WO1986001194A1 - Polymeric alkylenephosphoric acid piperazine derivatives as set retarding compounds for use in cement slurries - Google Patents

Polymeric alkylenephosphoric acid piperazine derivatives as set retarding compounds for use in cement slurries Download PDF

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Publication number
WO1986001194A1
WO1986001194A1 PCT/US1984/001282 US8401282W WO8601194A1 WO 1986001194 A1 WO1986001194 A1 WO 1986001194A1 US 8401282 W US8401282 W US 8401282W WO 8601194 A1 WO8601194 A1 WO 8601194A1
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Prior art keywords
compound
cement
dihalo
organic
hydrogen
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PCT/US1984/001282
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French (fr)
Inventor
Druce K. Crump
David A. Wilson
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The Dow Chemical Company
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Priority to BR8407350A priority Critical patent/BR8407350A/en
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to JP59503136A priority patent/JPS61503029A/en
Priority to PCT/US1984/001282 priority patent/WO1986001194A1/en
Publication of WO1986001194A1 publication Critical patent/WO1986001194A1/en
Priority to NO861448A priority patent/NO861448L/en

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Classifications

    • 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
    • C04B24/003—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/20—Retarders
    • C04B2103/22—Set retarders

Definitions

  • the invention pertains to aqueous hydraulic cement slurry compositions containing particular set retarders which are phosphonic acid derivatives of adducts of N-aminoethylpiperazine and a dihalo or epoxyhalo compound.
  • Hydrophobic-substituted phosphonic or phosphinic acids and their alkali metal salts have been used in cements, primarily soil/cement mixtures, to improve the freeze-thaw properties and salt-resistance.
  • Six- to eighteen-carbon alkyl phosphonic acids or their alkali metal salts are so described in U.S. Patent 3, 794, 506.
  • a plugging mixture for high temperature oil and gas. wells comprising Portland cement and 1-hydroxy ethylidene-phosphonic acid trisodium or tripotassium salts as set time extenders is described in Derwent abstract 71376B/39 (1979) of USSR Patent 640, 019.
  • Alkylene diphosphonic acids and their water soluble salts are described as set time extenders and water reducing agents for gypsum plasters (U.S. 4, 225, 361) .
  • Lignins which have been phosphonoalkylated through an ether linkage or corresponding sulfonates, sulfides, hydroxyl or amine derivatives are taught to be useful primarily as dispersants or surfactants (U.S. 3, 865, 803) and are also said to be useful as "cement additives" without indicating specific uses.
  • Ultra-rapid hardening Portland cement compositions which contain various acid salt additives (U.S. 4, 066, 469). It states that use of acid phosphates as the acid salt additives is excluded since the phosphates have a characteristically powerful retarding property peculiar to them.
  • Portland cement is manufactured by calcining raw materials consisting of limestone, clay, shale, and slag together at 2,600°F to 2,800°F (1410°C to 1520°C) in a rotary kiln.
  • the resulting material is cooled and interground with small percentages of gypsum to form portland cement.
  • other components such as sand, bauxite, iron oxide, etc., may be added to adjust the chemical composition depending upon the type of portland cement desired.
  • the principal components of the finished portland cement are lime, silica, alumina, and iron. These components form the following complex compounds:
  • Tricalcium aluminate (3CaO.Al 2 O 3 ), tetracalcium aluminoferrite, (4CaO.Al 2 O 3 .Fe 2 O 3 ), tricalcium silicate, (3CaO.SiO 2 ), and dicalcium silicate, (2CaO-SiO 2 ).
  • Thickening time is the time that the cement remains pumpable in the well. This is the most critical property of an oil-well cement. The thickening time has to be long enough to be pumped into place and short enough to permit operations to resume quickly. Generally, 3 hours provides the necessary placement time plus a safety factor.
  • the polymers useful in the present invention are made by reacting N-aminoethylpiperazine (AEP) with a dihalo or epoxyhalo compound and subsequently reacting the polymer formed thereby with phosphorous acid and an alkanal (aldehyde) at a low pH, usually provided by the presence of a mineral acid, e.g. hydrochloric acid.
  • AEP N-aminoethylpiperazine
  • alkanal alkanal
  • AEP 1-(2-aminoethyl)piperazine
  • the AEP can be reacted with any number of dihalo or epoxyhalo compounds in order to form a dimer or polymer.
  • Any suitable epoxyhaloalkane epihalohydrin
  • 1,2-epoxy-3-chloropropane epichlorohydrin
  • the epoxyhalo compound will have 3-10 carbon atoms .
  • Other epichlorohydrin-type compounds include: 1,2-epoxy-4chlorobutane, 2,3-epoxy-4-chlorobutane, l,2-epoxy-5- chloropentane, 2,3-epoxy-5-chloropentane, etc.
  • the chloro derivatives are preferred, although the corresponding bromo or iodo compounds may be employed. Mixtures of epoxyhaloalkanes may also be employed.
  • Dihalides having from 1-20 carbon atoms may be used.
  • Saturated dihalides having the formula X(CH 2 ) n X, where X may be chlorine, bromine, iodine or combinations 10, but preferably 2 to 6, may be employed.
  • dichloromethane methylene chloride
  • 1,2-dichloroethane ethylene dichloride
  • 1,2- or 1,3-dichloropropane 1,4- or 1,2-dibromobutane and the like
  • Aralkylene dihalides can also be employed having the formula X-H 2 C-Ar-CH 2 -X wherein Ar is
  • R may be hydrogen, halogen, alkyl, having 1 to 4 carbon atoms, hydroxy and hydroxyalkyl, having 1 to 4 carbon atoms and X is a halogen atom.
  • Dihaloalkylene ethers can also be employed, e.g. bis (chloromethyl)ether or bis (chloroethyl)ether. Formulas for such ethers also include
  • X is a halogen atom
  • the dihalides may also be unsaturated.
  • 1,2-dichloroethene, l,4-dichloro-2-butene and the like may be employed.
  • the conditions for making the polymer are to employ the reactants in an amount of from about 0.2 to about 1 mole of the chain extender compound, preferably about 0.25 to about 0.6, i.e. the diepoxy-, dihalo- or epoxyhalo-compound, per mole of AEP.
  • the temperature of reaction is from about 50° to about 100°C, preferably 70°-80°C at a pressure sufficient to maintain the reactants in the liquid phase.
  • the phosphonomethylation (Mannich reaction) is then carried out on the product in the presence of a strong acid to maintain the pH at less than 1.
  • reaction medium While the reaction will proceed at temperatures over a wide range, i.e., from 85° to 150°C, it is preferred that the reaction medium be maintained at refluxing.
  • the reaction is preferably conducted at atmospheric pressure, although sub-atmospheric and superatmospheric pressures may be utilized if desired. Reaction times will vary, depending upon a number of variables, but the preferred reaction time is 1 to 5 hours, and the most preferred reaction time is 2 to 4 hours.
  • the phosphorous acid and the alkanal may be added together or separately in any order to the reaction mixture, it is preferred to add the phosphorous acid to the polyamine and then to slowly add the alkanal under refluxing conditions.
  • alkanal and phosphorous acid are employed for the phosphonomethylation of the amine. Excess of either the alkanal or acid can be utilized although large excesses of either would be uneconomical. The preferred process will use an amount of alkanal equivalent to the amine hydrogens available and a slight stoichiometric excess of the phosphorous acid.
  • methanal formaldehyde
  • alkanals aldehydes
  • ethanal acetaldehyde
  • propanal propanal
  • the alkanal may contain a straight or branched chain containing up to ten carbon atoms.
  • A(BA)m wherein A is an organic radical having the formula
  • Z is hydrogen, hydroxyethyl, hydroxypropyl
  • M is hydrogen, an alkali metal or ammonium
  • B is a divalent radical derived from a dihalo, diepoxy or haloepoxy organic compound having one of the following structures
  • n 1-10, n' is 1-3, and wherein R is hydrogen or methyl and R' is hydrogen, an alkyl radical or a hydroxyalkyl radical having 1 to 4 carbons, a hydroxy radical or a halogen atom, m is 1-10
  • Preferred compounds of the invention are those wherein the B moiety is derived from 1, 2-epoxy-3-chloropropane (epichlorohydrin) or 1,2-dichloroethane, wherein m is 1 or 2, the Z moiety
  • DCE 1, 2-dichlorethane
  • reaction product was then phosphonomethylated by adding approximately 75 g of concentrated hydrochloric acid and 32.6 g (0.40 mole) of phosphorous acid to the aqueous amine solution and the reaction mixture heated to reflux and maintained for one hour.
  • Aqueous 37% methanal solution (28.1 g - 0.35 mole) was added through the addition funnel over a one and one-half hour period.
  • the reaction mixture was heated at reflux for an additional three hours and then cooled.
  • Table I shows the use of some of the above products in retarding the setting of cement.
  • the test procedure for the determination of retardation of setting is as follows:
  • Bottle was placed in a pre-heated 180°F (83°C) bath;
  • the additive is the phosphonomethylated product identified by the mol ratio of DCE/AEP.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

Polymers which are the reaction product of N-aminoethylpiperazine and a dihalo or epoxy-halo compound are subsequently phosphonomethylated to provide products which are useful as cement set retarders.

Description

POLYMERIC ALKYLENEPHOSPHORIC ACID PIPERAZINE
DERIVATIVES AS SET RETARDING COPPOUNDS FOR
USE IN CEMENT SLURRIES
The invention pertains to aqueous hydraulic cement slurry compositions containing particular set retarders which are phosphonic acid derivatives of adducts of N-aminoethylpiperazine and a dihalo or epoxyhalo compound.
Hydrophobic-substituted phosphonic or phosphinic acids and their alkali metal salts have been used in cements, primarily soil/cement mixtures, to improve the freeze-thaw properties and salt-resistance. Six- to eighteen-carbon alkyl phosphonic acids or their alkali metal salts are so described in U.S. Patent 3, 794, 506. A plugging mixture for high temperature oil and gas. wells comprising Portland cement and 1-hydroxy ethylidene-phosphonic acid trisodium or tripotassium salts as set time extenders is described in Derwent abstract 71376B/39 (1979) of USSR Patent 640, 019. The use of these phosphonate salts at temperatures of 75°C to 150°C in amounts of 0.1-0.3 percent by weight is described in the abstract. Other organic phosphorous acid derivatives are taught to be useful additives in cement compositions as turbulence-inducing and flow-property improver additives (U.S. 3, 964, 921 and 4, 040, 854, respectively). Another turbulence-inducer is a pyrolysis product of urea and a bis (alkylenepyrophosphate) (U.S. 3,409,080).
Alkylene diphosphonic acids and their water soluble salts are described as set time extenders and water reducing agents for gypsum plasters (U.S. 4, 225, 361) . Lignins which have been phosphonoalkylated through an ether linkage or corresponding sulfonates, sulfides, hydroxyl or amine derivatives are taught to be useful primarily as dispersants or surfactants (U.S. 3, 865, 803) and are also said to be useful as "cement additives" without indicating specific uses.
Ultra-rapid hardening Portland cement compositions are described which contain various acid salt additives (U.S. 4, 066, 469). It states that use of acid phosphates as the acid salt additives is excluded since the phosphates have a characteristically powerful retarding property peculiar to them.
Most of the cement used in oil wells is called portland cement. Portland cement is manufactured by calcining raw materials consisting of limestone, clay, shale, and slag together at 2,600°F to 2,800°F (1410°C to 1520°C) in a rotary kiln.
The resulting material, is cooled and interground with small percentages of gypsum to form portland cement. In addition to the above raw materials, other components such as sand, bauxite, iron oxide, etc., may be added to adjust the chemical composition depending upon the type of portland cement desired.
The principal components of the finished portland cement are lime, silica, alumina, and iron. These components form the following complex compounds:
Tricalcium aluminate, (3CaO.Al2O3), tetracalcium aluminoferrite, (4CaO.Al2O3.Fe2O3), tricalcium silicate, (3CaO.SiO2), and dicalcium silicate, (2CaO-SiO2).
When water is added to cement, setting and hardening reactions begin immediately. The chemical compounds in the cement undergo the processes of hydration and recrystallization which results in a set product. The maximum amount of water that can be used with an oil-well cement is the amount which can be added before solids separation occurs. The minimum amount of water is the amount required to make the slurry pumpable. Therefore, the normal water ratio is governed by the maximum and minimum limits for a particular class of cement.
Thickening time is the time that the cement remains pumpable in the well. This is the most critical property of an oil-well cement. The thickening time has to be long enough to be pumped into place and short enough to permit operations to resume quickly. Generally, 3 hours provides the necessary placement time plus a safety factor.
Other factors, such as fluid loss, viscosity and density must be taken into consideration and additives are known to the art-skilled which affect each of these factors as well as that of set, or thickening, time as mentioned above. Another parameter which has an effect on set time is temperature. Cement sets more rapidly as the temperature increases. This must be taken into consideration particularly when pumping cement into deeper wells since temperature increases as the depth of the well becomes greater. Temperature also affects the strength of the cement, the strength becoming less as the temperature increases.
Because of this temperature effect, it is important to retard the setting of the cement employed in the deeper wells.
It has now been discovered that certain new phosphonomethylated compounds are useful in aqueous cement slurries as set retarding additives. Some of these compounds are chelating agents, while others are useful as threshold agents in retarding the precipitation of metal ions from aqueous solution. However, not all chelating agents or threshold agents are useful as cement set-retarders.
The polymers useful in the present invention are made by reacting N-aminoethylpiperazine (AEP) with a dihalo or epoxyhalo compound and subsequently reacting the polymer formed thereby with phosphorous acid and an alkanal (aldehyde) at a low pH, usually provided by the presence of a mineral acid, e.g. hydrochloric acid. N-aminoethylpiperazine has the structure:
Figure imgf000007_0001
and may be referred to by the name 1-(2-aminoethyl)piperazine. Hereinafter, it will be abbreviated "AEP".
The AEP can be reacted with any number of dihalo or epoxyhalo compounds in order to form a dimer or polymer. Any suitable epoxyhaloalkane (epihalohydrin) may be reacted, 1,2-epoxy-3-chloropropane (epichlorohydrin) being preferred. Generally, the epoxyhalo compound will have 3-10 carbon atoms . Other epichlorohydrin-type compounds include: 1,2-epoxy-4chlorobutane, 2,3-epoxy-4-chlorobutane, l,2-epoxy-5- chloropentane, 2,3-epoxy-5-chloropentane, etc. In general, the chloro derivatives are preferred, although the corresponding bromo or iodo compounds may be employed. Mixtures of epoxyhaloalkanes may also be employed.
Dihalides having from 1-20 carbon atoms may be used. Saturated dihalides having the formula X(CH2)nX, where X may be chlorine, bromine, iodine or combinations 10, but preferably 2 to 6, may be employed. Thus, for example, dichloromethane (methylene chloride), 1,2-dichloroethane (ethylene dichloride), 1,2- or 1,3-dichloropropane, 1,4- or 1,2-dibromobutane and the like may be employed. Aralkylene dihalides can also be employed having the formula X-H2C-Ar-CH2-X wherein Ar is
Figure imgf000008_0002
wherein R may be hydrogen, halogen, alkyl, having 1 to 4 carbon atoms, hydroxy and hydroxyalkyl, having 1 to 4 carbon atoms and X is a halogen atom.
Dihaloalkylene ethers can also be employed, e.g. bis (chloromethyl)ether or bis (chloroethyl)ether. Formulas for such ethers also include
X-CH2CH2(OCH2CH2)n,X wherein n is 1 to 3 and
Figure imgf000008_0001
wherein X is a halogen atom.
The dihalides may also be unsaturated. Thus,
1,2-dichloroethene, l,4-dichloro-2-butene and the like may be employed.
The conditions for making the polymer are to employ the reactants in an amount of from about 0.2 to about 1 mole of the chain extender compound, preferably about 0.25 to about 0.6, i.e. the diepoxy-, dihalo- or epoxyhalo-compound, per mole of AEP. The temperature of reaction is from about 50° to about 100°C, preferably 70°-80°C at a pressure sufficient to maintain the reactants in the liquid phase.
The phosphonomethylation (Mannich reaction) is then carried out on the product in the presence of a strong acid to maintain the pH at less than 1.
While the reaction will proceed at temperatures over a wide range, i.e., from 85° to 150°C, it is preferred that the reaction medium be maintained at refluxing. The reaction is preferably conducted at atmospheric pressure, although sub-atmospheric and superatmospheric pressures may be utilized if desired. Reaction times will vary, depending upon a number of variables, but the preferred reaction time is 1 to 5 hours, and the most preferred reaction time is 2 to 4 hours.
Although the phosphorous acid and the alkanal may be added together or separately in any order to the reaction mixture, it is preferred to add the phosphorous acid to the polyamine and then to slowly add the alkanal under refluxing conditions.
Approximately equimolar amounts of alkanal and phosphorous acid are employed for the phosphonomethylation of the amine. Excess of either the alkanal or acid can be utilized although large excesses of either would be uneconomical. The preferred process will use an amount of alkanal equivalent to the amine hydrogens available and a slight stoichiometric excess of the phosphorous acid. Although methanal (formaldehyde) is preferred, other alkanals (aldehydes) may be employed in place of methanal such as ethanal ( acetaldehyde), propanal (propionaldehyde), and the like, wherein the alkanal may contain a straight or branched chain containing up to ten carbon atoms.
Thus, the compounds useful in the present invention can be represented by the formula
A(BA)m wherein A is an organic radical having the formula
Figure imgf000010_0002
wherein Z is hydrogen, hydroxyethyl, hydroxypropyl,
or BA wherein M is hydrogen, an
Figure imgf000010_0003
alkali metal or ammonium, and wherein B is a divalent radical derived from a dihalo, diepoxy or haloepoxy organic compound having one of the following structures
Figure imgf000010_0001
Figure imgf000011_0002
wherein n is 1-10, n' is 1-3, and wherein R is hydrogen or methyl and R' is hydrogen, an alkyl radical or a hydroxyalkyl radical having 1 to 4 carbons, a hydroxy radical or a halogen atom, m is 1-10
and at least 50% of the Z groups are groups.
Figure imgf000011_0003
Preferred compounds of the invention are those wherein the B moiety is derived from 1, 2-epoxy-3-chloropropane (epichlorohydrin) or 1,2-dichloroethane, wherein m is 1 or 2, the Z moiety
is and M is H, Na or NH4
Figure imgf000011_0001
The following examples illustrate the invention:
Example 1
An N-aminoethylpiperazine (AEP) based amine was prepared by reacting 22.7 g of N-aminoethylpiperazine (0.176 mole), 9.8 g of 1, 2-dichlorethane (DCE) (0.099 mole), and 17.5 g of deionized water (DCE/AEP mole ratio = 0.56) in a 500-ml round-bottom reaction flask equipped with a water-cooled reflux condenser, mechanical stirrer, thermometer with a temperature controller, and an addition funnel. The reaction product was then phosphonomethylated by adding approximately 75 g of concentrated hydrochloric acid and 32.6 g (0.40 mole) of phosphorous acid to the aqueous amine solution and the reaction mixture heated to reflux and maintained for one hour. Aqueous 37% methanal solution (28.1 g - 0.35 mole) was added through the addition funnel over a one and one-half hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled.
The above procedure is then repeated using different DCE/AEP ratios.
Table I shows the use of some of the above products in retarding the setting of cement. The test procedure for the determination of retardation of setting is as follows:
1. The following ingredients were weighed: cement - 100 g water - 38 g additive - 0.2 g active
2. Water and liquid additive were mixed;
3. Cement was added to liquid, the bottle tightly closed and shaken to mix;
4. Bottle was placed in a pre-heated 180°F (83°C) bath;
5. Setting of cement was checked after 6 and 24 hours.
A blank (no additive) was run for comparison with each of the additives.
TABLE I
Figure imgf000013_0001
(1) The additive is the phosphonomethylated product identified by the mol ratio of DCE/AEP.
(2) 1,2-epoxy-3-chloropropane was used in place of DCE for making this additive.
* Not an example of the invention.

Claims

1. A process for retarding the setting of an aqueous cement slurry which comprises adding to said slurry an organic phosphonate, CHARACTERIZED IN THAT the organic phosphonate is the phosphonomethylated reaction product of (1) a dihalo or haloepoxy organic compound with (2) N-aminoethylpiperazine; wherein the mole ratio of dihalo or haloepoxy compound to the amine compound is from 0.20 to about 1.0, and wherein at least 50 percent of the amine hydrogens are phosphonomethylated.
2. The product of Claim 1 wherein the dihalo compound, if present, is a C1 to C20 compound, and the haloepoxy compound, if present, is a C3 to C10 compound.
3. A process fox retarding the setting of an aqueous cement slurry which comprises adding to said slurry an organic phosphonate, CHARACTERIZED IN THAT the organic phosphonate is a compound of the formula
A(BA)m
wherein A is an organic radical having the formula
Figure imgf000015_0005
wherein Z is hydrogen, hydroxyethyl, hydroxypropyl,
Figure imgf000015_0004
2 or BA wherein M is hydrogen, an alkali metal or ammonium, and wherein B is a divalent radical derived from a dihalo, diepoxy or haloepoxy organic compound having one of the following structures
Figure imgf000015_0003
R'1 4 R'1 4 , wherein n is 1-10, n' is 1-3, and wherein R is hydrogen or methyl and R' is hydrogen, an alkyl radical or a hydroxyalkyl radical having 1 to 4 carbons, a hydroxy radical or a halogen atom, m is 1-10
and at least 50% of the Z groups are groups.
Figure imgf000015_0002
4. The process of Claim 4 wherein m is 1 or 2,
B is
Figure imgf000015_0001
PCT/US1984/001282 1984-08-15 1984-08-15 Polymeric alkylenephosphoric acid piperazine derivatives as set retarding compounds for use in cement slurries WO1986001194A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR8407350A BR8407350A (en) 1984-08-15 1984-04-15 POLYMERIC ALKYLENE PHOSPHORIC PIPERAZINE DERIVATIVES ACTING AS CONSOLIDATION RETARDING COMPOUNDS FOR USE IN CEMENT SLUDGE
JP59503136A JPS61503029A (en) 1984-08-15 1984-08-15 Polymeric alkylene phosphate piperazine derivatives as set-retarding compounds useful in cement slurries
PCT/US1984/001282 WO1986001194A1 (en) 1984-08-15 1984-08-15 Polymeric alkylenephosphoric acid piperazine derivatives as set retarding compounds for use in cement slurries
NO861448A NO861448L (en) 1984-08-15 1986-04-14 POLYMERIC ALKYLENE PHOSPHORIC ACID PIPERARZINE DERIVATIVES FOR RETARDING THE CEMENT SUSPENSION.

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3657134A (en) * 1970-04-13 1972-04-18 Monsanto Co Deflocculation of solid materials in aqueous medium
US3964921A (en) * 1975-02-27 1976-06-22 Calgon Corporation Well cementing composition having improved flow properties, containing phosphonobutane tricarboxylic acid, and method of use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3657134A (en) * 1970-04-13 1972-04-18 Monsanto Co Deflocculation of solid materials in aqueous medium
US3964921A (en) * 1975-02-27 1976-06-22 Calgon Corporation Well cementing composition having improved flow properties, containing phosphonobutane tricarboxylic acid, and method of use

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