. 28, 1961, Ser. No. 92,157 21 Claims. (Cl. 260-393)

erization of acrylamide and acrylic substances it has been discovered that acrylaniide may be polymerized in the

presence of at least about 1><1O*3 mol of ammonia per mol of acrylamide, or in the presence of at least about 1><l0-3 gram ion of ammonium ion, and at a pH of This invention relates to an improved process for the 10 about 7.5 to 10 to provide a highly satisfactory solution

polymerization of acrylamide and the product thus pro

duced. More particularly, this invention relates to a

method for preparing very high molecular weight poly

acrylamide which is still water-swellable and water-dis

to the problems normally associated with the polymeriza tion of acrylamide. Not only are the aforesaid problems associated with the polymerization of acrylamide and its

coplymers solved, but the polyacrylamide and polyacryl

15 amide copolymers made in accordance with the invention
properties. ' I ~

Vpersible and exhibits substantial stability against degrada

tion of its aqueous dispersions.
This application is a continuation-in-part of my co

are superior ?occulating agents and have other desirable

It was further discovered that the presence of a small

pending application Serial No. 755,120, ?led August 15,

1958, now abandoned.

essentially catalytic amount of ammonia, ammonium

in recent years polyacrylamide and copolymers thereof

have become available commercially and some of these are widely used in ore processing as ?occulants for slimes. Also, the literature describes the use of polyacrylamide

hydroxide, orthe equivalent (for example, an ammonium

salt plus base to produce free ammonia), referred to here in as free ammonia, at the time the acrylamide is being polymerized does not tend to inhibit the polymerization

and its copolymers as thickening agents, adhesives, paper sizing aids, ?occulants, etc. All of these uses require that the polyacrylamide or its copolymers be dispersed or
dissolved in a suitable medium such as water to facilitate

reaction, but instead promotes the polymerization and

gives a number of unexpected and very beneficial results. For example, the presence of a small amount of free ammonia in the form of, for example, ammonia or am monium hydroxide at the time the polymerization is oc

the application of the polymers. Experience has demonstrated that the higher the molec
ular weight of the polyacrylamide the better it is for use
as a flocculant and for some of the other uses, provided

curring produces the following observable and unex

it is still water-swellable and water-dispersible. Al though a number'of methods are available for making

pected results: (1) It decreases the induction period needed to start the active polymerization; (2) The rate of polymerization appears to be accel
erated when compared with a similar polymerization
35 carried out in the absence of ammonia or ammonium

high molecular weight polyacrylamide and polyacryl amide copolymers, these methods give polyacrylamides
which form aqueous dispersions that offer poor resistance to degradation on standing.

In general, the polymerization of acrylamide to make

good iiocculants gives rise to a number of problems which are dif?cult to overcome; namely, (1) the large heat of

hydroxide and at a pH less than about 7.5; (3) The polymerization product is more stable in dilute aqueous dispersions to degradation on standing than similar products prepared in the absence of ammonia;

polymerization has to be dissipated; (2) the resulting polymer should have a high molecular weight but still be easily dispersed in water; (3) little, if any, of the toxic monomeric acrylamide should be left in the polymer; and (4) the water dispersion of said polymer should be stable against degradation with age. As indicated above, there are several methods for polymerizing acrylamide but these methods do not pro
vide a completely satisfactory solution to all of the above

(4) The polymerization products are of higher molec ular weight than those polymers prepared under similar conditions in the absence of ammonia; (5) Although the polymerization products are of higher molecular weight than those prepared in the absence of ammonia, these higher molecular weight polymers are,

relatively speaking, easily and readily dispersed in water;

and

(6) The water dispersions of the polyacrylamides

prepared in the presence of added ammonia or am

problems. To further illustrate these de?ciencies, it may 50 'monium hydroxide have superior flocculating ability for slimes when compared with those prepared from polymers be noted that the dilute concentration process for polym made in the absence thereof, or a polymer which has been erizing acrylamide described in US. Patent 2,625,529 treated with ammonia in accordance with the teachings solves the heat dissipation problem at the expense of ob taining a lower molecular weight polymer. The con of US. Patent 2,831,841.

centration or runaway polymerization process produces 55 The quantity of additive providing the free ammonia such as ammonia, ammonium hydroxide, ammonium car a high molecular weight polymer but the heat dissipation bonate, or the equivalent which is present at the time of and water dispersion problems are aggravated. in like polymerization is critical. If the acrylarnide is essentially manner, other polymerization processes for acrylamide
may be satisfactory in one or more aspects but very un

free of harmful contamination, as little as 1><l()-3 mol

satisfactory in other aspects. Hence, it is well known

that the polymer industry is avidly seeking better methods for effecting the controlled polymerization of acrylamide
and its comonomers, i.e., the polymerization of a reac

of free ammonia per mol of acrylamide may be used and still obtain the six bene?cial results enumerated above.

Since the amount of impurities present in acrylamide

varies due to variations in its method of preparation and

tion mixture containing acrylamide.

Griffin D. Jones in US. Patent 2,831,841 discloses an

puri?cation, it is preferred to employ from 4.5X10_3 to 15x102 mol of free ammonia per mol of acrylamide.
These levels are found to be quite satisfactory with all the commercial acrylamides and no real advantage is to be gained by using more free ammonia. Treatment with free ammonia in excess of about 3X101 mol per mol of acrylamide may lead to loss of

interesting solution to the problem of elimination of toxic amounts of acrylamide from its polymers and copoly
mers. Jones treats the polyacrylamide product with am

:monia to detoxify the polymeric product. Although this

is an elegant solution to the toxicity problem, the process

requires that the polymerization step be ?nished prior to

appreciable quantities of acrylamide by side reactions

such as formation of nitrilo trispropionamide. This is

the treatmentyof the polymer with ammonia. Hence, the

3
particularly true when the polymerization is carried out
in relatively concentrated solution but it is minimized in dilute solution. Accordingly there is an upper limit both in the mol ratio of, free ammonia to acrylamide (of about
'3><10-1) as well as of the absolute free ammonia con

Al
results from batch to batch is greatly enhanced. This is true for highly puri?ed acrylamide' as well as for acryl amide obtained from differentcommercial sources. Thus
an ancillary bene?t derived from the presence of an additive such as ammonia or ammonium hydroxide and polymerization at a pH of about 7.5 to 10 is to increase the ease with which the results may be duplicated from batch to batch. It has been observed that pH values of about 7.5 to 10 10 and preferably about 8 to 9 are not conducive to rapid

pH to between about 7.5 and 8.5. The use of catalysts or initiators for polymerization reactions is well known achieved without signi?cant risk of encountering undesir 15 and .is disclosed in US Patent 2,820,777, the. teachings of able side reactions. which are incorporated herein by reference. In general, ' The additive may be added to the reactants prior to the polymerization catalyst or initiators are free radical the start of the reaction or during the reaction as gaseous catalysts and may be, for example, of the redox (reduc tion-oxidation) type or a catalyst such as an organic ammonia, liquid ammonia, aqueous ammonium hydroxide solution, or other suitable substance which is a source of 20 peroxide may be used alone. The concentration of- acrylamide in the reaction mixture ammonium ion. The addition of basic ammonium salts, is of importance as products which are not readily water such as ammonium carbonate, to the reactants gives the .swellable and dispersible may be obtained at high con bene?cial effects aiforded by the addition of ammonia or

centration of about 0.75l.0 molar), the combination of which should be borne inmind. The various free am monia to acrylamide mol ratios may be employed effec tively so long as the actual free ammonia concentration does not exceed about 0.75l.0 molar. A preferred range of ratios is in the region of 4.5><10-3 to 1.5><l0_2 mol free ammonia per mol acrylamide with a preferred ab solute free ammonia concentration of about .05 to 0.25 molar. Under these conditions the desired effects are

hydrolysis of acrylamide at low temperature, but if higher

temperatures are used, .thenit is preferred to adjust the

ammonium hydroxide, 'but if ammonium sulfate and acidic

or neutral ammonium salts are employed the pH of the reactants should be adjusted to about 7.5_10 so that the
salt is converted to the free ammonia form.

centrations. Usually, the. concentration of acrylamide

should not exceed about 15% by weight in aqueous polym erization systems. Preferably, the reaction mixture should contain about 2.5l5% by weight acrylamide. Examples of ethylenically unsaturated co-monomers that are frequently copolymerized with acrylamide to

Generally, it is preferred to add the additive to an

aqueous solution of acrylamide prior to the introduction ,of the initiators 0r polymerization catalyst. Thus, free 30 obtain copolymers having different chemical and'phys ical properties are acrylic acid, vinyl chloride, vinyl ammonia, i.e., ammonia or its equivalent can-reduce the
undesirable effects of metallic type inhibitors such as iron and copper by forming a complex or removing them as a

acetate, vinyl alcohol, methacrylic acid, methacryl

amide, methyiene-bis-acrylamide, etc. One of the most

precipitate from the solution. However, if the acryl

amide is essentially free of contaminants, it is immaterial

noticeable advantages obtained by copolymerizing acryl

amide with co-monomer in the presence of an additive such as ammonia at basic pH conditions is the enhanced stability of the aqueous dispersion of the copolymer

whether the additive, the initiator or catalyst is added ?rst. The terms puri?ed acrylamide and acrylamide essentially free of contaminants are used to designate acrylamide thathas received a special puri?cation treat
ment such as sublimation, low pressure distillation or a 40

against degradation. Also, the copolymers prepared in

the presence of ammonia are more readily dispersed in
aqueous medium. .

careful fractionation from a mixed solvent, .e.g., ethyl acetate-benzene.

It may be demonstrated that the impurities obtained as ,

The foregoing detailed discussion and the following

speci?c examples are for purposes of illustration only and
are not to be taken as limiting to the appended claims.

residues by treatment of commercial acrylamide by one of

' the above puri?cation methods, for instance by sublima tion, cause the erratic results often obtained when acryl amide is polymerized. For example, the addition of a

in the examples which 'follow the. reagent concentra

tions employed throughout are:

K2320, ____________________________ __g./liter__ 5.0
Na2SO3 ____________ __'___,_, ________ __g./liter__ 1.0
NH4OH _________ __; __________ __'______molar__ 3.0

small amount of such residues to puri?ed acrylamidel or

some commercial acrylamides results in the polymer be- . . ing a rigid, intractable gel while a control batch prepared

without addition of the residue may normally be Water

i _ swellable and Water-dispersible.

It has been discovered that the above indicated varia tions in the polymer properties from batch to batch are due to the presence of certain impurities or contaminants which are easilyremoved by the following methods: care

and the parts reagent added to the recited volume of the aqueous solution of acrylamide (save for acrylamide, co monomer and water) are parts by volume (of the aqueous

solutions of the concentrations given above. The parts

acrylarnide, comonomer and water used in preparing the

aqueous solution for polymerization are in parts by Weight.

Examples I and Ii illustrate the improvement obtained ,

ful fractionation from amixed solvent, sublimation and distillation at reduced pressure. vFrom'an analysis of the residue obtained by subjecting commercial acrylamide to
-one of the above puri?cation processes, these impurities are thought to be certain inorganic materials which are 60
metallic in nature such as iron, copper and nickel, and

by the dilute concentration polymerization of acrylamide

1n the presence of a soluble substance providing free ammonia in solution.

Example .I
An aqueous solution of 1.0 part of acrylamide dissolved in 9.5 parts of water was sparged withxpuri?ed nitrogen and into the solution was introduced 0.5 part. potassium persulfate reagent and 0.2 part of sodium sul?te reagent.
After ten minutes at. room'temperature, there was no

certain organic materials which :are ole?nic in nature and copolymerizable with acrylamide, water-soluble low mo lecular weight polymers and material of a related nature. When these impurities are removed the results obtained from batch to batch by the same polymerization method
are moreeasily duplicated. '

evidence of polymerization as indicated by viscosity

Although puri?cation of commercial acrylamide by the Q aforesaid methods increases the probability that different

changes (re?ected in the manner in which the nitrogen bubbles rise through the aqueous solution), and negative
'?occulating results were given when a small aliquot of
the solution was added to a potash slime suspension.

batches of polyacrylamide polymer prepared -by identical

methods will have the same properties, it has been further :discoveredthat if the polymerization is carried out in the
presence of an additive such asammonia and at a pH of

After several hours polymerization began and the result ing polymer was easily. dispersed in water. The result
ing water. dispersionwas tested as a ?occulant for potash

about 7.5 to ,10, the probability of obtaining identical

slimes and found to- be only slightly better a high grade

3,200,098

5
glue as a ?occulant. After several days, the aqueous

as sublimed acrylamide and is equivalent to highly puri?ed

dispersion had degraded sufficiently to be essentially in

effective as a ?occulant.

acrylamide.
Example VI 1.0 part of highly puri?ed sublimed acrylamide sample
from Example V was dissolved in 20 parts of water, sparged with nitrogen for 10 minutes and then 1.0 part

Example 11
One-half part of 3 M ammonium hydroxide was added to an aqueous solution consisting of 1.0 part of acrylamide dissolved in 9.0 parts of water. While the mixture was

of the potassium persulfate solution was added. Sparg

ing was continued and after ?ve minutes 1.0 part of the sodium sul?te solution was added. During a period of 80 > persulfate reagent and 0.2 part of sodium sul?te reagent 10 minutes there was no evidence of polymerization, and were added as a redox catalyst. Within three minutes ate 71/2 hours only a slight increase in viscosity was after the addition of the redox catalyst, polymerization evident. The mixture was sparged for 48 hours at am was evidenced by the increase in viscosity. Within three bient temperature and then heated for 15 hours at 60 C. hours, the polymerization had proceeded sufficiently to When dispersed to 0.5% concentration in water the pro

being sparged with puri?ed nitrogen, 0.5 part of potassium

produce a highly viscous almost gelled solution without 15 duct had very little viscosity. undue heat effect and the resulting mixture was essential Example VII ly non-toxic. The dilute water dispersion of this polymer

was an excellent ?occulant and after 14 days, showed The conditions of Example VI were duplicated with a little evidence of degradation or loss of ?occulant power. second sample of highly puri?ed sublimed acrylamide To illustrate the bene?cial effects on the rate of polym 20 from Example V except that 0.5 part of 3 molar am erization of acrylamide in the presence of ammonia, very monium hydroxide were added to the solution before dilute polymerization conditions are used in Example HI. the initiator and activator Were added. There followed an induction period of less than seven minutes when vis Example III cosity increase became evident. The polymerization was

for ten minutes at which time 2.5 parts sodium sul?te persed in water to 0.5% concentration. solution were added and the sparging continued. The What is claimed is: reactants were initially at room temperature and the 1. A polymerization process comprising reacting an viscosity of the solution gradually rose during a three 30 alkaline aqueous reaction mixture containing initially not hour period. The reaction vessel was stoppered and the more than about 15% by weight of acrylamide monomer mixture allowed to stand for an additional 20 hours, after in the presence of a free radical catalyst and a water which it was heated at 65 C. for 7% hours. The product soluble substance providing l><l08 to 3><1()"1 mol of was dispersed in water to a concentration of 0.5%. free ammonia per mol of acrylamide monomer initially (b) For comparison an identical experiment was car 35 present to produce a water swellable and dispersible ried out save that only 21 parts of water was used and polymerization product. 1.5 parts of 3 M ammonium hydroxide was added._ With 2. A polymerization process comprising reacting an in thirty minutes of the addition of the activator the alkaline aqueous reaction mixture containing initially not solution had become very viscous. The remainder of more than about 15% by Weight of acrylamide monomer the treatment was the same as in part (a). The product in the presence of a free radical catalyst and a Water was de?nitely more viscous when dispersed then product soluble substance providing 1><l03 to 3><l0*1 mol of (a). However, both products exhibited very good ?oc free ammonia per mol of acrylamide monomer initially

(a) 1.0 part acrylamide, 22.5 parts water and 1 part 25 continued and completed exactly as in Example VI and potassium persulfate solution were sparged with nitrogen the product was a ?rm semi-gel which was readily dis

culating activity toward slimes obtained in the leaching

present at a pH of about 7.5 to 10 to produce a water

behavior was consistently observed in pairs of numerous samples polymerized under a variety of conditions as re gards concentration and monomer to catalyst ratio, but differing only in the presence or absence of ammonia.

During the succeeding fourteen days the solution of molar concentration of free ammonia in the aqueous re product (a) above lost its viscosity until it resembled 45 action mixture not exceeding about 1.0. little more than Water, while the solution of product (b) 3. A process for preparing polyacrylamide comprising above retained its viscosity. At the same time the ?oc polymerizing acrylamide monomer in aqueous solution culating activity of product (a) diminished to a low un in the presence of a free radical catalyst and a water satisfactory level, while that of (b) was unaltered. Such 50 soluble substance providing about 1X103 to 3X10~1
mol of free ammonia per mol of acrylamide monomer initially present at a pH of about 7.5 to 10 to produce a water swellable and dispersible polymerization product, the aqueous solution containing initially about 2.5 to 15% by weight of acrylamide monomer.
in the presence of a free radical catalyst and at least one

of uranium ore.

swellable and dispersible polymerization product, the

Example IV
The experiment of Example III was repeated except
0.001 part of methylene-bis-acrylamide was added to the

4. A process for preparing polyacrylamide comprising

polymerizing acrylamide monomer in aqueous solution
substance providing free ammonia selected from the group consisting of ammonia and amonium hydroxide in an amount of about 1><l03 to 3><101 mol per mol of acrylamide monomer initially present at a pH of about 7.5 to 10 to produce a water swellable and dispersible
65

acrylamide solution before the polymerization started. The copolymer prepared in the presence of the ammonia
gave a dilute dispersion which was superior in ?occulat

ing ability and in aging stability to the dilute dispersion of the product prepared in the absence of ammonia. Example V

polymerization product, the aqueous solution containing initially about 2.5 to 15% by weight of acrylamide
monomer.

A large sample of commercial acrylamide, which fre quently gave polymers that were intractable gels when polymerized in the absence of ammonia, was charged to
absolute pressure and a sublimate of acrylamide was ob

5. A process for preparing polyacrylamide comprising

polymerizing acrylamide monomer in aqueous solution in
free ammonia per mol of acrylamide monomer initially

the presence of a free radical catalyst and a water soluble a vacuum sublimation apparatus. The pressure on the vacuum sublimation apparatus was maintained at 1 mm. 70 substance providing about l><l03 to 3><1()1 mol of

tained at temperatures from ambient up to just below

present at a pH of about 8 to 9 to produce a water swell

the melting point of acrylamide. The sublimate of

acrylamide was caught on a cold ?nger forming part of the apparatus. This product is referred to hereinafter

able and dispersible polymerization product, the aqueous solution containing initially about 2.5 to 15 % by Weight
of acrylamide monomer.

3,200,098

&
6. A process for preparing polyacrylamide comprising polymerizing acrylamide monomer in aqueoussolution in
the presence of a free radical catalyst and at least one

water swell'able and dispersible copolymerization product. 12. The process of, claim '11 wherein'the acrylamide
monomer consists essentiallyof acrylamide. ,

substance providing free ammonia selected from the group 13. The process of claim 11 wherein the ethylenically consisting of ammonia and ammonium hydroxide in an 5 unsaturated comonomer is rn'ethylenebis-acrylamide. 14. Apolymerization process comprising reacting an amount of about l><103 to 3><1O~1 mol per mol of acrylamide monomer initially present at a pH of about alkaline aqueous reaction mixture containing. initially not 8 to 9 to produce a water swellable and dispersible polym more than about 15 % by weight of acrylamide monomer erization product, the aqueous solution containing initially and an ethylenically unsaturated comonomer copolym about 2.5 to 15% by weight of acrylamide monomer. 10 erizable therewith in the presence of .a free radical catalyst 7. A process for preparing polyacrylamide comprising and a water soluble substance providing 1X103 to polymerizing acrylamide monomer in aqueous solution in 3X101 mol of free ammonia per mol of acrylamide the presence of a free radical catalyst and a water soluble monomer and comonomer initially present at a pH of substance providing about 4.5><103 to 1.5 x 102 mol of about 7.5 to 10 to produce a water swellable and dispers free ammonia per mol of acrylamide monomer initially 15 ible copolymerization product, the molar concentration of present at a pH of about 7.5 to 10 to produce a water free ammonia in the aqueous reaction mixture not exceed

swellable and dispersible polymerization product, the aqueous solution containing initiallyaoout 2.5 to 15% by
weight of acrylamide monomer.

ing about 1.0.

' '

8. A process for preparing polyacrylamide comprising

15. The process of claim 14 wherein the acrylamide monomer consists essentially of acrylamide. 16. The process of claim 14 wherein the ethylenically

polymerizing acrylamide monomer in aqueous solution in unsaturated comonomer is methylene-bis-acrylamide. the presence of afree radical catalyst and at least one 17. A polymerization process comprising reacting an substance providing free ammonia selected from the group alkaline aqueous reaction mixture containing initially not consisting of ammonia and ammonium hydroxide in an more thanabout 15 % by weight of acrylamide monomer amount of about 4.5 x 103 to 1.5><102 mol per. mol of 25 and an ethylenica'lly unsaturated comonomer copolym acrylamide monomer initially present at a pH of about erizable therewith in the presence of va free radical 7.5 to 10 to produce a water swellable and dispersible catalyst and at least one substance providing free am~

polymerization product, the aqueous solution containing initially about 2.5 to 15% by weight of acrylamide
monomer. ,

monia selected from the group consisting of ammonia and

ammonium hydroxide in an amount of about 4.5 X l03 to
30 1.5 x10_2 mol per mol of acrylamide monomer and

9. A process for preparing polyacrylamide comprising

polymerizing acrylamide monomer in aqueous solution in
the presence of a free radical catalyst and a water soluble

comonomer initially present at a pH of about 7.5 to 10

to produce water swellable and dispersible copolymeriza

tion product. ' '

substance providing about 4.5><10_- to 1.5 X 102 mol of free ammonia per mol of acrylamide monomer initially present at a pH of about 8 to 9 to produce a water swell

able and dispersible polymerization product, the aqueous solution containing initially about 2.5 to 15 %v by weight

of acrylamide. 10. A process for preparing polyacrylamide comprising

polymerizing acrylamide monomer in aqueous solution in
the presence of a free catalyst and at least .one substance

18. The process of claim 17 wherein the acrylamide monomer consists essentially of acrylamide. 19. The process of claim 18 wherein the ethylenically unsaturated comonomer is methylene-ibis-acrylamide. 20. The process of claim 19 wherein about 0.001 part

by weight, of the methylene-bis-acryl'amide is present

40

based upon the Weight of the aqueous reaction mixture.

7 21. The process of claim 10 wherein the polymeriza

providing free ammonia selected from the group consist ing of ammonia and ammonium hydroxide in an amount
of about 4.5><'l03 to 1.5 X 102 mol per mol of acryl 45 amide monomer initially present at a pH of about 8 to 9 to produce a water swellable and dispersible polymeriza

tion catalyst comp-rises a water soluble persulfate and a water soluble sul?te.

References Cited by the Examiner

UNITED STATES PATENTS

2,120,933 6/38 Dittrnar ___________ __ 26089.7

tion product, the aqueous solution containing initially

about 2.5 to 15% by weight of acrylamide monomer. 111. A polymerization process comprising reacting an 50 alkaline aqueous reaction mixture containing initially not more than about 15% by weight of acrylamide mono
mer and an ethylen-ically unsaturated comonomer copo

2,289,540

7/42

Dittmar ___________ __ 26089.7

2,775,579
2,806,018 2,820,777 2,831,841

12/56
9/57 1/58 4/58

Erchak ___; _________ __ 260-80

Price _____________ __ v26089.7 Suen ______________ __ 26089.7 Jones ________ __._____ 26089.7

lymerizable therewith in the presence of a free radical catalyst and a water solution substance providing 1><10~3 55 JOSEPH L. scuonnn, Primary Examiner, to 3><1O~1 mol of free ammonia per mol of acrylamide H. N. BURSTEIN, WILLIAM 'H. SHORT, LEON J. monomer and comonomer initially present to produce a BERCOVI'TZ, Examiners.