CA1207943A - Intramolecular polymeric complexes - viscosifiers for acid, base and salt (aqueous) solutions - Google Patents
Intramolecular polymeric complexes - viscosifiers for acid, base and salt (aqueous) solutionsInfo
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- CA1207943A CA1207943A CA000448911A CA448911A CA1207943A CA 1207943 A CA1207943 A CA 1207943A CA 000448911 A CA000448911 A CA 000448911A CA 448911 A CA448911 A CA 448911A CA 1207943 A CA1207943 A CA 1207943A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
- C09K8/24—Polymers
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to improved viscosification agents for a variety of aqueous solu-tions which comprise a family of intramolecular poly-meric complexes (i.e., polyampholytes) which are ter-polymers of acrylamide/metal styrene sulfonate/meth-acrylamidopropyltrimethylammonium chloride (MAPTAC).
The metal styrene sulfonate is an anionic monomer, while MAPTAC is cationically charged. These acrylamide-based polyampholytes have 1 to 50 mole % of the anionic monomer and 1 to 50 mole % of the cationic moiety present within the macromolecular structure.
These groups are not necessarily present in an equi-molar charge ratio. The excess undissociated charge allows for facile dispensability or solubility of the polyampholytes into fresh water.
The present invention relates to improved viscosification agents for a variety of aqueous solu-tions which comprise a family of intramolecular poly-meric complexes (i.e., polyampholytes) which are ter-polymers of acrylamide/metal styrene sulfonate/meth-acrylamidopropyltrimethylammonium chloride (MAPTAC).
The metal styrene sulfonate is an anionic monomer, while MAPTAC is cationically charged. These acrylamide-based polyampholytes have 1 to 50 mole % of the anionic monomer and 1 to 50 mole % of the cationic moiety present within the macromolecular structure.
These groups are not necessarily present in an equi-molar charge ratio. The excess undissociated charge allows for facile dispensability or solubility of the polyampholytes into fresh water.
Description
2 The instant invention describes a new class
3 of terpolymers which are improved viscosification
4 agents for aqueous solutions containing acid base, or salt. Typically, these terpolymers are formed by a free 6 radical terpolymerization process in an aqueous medium 7 of an acrylamide monomer, a sodium styrene sulfonate 8 monomer and a methacrylamidopropyltrimethylammonium 9 chloride monomerO The resultant water soluble terpoly-mer has the formula:
12 - (CH2-CH)X ; (CH2-CH)Y ~ (CH2-Cz) -13 C=O ~ 1-0 14 IH2 ~03-M~ NH
18 Cl-+N(CH3)3 19 wherein x is 40 to 98 mole %, more preferably 50 to 95 mole %, and most preferably 80 to 90, y is 1 to 50 mole 21 %, more preferably 2 to 20 mole ~, and most preferably 22 5 to 10 mole %, and z is 1 to 50 mole %, more prefer-23 ably 2 to 20, and most preferably 5 to 10, wherein y 24 and z are less than 60 mole % and M is an amine or a metal cation selected from the group consistiny of 26 aluminum, iron, lead, Groups IA, IIA, IB and IIB of the 27 Periodic Table of Elements.
28 The molecular weight, as derived from 29 intrinsic viscosities, for the terpolymers of acryl-amide/sodium styrene sulfonate/methacrylamidopropyl-31 trimethylammonium chloride is 103 to 5x106, more 32 preferably 104 to 2X106 and most preferably 105 to 105.
~, .
~Z~;)'7~
1 The means for determining the molecular weights of the 2 water soluble terpolymers from the viscosity of solu-3 tions of the terpolymers comprises the initial 4 isolation of the water soluble terpolymers, purifica-tion and redissolving the terpolymers in water to give 6 solutions with known concen~rations. The flow times of 7 the solutions and the pure solvent were measured in a 8 standard Ubbelholde viscometer. Subsequently, the 9 reduced viscosity is calculated through standard methods utilizing these values. Extrapolation to zero 11 polymer concentration leads to the intrinsic viscosity 12 of the polymer solution. The intrinsic viscosity is 13 directly related to the molecular weight through the 14 well-known Mark-Houwink relationship.
The water soluble terpolymers of acrylamide/
16 sodium styrene sulfonate/methacrylamidopropyltrimethyl-17 ammonium chloride are formed by a conventional free 18 radical terpolymerization in an aqueous medium which 19 comprises the steps of forming a reaction solution of acrylamide monomer, sodium styrene sulfonate monomer 21 and methacrylamidopropyltrimethylammonium chloride 22 monomer (50 wt. % solution in water) in distilled 23 water, wherein the total monomer concentxation is 1 to 24 40 grams of total monomer per 100 grams of water, more preferably 5 to 30, and most preferably 10 to 20;
26 purging the reaction solution with nitrogen; adding 27 sufficient acid to the reaction solution to adjust the 28 pH of the reaction solution to 4.5 to 5.0; heating the 29 reaction solution to at least 55C while maintaining the nitrogen purge; adding sufficient free radical 31 initiator to the reaction solution at 55C to initiate 32 terpolymerization of the acrylamide monomer, the sodium 33 styrene sulfonate monomer, and the methacrylamidopro-34 pyltrimethylammonium chloride monomer; terpolymerizing said monomers of acrylamide, sodium styrene sulfonate ~.Z~)7~ 3 l and methacrylamidopropyltrimethylammonium chloride at a 2 sufficient temperature and for a sufficient period of 3 time to form said water soluble terpolymer; and 4 recovering said water soluble terpolymer from said reaction solution.
6 The total concentration of monomers in the 7 water is l to 40 grams of total monomer per lO0 grams 8 of water, more preferably 5 to 30 and most preferably 9 10 to 20. Terpolymerization of the acrylamide monomer, sodium styrene sulfonate monomer, and methacrylamido-ll propyltrimethylammonium chloride monomer is effected at 12 a temperature of 30 to 90, more preferably at 40 to 70, 13 and most preferably at 50 to 60 for a period of time of 14 1 to 24 hours, more preferably 3 to 10, and most pre-ferably 4 to 8.
16 A suitable method of recovery of the formed 17 water soluble terpolymer from the aqueous reaction 18 solution comprises precipitation in acetone, methanol, 19 ethanol and the like.
Suitable free radical initiators for the 21 free radical terpolymerization of the acrylamide 22 monomers, the sodium styrena suflonate monomer, and the 23 methacrylamidopropyltrimethylammonium chloride monomer 24 are selected from the group consisting of potassium persulfate, ammonium persulfate, benzoyl peroxide, 26 hydrogen peroxide, azobisisobutyronitrile, and the 27 like. The concentration of the free radical initiator 28 is 0.001 to 2.0 grams of free radical initiator per lO0 29 grams of total monomer, more preferably 0.01 to 1~0 and most preferably 0.05 to 0.1.
~Lfi'07S~3 1 It should be pointed out that neither the 2 mode of polymerization (solution, suspension, or 3 emulsion polymerization technique and the like), nor 4 the initiation is critical, provided that the method or the products of the initiation step does not inhibit 6 production of the polyampholyte or chemically modify 7 the initial molecular structure of reacting monomers.
8 Typical water soluble monomers incorporated 9 into the terpolymers that are envisioned in the present invention are listed as follows:
11 Anionic: 2-acrylamido-2--methylpropane sul-12 fonic acid, sodium styrene sul-13 fonate, (meth)acrylic acid, 2-14 sulfoethylmethacrylate, and the like.
16 Cationic: methacrylamidopropyltrimethyl-17 ammonium chloride, dimethyldial~
18 lylammonium chloride, diethyl-19 diallylammonium chloride, 2-meth-acryloxy-2-ethyltrimethylammonium 21 chloride, trimethylmethacryloxy-22 ethylammoniym methosulfate, 2-23 acrylamido-2-methylpropyltrimeth-24 ylammonium chloride, vinylbenzyl-trimethylammonium chloride, and 26 the like.
27 Nonionic: (N,N-dimethyl)acrylamide, hydrox-28 yethyl(meth)acrylate, alkyl sub-29 stituted acrylamides,(meth)acry-lates, N-vinyllactanes (e.~., ~07~43
12 - (CH2-CH)X ; (CH2-CH)Y ~ (CH2-Cz) -13 C=O ~ 1-0 14 IH2 ~03-M~ NH
18 Cl-+N(CH3)3 19 wherein x is 40 to 98 mole %, more preferably 50 to 95 mole %, and most preferably 80 to 90, y is 1 to 50 mole 21 %, more preferably 2 to 20 mole ~, and most preferably 22 5 to 10 mole %, and z is 1 to 50 mole %, more prefer-23 ably 2 to 20, and most preferably 5 to 10, wherein y 24 and z are less than 60 mole % and M is an amine or a metal cation selected from the group consistiny of 26 aluminum, iron, lead, Groups IA, IIA, IB and IIB of the 27 Periodic Table of Elements.
28 The molecular weight, as derived from 29 intrinsic viscosities, for the terpolymers of acryl-amide/sodium styrene sulfonate/methacrylamidopropyl-31 trimethylammonium chloride is 103 to 5x106, more 32 preferably 104 to 2X106 and most preferably 105 to 105.
~, .
~Z~;)'7~
1 The means for determining the molecular weights of the 2 water soluble terpolymers from the viscosity of solu-3 tions of the terpolymers comprises the initial 4 isolation of the water soluble terpolymers, purifica-tion and redissolving the terpolymers in water to give 6 solutions with known concen~rations. The flow times of 7 the solutions and the pure solvent were measured in a 8 standard Ubbelholde viscometer. Subsequently, the 9 reduced viscosity is calculated through standard methods utilizing these values. Extrapolation to zero 11 polymer concentration leads to the intrinsic viscosity 12 of the polymer solution. The intrinsic viscosity is 13 directly related to the molecular weight through the 14 well-known Mark-Houwink relationship.
The water soluble terpolymers of acrylamide/
16 sodium styrene sulfonate/methacrylamidopropyltrimethyl-17 ammonium chloride are formed by a conventional free 18 radical terpolymerization in an aqueous medium which 19 comprises the steps of forming a reaction solution of acrylamide monomer, sodium styrene sulfonate monomer 21 and methacrylamidopropyltrimethylammonium chloride 22 monomer (50 wt. % solution in water) in distilled 23 water, wherein the total monomer concentxation is 1 to 24 40 grams of total monomer per 100 grams of water, more preferably 5 to 30, and most preferably 10 to 20;
26 purging the reaction solution with nitrogen; adding 27 sufficient acid to the reaction solution to adjust the 28 pH of the reaction solution to 4.5 to 5.0; heating the 29 reaction solution to at least 55C while maintaining the nitrogen purge; adding sufficient free radical 31 initiator to the reaction solution at 55C to initiate 32 terpolymerization of the acrylamide monomer, the sodium 33 styrene sulfonate monomer, and the methacrylamidopro-34 pyltrimethylammonium chloride monomer; terpolymerizing said monomers of acrylamide, sodium styrene sulfonate ~.Z~)7~ 3 l and methacrylamidopropyltrimethylammonium chloride at a 2 sufficient temperature and for a sufficient period of 3 time to form said water soluble terpolymer; and 4 recovering said water soluble terpolymer from said reaction solution.
6 The total concentration of monomers in the 7 water is l to 40 grams of total monomer per lO0 grams 8 of water, more preferably 5 to 30 and most preferably 9 10 to 20. Terpolymerization of the acrylamide monomer, sodium styrene sulfonate monomer, and methacrylamido-ll propyltrimethylammonium chloride monomer is effected at 12 a temperature of 30 to 90, more preferably at 40 to 70, 13 and most preferably at 50 to 60 for a period of time of 14 1 to 24 hours, more preferably 3 to 10, and most pre-ferably 4 to 8.
16 A suitable method of recovery of the formed 17 water soluble terpolymer from the aqueous reaction 18 solution comprises precipitation in acetone, methanol, 19 ethanol and the like.
Suitable free radical initiators for the 21 free radical terpolymerization of the acrylamide 22 monomers, the sodium styrena suflonate monomer, and the 23 methacrylamidopropyltrimethylammonium chloride monomer 24 are selected from the group consisting of potassium persulfate, ammonium persulfate, benzoyl peroxide, 26 hydrogen peroxide, azobisisobutyronitrile, and the 27 like. The concentration of the free radical initiator 28 is 0.001 to 2.0 grams of free radical initiator per lO0 29 grams of total monomer, more preferably 0.01 to 1~0 and most preferably 0.05 to 0.1.
~Lfi'07S~3 1 It should be pointed out that neither the 2 mode of polymerization (solution, suspension, or 3 emulsion polymerization technique and the like), nor 4 the initiation is critical, provided that the method or the products of the initiation step does not inhibit 6 production of the polyampholyte or chemically modify 7 the initial molecular structure of reacting monomers.
8 Typical water soluble monomers incorporated 9 into the terpolymers that are envisioned in the present invention are listed as follows:
11 Anionic: 2-acrylamido-2--methylpropane sul-12 fonic acid, sodium styrene sul-13 fonate, (meth)acrylic acid, 2-14 sulfoethylmethacrylate, and the like.
16 Cationic: methacrylamidopropyltrimethyl-17 ammonium chloride, dimethyldial~
18 lylammonium chloride, diethyl-19 diallylammonium chloride, 2-meth-acryloxy-2-ethyltrimethylammonium 21 chloride, trimethylmethacryloxy-22 ethylammoniym methosulfate, 2-23 acrylamido-2-methylpropyltrimeth-24 ylammonium chloride, vinylbenzyl-trimethylammonium chloride, and 26 the like.
27 Nonionic: (N,N-dimethyl)acrylamide, hydrox-28 yethyl(meth)acrylate, alkyl sub-29 stituted acrylamides,(meth)acry-lates, N-vinyllactanes (e.~., ~07~43
- 5 -1 n-vinyl-2-pyrrolidone)~ and the 2 like.
3 These monomers possess the appropriate water 4 solubility for polymerization to take place.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
3 These monomers possess the appropriate water 4 solubility for polymerization to take place.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
6 The following examples illustrate the
7 present invention, without; however, limiting the same
8 hereto.
g EXAMPLE 1 Into a 1 liter, 4-necked flask was added~
11 13.8 g. MAPTAC (50% solution in water), 12 40.0 g. acrylamide, 13 6.44 g. sodium styrene sulfonate, and 14 300 ml. distilled water The pH of the solution was adjusted to 4.5 16 to 5.0 with 20% phosphonic acid solution. The solution 17 was purged with nitrogen gas for 1 hour to remove dis-18 solved oxygen. As the nitrogen gas purging began, the 19 solution was heated to 55C. At this point, 0.1 9.
potassium persulfate was added to the solution. After 4 21 hours, the polymer was precipitated from solution with 2~ acetone. Subsequently, the resulting polymer was washed 28 several times with a large excess of acetone and dried 24 in a vacuum oven at 60C for 24 hours.
~L'ZU79~3 1 Elemental analysis shows that this polyam-2 pholyte or intramolecular complex conta;ns 90.5 mole %
3 acrylamide, 1.86 mole % sodium styrene sulfonate and 4 7.64 mole % methacrylamidopropyltrimethylammonium-styrene sulfonate complex.
7 Shown in Table I are representative data on 8 the viscosity as a function of polymer concentration of g a terpolymer composed of approximately 90.5 mole %
acrylamide (~M), 7.64 mole % methacrylamidopropyltri-11 methylammonium styrene sulfonate complex and 1.86 mole 12 % sodium styrene sulfonate (SSS). This polymer was 13 synthesized by the free radical type polymerization in 14 an aqueous solvent system as described in Example 1~
1~0~5~9L3 2Rheological Properties of an Acrylamide-Based 3PolYampholyte in Fresh and Salt Water 4 Polymer Salt 5ConcentrationConcentration(a)ViScosity(b) 6 (g/dl) (Molar) (cps) 7 0.5 0.0 5.
8 1.0 0.0 15.
g EXAMPLE 1 Into a 1 liter, 4-necked flask was added~
11 13.8 g. MAPTAC (50% solution in water), 12 40.0 g. acrylamide, 13 6.44 g. sodium styrene sulfonate, and 14 300 ml. distilled water The pH of the solution was adjusted to 4.5 16 to 5.0 with 20% phosphonic acid solution. The solution 17 was purged with nitrogen gas for 1 hour to remove dis-18 solved oxygen. As the nitrogen gas purging began, the 19 solution was heated to 55C. At this point, 0.1 9.
potassium persulfate was added to the solution. After 4 21 hours, the polymer was precipitated from solution with 2~ acetone. Subsequently, the resulting polymer was washed 28 several times with a large excess of acetone and dried 24 in a vacuum oven at 60C for 24 hours.
~L'ZU79~3 1 Elemental analysis shows that this polyam-2 pholyte or intramolecular complex conta;ns 90.5 mole %
3 acrylamide, 1.86 mole % sodium styrene sulfonate and 4 7.64 mole % methacrylamidopropyltrimethylammonium-styrene sulfonate complex.
7 Shown in Table I are representative data on 8 the viscosity as a function of polymer concentration of g a terpolymer composed of approximately 90.5 mole %
acrylamide (~M), 7.64 mole % methacrylamidopropyltri-11 methylammonium styrene sulfonate complex and 1.86 mole 12 % sodium styrene sulfonate (SSS). This polymer was 13 synthesized by the free radical type polymerization in 14 an aqueous solvent system as described in Example 1~
1~0~5~9L3 2Rheological Properties of an Acrylamide-Based 3PolYampholyte in Fresh and Salt Water 4 Polymer Salt 5ConcentrationConcentration(a)ViScosity(b) 6 (g/dl) (Molar) (cps) 7 0.5 0.0 5.
8 1.0 0.0 15.
9 2.0 0.0 35-3.0 0.0 225.
11 0-5 1.7 15.
12 1.0 1.7 25~
13 2.0 1.7 100.
14 3.0 1.7 370.
0.5 3.4 25.
16 1.0 3.~ 35-17 2.0 3.4 115.
18 3-0 3.4 430~
.
19 (a) Sodium chloride.
(b) Measurements obtained on a Brookfiel 21Viscometer at 12 RPM.
22We note that the viscosity was measured in 23 both fresh and salt (in this example, sodium chloride) 24 water as the data in Table I shows. An importan~ con-clusion that can be drawn from the data is the marked 26 viscosity enhancement (at all polymer levels) as the 27 concentration o sodium chloride is increased, The 28 viscosity (at 3 g/dl polymer level) has increased, 29 approximately by a factor of a ~, with the addition of 3.4 M (i.e., 3.4 ~olar) sodium chloride. Essentially 31 similar results are observed in hydrochloric acid ~.Z0~79~3 1 solutions (see Table II). That is, the viscosity of the 2 terpolymer increases until a point is reached at very 3 high acid levels where the viscosity drops slightly~
4 This drop-off could be due to a slight compression of the expanded polymer chain by the high acid concentra-6 tion. Even at these acid levels, the viscosity of the 7 solution does not fall below the fresh water system.
g Rheological Properties of an Acrylamide-Based Polyampholyte in Fresh and Acid Solutions 11 Polymer Acid 12 Concentration Concentration(a) Viscosity(b) 13 (g/dl) (Molar)(cps) 14 0.~ 0.0 5.
1.0 0.0 15.
16 2.0 0.0 35-17 3.0 0.0225.
18 0.5 2.7412.
19 1.0 2.7~22.
2.n 2.7455.
21 3.0 2.74290.
22 0.5 8.22 8.
23 1.0 8.2218.
24 2.0 8.2242.
3.0 8.22235.
26 (a) Hydrochloric acid.
27 (b) Measurements obtained on a Brookfiel 28 Viscometer at 12 RPM.
1 A study of copolymers with either the 2 cationic or anionic monomer units absent (i.e., homo-3 geneously changed) would be informative in showing the 4 necessity of having both charged species present within the polymer structure. Shown in Tables III and IV are 6 viscosity concentration data at a sodium styrene sul-7 fonate (SSS)/acrylamide copolymer (32.9 mole ~ SSS) in 8 hydrochloric acid and sodium chloride solutions. The g viscosity in fresh water is high at all polymer levels, but falls dramatically with the addition of acid or 11 salt. This behavior is in marked contrast with the 12 viscosity enhancement of the terpolymer.
~LZ()7943 1 l'ABLE III
2 Rheological Properties of an Acrylamide-Sodium Styrene 3 Sulfonate Copolymer in Fresh and Acidified Water 4 Polymer Acid 5Concentration ConcentrationViscosity~a) 6 (g/dl) (M) (cps) 7 0O5 0.0 55.
8 1.0 o.o 95 9 2.0 0.0 215.
3.0 0.0 350.
11 0.5 2.74 2 12 1.0 2.74 5 13 2.0 2.74 8 1~ 3.0 2.74 12 0.5 8.22 16 1.0 8.22 3 17 2.0 8.22 5 18 3.0 8.22 8 19 ta) Measurements obtained on a Brookfield~
Viscometer at 12 RPM.
9~3 2Rheological Properties of an Acrylamide-Sodium 3Styrene Sulfonate Copolymer in Fresh and Salt Water 4 Polymer Salt 5 Concentration Concentration Viscosity(a) 6 (g/dl) (M)(cps) 7 0~5 0.0 55-8 1.0 o.o 95 9 2.0 0.0 215.
3.0 0.0 350.
11 0.5 1.7 5 12 1.0 1.7 10 13 2.0 1.7 18 14 3.0 1.7 35 0.5 3.4 2 16 1.0 3.4 7 17 2.0 3.4 14 18 3.0 3.4 20 19 (a) Measurements obtained on a Brookfiel Viscometer at 12 RPM.
21 Data (viscosity-concentration) of a meth-22 acrylamidopropyltrimethylammonium chloride/acrylamide 23 copolymer in hydrochloric acid solution is presented in 24 Table V.
'7~3 2Rheological Properties of Acrylamide- MAPTAC
3Copolymer in Fresh and Acid Solutions 4 Polymer Acid 5Concentration ConcentrationvisCOSity(a) 6 (g/dl) (M) (cps) 7 0.5 0.0 20 8 1.0 0 0 9 2.0 0.0 210 3-0 0.0 965 11 0.5 2.74 15 12 1.0 2.74 30 13 2.0 2.74 130 14 3.0 2.74 5~0 0.5 8.22 10 16 1,0 8.22 22 17 2.0 8.22 105 18 3.0 8.22 430 19 (a) Measurements obtained on a Brookfield~
20Viscometer at 12 RPM.
21Again, we observe a decrease in viscosity as 22 the acid concentration increases. The drop-off is not 23 as dramatic as in Tables III and IV since the charge 24 density on the methacrylamidopropyltrimethylammonium chloride/acrylamide copolymer ~3.7 mole % M~PTAC) is 26 less. In any event, the behavior of this material can 27 also be contrasted with the terpolymer solution systems 28 (Tables I and II).
7~3 1 The polymeric materials used in this study 2 appear to be useful as a particular example of a 3 general phenomena. That is, the presence of monomeric 4 units comprising the broad class of water soluble anionic and cationic moieties within the polymer chain 6 are the necessary requirements for viscosity enhance-7 ment in acid, base or salt solutions. A stoichiometric 8 amount of these oppositely charged units is not a ~ requirement for effective thickening of these latter solutions. For example, we have shown the viscosity of 11 acid, base and salt solutions increase even with the 12 complete absence of acrylamide in the polya~pholyte 13 structure, In addition, the acrylamide monomer units 14 present within the terpolymer structure is only one example of many available water-soluble or water dis-16 persible monomer structures.
11 0-5 1.7 15.
12 1.0 1.7 25~
13 2.0 1.7 100.
14 3.0 1.7 370.
0.5 3.4 25.
16 1.0 3.~ 35-17 2.0 3.4 115.
18 3-0 3.4 430~
.
19 (a) Sodium chloride.
(b) Measurements obtained on a Brookfiel 21Viscometer at 12 RPM.
22We note that the viscosity was measured in 23 both fresh and salt (in this example, sodium chloride) 24 water as the data in Table I shows. An importan~ con-clusion that can be drawn from the data is the marked 26 viscosity enhancement (at all polymer levels) as the 27 concentration o sodium chloride is increased, The 28 viscosity (at 3 g/dl polymer level) has increased, 29 approximately by a factor of a ~, with the addition of 3.4 M (i.e., 3.4 ~olar) sodium chloride. Essentially 31 similar results are observed in hydrochloric acid ~.Z0~79~3 1 solutions (see Table II). That is, the viscosity of the 2 terpolymer increases until a point is reached at very 3 high acid levels where the viscosity drops slightly~
4 This drop-off could be due to a slight compression of the expanded polymer chain by the high acid concentra-6 tion. Even at these acid levels, the viscosity of the 7 solution does not fall below the fresh water system.
g Rheological Properties of an Acrylamide-Based Polyampholyte in Fresh and Acid Solutions 11 Polymer Acid 12 Concentration Concentration(a) Viscosity(b) 13 (g/dl) (Molar)(cps) 14 0.~ 0.0 5.
1.0 0.0 15.
16 2.0 0.0 35-17 3.0 0.0225.
18 0.5 2.7412.
19 1.0 2.7~22.
2.n 2.7455.
21 3.0 2.74290.
22 0.5 8.22 8.
23 1.0 8.2218.
24 2.0 8.2242.
3.0 8.22235.
26 (a) Hydrochloric acid.
27 (b) Measurements obtained on a Brookfiel 28 Viscometer at 12 RPM.
1 A study of copolymers with either the 2 cationic or anionic monomer units absent (i.e., homo-3 geneously changed) would be informative in showing the 4 necessity of having both charged species present within the polymer structure. Shown in Tables III and IV are 6 viscosity concentration data at a sodium styrene sul-7 fonate (SSS)/acrylamide copolymer (32.9 mole ~ SSS) in 8 hydrochloric acid and sodium chloride solutions. The g viscosity in fresh water is high at all polymer levels, but falls dramatically with the addition of acid or 11 salt. This behavior is in marked contrast with the 12 viscosity enhancement of the terpolymer.
~LZ()7943 1 l'ABLE III
2 Rheological Properties of an Acrylamide-Sodium Styrene 3 Sulfonate Copolymer in Fresh and Acidified Water 4 Polymer Acid 5Concentration ConcentrationViscosity~a) 6 (g/dl) (M) (cps) 7 0O5 0.0 55.
8 1.0 o.o 95 9 2.0 0.0 215.
3.0 0.0 350.
11 0.5 2.74 2 12 1.0 2.74 5 13 2.0 2.74 8 1~ 3.0 2.74 12 0.5 8.22 16 1.0 8.22 3 17 2.0 8.22 5 18 3.0 8.22 8 19 ta) Measurements obtained on a Brookfield~
Viscometer at 12 RPM.
9~3 2Rheological Properties of an Acrylamide-Sodium 3Styrene Sulfonate Copolymer in Fresh and Salt Water 4 Polymer Salt 5 Concentration Concentration Viscosity(a) 6 (g/dl) (M)(cps) 7 0~5 0.0 55-8 1.0 o.o 95 9 2.0 0.0 215.
3.0 0.0 350.
11 0.5 1.7 5 12 1.0 1.7 10 13 2.0 1.7 18 14 3.0 1.7 35 0.5 3.4 2 16 1.0 3.4 7 17 2.0 3.4 14 18 3.0 3.4 20 19 (a) Measurements obtained on a Brookfiel Viscometer at 12 RPM.
21 Data (viscosity-concentration) of a meth-22 acrylamidopropyltrimethylammonium chloride/acrylamide 23 copolymer in hydrochloric acid solution is presented in 24 Table V.
'7~3 2Rheological Properties of Acrylamide- MAPTAC
3Copolymer in Fresh and Acid Solutions 4 Polymer Acid 5Concentration ConcentrationvisCOSity(a) 6 (g/dl) (M) (cps) 7 0.5 0.0 20 8 1.0 0 0 9 2.0 0.0 210 3-0 0.0 965 11 0.5 2.74 15 12 1.0 2.74 30 13 2.0 2.74 130 14 3.0 2.74 5~0 0.5 8.22 10 16 1,0 8.22 22 17 2.0 8.22 105 18 3.0 8.22 430 19 (a) Measurements obtained on a Brookfield~
20Viscometer at 12 RPM.
21Again, we observe a decrease in viscosity as 22 the acid concentration increases. The drop-off is not 23 as dramatic as in Tables III and IV since the charge 24 density on the methacrylamidopropyltrimethylammonium chloride/acrylamide copolymer ~3.7 mole % M~PTAC) is 26 less. In any event, the behavior of this material can 27 also be contrasted with the terpolymer solution systems 28 (Tables I and II).
7~3 1 The polymeric materials used in this study 2 appear to be useful as a particular example of a 3 general phenomena. That is, the presence of monomeric 4 units comprising the broad class of water soluble anionic and cationic moieties within the polymer chain 6 are the necessary requirements for viscosity enhance-7 ment in acid, base or salt solutions. A stoichiometric 8 amount of these oppositely charged units is not a ~ requirement for effective thickening of these latter solutions. For example, we have shown the viscosity of 11 acid, base and salt solutions increase even with the 12 complete absence of acrylamide in the polya~pholyte 13 structure, In addition, the acrylamide monomer units 14 present within the terpolymer structure is only one example of many available water-soluble or water dis-16 persible monomer structures.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A terpolymer having the formula:
wherein x is 40 to 98 mole %, y is 1 to 50 mole %, z is 1 to 50 mole %, wherein y and z are less than 60 mole %, and M is selected from the group consisting of amines and a metallic cation being selected from the group consisting of lead, iron, aluminum, Groups IA, IIA, IB and IIB of the Periodic Table of Elements.
wherein x is 40 to 98 mole %, y is 1 to 50 mole %, z is 1 to 50 mole %, wherein y and z are less than 60 mole %, and M is selected from the group consisting of amines and a metallic cation being selected from the group consisting of lead, iron, aluminum, Groups IA, IIA, IB and IIB of the Periodic Table of Elements.
2. A terpolymer according to claim 1 wherein M is sodium.
3. A terpolymer according to claim 1 wherein said terpolymer is dissolved in an aqueous medium at a concentration of 0.001 to 20 grams of terpolymer per 100 grams of water.
4. A terpolymer according to claim 1 wherein said terpolymer is dissolved in a salt solution at a concentration of 0.001 to 20 grams of terpolymer per 100 grams of water, said salt solution having 0.001 to 60 grams of salt per 100 grams of said salt solution.
5. A terpolymer according to claim 1 wherein said terpolymer is dissolved in an acid solu-tion at a concentration of 0.001 to 20 grams of ter-polymer per 100 grams of water, said acid solution having 0.001 to 30 grams of acid per 100 grams of said acid solution.
6. A terpolymer according to claim 1 wherein said terpolymer is dissolved in a base solution at a concentration of 0.001 to 20 grams of terpolymer per 100 grams of water, said base solution having 0.001 to 60 grams of base per 100 grams of said base solu-tion.
7. A terpolymer according to claim 1 wherein said terpolymer possesses a nonstoichiometric amount of anionic and cationic groups.
8. A terpolymer according to claim wherein said terpolymer is readily soluble or dispen-sible in fresh water.
9. A terpolymer according to claim 1 wherein said terpolymer possesses enhanced solvent thickening efficiency in acid, base, or salt solutions as compared to homogeneously charged copolymers.
10. A terpolymer according to claim 1 wherein said terpolymer is derived from water soluble nonionic, anionic and cationic monomers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US478,657 | 1983-03-25 | ||
| US06/478,657 US4461884A (en) | 1983-03-25 | 1983-03-25 | Intramolecular polymeric complexes-viscosifiers for acid, base and salt (aqueous) solutions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1207943A true CA1207943A (en) | 1986-07-15 |
Family
ID=23900846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000448911A Expired CA1207943A (en) | 1983-03-25 | 1984-03-06 | Intramolecular polymeric complexes - viscosifiers for acid, base and salt (aqueous) solutions |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4461884A (en) |
| EP (1) | EP0123420A1 (en) |
| JP (1) | JPS6011516A (en) |
| CA (1) | CA1207943A (en) |
| MX (1) | MX165979B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4460758A (en) * | 1983-11-02 | 1984-07-17 | Exxon Research And Engineering Co. | Drag reduction agents for aqueous salt solutions |
| US4540510A (en) * | 1984-02-13 | 1985-09-10 | Henkel Corporation | Synergistic thickener mixtures of amps polymers with other thickeners |
| US4554081A (en) * | 1984-05-21 | 1985-11-19 | Halliburton Company | High density well drilling, completion and workover brines, fluid loss reducing additives therefor and methods of use |
| US4710555A (en) * | 1985-01-02 | 1987-12-01 | Exxon Research And Engineering Company | Novel polyampholyte compositions possessing high degrees of acid, base, or salt tolerance in solution |
| US4837288A (en) * | 1985-01-02 | 1989-06-06 | Exxon Research & Engineering Company | Novel polyampholyte compositions possessing high degrees of acid, base, or salt tolerance in solution |
| US4946916A (en) * | 1987-08-05 | 1990-08-07 | Exxon Research And Engineering Company | Novel polyampholyte compositions possessing high degree of acid, base, or salt tolerance in solution |
| US5068278A (en) * | 1988-12-23 | 1991-11-26 | Exxon Research And Engineering Company | Novel polyampholyte compositions possessing high degrees of acid, base, or salt tolerance in solution |
| EP0427107A3 (en) * | 1989-11-06 | 1992-04-08 | M-I Drilling Fluids Company | Drilling fluid additive |
| FR2764900B1 (en) * | 1997-06-24 | 2001-06-01 | Inst Francais Du Petrole | FILTRATE REDUCING ADDITIVE AND WELL FLUID |
| WO2005003192A1 (en) * | 2003-06-26 | 2005-01-13 | Symyx Technologies, Inc. | Synthesis of photoresist polymers |
| US20050152855A1 (en) * | 2003-09-19 | 2005-07-14 | Damian Hajduk | Materials for enhanced delivery of hydrophilic active agents in personal care formulations |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1181914B (en) * | 1959-07-03 | 1964-11-19 | Dow Chemical Co | Process for the production of mixed polymers from acrylic acid amide and vinyl aromatic compounds |
| US4115339A (en) * | 1971-11-18 | 1978-09-19 | Hercules Incorporated | High molecular-weight, water-soluble vinyl polymers |
| GB1510689A (en) * | 1974-12-19 | 1978-05-10 | Sumitomo Chemical Co | Preparation of water-soluble cationic high polymer |
| DE3027422A1 (en) * | 1980-07-19 | 1982-02-25 | Cassella Ag, 6000 Frankfurt | HIGH MOLECULAR WATER-SOLUBLE COPOLYMERS, THEIR PRODUCTION AND USE |
-
1983
- 1983-03-25 US US06/478,657 patent/US4461884A/en not_active Expired - Fee Related
-
1984
- 1984-03-06 CA CA000448911A patent/CA1207943A/en not_active Expired
- 1984-03-20 EP EP84301894A patent/EP0123420A1/en not_active Withdrawn
- 1984-03-22 MX MX008339A patent/MX165979B/en unknown
- 1984-03-23 JP JP59055932A patent/JPS6011516A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| MX165979B (en) | 1992-12-15 |
| JPS6011516A (en) | 1985-01-21 |
| JPH0437846B2 (en) | 1992-06-22 |
| US4461884A (en) | 1984-07-24 |
| EP0123420A1 (en) | 1984-10-31 |
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