Europaisches Patentamt

3 European Patent Office Publication number: 0 142 929

Office europeen des brevets A2

EUROPEAN PATENT A P P L I C A T I O N

Application number: 84306786.9 IntCI.*: C 02 F 5 / 0 8

C 02 F 5 / 1 0
() Date of filing: 05.10.84

@ Priority: 26.10.83 US 545563 (71} Applicant: BETZ EUROPE, INC.

20.03.84 US 591643 4636 Somerton Road
Trevose Pennsylvania 19047(US)
Date of publication of application: @ Inventor: Chen, Fu
29.05.85 Bulletin 85/22 19 Meadow View Drive
Newtown Pennsylvania 18940(US)
@ Designated Contracting States:
BE DE FR GB IT NL Representative: Gore, Peter Manson et al,
W.P. THOMPSON &CO. Coopers Building Church Street
Liverpool LI 3AB(GB)

Water soluble polymers and methods of use thereof.

The present invention relates to the use of water soluble treated metal surfaces when used conjointly with a water
polymers comprising repeat unit moieties soluble orthophosphate source.

<
wherein R, is H or lower alkyl (C,-C3); R2 is OH, OM, or NH2;
0) M is a water soluble cation; R3 is a hydroxy substituted alkyl
CM or alkylene radical having from 1 to about 6 carbon atoms or
O) a non-substituted alkyl or alkylene radical having from 1 to 6
carbon atoms; X is an anionic radical; Z is Hor hydrogens or
N
a water soluble cation or cations which together counter-
balance the valence of X, and a is 0 or 1.
These copolymers, and terpolymeric derivatives, can be
used in a method for inhibiting calcium phosphate or
calcium phosphonate deposition in aqueous systems; and
also to function to provide a passivated oxide film along
LU
 The present invention pertains to a composition
and method of utilization of same to inhibit corrosion
and control the formation and deposition of scale
imparting compounds in water systems such as cooling
and gas scrubbing systems.

The problems of corrosion and scale formation and

attendant effects have troubled water systems for
years. For instance, scale tends to accumulate on
internal walls of various water systems and thereby
materially lessens the operational efficiency of the
system.

Corrosion, on the other hand, is a degradative

electro-chemical reaction of a metal with its
environment. Simply stated, it is the reversion of
refined metals to their natural state. For example,
iron ore is iron oxide. Iron oxide is refined into
steel. When the steel corrodes, it forms iron oxide
which, if unattended, may result in failure o r
destruction of the metal, causing the particular water
system to be shut down until the necesary repairs can
be made.
 Due to the recent popularity of c o o l i n g water treat-
ment programs using high levels of o r t h o p h o s p h a t e to promote
passivation of t h e m e t a l surfaces in c o n t a c t with the system
water, it has become c r i t i c a l l y important to c o n t r o l calcium
phosphate crystallization so t h a t relatively high levels of
orthophosphate may be m a i n t a i n e d in the system to achieve the
desired passivation without resulting in f o u l i n g or impeded h e a t
transfer functions which would normally be caused by c a l c i u m
phosphate deposition. Additionally, in c e r t a i n highly alkaline
water systems, calcium phosphonate p r e c i p i t a t i o n has become a
problem when phosphonic acid compounds have b e e n u s e d as p a r t of
the treatment approach to inhibit calcium carbonate deposition.

In accordance with one embodiment of the present

invention, it has been s u r p r i s i n g l y discovered that water -
soluble copolymers, as shown i n F o r m u l a I hereinafter, are
effective in c o n t r o l l i n g the formation of calcium phosphate,
and calcium phosphonate deposits and i n i n h i b i t i n g c o r r o s i o n i n
various water systems. When the polymer is c o n j o i n t l y u s e d
with a water soluble orthophosphate compound, the metal
surfaces in c o n t a c t with the system water are passivated and
therefore corrosion is inhibited without resulting in
substantial deposition of scale thereon.

The water solublecopolymers used in the present

invention have the s t r u c t u r e :
wherein R1 is H or lower alkyl (C1-C3); R2 is OH or OM,
or NH2; M is a water soluble cation; R3is a hydroxy
substituted alkyl or a l k y l e n e radical having from 1 to 6 c a r b o n
atoms or a non-substituted alkyl or a l k y l e n e radical having from
1 to a b o u t 6 carbon atoms; X, when p r e s e n t , is an a n i o n i c
radical selected from the group consisting of S03, P03,
P04, and COO; Z, when p r e s e n t , is H or hydrogens or any w a t e r
soluble cation or c a t i o n s which together counterbalance the
valence of the anionic radical; a is 0 or 1 .

The number average molecular weight of the water

soluble copolymers of FORMULA I may f a l l within the range of
1,000 to 1,000,000. Preferably the number average molecular
weight will be w i t h i n the range of from about 1,500 to 500,000,
with the range of about 1,500 to about 10,000 being even more
highly desirable. The key c r i t e r i o n is that the polymer be
water soluble.
 The molar ratio x:y of the monomers of FORMULA I may
fall within the range of between about 30:1 to 1:20, with the

x:y molar ratio range of from about 10:1 to 1:5 being preferred.

At p r e s e n t , the water soluble polymer preferred for

use in c o o l i n g water systems is:

vherein M is the same as given in FORMULA I. This'polymer

(FORMULA II) is referred to as a c r y l i c acid/allyl hydroxy propyl
sulfonate ether (AA/AHPSE). The IUPAC n o m e n c l a t u r e for AHPSE i s
1-propane sulfonic acid, 2-hydroxy-3-(2-propenyl oxy)-mono
sodium salt.

With r e s p e c t to both repeat units of the polymers of

the present invention, they may e x i s t in acid or water soluble
salt form when used in the desired water system.
 As to p r e p a r a t i o n of the monomer d e s i g n a t e d as x
above, in FORMULA I, acrylic acid is well known. It may be
produced by h y d r o l y s i s of a c r y l o n i t r i l e or via oxidation of
acrolein. Other well known vinyl containing monomers such as
methacrylic acid and a c r y l a m i d e may also be u t i l i z e d as monomer
x of FORMULA I in accordance with the invention.

Turning to the allyl containing monomer, monomer y, in

the FORMULA I above, these may be produced by r e a c t i n g allyl
alcohol with a non-tertiary alcohol in the temperature range of
about 25-150C as is detailed in U.S. Patent 2,847,477 (the
entire disclosure of which is hereby incorporated by r e f e r e n c e )
followed by, if desired, sulfonation, phosphorylation, phosphona-
tion or c a r b o x y l a t i o n of the monomer via well-known techniques.

The p r e f e r r e d allyl hydroxy propyl sulfonate ether

monomers (monomer y FORMULA II) may c o n v e n i e n t l y be prepared via
a ring opening reaction of the epoxy group of an allyl glycidyl
ether precursor. Sulfonation of the epoxy group with sodium
sulfite in the presence of a phase transfer catalyst such as
tetra-n-butylammonium bisulfite or with fuming sulfuric acid
containing sulfur trioxide will produce the sulfonic acid group
and hydroxy group of the AHPSE. The r e s u l t i n g monomer can be
further neutralized with caustic orother basic material. The
reaction is illustrated by the following mechanism:
 Similar ring opening reactions can be c a r r i e d out by
using phosphorous acid and its derivatives including phosphorous
trichloride to obtain the phosphonic acid substituents.

If orthophosphoric acid (H3P04) and i t s deriva-

tives are used in the ring opening reaction, phosphoric acid
ester substituents may be formed in a c c o r d a n c e with the
mechanism:

Such reaction is described in U.S. Patent 2,723,971.

Carboxylate functions can be provided on the allyl

hydroxy propyl ether monomer via the reaction of allyl alcohol
and c h l o r o h y d r o x y butanoic acid according to the mechanism:
 It should be noted that the monomer y (FORMULA I) may
itself be a l l y l glycidyl ether which is commercially available
from s e v e r a l sources.

Z in the allyl monomer, (monomer y of FORMULA I) if

present, may be hydrogen, hydrogens or any soluble cation or
cations which together counterbalance the valence of the anionic
moiety X. Suitable cations include Na, NH4+, Ca, and K.
X, when p r e s e n t , may be chosen from the group consisting of

S03, P03, P04, and COO.

After the desired monomers have been o b t a i n e d , f r e e

radical chain a d d i t i o n p o l y m e r i z a t i o n may proceed in a c c o r d a n c e
with conventional solution polymerization techniques. Polymeri-
zation initiators such as p e r s u l f a t e initiators, peroxide
initiators, etc. may be used. Preferably the requisite monomers
are mixed with water and alcohol (preferably isopropanol). The
resulting polymer may be i s o l a t e d by well-known methods such a s
distillation, etc. or the polymer may simply be used in i t s

aqueous solution.

It should be mentioned that water soluble terpolymers

comprising monomers x and y of FORMULAE I or II may also be
prepared for use as d e p o s i t control agents and/or corrosion
control agents and are fully covered and d e s c r i b e d herein by u s e
of the term "copolymer." For i n s t a n c e , AHPSE monomers may be
incorporated into a water soluble terpolymer backbone having
other repeat units including acrylic acid monomers, alkyl
acrylate monomers, hydroxylated lower alkyl acrylate (C1-C6)
monomers, methacrylic acid monomers, acrylamide monomers, etc.
Such t e r p o l y m e r s may have a molar ratio of from about 30:1 to
1:20 non-monomer y to monomer y r e p e a t units (see Formula I).
 The polymers should be added to the aqueous system,
for which corrosion inhibiting, and/or deposit control activity
is desired, in an amount effective for the purpose. This amount
will vary depending upon the particular system for which
treatment is desired and will be i n f l u e n c e d by factors such as,
the area subject to corrosion, pH, temperature, water quantity
and the respective concentrations in the water of the potential
scale and d e p o s i t forming species. For the most part, the
polymers will be e f f e c t i v e when used at l e v e l s of about 0.1-500
parts per m i l l i o n parts of w a t e r , and p r e f e r a b l y from about 1.0
to 100 parts per m i l l i o n of water contained in the aqueous
system to be t r e a t e d . The polymers may be added directly into
the desired water system in a fixed quantify and in the state of
an aqueous solution, continuously or intermittently.

The polymers of the present invention are not limited

to use in any s p e c i f i c category of water system. For instance,
in a d d i t i o n to cooling water systems, the polymers may also be
effectively utilized in scrubber systems and the like wherein
corrosion and/or the formation and d e p o s i t i o n of c a l c i u m
phosphate and/or calcium phosphonate scale may be a p r o b l e m .

The water soluble polymers of the present invention

can a l s o be used with topping agent components in o r d e r to
enhance the corrosion inhibition and s c a l e controlling
properties thereof. For instance the polymers may be used in
combination with one or more kinds of compounds selected from
the group consisting of inorganic phosphoric acids, phosphonic
acid salts, organic phosphoric acid esters, and p o l y v a l e n t metal
salts. Such t o p p i n g agents may be added to the system in an
amount of from about 1 to 500 ppm.
 Examples of such inorganic phosphoric acids include
condensed phosphoric acids and water soluble salts thereof. The
phosphoric acids include an o r t h o p h o s p h o r i c acid, a primary
phosphoric acid and a secondary phosphoric acid. Inorganic
condensed phosphoric acids include polyphosphoric acids such a s
pyrophosphoric acid, tripolyphosphoric acid and the like,
metaphosphoric acids such as t r i m e t a p h o s p h o r i c acid, and
tetrametaphosphoric acid.

As to the other phosphonic acid derivatives which are

to be added in addition to the polymers of the present invention,
there may be mentioned aminopolyphosphonic acids such as amino-
trimethylene phosphonic acid, ethylene diaminetetramethylene
phosphonic acid and the like, methylene diphosphonic acid,
hydroxyethylidene diphosphonic acid, 2-phosphonobutane 1,2,4,
tricarboxylic acid, etc.

Exemplary organic phosphoric acid esters which may be

combined with the polymers of the present invention include phos-
phoric acid esters of alkyl alcohols such as methyl phosphoric
acid ester, ethyl phosphoric acid ester, etc., phosphoric acid
esters of methyl cellosol-ve and ethyl cellosolve, and p h o s p h o r i c
acid esters of p o l y o x y a l k y l a t e d polyhydroxy compounds obtained
by adding ethylene oxide to polyhydroxy compounds such as
glycerol, mannitol, sorbitol, etc. Other suitable organic
phosphoric esters are the p h o s p h o r i c acid esters of amino
alcohols such as mono, di, and t r i - e t h a n o l amines.

Inorganic phosphoric acid, phosphonic acid, and

organic phosphoric acid esters may be s a l t s , preferably salts of
alkali metal, ammonia, amine and so f o r t h .
 Exemplary polyvalent metal salts which may be c o m b i n e d
with the water soluble polymers of the invention include those
capable of d i s s o c i a t i n g polyvalent metal cations in water such
as Z n , Ni++, etc., which i n c l u d e zinc chloride, zinc
sulfate, nickel sulfate, nickel chloride and so f o r t h .

The water soluble polymers of the present invention

may also be used in c o n j u n c t i o n with water soluble chromate

compounds that are adapted to provide chromate radicals in w a t e r
solutions. Illustrative water soluble chromate compounds
include sodium c h r o m a t e d i h y d r a t e , sodium chromate anhydrous,
sodium chromate tetrahydrate, sodium chromate hexahydrate,
sodium chromate decahydrate, potassium dichromate, potassium
chromate, ammonium d i c h r o m a t e and chromic acid.

In a d d i t i o n , water soluble azole compounds can be u s e d

in c o m b i n a t i o n with the water soluble polymers herein
disclosed. Such azoles have the formula

Included within the scope of the invention are N-alkyl substi-

tuted 1,2,3-triazole, or a s u b s t i t u t e d water soluble 1,2,3-
triazole where substitution occurs at the 4 and/or 5 position of
the ring. The p r e f e r r e d 1,2,3-triazole is 1,2,3-tolyltriazole
of the formula
Other exemplary 1,2,3-triazoles include benzotriazole, 4-phenol-
1,2,3-triazole, 4-methyl-1,2,3-triazole, 4-ethyl-1,2,3-triazole,
5 methyl-1,2,3-triazole, 5-ethyl-1,2,3-triazole, 5-propyl-1,2,3-
triazole, and 5 - b u t y l - 1 , 2 , 3 - t r i a z o l e . Alkali metal or ammonium
salts of these compounds may be u s e d .

Other azole compounds include thiazole compounds of

the formula:

Suitable thiazoles include thiazole, 2 mercaptothiazole,

2-mercapto-benzothiazole, benzothiazole and the like.

The water soluble polymers may also be used in

conjunction with molybdates such as, inter alia, sodium
molybdate, potassium molybdate, lithium molybdate, anmonium
molybdate, etc.

When the water soluble polymer of the invention

(FORMULA I) is added to the aqueous system in c o m b i n a t i o n with a
topping agent component selected from the group consisting of
inorganic phosphoric acids, phosphonic acids, organic phosphoric
acids esters, their water-soluble salts (all being referred to
hereinafter as p h o s p h o r i c compounds), polyvalent metal salts,
chromates, molybdates, and a z o l e s , a fixed quantity of s a i d
polymer may be added separately and in the state of a q u e o u s
solution into the system. The water soluble polymers may be
added either continuously or intermittently. Alternatively, the
polymer may be blended with the above noted topping agent
compounds and then added in the state of aqueous solution into
the water system e i t h e r continuously or i n t e r m i t t e n t l y . The
topping agents are utilized in the usual manner for corrosion-
and s c a l e preventing purposes. For i n s t a n c e , the phosphoric
compounds or p o l y v a l e n t metal salts may be added to a w a t e r
system continuously or intermittently to M a i n t a i n their

necessary concentrations.

Generally, the phosphoric compounds should be p r e s e n t

in the aqueous system in an amount of about 1-100 ppm (as P04)
or the polyvalent metal salts should be p r e s e n t in an amount o f
about 1 to 50 ppm (as metal cation).

As is conventional in the art, the phosphoric compounds

or polyvalent metal salts may be added, as p r e t r e a t m e n t d o s a g e s ,
to the water system in an amount of about 20 to about 500 ppm,
and t h e r e a f t e r a small quantity of c h e m i c a l s may be added, as
maintenance dosages.

The polymers may be used in c o m b i n a t i o n with yet other

topping agents including corrosion inhibitors for iron, steel,

copper, copper alloys or o t h e r metals, conventional scale and

contamination inhibitors, metal ion sequestering agents, and
other conventional water treating agents. Other corrosion
inhibitors comprise tungstate, nitrites, borates, silicates,
oxycarboxylic acids, amino acids, catechols, aliphatic amino
surface active agents, benzotriazole, and m e r c a p t o b e n z o t h i a z o l e .
Other scale and c o n t a m i n a t i o n inhibitors include lignin deriva-
tives, tannic acids, starch, polyacrylic soda, polyacrylic
amide, etc. Metal ion sequestering agents include polyamines,
such as e t h y l e n e diamine, diethylene triamine and the like and
polyamino carboxylic acids, such as n i t r i l o triacetic acid,
ethylene diamine tetraacetic acid, and d i e t h y l e n e triamine
pentaacetic acid.

Examples

The i n v e n t i o n will now be f u r t h e r described w i t h

reference to a number of s p e c i f i c examples which are to b e
regarded solely as i l l u s t r a t i v e , and not as restricting the
scope of the invention.

Example 1- Preparation of A c r y l i c Acid/

Allyl Hydroxylpropyl Sulfonate Ether Copolymer

A suitable-reaction flask was equipped with a mechan-

ical agitator, a thermometer, a reflux condenser, a nitrogen
inlet and two a d d i t i o n inlets for the initiator and monomer
solutions. The f l a s k was charged with 200g of d e i o n i z e d water
and 26g of i s o p r o p a n o l . The r e s u l t i n g solution was then heated
to reflux under a nitrogen blanket. 72g of a c r y l i c acid (1 mole)
and 136g of 1-propane sulfonic acid, 2-hydroxy-3-(2-propenyl oxy)
mono sodium salt [AHPSE] (40%, 0.25 mole) were mixed in a
separate flask so as to provide a mixed monomer solution. The
mixed monomer solution was then transferred to an a d d i t i o n
funnel. An i n i t i a t o r solution containing 27.3% of sodium
persulfate in deionized water was p r e p a r e d separately and
sparged with nitrogen. The i n i t i a t o r solution (20 ml) was t h e n
added to the reaction flask along with the mixed monomer
solution over a period of 2 hours. After this addition, the
resulting mixture was heated for 2 more hours at 85C and
subsequently, 66.5g of the isopropanol/water solution was
stripped off. The r e a c t i o n mixture was then cooled to less than
40C and 60g of 50% c a u s t i c solution was then added.

The s t r u c t u r e of the resulting copolymer was v e r i f i e d

by Carbon 13 NMR. The polymer solution, after being diluted to
25% s o l i d s with water, had a B r o o k f i e l d viscosity of 14.5 cps at
25C. It was a s t a b l e solution with a slightly yellow color.

Example 2

Utilizing both apparatus and p r o c e d u r e similar to that

described in Example 1, 200g of d e i o n i z e d water and 13g of i s o -
propanol were charged to a reaction flask. The solution was
then heated to reflux temperature under a nitrogen blanket. 72g
of a c r y l i c acid and 136g of AHPSE (4@%) were added to a separate
flask so as to p r o v i d e a mixed monomer s o l u t i o n . The mixed
monomer solution was then added to the reaction flask along with
an i n i t i a t o r solution comprising sodium persulfate over a 2 hour
period. The r e a c t i o n mixture was heated for 2 more hours and
subsequently, 36.4g of isopropanol/water solution was s t r i p p e d
off. The m i x t u r e was cooled to lower than 40C and 60g of 50%
caustic solution was a d d e d .
 The r e s u l t i n g polymer solution, after being diluted to
25% with water, had a B r o o k f i e l d viscosity of 19.8 cps (at 25C).

Example 3

Utilizing both apparatus and p r o c e d u r e similar to t h a t

described in Example 1, 15g of i s o p r o p a n o l and 228g of w a t e r
were added to a reaction flask. 72g of a c r y l i c acid (1 mole)
and 180gof AHPSE (40% s o l u t i o n , 0.33 mole) were added to an
addition funnel so as to provide a mixed monomer s o l u t i o n . The
mixed monomer s o l u t i o n w a s then added to the reaction flask
along with a sodium p e r s u l f a t e containing initiator solution
over a 2 hour period. One hour after this addition, a solution
of t - b u t y l hydroperoxide (0.2g in 10 ml of water) was added to
the reaction mixture. The mixture was heated for 1 more h o u r
and s u b s e q u e n t l y , 39.4g of i s o p r o p a n o l / w a t e r solution was
stripped off. The mixture was cooled to lower than 40C and 60g
of 5 0 % c a u s t i c was a d d e d .

The r e s u l t i n g copolymer solution, after being diluted

to 25% s o l i d s , had a B r o o k f i e l d viscosity of 15.9 cps at 25C.

Example 4

Utilizing the apparatus and p r o c e d u r e described in

Example 1, 72g of a c r y l i c acid (1 mole) and 90.8g of AHPSE (40%,
0.167 mole) were used for copolymerization. The r e s u l t i n g
polymer solution, after being diluted to 25%, had a B r o o k f i e l d
viscosity of 14.5 cps (at 25C). The structure of the copolymer
was v e r i f i e d by Carbon 13 NI'4R.
 Example 5

Utilizing the apparatus and p r o c e d u r e as d e s c r i b e d in

Example 1, 72g of a c r y l i c acid (1 mole) and 68.1g of AHPSE (40%,
0.125 mole) were used for copolymerization. The r e s u l t i n g
polymer solution, after being diluted to 25% had a B r o o k f i e l d
viscosity of 15.1 cps (at 25C).

Example 6

Apparatus, procedure and reagent charge similar to

that described in Example 3 were used, except that this time,
AHPSE (180g, 40% s o l u t i o n ) was i n i t i a l l y charged into a reaction
flask along with isopropanol and w a t e r . Acrylic acid (72g) and
sodium persulfate solution were then added to the reaction flask
over a 2 hour period. The r e s u l t i n g copolymer solution, after
isopropanol distillation, caustic addition and water dilution
(to 25% s o l i d s ) had a B r o o k f i e l d viscosity of 22.5 cps at 25C.

Example 7

Apparatus, procedure and r e a g e n t charge similar to

that described in Example 4 were used except that this time
AHPSE ( 9 0 . 8 g , 40% s o l u t i o n ) was charged initially into the
reaction flask along with isopropanol and w a t e r . Acrylic acid
(72g) and sodium persulfate solution were then added to the
reaction mixture over a 2 hour p e r i o d . The r e s u l t i n g copolyn
solution, after isopropanol distillation, caustic addition, and
water dilution, (to 25% s o l i d s ) had a B r o o k f i e l d viscosity of
15.4 cps (at 25C).
 Table I hereinbelow presents a summary of the physical
properties of the copolymers produced in a c c o r d a n c e with
Examples 1 through 7.

Deposit Control Activity

One method of e v a l u a t i n g deposit control activity of a

material consists of measuring its ability to p r e v e n t bulk phase
precipitation of a s a l t at conditions for which the salt would
normally precipitate. It is additionally important to recognize
that the m a t e r i a l being evaluated is tested at "substoichio-
metric" concentrations. That is, typical molar ratios of
precipitating cation to the material being evaluated are on t h e
order of 20:1 and much g r e a t e r . Consequently, stoichiometric
sequestration is not the route through which bulk phase precipi-
tation is prevented. This well known phenomenon is also called
."threshold" treatment and is widely practiced in water treatment
technology for the prevention of s c a l e (salt) deposits from
forming on v a r i o u s surfaces. In the results that follow calcium
phosphate and calcium phosphonate salts have been selected as
precipitants. Inhibition of calcium phosphate is important in
those treatment approaches wherein orthophosphates are used in
the system to promote formation of the passivated gamma i r o n
oxide film along the treated metal surfaces. Presently, in
highly alkaline systems, phosphonic acid derivatives are
commonly used to inhibit calcium carbonate formation. In t h e s e
systems the precipitation of calcium phosphonate has proven to
be a problem. The polymers of the present invention has been
evaluated for their ability to p r e v e n t precipitation (i.e.,
inhibit crystallization) of these salts. The results are
expressed as "percent inhibition", positive values indicate that
the stated percentage of p r e c i p i t a t e was p r e v e n t e d from b e i n g
formed. Except as where noted to the contrary, the following
conditions, solutions, and t e s t i n g procedure were utilized to
perform the inhibition tests, the results of which are reported
herein in Tables II to IVa.

CALCIUM PHOSPHATE INHIBITION PROCEDURE

Procedure

1) To about 1800 ml DIH20 in a 2 l i t e r volumetric flask,

add 20 ml of C a C l 2 ' 2H20 s o l u t i o n followed by 2
drops of conc. HC1.
2) Add 40 ml of Na2HPO4 s o l u t i o n .
3) Bring volume to 2 l i t e r s with DI w a t e r .
4) Place 100 ml a l i q u o t s of s o l u t i o n in 4 oz glass bottles.
5) Add t r e a t m e n t .
6) Adjust pH as d e s i r e d .
7) Place in 70C water bath and e q u i l i b r a t e for 17 h o u r s .
8) Remove samples and f i l t e r while hot through 0.2 u filters.
9) Cool to room t e m p e r a t u r e and take Absorbance measurements
using Leitz photometer (640 nm).
Preparation for Leitz
a. 5 mls f i l t r a t e
b. 10 mls Molybdate Reagent
c. 1 dipper Stannous Reagent
d. Swirl 1 minute, pour into Leitz cuvette;
wait 1 minute before reading.
10) Using current calibration curve (Absorbance vs ppm
P04-3) find ppm PO4-3 of each sample.

Calculation:
 CALCIUM PHOSPHONATE PRECIPITATION INHIBITION PROCEDURE

Conditions: Static Beaker Study; 750 ppm Ca+2 as CaGO3;

pH = 8.7; T = 158F; 18 hour Equilibration Time; 10 ppm
1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) .

Experimental
Prepare following solutions:
Stock Sol'n- 2.206g CaCl2' 2H20 + 0.033g HEDP/2 l i t e r s .
Treatment - 1,000 ppm a c t i v e solutions

Procedure

1) To clean 4 oz b o t t l e add 100 ml of stock solution.

2) Add t r e a t m e n t with stirring.
3) Adjust pH to 8.7 with a dilute NaOH s o l ' n .
4) Place samples in water bath at T = 158F, for 18 h o u r s ,
after which time filter aliquot through 0.2 u filter paper.
5) Analyze filtrate for organic phosphate (TP).

Calculation of % Inhibition
 Ferric Oxide Dispersion

In o r d e r to demonstrate the effectiveness of t h e

polymers of the invention in d i s p e r s i n g suspended particulate
matter, the following procedure, using Fe203 as suspended
solids, was u n d e r t a k e n . Results appear in Table V. In t h e
results, it is noted that increasing %T values indicate better
treatment as more p a r t i c l e s remain suspended in the aqueous
medium.

Fe203 D i s p e r s i o n Procedure

Procedure

(1) Prepare a suspension of 0.1% Fe203 in DI H20.

(2) Adjust hardness to 200 ppm Ca+2 as CaC03 using CaCl2'

2H20 s o l u t i o n - 8 ml/1000 ml of Fe203 solution.

(3) Using overhead mixer, mix s u s p e n s i o n 1/2 hour at 1000 rpms.

(4) Remove s o l u t i o n to magnetic stirrer and a d j u s t to pH 7.5 (about

20 minutes to stabilize pH).

(5) Return solution to overhead mixer.

 (6) Take 90 ml a l i q u o t s of s u s p e n s i o n and place 4 oz. glass bottle.

(7) Add t r e a t m e n t and DI water to bring total volume to 100 m l .

(8) Cap b o t t l e , invert several times and place on r e c i p r o c a t i n g

shaker at a moderate speed of about 40 spm for 1/2 hour.

(9) Place on v i b r a t i o n - p r o o f surface and allow to stand 18 h o u r s .

(10) Without disturbing settled phase, pipet the top 40 mls off the
sample. Place in a cell and read %T (at 415 nm).

Calculation
 Recirculator Studies

In order to approximate those conditions experienced

in a c o o l i n g tower, tests were conducted under recirculatory
conditions with heat transfer provided.

These conditions closely simulate the environment in a

field cooling system. In t h i s test system treated water is
circulated by a c e n t r i f u g a l pump through a corrosion coupon
by-pass into which corrosion coupons are inserted, and past a
mild steel (AISI-1010) heat exchanger tube contained in a
plexiglass block. The i n s i d e of the exchanger tube is filled
with silicone oil and heated with an e l e c t r i c heater. The
temperature of the silicone oil can be r e g u l a t e d . The w a t e r
velocity past the corrosion coupons and heat exchanger tube can
be c o n t r o l l e d anywhere from 0 to 4.5 ft/sec.
 The pH and t e m p e r a t u r e of the bulk water are automat-
ically controlled. The t r e a t e d water is prepared by c h e m i c a l
addition to deionized water. Provisions for continuous make-up
and blowdown are made by pumping fresh treated water from s u p p l y
tanks to the sump, with overflow from the sump s e r v i n g as
blowdown.

Corrosion rates are determined by exposing precleaned

and weighed metal specimens for a specified period of t i m e ,
.after which they are removed, cleaned and reweighed. Corrosion
rates are calculated by d i v i d i n g the total coupon weight loss by
the number of days of e x p o s u r e .

The c o n d i t i o n s used were: Heat Flux 8000 B T U / f t 2 / h r ;

Water Velocity = 3 ft/sec; Water T e m p e r a t u r e = 120F; Retention
Time = 1 . 3 days; Mild Steel Heat T r a n s f e r Surface.

Water Chemistry: 600 ppm Ca as CaC03; 300 ppm Mg+2

as CaC03; 83 ppm NaHC03; pH = 7 . 3 + 0.2.

Treatment: 12.5 ppm a c t i v e polymer; 3.0 ppm

tolyltriazole; 10.5 ppm t e t r a p o t a s s i u m pyrophosphate; 15.2 ppm
monosodium phosphate; HEDP 4.0 ppm.
 The f o l l o w i n g results were obtained:

Utilizing both apparatus and procedure similar to that

described in Example 1 , 2 2 8 g. of water and 180 g of AHPSE (40%
solution, 0.33 mole) were added to a reaction flask, 86 g. of
methacrylic acid (1 mole) and sodium persulfate solution were
then separately added to the reaction mixture over a two h o u r
period at 85C. The r e s u l t i n g polymer solution was f u r t h e r
neutralized with 70 g of c a u s t i c (50%) and d i l u t e d to a 25%
solids solution. The f i n a l solution had a B r o o k f i e l d viscosity
of 28.2 cps at 25C. The m o l e c u l a r weight Mn of the copolymer
was 3 , 4 0 0 .
Example 9: Preparation of A c r y l i c Acid/Methacrylic Acid/AHPSE
Terpolymer

A suitable reaction flask was equipped with a mechan-

ical agitator, a thermometer, a reflux condenser, a nitrogen
inlet and two a d d i t i o n inlets for the initiator and monomer
solutions, respectively. The f l a s k was charged with 220g o f
deionized water, 43g of i s o p r o p a n o l and 109g of 1 - p r o p a n e
sulfonic acid, 2-hydroxy-3-(2-propenyl oxy) mono sodium salt
[AHPSE] (40%, 0.2 mole). The s o l u t i o n was then heated to 85C
under a nitrogen blanket. 72g of a c r y l i c acid (1 mole) and
17.2g of m e t h a c r y l i c acid (0.2 mole) were mixed in a separate
flask so as to provide a mixed monomer s o l u t i o n . The m i x e d
monomer solution was t r a n s f e r r e d to an a d d i t i o n a l funnel. An
initiator solution containing 31% of sodium persulfate in
deionized water was p r e p a r e d separately and sparged with
nitrogen. The i n i t i a t o r solution (17 ml) was then added to the
reaction flask along with the mixed monomer s o l u t i o n over a
period of 2 hours. After the addition, the mixture was h e a t e d
for 2 more hours at 85C and s u b s e q u e n t l y , 129g of i s o p r o p a n o l /
water solution were stripped off. The r e a c t i o n mixture was t h e n
cooled to less than 40C and 60g of 50% c a u s t i c solution were
then added.

The s t r u c t u r e of the resulting terpolymer was v e r i f i e d

by Carbon 13 NMR. The polymer solution, after being diluted to
25% s o l i d s with water, had a B r o o k f i e l d viscosity of 14.8 cps at
25C. It was a s t a b l e solution with a slightly yellow color.
Example 10: Acrylic Acid/Methacrylic Acid/AHPSE T e r p o l y m e r

Utilizing both apparatus and p r o c e d u r e similar to t h a t

described in Example 9, 28g of d e i o n i z e d water and 15g o f
isopropanol were charged to a reaction flask. The s o l u t i o n was
then heated to reflux temperature under a nitrogen blanket. 36g
of a c r y l i c acid (0.5 mole), 43g of m e t h a c r y l i c acid (0.5 mole)
and 180g of AHPSE (40%, 0.33 mole) were added to a s e p a r a t e
flask so.as to p r o v i d e a mixed monomer s o l u t i o n . The mixed
monomer s o l u t i o n was then added to the reaction flask along with
an i n i t i a t o r solution comprising sodium p e r s u l f a t e over a 2 hour
period. The r e a c t i o n mixture was heated for 2 more hours and
subsequently, 39g of isopropanol/water solution were stripped
off. The mixture was cooled to lower than 40C and 60g of 50%
caustic solution were added.

The r e s u l t i n g terpolymer solution, after being diluted

to 25% with water, had a B r o o k f i e l d viscosity of 18.9 cps (at
25C).

Example 11: Acrylic Acid/Methacrylic Acid/AHPSE T e r p o l y m e r

Utilizing both apparatus and p r o c e d u r e similar to t h a t

described in Example 9, 15g of i s o p r o p a n o l , 228g of water and
180g of AHPSE (40% s o l u t i o n , 0.33 mole) were added to a r e a c t i o n
flask. The m i x t u r e was heated to 85C under nitrogen. 36g o f
acrylic acid (0.5 mole) and 43g of m e t h a c r y l i c acid were added
to an a d d i t i o n a l funnel so as to provide a mixed solution. The
mixed monomer s o l u t i o n was then added to the reaction flask
along with a sodium persulfate solution over a 2 hour period.
One hour a f t e r the addition, a solution of t - b u t y l hydroperoxide
(0.2g in 5 ml of w a t e r ) was added to the reaction mixture. The
mixture was h e a t e d for 1 more hour and s u b s e q u e n t l y an i s o p r o -
panol/water solution was s t r i p p e d off. The m i x t u r e was c o o l e d
to lower than 40C and 65g of 50% c a u s t i c were added.

The r e s u l t i n g terpolymer solution after being diluted

to 25% s o l i d s had a B r o o k f i e l d viscosity of 24.7 cps at 25C.

Example 12: Acrylic Acid/Methacrylic Acid/AHPSE T e r p o l y m e r

Apparatus,'procedure and r e a g e n t charge similar to

that described in Example 11 were used, except no i s o p r o p a n o l
was used. The resulting terpolymer solution after being diluted
to 25% had a B r o o k f i e l d viscosity of 30.7 cps at 25C.

Example 13: Preparation of A c r y l i c Acid/Acrylamide/AHPSE

Terpolymer

Utilizing both apparatus and p r o c e d u r e similar to t h a t

described in Example 9, 220g of d e i o n i z e d water, 43g of i s o p r o -
panol and 90.8g of AHPSE (40%, 0.17 mole) were charged to a
reaction flask. The solution was then heated to 85C under a
nitrogen blanket. 36g of a c r y l i c acid (0.5 mole) and 72.1g of
acrylamide solution (90%, 0.5 mole) were added to a separate
flask so as to provide a mixed monomer s o l u t i o n . The mixed
monomer s o l u t i o n was then added to the reaction flask along w i t h
a solution persulfate containing solution over a 2 hour p e r i o d .
One hour a f t e r the addition, a solution of t - b u t y l hydroperoxide
(0.2g in 5 ml of water) was added to the reaction mixture. The
mixture was h e a t e d for 1 more hour and s u b s e q u e n t l y , 136g o f
isopropanol/water solution were stripped t h e w h e v e r was
cooled to lower than 40C and c a u s t i c solution was added to
adjust the solution to pH 6 .

The s t r u c t u r e of the terpolymer was v e r i f i e d by C a r b o n

13 NMR, no r e s i d u a l monomer was detected. The polymer solution
had a B r o o k f i e l d viscosity of 13.2 cps at 25% s o l i d s (at 25C).

Example 14: Preparation of A c r y l i c Acid/Hydroxypropyl Acrylate

and AHPSE T e r p o l y m e r

Utilizing both apparatus and procedure similar to that

described in Example 13, 72.1g of a c r y l i c acid (1 mole), 18.6g
of 2 - h y d r o x y p r o p y l acrylate (0.14 mole) and 77.9g of AHPSE (40%,
0.14 mole) were used for polymerization. The r e s u l t i n g polymer
solution, after being diluted to 25%, had a B r o o k f i e l d viscosity
of 14.5 cps (at 25C).

Tables VII - IX herein below present a summary of t h e

physical properties of the terpolymers produced in accordance
with Examples 9 through 14.
 Certain of the terpolymers of examples 9-14 were sub-
jected to calcium phosphate deposit control tests, the procedure
for which is detailed hereinabove. Results are reported in
Table X.
 In o r d e r to ascertain the efficacy of the terpolymers
of the present invention in d i s p e r s i n g "particulate matter" in
an aqueous medium, the tests were undertaken using montmorillo-
nite clay as suspended solids material. The p r o c e d u r e utilized
was s i m i l a r to t h a t reported hereinabove for the ferric oxide
dispersion tests with the obvious exception that montmorillonite
clay was s u b s t i t u t e d for ferric oxide as the suspended
particulate matter. Results of t h i s test appear in Table XI.
 Spinner tests were performed to e v a l u a t e the use o f
acrylic acid and AHPSE c o n t a i n i n g polymers as a c o r r o s i o n
inhibitor in soft water. The t e s t s were each conducted with two
non-pretreated low carbon steel coupons which were immersed and
rotated in aerated synthetic cooling water for a 3 or 4 day
period. The water was a d j u s t e d to the desired pH and r e a d j u s t e d
after one day if necessary; no f u r t h e r adjustments were made.
Water temperature was 120F, and r o t a t i o n a l speed was m a i n t a i n e d
to give a water velocity of 1.3 feet per second past the

coupons. Cooling water was m a n u f a c t u r e d to give the conditions

indicated in Table XII.

Corrosion rates were determined by weight loss measure-

ment. Prior to immersion, coupons were scrubbed with a mixture
of t r i s o d i u m phosphate-pumice, rinsed with water, rinsed with
isopropanol and then air dried. Weight measurement to t h e
nearest milligram was made. At the end of one day, a weighed
coupon was removed and c l e a n e d . Cleaning consisted of i m m e r s i o n
into a 50% s o l u t i o n of HCl for about 20 seconds, rinsing with
tap water, scrubbing with a mixture of t r i s o d i u m phosphate -
pumice until clean and. then rinsing with tap water and i s o p r o -
panol. When dry, a second weight measurement to the nearest
milligram was made. At the termination of the tests, the
remaining coupon was removed, cleaned and w e i g h e d .

Corrosion rates were c a l c u l a t e d by d i f f e r e n t i a l weight

loss according to the equation:
 As shown in Table XVI, these polymers all gave
substantial corrosion protection when used in c o m b i n a t i o n with
molybdate (Mo0-4).
 The examples demonstrate that the copolymers and t e r -
polymers of the present invention are effective in i n h i b i t i n g
the formation of calcium phosphate and calcium phosphonate.

As the polymers are effective in i n h i b i t i n g calcium

phosphate formation, they would also be e f f e c t i v e in gas
scrubbing systems where scrubbing mediums such as sewage t r e a t -
ment e f f l u e n t s contain high phosphate levels. Such s y s t e m s
would have the prerequisite for the f o r m a t i o n and d e p o s i t i o n of
calcium phosphate which is to be avoided. Additional areas of
application such as the phosphate production and p r o c e s s i n g
field, fertilizer field, automotive metallic part pretreatment
field, etc. will be apparent to those skilled in the art.

Further, the copolymers are effective in d i s p e r s i n g

iron oxide (Table V) which is sometimes encountered as a
troublesome fouling species. Additionally, the t e r p o l y m e r s are
effective in d i s p e r s i n g montmorillonite clay (Table XII) another
commonly e n c o u n t e r e d fouling species.

In another aspect of the present invention, the water

soluble copolymers and t e r p o l y m e r s herein specified, when used
conjointly with orthophosphate, passivate metal surfaces in
contact with the water system. Under t h i s treatment approach,
corrosion is inhibited without productiuon of s u b s t a n t i a l
attendant scale deposition along the treated metal surface (as
would be expected in b a r r i e r film approaches).
 In o r d e r to passivate the metal surfaces, the aqueous
system should first be a d j u s t e d to a pH of 5.5 or above, and
secondly measured to assure a calcium ion c o n t e n t (or o t h e r
appropriate ion such as z i n c , nickel, chromium and m i x t u r e s
thereof). The water soluble copolymers or t e r p o l y m e r s should
then be c o n j o i n t l y used with a water soluble orthophosphate
compound. Exemplary orthophosphate compounds include:
phosphoric acid, the sodium orthophosphates, the potassium
orthophosphates, the lithium orthophosphates and ammonium
orthophosphates. The f o l l o w i n g specific compounds are exemplary:

In a d d i t i o n to the inorganic orthophosphates set forth

above may be mentioned the organic orthophosphates which are set
forth in U.S. Pat. No. 3,510,436. The s p e c i f i c compounds are
those which possess the basic formula
where R is an organic radical as d e s c r i b e d in the patent, X is A
or R, and A i s . H , Na, Li, K or NH4. Compounds of the above
nature are an e x c e l l e n t source of o r t h o p h o s p h a t e .

In accordance with the passivation aspect of the inven-

tion, it is essential to use the polymers with an a p p r o p r i a t e
orthophosphate source. For enhanced protection, the polymer and
orthophosphate may be combined with an o r g a n o - p h o s p h o n a t e , such
as hydroxyethylidene diphosphonic acid and/or a polyphosphate.

Accordingly, the invention contemplates the use of a

composition containing the copolymers and t e r p o l y m e r s and t h e
orthophosphate and o p t i o n a l l y but preferably the phosphonate,
the polyphosphate and copper corrosion inhibitors. A typical
composition contains on a weight ratio basis of polymer to
orthophosphate expressed as P04-3 of about 1:8 to about 4:1
and p r e f e r a b l y about 1:6 to 2:1. When a p o l y p h o s p h a t e is
included, the weight ratio of o r t h o p h o s p h a t e to p o l y p h o s p h a t e on
a PO43 to P043 basis is 15:1 to 1:3, and p r e f e r a b l y
2.5:1 to 1:1. Similarly, if the organo-phosphate is included,
the ratio of the orthophosphate to the phosphonate expressed as
P04-3 to P04-3 is 1:2 to 13:1, and preferably 2:1 to
8:1. Any copper corrosion inhibitor may be included in t h e
composition (0.01 to 5% by weight) in an amount which will be
effective for controlling the copper corrosion in a g i v e n
system: 0.05 to 10 p a r t s per m i l l i o n and p r e f e r a b l y 0.5 to 5
parts per m i l l i o n .

In t r e a t i n g the aqueous systems the following dosages

are desirable, with the dosages, of c o u r s e , being based upon t h e
severity of the corrosion problem foreseen or experienced:

orthophosphate (expressed as PO4-3): 2 to 50

parts per m i l l i o n parts of water (ppm) and p r e f e r a b l y 6 to 30
ppm;
polymer: 0.3 to 120 ppm and p r e f e r a b l y 3 to 25 ppm o f
water;
polyphosphate (expressed as P4-3): 0.1 to 3 0 ,
and p r e f e r a b l y 3 to 10, parts per m i l l i o n parts of w a t e r ;
phosphonate (expressed as PO4-3): 0.04 to 20, and
preferably 1 to 6 parts per m i l l i o n parts of w a t e r .

The p r e f e r r e d rate of a p p l i c a t i o n of t h i s treatment to

cooling water systems and the ratios of v a r i o u s components
depends on the calcium concentration of the cooling water. The
treatment is preferably applied in waters having between 15 ppm
and 1,000 ppm c a l c i u m . Within this range the weight ratio of
calcium to orthophosphate is varied from 1:1 to 8 3 . 3 : 1 , the
weight ratio of the copolymers or t e r p o l y m e r s to o r t h o p h o s p h a t e
is varied from 1:3 to 1.5:1.

As e a r l i e r disclosed, the orthophosphate is generally

obtained by d i r e c t addition. However, it is understood that the
orthophosphate can also arise due to reversion of e i t h e r
inorganic polyphosphates or the organo-phosphonates, or any
other appropriate source or precursor thereof.
 The above dosages represent the most desirable ranges
since most systems will be t r e a t a b l e therewith. Higher d o s a g e s
are permissible when the situation demands, but of course are
most c o s t l y . The e f f e c t i v e n e s s of the inventive-treatments is
dependent upon the aqueous medium having a pH of 5.5 and a b o v e ,
and p r e f e r a b l y 6.5 to 9.5, and c o n t a i n i n g calcium ion c o n c e n t r a -
tions of, preferably about 15 p a r t s per m i l l i o n parts of w a t e r .
Below t h i s range, it may be n e c e s s a r y for overall effectiveness
to add m e t a l l i c ions such as zinc, nickel, chromium, etc., as
described in column 3, lines-4 to 24 of U.S. Pat. No. 3 , 8 3 7 , 8 0 3 .
 1. A method of controlling the deposition of
calcium phosphate or phosphonate on the structural

parts of a system exposed to an aqueous medium, which

comprises adding to said aqueous medium an effective
amount for the purpose of a water soluble polymer
comprising repeat unit moieties (a) and (b), wherein
said repeat unit (a) comprises

and wherein-said repeat unit-(b) comprises the

structure

wherein Rl is H or lower alkyl (C1-C3), R2 is OH, OM,

or NH2, M is a water soluble cation, R3 is a hydroxy
substituted alkyl or alkylene radical having from 1 to
about 6 carbon atoms or a non-substituted alkyl or
alkylene radical having from 1 to about 6 carbon
atoms, X is an anionic radical, Z is H or hydrogens or
a water soluble cation or cations which together
counterbalance the valence of X, and a is 0 or 1.
2. A method as claimed in claim I for controlling
the deposition of calcium phosphate on the structural
parts of a system exposed to an aqueous medium
containing calcium cations and phosphate anions under
deposit forming conditions.
3. A method as claimed in claim 1 for controlling
the deposition of calcium phosphonate on the
structural parts of a system exposed to an aqueous
medium prone to such deposition.
4. A method as claimed in any of claims 1 to 3,
in which the water soluble polymer comprises a third
repeat unit moiety (c), said repeat unit (c)
comprising a monomeric repeat unit selected from
acrylic acid, alkyl acrylate, hydroxylated lower alkyl
(C1 - C6) acrylate, methacrylic acid, and acrylamide
and water soluble salt forms thereof, with the proviso
that repeat unit (a) and repeat unit (c) are different.
5. A method as claimed in any of claims 1 to 4,
in which Ri is hydrogen, R2 is OH or OM, R3 is
2-hydroxypropylidene, X is S03, and Z is a member or
members selected from H, Na, NH+4, Ca and K and wherein
a is one.
6. A method as claimed in any of claims 1 to 5,
in which the number average molecular weight of said
water soluble polymer is between about 1,000 to
1,000,000 and wherein the molar ratio x:y is between
10:1 and 1:5 and wherein said system is a cooling
water system.
7. A method of inhibiting the corrosion of
ferrous metal parts in contact with an aqueous
solution with little or no attendant deposition of
scale on said ferrous parts, which corrosion
inhibition is obtained by providing for the formation
of a protective passive oxide film on the metal
surface in contact with said aqueous medium, which
method comprises adding to said aqueous medium (A) a
water soluble polymer comprising repeat unit moieties
(a) and (b) wherein said repeat unit (a) comprises the
structure
 and wherein said repeat unit (b) comprises the structure

wherein R1 is H or lower alkyl (Ci-C3), R2 is OH, OM, o r

NH2, M is a water soluble cation, R3 is a hydroxy s u b s t i t u t e d
alkyl or a l k y l e n e radical having from 1 to about 6 carbon a t o m s
or a n o n - s u b s t i t u t e d a l k y l or a l k y l e n e radical having from 1 t o
about 6 carbon atoms, X is an a n i o n i c radical, Z is H or h y d r o -

gens or a water soluble cation or c a t i o n s which t o g e t h e r counter-

balance the valence of X, and a is 0 or 1, and (B) a w a t e r
soluble orthophosphate compound, said polymer and the orthophos-
phate compound being sufficient to provide a substantially
scale-free protective passive oxide film on the m e t a l l i c surface.
 8. A method as claimed in claim 7, in which said
water soluble polymer comprises a third repeat unit

moiety (c), said repeat unit (c) comprising a.

monomeric repeat unit selected from acrylic acid,
alkyl acrylate, hydroxylated lower alkyl (Cl - C6)
acrylate, methacrylic acid, and acrylamide and water
soluble salt forms thereof, with the proviso that
repeat unit (a) and repeat unit.(c) are different.
9. A method as claimed in claim 7 or 8, in which

R1 is hydrogen, R2 is OH or OM, R3 is 2-hydroxy-

propylidene, X is SO3 and Z is a member or members
selected from H, Na, NH4, Ca and K and wherein a is
one.
10. A method as claimed in any of claims 7 to 9,
in which the number average molecular weight of said
water soluble polymer is between about 1,000 to
1,000,000 and wherein the molar ratio x:y is between
10:1 to 1:5 and wherein said aqueous medium comprises
a cooling water system.
11. A composition for providing a protective
passive oxide film on the surface of a ferrous
metallic part in contact with an aqueous solution with
little or no attendant deposition of scale on said
part, said composition comprising (A) a water soluble
polymer comprising repeat unit moieties (a) and (b)
wherein said repeat unit (a) comprises the structure
and wherein said repeat unit (b) comprises the
s t r u c t u r e :

wherein R1 is H or lower alkyl (Cl-C3), R2 is OH, OM,

or NH2, M is a water soluble cation, R3 is a hydroxy
substituted alkyl or alkylene radical having from 1 to
about 6 carbon atoms or a non-substituted alkyl or
alkylene radical having from 1 to about 6 carbon
atoms, X is an anionic radical, Z is H or hydrogens or
a water soluble cation or cations which together
counterbalance the valence of X, and a is 0 or 1, and
(B) a water-soluble orthophosphate compound, the ratio
on a weight basis of the polymer to the orthophosphate
expressed as P04 being from 1:8 to 4:1.
12. A composition as claimed in claim 11, in
which said water soluble polymer comprises a third
repeat unit moiety (c), said repeat unit (c)
comprising a monomeric repeat unit selected from
acrylic acid, alkyl acrylate, hydroxylated lower alkyl
(Cl - C6) acrylate, methacrylic acid, and acrylamide
and water soluble salt forms thereof, with the proviso
that repeat unit (a) and repeat unit (c) are different.
13. A composition as claimed in claim 11 or 12,
in which R1 is hydrogen, R2 is OH or OM, R3 is
2-hydroxypropylidene, X is S03, and Z is a member or
members selected from H, Na, NH4+, Ca and K and wherein
a is one.
 14. A composition as claimed in any of claims 11
to 13, in which the number average molecular weight of
said water soluble polymer is between 1,000 to
1,000,000 and wherein the molar ratio is
x:y between
10:1 to 1:5.