CA1258947A - Water-soluble copolymers and their use as dispersing agents for solids - Google Patents
Water-soluble copolymers and their use as dispersing agents for solidsInfo
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- CA1258947A CA1258947A CA000465864A CA465864A CA1258947A CA 1258947 A CA1258947 A CA 1258947A CA 000465864 A CA000465864 A CA 000465864A CA 465864 A CA465864 A CA 465864A CA 1258947 A CA1258947 A CA 1258947A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F228/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
-
- 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
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Abstract of the disclosure:
Copolymers of a) (meth)acrylic acid or (meth)-acrylic acid derivatives, b) vinylsulfonic acid, methal-lylsulfonic acid or acrylamidopropenylmethylenesulfonic acid and c) N-vinylcarboxylic acid amides, and their use as dispersing agents, in particular for drilling muds and cement slurries.
Copolymers of a) (meth)acrylic acid or (meth)-acrylic acid derivatives, b) vinylsulfonic acid, methal-lylsulfonic acid or acrylamidopropenylmethylenesulfonic acid and c) N-vinylcarboxylic acid amides, and their use as dispersing agents, in particular for drilling muds and cement slurries.
Description
- 2 ~ 5~3~
The present invention relates to copoLymers as d;spersing agents for solidsO preferably in aqueous solu-tion. The solids can differ greatly in nature, and their concentrations in the liquid phase can vary to a very considerable degree~ Thus, the compounds according to the invention disperse solids in concentrations of a few mg/l ~ust as effectively as in systems with a high solids content, for example drilling muds and mineral binders, such as cement and gypsum sLurries and kaol;n, carbon and calcium carbonate slurries and the like~ sometimes with extremely low solvent contents. In the case of the highly concentrated dispersions of solids, the compounds accor-ding to the invention enable the water content to be mini~
mi~ed and the v;scosity to be reduced, which offers indus-trial advantages.
Very different dispers;ng auxiliaries are used to opt;mize the properties of the most diverse disper-sions, such as drilling muds, cement slurrie3~ carbon slurr;es and d;spersions of pesticides and color pigments.
Dispersing agents which are used in drill~ng muds are, for example, polyphosphates~ quebracho and, in par-ticular, lignosulfonates and lignites, for example in accordance with German ALIS legeschrift 1,1 3,874. Copoly-mers of styrene sulfonate and maleic anhydride according 25 to U.S. Patent No. 3,730,900 have recently found use in the field of drilling mudsO as liquefiers for high temperatures.
If saline water has to be used -for drilling muds when drilling through salt formations or when drilling in the open sea, protective colloids, such as starch and starch derivatives, carboxymethylhydroxyethyl-carboxy-methylcellLIloses~ biopolymers and partly hydrolyzed acryl-amicles are necessary for stabilizing these dispersions.
At very h;gh solids contents, low molecular weight ionic polymers are preferred. The use of additives for drilling muds is descr;bed ;n great cletail in: George ~ Gray,
The present invention relates to copoLymers as d;spersing agents for solidsO preferably in aqueous solu-tion. The solids can differ greatly in nature, and their concentrations in the liquid phase can vary to a very considerable degree~ Thus, the compounds according to the invention disperse solids in concentrations of a few mg/l ~ust as effectively as in systems with a high solids content, for example drilling muds and mineral binders, such as cement and gypsum sLurries and kaol;n, carbon and calcium carbonate slurries and the like~ sometimes with extremely low solvent contents. In the case of the highly concentrated dispersions of solids, the compounds accor-ding to the invention enable the water content to be mini~
mi~ed and the v;scosity to be reduced, which offers indus-trial advantages.
Very different dispers;ng auxiliaries are used to opt;mize the properties of the most diverse disper-sions, such as drilling muds, cement slurrie3~ carbon slurr;es and d;spersions of pesticides and color pigments.
Dispersing agents which are used in drill~ng muds are, for example, polyphosphates~ quebracho and, in par-ticular, lignosulfonates and lignites, for example in accordance with German ALIS legeschrift 1,1 3,874. Copoly-mers of styrene sulfonate and maleic anhydride according 25 to U.S. Patent No. 3,730,900 have recently found use in the field of drilling mudsO as liquefiers for high temperatures.
If saline water has to be used -for drilling muds when drilling through salt formations or when drilling in the open sea, protective colloids, such as starch and starch derivatives, carboxymethylhydroxyethyl-carboxy-methylcellLIloses~ biopolymers and partly hydrolyzed acryl-amicles are necessary for stabilizing these dispersions.
At very h;gh solids contents, low molecular weight ionic polymers are preferred. The use of additives for drilling muds is descr;bed ;n great cletail in: George ~ Gray,
3 ~ i8~7 H~C~Ho Darly, Walter F. Rogers "Composition and Properties of Oil Well Drilling Fluids, Fourth Edition~ Gulf Publishing Company Houston/Texas 1980.
Copolymers of v;nyl sulfonate and vinylamide according to German Offenlegungsschrift 2,931,897 and German Auslegeschrift 2,444S108 haue recently proved par-ticularly suitable, when used in saline dri~ling muds, for stabilizing properties established beforehand in very deep hot bores.
In cement slurries which are pumped, d;spersing agents reduce the v;scos;ty~ Th;s fac;litates the pum-ping operation and enables the water content ~o be re-duced, which improves the mechanical properties of the hardened concrete. Lignosulfonates, polyacryLic acids, condensation products of mononaphthalenesulfonates and formaLdehyde according to U.S. Patent 3,465,825 and N-sulfoalkyl-substituted acrylamides according to U.S.
Patent 4,053,323 are used as d;spers;ng agents ;n cement slurr;esO Depend;ng on the f;eld of appl;cat;onr agents ~hich reduce water loss, setting retarders or setting accelerators are added to cement slurr;es, and these must be compatible with the particular dispersing agent. This l;m;ts the appl;cabil;ty of the types of d;spersi~g agent.
Thus, for example, if calcium salts are used as setting accelerators, polyacrylic ac;ds cannot be used 25 the d;spersing agents.
The effect of partly hydrolyzed polyacrylamides as agents which reduce water loss is also greatly de-creased in the presence of calcium chloride. Where the dispersions are exposed to particularly high stresses, for example in the case of cement slurr;es and drill;ng muds based on salt water for very deep hot bores, it is diff;cult to establish opt;mum properties.
The most diverse non;on;c, anionic and cat;onic surfactants are also used as dispersing agents.
The invention relates to novel copolymers con-sisting of 5 - 95% by weight of groups of the formula I
, ~
-~ ~.2~ 7 ~1 (I) - C~l-C~.--in wh;ch R~ denotes hydrogen or methyl and R2 denotes carboxamido, carbomethoxy, cyano or, preferably, carboxyl, 5 - 95% by we;ght of groups of the formula II, III or IV
~3 I CH
--1H-CH~ OEl ~CH- (III) lo ~3 K ~ . CH ~S03XO
~ R4 --CH--CH-- (IVj Co~H-R5- SO ;,e K~B
in which R3 denotes hydrogen, C1-C6-alkyl or phenyl, R4 denotes a hydrogen atom or CH3, R5 denotes C1-C1Q-alkylene and K+ denotes ammonium, lithium, sodium or potas- .
sium, and 0 - 5% by weight of groups of the formula V
-CH -C~l-N-R (V3 b=o ~7 ~herein R6 denotes hydrogen, CH3 or C2H5 and R7 denotes CH3 or C2H5, or R6 and R~ together deno~e a propylene group which forms a pyrrolidone radical together ~ith the radîcal -N~
O
~ . .
. . . ~ - .
_ 5 ~ 947 ~ opolymers which contain up to ZO - 90% of mono-mers of the ~ormula I and 5 - 50% of the formula II and/
or III or 20 - 70~ of the formula IV are preferred~ The monomer o~ the formula V is additionally copolymerized into copolymers used for suspensions of coarser part1cle s;ze. The molecular weights of the copolymers are between 2,000 and 6 million, preferably between 10,000 and 500,000.
Higher molecular weights are necessary if extreme require-ments are imposed on the suspension, such as h;gh tempera-1~ tures and salt contents and low release of water~
The copolymers to be used can be prepared in amanner which is known per se by reaction of the monomers at temperatures between about -10 and ~80~, preferably at 20 to 60C~ in the presence of suitable polymer;za~
tion catalysts. The polymeri~at;on is advantageously car-r;ed out in an aqueous phase, but if appropriate aqueous solutions of water-miscible organic solvents, such as, for example methanol, ethanol, tert.-butyl alcohol~ tetra-hydrofuran or dime~hylFormamide, can also serve as the polymeri~ation medium. Possible polymerization catalysts are, ;n part;cular, per-compounds, such as benzoyl per-oxide, acetyl peroxide, tert.-butyl hydroperoxide or alkal; metal or ammon;um perox;de-disulfate, or redox systems, such as N-p-tolylsulfonylmethylcarbamic acid methyl ester/ammonium peroxide-disulfate.
If appropriate~ it may also be advantageous to add cocatalysts, such as dibutylamine hydrochlor;de or traces of copper salts. Compounds such as, for example, azobisisobutyronitrile, can also be added as polymeri7a-tion initiators.
On the bas;s of the formulae I, II, III, I~ and V, the following monomers are preferably used for the copolymers according to the invention:
1. acrylic acid 2. vinylsulfonic acid 3. me~hallylsulfonic acid
Copolymers of v;nyl sulfonate and vinylamide according to German Offenlegungsschrift 2,931,897 and German Auslegeschrift 2,444S108 haue recently proved par-ticularly suitable, when used in saline dri~ling muds, for stabilizing properties established beforehand in very deep hot bores.
In cement slurries which are pumped, d;spersing agents reduce the v;scos;ty~ Th;s fac;litates the pum-ping operation and enables the water content ~o be re-duced, which improves the mechanical properties of the hardened concrete. Lignosulfonates, polyacryLic acids, condensation products of mononaphthalenesulfonates and formaLdehyde according to U.S. Patent 3,465,825 and N-sulfoalkyl-substituted acrylamides according to U.S.
Patent 4,053,323 are used as d;spers;ng agents ;n cement slurr;esO Depend;ng on the f;eld of appl;cat;onr agents ~hich reduce water loss, setting retarders or setting accelerators are added to cement slurr;es, and these must be compatible with the particular dispersing agent. This l;m;ts the appl;cabil;ty of the types of d;spersi~g agent.
Thus, for example, if calcium salts are used as setting accelerators, polyacrylic ac;ds cannot be used 25 the d;spersing agents.
The effect of partly hydrolyzed polyacrylamides as agents which reduce water loss is also greatly de-creased in the presence of calcium chloride. Where the dispersions are exposed to particularly high stresses, for example in the case of cement slurr;es and drill;ng muds based on salt water for very deep hot bores, it is diff;cult to establish opt;mum properties.
The most diverse non;on;c, anionic and cat;onic surfactants are also used as dispersing agents.
The invention relates to novel copolymers con-sisting of 5 - 95% by weight of groups of the formula I
, ~
-~ ~.2~ 7 ~1 (I) - C~l-C~.--in wh;ch R~ denotes hydrogen or methyl and R2 denotes carboxamido, carbomethoxy, cyano or, preferably, carboxyl, 5 - 95% by we;ght of groups of the formula II, III or IV
~3 I CH
--1H-CH~ OEl ~CH- (III) lo ~3 K ~ . CH ~S03XO
~ R4 --CH--CH-- (IVj Co~H-R5- SO ;,e K~B
in which R3 denotes hydrogen, C1-C6-alkyl or phenyl, R4 denotes a hydrogen atom or CH3, R5 denotes C1-C1Q-alkylene and K+ denotes ammonium, lithium, sodium or potas- .
sium, and 0 - 5% by weight of groups of the formula V
-CH -C~l-N-R (V3 b=o ~7 ~herein R6 denotes hydrogen, CH3 or C2H5 and R7 denotes CH3 or C2H5, or R6 and R~ together deno~e a propylene group which forms a pyrrolidone radical together ~ith the radîcal -N~
O
~ . .
. . . ~ - .
_ 5 ~ 947 ~ opolymers which contain up to ZO - 90% of mono-mers of the ~ormula I and 5 - 50% of the formula II and/
or III or 20 - 70~ of the formula IV are preferred~ The monomer o~ the formula V is additionally copolymerized into copolymers used for suspensions of coarser part1cle s;ze. The molecular weights of the copolymers are between 2,000 and 6 million, preferably between 10,000 and 500,000.
Higher molecular weights are necessary if extreme require-ments are imposed on the suspension, such as h;gh tempera-1~ tures and salt contents and low release of water~
The copolymers to be used can be prepared in amanner which is known per se by reaction of the monomers at temperatures between about -10 and ~80~, preferably at 20 to 60C~ in the presence of suitable polymer;za~
tion catalysts. The polymeri~at;on is advantageously car-r;ed out in an aqueous phase, but if appropriate aqueous solutions of water-miscible organic solvents, such as, for example methanol, ethanol, tert.-butyl alcohol~ tetra-hydrofuran or dime~hylFormamide, can also serve as the polymeri~ation medium. Possible polymerization catalysts are, ;n part;cular, per-compounds, such as benzoyl per-oxide, acetyl peroxide, tert.-butyl hydroperoxide or alkal; metal or ammon;um perox;de-disulfate, or redox systems, such as N-p-tolylsulfonylmethylcarbamic acid methyl ester/ammonium peroxide-disulfate.
If appropriate~ it may also be advantageous to add cocatalysts, such as dibutylamine hydrochlor;de or traces of copper salts. Compounds such as, for example, azobisisobutyronitrile, can also be added as polymeri7a-tion initiators.
On the bas;s of the formulae I, II, III, I~ and V, the following monomers are preferably used for the copolymers according to the invention:
1. acrylic acid 2. vinylsulfonic acid 3. me~hallylsulfonic acid
4. acrylamidopropenylmethylenesulfonic acid
5. N-vinyl N-methylacetamide The copolvmers are obtained as viscous, preferably ,=, 125~39f~7 aqueous, solut;ons. They can be used in this form~ If ;t is intended to prepare the copolymers in solid form, the polymer solutions can be subjected to an evaporation or drying process, for example spray-drying or drum-drying. For use, it is appropriate for the sulfo groupsin the copolymers to be in the form of the ammonium or alkal; metal salts.
The copolymers according to the ;nvent;on have a very effective dispersing action on very small amounts of solids~ for example calcium carbonate ;n industr;al cooling c;rculations of only, for example, 10 ppm, or on cement slurries w;th a very h;gh sol;ds content of up to 80X. The minimum concentrat;on used in the cooling waters ;s 5 ppm, ~hilst ;t can be up to 20% in the cement sLur-r;es. The h;gh concentrat;ons ;n the cement slurr;esnot;ceably ;mprove the mechan;cal propert;es of the har-dened cement~ Only the very good d;spersing effect of the copolymers accord;ng to the ;nvent;on enable the h;gh concentration ment oned for these polymers to be homo-geneously distributed in the cement slurry.Examples:
1. D;spers;on of calcium carbonate A slurry of freshly prec;p;tated calc;um carbo-nate (100 mgll) in water was used~ 25, 100 and 500 ppm of a copolymer consist;ng of 10% of me~halLylsulfon;c acid and 90X of acryl;c acid tK value about 30) were added to 500 ml of th;s slurry in measur;ng cyl;nders. The m;xture was shaken and left to stand for about 2 hours and the supernatant amount of water t250 m3) ~as then decanted and the sol;ds content therein determined.
Result Table 1 Amount used dispersed caLc;um carbonate in the decanted water in % of the starting concentration O ppm O
Z5 ppm 22 100 ppm 47 500 ppm 77 ~2~ 7 ., oo o ~ o ~ ~ ~ ~ ~o ~
,o ~ U~
r--~o J~
Q ~-o n 0. ~ ~ oo o~
O ~ .-W ....
C
o C)O
L O
Q N oo 1~ 0 ~ N
~J la ~o ~) >~ _ E O
~ ~ oo ~ U~
.~ ~ ~ r~ O
eL
C U~
O o W L
o C~
O ~
~ U) L ~ 1/~ U) 0 In In a) o L O 00 C~ 1~ ~ `O 00 O` ~J
O
a) cl: ~ m m ~ . .~
U) ., ~ L L i_ L _ J
~5 _ o W E E~ E E E ~ E
E ~ ~ _ ~ _ _ ~ 0 t , U~ ~1 ~ ~ ~ ~
C .. ~ O O ~ o O >~ O O
., ~ ~ + U ~ ~) U U ~:D Q Q
_ ~ E -O ~ ~ o ~ ~I Y- ~
_ E c:5~ ~ ~ ~1 0 ~ O o ~ O ~ O O ~ O ~ O O
., C E E E E E E E E
L U ., W ~I W W W W C5) W W
~a ., _ ~ ~ ~ O ~ O O ~ O -- O O -- O ~ O O
~t) ., 0~ O~
. 0 ~ ~ 0 ~ ~ ~ ~ ' 0 ~ m c, ~ m m + m ~ + m + m + ~ m ~ m ~ +
., .
~L2 5~9L~7 Copolymer A: 90% acrylic acid 10% of Na methal~ylsulfonate Copolymer B: 65% of acrylic acid 35% of acrylamidopropenyl methylenesulfonate The dr;lling muds were measured at 20C and then after 15 hours of aging at 200C~ The K value of the polymers (Fikentscher, Cellulose Chemie 13~ 1932, page 58) was about 60. The apparent viscos;ty and the liquid lim;t were measured with a 35 SA FANN viscometer. The ~ater loss accord;ng to API is the filtrat;on rate in 30 minutes according to "API Code 29" wi~h a standardized filter press at 7 kg/cm2.
3~ Cement slurries a. Composition. 349 g of water 792 g of cement grade G
Water loss apparent ~iquid limit API (cm3) viscosity (lbs/100 sq.ft.) (mPas) . _ Cement slurry 20 without additive CX3 54 53 Copolymer A from Example 2 9.0 30 Z
Copolymer 9 from Example 2 6.5 27 _ The amount of copolymers used is in each case 0~75%. The apparent viscos;ty and liqu;d limit were determined with a 35 SA FAN~ viscometer, b. Composition: 349 g of ~later 79Z g of cement grade D
34~
_ 9 ~
Amount Water apparent Liquid limit used % loss viscosity (lbs/
APIlcm3 (mPas) 100 sq. ft~) Cement sLurry 5 without additive 44 16 Copolymer s 0~3531.0 30 2 from Example 2 1 4D0 31 3 1.9 34
The copolymers according to the ;nvent;on have a very effective dispersing action on very small amounts of solids~ for example calcium carbonate ;n industr;al cooling c;rculations of only, for example, 10 ppm, or on cement slurries w;th a very h;gh sol;ds content of up to 80X. The minimum concentrat;on used in the cooling waters ;s 5 ppm, ~hilst ;t can be up to 20% in the cement sLur-r;es. The h;gh concentrat;ons ;n the cement slurr;esnot;ceably ;mprove the mechan;cal propert;es of the har-dened cement~ Only the very good d;spersing effect of the copolymers accord;ng to the ;nvent;on enable the h;gh concentration ment oned for these polymers to be homo-geneously distributed in the cement slurry.Examples:
1. D;spers;on of calcium carbonate A slurry of freshly prec;p;tated calc;um carbo-nate (100 mgll) in water was used~ 25, 100 and 500 ppm of a copolymer consist;ng of 10% of me~halLylsulfon;c acid and 90X of acryl;c acid tK value about 30) were added to 500 ml of th;s slurry in measur;ng cyl;nders. The m;xture was shaken and left to stand for about 2 hours and the supernatant amount of water t250 m3) ~as then decanted and the sol;ds content therein determined.
Result Table 1 Amount used dispersed caLc;um carbonate in the decanted water in % of the starting concentration O ppm O
Z5 ppm 22 100 ppm 47 500 ppm 77 ~2~ 7 ., oo o ~ o ~ ~ ~ ~ ~o ~
,o ~ U~
r--~o J~
Q ~-o n 0. ~ ~ oo o~
O ~ .-W ....
C
o C)O
L O
Q N oo 1~ 0 ~ N
~J la ~o ~) >~ _ E O
~ ~ oo ~ U~
.~ ~ ~ r~ O
eL
C U~
O o W L
o C~
O ~
~ U) L ~ 1/~ U) 0 In In a) o L O 00 C~ 1~ ~ `O 00 O` ~J
O
a) cl: ~ m m ~ . .~
U) ., ~ L L i_ L _ J
~5 _ o W E E~ E E E ~ E
E ~ ~ _ ~ _ _ ~ 0 t , U~ ~1 ~ ~ ~ ~
C .. ~ O O ~ o O >~ O O
., ~ ~ + U ~ ~) U U ~:D Q Q
_ ~ E -O ~ ~ o ~ ~I Y- ~
_ E c:5~ ~ ~ ~1 0 ~ O o ~ O ~ O O ~ O ~ O O
., C E E E E E E E E
L U ., W ~I W W W W C5) W W
~a ., _ ~ ~ ~ O ~ O O ~ O -- O O -- O ~ O O
~t) ., 0~ O~
. 0 ~ ~ 0 ~ ~ ~ ~ ' 0 ~ m c, ~ m m + m ~ + m + m + ~ m ~ m ~ +
., .
~L2 5~9L~7 Copolymer A: 90% acrylic acid 10% of Na methal~ylsulfonate Copolymer B: 65% of acrylic acid 35% of acrylamidopropenyl methylenesulfonate The dr;lling muds were measured at 20C and then after 15 hours of aging at 200C~ The K value of the polymers (Fikentscher, Cellulose Chemie 13~ 1932, page 58) was about 60. The apparent viscos;ty and the liquid lim;t were measured with a 35 SA FANN viscometer. The ~ater loss accord;ng to API is the filtrat;on rate in 30 minutes according to "API Code 29" wi~h a standardized filter press at 7 kg/cm2.
3~ Cement slurries a. Composition. 349 g of water 792 g of cement grade G
Water loss apparent ~iquid limit API (cm3) viscosity (lbs/100 sq.ft.) (mPas) . _ Cement slurry 20 without additive CX3 54 53 Copolymer A from Example 2 9.0 30 Z
Copolymer 9 from Example 2 6.5 27 _ The amount of copolymers used is in each case 0~75%. The apparent viscos;ty and liqu;d limit were determined with a 35 SA FAN~ viscometer, b. Composition: 349 g of ~later 79Z g of cement grade D
34~
_ 9 ~
Amount Water apparent Liquid limit used % loss viscosity (lbs/
APIlcm3 (mPas) 100 sq. ft~) Cement sLurry 5 without additive 44 16 Copolymer s 0~3531.0 30 2 from Example 2 1 4D0 31 3 1.9 34
6 0.~ 38 2 4. Solids suspens;on based on barium sulfate, gypsum, cal-cium carbonate and carbon.
a) Bar;um sulfate The solids content is 80% by weight, the dispersing agent concentration is O~Z5X by ~e;ght b) Gypsum: CaSO~t.2 H20 The solids content ;s 55~ by weight, the d;spers;ng agent concentration is 1~0% by weight c) Calciurn carbonate The solids content is 55% by weight, the dispers;ng agent concentration is 0.25% by weight d) Carbon The solids content is 70% by weight, the dispersing agent concentration is OD25% by weight.
All the experiments were carr;ed out with a dis-persing agent ~hich had a K value of about 60 and had the following compos;tion:
65% by weight of acrylic acid 30% by weight of acrylamidomethylenepropenylsulfonic acid 5% by we;ght of methylsulfonic acid all the monorners were ;n the form of sodiurn salts.
The v;scosity was determined with a Fann VG-35 rotary v;scome~er a~ 6 rpm. The values thereby obtained . . .
.~ .
~;~5~ 7 are given in the folLo~ing table.
Barium sulfate Gypsum Chalk Carbon w;~hou~ a dis-persing agent 31 4Z 19 52 5 ~ith a disper-s;ng agent2 1~ 3 14 The examples show that the copolymers according to the invention very effectively disperse both very small amounts of solids in aqueous solutions and solids in high concentrations, such as in dr;lling muds and cement slur-ries. In drilling muds, they are particularly distingu-ished by their stability to heat and the compatibility of divalent ions toward polyacrylates.
As a result of their effectiveness in the neutral range, they are superior to chromium lignosulfona~e and chrom;um lignite, which are dispersing agents which have hitherto been widely used for drilL;ng muds and only operate we~l at h;gher pH va~ues, because high p~1 values cannot be maintained a~ high temperatures in boreholes because of reaction of the argillaceous constituents of the mud with the alkali. In addition, chromium-containing drill;ng muds are being increasingly subjected to~restric-tions for environmental protection reasons.
The compounds according to the invention reduce the viscosity of cement slurries, wh;ch significantly improves their ease of pumping. ~he water content of the cement slurries can be kept low, as a result of the good dispers;ng effect, which r,1eans that the strength of the hardened cement is increased. In addition, the mechani-cal properties of the set cement improve as the polymercontent increases. The resu~ts with barium sulfate, gyp-sum, cha~k and carbon suspensions show how the compounds according to the inven~ion effectively disperse the most diverse solids suspensions. Optimum results for the vari-ous soLids can be achieved by varying the monomer concen-trations and molecular weights of the compounds according to the invention.
a) Bar;um sulfate The solids content is 80% by weight, the dispersing agent concentration is O~Z5X by ~e;ght b) Gypsum: CaSO~t.2 H20 The solids content ;s 55~ by weight, the d;spers;ng agent concentration is 1~0% by weight c) Calciurn carbonate The solids content is 55% by weight, the dispers;ng agent concentration is 0.25% by weight d) Carbon The solids content is 70% by weight, the dispersing agent concentration is OD25% by weight.
All the experiments were carr;ed out with a dis-persing agent ~hich had a K value of about 60 and had the following compos;tion:
65% by weight of acrylic acid 30% by weight of acrylamidomethylenepropenylsulfonic acid 5% by we;ght of methylsulfonic acid all the monorners were ;n the form of sodiurn salts.
The v;scosity was determined with a Fann VG-35 rotary v;scome~er a~ 6 rpm. The values thereby obtained . . .
.~ .
~;~5~ 7 are given in the folLo~ing table.
Barium sulfate Gypsum Chalk Carbon w;~hou~ a dis-persing agent 31 4Z 19 52 5 ~ith a disper-s;ng agent2 1~ 3 14 The examples show that the copolymers according to the invention very effectively disperse both very small amounts of solids in aqueous solutions and solids in high concentrations, such as in dr;lling muds and cement slur-ries. In drilling muds, they are particularly distingu-ished by their stability to heat and the compatibility of divalent ions toward polyacrylates.
As a result of their effectiveness in the neutral range, they are superior to chromium lignosulfona~e and chrom;um lignite, which are dispersing agents which have hitherto been widely used for drilL;ng muds and only operate we~l at h;gher pH va~ues, because high p~1 values cannot be maintained a~ high temperatures in boreholes because of reaction of the argillaceous constituents of the mud with the alkali. In addition, chromium-containing drill;ng muds are being increasingly subjected to~restric-tions for environmental protection reasons.
The compounds according to the invention reduce the viscosity of cement slurries, wh;ch significantly improves their ease of pumping. ~he water content of the cement slurries can be kept low, as a result of the good dispers;ng effect, which r,1eans that the strength of the hardened cement is increased. In addition, the mechani-cal properties of the set cement improve as the polymercontent increases. The resu~ts with barium sulfate, gyp-sum, cha~k and carbon suspensions show how the compounds according to the inven~ion effectively disperse the most diverse solids suspensions. Optimum results for the vari-ous soLids can be achieved by varying the monomer concen-trations and molecular weights of the compounds according to the invention.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A copolymer consisting of 5 - 95% by weight of groups of the formula I
(I) in which R1 denotes hydrogen or methyl and R2 denotes carboxamido, carbomethoxy, cyano or carboxyl, 5 - 95% by weight of groups of the formula II, III or IV
(II) (III) (IV) in which R3 denotes hydrogen, C1-C6-alkyl or phenyl, R4 denotes a hydrogen atom or CH3, R5 denotes C1-C10-alkylene and K+ denotes ammonium, lithium,sodium or potassium, and 0 - 5% by weight of groups of the formula V
(V) wherein R6 denotes hydrogen, CH3 or C2H5 and R7 denotes CH3 or C2H5, or R6 and R7 together denote a propylene group which forms a pyrrolidine radical together with the radical
(I) in which R1 denotes hydrogen or methyl and R2 denotes carboxamido, carbomethoxy, cyano or carboxyl, 5 - 95% by weight of groups of the formula II, III or IV
(II) (III) (IV) in which R3 denotes hydrogen, C1-C6-alkyl or phenyl, R4 denotes a hydrogen atom or CH3, R5 denotes C1-C10-alkylene and K+ denotes ammonium, lithium,sodium or potassium, and 0 - 5% by weight of groups of the formula V
(V) wherein R6 denotes hydrogen, CH3 or C2H5 and R7 denotes CH3 or C2H5, or R6 and R7 together denote a propylene group which forms a pyrrolidine radical together with the radical
2. A copolymer as claimed in claim 1, consisting of 20 - 90%
by weight of groups of the formula I and 5 - 50% by weight of groups of the formula II or III or 20 - 70% by weight of groups of the formula III.
by weight of groups of the formula I and 5 - 50% by weight of groups of the formula II or III or 20 - 70% by weight of groups of the formula III.
3. A solids dispersion which contains a copolymer as claimed in claim 1 in a concentration of about 5 ppm to 20% by weight.
4. A solids dispersion as claimed in claim 3, which contains the dispersed solids in a concentration of about 10 ppm to 80% by weight.
5. A solids dispersion as claimed in claim 3, which contains the copolymer in a concentration of about 10 ppm to 5% by weight.
6. A solids dispersion as claimed in claim 4 which contains the dispersed solids in a concentration of about 50 ppm to 65% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833338431 DE3338431A1 (en) | 1983-10-22 | 1983-10-22 | WATER-SOLUBLE MIXED POLYMERS AND THE USE THEREOF AS DISPERGERS FOR SOLIDS |
| DEP3338431.2 | 1983-10-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258947A true CA1258947A (en) | 1989-08-29 |
Family
ID=6212503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000465864A Expired CA1258947A (en) | 1983-10-22 | 1984-10-19 | Water-soluble copolymers and their use as dispersing agents for solids |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0141327B2 (en) |
| JP (1) | JPS60104109A (en) |
| CN (1) | CN1003592B (en) |
| AT (1) | ATE42757T1 (en) |
| AU (1) | AU583481B2 (en) |
| BR (1) | BR8405319A (en) |
| CA (1) | CA1258947A (en) |
| DE (2) | DE3338431A1 (en) |
| ES (1) | ES536902A0 (en) |
| NO (1) | NO844203L (en) |
| ZA (1) | ZA848178B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221489A (en) * | 1990-04-26 | 1993-06-22 | Atlantic Richfield Company | Sulfonated polymeric dispersant compositions for subterranean well drilling, completion, and cementing |
| US7247662B2 (en) | 2001-10-07 | 2007-07-24 | Nippon Shokubai Co., Ltd. | Cement dispersant, its production process, and cement composition using the cement dispersant |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4652623A (en) * | 1984-11-23 | 1987-03-24 | Calgon Corporation | Polymers for use as filtration control aids in drilling muds |
| JPH0625317B2 (en) * | 1986-08-26 | 1994-04-06 | 日本ペイント株式会社 | Spherical collapsible vinyl resin particles for antifouling paint |
| JPH01226757A (en) * | 1988-03-04 | 1989-09-11 | Takemoto Oil & Fat Co Ltd | Dispersing agent for cement |
| WO1991016365A1 (en) * | 1990-04-26 | 1991-10-31 | Atlantic Richfield Company | Dispersant compositions for subterranean well drilling and completion |
| DE4320220A1 (en) * | 1993-06-18 | 1994-12-22 | Basf Ag | Use of polymers I which contain copolymerized special monoethylenically unsaturated sulfonic acids as auxiliaries in the spray drying of aqueous dispersions of polymers II |
| FR2732009B1 (en) * | 1995-03-22 | 1997-06-06 | Schlumberger Cie Dowell | CEMENTING COMPOSITION COMPRISING A DISPERSING AGENT AND ITS APPLICATION TO CEMENTING OIL WELLS |
| DE19909231C2 (en) | 1999-03-03 | 2001-04-19 | Clariant Gmbh | Water-soluble copolymers based on AMPS and their use as drilling aids |
| CN1093095C (en) * | 2000-11-07 | 2002-10-23 | 复旦大学 | Efficient carboxilic acid grafting water-reducing agent and its synthesis |
| JP2008208016A (en) * | 2007-02-28 | 2008-09-11 | Nippon Shokubai Co Ltd | Powdery cement dispersant |
| WO2017158441A1 (en) * | 2016-03-17 | 2017-09-21 | Lubrizol Oilfield Solutions, Inc. | Carboxylic acid/acrylamidoalkane sulfonic acid/styrene sulfonate copolymers for ultrahigh temperature and pressure retardation of oil-well cement |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730900A (en) | 1972-09-25 | 1973-05-01 | Milchem Inc | Composition and process for drilling subterranean wells |
| DE2444108C2 (en) | 1974-09-14 | 1978-01-19 | Hoechst Ag | WATER-BASED CLAY FLUSHING FOR DEEP HOLES AND THE USE OF A MIXED POLYMERIZED FOR SUCH FLUSHING |
| US4053323A (en) | 1976-11-11 | 1977-10-11 | Calgon Corporation | Method of using cementing composition having improved flow properties |
| US4293427A (en) * | 1979-03-09 | 1981-10-06 | Milchem Incorporated | Drilling fluid containing a copolymer filtration control agent |
-
1983
- 1983-10-22 DE DE19833338431 patent/DE3338431A1/en not_active Withdrawn
-
1984
- 1984-10-13 AT AT84112373T patent/ATE42757T1/en not_active IP Right Cessation
- 1984-10-13 EP EP84112373A patent/EP0141327B2/en not_active Expired - Lifetime
- 1984-10-13 DE DE8484112373T patent/DE3478028D1/en not_active Expired
- 1984-10-19 JP JP59218788A patent/JPS60104109A/en active Pending
- 1984-10-19 BR BR8405319A patent/BR8405319A/en unknown
- 1984-10-19 ZA ZA848178A patent/ZA848178B/en unknown
- 1984-10-19 NO NO844203A patent/NO844203L/en unknown
- 1984-10-19 CA CA000465864A patent/CA1258947A/en not_active Expired
- 1984-10-19 AU AU34528/84A patent/AU583481B2/en not_active Ceased
- 1984-10-19 ES ES536902A patent/ES536902A0/en active Granted
-
1985
- 1985-04-01 CN CN85101102.0A patent/CN1003592B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221489A (en) * | 1990-04-26 | 1993-06-22 | Atlantic Richfield Company | Sulfonated polymeric dispersant compositions for subterranean well drilling, completion, and cementing |
| US5287929A (en) * | 1990-04-26 | 1994-02-22 | Atlantic Richfield Company | Method of using dispersant compositions for subterranean well drilling and completion |
| US7247662B2 (en) | 2001-10-07 | 2007-07-24 | Nippon Shokubai Co., Ltd. | Cement dispersant, its production process, and cement composition using the cement dispersant |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3338431A1 (en) | 1985-05-02 |
| ES8506331A1 (en) | 1985-07-01 |
| DE3478028D1 (en) | 1989-06-08 |
| ATE42757T1 (en) | 1989-05-15 |
| NO844203L (en) | 1985-04-23 |
| JPS60104109A (en) | 1985-06-08 |
| EP0141327B2 (en) | 1992-08-19 |
| AU583481B2 (en) | 1989-05-04 |
| BR8405319A (en) | 1985-09-03 |
| EP0141327A1 (en) | 1985-05-15 |
| EP0141327B1 (en) | 1989-05-03 |
| ZA848178B (en) | 1985-06-26 |
| AU3452884A (en) | 1985-04-26 |
| CN85101102A (en) | 1987-01-24 |
| CN1003592B (en) | 1989-03-15 |
| ES536902A0 (en) | 1985-07-01 |
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