Anda di halaman 1dari 9

United States Patent [19] [11] Patent Number: 4,668,747

Cadel et al. [45] Date of Patent: May 26, 1987

[54] PREPARATION OF WATER SOLUBLE [56] References Cited

pH 3,344,100 9/1967 Donat et al. ..................... .. 260/23.7
3,929,751 12/1975 Gcrshberg ...... .. 526/303.1
[75] Inventors: Jeffrey S. Cadel, Camillus; Eric H. 4,024,040 5/1977 Phalangas et a1. 526/303.l
[73] Assignee: Allied
Marcellus Morris
of OTHER Sekmakas
Ct al. ................ ..

TOWnShiP, Morris County, N-J- Chemical Abstract No. 91212464511.

[21] Appl. NO: 761,089 Chemical Abstract No. 90:187925d.
_ Primary Examiner-Joseph L. Schofer
[22] Flled: Aug- 2, 1985 Assistant Examiner-Peter F. Kulkosky
Attorney, Agent, or Firm-Jay P. Friedenson
Related U.S. Apphcation Data [57] ABSTRACT
[63] commuanon'm'part of Ser' No 653253 Sep' 24 1984 Use of dicarboxylic acid in the preparation of cationic
abandoned. . .
water soluble polymers useful in ?occulation of sus
[51] Int. C13 ......................... .. C08F 2/32; C08F 2/00; pended solids in various waste waters is disclosed. The
C08F 220/60 dicarboxylic acids are shown to improve stability of
[52] U.S. Cl. .................................. .. 526/216; 526/307; cationic functionality and enhance distribution of
526/281; 526/292 L Charge.
[58] Field of Search ................... .. 526/303.l, 214, 216,
526/225, 307 10 Claims, 1 Drawing Figure




O 1 2 a 4
U. S. Patent May 26, 1987 4,668,747



o 1 2 s 4
TIME (wsexs)
1 2
The acidi?cation of a mixture containing ethyleni
PREPARATION OF WATER SOLUBLE CATIONIC cally unsaturated cationic and nonionic monomers is
ACRYLAMIDE POLYMER AND PRODUCT USING described in U.S. Pat. No. 3,929,751 (Gershberg); U.S.
WEAK ACID TO ADJUST PH Pat. No. 4,195,147 (Sekmakas, et al); and U.S. Pat. No.
4,024,040 (Phalanges, et al.).
DESCRIPTION The work of Gershberg discloses the addition of
sulfuric acid to adjust the pH of an aqueous phase reac
This application is a continuation-in-part of our appli
tion containing various monomers including cationic
cation Ser. No. 653,253 ?led Sept. 24, 1984, now aban monomers described in this invention. The pH range
doned. considered optimum for the invention described by
This invention relates to the use of acids in conjunc
Gershberg is clearly outside that considered optimum
tion with and to improve the performance and stability for the present invention and the use of strong acids
of cationic water soluble water treatment polymers does not give the desirable results of the weaker acids
having a quaternary amine functionality, and copoly disclosed as suitable in the present invention.
mers thereof, with ethylenically unsaturated monomers. Phalanges, et a1. discloses polymerization by radia
These polymers may be prepared by reaction in the tion in the range of pH 2 to 5 for the purpose of prevent
presence of free radical initiators or ionizing radiation. ing certain aluminum salts from precipitating out of
In the invention dicarboxylic acid is used to improve solution. These aluminum salts are in solution for the
the performance and stability of cationic water treat purpose of preventing crosslinking of the polymer
ment polymers. The procedure can be used in both which will occur as the conversion of the monomer
solution and emulsion (water/oil) reactions. The perfor nears completion. Phalanges does not disclose the ad
mance of water treatment polymers of this kind relates vantages of any particular type of acid, nor the bene?ts
to the dewatering capability of the polymer based on a of using acids other than those preventing the precipita
SFR (speci?c ?lter resistance) test of total drainage of tion of salts present in the system of that patentee.
the supernatant through the sludge in comparison to Sekmakas, et al. discloses the use of acids in the prep
dose. Stability relates to the performance of the poly aration of tertiary amine copolymers for use in electro
mer and retention of cationic charge. coating by neutralizing the amine functionality with
The performance of cationic polymer can be related various acids to a pH in the general range of 5 to 7. This
to a number of different variables including: (1) molecu pH range is outside the range of interest in the present
lar weight, (2) charge, (3) charge distribution. The invention. As the functional group involved in Sek
method of this invention involves the effect on the makas, et al., is a tertiary amine, the chemical nature of
charge distribution in the polymer during the course of the compounds is completely at variance with the sub
the reaction through the use of a dicarboxylic acid, and ject of this invention. In fact, Sekmakas discusses this
buffering capability in the reaction mass to maintain the possibility and rejects it as not feasible because of the
desired charge in the polymer after the completion of large amount of acid required to neutralize the amine
the reaction. salt functionality.
The use of these cationic polymers is widespread. A need accordingly exists for a means to enhance the
They are useful as drainage aids, ?otation aids, retention electrolytic stability of the cationic functionality of
aids, process water ?occulants, and in the manufacture acrylamide polymers and to improve the relative reac
of paper and paper products, waste effluent treatment, 40 tion rates of acrylamide and the cationic comonomer.
oil recovery operations, and mining operations.
The major dif?culty in preparing these cationic prod SUMMARY OF THE INVENTION
ucts relates to the differences in reactivity between the In accordance with the invention, an acid additive is
acrylamide (the major backbone in these polymer for utilized to control the polymerization to produce a
mulations) and the cationic co-monomers. In the prior more uniform comonomer rate of reaction.
art, in an effort to attain better co-monomer distribution The presence of acid in the resulting cationic product
in the copolymer, the cationic co-monomer was added increases its shelf life and hydrolytic stability. Particular
in increments over the course of the reaction to prevent processing advantages include the elimination of the
the homopolymerization of the cationic monomer sub requirement of continuous feed of cationic monomer
strate and force the reaction between the monomers and the resulting potential contamination of the reaction
present. A second problem is the lack of hydrolytic mass with air, and the production of solution gel prod
stability of quaternary cationic monomers and the re ucts of good charge distribution where continuous mon
sulting polymers; a means for suppressing this hydro omer feed is impractical because of the high viscosity
lytic degradation would therefore be desirable. and blending dif?culties inherent in the production of
Cationic water soluble polymers have been found to 55 solution gels.
be relatively dif?cult to produce and apply because of In accordance with the invention, novel polymeric
the poor hydrolytic stability of the product polymer compositions having exceptionally well distributed and
and in the case of most cationic monomers, dif?culties active cationic charge are prepared. These materials are
occur in the polymerization because the relative reac - highly useful in ?occulation, sludge dewatering as re
tivities of the cationic monomers are much higher than 60 tention and ?otation aids and other water treating appli
the usual comonomers. The high reactivity of the cati cations. These water soluble polymers contain segments
onic monomers leads to production of an initial fraction of acrylamide or methacrylamide, acrylic acid or meth
during the copolymerization of material that is exces acrylic acid, salts thereof, dimethylamino ethyl methyl
sively high in cationic content and a later fraction al acrylate quaternary salts, and other ethylenically unsat
most devoid of cationic content. Materials polymerized urated comonomers containing quaternary amine func
in this fashion do not exhibit the same application activ tional groups.
ity as materials produced with an even distribution of Typical quaternary amine cationic monomers in
charge during the polymerization. clude: l-trimethylammonium-Z-hydroxypropylmetha
4,668,747 4
crylate methosulfate, trimethylammonium-Z-hydroxy Products of this type are commonly manufactured by
propylacrylate methosulfate, l-trimethylammonium-2 a process consisting of the steps of raw material prepa
Z-hydroxypropylacrylate methosulfate, 3-metha ration, homogenization, reaction and product ?nishing.
crylamidopropyltrimethylammonium chloride, dime Raw material preparation is accomplished by mixing
thylaminoethylmethacrylate methylchloride quat, and the components of the aqueous and oil phases together
the like. The repeating monomer units of the polymer in two separate vessels and often adjusting the pH of the
will include anywhere from 1-70 mole % of the cati aqueous phase.
In the case of acrylamide-dimethylaminoethyl meth
onic monomer with the remainder being a nonionic
substrate such as: acrylamide, methacrylarnide, N
acrylate methyl chloride quaternary salt copolymeriza
tion, for example, the steps of raw material preparation
rnethyl acrylamide, N-methylmethacrylamide and the
are as follows:
like. The acid employed in the copolymerization may be 1. The addition of the required quantities of acrylam
a mineral acid, an organic carboxylic acid as a dicarbox ide, dimethylaminoethyl methacrylate methylchloride
ylic acid. Dicarboxylic acids, particularly adipic and quat, and deionized water.
succinic acids are preferred. 15 2. The addition to the above mixture or a quantity of
An object of the invention is the provision of a pro acid to adjust the pH to a value between 1.0 and 4.0,
cess for the development of cationic water soluble poly preferably between 3.0 and 4.0.
mers having excellent charge distribution and cationic 3. The addition of diethylene triamine penta acetic
charge stability. Polymers manufactured by this process acid, pentasodium salt to chelate the copper present as a
have many advantages over these currently available. polymerization inhibitor in the acrylamide and cationic
The primary advantage is improved charge distribution monomers.
over current systems. Another object of this invention 4. The oil phase is prepared by placing the required
is not to necessarily neutralize an amine salt functional amount of oil in the ultimate reaction vessel and mixing
ity but to provide a pH where the monomers described in the appropriate water-in-oil emulsifying agents.
are hydrolytically stable and where the copolymeriza 25 Under some conditions, it may be necessary to heat
tion kinetics are most favorable. Other advantages in the oil to ensure the good dissolution of emulsifying
clude increased activity and shelf life of the resulting agents. This is particularly true in the 'cases where mate
products, increased performance in high pH applica rials such as, sorbitan monostearate and other emulsify
' tions, and production of the material in various forms ing agents which are solid at ambient temperatures.
. including solutions, solution gels and emulsions. 30 Illustrative water-in-oil emulsifying agents that can
The invention permits the preparation of novel water be used are sorbitan monooleate, sorbitan monostearate,
I treatment polymers containing at least a small propor and ethoxylated derivatives of the former.
tion of cationic functionality provided by the comono Oils can be of the general classes of mineral oils,
mer. These new ?occulant compositions are obtained deodorized kerosene or solvents such as xylene. A pre
by polymerizing ethylenically unsaturated monomers ferred class of oils are deodorized kerosenes with an
containing quaternary amine functionalities with essen aromatic content below 10%.
tially nonionic monomers to obtain a polymer contain 5. The aqueous phase is then pumped into the reac
ing an improved charge distribution in the presence of tion vessel with agitation in the reaction vessel. The
acid. addition of aqueous phase to the oil assures proper ini
.- This invention can be applied to polymerizations 40 tial formation of a water-in-oil emulsion.
conducted in aqueous solutions, solution gels and emul 6. Homogenization of the resulting reaction mass can
sion products. The polymerization can be initiated by be accomplished by several means. Immersion homoge
nizers, external recirculation through colloid mills or
free radical initiators such as ammonium persulfate, 2,2
ultrasonic dispersion equipment and pumping the mate
azobis(2,4 dimethyl valeronitrile) and by UV light, rial at high pressure through small ori?ces can all be
gamma radiation and other ionizing radiation. One par" used effectively. The selection of the equipment to be
ticularly desirable implementation of the subject inven used will, in large part, be determined by the surface
tion is the production of cationic polymers in emulsion active properties of the water-in-oil emulsion formed in
form. _
Step 5. The key parameters are the average particle size
Additional objects and advantages of the invention and particle size distribution of the resulting emulsion.
will become apparent from the description and exam Normally it is suf?cient that all particles be below 5
ples provided hereinafter. microns in diameter and the average particle size be
7. The polymerization of the reaction mass must be
Illustrated in the ?gures of Drawing 1 is the effect of preceded by an inert gas purge to eliminate dissolved
the various types and level of acids on the stability of oxygen which suppresses the reaction. Nitrogen is most
the charge present on the product polymer. The draw commonly used for this. Once the dissolved oxygen is
ing is further discussed in conjunction with Example 9. removed, the free radical initiator is added. Various oil
soluble azo initiators are commonly used. Operating
temperature and amount of initiator should be selected
EMBODIMENT so that the reaction rate is as high as possible in large
The inverse emulsion products of this invention con scale vessels (>250 gallons) within heat transfer limita
sist of a continuous oil phase composition in which tions to minimize cleaning problems.
microscopic droplets of a dispersed aqueous phase con ' 8. Once the reaction is completed, a detergent which
taining the water soluble polymer are present. Also 65 aids in the release of the polymer must be added. This
present in the system are various surfactants which help detergent is most typically an ethoxylated nonylphenol
stabilize the emulsion and aid in the release of the poly and it is added at a level of 1.0m 4.0% relative to the
mer at the point of end use. overall reaction mass. This must be added gradually to
5 6
allow even distribution in the reaction mass. The result complete the activator was added to the emulsion poly
ing product is then ?ltered to remove any suspended mer. The results of the monomer analysis are set forth
coagulum and packaged. below in Table I.
The effectiveness of the cationic emulsion polymer is TABLE I
evidenced in the examples presented hereinbelow.
Because of the particularly high molecular weights Time (hrs) AM (%> QM (%) <1 (QM)/d (AM)
and activities of the subject polymers, they are espe 0.00 1 1.08 30.70 _
cially effective in applications such as thickening 2.00 10.19 27.32 3.73
4.50 6.93 5.45 6.73
agents, and ?occulants as well as in applications such as, 5.50 1.92 0.00 1.09
centrifuge sludge dewatering where they generally 6.50 0.40 0.00 0.00
function at low concentrations. They show particular 7.50 0.22 0.00 0.00
advantages, for example, in sewage treatment to
thicken, dewater and remove phosphorus therefrom; in The ratio of disappearance of QM to acrylamide is
mineral processing to flocculate slimes and slurries and shown in the fourth column. The ratio should be as
in paper manufacture to retain pigment, improve 15 constant as possible over the course of the reaction to
strength or alter the conductivity. insure good charge distribution.
The invention also contemplates copolymers and
terpolymers obtained by polymerization of mixtures of EXAMPLE 2
these monomers as well as water soluble mixtures of
such monomers with various other polymerizable mon 20
The procedure of Example 1 was followed except
omers in relative proportions that yield water soluble that hydrochloric acid was added to adjust the pH of
copolymers. Various copolymers may include acrylam the aqueous phase to pH 3.5. The results are summa
ide, methacrylamide, acrylonitrile, acrylic acid and salts rized in the following Table II.
thereof, dimethylamino ethyl methacrylate and quater TABLE II
nary salts thereof and other ethylenically unsaturated 25 Time (hrs) AM (%) QM (%) d (QM)/d (AM)
monomers. By selection of monomer combinations, 0.00 1 1.64 29.08 -
polymers which are cationic, anionic, or amphoteric, 2.00 11.22 24.58 10.84
can be made as desired. 4.50 7.57 10.10 3.96
The following examples are illustrative of the inven 6.00 4.38 0.44 3.03
tion. The enumeration of details in the examples should 6.50 1.84 0.00 0.17
7.00 0.89 0.00 0.00
not be interpreted as limitations except as may be ex
pressed in the appended claims. Parts are parts by
weight unless stated otherwise.
EXAMPLE 1 The procedure of Example 1 was followed except
A cationic copolymer was produced using the fol that succinic acid was used to bring the pH of the aque
lowing ingredients: ous phase to 4.7. The results are summarized in the
following Table III.
Material Quantity TABLE III
Acrylamide (50% aqueous solution) (AM) 110.0 grams Time (hrs) AM (%) QM (93) d (QM)/d (AM)
Dimethylaminoethylmethacrylate- 175.0 0.00 12.95 32.66 -
Methyl Chloride Quat (75% aqueous 2.00 9.89 21.39 3.69
solution) (QM) 4.50 5.34 1.19 4.44
Deionized water 35.0 6.00 . 1.41 0.00 0.30
Paraf?nic Solvent 150.0 45 7.00 0.52 0.00 0.00
Ethoxylated Lauryl Alcohol 8.75
Sorbitan Monooleate 8.75
Ethoxylated Nonylpheno] (activator) l5
Pentasodium salt of diethylenetriamine 0.1 EXAMPLE 4
pentaacetic acid
2,2-azobis (2,4-dimethyivaleronitrile) 0.015 50 The procedure of Example 1 was followed except
that succinic acid was used to bring the pH of the aque
All components, except surfactants, initiator and oil ous phase 3.5. The results are summarized in the follow
were combined and mixed while agitated in a vessel ing Table IV.
until homogeneous to form the aqueous phase. The pH TABLE IV
of the aqueous phase was measured and found to be 5.3. 55 Time (hrs) AM (%> QM (%) <1 (om/a (AM)
The oil and surfactants were combined in an agitated, 0.00 11.21 28.16 -
temperature controlled reactor. 2.00 10.47 25.86 3.09
The aqueous phase was then added to the reactor 4.50 11.00 11.62 5.77
containing the oil-surfactant blend with mixing. This 6.00 5.09 1.14 3.60
forms a crude emulsion. A homogenizer was then used 7.00 2.19 0.00 0.39
7.50 1.12 0.00 0.00
to decrease the particle size to below 5 microns before
The emulsion was then purged with nitrogen for
about one hour and then the reaction mass was heated
to 40 C. The initiator was then added and the reactor 65 The procedure of Example 1 was followed except
was then re?uxed for ten hours. Samples were taken that adipic acid was used to bring the pH of the aqueous
during the polymerization and analyzed for monomer phase 3.5. The results are summarized in the following
content by HPLC. When the reaction was substantially Table V.
7 8
TABLE V polymer to the sludge to be dewatered, ?ltering the
_ ?occulated sludge and monitoring the quantity of ?l
Tme (hrs) AM (%) QM (%) d (QMW (AM) trate drained over time.
Q00 11-14 27-64 " The SFR (speci?c ?lter resistance) is calculated by an
2'00 865 16'89 4'30 5 equation comparing the ?ltrate drained over time and a
4.50 4.88 1.15 4.18
6.00 1.78 0.00 0.37 number of parameters:
7.00 0.80 0.00 0.00
It is noted that when carboxylic acids are used, the
ratios of monomer disappearance are much more con- 0 wilirgme
Stant' v=Volume of ?ltrate
EXAMPLE 6 W=Weight of solids deposited per unit volume of
A cationic copolmer was produced using the follow- p ?llirgstglute viscosity of the water
mg ingredients usmg the procedure of Example 1. Apzpressure drop across the sludge cake
A=Cross-sectional area of the cake
Material Quantity a=Speci?c resistance of the sludge cake
Acrylamide (50% aqueous solution) (AM) 180.16 grams Plotting t/v vs v, and all the parameters are known
Dimethylamin'o?thylimeihacrylale- 43-38 20 except for a (speci?c resistance of the sludge cake); a
Qua (75% aquems can then be calculated by measuring the slope of the t/v
Deionized water 3540 vs-Y curve in the initial linear region.
Paraf?nic Solvent 150.0 Varying the dosages of the polymer, a series of points
Ethqxylated Lauryl A1h1 3-85 with different SFRs can be found for the polymer of
lsictgggtgllaxg?gley?henol (activator) if; 25 interest on a sludge, showing the dewatering ability of
pentasodium Salt of diethylenetriamine 0_1 that polymer. By using a dlfferent polymer on the same
pentaacetic acid _ _ _ sludge, a comparison between the two polymers can be
??liaizfzi8A4methylvalemmmla 0011(5) observed. A polymer working at lower SFRs use a
p 1 ' lower dose is, according to this well accepted test, the
30 more effective product. Further background informa
tion can be found in Weber, J. Physiochemical Pro
EXAMPLE 7 cesses for Water Quality Control, pp. 566-567 Wiley
The procedure of Example 6 was followed with the Interscience publishers, New York, 1972_
exception that 8 grams of adipic acid were used. The products of Examples 1 through 5 were evalu
EXAMPLE 8 35 ated using the following technique:
. Aliquots of 500 m1ll1l1ters of tap water were placed in
TheProcedure of Example_6_was followed wlth the 800 milliliter ?asks and 2.5 grams each of the products
exception that 12 grams of ad1p1c acld were used. of Examples 1 through 5 were added to each of the

The procedure of EXAMPLE

Example 6 was
9 followed with the 4O $3125-
flasks under
the coniditions
or oneo;a\{ifglprous
our 3 finixitrlllg.
er e a l
excepnon that 16 grams of adlplc acld were used Quantities of the resulting solution were added to 100
Samples of the products f.rom ExalPPles 6 through 9 milliliter aliquots of anaerobic digested sludge obtained
wfege then Stored upder amplent condltlons for a penod from the Syracuse Metrapolitan Waste Water Treat
0. (if weeks Dunng the time. the.samp1es were.analy' 45 ment Plant. Doses used were in the range of 20 to 140
sis .usmg
. a method of charge t1trat1on to determine the - -
parts per m1ll1on of polymer.
catlonlc content of the polymer (other methods, such as The resulting polymer_sludge mix was agitated by
infrared spectroscopy could be suitable). The results are pouring the mixture back and fourth from one mixing
presented below: cup to the next twelve times. The resulting flocculated
TABLE VI 50 sludge was then ?ltered in a 55 milliliter Buchner funnel
Time with a disk of ?lter cloth serving to retain the sludge
(Weeks) Example 6 Example 7 Example 8 Example 9 SOIldS. Filtration rates were then measured and the spe
O 12.48 1198 103 12,5 ci?c ?lter resistances calculated according to the previ
1 11.08 12.06 12.5 11.95 ous discussion. Results are set forth in Table VII below.
2 11.67 10.67 8.06 7.84 55
3 13.34 10.74 7.94 6.69
4 11.7 10.36 8.87 7.69-' TABLE VII
Dose (ppm) SFR (gmZ/sec)
As shown from the foregoing data and by reference Example 1
to the ?gure of the drawing, the general conclusion here 60 1.0413 + 02 1.0015 + 06
is that the cationic charge is relatively stable until a high 1105 + 02 1105 + 05
level of dicarboxylic acid is added. This level corre + 8% + g:
sponds roughly to decreasing the pH below 3. 1:67]; i 02 5:38]; i 05
Example 2
EXAMPLE 1O - 65 8.7013 + 01 6.5OE + 06
The speci?c ?lter resistance test compares the com- 1045 + 02 1605 + 06
parative dewatering capabilities of different polymers i 3% 228g 1 g;
on an individual sludge. The method consists of adding 115215 + 02 1:19]; + 05
ternary amine functional unit distribution which com
TABLE VII-continued
prise acidifying a co-monomer of the formula
Dose (ppm) SFR (gmz/sec)
l.67E + 02 680E + 04 CH2=RCCONH2 (3)
Example 3
1.045 + 02 7.005 + 05 wherein R is H or CH3 with an acid containing carbox
1.205 + 02 2.6OE + 05 ylate groups having a pKa greater than 1 to provide a
1.3615 + 02 7.085 + 04 pH in the range of between about 2.0 and 4.5 and poly
1.445 + 02 6.1015 + 04
1.515 + 02 1.6713 + 06
merizing said monomer (a) with a monomer having
Example 4 quaternary amine units and having the formula
1.045 + 02 9.005 + 05
1.205 + 02 5.905 + 05
1.365 + 02 2.565 + 05
1.445 + 02 1.005 + 05 where R] is H or CH3 and R2 is Cl- or CH3OSO3 and
1.525 + 02 2.285 + 05 polymerizing the mixture of (a) and (b) to substantial
Example 5 completion.
1.045 + 02 7.305 + 05 2. The method of claim 1 wherein the co-monomer
1.215 + 02 2.005 + 05
1.365 + 02 2.705 + 05
mixture contains also a different ethylenically unsatu
1.535 + 02 1.305 + 04 rated monomer.
1.295 + 02 8.205 + 04 3. The process of claim 1, where the acid is dicarbox
ylic acid.
4. The process of claim 3, where the acid is adipic
It is noted that, in general, the performance of the acid.
samples containing carboxylic acids was superior to 5. The process of claim 1, where the acid is succinic
those containing mineral acids and that the samples acid.
with the most favorable reaction rate ratios outper 25 6. The process of claim 1, where the pH is adjusted to
formed those with the less favorable reaction rate ratios. below 4.
It will be understood that various modi?cations may 7. The process of claim 1, where the pH is adjusted to
be effected without departing from the scope of the between 3 and 4.
invention and the several details disclosed herein as 8. The process of claim 1, where the acid is adipic
illustrative are not to be construed as placing limitations acid and the pH is between 3 and 4.
on the invention except as may be required by the reci 9. The process of claim 1 where the acid is succinic
tation in the appended claims. acid and the pH is between 3 and 4. .
What is claimed is: 10. The process of claim 1 wherein the polymeriza
1. A method of preparing a water soluble cationic 35 tion is effected by emulsion polymerization.
# i i i i
acrylamide polymer having more uniform cationic qua



PATENT N0. 1' 4 , 668 , 747
DATED ; May 26, 1987
INVENTUR(S) : Cadel et a1.
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby
corrected as shown below:

Claim 1, Column 10, line 12 of the Patent

"CH2=CHR,COOCH2CH2N(CH3) 3+R2 (b) should read
--CH 2 =CHRlCOOCH 2 CHZN (CH 3)3 +R2 (b) .

Signed and Sealed this

Sixth Day of October, 1987



Arresting O?icer _ Commissioner of Patents and Trademarks

4,668,747 Jeffrey S. Cadel, Camillus; Eric H. Larson, Marcellus, both of NY. PREPARATION
ACID TO ADJUST PH. Patent dated May 26, 1987. Disclaimer ?led March 10, 1997, by the assignee,
Hereby enters this disclaimer to all claims of said patent.
(Of?cial Gazette, April 29, 1997)