CA1270997A - Modified acrylamide polymers and the like for use as scale inhibitors - Google Patents
Modified acrylamide polymers and the like for use as scale inhibitorsInfo
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- CA1270997A CA1270997A CA000532586A CA532586A CA1270997A CA 1270997 A CA1270997 A CA 1270997A CA 000532586 A CA000532586 A CA 000532586A CA 532586 A CA532586 A CA 532586A CA 1270997 A CA1270997 A CA 1270997A
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Abstract
PATENT APPLICATION
MODIFIED ACRYLAMIDE POLYMERS AND THE LIKE
FOR USE AS SCALE INHIBITORS
ABSTRACT OF THE INVENTION
Water supplies are treated to inhibit the formation of scale deposits of alkaline earth phosphates, phosphonates, sulphates and carbonates using various hydrocarbon polymers which contain an amido functionality and which have been prepared by post-polymerization derivatization.
MODIFIED ACRYLAMIDE POLYMERS AND THE LIKE
FOR USE AS SCALE INHIBITORS
ABSTRACT OF THE INVENTION
Water supplies are treated to inhibit the formation of scale deposits of alkaline earth phosphates, phosphonates, sulphates and carbonates using various hydrocarbon polymers which contain an amido functionality and which have been prepared by post-polymerization derivatization.
Description
FO~G ~T AL CASE 4 ~ 7 6530-~27 FIELD OF THE IN~ENTION
This invention relates generally to the preparation and use of water-soluble polymeric compounds which have special utility as scale inhibiting agents.
BACKGROUND OF THE INVENTION
One important general application of water-treatment chemicals resides in controlling the mineral content of boiler feed water in elec~ric power generation facilities~ for example.
Even water supplies that have been pretreated by zeolite softening 1~ can form ~00 to 4~000 pounds of scale deposits per year in a typical boiler ~hat is generating 200,000 pounds of steam per hour, concomitantly reducing heat transfer efficiency and leading ultimately to corrosion and tube failure. The use o such chelants as nitrilotriacetic acid and ethylenediaminetetra-acetic acid has proved superior to treatment of boiler feed water with soluble inorganic phosphates; but such chelants require careful monitoring if corrosion is to be minimized.
Introduction of prior art wa~er-soluble, synthetic polymers to serve as dispersants and crystal modifiers, in conjunction with phosphates or chelants 9 has lessened the corrosion hazard but has not eliminated the need for periodic cleaning of the boiler system to remo~e scale deposits.
Cooling water systems pose equally serious problems in controlling scale accumulation in order to promote both thcrmal and pumping efficiency.
Scale deposits are generated and extended principally by means of crystal growth; and various approaches to reducing scale development have accordingly included inhibition of crystal growth~ modification of crystal growth and dispersion of the scale-forming minerals.
Certain polyacrylates and hydrolyzed polyacrylamides have been proposed heretofore as mineral dispersants in industrial water systems but have been found to exhibit undesirably low ~7~3997 tolerance for calcium ion, resulting in calcium precipitates o~
their own, especially in water of high hardness initially or as a result of concentration from recycling in a cooling water system. Lignosulfonate dispersants, on the other hand, while e~fective in many situations, particularly where iron-fouling is a problem, are subject to oxida~ive destruction and are, as consequence, comparatively uneconomical in the long run.
Accordingly, the present invention seeks to provide a ~amily of water-soluble polymers which are hydrolytically stable, which are comparatively unreactive with hardness cations, which 1~ are effective as dispersants and which are especially effective as scale inhibitors.
Thus in a second aspect the present invention seeks to achieve high-performance scale inhibition using a unique series of copolymers and terpolymers prepared by post-polymeri-~ation derivatization using direct amidation of polyalkyl car-boxylic acids and transamidation of copolymers containing carboxylic acid and (meth)acrylamide units.
In a third aspect, this invention further seeks to provide water-soluble polymeric sulfonates which have special ~a utility as water-treatment chemicals, together with advantageous methods of synthesizing such sulfonates.
In a fourth aspect this invention seeks to provide ~,3-dihydroxypropylamide-, 2-hydroxy-3-sulfopropylamide-, sulfo-methylamide-, sulfoethylamide- and sulfophenylamide-containing polymers, for use as scale inhibitors and the like in industriàl water systems.
SUMMARY OF THE INVENTION
Significant activity in inhibiting the formation of scale deposits has been exhibited by copolymers and terpolymers 3~ that have been prepared by post-polymerization derivatization.
The derivatizing agents of the invention are hydroearbon groups containing both an amino funetionality and at least one of the following groups:
[1] (poly~hydroxy alkyl(aryl);
[2~ alkyl and aryl(poly)carboxylic acids and ester analogues;
[3] amino alkyl(aryl) and quaternized amine analogues;
[4] halogenated alkyl(aryl);
[5] (poly)ether alkyl(aryl);
1~ [6] (di)alkyl;
[7~ alkyl phosphonic acid;
[8] alkyl ~eto carboxylic acid;
[9] hydroxyalkyl sulfonic acid; and [10] (aryl)alkyl sulfonic acid, wherein the prefix "poly" refers to two or more such functionali-ties. The derivatization process of the invention ineludes ~ireet amidation of polyalkyl earboxylie aeids and transamida-tion of copolymers eontaining earboxylie aeid and (meth)aeryl-3mide units.
Partieularly advantageous sulfomethylamide-, sulfo-etllylamide-, sulfophenylamide-, 2-hydroxy-3-sulfopropylamide-and 2,3-dihydroxypropylamide-containing polymers of the present invention are produced by transamidation using acrylamide homo-polymers and eopolymers, ineluding terpolymers, which have a molar eontent of acrylamide or homologous units of at least about 10~. The transmidation is achieved using such reactants as aminomethanesulfonie aeid, 2-aminoethanesulfonic aeid (taurine), ~-aminobenzenesulfonie acid (p-sulfanilic acid), l-amino-2-hydroxy-3-propanesulfonic acid, or 2,3-dihydroxypropylamine in 3a aqueous or like polar media at temperatures on the order o~
about 150 C. Onee initiated, the reactions go essentially to eompletion.
~7C~397 66530-~27 Other particularly advantageous polymeric sulfonate~
of the present 1nvention are produced by an addition reaction between an aminosulfonic acid, such as sulfanilic acid, and taurine, or their sodium salts, and a copolymer of maleic anhydride and a vinyllc compound such as styrene, methyl vinyl e~her, or (meth~ acrylam~de.
Thus, according to one aspect, the present lnvention provides a method of controlling scale deposits by adding to waters having a tendency to ~orm scale, a scale-inhibitorily effective amount of a hydrocarbon polymer selected from the class consisting of: N-substi~uted amide polymers with an amide s~ructure as follows:
~ 1 1 - -N-R-X
where ~1 is a hydrogen or an alkyl and ~ is alkylene or phenylene, and X ls sulfonate, phosphinate,, phosphonate, ~poly)hydroxyl, (poly)carboxyl or carbonyl, and combinations thereof.
According to another aspect, the present invention provldes a me~hod of controlling scale deposits by adding to ~aters having a tendency to form scale, a ~cale-inhibi~orily ef~ective amount of hydrocarbon polymer selected from the Glass consisting of, derivatized maleic anhydride homo-, co- and terpolymers having N-substituted maleamic acid units, N-substituted maleimide unlts and maleic acid (and ~alts) uni~s having ~ structure as follows:
(CH fH)x (fH. - - CH)y -(CH - f H~
C=O C=O o-c C=O C=O C=O
~
--Rl O Nl 3 M M
_ n d~ -5-;. ~
~7~g~
where R1, R2 and R3 are each independently chosen from the group consisting of hydrogen, hydroxyl, carboxyalkyl, carboxyamide, phenyl, substituted phenyl, linear or branched ~lkyl of from on~ ~o ten carbon atoms, and substituted alkyl of fxom one to ten carbon atoms, where the subs~i~uent is phosphonic acid; phosphinic acid; phosphate ester; sulfonic acid; sulfate ester, carbonyl, carboxyamide, ~poly)carboxy and l~ IPoly)hydroxy, alkoxy and carboxylate ester groups; and combinations ~hereof; and M may be H , alkali me~al ions, alkaline earth metal ions, ammonium ions or zinc ion and wherein:
n = total moles of derivatized and underivatized maleic units in the polymer and is an integer in ~he range from 10 to about 1200;
x = mole fraction of maleamic acid (salt) units in .
the polymer and can vary from O to about 1.0;
y = mole fractlon of maleimide units in the polymer _~ and can vary from O to about 0.95;
z ~ mole fraction of maleic acid (salts) units in the polymer and can vary from O to about 0.95;
and x + y ~ z - 1 According to still another aspect, the present invention provides the method of making polymers containing sulfoethylamide, sulfomethylamide, sulfophenylamide, 2-hydroxy-3-sulfopropylamide or 2,3-dihydroxypropylamide for use as scale inhibitors which comprises the step of reacting an aminosulfonic acid with a (meth)acrylamide-containing polymer.
O DETAILED DESCRIPTION OF THE INVENTION
It has been found that the post-polymerization derivatized hydrocarbon polymers of the invention are very -5a-A~`
~2~ 3~
66530-~27 effective scale inhibitors for cooling water, boiler water, industrial and petrole~m process water, ~nd oil well drilling water. Testing results tabulated in Tables I and VI set forth hereinafter show these materials are very effective scale inhibitors. Eminen~ly useful compounds according to the invention include:
(1) N-substituted amide polymers with an amide s~ructure dS follows:
O R
" ,1 -C-N-R-X
where Rl is hydrogen or alkyl and R is alkylene or phenylene, and X is sulfonate, phosphinate, phosphonate, (poly)hydroxy, (poly)carboxyl or carbonyl and combina~ions thereof; and
This invention relates generally to the preparation and use of water-soluble polymeric compounds which have special utility as scale inhibiting agents.
BACKGROUND OF THE INVENTION
One important general application of water-treatment chemicals resides in controlling the mineral content of boiler feed water in elec~ric power generation facilities~ for example.
Even water supplies that have been pretreated by zeolite softening 1~ can form ~00 to 4~000 pounds of scale deposits per year in a typical boiler ~hat is generating 200,000 pounds of steam per hour, concomitantly reducing heat transfer efficiency and leading ultimately to corrosion and tube failure. The use o such chelants as nitrilotriacetic acid and ethylenediaminetetra-acetic acid has proved superior to treatment of boiler feed water with soluble inorganic phosphates; but such chelants require careful monitoring if corrosion is to be minimized.
Introduction of prior art wa~er-soluble, synthetic polymers to serve as dispersants and crystal modifiers, in conjunction with phosphates or chelants 9 has lessened the corrosion hazard but has not eliminated the need for periodic cleaning of the boiler system to remo~e scale deposits.
Cooling water systems pose equally serious problems in controlling scale accumulation in order to promote both thcrmal and pumping efficiency.
Scale deposits are generated and extended principally by means of crystal growth; and various approaches to reducing scale development have accordingly included inhibition of crystal growth~ modification of crystal growth and dispersion of the scale-forming minerals.
Certain polyacrylates and hydrolyzed polyacrylamides have been proposed heretofore as mineral dispersants in industrial water systems but have been found to exhibit undesirably low ~7~3997 tolerance for calcium ion, resulting in calcium precipitates o~
their own, especially in water of high hardness initially or as a result of concentration from recycling in a cooling water system. Lignosulfonate dispersants, on the other hand, while e~fective in many situations, particularly where iron-fouling is a problem, are subject to oxida~ive destruction and are, as consequence, comparatively uneconomical in the long run.
Accordingly, the present invention seeks to provide a ~amily of water-soluble polymers which are hydrolytically stable, which are comparatively unreactive with hardness cations, which 1~ are effective as dispersants and which are especially effective as scale inhibitors.
Thus in a second aspect the present invention seeks to achieve high-performance scale inhibition using a unique series of copolymers and terpolymers prepared by post-polymeri-~ation derivatization using direct amidation of polyalkyl car-boxylic acids and transamidation of copolymers containing carboxylic acid and (meth)acrylamide units.
In a third aspect, this invention further seeks to provide water-soluble polymeric sulfonates which have special ~a utility as water-treatment chemicals, together with advantageous methods of synthesizing such sulfonates.
In a fourth aspect this invention seeks to provide ~,3-dihydroxypropylamide-, 2-hydroxy-3-sulfopropylamide-, sulfo-methylamide-, sulfoethylamide- and sulfophenylamide-containing polymers, for use as scale inhibitors and the like in industriàl water systems.
SUMMARY OF THE INVENTION
Significant activity in inhibiting the formation of scale deposits has been exhibited by copolymers and terpolymers 3~ that have been prepared by post-polymerization derivatization.
The derivatizing agents of the invention are hydroearbon groups containing both an amino funetionality and at least one of the following groups:
[1] (poly~hydroxy alkyl(aryl);
[2~ alkyl and aryl(poly)carboxylic acids and ester analogues;
[3] amino alkyl(aryl) and quaternized amine analogues;
[4] halogenated alkyl(aryl);
[5] (poly)ether alkyl(aryl);
1~ [6] (di)alkyl;
[7~ alkyl phosphonic acid;
[8] alkyl ~eto carboxylic acid;
[9] hydroxyalkyl sulfonic acid; and [10] (aryl)alkyl sulfonic acid, wherein the prefix "poly" refers to two or more such functionali-ties. The derivatization process of the invention ineludes ~ireet amidation of polyalkyl earboxylie aeids and transamida-tion of copolymers eontaining earboxylie aeid and (meth)aeryl-3mide units.
Partieularly advantageous sulfomethylamide-, sulfo-etllylamide-, sulfophenylamide-, 2-hydroxy-3-sulfopropylamide-and 2,3-dihydroxypropylamide-containing polymers of the present invention are produced by transamidation using acrylamide homo-polymers and eopolymers, ineluding terpolymers, which have a molar eontent of acrylamide or homologous units of at least about 10~. The transmidation is achieved using such reactants as aminomethanesulfonie aeid, 2-aminoethanesulfonic aeid (taurine), ~-aminobenzenesulfonie acid (p-sulfanilic acid), l-amino-2-hydroxy-3-propanesulfonic acid, or 2,3-dihydroxypropylamine in 3a aqueous or like polar media at temperatures on the order o~
about 150 C. Onee initiated, the reactions go essentially to eompletion.
~7C~397 66530-~27 Other particularly advantageous polymeric sulfonate~
of the present 1nvention are produced by an addition reaction between an aminosulfonic acid, such as sulfanilic acid, and taurine, or their sodium salts, and a copolymer of maleic anhydride and a vinyllc compound such as styrene, methyl vinyl e~her, or (meth~ acrylam~de.
Thus, according to one aspect, the present lnvention provides a method of controlling scale deposits by adding to waters having a tendency to ~orm scale, a scale-inhibitorily effective amount of a hydrocarbon polymer selected from the class consisting of: N-substi~uted amide polymers with an amide s~ructure as follows:
~ 1 1 - -N-R-X
where ~1 is a hydrogen or an alkyl and ~ is alkylene or phenylene, and X ls sulfonate, phosphinate,, phosphonate, ~poly)hydroxyl, (poly)carboxyl or carbonyl, and combinations thereof.
According to another aspect, the present invention provldes a me~hod of controlling scale deposits by adding to ~aters having a tendency to form scale, a ~cale-inhibi~orily ef~ective amount of hydrocarbon polymer selected from the Glass consisting of, derivatized maleic anhydride homo-, co- and terpolymers having N-substituted maleamic acid units, N-substituted maleimide unlts and maleic acid (and ~alts) uni~s having ~ structure as follows:
(CH fH)x (fH. - - CH)y -(CH - f H~
C=O C=O o-c C=O C=O C=O
~
--Rl O Nl 3 M M
_ n d~ -5-;. ~
~7~g~
where R1, R2 and R3 are each independently chosen from the group consisting of hydrogen, hydroxyl, carboxyalkyl, carboxyamide, phenyl, substituted phenyl, linear or branched ~lkyl of from on~ ~o ten carbon atoms, and substituted alkyl of fxom one to ten carbon atoms, where the subs~i~uent is phosphonic acid; phosphinic acid; phosphate ester; sulfonic acid; sulfate ester, carbonyl, carboxyamide, ~poly)carboxy and l~ IPoly)hydroxy, alkoxy and carboxylate ester groups; and combinations ~hereof; and M may be H , alkali me~al ions, alkaline earth metal ions, ammonium ions or zinc ion and wherein:
n = total moles of derivatized and underivatized maleic units in the polymer and is an integer in ~he range from 10 to about 1200;
x = mole fraction of maleamic acid (salt) units in .
the polymer and can vary from O to about 1.0;
y = mole fractlon of maleimide units in the polymer _~ and can vary from O to about 0.95;
z ~ mole fraction of maleic acid (salts) units in the polymer and can vary from O to about 0.95;
and x + y ~ z - 1 According to still another aspect, the present invention provides the method of making polymers containing sulfoethylamide, sulfomethylamide, sulfophenylamide, 2-hydroxy-3-sulfopropylamide or 2,3-dihydroxypropylamide for use as scale inhibitors which comprises the step of reacting an aminosulfonic acid with a (meth)acrylamide-containing polymer.
O DETAILED DESCRIPTION OF THE INVENTION
It has been found that the post-polymerization derivatized hydrocarbon polymers of the invention are very -5a-A~`
~2~ 3~
66530-~27 effective scale inhibitors for cooling water, boiler water, industrial and petrole~m process water, ~nd oil well drilling water. Testing results tabulated in Tables I and VI set forth hereinafter show these materials are very effective scale inhibitors. Eminen~ly useful compounds according to the invention include:
(1) N-substituted amide polymers with an amide s~ructure dS follows:
O R
" ,1 -C-N-R-X
where Rl is hydrogen or alkyl and R is alkylene or phenylene, and X is sulfonate, phosphinate, phosphonate, (poly)hydroxy, (poly)carboxyl or carbonyl and combina~ions thereof; and
(2) derivatized maleic anhydride homo-, co- and ter-polymers having N-substituted maleamic acid units, N-~ubstitu~ed maleimide unitæ and maleic acid (and salts) units having a structure as follows:
T f (fH CH)y (CH CH
f=o f=o o=c\ /=o f_o cl o N-RI O N O O
~ M ~3 M M
where Rl, R2 and R3 are each independently chosen from the group consistlng of hydrogen, hydroxyl, carboxyalkyl, carboxyamide, phenyl, substituted phenyl, linear and branched alkyl of from one
T f (fH CH)y (CH CH
f=o f=o o=c\ /=o f_o cl o N-RI O N O O
~ M ~3 M M
where Rl, R2 and R3 are each independently chosen from the group consistlng of hydrogen, hydroxyl, carboxyalkyl, carboxyamide, phenyl, substituted phenyl, linear and branched alkyl of from one
3~
-5b-~ .
to ten carbon atoms, and substi-tuted alkyl of from one to ten carbon atoms, where the substituent may be (poly)hydroxyl;
carbonyl; phosphonic acid; phosphinic acid; sulfonic acid; sul-fate ester; phosphate ester; alkoxy and carboxylate ester groups;
carbo~yamide and (poly)carboxylic groups; and combinations there-of; and M+ may be H+, alkali metal ions, alkaline earth metal ions, ammonium ions or zinc ion and wherein:
n = total moles of derivatized and underivatized maleic un~its in the polymer and is an integer in the range from 10 to ut l~0 x = mole fraction of maleamic acid (salt) units in the polymer and can vary from 0 to about 1.0 y = mole fraction of maleimide units in the polymer and can vary from 0 to about 0.95 z = mole fraction of maleic acid (salts) units in the polymer and can vary from 0 to about 0.95;
and ~ ~ y + z = 1 The scale inhibitory power of various polymers has been evaluated using the following screening procedures employ-in~ test chemicals of reagent grade:
Calcium, magnesium, and bicarbonate were supplied by ~aCl~4H~O; MgSO4.7H2O; and NaHCO3 respectively. The inhibitor concentrations were equivalent in each test class, unless other-wise indicated. The orthophosphate was supplied by H3PO4 and the organophosphorus materials obtained from commercial suppliers.
Each test solution was stirred with a teflon* coated stir bar in a jacketed glass beaker. Temperature was maintained using a Lauda* recirculating, constant-temperature bath. The pH was determined with Fisher Accumet* meter (Model 610A) and a combina-3~ tion electrode. The pH meter was calibrated with two standard buffers (pH 7 and 10) and corrections were made for temperature changes.
*Trade Mark - 6 -FOi kA .~L ~.~SE ~0] 1 ~ 7 ~397 Calcium and ~la~nesium Phosphate Inhibition - Calcium and magnesium were added to provide initial conccntra-tions of 250 and 125 mg/L. An equal amount of phosphate was added to each test solution, and the inhibitor concentrations are listed in Tables I and II. The temperature of the test solutions was maintained at 15SF. (70C). Using dilute aqueous NaOH, the pH
~as slowly increased to 8.5 and maintained during the ~OUl` hour duration of the test. ~ineral solubility l~) c~lculations indicate supersaturation ratios for calcium phosphate ~ 10,000 and magnesiu~ phosphate >
~00 were initially present and the system was under highly stressed conditions. At the conclusion of each test, each solution was filtered (0.45 um) and the orthophosphate concentration was determined spectrophotometrically (700 nm) after formation of a blue phosphomolybdate complex. The inhibition of calcium phosphate is determined by Equation 1:
. . filtered sam le - blank (1) ~6 Inhlbltlon = unfiltere~sample - blank ~a In the absence of the polymers described herein, %
Inllibition equals 0. Non-zero values represent scale inhibition benefits associated with the addition of an active polymer to the system being tested.
The foregoing procedure was used to collect data on specific copolymers and terpolymers according to the invention; and the results are set forth in Table I and Table II below.
~ ~ ,":
TABLE I
-SULFOAL~YLACRYLAMIDE-, SULFOPHENYLACRYLAMIDE-, PHOSPHO~OALKYLACRYLA~IIDE-, CAR~OXYAlKYLAGRYLA~IDE-, AND POLYHYDROXYALKYLAMIDE-CONTAINING POLYMERS
% PHOSPHATE
SALT INHIBITION
MOLECULAR P.P.M. POLYMER ACTIVES
S.~LE POLYMER CONPOSITION MOLE ~ ~EIGHT, Mw 5 7.5 10 20 A Acrylic Acid 84/
Sulfoethylacrylamide 1631,300 790 97 Al Acrylic Acid 79/
Sulfoethylacrylamide 21 6,000 60 95 L Acrylic Acid 60/Acrylamide 25/
Sul~oethylacrylamide 1510,600 38 99 ~1 Acrylic Acid 52/Acrylamide 40/
Sulfoethylacrylamide 7 45,300 70 93 B2 Acrylic Acid 78/Acrylamide 11/
Sulfoethylacrylamide 1153,800 0 94 B3 Acrylic Acid 23/Acrylamide 51/
Sulfoethylacrylamide 2643,400 97 93 B Acrylic Acid 66/Acrylamide 9/
-5b-~ .
to ten carbon atoms, and substi-tuted alkyl of from one to ten carbon atoms, where the substituent may be (poly)hydroxyl;
carbonyl; phosphonic acid; phosphinic acid; sulfonic acid; sul-fate ester; phosphate ester; alkoxy and carboxylate ester groups;
carbo~yamide and (poly)carboxylic groups; and combinations there-of; and M+ may be H+, alkali metal ions, alkaline earth metal ions, ammonium ions or zinc ion and wherein:
n = total moles of derivatized and underivatized maleic un~its in the polymer and is an integer in the range from 10 to ut l~0 x = mole fraction of maleamic acid (salt) units in the polymer and can vary from 0 to about 1.0 y = mole fraction of maleimide units in the polymer and can vary from 0 to about 0.95 z = mole fraction of maleic acid (salts) units in the polymer and can vary from 0 to about 0.95;
and ~ ~ y + z = 1 The scale inhibitory power of various polymers has been evaluated using the following screening procedures employ-in~ test chemicals of reagent grade:
Calcium, magnesium, and bicarbonate were supplied by ~aCl~4H~O; MgSO4.7H2O; and NaHCO3 respectively. The inhibitor concentrations were equivalent in each test class, unless other-wise indicated. The orthophosphate was supplied by H3PO4 and the organophosphorus materials obtained from commercial suppliers.
Each test solution was stirred with a teflon* coated stir bar in a jacketed glass beaker. Temperature was maintained using a Lauda* recirculating, constant-temperature bath. The pH was determined with Fisher Accumet* meter (Model 610A) and a combina-3~ tion electrode. The pH meter was calibrated with two standard buffers (pH 7 and 10) and corrections were made for temperature changes.
*Trade Mark - 6 -FOi kA .~L ~.~SE ~0] 1 ~ 7 ~397 Calcium and ~la~nesium Phosphate Inhibition - Calcium and magnesium were added to provide initial conccntra-tions of 250 and 125 mg/L. An equal amount of phosphate was added to each test solution, and the inhibitor concentrations are listed in Tables I and II. The temperature of the test solutions was maintained at 15SF. (70C). Using dilute aqueous NaOH, the pH
~as slowly increased to 8.5 and maintained during the ~OUl` hour duration of the test. ~ineral solubility l~) c~lculations indicate supersaturation ratios for calcium phosphate ~ 10,000 and magnesiu~ phosphate >
~00 were initially present and the system was under highly stressed conditions. At the conclusion of each test, each solution was filtered (0.45 um) and the orthophosphate concentration was determined spectrophotometrically (700 nm) after formation of a blue phosphomolybdate complex. The inhibition of calcium phosphate is determined by Equation 1:
. . filtered sam le - blank (1) ~6 Inhlbltlon = unfiltere~sample - blank ~a In the absence of the polymers described herein, %
Inllibition equals 0. Non-zero values represent scale inhibition benefits associated with the addition of an active polymer to the system being tested.
The foregoing procedure was used to collect data on specific copolymers and terpolymers according to the invention; and the results are set forth in Table I and Table II below.
~ ~ ,":
TABLE I
-SULFOAL~YLACRYLAMIDE-, SULFOPHENYLACRYLAMIDE-, PHOSPHO~OALKYLACRYLA~IIDE-, CAR~OXYAlKYLAGRYLA~IDE-, AND POLYHYDROXYALKYLAMIDE-CONTAINING POLYMERS
% PHOSPHATE
SALT INHIBITION
MOLECULAR P.P.M. POLYMER ACTIVES
S.~LE POLYMER CONPOSITION MOLE ~ ~EIGHT, Mw 5 7.5 10 20 A Acrylic Acid 84/
Sulfoethylacrylamide 1631,300 790 97 Al Acrylic Acid 79/
Sulfoethylacrylamide 21 6,000 60 95 L Acrylic Acid 60/Acrylamide 25/
Sul~oethylacrylamide 1510,600 38 99 ~1 Acrylic Acid 52/Acrylamide 40/
Sulfoethylacrylamide 7 45,300 70 93 B2 Acrylic Acid 78/Acrylamide 11/
Sulfoethylacrylamide 1153,800 0 94 B3 Acrylic Acid 23/Acrylamide 51/
Sulfoethylacrylamide 2643,400 97 93 B Acrylic Acid 66/Acrylamide 9/
4 Sulfoethylacrylamide 2655,900 70 92 B5 Acrylic Acid 27/Acrylamide 27/
Sulfoethylacrylamide 4648,400 94 100 B6 Acrylic Acid 67/Acrylamide 10/
Sulfoethylacrylamide 2222,100 73 99 B Acrylic Acid 56/Acrylamide 13/
7 Sulfoethylacrylamide 3255,700 66 100 B Acrylic Acid 34/Acrylamide 16 8 Sulfoethylacrylamide 5052,200 97 94 C Acrylic Acid 51/Acrylamide 32/
Sulfoethylacrylamide 1733,00G 94 97 Cl Acrylic Acid l9/Acrylamide 27/
SulEoethylacrylamide 5444,100 97 99 D Acrylic Acid/Ethyl Acrylate/
Sulfoethylacrylamide 14 3,700 93 100 E Acrylic Acid 60/Acrylamide 20/
Sulfomethylacrylamide 2055,800 38 95 F Acrylic Acid ~9/Acrylamide 17/
Sulfomethylacrylamide 1419,600 43 98 G Acryllc Acid 25/Acrylamide 55/
Sulfomethylacrylamide 2012,200 10 34 80 Gl Acrylic Acid 37/Acrylamide 23/
Sulfomethylacrylamide 4181,700 94 94 G2 Acrylic Acid 80/Acrylamide 10/
Sulfomethylacrylamide 1037,500 94 FONG ET .~L CASE 4016 ~7g3~3~3~7 TABLE I
-(Continued) 7~ PllOSPilATE
SALT INHIBITION
MOLECULAR P.P.M. POLYMER ACTIVES
S~L2 POL~MER CO~OSITION MOL _7, WEIGHT, Mw 5 7.5 10 20 G Acrylic Acid 30/Acrylamide 60/
3 Sulfomethylacrylamide 10 80,300 94 G Acrylic Acid 95/Acrylamide 0/
4 Sulfomethylacrylamide 5 18,000 95 . _ . _ , . . . . .
G5 Acrylic Acid 13/Acrylamide 85/
Sulfomethylacrylamide 2 11,700 90 H Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-ncrylamide 15 17,400 9 99 I Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-acrylamide 15 68,500 6 100 J Acrylic Acid 50/Acry1amide 15/
2-Hydroxy-3-sulfopropyl-acrylamide 35 25,800 84 Acrylic Acid 20/Acrylamide 10/
2-Hydroxy-3-sulfopropyl-acrylamide 70 28,600 89 L Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-acrylamide 15 36,500 12 45 100 M Acrylic Acid 30/Acrylamide 62/
Phosphonopropylacrylamide 8 11,100 10 10 95 N Acrylic Acid 45/Acrylamide 45/
Sulfophenylacrylamide 10 11,500 7 90 97 Acrylic Acid 85/Acrylamide 5/
Carboxymethylacrylamide 10 38,600 4 78 P Acrylic Acid 50/Acrylamide 35/
Carboxypentylacrylamide 15 14,100 8 9498 Q Acrylic Acid/Acrylamide/
N-(1,2-Dicarboxy)ethylacrylamide 13,500 8 89 100 R Acrylic Acid 51/Acrylamide 32/
N-(2,3-Dihydroxy)propyl-acrylamide 17 14,600 10 7598 S Acrylic Acid 50/Acrylamide 38/
N-(2,3-Dihydroxy)propyl-acrylamide 12 76,600 33 99 T Acrylic Acid 7.5/Acrylamide 15/
N-(2-Methyl-1,3-dihydroxy)-2-propylacrylamide 10 16,000 23 82 U Acrylic Acid 45/Acrylamide 50/
N-(2-Hydroxymethyl-1,3-dihydroxy)-2-propylacrylamide 5 11,600 99 _ 9 _ ~7~
NG ET .~ CASE 401 TABLE II
~L~LEIC ~NHYDRIDE POLYMERS
REACTED WITH ~MINO-SULFONATE CO~POUNDS
~ PHOSPHATE
SALT INHIBITION
~DRIDE POLY~R ~ND MOLEMw P.P.M. POLYME~ ACTIVES
.~L~ ~TIO ANHYD. GP: AMINE* (GPC) 10 20 A~ S~-1000 ~ Na Sulfanilate ~ 7 o,560 22 95 BB Gantrez*AN-ll9 + Na Sulfanilate 1:0.67 9,800 16 92 CC S~-3000 + Na Sulfanilate 1:111,000 21 90 DD Gantrez AN-149 + Na Sulfanilate 1:195,400 63 80 EE Gantrez AN-149 + Na T~urate 1:1 98,900 56 83 FF MAH/~NE (~led. ~) +
Na Taurate 1:132,800 82 GG ~H/~NE (Med. ~) +
Na Sulfanilate 1:1 39,700 49 HH ~H/NVP + Na Taurate 1:1 17,800 77 99 II ~L~H¦l~m ~ Na Taurate 1:1 8,330 17 98 JJ Gantrez AN-149 + Na Sulfanilate 1:0.528J000 84 X~ ~H/~NE (Med. ~) +
Na Taurate 1:0.5 41,600 19 50 LL ~X/Hexene ~ Na Taurate 1:0.5 37,300 11 69 *Abbreviations as follows:
S~ - 1000 or 3000 (ARCO) styrene-maleic anhydride copolymer Gantrez - (GAF)*maleic anhydride-methyl vinyl ether copolymer M~H - maleic anhydride MVE - methyl vinyl ether NVP - N-vinylpyrrolidone Am - acrylamide Trade Ma~rk ~ ~ t'~ 7 Phosphate Salt Inhibition in Presence of Iron -The test procedure is identical to the one previously described "Calcium and Magnesium Phosphates", except that 3 p.p.m. of soluble Fe(II) and l0 p.p.m. of polymeric inhibitor are added. The criterion for determining scale inhibiting activity is the same as in the original test. The presence of iron applies additional stress upon the polymeric material and %
inhibition values tend to show a decrease. As the activity of the polymer increases, that decrease in ~ inhibition is minimized. This procedure was used to collect data on specific co- and terpolymers (lO p.p.m. actives dosage) and the results are set forth in Table III below:
~O~'G ET AL CA~sE ~ 0 1 ~7~ 7 TABLE III
SULFOL~LKYLACRYLAMIDE-, SULFOPHENYLACRYLAMIDE-, PHOSPHO~O.~LKYLACRYLAMIDE-, CARBOXYALKYLACRYLAMIDE-, AND POLYHYDROXYALKYLAMIDE-CONTAINING POLYMERS
MOLECULAR % PHOSPHATE SALT INHIBITION
S.4MPL~ Po~YMER COMPOSITION MO~E % _ WEIGHT, Mw (with 3 ppm soluble iron) A Acrylic Acid 84/
Sulfoethylacrylamide 16 31,300 8 1 Acrylic Acid 79/
~ SulfQethylacrylamide 21 6,000 23 B Aerylic Acid 60/Acrylamide 25/
Sulfoethylacrylamide 15 10,600 98 Bl Ac~ylic Acid 52/Acrylamide 40l Sulfoethylacrylamide 7 45,300 96 B~ Acrylic Acid 78/Acrylamide 11/
Sulfoethylacrylamide 11 53,800 51 B3 Acrylic Acld 23/Acrylamlde 51/
Sulfoethylacrylamlde 26 43,400 B Acryllc Acld 66/Acrylamide 9/
4 Sulf~ethylacrylamlde 26 55,900 92 B Acryllc Acid 27/Acrylamide 27/
Sulfoethylacrylamide 46 48,400 76 B6 Acrylic Acid 67/Acrylamide 10/
SulEoethylacrylamide 22 22,100 8 B Acrylic Acid 56/Acrylamlde 13/
7 Sulfoethylacrylamide 32 55,700 97 B Acrylic Acid 34/Acrylamide 16 8 SulEoethylacrylamide 50 52,200 83 G Acry1ic Acid 51/Acrylamide 32/
Sulfoethylacrylamide 17 33,000 98 D Acrylic Acld/Ethyl Acrylate/
Sulfoethylacryl~mide 14 3,700 19 E Acrylic Acid 60/Acrylamlde 20¦
Sulfomethylacrylamlde 2055,800 . 90 F Acrylic Acid 69/Acrylamide 17/
Sulfomethylacrylamide 1419,600 28 G Acrylic Acid 25/Acrylamide 55/
Sulfomethylacrylamide 2012,200 22 Gl Acrylic ~cid 37/Acrylamide 23/
Sulfomethylacrylamide 4181,700 93 G Acrylic Acid 80/Acrylamide 10/
2 Sulfomethylacrylamlde 1037,500 11 .. , . _ .. . .. . _ . ..
FO~G ET AL CASE 4016 ~ 7 TABLE III
(Continued) MOLECUL.4R % PHOSPHATE SALT INHIBITION
S.~LB POLY~R COMPOSITION MO~E % WEIGHT, Mw (with 3 ppm soluble iron) G Acrylic Acid 30/Acrylamide 60/
3 Sulfomethylacrylamide 10 80,300 5 G Acrylic Acid 95/Acrylamide 0/
4 Sulfomethylacrylamide 5 18,000 98 H Acrylic Acid BO/Acrylamide 5/
~-Hydroxy-3-~ul~opropyl~
acrylamide 15 17,400 21 I Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-acrylamide 15 68,500 7 J Acrylic Acid 50/Acrylamide 15/
2-Hydroxy-3-sul~opropyl-acrylamide 35 25J800 47 K Acrylic Acid 20/Acrylamlde 10/
2-Hydroxy-3-sulfopropyl-acrylamide 70 28,600 95 L Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-acrylamide 15 36,500 8 M Acrylic Acid 30/Acrylamide 62/
Phosphonopropylacrylamide 8 11,100 N Acrylic Acid 45/Acrylamide 45/
Sulfophenylacrylamide 10 11,500 O Acrylic Acid 85/Acrylamide 5/
Carboxymethylacrylamide 10 38,600 P Acrylic Acid 50/Acrylamide 3S/
Carboxypentylacrylamide 15 14,100 88 Q Acrylic Acid/Acrylamide/
N-(1,2-Dicarboxy)ethylacrylamide 13,500 35.
R Acrylic Acid 51/Acrylamide 32/
N-(2,3-Dihydroxy)propyl-acrylamide 17 14,600 . 10 S Acrylic Acid 50/Acrylamide 38/
N-(2,3-Dihydroxy)propyl-. acrylamide 12 76,600 T Acrylic Acid 75/Acrylamide 15/
N-(2-Met~hy.l.-1 J 3-dihydroxy)-2-propylAcrylamide 10 16,000 22 U Acrylic Acid 45/Acrylamide 50/
N-(2-Hydroxymethyl-1,3-dihydroxy)-2-propylacrylamide 5 11,600 _ .. _ _ _ . .. . _ .. . _ .. .
FONG ET AL CAS~ l6 ,~
~ ~ 7 ~
Barium Sulfa~e Inhibition - Calcium and magnesium were added to provide initial concentr~tions of 150 and 50 mg/L. Sodium sulfate was used to increase the initial SO4 2 concentration to 500 mg/L. The inhibitor was added (25 mg/L as is) to each ~est solution, and the temperature was maintained at 104P. (40C.). The pH was slowly adjusted to 4.5 and the solution's transmittance determined with a Brin~mann probe colorimeter (PC S01). The barium titrant solution ld ~500 mg/L) was added a~ a slow, constan~ rate and the transmittance of ~he ~est solution monitored continuously.
The test was terminated when ~urbidity was initially observed (1% transmittance decrease) and the barium level determined from the amount of titrant added.
Atomic absorption was used to verify the barium concentratio~ in selected samples.
Data recorded for ~arious terpolymers are included in Table IV below.
TABLE IV
BARIUM S~LPHATE I~HIBITION
Polymex Dosage~* Ba+2 Level Sample Composition* ~mol %~ Mw (ppm Actives)_ (ppm)***
Blank ~ - 2-3 aM/Am/AMS (30/50/20) 4,600 7.6 4.2 b " (69/17/14) 18,900 9.0 5.4 c " (69/17/14) 64,200 9.0 6.6 dM/Am/2-AES (79/0/21) 5,800 6.2 5.3 e " (90/0/10) 5,800 5-4 4-5 ~ " (56/27/17) 4,500 8.0 10.8 g " (60/25/15) 10,600 8.0 4.4 hAA/AmlAHPS(40/50/10) 21,700 8.8 4~4 i " (50/30/20) 24,20010.0 4-5 ~ " (50115/35) 25,800 9.5 10.2 k " (20/10/70) 28,60012~0 4.1 * refer to abbreviations lls~ed hereinafter ** all products tested at a level of 25 ppm (as is) TABLE IV (Con-tinued) *** laL~er values represent grea-ter performance Abbreviations:*
.~A = acrylic acid A~A = 2-acrylamido-butanedioic acid ~m = acrylamide AMPD = 2-acrylamido-2-methyl-1,3-propanediol ~IS = acrylamidomethanesulfonic acid 2-A~S = ~-acrylamidoethanesulfonic acid ~IIP8 = 3-acrylamido-2-hydroxypropanesulfonic acid AIIEA = acrylamido-2-hydroxyethanoic acid ~I~A = methylbutylamine Calcium Carbonate Inhibition - Calcium, magnesium, and bicarbonate were respectively added to provide initial concentrations of 360, 200 and 500 mg/L. The performance of eacll inhibitor was determined as indicated in Table V. The test temperature was maintained at 140F. (60C.). Aqueous ~aOH titrant was added at a constant rate, and the pH increase was continuously monitored. When bulk precipitation of calcium ~rbonat~ occurred, a slight decrease in the pH was observed.
ld Based on the test conditions at the pH breakpoint, a mineral solubility computer program is used to calculate the CaC03 s-lpersaturatiorl ratio as indicated in Table V below. Calcium ~arbonate inhibition performance is believed related to the supersaturation ratio which can be maintained. After each test, dilute aqueous HCl was used to remove all precipitated calcium carbonate from the test apparatus.
Calcium Phosphonate Inhibition - Calcium and a mix-ture of l-hydroxy-l,l-ethane diphosphonic acid (HEDP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) were added to ~0 provide initial concentrations of 360 mg/L and 8 ppm (total phosphorus as PO4), respectively. The temperature was main-tained at 140F. (60C.). Using dilute aqueous NaOH, the pH
FONG ET AL CASE l6 ~ ~7~ ~q~
was slowly increased to 9.2 and maintained during the four hour duration of the test. At the conclusion of each tes~, each solution was filtered (0.45 um) and the total phosphorus concentration was determined by a standard spec~rophotometric procedure. The inhibition of calcium organophosphorus compounds were de~ermined by Equation l; and data are set forth in Table V below.
TA~LE V
CALCIUM CARBONATE AND CALCIUM ORGANOPHOSPHORUS INHIBITION
Ca Phosphonate (% Ca Carbonate (Sat.
Polymer Inhibition) 10 ppm Ratio) 10 ppm ~mple Composition* (mol %) Mw Poly~er Actlves Polymer Artives Blank -- -- -- O 16 HEDP ~ - 160 .~b AA/Am/AMS (25/55/20) 12,200 94 58 IC Gantrez-~A 69,200 98 72 AA/Am/AHEA 42,900 98 180 ~a A~/Am/ABA 13,500 100 91 ~f M/Am/AHPS 11,300 100 47 ~g M~Am/AMPD (50/30/20) 16,000 100 89 * refer to listing of abbrevia~ions hereinabove in TableIV
NOTE: Larger values for % inhibition and saturation ratio indicate greater performance.
Benchtop Test Procedures for Particle Dispersion:
The particulate matter used in these tests was obtained l~ from commercial sources. Calcium and magnesium were presen~ at concentrations of 90 and 50 mg/L, respectively. Bicarbonate was added to provide an "M" alkalinity of ~-~100 mg/L. The dispersing agent and particulate matter were added and the solution stirred at 100 rpm using a motor-driven, stainless steel paddle. At the end of each test, the level of dispersion was measured with visible light absorption or nephelollletly. Variations in the gene-ral procedure are listed below:
Iron Oxide - Fe203 powder (100 mg) was used and FO~G ET AL CASE 'J '6 the test solution s~irred for two hours. Dispersion was measured using a Brinkmann probe colorimeter (470 nm) as the solution was stirred. The relative level of dispersion was calculated using Equation 2:
R~lative dispersion = SamPle Wi~hodtsdesperging a-gent (2) Calcium Carbonate - CaC03 powder (200 mg) was used and the test solution was stirred for one hour.
The particulates were allowed ~o settle for one hour ~) and an aliquot withdrawn from 1 cm beneath ~he sample's surface. An HF Instruments nephelome~er ~Model DRT 1000) was used to determine the final level of suspended solids. Equa~ion 2 was used to calculate the relative dispersion.
Calcium Phosphate - Ca3(P04)2 powder ~200 mg) was used and the test procedure conducted in a manner similar to that used for calcium carbonate.
The data from particle dispersion determinations are collected in Table VI below.
TABLE VI
MINERAL DISPERSANCY
_ RelatiYe Dispersancy**
PolymerIron Calcium Calcium Sample Composition* (mol %~ Mw Oxide Carbona~e Phosphate Blank ~ 1.0 1.0 1.0 ba M/Am/AMS (25/55/20) 12,200 7.2 5.8 3.1 bb Gantrez-~A 69,200 3.8 3.0 3.1 bc M /Am/AHEA 42,900 1.6 5.0 2.3 bd AA/Am/ABA 13,500 7.3 5.2 3.4 be AA/Am/AHPS 11,300 7.0 4.~ 3.6 bf AAjAm/AMPD (50/30/20) 16,000 5.0 5.0 2.9 * refer to listing of abbreviations hereinabove in Tables II and IV
** see Equation 2, 1 ppm polymer ac~ive NOTE: Larger values for relatlve dispersancy indicate greater performance FONG ET AL CASE `16 ~ ~ 7 ~53~3~
The data presented in Tables I-VI inclusive amply demonstra-te that polymers and terpolymers according to the inven~ion are capable of functioning positively in a commercial, scale inhibi~ion and dispersancy environment.
Sulfomethylamide-, Sulfoethylamide-~ 2-Hydroxy-3-Sulf~ ylamide^~
2~3-Dihydroxypropyiamide-, and Sulfophenylamide-Polymer S~ecies In one important aspect, the present inven~ion is chalacterized by the molecular modification o-f a pre-existing polymer chain of suitable length so as to incorporate a sulfonate ubstituen~, as distinguished from attempts to build up a sllficiently large polymer from sulfonated monomers. One post-modification procedure of the inven~ion calls for the reaction of an acrylamide-containing polymer and a selected aminosulfonic acid; and this reaction is believed to proceed by a transamidation mechanism.
Preferred aminosulfonic acids for use in this aspect of the invention include aminomethanesulfonic acid, l-amino-2-hydroxy-3-propanesulfonic acid, 2,3-dihydroxypropylamine, 2-aminoethanesulfonic acid (taurine), and 4-aminobenzenesulfonic ~a acid (p-sulanilic acid), although 3-aminobenzenesulfonic acid ~metanilic acid) may also be employed. In addition, the alkali metal salts of these acids can be used in the practice of the invention.
The selected aminosulfonic acid is advantageously added to a water solution of sodium hydroxide and the polyacrylamide reactant; and the resultant mixture is then heated in a pressure reactor to a suitable temperature, such as 150C., for a suitable length of time, such as 4-5 hours. After the reaction has gone to the desired extent, the mixture is cooled and thereafter either concelltra~ed or dewatered to recover the adduct.
Sulfomethylamide polymers can also be prepared by reacting polyacrylamide with -formaldehyde-bisulfita or with ~7~
aminomethane sulfonic acid at a suitable -temperature, such as 150C., for a suitable length o~ time, such as 4-5 hours.
The acrylamide-containing polymers for use in the present invention include homopolymers of acrylamide and their homologs, such as the homopolymers of methacrylamide, and co-polymers, including terpolymers, of acrylamide, or its homologs, with acrylic acid, or its homologs, such as methacrylic acid, as well as homopolymers of (meth)acrylate esters, itaconic acid and est~l-s, crotonic acid and esters, acrylonitrile and the like.
It has been discovered that desirable, secondary amide formation is promoted in the reaction system of the invention when the acrylamide-containing polymer is selected to contain a mole ratio of acrylamide or homologous units of at least about 10 and preferably 30% or higher.
The sulfonated reaction products of the invention are useful scale inhibitors as evidenced by phosphate-inhibition test results, which are also strongly indicative of the suit-ability of these adducts in various product environments.
In order to describe the instant species of the inven-0 tion more fully, the following working examples are given:EXAMPLE 1 A mixture of poly(acrylamide [50 mole %]-acrylic acid) (150 g 31.5% solution in water, Mw 55,700); taurine (16.7 g);
and sodium hydroxide (10.6 g 50% solution in water) was heated in a mini Parr pressure reactor at 150C. for four hours. The reaction mixture was then cooled to room temperature. The molecular weight of the resulting polymer, determined by gel permeation chromatography (GPC) using polystyrene sulfonate standard, was 56,0000 The composition of the polymer was de-ter 3~ mined both by C-13 NMR and colloid titration and was -found to contain about 50~ carboxylate, 31% primary amide and 19% sulfo-ethylamide.
, 3~
A mixture of poly(acrylamide [75 mole ~]-acrylic acid) ~150 g of 27.5~ solution in water)i sulfanilic acid (20.4 g);
sodium hydroxide (9.3 g of 50% solution); and 10.5 g of ~Yater was heated in a mini Parr pressure reactor at 150C. for five hours~ The reaction mixture was thereafter cooled to room temperature The molecular weight of the resulting polymer was 11,500 as determined by GPC using polystyrene sulfonate s~andard r The polymer contained about 5~ sulfophenylamide, 47.5% primary lo amide and 47.5% carboxyla~e as estimated by C-13 NMR. At 5 ppm of the polymer, there was 7% phosphate inhibitioni at 7.5 ppm polymer, 96% phosphate inhibition; and at 10 ppm, 100% phosphate inhibition.
A mixture of poly(acrylamide [75 mole %]-acrylic acid) ~150 g o~ 27.5% solution in water); aminomethane sulfonic acid tl3.2 g); and sodium hydroxide ~10.2 g of 50% solution) was heated in a mini Parr pressure reactor at 125C. for four-and-a-half hours. The reaction mixture was therea-fter cooled to room temperature. The molecular weight of the resulting polymer was 15,900 as determined by GPC using polystyrene sulfonate s~andard.
The polymer contained about 45% acrylic acid, 40~ acrylamide and 15~ sul~omethylacrylamide as estimated by C-13 NMR.
S lfonated Maleic Anh dride Pol mer S ecies u _ _ Y _ _ Y .P '_ This aspect of the post-modification procedure of the invention calls for the addition reaction of a selected amino-sulfonic acid, or its alkali metal salt, and maleic anhydride homopolymer, copolymer or terpolymer of maleic anhydride and ~inylic compounds.
The present reaction is caused to take place in a suitable solvent, such as dimethylformamide, under heating) agitation and reflux conditions; and preferred aminosulfonate sources include 4-aminobenzenesulfonic acid ~p-sulfanilic acid), 2-aminoethane-FO~G ET AL CASE 16 ~ 7~3~ ~ ~
sulfonic acid (taurine), and the alkali metal salts thereof.3-Aminobenzenesulfonic acid (metanilic acid~ and its alkali metal salts may also be employed.
The copolymers, including terpolymers, which find utility in the present species of the invention are made up of maleic anhydride and like ring compounds which have been reacted ~ith suitable monomers such as styrene, methyl vinyl ether, N-vinylpyrrolidone, N-vinylcaprolactam and N-methyl-N-vinyl-acetamide, ~meth)acrylamide, ~meth)acrylic acid, (meth)acrylate 1~ esters, vinyl esters SUC]I as vinyl acetate, alkenes such as l-hexene, l-butene and dienes such as butadiene and cyclopenta-diene~ for example.
The maleic anhydride homo-, co- and terpolymers are reacted ~ith from 5 to 100 mole ~ of the aminosulfonate compound per mole of anhydride group in the polymer. The molecular weight of the resulting polymers have a weight average molecular weight in the range of from about 1000 to about 120,000 and preferably from about 3000 to 100,000 as determined by gel permeation chromatography.
2~ In order to describe this aspect of the invention more fully, the following working example is given:
To a reaction flask fitted with a reflux condenser, mechanical stirrer, nitrogen sparging tube and a thermometer, there was added 15.6 g (0.1 mole) of Gantrez AN-149 (a 1:1 mole ratio copolymer of maleic anhydride and methyl vinyl ether) and 200 g of dimethylformamide solvent. The resultant mixture was heated under a nitrogen gas at~osphere to dissolve the polymer.
A highly colored solution, red-violet in hue, resulted. After all -~ the polymer was visibly dissolved, at a temperature of about 120C.
21.3 g ~0.1 mole) of sodium sulfanilate monohydrate was added to .. ..
~7~ 7 `~'G ET AL ~SE ~16 the reaction flask together with a further 100 g of dimcthy1forma-mide.
Heating was continued until the solution refluxed, at a temperature of about 144-1~18C.; and refluxing was continued ~or four hours. During this time, an intense blue-purple color developed and solids precipitated. After refluxing was completed, the entire reaction mixture ~precipate and solvent solution) . ~ , . .
w~s concentrated`on a rotary evaporator~under vacuum. A dark bl~le soli-l resulted, and this was subject to final drying in td a v~ct1um oven at 50C. for 24 hours. A very dark colored solid, 3S g in weight, remained. This solid was dissolved easily in ~ate~ ~Yith the addition of a small amount of sodium hydroxide to give a solution of deep blue color.
The molecular weight of the resultant polymer was c~timated to be 95,400 by GPC using polystyrene sulfonate stnndard and its infra-red spectrum showed absorptions at 1770 cm l (cyclic imide), 1700 cm l ~cyclic imide and carboxyl) 9 lfi~0 cm l tamide carbonyl), 1590 cm 1 (carboxylate) and 1560 cm l ~amide II band). The polymer contained about 81 M % m~leimide 2~ lmits, about 14 ~1 ~ maleic acid units and about 5 M % maleamic ~cid ~mits as estimated by infra-red and LC analysis for residual amonisl1lfonate compound.
The calcium phosphate inhibition propensity of the product of Example 4 was tested and is compared with other maleic anhydride, aminosulfonated polymers made according to the invention in Table II hereinabove.
The manner in which the present invention may be practiced and the purpose to which it may be put are evident rom the foregoing descriptions.
Sulfoethylacrylamide 4648,400 94 100 B6 Acrylic Acid 67/Acrylamide 10/
Sulfoethylacrylamide 2222,100 73 99 B Acrylic Acid 56/Acrylamide 13/
7 Sulfoethylacrylamide 3255,700 66 100 B Acrylic Acid 34/Acrylamide 16 8 Sulfoethylacrylamide 5052,200 97 94 C Acrylic Acid 51/Acrylamide 32/
Sulfoethylacrylamide 1733,00G 94 97 Cl Acrylic Acid l9/Acrylamide 27/
SulEoethylacrylamide 5444,100 97 99 D Acrylic Acid/Ethyl Acrylate/
Sulfoethylacrylamide 14 3,700 93 100 E Acrylic Acid 60/Acrylamide 20/
Sulfomethylacrylamide 2055,800 38 95 F Acrylic Acid ~9/Acrylamide 17/
Sulfomethylacrylamide 1419,600 43 98 G Acryllc Acid 25/Acrylamide 55/
Sulfomethylacrylamide 2012,200 10 34 80 Gl Acrylic Acid 37/Acrylamide 23/
Sulfomethylacrylamide 4181,700 94 94 G2 Acrylic Acid 80/Acrylamide 10/
Sulfomethylacrylamide 1037,500 94 FONG ET .~L CASE 4016 ~7g3~3~3~7 TABLE I
-(Continued) 7~ PllOSPilATE
SALT INHIBITION
MOLECULAR P.P.M. POLYMER ACTIVES
S~L2 POL~MER CO~OSITION MOL _7, WEIGHT, Mw 5 7.5 10 20 G Acrylic Acid 30/Acrylamide 60/
3 Sulfomethylacrylamide 10 80,300 94 G Acrylic Acid 95/Acrylamide 0/
4 Sulfomethylacrylamide 5 18,000 95 . _ . _ , . . . . .
G5 Acrylic Acid 13/Acrylamide 85/
Sulfomethylacrylamide 2 11,700 90 H Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-ncrylamide 15 17,400 9 99 I Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-acrylamide 15 68,500 6 100 J Acrylic Acid 50/Acry1amide 15/
2-Hydroxy-3-sulfopropyl-acrylamide 35 25,800 84 Acrylic Acid 20/Acrylamide 10/
2-Hydroxy-3-sulfopropyl-acrylamide 70 28,600 89 L Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-acrylamide 15 36,500 12 45 100 M Acrylic Acid 30/Acrylamide 62/
Phosphonopropylacrylamide 8 11,100 10 10 95 N Acrylic Acid 45/Acrylamide 45/
Sulfophenylacrylamide 10 11,500 7 90 97 Acrylic Acid 85/Acrylamide 5/
Carboxymethylacrylamide 10 38,600 4 78 P Acrylic Acid 50/Acrylamide 35/
Carboxypentylacrylamide 15 14,100 8 9498 Q Acrylic Acid/Acrylamide/
N-(1,2-Dicarboxy)ethylacrylamide 13,500 8 89 100 R Acrylic Acid 51/Acrylamide 32/
N-(2,3-Dihydroxy)propyl-acrylamide 17 14,600 10 7598 S Acrylic Acid 50/Acrylamide 38/
N-(2,3-Dihydroxy)propyl-acrylamide 12 76,600 33 99 T Acrylic Acid 7.5/Acrylamide 15/
N-(2-Methyl-1,3-dihydroxy)-2-propylacrylamide 10 16,000 23 82 U Acrylic Acid 45/Acrylamide 50/
N-(2-Hydroxymethyl-1,3-dihydroxy)-2-propylacrylamide 5 11,600 99 _ 9 _ ~7~
NG ET .~ CASE 401 TABLE II
~L~LEIC ~NHYDRIDE POLYMERS
REACTED WITH ~MINO-SULFONATE CO~POUNDS
~ PHOSPHATE
SALT INHIBITION
~DRIDE POLY~R ~ND MOLEMw P.P.M. POLYME~ ACTIVES
.~L~ ~TIO ANHYD. GP: AMINE* (GPC) 10 20 A~ S~-1000 ~ Na Sulfanilate ~ 7 o,560 22 95 BB Gantrez*AN-ll9 + Na Sulfanilate 1:0.67 9,800 16 92 CC S~-3000 + Na Sulfanilate 1:111,000 21 90 DD Gantrez AN-149 + Na Sulfanilate 1:195,400 63 80 EE Gantrez AN-149 + Na T~urate 1:1 98,900 56 83 FF MAH/~NE (~led. ~) +
Na Taurate 1:132,800 82 GG ~H/~NE (Med. ~) +
Na Sulfanilate 1:1 39,700 49 HH ~H/NVP + Na Taurate 1:1 17,800 77 99 II ~L~H¦l~m ~ Na Taurate 1:1 8,330 17 98 JJ Gantrez AN-149 + Na Sulfanilate 1:0.528J000 84 X~ ~H/~NE (Med. ~) +
Na Taurate 1:0.5 41,600 19 50 LL ~X/Hexene ~ Na Taurate 1:0.5 37,300 11 69 *Abbreviations as follows:
S~ - 1000 or 3000 (ARCO) styrene-maleic anhydride copolymer Gantrez - (GAF)*maleic anhydride-methyl vinyl ether copolymer M~H - maleic anhydride MVE - methyl vinyl ether NVP - N-vinylpyrrolidone Am - acrylamide Trade Ma~rk ~ ~ t'~ 7 Phosphate Salt Inhibition in Presence of Iron -The test procedure is identical to the one previously described "Calcium and Magnesium Phosphates", except that 3 p.p.m. of soluble Fe(II) and l0 p.p.m. of polymeric inhibitor are added. The criterion for determining scale inhibiting activity is the same as in the original test. The presence of iron applies additional stress upon the polymeric material and %
inhibition values tend to show a decrease. As the activity of the polymer increases, that decrease in ~ inhibition is minimized. This procedure was used to collect data on specific co- and terpolymers (lO p.p.m. actives dosage) and the results are set forth in Table III below:
~O~'G ET AL CA~sE ~ 0 1 ~7~ 7 TABLE III
SULFOL~LKYLACRYLAMIDE-, SULFOPHENYLACRYLAMIDE-, PHOSPHO~O.~LKYLACRYLAMIDE-, CARBOXYALKYLACRYLAMIDE-, AND POLYHYDROXYALKYLAMIDE-CONTAINING POLYMERS
MOLECULAR % PHOSPHATE SALT INHIBITION
S.4MPL~ Po~YMER COMPOSITION MO~E % _ WEIGHT, Mw (with 3 ppm soluble iron) A Acrylic Acid 84/
Sulfoethylacrylamide 16 31,300 8 1 Acrylic Acid 79/
~ SulfQethylacrylamide 21 6,000 23 B Aerylic Acid 60/Acrylamide 25/
Sulfoethylacrylamide 15 10,600 98 Bl Ac~ylic Acid 52/Acrylamide 40l Sulfoethylacrylamide 7 45,300 96 B~ Acrylic Acid 78/Acrylamide 11/
Sulfoethylacrylamide 11 53,800 51 B3 Acrylic Acld 23/Acrylamlde 51/
Sulfoethylacrylamlde 26 43,400 B Acryllc Acld 66/Acrylamide 9/
4 Sulf~ethylacrylamlde 26 55,900 92 B Acryllc Acid 27/Acrylamide 27/
Sulfoethylacrylamide 46 48,400 76 B6 Acrylic Acid 67/Acrylamide 10/
SulEoethylacrylamide 22 22,100 8 B Acrylic Acid 56/Acrylamlde 13/
7 Sulfoethylacrylamide 32 55,700 97 B Acrylic Acid 34/Acrylamide 16 8 SulEoethylacrylamide 50 52,200 83 G Acry1ic Acid 51/Acrylamide 32/
Sulfoethylacrylamide 17 33,000 98 D Acrylic Acld/Ethyl Acrylate/
Sulfoethylacryl~mide 14 3,700 19 E Acrylic Acid 60/Acrylamlde 20¦
Sulfomethylacrylamlde 2055,800 . 90 F Acrylic Acid 69/Acrylamide 17/
Sulfomethylacrylamide 1419,600 28 G Acrylic Acid 25/Acrylamide 55/
Sulfomethylacrylamide 2012,200 22 Gl Acrylic ~cid 37/Acrylamide 23/
Sulfomethylacrylamide 4181,700 93 G Acrylic Acid 80/Acrylamide 10/
2 Sulfomethylacrylamlde 1037,500 11 .. , . _ .. . .. . _ . ..
FO~G ET AL CASE 4016 ~ 7 TABLE III
(Continued) MOLECUL.4R % PHOSPHATE SALT INHIBITION
S.~LB POLY~R COMPOSITION MO~E % WEIGHT, Mw (with 3 ppm soluble iron) G Acrylic Acid 30/Acrylamide 60/
3 Sulfomethylacrylamide 10 80,300 5 G Acrylic Acid 95/Acrylamide 0/
4 Sulfomethylacrylamide 5 18,000 98 H Acrylic Acid BO/Acrylamide 5/
~-Hydroxy-3-~ul~opropyl~
acrylamide 15 17,400 21 I Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-acrylamide 15 68,500 7 J Acrylic Acid 50/Acrylamide 15/
2-Hydroxy-3-sul~opropyl-acrylamide 35 25J800 47 K Acrylic Acid 20/Acrylamlde 10/
2-Hydroxy-3-sulfopropyl-acrylamide 70 28,600 95 L Acrylic Acid 80/Acrylamide 5/
2-Hydroxy-3-sulfopropyl-acrylamide 15 36,500 8 M Acrylic Acid 30/Acrylamide 62/
Phosphonopropylacrylamide 8 11,100 N Acrylic Acid 45/Acrylamide 45/
Sulfophenylacrylamide 10 11,500 O Acrylic Acid 85/Acrylamide 5/
Carboxymethylacrylamide 10 38,600 P Acrylic Acid 50/Acrylamide 3S/
Carboxypentylacrylamide 15 14,100 88 Q Acrylic Acid/Acrylamide/
N-(1,2-Dicarboxy)ethylacrylamide 13,500 35.
R Acrylic Acid 51/Acrylamide 32/
N-(2,3-Dihydroxy)propyl-acrylamide 17 14,600 . 10 S Acrylic Acid 50/Acrylamide 38/
N-(2,3-Dihydroxy)propyl-. acrylamide 12 76,600 T Acrylic Acid 75/Acrylamide 15/
N-(2-Met~hy.l.-1 J 3-dihydroxy)-2-propylAcrylamide 10 16,000 22 U Acrylic Acid 45/Acrylamide 50/
N-(2-Hydroxymethyl-1,3-dihydroxy)-2-propylacrylamide 5 11,600 _ .. _ _ _ . .. . _ .. . _ .. .
FONG ET AL CAS~ l6 ,~
~ ~ 7 ~
Barium Sulfa~e Inhibition - Calcium and magnesium were added to provide initial concentr~tions of 150 and 50 mg/L. Sodium sulfate was used to increase the initial SO4 2 concentration to 500 mg/L. The inhibitor was added (25 mg/L as is) to each ~est solution, and the temperature was maintained at 104P. (40C.). The pH was slowly adjusted to 4.5 and the solution's transmittance determined with a Brin~mann probe colorimeter (PC S01). The barium titrant solution ld ~500 mg/L) was added a~ a slow, constan~ rate and the transmittance of ~he ~est solution monitored continuously.
The test was terminated when ~urbidity was initially observed (1% transmittance decrease) and the barium level determined from the amount of titrant added.
Atomic absorption was used to verify the barium concentratio~ in selected samples.
Data recorded for ~arious terpolymers are included in Table IV below.
TABLE IV
BARIUM S~LPHATE I~HIBITION
Polymex Dosage~* Ba+2 Level Sample Composition* ~mol %~ Mw (ppm Actives)_ (ppm)***
Blank ~ - 2-3 aM/Am/AMS (30/50/20) 4,600 7.6 4.2 b " (69/17/14) 18,900 9.0 5.4 c " (69/17/14) 64,200 9.0 6.6 dM/Am/2-AES (79/0/21) 5,800 6.2 5.3 e " (90/0/10) 5,800 5-4 4-5 ~ " (56/27/17) 4,500 8.0 10.8 g " (60/25/15) 10,600 8.0 4.4 hAA/AmlAHPS(40/50/10) 21,700 8.8 4~4 i " (50/30/20) 24,20010.0 4-5 ~ " (50115/35) 25,800 9.5 10.2 k " (20/10/70) 28,60012~0 4.1 * refer to abbreviations lls~ed hereinafter ** all products tested at a level of 25 ppm (as is) TABLE IV (Con-tinued) *** laL~er values represent grea-ter performance Abbreviations:*
.~A = acrylic acid A~A = 2-acrylamido-butanedioic acid ~m = acrylamide AMPD = 2-acrylamido-2-methyl-1,3-propanediol ~IS = acrylamidomethanesulfonic acid 2-A~S = ~-acrylamidoethanesulfonic acid ~IIP8 = 3-acrylamido-2-hydroxypropanesulfonic acid AIIEA = acrylamido-2-hydroxyethanoic acid ~I~A = methylbutylamine Calcium Carbonate Inhibition - Calcium, magnesium, and bicarbonate were respectively added to provide initial concentrations of 360, 200 and 500 mg/L. The performance of eacll inhibitor was determined as indicated in Table V. The test temperature was maintained at 140F. (60C.). Aqueous ~aOH titrant was added at a constant rate, and the pH increase was continuously monitored. When bulk precipitation of calcium ~rbonat~ occurred, a slight decrease in the pH was observed.
ld Based on the test conditions at the pH breakpoint, a mineral solubility computer program is used to calculate the CaC03 s-lpersaturatiorl ratio as indicated in Table V below. Calcium ~arbonate inhibition performance is believed related to the supersaturation ratio which can be maintained. After each test, dilute aqueous HCl was used to remove all precipitated calcium carbonate from the test apparatus.
Calcium Phosphonate Inhibition - Calcium and a mix-ture of l-hydroxy-l,l-ethane diphosphonic acid (HEDP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) were added to ~0 provide initial concentrations of 360 mg/L and 8 ppm (total phosphorus as PO4), respectively. The temperature was main-tained at 140F. (60C.). Using dilute aqueous NaOH, the pH
FONG ET AL CASE l6 ~ ~7~ ~q~
was slowly increased to 9.2 and maintained during the four hour duration of the test. At the conclusion of each tes~, each solution was filtered (0.45 um) and the total phosphorus concentration was determined by a standard spec~rophotometric procedure. The inhibition of calcium organophosphorus compounds were de~ermined by Equation l; and data are set forth in Table V below.
TA~LE V
CALCIUM CARBONATE AND CALCIUM ORGANOPHOSPHORUS INHIBITION
Ca Phosphonate (% Ca Carbonate (Sat.
Polymer Inhibition) 10 ppm Ratio) 10 ppm ~mple Composition* (mol %) Mw Poly~er Actlves Polymer Artives Blank -- -- -- O 16 HEDP ~ - 160 .~b AA/Am/AMS (25/55/20) 12,200 94 58 IC Gantrez-~A 69,200 98 72 AA/Am/AHEA 42,900 98 180 ~a A~/Am/ABA 13,500 100 91 ~f M/Am/AHPS 11,300 100 47 ~g M~Am/AMPD (50/30/20) 16,000 100 89 * refer to listing of abbrevia~ions hereinabove in TableIV
NOTE: Larger values for % inhibition and saturation ratio indicate greater performance.
Benchtop Test Procedures for Particle Dispersion:
The particulate matter used in these tests was obtained l~ from commercial sources. Calcium and magnesium were presen~ at concentrations of 90 and 50 mg/L, respectively. Bicarbonate was added to provide an "M" alkalinity of ~-~100 mg/L. The dispersing agent and particulate matter were added and the solution stirred at 100 rpm using a motor-driven, stainless steel paddle. At the end of each test, the level of dispersion was measured with visible light absorption or nephelollletly. Variations in the gene-ral procedure are listed below:
Iron Oxide - Fe203 powder (100 mg) was used and FO~G ET AL CASE 'J '6 the test solution s~irred for two hours. Dispersion was measured using a Brinkmann probe colorimeter (470 nm) as the solution was stirred. The relative level of dispersion was calculated using Equation 2:
R~lative dispersion = SamPle Wi~hodtsdesperging a-gent (2) Calcium Carbonate - CaC03 powder (200 mg) was used and the test solution was stirred for one hour.
The particulates were allowed ~o settle for one hour ~) and an aliquot withdrawn from 1 cm beneath ~he sample's surface. An HF Instruments nephelome~er ~Model DRT 1000) was used to determine the final level of suspended solids. Equa~ion 2 was used to calculate the relative dispersion.
Calcium Phosphate - Ca3(P04)2 powder ~200 mg) was used and the test procedure conducted in a manner similar to that used for calcium carbonate.
The data from particle dispersion determinations are collected in Table VI below.
TABLE VI
MINERAL DISPERSANCY
_ RelatiYe Dispersancy**
PolymerIron Calcium Calcium Sample Composition* (mol %~ Mw Oxide Carbona~e Phosphate Blank ~ 1.0 1.0 1.0 ba M/Am/AMS (25/55/20) 12,200 7.2 5.8 3.1 bb Gantrez-~A 69,200 3.8 3.0 3.1 bc M /Am/AHEA 42,900 1.6 5.0 2.3 bd AA/Am/ABA 13,500 7.3 5.2 3.4 be AA/Am/AHPS 11,300 7.0 4.~ 3.6 bf AAjAm/AMPD (50/30/20) 16,000 5.0 5.0 2.9 * refer to listing of abbreviations hereinabove in Tables II and IV
** see Equation 2, 1 ppm polymer ac~ive NOTE: Larger values for relatlve dispersancy indicate greater performance FONG ET AL CASE `16 ~ ~ 7 ~53~3~
The data presented in Tables I-VI inclusive amply demonstra-te that polymers and terpolymers according to the inven~ion are capable of functioning positively in a commercial, scale inhibi~ion and dispersancy environment.
Sulfomethylamide-, Sulfoethylamide-~ 2-Hydroxy-3-Sulf~ ylamide^~
2~3-Dihydroxypropyiamide-, and Sulfophenylamide-Polymer S~ecies In one important aspect, the present inven~ion is chalacterized by the molecular modification o-f a pre-existing polymer chain of suitable length so as to incorporate a sulfonate ubstituen~, as distinguished from attempts to build up a sllficiently large polymer from sulfonated monomers. One post-modification procedure of the inven~ion calls for the reaction of an acrylamide-containing polymer and a selected aminosulfonic acid; and this reaction is believed to proceed by a transamidation mechanism.
Preferred aminosulfonic acids for use in this aspect of the invention include aminomethanesulfonic acid, l-amino-2-hydroxy-3-propanesulfonic acid, 2,3-dihydroxypropylamine, 2-aminoethanesulfonic acid (taurine), and 4-aminobenzenesulfonic ~a acid (p-sulanilic acid), although 3-aminobenzenesulfonic acid ~metanilic acid) may also be employed. In addition, the alkali metal salts of these acids can be used in the practice of the invention.
The selected aminosulfonic acid is advantageously added to a water solution of sodium hydroxide and the polyacrylamide reactant; and the resultant mixture is then heated in a pressure reactor to a suitable temperature, such as 150C., for a suitable length of time, such as 4-5 hours. After the reaction has gone to the desired extent, the mixture is cooled and thereafter either concelltra~ed or dewatered to recover the adduct.
Sulfomethylamide polymers can also be prepared by reacting polyacrylamide with -formaldehyde-bisulfita or with ~7~
aminomethane sulfonic acid at a suitable -temperature, such as 150C., for a suitable length o~ time, such as 4-5 hours.
The acrylamide-containing polymers for use in the present invention include homopolymers of acrylamide and their homologs, such as the homopolymers of methacrylamide, and co-polymers, including terpolymers, of acrylamide, or its homologs, with acrylic acid, or its homologs, such as methacrylic acid, as well as homopolymers of (meth)acrylate esters, itaconic acid and est~l-s, crotonic acid and esters, acrylonitrile and the like.
It has been discovered that desirable, secondary amide formation is promoted in the reaction system of the invention when the acrylamide-containing polymer is selected to contain a mole ratio of acrylamide or homologous units of at least about 10 and preferably 30% or higher.
The sulfonated reaction products of the invention are useful scale inhibitors as evidenced by phosphate-inhibition test results, which are also strongly indicative of the suit-ability of these adducts in various product environments.
In order to describe the instant species of the inven-0 tion more fully, the following working examples are given:EXAMPLE 1 A mixture of poly(acrylamide [50 mole %]-acrylic acid) (150 g 31.5% solution in water, Mw 55,700); taurine (16.7 g);
and sodium hydroxide (10.6 g 50% solution in water) was heated in a mini Parr pressure reactor at 150C. for four hours. The reaction mixture was then cooled to room temperature. The molecular weight of the resulting polymer, determined by gel permeation chromatography (GPC) using polystyrene sulfonate standard, was 56,0000 The composition of the polymer was de-ter 3~ mined both by C-13 NMR and colloid titration and was -found to contain about 50~ carboxylate, 31% primary amide and 19% sulfo-ethylamide.
, 3~
A mixture of poly(acrylamide [75 mole ~]-acrylic acid) ~150 g of 27.5~ solution in water)i sulfanilic acid (20.4 g);
sodium hydroxide (9.3 g of 50% solution); and 10.5 g of ~Yater was heated in a mini Parr pressure reactor at 150C. for five hours~ The reaction mixture was thereafter cooled to room temperature The molecular weight of the resulting polymer was 11,500 as determined by GPC using polystyrene sulfonate s~andard r The polymer contained about 5~ sulfophenylamide, 47.5% primary lo amide and 47.5% carboxyla~e as estimated by C-13 NMR. At 5 ppm of the polymer, there was 7% phosphate inhibitioni at 7.5 ppm polymer, 96% phosphate inhibition; and at 10 ppm, 100% phosphate inhibition.
A mixture of poly(acrylamide [75 mole %]-acrylic acid) ~150 g o~ 27.5% solution in water); aminomethane sulfonic acid tl3.2 g); and sodium hydroxide ~10.2 g of 50% solution) was heated in a mini Parr pressure reactor at 125C. for four-and-a-half hours. The reaction mixture was therea-fter cooled to room temperature. The molecular weight of the resulting polymer was 15,900 as determined by GPC using polystyrene sulfonate s~andard.
The polymer contained about 45% acrylic acid, 40~ acrylamide and 15~ sul~omethylacrylamide as estimated by C-13 NMR.
S lfonated Maleic Anh dride Pol mer S ecies u _ _ Y _ _ Y .P '_ This aspect of the post-modification procedure of the invention calls for the addition reaction of a selected amino-sulfonic acid, or its alkali metal salt, and maleic anhydride homopolymer, copolymer or terpolymer of maleic anhydride and ~inylic compounds.
The present reaction is caused to take place in a suitable solvent, such as dimethylformamide, under heating) agitation and reflux conditions; and preferred aminosulfonate sources include 4-aminobenzenesulfonic acid ~p-sulfanilic acid), 2-aminoethane-FO~G ET AL CASE 16 ~ 7~3~ ~ ~
sulfonic acid (taurine), and the alkali metal salts thereof.3-Aminobenzenesulfonic acid (metanilic acid~ and its alkali metal salts may also be employed.
The copolymers, including terpolymers, which find utility in the present species of the invention are made up of maleic anhydride and like ring compounds which have been reacted ~ith suitable monomers such as styrene, methyl vinyl ether, N-vinylpyrrolidone, N-vinylcaprolactam and N-methyl-N-vinyl-acetamide, ~meth)acrylamide, ~meth)acrylic acid, (meth)acrylate 1~ esters, vinyl esters SUC]I as vinyl acetate, alkenes such as l-hexene, l-butene and dienes such as butadiene and cyclopenta-diene~ for example.
The maleic anhydride homo-, co- and terpolymers are reacted ~ith from 5 to 100 mole ~ of the aminosulfonate compound per mole of anhydride group in the polymer. The molecular weight of the resulting polymers have a weight average molecular weight in the range of from about 1000 to about 120,000 and preferably from about 3000 to 100,000 as determined by gel permeation chromatography.
2~ In order to describe this aspect of the invention more fully, the following working example is given:
To a reaction flask fitted with a reflux condenser, mechanical stirrer, nitrogen sparging tube and a thermometer, there was added 15.6 g (0.1 mole) of Gantrez AN-149 (a 1:1 mole ratio copolymer of maleic anhydride and methyl vinyl ether) and 200 g of dimethylformamide solvent. The resultant mixture was heated under a nitrogen gas at~osphere to dissolve the polymer.
A highly colored solution, red-violet in hue, resulted. After all -~ the polymer was visibly dissolved, at a temperature of about 120C.
21.3 g ~0.1 mole) of sodium sulfanilate monohydrate was added to .. ..
~7~ 7 `~'G ET AL ~SE ~16 the reaction flask together with a further 100 g of dimcthy1forma-mide.
Heating was continued until the solution refluxed, at a temperature of about 144-1~18C.; and refluxing was continued ~or four hours. During this time, an intense blue-purple color developed and solids precipitated. After refluxing was completed, the entire reaction mixture ~precipate and solvent solution) . ~ , . .
w~s concentrated`on a rotary evaporator~under vacuum. A dark bl~le soli-l resulted, and this was subject to final drying in td a v~ct1um oven at 50C. for 24 hours. A very dark colored solid, 3S g in weight, remained. This solid was dissolved easily in ~ate~ ~Yith the addition of a small amount of sodium hydroxide to give a solution of deep blue color.
The molecular weight of the resultant polymer was c~timated to be 95,400 by GPC using polystyrene sulfonate stnndard and its infra-red spectrum showed absorptions at 1770 cm l (cyclic imide), 1700 cm l ~cyclic imide and carboxyl) 9 lfi~0 cm l tamide carbonyl), 1590 cm 1 (carboxylate) and 1560 cm l ~amide II band). The polymer contained about 81 M % m~leimide 2~ lmits, about 14 ~1 ~ maleic acid units and about 5 M % maleamic ~cid ~mits as estimated by infra-red and LC analysis for residual amonisl1lfonate compound.
The calcium phosphate inhibition propensity of the product of Example 4 was tested and is compared with other maleic anhydride, aminosulfonated polymers made according to the invention in Table II hereinabove.
The manner in which the present invention may be practiced and the purpose to which it may be put are evident rom the foregoing descriptions.
Claims (47)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of controlling scale deposits by adding to waters having a tendency to form scale, a scale-inhibitorily effective amount of a hydrocarbon polymer selected from the class consisting of: N-substituted amide polymers with an amide structure as follows:
where R1 is a hydrogen or an alkyl and R is alkylene or phenyl-ene, and X is sulfonate, phosphinate, phosphonate, (poly)-hydroxyl, (poly)carboxyl or carbonyl, and combinations there-of.
where R1 is a hydrogen or an alkyl and R is alkylene or phenyl-ene, and X is sulfonate, phosphinate, phosphonate, (poly)-hydroxyl, (poly)carboxyl or carbonyl, and combinations there-of.
2. A method of controlling scale deposits by adding to waters having a tendency to form scale, a scale-inhibitorily effective amount of hydrocarbon polymer selected from the class consisting of: derivatized maleic anhydride homo-, co- and terpolymers having N-substituted maleamic acid units, N-sub-stituted maleimide units and maleic acid (and salts) units having a structure as follows:
where R1, R2 and R3 are each independently chosen from the group consisting of hydrogen, hydroxyl, carboxyalkyl, carboxy-amide, phenyl, substituted phenyl, linear or branched alkyl of from one to ten carbon atoms, and substituted alkyl of from one to ten carbon atoms, where the substituent is phosphonic acid;
phosphinic acid; phosphate ester; sulfonic acid; sulfate ester, carbonyl, carboxyamide, (poly)carboxy and (poly)hydroxy, alkoxy and carboxylate ester groups; and combinations thereof; and M+
may be H+, alkali metal ions, alkaline earth metal ions, - 23a -?ONG ET AL CASE ?16 ammonium ions or zinc ion and wherein:
n = total moles of derivatized and underivatized maleic units in the polymer and is an integer in the range from 10 to about 1200;
= mole fraction of maleamic acid (salt) units in the polymer and can vary from 0 to about 1.0;
y = mole fraction of maleimide units in the polymer and can vary from 0 to about 0.95;
z = mole fraction of maleic acid (salts) units in the polymer and can vary from 0 to about 0.95;
and x + y + z = 1
where R1, R2 and R3 are each independently chosen from the group consisting of hydrogen, hydroxyl, carboxyalkyl, carboxy-amide, phenyl, substituted phenyl, linear or branched alkyl of from one to ten carbon atoms, and substituted alkyl of from one to ten carbon atoms, where the substituent is phosphonic acid;
phosphinic acid; phosphate ester; sulfonic acid; sulfate ester, carbonyl, carboxyamide, (poly)carboxy and (poly)hydroxy, alkoxy and carboxylate ester groups; and combinations thereof; and M+
may be H+, alkali metal ions, alkaline earth metal ions, - 23a -?ONG ET AL CASE ?16 ammonium ions or zinc ion and wherein:
n = total moles of derivatized and underivatized maleic units in the polymer and is an integer in the range from 10 to about 1200;
= mole fraction of maleamic acid (salt) units in the polymer and can vary from 0 to about 1.0;
y = mole fraction of maleimide units in the polymer and can vary from 0 to about 0.95;
z = mole fraction of maleic acid (salts) units in the polymer and can vary from 0 to about 0.95;
and x + y + z = 1
3. The method according to either Claim l or Claim 2 wherein the scale is at least one of calcium phosphate, iron phosphate and magnesium phosphate.
. The method according to either Claim 1 or Claim Z
wherein the scale is calcium carbonate.
wherein the scale is calcium carbonate.
5. The method according to either Claim 1 or Claim 2 wherein the scale is calcium phosphonate.
6. The method according to either Claim 1 or Claim 2 wherein the scale is at least one of iron oxide and iron hydroxide.
7. The method according to either Claim 1 or Claim 2 wherein the scale is barium sulfate.
8. The method according to either Claim 1 or Claim 2 wherein said effective amount is from about 1 to about 200 p.p.m.
9. The method according to Claim 1 wherein said hydrocarbon polymer is a copolymer of from about 25 to about 95 mole % (meth)acrylic acid and from about 5 to about 75 mole % sulfoalkyl(meth)acrylamide having a molecular weight of about 5,000 to 80,000 and wherein said sulfoalkyl(meth)-acrylamide includes a moiety having the general structural formula:
FONG ET AL CASE ?16 wherein R1 is a hydrogen or an alkyl and R is a hydrocarbon group containing from one to three carbon atoms.
FONG ET AL CASE ?16 wherein R1 is a hydrogen or an alkyl and R is a hydrocarbon group containing from one to three carbon atoms.
10. The method according to Claim 1 wherein said hydrocarbon polymer is a copolymer of from about 50 to about 95 mole % (meth)acrylic acid and from about 5 to about 50 mole % sulfoalkyl(meth)acrylamide having a molecular weight of about 5,000 to 80,000 and wherein said sulfoalkyl(meth)acrylamide includes a moiety having the general structural formula:
wherein R1 is a hydrogen or an alkyl and R is phenyl or a hydrocarbon group containing from one to three carbon atoms.
wherein R1 is a hydrogen or an alkyl and R is phenyl or a hydrocarbon group containing from one to three carbon atoms.
11. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 10 to about 90 mole % (meth)acrylic acid, from about 5 to about 85 mole % (meth)acrylamide, and from about 5 to 85 mole %
N-substituted(meth)acrylamide having a molecular weight of about 5,000 to 80,000 and wherein said sulfoalkyl(meth)acrylamide includes a moiety having the general structural formula:
wherein R1 is a hydrogen or an alkyl and R is phenyl or a hydrocarbon group containing from one to three carbon atoms.
N-substituted(meth)acrylamide having a molecular weight of about 5,000 to 80,000 and wherein said sulfoalkyl(meth)acrylamide includes a moiety having the general structural formula:
wherein R1 is a hydrogen or an alkyl and R is phenyl or a hydrocarbon group containing from one to three carbon atoms.
12. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 70 mole %
N-substituted(meth)acrylamide haying a molecular weight of about 5,000 to about 100,000 and wherein said N-substituted(meth)acryl-FONG ET AL CASE ?16 amide includes a moiety having the structural formula:
wherein (l) X is -SO3 and R1 is a hydrogen or an alkyl and R is either phenyl or a hydrocarbon group containing one to three carbon atoms; (2) X is -(OH)n in which n is an integer from 2 to 4 and R is phenyl or a hydrocarbon group containing one to four carbon atoms; or (3) X is a combination of -SO3 and -(OH)n in which n is an integer from one to four and R is phenyl or a hydrocarbon group containing one to four carbon atoms.
(meth)acrylamide, and from about 5 to about 70 mole %
N-substituted(meth)acrylamide haying a molecular weight of about 5,000 to about 100,000 and wherein said N-substituted(meth)acryl-FONG ET AL CASE ?16 amide includes a moiety having the structural formula:
wherein (l) X is -SO3 and R1 is a hydrogen or an alkyl and R is either phenyl or a hydrocarbon group containing one to three carbon atoms; (2) X is -(OH)n in which n is an integer from 2 to 4 and R is phenyl or a hydrocarbon group containing one to four carbon atoms; or (3) X is a combination of -SO3 and -(OH)n in which n is an integer from one to four and R is phenyl or a hydrocarbon group containing one to four carbon atoms.
13. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole %
sulfomethyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylamide, and from about 5 to about 55 mole %
sulfomethyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
14. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
sulfmethyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
sulfmethyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
15. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole % sulfophenyl-(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylamide, and from about 5 to about 55 mole % sulfophenyl-(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
16. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 35 to about 55 mole % (meth)acrylic acid, from about 10 to about 40 mole FONG ET AL CASE ?16 (meth)acrylamide, and from about 10 to about 30 mole %
sulfopheny(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
sulfopheny(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
17. The method according to Claim 1 wherein said hydrocarbon polymer contains from about 20 to about 80 mole %
(meth)acrylic acid, from about 0 to about 60 mole % (meth)-acrylamide, and from about 5 to about 70 mole % 2-hydroxy-3-sulfopropyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylic acid, from about 0 to about 60 mole % (meth)-acrylamide, and from about 5 to about 70 mole % 2-hydroxy-3-sulfopropyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
18. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 70 mole %
2-hydroxy-3-sulfopropyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylamide, and from about 5 to about 70 mole %
2-hydroxy-3-sulfopropyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
19. The method according to Claim 1 wherein said hydrocarbon polymer contains from about 20 to about 80 mole %
(meth)acrylic acid, from about 0 to about 60 mole % (meth)-acrylamide, and from about 5 to about 55 mole % 2,3-dihydroxy-propyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000
(meth)acrylic acid, from about 0 to about 60 mole % (meth)-acrylamide, and from about 5 to about 55 mole % 2,3-dihydroxy-propyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000
20. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole %
2,3-dihydroxypropyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylamide, and from about 5 to about 55 mole %
2,3-dihydroxypropyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
21. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 10 to about 90 mole % (meth)acrylic acid, from about 5 to about 40 mole %
alkyl(meth)acrylate ester and from about 5 to about 55 mole %
N-substituted(meth)acrylamide having a molecular weight of from about 3,500 to about 80,000; wherein said alkyl(meth)acrylate ester includes a moiety having the structural formula:
wherein R is a hydrocarbon group containing from one to six carbon atoms; and wherein said N-substituted(meth)acrylamide includes a moiety having the structural formula:
wherein (1) X is -SO3- and R1 is hydrogen or alkyl and R is either phenyl or a hydrocarbon group containing one to three carbon atoms; (2) X is -(OH)n in which n is an integer from 2 to 4 and R is phenyl or a hydrocarbon group containing one to four carbon atoms; or (3) X is a combination of -SO3- and -(OH)n in which n is an integer from one to four and R is phenyl or a hydrocarbon group containing one to four carbon atoms.
alkyl(meth)acrylate ester and from about 5 to about 55 mole %
N-substituted(meth)acrylamide having a molecular weight of from about 3,500 to about 80,000; wherein said alkyl(meth)acrylate ester includes a moiety having the structural formula:
wherein R is a hydrocarbon group containing from one to six carbon atoms; and wherein said N-substituted(meth)acrylamide includes a moiety having the structural formula:
wherein (1) X is -SO3- and R1 is hydrogen or alkyl and R is either phenyl or a hydrocarbon group containing one to three carbon atoms; (2) X is -(OH)n in which n is an integer from 2 to 4 and R is phenyl or a hydrocarbon group containing one to four carbon atoms; or (3) X is a combination of -SO3- and -(OH)n in which n is an integer from one to four and R is phenyl or a hydrocarbon group containing one to four carbon atoms.
22. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole % phosphono-alkyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000 and wherein said phosphonoalkyl(meth)-acrylamide includes a moiety having the structural formula:
wherein is a hydrogen or an alkyl and R is a hydrocarbon group containing one to four carbon atoms.
(meth)acrylamide, and from about 5 to about 55 mole % phosphono-alkyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000 and wherein said phosphonoalkyl(meth)-acrylamide includes a moiety having the structural formula:
wherein is a hydrogen or an alkyl and R is a hydrocarbon group containing one to four carbon atoms.
23. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
FONG ET AL CASE ?16 (meth)acrylamide, and from about 5 to about 55 mole %
phosphonopropyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
FONG ET AL CASE ?16 (meth)acrylamide, and from about 5 to about 55 mole %
phosphonopropyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
24. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole %
carboxyalkyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000 wherein said carboxyalkyl(meth)-acrylamide includes a moiety having the structural formula:
wherein R1 is a hydrogen or an alkyl and R is a hydrocarbon containing one to six carbon atoms and X is -(CO2H)n wherein n is an integer from one to two.
(meth)acrylamide, and from about 5 to about 55 mole %
carboxyalkyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000 wherein said carboxyalkyl(meth)-acrylamide includes a moiety having the structural formula:
wherein R1 is a hydrogen or an alkyl and R is a hydrocarbon containing one to six carbon atoms and X is -(CO2H)n wherein n is an integer from one to two.
25. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole %
carboxypentylacrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylamide, and from about 5 to about 55 mole %
carboxypentylacrylamide having a molecular weight of from about 7,000 to about 90,000.
26. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole %
N-(1,2-dicarboxy)ethyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylamide, and from about 5 to about 55 mole %
N-(1,2-dicarboxy)ethyl(meth)acrylamide having a molecular weight of from about 7,000 to about 90,000.
27. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
FONG ET AL CASE 4?16 (meth)acrylamide, and from about 5 to about 55 mole %
N-substituted(meth)acrylamide having molecular weight of from about 7,000 to about 90,000 wherein said N-substituted(meth)-acrylamide includes a moiety having the structural formula:
wherein R1 is a hydrogen or an alkyl and R is a hydrocarbon group containing from one to four carbon atoms and X is -(OH)n wherein n is an integer from two to four.
FONG ET AL CASE 4?16 (meth)acrylamide, and from about 5 to about 55 mole %
N-substituted(meth)acrylamide having molecular weight of from about 7,000 to about 90,000 wherein said N-substituted(meth)-acrylamide includes a moiety having the structural formula:
wherein R1 is a hydrogen or an alkyl and R is a hydrocarbon group containing from one to four carbon atoms and X is -(OH)n wherein n is an integer from two to four.
28. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole %
N-(2,3-dihydroxy)propylacrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylamide, and from about 5 to about 55 mole %
N-(2,3-dihydroxy)propylacrylamide having a molecular weight of from about 7,000 to about 90,000.
29. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole (meth)acrylamide, and from about 5 to about 55 mole %
N-(2-methyl-1,3-dihydroxy)-2-propylacrylamide having a molecular weight of from about 7,000 to about 90,000.
N-(2-methyl-1,3-dihydroxy)-2-propylacrylamide having a molecular weight of from about 7,000 to about 90,000.
30. The method according to Claim 1 wherein said hydrocarbon polymer is a terpolymer of from about 20 to about 80 mole % (meth)acrylic acid, from about 5 to about 60 mole %
(meth)acrylamide, and from about 5 to about 55 mole %
N-(2-hydroxymethyl-1-3-dihydroxy)-2-propylacrylamide having a molecular weight of from about 7,000 to about 90,000.
(meth)acrylamide, and from about 5 to about 55 mole %
N-(2-hydroxymethyl-1-3-dihydroxy)-2-propylacrylamide having a molecular weight of from about 7,000 to about 90,000.
31. The method of making polymers containing sulfo-ethylamide, sulfomethylamide, sulfophenylamide, 2-hydroxy-3-sulfopropylamide or 2,3-dihydroxypropylamide for use as scale inhibitors which comprises the step of reacting an aminosulfonic acid with a (meth)acrylamide-containing polymer.
32. The method according to Claim 31 wherein the aminosulfonic acid is 2-aminoethanesulfonic acid.
33. The method according to Claim 31 wherein the aminosulfonic acid is 4-aminobenzenesulfonic acid.
34. The method according to Claim 31 wherein the aminosulfonic acid is aminomethanesulfonic acid.
35. The method according to Claim 31 wherein the aminosulfonic acid is 1-amino-2-hydroxy-3-propanesulfonic acid.
36. The method according to Claim 31 wherein the aminosulfonic acid is 2,3-dihydroxypropylamine.
37. The method according to Claim 31 wherein the (meth)acrylamide-containing polymer contains a mole ratio of (meth)acrylamide and homologous units of at least about 10%.
38. A sulfoethylamide-containing polymer made according to the method of Claim 32.
39. A sulfophenylamide-containing polymer made according to the method of Claim 33.
40. A sulfomethylamide-containing polymer made according to the method of Claim 34.
41. A 2-hydroxy-3-sulfopropylamide-containing polymer made according to the method of Claim 35.
42. A 2,3-dihydroxypropylamide-containing polymer made according to the method of Claim 36.
43. The method of treating an industrial water supply to inhibit scale formation comprising the step of adding to FONG ET AL CASE ?16 the water supply from about 5 to about 20 p.p.m. of a sulfonated polyamide made according to the method of Claim 31.
44. The method according to Claim 2 wherein the scale-inhibiting chemicals are derivatized maleic anhydride homo-, co- and terpolymers having N-substituted maleamic acid units, N-substituted maleimide units and maleic acid (and salts) units made by reacting maleic anhydride homo-, co- and ter-polymers with an aminosulfonate source selected from the class consisting essentially of aminoalkylsulfonic acids where the alkyl group is linear or branched, from one to ten carbon atoms and may be further substituted by hydroxyl, carboxylic and phosphonic groups and combinations thereof; and alkali metal and ammonium salts of said aminoalkylsulfonic acids wherein:
n = total moles of derivatized and underivatized maleic units in the polymer and is an integer in the range from about 30 to about 1000.
x = mole fraction of maleamic acid (salt) units in the polymer and can vary from about 0.05 to about 0.95.
y = mole fraction of maleimide units in the polymer and can vary from about 0.05 to about 0.05.
z = mole fraction of maleic acid (salts) units in the polymer and can vary from 0.05 to 0.95.
x + y + z = 1
n = total moles of derivatized and underivatized maleic units in the polymer and is an integer in the range from about 30 to about 1000.
x = mole fraction of maleamic acid (salt) units in the polymer and can vary from about 0.05 to about 0.95.
y = mole fraction of maleimide units in the polymer and can vary from about 0.05 to about 0.05.
z = mole fraction of maleic acid (salts) units in the polymer and can vary from 0.05 to 0.95.
x + y + z = 1
45. The method according to Claim 44 wherein said aminosulfonate source is taurine (2-aminoethylsulfonic acid) or alkali or ammonium salts of taurine.
46. The method according to Claim 44 wherein said aminosulfonate source is p-sulfanilic acid or metanilic acid or alkali metal or ammonium salts thereof.
47. The method according to either Claim 44 or Claim 45 or Claim 46-wherein said derivatized maleic anhydride polymers are prepared from maleic anhydride co- and terpolymers where the FONG ET AL CASE ?16 co- and termonomers are selected from the class consisting of styrene, vinyl ethers including methyl vinyl ether, N-vinyl-pyrrolidone, N-vinylcaprolactam, N-methyl-N-vinylacetamide, N-vinylsuccinimide, (meth)acrylamide, (meth)acrylic acid, (meth)acrylate esters, vinyl esters including vinyl acetate, alkenes including ethylene, 1-hexene and 1-butene, and dienes including butadiene, isoprene and cyclopentadiene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84256886A | 1986-03-21 | 1986-03-21 | |
| US842,568 | 1986-03-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1270997A true CA1270997A (en) | 1990-06-26 |
Family
ID=25287665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000532586A Expired - Lifetime CA1270997A (en) | 1986-03-21 | 1987-03-20 | Modified acrylamide polymers and the like for use as scale inhibitors |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS62221499A (en) |
| CA (1) | CA1270997A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5143622A (en) * | 1991-06-05 | 1992-09-01 | Nalco Chemical Company | Phosphinic acid-containing polymers and their use in preventing scale and corrosion |
| US5358640A (en) * | 1992-07-20 | 1994-10-25 | Nalco Chemical Company | Method for inhibiting scale formation and/or dispersing iron in reverse osmosis systems |
| JP4645978B2 (en) * | 2001-01-24 | 2011-03-09 | 栗田工業株式会社 | Scale inhibitor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3928196A (en) * | 1973-12-05 | 1975-12-23 | Calgon Corp | Inhibition of scale deposition |
| FR2471390A1 (en) * | 1979-12-13 | 1981-06-19 | Inst Francais Du Petrole | Terpolymer from acrylic! ester, di:isobutylene! - and di:carboxylic acid deriv., as low temp. flow improver for hydrocarbon oils |
| JPS5757084A (en) * | 1980-09-24 | 1982-04-06 | Hitachi Ltd | Facsimile device |
| DE3210775A1 (en) * | 1982-03-24 | 1983-09-29 | Hoechst Ag, 6230 Frankfurt | 2-ACRYLAMIDO-2-METHYL-PROPANPHOSPHONIC ACID AND ITS SALTS, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF FOR THE PRODUCTION OF COPOLYMERS |
| JPS59162999A (en) * | 1983-03-07 | 1984-09-13 | カルゴン・コ−ポレ−シヨン | Synergistic scale and corrosion control mixture containing carboxylic acid/sulfonic acid polymer |
-
1986
- 1986-10-30 JP JP25712286A patent/JPS62221499A/en active Pending
-
1987
- 1987-03-20 CA CA000532586A patent/CA1270997A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62221499A (en) | 1987-09-29 |
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