AU592111B2

AU592111B2 - Acrylic acid/2-acrylamido-2-methylpropyl- sulfonic acid/2- acrylamido-2-methylpropyl phosphonic acid polymers

Info

Publication number: AU592111B2
Application number: AU62070/86A
Authority: AU
Inventors: Jerry E. Boothe; Raymond J. Schaper
Original assignee: Calgon Corp
Current assignee: Calgon Corp
Priority date: 1985-08-30
Filing date: 1986-08-29
Publication date: 1990-01-04
Anticipated expiration: 2006-08-29
Also published as: JPS6253314A; AU6207086A; CA1244997A

Description

II

i :I i i; 592 11 Fi SPRUSON FERGUSON FORM 10 COMMONWEALTH OF AUSTRA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int. Class Complete Specification Lodged: Accepted: Published: Priority: Thdc con ta s the azmendnis made dindir U &Yction 49 and is cojir,- PI-Iri~g Related Art: as a a a.

a a 4 aI) a 44, Name of Applicant: Address of Applicant: Actual Inventor(s): Address for Service: CALGON CORPORATION Route 60-Campbell's Run Road, Robinson Township, Pennsylvania, United States of America JERRY E. BOOTHE and RAYMOND J. SCHAPER Spruson Ferguson, Patent Attorneys, Level 33 St Martins Tower, 31 Market Street, Sydney, New South Wales, 2000, Australia 1 Complete Specification for the invention entitled: "ACRYLIC ACID/2-ACRYLAMIDO-2-METHYLPROPYL-SULFONIC ACID/2-ACRYLAMIDO-2-METHYLPROPYL PHOSPHONIC POLYMERS" The following statement is a full description of this invention, including the best method of performing it known to us SBR/JS/0138T 2050S/1003A C-1405 TITLE OF SULFON IC

POLYMERS

THE INVENTION ACRYLIC ACID/2-ACRYLAMIDO-2-METHYLPROPYL- ACID/2-ACRYLAMIDO- 2-METHYLPROPYL PHOSPHONIC ABSTRACT OF THE DISCLOSURE The present invention is directed to a polymer, having an intrinsic viscosity of'0.05 to dl/g, in 1.0 M NaCi, prepared from: 35 to 65%, by weight, of acrylic acid or methacrylic acid; (Bl) 15 to 45%, by weight, of 2-acrylainido-2-methylpropylsulfonic acid or 2-methacrylamido-2-metbylpropylsulfonic acid; and 15 to 25%, by weight, of 2-acrylamido-2-methylpropyl phosphonic acid or 2.-letbacrylamido-2methyipropyiphosphonic acid, 1, _j r I I 1- C 7-1 r, 2050S/1003A o- C-1405 TITLE OF THE INVENTION ACRYLIC ACID/2-ACRYLAMIDO-2-METHYLPROPYL- SULFONIC ACID/2-ACRYLAMIDO-2-METHYLPROPYL PHOSPHONIC

POLYMERS

BACKGROUND OF THE INVENTION U.S. Patent 3,928,196 discloses the use of a copolymer of 2-acrylamido-2-methylpropylsulfonic acid and acrylic acid as scale inhibitors.

Published European Patent Application 89,654 discloses copolymers of 2-acrylamido-2-methylpropyl S, phosphonic acid and acrylamide or acrylic acid as scale inhibitors.

DESCRIPTION OF THE INVENTION The present invention is directed to a polymer, having an intrinsic viscosity of 0.05 to dl/g, in 1.0 M NaCI, prepared from: 35 to 65%, by weight, of acrylic acid or methacrylic acid; -97_ 2050S/1003A 2 C-1405 4 F I I 4 4 4 t C 15 to 45%, by weight, of 2-acrylamido-2-methylpropylsulfonic acid or 2-methacrylamido-2-methylpropylsulfonic acid; and 15 to 25%, by weight, of 2-acrylamido-2-methylpropyl phosphonic acid or 2-methacrylamido-2methylpropylphosphonic acid.

The polymers are prepared from 35 to preferably 0t to 60%, by weight, acrylic acid or methacrylic acid, preferably acrylic acid; 15 to preferably 20 to 40%, by weight, 2-acrylamido-2methylpropylsulfonic acid (hereinafter "AMPS") or 2-methacrylamido-2-methylpropylsulfonic acid, preferably AMPS; and 15 to 25%, preferably 20%, by weight, 2-acrylamido-2-methylpropyl phosphonic acid (hereinafter "AMPPA") or 2-methacrylamido-2-methylpropylphosphonic acid. seT- p AMPPA may be prepared as described in U.S. Patent 4,526,728.

The polymers may be prepared by mixing the 20 monomers preferably in the presence of a free radical initiator. Any free radical initiator may be used.

Examples include peroxides, azo initiators and redox systems. The polymerization may also be initiated photochemically. The preferred catalysts are sodium persulfate or a mixture of ammonium persulfate and any azo type initiator, such as 2,2'-azobis-(2,4dimethyl-4-methoxyvaleronitrile).

The polymerization may be conducted by any of a variety of procedures, for example, in solution, suspension, bulk and emulsions.

The reaction temperature is not critical.

The reaction will generally occur between 10 and 100°C, preferably 40 to 60 0 C. It is generally impractical to run the reaction below room temperature because the reaction is too slow. Above 11 I1I___I~--1_LII1~ I 2050S/1003A 3 C-1405 *0 a temperature of 60 0 C, the molecular weight of the polymer tends to decrease. The reaction, depending on the temperature, generally takes from 1 to 12 hours. Measuring for residual monomer will verify when the reaction is complete.

The pH of the reaction mixture is not critical. The pH is generally in the range of 3.5 to The percent solids in the reaction mixture is not critical. The preferred range is 1 to 50%, by weight, solids, The molecular weight of polymers is difficult to accurately measure. The polymers are, instead, usually identified by intrinsic viscosity.

The intrinsic viscosity of the polymer is critical in the instant invention. The intrinsic viscosity should be .05 to 4.5, preferably 0.05 to 2.5 dl/g, in 1.0 M sodium chloride (measured in a 75 Cannon Ubbelohde capillary viscometer).

The polymers of the instant invention have been found to be effective as scale inhibitors, particularly in inhibiting calcium phosphate scale.

EXAMPLES 1 AND 2 25 The polymers of the examples were produced by mixing the monomers indicated in Table 1, in the amounts, solids concentration, initial temperatures and pH indicated. The monomer mix was purged with nitrogen for one hour. The solvent was deionized water. The initiator was added and the components allowed to react for about 3 hours.

4. a.

4 aa.Q O a *i I1 2050S/1003 Example 1 2 A C-1405 TABLE I Monomers Wt% Initiator AA IlAMPS 2/AJ4PPA3 60/20/20

JU

1. 1% SPS 4 1.7% NaHSO 3 1.1% SPS/ 1.7% NaHSO 3 Solids pH TemR-In 28% 4.4 250C 0.21 28% 4.4 25*C 0.11 AMPS /AMPPA 40/40/20 1 AA acrylic acid 2 AMPS -2-acrylamido--2-methylpropylsulfonic acid 3 AMPPA 2-acrylamido-2-methylpropyl phosphonic acid 4 sps sodium persulfate NMaHSOI sodium bisulfite 6 dl/g in 1.0 14 N&AC14 measured' in~ a 75 Cannon Ubbelohde capillary viscometer 2050S/1003A 5 C-1405 EXAMPLES 3 AND 4 Various polymers were screened for threshold inhibition of calcium carbonate and calcium phosphate.

Stagnant flask tests were used with solutions stored for 24 hours at constant temperature. The standard test conditions used were as follows: Calcium Calcium Carbonate Phosphate Calcium, mg/l 200 200 Bicarbonate, mg/l 600 Phosphate, mg/1 9 pH 8.0 Temperature, oC 60 tt •Two flasks were used for each test; one for a control (no inhibitor) and one with the polymer.

The percent inhibition was determined by the 2 0 o following equation: S S T c Percent Inhibition x 100 where: t 4 S S I C 25 S I level of test specie initially;

S

c level of test specie at end of control test; and S level of test specie at end of inhibitor test.

Calcium was used as the test specie in the calcium carbonate test, and phosphate was the test specie in the calcium phosphate test. The results are summarized in Table II.

i 0g *9 I a 4.

'S a 0 0 0 e 2050S/1003A C-1405 TABLE I Scale Inhibition Performance Results Exale CoQosition NJl dl/g 3 60/20/20 AA I/PS 2

/AIPPA

3 0.21 (Exaple 1) 4 40/40/20 M/NIS/AN? 11 (Example 2)7 Ca!3 C(H 8.0) at 1Ma/I at 2Mg/I at 4g/i 81 100 100 16 82' 80 Ca/PO (PH at 5 mg/l at 6 ol at 8 at 10 Mg/I 2 15 100 100 go 99 100 IM acrylic acid Ic 2 APS 2-acrylamido-2--thylpropyvlsulfonic acid 3 MIrPPA 2-arylaido-2-mthylpol p~sponc acid IIIIIIIIIC 1

Claims

1. A polymer, having an intrinsic viscosity of 0.05 to 4.5 dl/g, in M NaCl, prepared from: 35 to 65%, by weight, of acrylic acid or methacrylic acid; 15 to 45%, by weight, of 2-acrylamido-2-methyl-propylsulfonic acid or

2-methacrylamido-2-methyl-propylsulfonic acid; and 15 to 25%, by weight, of 2-acrylamido-2-methyl-propyl phosphonic acid or 2-methacrylamido-2-methylpropylphosphonic acid. 2. The polymer of Claim 1, prepared from acrylic acid, 2-acrylamido-2-methylpropylsulfonic acid, and 2-acrylamido-2- methylpropyl phosphonic acid.

3. The polymer of Claim 1, prepared from 40 to 60%, by weight, acrylic acid; 20 to 40%, by weight, 2-acrylamido-2-methylpropylsulfonic acid, and 15 to 25%, by weight, 2-acrylamido-2-methylpropyl phosphonic acid.

4. The polymer of any one of Claims 1 to 3, having an intrinsic S viscosity of 0.05 to 2.5 dl/g, in 1.0 M NaCl. A polymer substantially as herein described with reference to Example 1 or 2. DATED this TWENTY-NINTH day of SEPTEMBER 1989 S° Calgon Corporation 0o 0 o0 0 00 00 Patent Attorneys for the Applicant SPRUSON FERGUSON 0 A MRC/145x