CA1133788A - Water-in-oil emulsions containing copolymers of maptac and acrylamide - Google Patents

Abstract

Described are water-in-oil emulsions which contain dispersed in the aqueous phase particles of a water-soluble copolymer having a ratio varying between 5-60 parts by weight of methacrylamidopropyltrimethylammonium chloride (hereafter referred to as MAPTAC) to 95-40 parts by weight of acrylamide, said emulsion having the following comp???ion a. from 5-60% by weight of the MAPTAC acrylamide copolymer; b. from 20 -90% by weight of water; c. from 5-75% by weight of a hydrophobic liquid; and d. from 0,1-21% by weight of a water-in-oil emulsifying agent. These water-in-oil emulsions, particularly when derived form charcoal pre-purified MAPTAC momomers, give superior results when they are used to dewater sludges of the type found in municipal sewage and industrial waste treating plants. They are also useful in improving the fine and filler retention during the paper-making process. Further, they may be used for reducing fluid friction in pipelines and the like.

Description

~I~L33788 It is now known that water-soluble homo and copolymers can be prepared in the form of water-in-oil emulsions which, when inverted in the presence of water, are rapidly dissolved in the water. The inversion to rapidly dissolve the polymer is most ef~iciently accomplished by use of a water-soluble surfactant al-- though other ~eans may be used to achieve the inversion and rapid solubilizing of the polymer. This phenomena is described in United States Reissue Patents 28,474 and 28,576.
Acrylamide polymers in the form of water-in-oil emul-sions, ~although not their inversion to rapidly solubili~e these polymers in water,] are further disclosed in Vanderhoff, United States 3,284,393. These polymers, as well as the copolymers of acrylamide, have a variety of industrial uses, most notably:
a. for treating aqueous suspensions to improve the ; settling thereof;
b. as dewatering agents for sewage and industrial wastes;
c. for decreasing friction of aqueous fluids as they are pumped through pipes or conduits;
d. for improving the fine and filler retention in the manufac~ure of paper.
Recently there has been made available to industry a new water-soluble vinyl monomer, methacrylamidopropyltrimethylammonium chloride (hereafter called MAPTAC), which has the structural formula:

_ ~ CH - - C -0 - CNHC~H2 ~ CCH3)3

- 2 -I ~33788 Copolymers of this monomer with acrylamide have been described in the literature (see technical bulletin by the Jefferson Chemical Sompany, Inc., entitled _ationic Monomers, dated March 25, 1976~) l~hile copolymers of acrylamide and MAPTAC have been described, it is believed they have not been preparea in the form of water-in-oil emulsions. The present invention is directed to such emulsions, their method of preparation, the procedures to use for maximized molecular weight, and their use in treating a variety of industrial systems.
In particular, the invention is directed to the use of acrylamide MAPTAC water-in-oil emulsions as sludge dewatering aids, as paper retention aids, and or improving the flow of aqueous fluids through pipes and related operations.

Sludge Dewatering Sludge dewatering relates to the disposal of solids after sewage treatment which has been a problem for many years. At one time sewage sludge was simply discharged into nearby streams or lakes. Increasing sensitivity to pollution problems, however, eventually forced sewage treatment plants to barge the sewage to sea or to lagoon it in large evacuated areas. Later approaches to the sewage sludge disposal problem entailed the use of vacuum filtration to separate sewage solids from slurries which was then followed by incineration and use in land fills or use as fertilizer.
App'ication of the sewage sluage as land fill material or as fertil-izer required that the sewage solids be dewatered prior to use.
Typically, vacuum filtration involves the use of a large rotary drum covered with open mesh metal or a wiper filter. The drum is rotated through the sewage slurry which is contained in a filter pan belo~7 the drum. Vacuum is applied toward the center of the drum through the filter cloth. Sewage solids are continuously picked UD on the filter and removed from it.

.., . I ~ ~3 ~33781~

Flocculants or coagulants are added to the se~age slurry in order to enhance the vacuum filtration. In the absence of these flocculants, the se~Jage solids tend to remain in the form of small hydrated particles which are not easily filtered. ~he flocculant makes these small particles cling together in order to form larger flocs that tend to release and bond wa-ter and are more readil~
filtered. Normally speaking, within a certain classification of polymer or copolymer used as a flocculating agent, the higher the molecular weight of the flocculent, the more efficient it is as a flocculent. This is particularly true with cationically charged ~flocculents.

Fine and Filler Retention Paper is manufactured, for the most part, from wood pulp. If the pulp fibers T~ere the only constituents of a paper sheet, how-ever, the usefulness of the paper would be very restricted because the sheet would be soft, have a yellowish color, and could not be written or printed upon with ink. If the sheet were thin, it would~
be transparent to rnatter printed upon the opposite side.
` Therefore, it is necessary to add other substances such as sizing, coloring agents and fillers to the cellulosic fibers to produce paper suited to its many current uses. Many papers, except the absorbent types, filter papers and most packaging papers, must have a finely ground filler added to thim. This filler occupies the spaces between the pulp fibers, thus giving the paper a smooth surface, a more brilliant whiteness, improved printability and im-proved o acity. Generally, the fillers are inorganic substances and may be either naturally occurring materials such as talc, agalite, pearl filler, barytes and certain clays such as china clay or art-ificial fillers such as suitably precipitated calcium carbonate, crown filler tpearl hardening,) blanc fixe, and titanium dioxide pigments. In addition to the fillers, sizing is added to the paper (other than absorbent papers and filter paper) to imp~rt resistance ~ ~337~8 to penetration by liquids. Common sizing agents added to the pulp before it is formed into a sheet are wax emulsions or soaps made by the saponification of rosin with alkali. The sizes are precipitated with alum.
Pulp stock is prepared for formation into paper by two general processes, beating and refining. Mills use either one or the other alone or both together. Beating the fibers makes the paper stronger, more uniform, more dense, and less porous. It is in the beater that fillers, coloring agents and sizing may be added. The standard practice in making the finer grades of paper is to follow the beaters with the refiners, since the latter are continuous machines.
While the usual practice is to add filler, sizing and color to the beaters, they may also be added prior to the beaters or at a combin~tion of points in the system. The fillers may also be added after to the beating operation but prior to the refining step.
~ he order in which the materials are added to the beaters may vary with different mills. Generally, however, the filler is first added to the blended pulp, and after suffic~ent beating, the sizing and the coloring are added.
The machines used for the actual formation of the paper sheet are of two general types, the Fourdrinier machine and the cylinder machine. The basic principles of operation are essentially the same for both machines: the sheet is formed on a travelling bronze screen or cylinder, dewatered under rollers, dried by heated rollers and finished by calender rolls.
In an attempt to improve filler and fines retention in the paper manufacturing operation, several attempts have been made to in-corporate chemical additives with the paper stock before it reacnes either the cylinder vat or the Fourdrinièr wire. These additives, for the most part, have not been entirely satisfactory from several operational points of view.

' ~ ~

~L~337~
One of the chief drawbacks of most chemicals used to improve a fiber and fine retention in the manufacture of paper is that they nust possess a number of characteristics and properties which are extremely difficult to achieve in any single chemical. For instance, the particular chemical used should not be affected by other add-itives normally used in the ~a~er processing operations such as rosin size, alum, sodium aluminate, starch, clays, and the like. Also, the chemical must not be affected by variations in pH. The ideal add-itive chemical should not be affected by a particular electrokinetic charge on the cellulose fibers and fines. Finally, the use o~ a chemical mus~ not adversely affect the finished sheet and it should be relatively safe to handle.
In addition to ~ossessing the above desirable characteristics, an additive for improving filler and fines retention must be capable of ac~ing both upon the filler and fines in the system to efficiently cause such materials to be retained in the finished sheet. The chemical must be capable of operating on a wide variety of stocks.
It must not affect dyestuffs which are fre~uently used as coloring agents for various types of paper stocks, nor must it interfere with the beneficial effects imparted to paper stock~ by coatings which are frequently placed on different types of paper during its manufacture.
Many prior art filler and fiber fines retention aids fail to satisfy the above criterial. In addition, certain of these known re-tention additives cannot be employed in effective combinations with various fillers or other paper additives. Oftentimes efficiency is low requiring that uneconomical amounts of the additive be used. Ad-verse effects upon the finished paper broduct are noted when these re tention aids cause poor dispersibility of the system additives with resultant localized non-uniform areas. Lastly, many additives fail by promoting filler trapage on the top side of the fiber material.

At the present time it is customary to use acrylamide co-polymers for improving filler and ~iber fine retention in paper mill -6~

~37~8 operation. Illustrative of such usage are certain acrylamide poly-mers described in United States 31450,680. The present acrylamide-MAPTAC latex copolymers represent an important advance over the use of these acrylamide polymers and other prior retention aids. This adval~ce in the art of using retention aids is particularly notice-able when the acrylamide-MAPTAC latex copolymers are synthesized using a charcoal or activated carbon pre-purified MAPTAC monomer.
The problem of reducing pumping costs in moving large volumes of fluids is ever present. ~or instance, many chemical plants require the movement of substantial volumes of fluids. Addi-tionally, in diverse operations, such as hydraulic fracturing of gas or oil wall sites, large volumes of aqueous fluids are demanded. To effect necessary economies in pumping costs, polymeric additives to fluids designed for decreasing friction loss in flowing fluids have been suggested. The acrylamide-MAPTAC latex polymers of this inven-tion give excellent friction reduction at low dosages.
OBJECTS
The present invention discloses novel acrylamide-MAPTAC
latex copoly~ers and a process for their manufacture.
~O Another aspect of this invention discloses an improved method for sludge de~atering which employs these novel acrylamide-MAPTAC latex copolymers.
In another aspect this invention discloses a method of enhancing filler and fine retention in the manufacture of paper which entails use of these novel acrylamide-MAPTAC latex copoly-mers.
Alternatively in another aspect this invention discloses the use of these copolymers as aids for enhancing the flow of fluids.
In a further aspect this invention discloses processes to maximize the molecular weight of the copolymers and to maximize the control of molecular weight of these copolymers by providing a charcoal purified monomer of MAPTAC.

~ ~33788 . T~IE INVENTION -The invention is directed primarily to a water-in-oil emulsion which contains dispersed in the aqueous phase particles of a water-soluble copolymer havïng a ratio varying between 5 - 60 parts by weight of ~PTAC to 95 - 40 parts ~y weight of acrylamide.
These emulsions have the following general composition:
a. from 5 - 60% by weight of the MAPTAC-acrylamide copolymer;
b. rom 20 - 90% by weight of water;
c. from 5 - 75% by weight of a hydrophobic liquid;
and d. from 0.1 - 21% by weight of a water-in-oil emulsiying agent.
In a preferred embodiment, the water-in-oil emulsion has the following composition:
a. from 20 - 40~ by weight of the MAPTAC-acrylamide copolymer î
b. from 20 - 70% by weight of water;
~- c. from 5 - 40% by weight of a hydrophobic liquid;
and d. from 1 - 51% by weight of a water-in-oil emulsifying agent.
In a most preferred embodiment, the water-in-oil emulsion has the following composition:
a. from 25 - 35% by weight of the I~PTAC acrylamide copolymer;
b. from 30 - 55% by weight or water;
c. from 20 - 30% by weight of a hydrophobic liquid;
and d. rom 1.2 - 10% by weight of a water--in-oil emulsifying agent.

~ 3378~

As previously indicated, the invention also is directed to the use of these emulsions containing the copolymers of MAPTAC
and acrylamide for use in fine and filler retention in the dewater-ing of domestic and industrial wastes and for enhancing the flow of fluids. Charcoal purification of the ~IAPTAC improves the quality of the copolymers produced therefrom.
The Water-in-Oil Emulsions of MAPTAC Acrylamide ~olymers A method for the preparation of emulsions of the type described above is contained in Vanderhoff, United States 3,284,393.
A typical procedure for preparing water-in-oil emulsions of this type includes preparing an aqueous solution of a MAPTAC acrylamide copolymer and adding this solution to one of the hydroca~bon oils described above. With the addition of a suitable water-in-oil emul-sifying agent and under agitation, the emulsion is then subjected to free radical polymerization conditions and a water-in-oil emulsion o the MAPT~C acrylamide copolymer is obtained. It should be pointed out that the ingredients are chosen based upon the weigh~ percent-ages given above and their compatability with e~ch other. As to choice of free radical catalyst, these materials may be either oil r or water soluble and may be from the group consisting of organic peroxides, Vazo type materials, red-ox type initiator systems, etc.
Additionally, ultraviolet light, microwaves, etc. will also cause the polymerization of water-in-oil emulsions of this type.
In the manufacture of emulsions of this type, which are further detailed in United States 3,624,019, United States 3,734,873, United States 3,826,771 and United States Reissue Patents 28,474 and 28,576, the use of air may he employed to control polymerization.
This technique is described in United States 3,767,629.

"- - æb ~ I

I In addition to the above references, U.S. 3,996,180 describes ¦the preparation of water-in-oil emulsions of the types utilized in ¦this invention by f;rst forming an emulsion containing small ¦particle size droplets ~etween the oil, water, monomer and water-in-¦oil emulsifying agent utiliæing a high shear mixing technique Ifollowed by subjecting this emulsion to free radical polymerization ¦conditions ~lso of interest is U.S. 4,024,097 which describes ¦water-in-oil emulsions such as those described above utilizing particular surfactant systems for the water-in-oil emulsifying agent, allowing for the preparation of latexes having small polymer particle sizes and improved storage stability.
Another reference, U.S. 3,915,920, discloses stabilizing water-in-oil emulsions of the type above described utilizing various oil-soluble polymers such as polyisobutylene. Employment of techniques of this type provides for superior stabilized emulsions.
Of still further interest is U.S. 3,997,492 which describes the formation of water-in-oil emulsions of the type above describeld utilizing emulsifiers having HLB values of between 4 - 9.

Physical Properties of The Water-in~Oil Emulsions The water-in-oil emulsions of the finely divided water-soluble polymers useful in this invention contain relatively lar~e amounts of polymer. The polymers dispersed in the emulsion are quite stable when the particle size of the polymer is from the range of 0.1 microns up to about 5 microns. The preferred particle size is generally within the range of 0.2 microns to about 3 microns.
A most preferred particle size is generally within the range of ¦ 0.2 to 2.0 microns.

~ ~33~
The emulsions prepared having the aboYe composition generally have a viscosity in the range of from 50 to 1000 cps. It will be seen, however, that the ~iscosity of these e~ulsions can be affected greatly by increasing or decreasing the polymer content, oil content, or water content as ~ell as the choice of a suitable ~ater-in-oil emulsifier.
Another factor attributing to the viscosity of these types of emulsions is the particle size of the polymer which is dispersed in the discontinuous aqueous phase. Generally, the smaller the particle obtained, the less viscous the emulsion. At any rate, it will be readily apparent to those skilled in the art as to how the viscosity of these types of materials can be altered.
It will be seen that all that is important in this lnvention is the fact that the emulsion be somewhat fluid, i.e. pumpable.
The Inversion of the Water-in-Oil Emulsions of the MAPTAC Acrylamide Copolymers The water-in-oil emulsions of the MAPTAC acrylamide co-polymers discussed above have unique ability to rapidly invert when added to aqueous solution in the presence of an inverting agent or physical stress. Upon inversion, the emulsion releases - the polymer into water in a very short period of time when compared to ~he length of time required to dissolve a solid form of the polymer. This inversion ~echnique is described in United States

3,624,019. As stated in this reference, the polymer containing emulsions may be inverted by any number of means. The most convenient means resides in the use of a surfactant added to either the polymer-containing emulsion or the ~ater into wh;ch it is to be placed. The placement of a surfactant into the water causes the emulsion to rapidly invert and release the polymer in the form of an aqueous solution. ~hen this technique is used to invert the polymer-containing emulsion, the amount of surfactant present in ~ 337~3~

the water may vary over a range of 0.01 to 5Q pQrcent based on the polymer. Good inversion often occurs within the range of 1.0 - 10 percent based on polymer.
It is often possible to incorporate the inverting agent into the fini.shed water-in-oil emulsion which contains the polymer, thereby allowing a single unitary product to be shipped. When this method is employed, it is desirable that the amount of surfactant incorporated into the latex not exceed about 10% by weight and, preferably, it does not exceed 5% by weight. Typical ranges of the inverting agent in the latex are between 0.1 - 3% with 1 - 3% being preferred, with these amounts being based on the weight of the latex.
Further, when this tec~mique is used, it is necessary that the inverting agent--surfactant be compatible with the latex since if it isn't, the latex tends to destabilize under conditions of long-term storage and polymer precipitates therefrom andlor phase separation occurs.
The inverting agent surfactant should have an HLB range between 9-1/2 to 16 and, preferably, 12 to 13. In certain instances there are surfactants capable of inverting the emulsions ~hich do not have HLB values. It is understood that these suractants are included for use in the practice of the invention and are considered to be within the ~ILB values given.
The preferred surfactants utîlized to cause the inversion of the water-in-oil emulsion of this invention, when the emulsion is added to water, are hydrophilic and are further characterized as being water soluble. Any hydrophilic type surfactant such as ethoxylated nonyl phenols~ ethoxylated nonyl phenol formaldehyde resins, dioctyl esters of sodium succinate and octyl phenol poly~
ethoxy ethanols, etc. can be used. Preferred surfactants are generally nonyl phenols which have been ethoxylated with between / ~
/
~133788 ~- ~?: 8 - 15 moles of ethylene oxide. A more complete list of surfactants used to invert the emulsion are found in Anderson, U.S. 3,624,019 at columns 4 and 5.
To illustrate the preparation of the MAPTAC acrylamide copolymers, the following are given by way of example:

Example I
Preparation of a 25% MAPTAC--75% acrylamide copolymer:
Oil Phase~
154.62 gms~ low odor parafin solvent;

4.28 gms. Sorbitan*mono-oleate;
4.28 gms. cationic alkyl oxazoline emulsi~ier Monomer Phase:
263.64 gms. - 46.2% aqueous solution acrylamide 81.20 gms. MAPTAC 50% aqueous solution (charcoal treated) 69.87 gms. D.I. water 0.29 yms. isopropanol - 2.40 gms. 2% versene*
few drops concentrated H2SO4 to pH 3.0 Initiator:
0.81 gms. 2,2' Azobis-isobutyronitrile (V-64)*
Procedure:
A 1 liter resin flask equipped with mechanical ayitation, thermometer, Friedrich condenser and purge tube was used as a reactor. To the reactor was charged the oil phase. With agitation at 900 rpm, the monomer phase was added. While heating to a reaction temperatur~
of 46~C. over one-half hour, the latex was purged with nitrogen at 1,000 cc~min. Initiator was added as a powder throuyh a funnel into the latex. Pol~merization ra mark -13- ¦

3378~

.. . was allowed to continue at 46 - 47C for four hours.
,~ ,,.
This was followed by a post-heat of 75C for one hour.
The product had an /n/ = 11.4, [RSV]1 = 14.4, and .
residual acrylamide of ~ 0.4%.

Example II
Preparation of a 40% MAPT~C--~0% acrylamide copolymer:
. Oil Phase:
154.62 gms. low odor parafin solvent;
4.28 gms. Sorbitan*mono-oleate;
4.28 gms. cationic alkyl oxazoline emulsifier Monomer Phase:
210.91 gms.- 50% aqueous solution acrylamide 129.92 gms. MAPTAC 50% aqueous solution (charcoal treatea) 73.88 gms. D.I. water O.29 gms. isopropanol 2,40 gms. 2% versene*
few drops concentrated M2SO4 to pH 3.0 ¦ Initiator:
.
0.97 gms. 2 J 2' Azobis-isobutyronitrile (V-64)*
Procedure: - .
. The same procedure was used as described for Example I.
The product had /n/ = 8.98, [RSV] ~ = 10 .8 and . residual acrylamide < 0.4%.

*Trademark Reduced Speciic Viscosity -14-~ 3~7~8 ¦ Example III
¦ MAPTAC Charcoal Purification 300 gms. MAPTAC 50% aqueous solution 15 gms. activated carbon .02 gms. CuS0~ 5 EI20 Procedure:
MAPTAC solution was weighed înto a 600 ml beaker.
Activated carbon and CuS04 ~5H20 were added to the MAPTAC
solution and mixed for two hours with a magnetic bar stirrer. The charcoal was removed from the MAPTAC solution by vacuum filtration through a Pyrex*sintered glass filter funnel containing a thin pad of a super-cell filter ¦ aid. The collected MAPTAC had changed from clear orange ¦ to light yellow. This MAPTAC solution was used in the I preparation of Example I and Example II.

Example IV
Preparation of Single Component Latices:
140 gms. MAPTAC latex (25/75~
26 gms. low odor paraffin solvent 16 gms. NaCl 10 gms. tall oil fatty acid ¦ 8 gms. - 26% diamylphenol-74% ethylene oxide Procedure:
The latex was weighed into an 8 oz. glass jar and was mixed with a four-bladed glass stirring rod mounted in a cone driv~ stirrer. With agitation set midway on the cone, low odor paraffin solvent and salt are addea. The mixture then stirred for 1 hour. Tall oil fatty acid was added, followed by slow addition o~

*Trademark -15-.
.
I

/ ~
/ 1 ~33788 ~., , melted solution of 26% diamylphenol-74~ ethylene oxide. This final m;xture'stirred an additional 1 hour.
The sample is freeze-thaw stable after three overnight cycles at 0F. ~ull inversion occurs in the friction reduction loop in less than 60'seconds.
In addition to the previously described experiments, additional copolymers were prepared. These experiments are set orth below in Table I.

M~PTAC Monomer Purification As is known in the art for polymerization of monomers to high molecular weight, the purity of the'monomer is of critical importance in obtaining this high molecular weight. The ~-~PTAC
monomer as received from the supplier is clear orange-colored solution which contains several impu,rities which have not yet been adequately identified. The use of these impure monomers to prepare acrylamide often results in copolymers of low molecular weights depending on the monomer ratios with acrylamide and other conditions of the reaction. As can be seen in Table I, charcoal treated MAPTAC, when compared with untreatea MAPTAC or with ion exchanged material~"
far excells the molecular weights achieved with either untreated or ion exchange treated MAPTAC monomers. The molecular weight is primarily measured by the intrinsic viscosity or the reduced viscos-it~ of the solutions made from the copolymers obtained from these two monomers.
As can be seen from Table I, at a single monomer ratio, the higher intrinsic and reduced viscosities are obtained when the ~PTAC
monomer solution used in the polymerization has previously been treated with activated charcoal. Other purification procedures were attempted. -These included ion exchange and other adsorptive techniques.

f 113378B

The use of activated carbon for the purification of these ~PTAC monomer solutions is practiced primarily by slurr~ing added charcoal which has been finely divided and powdered with solutions of the MAPTAC monomer in water. This charcoal slurry is then stirred for approximately an hour followed by filtration to remove the suspended charcoal particulates and the adsorbed impurities.
An initial orange-colored solution of ~APTAC, thus treated, yielded a clear straw yellow solution after carbon adsorption and filtration.
The quantity of activated charcoal necessary to remove the unwanted impurities was found to be approximately 5% by weight of the monomer solutions to justify the additional cost and inconvenience of using this much more activated charcoal. Therefore, a preferred embodi-ment would include the use of up to 5% activated charcoal in a slurry of the MAPTAC monomer solution, followed by agitation for approximately one hour, and eventually followed by filtration of the activated charcoal adsorbant and adsorbed impurities from the ~APTAC monomer solution. This pre-purified monomer solution would then be used in the synthesis of the unique latex copolymers of the instant invention.
The quality of the monomer is obviously improved as can be judged by the higher molecular weights obtained from this pre-purified monomer solution when it is used to achieve the polymers of this instant invention. The data in Table I elo~uently demon-strates the improved molecular weight, as judged by ~he higher intrinsic and reduced ~iscosities, of the polymers which are synthesized using the pre-purified MAPTAC monomer solutions.

~133788 TABLE I
MAPTAC-ACRYLAMIDE LATEX COPOLYhlERS
Monomer V-64 Sample Ratio Ml [RSV] K'lCatalyst Comments l 18/82 9.71 -- --- 0.4% No i-PrOH
2 18/82 8.67 -- --- 0.2% 0.2% i-PrOH
3 30/70 6.01 -- --- 0.2% No i-PrOH
4 30/70 6.10 -- --- 0.2% 0.2% i-PrOH
30/70 6.398.1 --- 0.2% 0.2% i-PrOH
18% NaCl FR=77-73%
! 6 25/75 8.5510.8 0.68 0.2%
` 7 23/77 8.9611.0 0.56 0.3% beads 8 20/80 9.4611.8 0.57 0.3%
9 11/89 11.717.1 0.87 0.3% beads 11/89 12.817.6 0.65 0.3% 0.3% i-PrOH
11 11/89 12.915.9 --- 0.3% 0.2% i-PrOH
12 ll/89 10.813.7 0.73 0.3% 0.3% i-PrOH

1 I-luggin's Constant - 18 -:

1~337~8 TABLE I (Continued) MAPTAC-ACRYLAMIDE LATEX COPOLYMERS
Monomer V-64 Sample Ratio hll [RSV~ K'Catalyst Comments la 5/95 17.2 25.1 0.60.5%
2a 10/90 12.0 16.5 0.680.5%
; 3a 10/90 16.8 20.7 0.310.5%
4a 10/90 11.8 15.5 0.610.5%
5a 10/90 13.4 17.9 0.550.5%
6a 10/90 12.4 16.3 0.560.5%
7a 10/90 11.5 15.8 0.730.5%
8a 10/90 12.1 16.0 0.600.5%
9a 10/90 11.6 16.3 0.780.5%
10a 10/90 13.1 17.9 0.610.5% low polymer solids lla 11/89 9.66 14.4 1.10.3% FR-91-87%
12a 11/89 12.2 19.4 1.10.4%
13a 11/89 15.2 21.2 0.570.5%
14a 11/89 16.1 20.7 0.390.3% h~PTAC
Charcoal treated FR=87-85%
15a 15/85 12.5 17.5 0.700.3% h~PTAC
Charcoal treated 16a 15/85 11.9 17.2 0.820.5% MAPTAC
Charcoal treated 17a 15/85 13.6 19.8 0.740.5%
18a 15/85 14.5 18.4 0.420.5%
l9a 15/85 12.3 16.5 0.610.5%
20a 15/85 10.8 13.9 0.590.5%

;;J`' 1133781~

TABLE I
~Continued) Monomer V-64 SampleRatlo Ml [RSV] K ' Catalyst Comments lb 15/85 13.i 16.2 0.41 0.5%
2b 15/85 14.5 19.5 0.52 0.5%
3b 15/85 12.0 16.5 0.68 0.5%
4b 15/85 11.6 15.7 0.69 0.5%
5b 15/85 12.6 16.2 0.50 0.5% low polymer solids 6b 20/80 12.1 15.7 0.55 0.5%
7b 25/75 5.56 8.93 2.4 0.3%
8b 25/75 6.51 10.2 1.9 0.3% additional hour at 46-47C
9b 25/75 6.24 9.61 1.9 0.3% 35% conversion before post-heat 10b 25/75 7.88 12.1 1.5 0.3% MAPTAC
ion-exchanged llb 25/75 11.1 16.6 1.1 0.3% MAPTAC
Charcoal treated 12b 25/75 11.6 13.2 0.26 0.3% NaHSO3 13b 25/75 10.4 12.8 0.5 0.4%
14b 25/75 13.6 15.2 0.19 0.5%
15b 25/75 12.4 15.5 0.45 0.5%
16b 25/75 13.8 17.5 0.43 0.5% MAPTAC
Charcoal treated 17b 25/75 11.1 13.6 0.45 0.5% NaHSO3 18b 25/75 11.7 14.5 0.45 0.5% No i-PrOH
l9b 25/75 11.5 14.0 0.42 0.5% 3X i-PrOH
20b 25/75 10.6 13.3 0.54 0.5%
21b 25/75 11.3 13.7 0.41 0.5%

_ 20 -~ '' ','' ~3378~

TABLE I
~Continued) Monomer V-64 SampleRatio Ml [RSVJ K' Catalyst Comments lc 25/75 10.4 13.5 0.65 0.5%
2c 25/75 10.0 12.2 0.48 0.5%
3c 25/75 9.49 11.8 0.58 0.5% low polymer solids 4c 25/75 10.1 13.4 0.72 0.3% MAPTAC
Charcoal treated 5c 25/75 10.1 13.3 0.71 0.3% MAPTAC
Charcoal treated 2200 ppm MEHQ
added hack 6c 25/75 10.6 14.1 0.69 0.6%
7c 40/60 5.51 6.59 0.79 0.5%
8c 40/60 10.7 14.2 0.66 0.5% MAPTAC
Charcoal treated 9c 40/60 7.52 8.87 0.53 1.0%
lOc 40/60 8.46 10.2 0.53 1.5%
llc 60/40 3.72 4.05 -- 0.5%
12c 60/40 7.45 8.79 0.54 0.5% MAPTAC
Charcoal treated :~337i~38 TABLE I (Continued) MAPTAC-ACRYLAMIDE LATEX COPOLYMERS
Monomer V-64 Sample Ratio Ml[RSV] KlCatalyst Comments ld 25/75 6.84 9.0 1.1 0.4%
2d 25t75 7.910.9 1.10.5% 2X i-PrOH
3d 25/75 9.211.8 0.680.6% 2X Versene 4d 25/75 lO.313.5 0.680.3% MAPTAC
Charcoal treated (5%3 5d 25/75 10.414.6 0.85 0.4% MAPTAC
Charcoal treated (10%) 6d 25/75 11.414.4 0.51 0.5% MAPTAC
Charcoal treated (5%) 7d 40/60 6.82 8.4 0.75 1.0%
8d 40/60 8.78 10.2 0.42 0.5% MAPTAC
Charcoal treated ~5%) 9d 40/60 8.98 10.8 0.51 0.6% MAPTAC
Charcoal treated (10%) 10d 40/60 ~.93 10.3 0.38 0.75% MAPTAC
Charcoal treated ~5%) ,, .

~// 1133788 . ~ Friction Reduction To illustrate the advantageous use of the polymer latices ¦ of the invention as friction reduction agents, the following test method was used:
The apparatus used to measure friction reducing activity consists of a stainless steel mixing tank from which fluid is circulated into an 8' x 3~8" stainless steel pipe and back into the tank by a progressive cavity pump. During operation, the pressure drop across a 4' section of the pipe is measured by 2 pressure transducers. A 10 volt excitation voltage is applied to the trans-ducers and the millivolt output is recorded.
To evaluate polymers for friction reduction, the closed loop system is filled with base fluid~ A zero friction reEerence line is recorded with the pump at rest. Pumping action is then begun to mark the 100% friction line. After 100% friction is established, the sampl~ to be tested is injected directly into the mixing reservoir and the time is noted. Friction reduction measure-ments are then recorded for 7 minutes.
Percent friction reduction is expressed as:

MV sample - Mu zero friction 1 X 100 MV 100% friction - Mu zero friction~
Generally, the copolymers are used as friction reducers at a dosage between the range of 250 - 2500 ppm; preferably, between the range o~ 250 - 1000 ppm; and most preferably, between the range of 250 - 500 ppm.
¦¦. The s~lts of this test are shown in Table II.

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o~ o~ o~ o~ o~ o~ ~ . o~O o~O o~O o~O o~O o~O X
. t~') V N 1~ '~t O V ~--1 N O t~ ~ Il>

U~ t~ 1 1` ~ ~d O In Ll~ Il) .,1 1_ 1~ ~ o~o ~ N N N
a~ l ~ C7~ ~) 0~ N
V~
- 31~ -.
~, ~ s indicated, the materials are exceptional ~lhen used as a ¦ fine and filler retention aid. They are employed at dosages adopted ¦¦ to give between .1 to 8 lbs. per ton of a 30% copolymer. Prefer-ably,they are used between .5 to 5 lbs. per ton and, most preferably I between .75 to 3 lbs. per ton. The use of these copolymers for ¦ this purp(se is set forth below as Table III.
. ~

.

~3:3~7i~E~

TABLE III
PT.~C-t~CRYL~1~llDE LATcX COPOLY~,IERS AS PAP~R ~ETE~TIO~ IDS

Monomer Sam~le Ratio /~/ Paper RR~(Polymer ~=1.0) RR (Polymer B=l.O) 5/95 17.2 0.54 0.87 2 10l90 13.4 0.46 0.80 3 15/85 12.5 0.45 o.
4 ~0!80 1 z. 1 0.47 0.8~
z5/75 13.~ 0.36 0.7s

6 40/60 10.7 0.27 0.57

7 6~ o 7.~5 0."6 3 0.79 0.47 ~Polymer B ) _ Replacement Ratio 2 - Polymer A: Latex copolymer of 25/75 wt. ratio dimethylaminoethylmeth-acrylate dimethyl sulfate quaternary acrylamide.
3 - Polymer B: A slngle component latex of 12.5/87.5 weight ratio dimethyl-aminoethyl methacrylate dimethyl sulfate quaternary/acryl-amide.

' ~33'78B

The replacement ratio is defined as the weight of a compound used to obtain a desired test result divided by the weight of a standard or known material which is efficacious in obtaining t}le desired results. For example, if a solid dispersion in water was being used to test the effectiveness of a polyelectrolyte for solid settling, a compound having known efficacy, for the most part a commercially available product, would first be tested at its effective dosages. Once the optimum dosage of this commercially available polyelectrolyte has been determined, the testing of candidate replacement polyelectrolytes is initiated. If the weight or amount of candidate replace-ment is found to be equal to weight or amount of commercially available ma-terial required to perform the settling tests with identical results, the candidate material is judged to have a replacement ratio of unity.
If, on the other hand, the candidate material is 30% less effi-cient, i.e. it required 130% by weight of the amount of the standard material to obtain the identical result, the replacement ratio is said to be 1.3. If the candidate material is 30% more efficient, i.e. it requires only 70% by weight of the amount necessary to obtain the identical results with the com-parison compounds, the replacement ratio is said to be 0.7.
Sludge Conditioning MAPTAC-acrylamide copolymers prepared with 5 - 60 weight % cationic monomer showed encouraging results when tested in the laboratory for sludge dewatering activity. The trend indicated that the higher the cationic con-tent, the more effective was the polymer. A 40/60 MAPTAC-acrylamide copoly-mer had R.R. = 0.9 versus Mannich solution polymer of low molecular weight polyacrylamide. In evaluations at high pH a 40/60 MAPTAC-acrylamide copoly-mer (/~/=5.51) and a 60/40 copolymer ~/~/=7.45) were equivalent to ~R.R. =
1.0) and slightly better (R.R. = 0.9), respectively, than Mannich quaternary of low molecular weight latex polyacrylamide.

~37~8 Ho~ever, from limited ield eyaluations MAPTAC's C25-4Q~ were generally le~s effective than ~annich quaternary of low molecular weight latex polyacr~lamide in locations where high cationic charge products are required.
Generally, the copolymer latexes are used at a dosage between the range of 5 to 60 lbs. per ton, preferably, between the range of lO to 50 lbs. per ton; and most preferably, between the range of 15 to 25 lbs. per ton.

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOW:

1. A water-in-oil emulsion which contains dispersed in the aqueous phase particles of a water soluble copolymer having a ratio varying between 5 - 60 parts by weight of methacrylamidopropyltri-methylammonium chloride (MAPTAC) to 95 - 40 parts by weight of acrylamide, said emulsion having the following composition:
a. from 5 - 60% by weight of the MAPTAC acrylamide co-polymer;
b. from 20 - 90% by weight of water;
c. from S - 75% by weight of a hydrophobic liquid;
and d. from 0.1 - 21% by weight of a water-in-oil emulsifying agent.

2. The water-in-oil emulsion of Claim 1 where the emulsion has the following composition:
a. from 20 - 40% by weight of the MAPTAC acrylamide co-polymer;
b. from 20 - 70% by weight of water;
c. from 5 - 40% by weight of a hydrophobic liquid;
and d. from 1 - 51% by weight of a water-in-oil emulsifying agent.

3. The water-in-oil emulsion of Claim 1 where the emulsion has the following composition:
a. from 25 - 35% by weight of the MAPTAC acrylamide co-polymer;
b. from 30 - 55% by weight of water;

c. from 20 - 30% by weight of a hydrophobic liquid;
and d. from 1.2 - 10% by weight of a water-in-oil emulsifying agent.

4. The water-in-oil emulsion of Claim 1 being further characterized as containing from 0.1 to 10% by weight of a compatible water-soluble surfactant having an HLB within the range of 9-1/2 to 16.

5. A method of dewatering municipal and industrial sewage sludges which comprises treating said sludges prior to dewatering with from 5 - 60 lbs. per ton of the water-in-oil emulsion of Claim 1.

6. A method of dewatering municipal and industrial sewage sludges which comprises treating said sludges prior to dewatering with from 5 to 60 lbs. per ton of the water-in-oil emulsion of Claim 2.

7. A method of dewatering municipal and industrial sewage sludges which comprises treating said sludges prior to dewatering with from 15 to 25 lbs. per ton of the water-in-oil emulsion of Claim 3.

8. A method of improving fine and filler retention which comprises treating paper pulp prior to sheet formation with from .1 to 8 lbs. per ton based on a 30% copolymer containing water-in-oil emulsion of Claim 1.

9. A method of improving fine and filler retention which comprises treating paper pulp prior to sheet formation with from .5 to 5 lbs. per ton based on a 30% copolymer containing the water-in-oil emulsion of Claim 2.

10. A method of improving fine and filler retention which comprises treating paper pulp prior to sheet formation with from .75 to 3 lbs. per ton based on a 30% copolymer containing water-in-oil emulsion of Claim 3.

11. In a process wherein an aqueous fluid is pumped in turbulent flow under substantially steady state conditions, the improvement which comprises admixing with the aqueous fluid from 250 to 2500 parts permillion of the copolymers of Claim 1.

12. The composition of Claim 1 where the MAPTAC monomer used has been purified by treating an aqueous solution thereof with about 5% by weight of activated carbon.