CA1228080A - Set retarding additives for cement from aminomethylenephosphonic acid derivatives - Google Patents
Set retarding additives for cement from aminomethylenephosphonic acid derivativesInfo
- Publication number
- CA1228080A CA1228080A CA000457393A CA457393A CA1228080A CA 1228080 A CA1228080 A CA 1228080A CA 000457393 A CA000457393 A CA 000457393A CA 457393 A CA457393 A CA 457393A CA 1228080 A CA1228080 A CA 1228080A
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Abstract
ABSTRACT OF THE DISCLOSURE
Compounds useful as cement set retarding additives have been found which have the formula wherein (a) n is 0 to 15; (b) A, B, C, and D
are each independently selected from (i) hydrogen;
(ii) methylenephosphonic acid and salts thereof;
(iii) 2-hydroxy-3(trialkylammonium halide) propyl moieties wherein each alkyl moiety has from 1 to 5 carbon atoms; and (iv) a moiety of the formula wherein R is an unsubstituted or inertly substituted alkyl group having 1 to 6 carbon atoms, or salts thereof; such that at least one of A, B, C, and D
is (ii) and at least one is (iii).
31,888-F
Compounds useful as cement set retarding additives have been found which have the formula wherein (a) n is 0 to 15; (b) A, B, C, and D
are each independently selected from (i) hydrogen;
(ii) methylenephosphonic acid and salts thereof;
(iii) 2-hydroxy-3(trialkylammonium halide) propyl moieties wherein each alkyl moiety has from 1 to 5 carbon atoms; and (iv) a moiety of the formula wherein R is an unsubstituted or inertly substituted alkyl group having 1 to 6 carbon atoms, or salts thereof; such that at least one of A, B, C, and D
is (ii) and at least one is (iii).
31,888-F
Description
8~
SET RETARDING ADDITIVES FOR CEMENT FROM
~MINOMETHYLE~EPHOSPHONIC ACID DERIVATIVES
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 plug~ing mixture for high temperature oil and gas wells comprising Portland cement and l-hydroxy ethylidene-phosphonic acid trisodium or tripotassium salts as set 10 time extenders is descr~bed in Derwent abstract 71376B/39 (1979) of USSR Patent 640,019. The use of these phosphon-ate salts at temperatures of 75 to 150C 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 improved 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 plas-ters (U.S. 4,225,361).
31,88$-E' -1-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 composi-tions 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 to 2,800 F in a rotary kiln.
The resulting material, is cooled and inter-ground 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 lirne, silica, alumina, and iron.
These components form the following complex compounds:
Tricalcium aluminate, (3CaO Al2O3), tetracalcium al~lmino-ferrite, (4CaO Alz03 Fe2O3), tricalcium silicate, (3CaO-SiO2), and dicalcium silica-te, (2CaO SiO23.
31,888-F -2-)8(~i When water is added to cement, setting and hardening reactions begin immediately. The chemical compounds in the cement undergo the processes of hydra-tion and recrystallization which results in a set prGduct. 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 partic-ular 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.
31,888 F -3-Because of this temperature effect, it is important to retard the setting of the cemen-t employed in the deeper wells.
It has now been discovered that certain new compounds are useful in aqueous cemen-t slurries as set retarding additives.
These compounds have the Eormula B C
A-N-~CH2CH2Nt~l) wherein substituents A, B, C and D are each independ-ently selected from hydrogen; methylenephosphonic acid or salts thereof; 2-hydroxy-3(trialkylammonium halide) propyl wherein each alkyl moiety contains from 1 to 5 carbon atoms; a moiety of the formula o -R-C-OH
wherein R is an unsubstituted or inertly sub-stituted alkyl group having l to 6, preferably 1 to 3, more preferahly 1 carbon atoms, or salts thereof; n is 0 to 15; and wherein said substituents include at least one methylenephosphonic acid group, or salt thereof, and at least one 2-hydroxy-3(tri-alkylammonium halide~ propyl group.
The compounds useful in the present inventionare substitllted ammonia and amines in which at least one of the amine hydrogens is substituted witn a methyi-enephosphonic acid group or salts thereof and at: least one with a quaternary ammonium radical.
3l,888-F -~-~LZ~:~30~3 It has now been discovered that such a functionality when attached -to a diamine or polyamine which also contains a methylenephosphonic acid group will when added to an aqueous cemen-t slurry retard the setting of the cement.
The following describes a typical preparation of the compounds useful in the present invention.
Example 1 Ethylenediamine (EDA) (15 g, 0.25 mole) and 10 94 g (0.25 mole) of a 50 percent aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride were added to 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 mixture was heated to 9GC and digested ~or about one hour and cooled. Approximately 60 g of concen-trated hydrochloric acid solution and 67.5 g (0.82 mole) of phosphorous acid were added to the reaction flask and heated to reflux and maintained for one hour.
Aqueous 37 percent formaldehyde solution (67.4 g, 0.83 mole) was weighed into the addition funnel and added over a two-hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the derivative of EDA
in which one hydrogen had been replaced with a
SET RETARDING ADDITIVES FOR CEMENT FROM
~MINOMETHYLE~EPHOSPHONIC ACID DERIVATIVES
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 plug~ing mixture for high temperature oil and gas wells comprising Portland cement and l-hydroxy ethylidene-phosphonic acid trisodium or tripotassium salts as set 10 time extenders is descr~bed in Derwent abstract 71376B/39 (1979) of USSR Patent 640,019. The use of these phosphon-ate salts at temperatures of 75 to 150C 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 improved 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 plas-ters (U.S. 4,225,361).
31,88$-E' -1-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 composi-tions 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 to 2,800 F in a rotary kiln.
The resulting material, is cooled and inter-ground 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 lirne, silica, alumina, and iron.
These components form the following complex compounds:
Tricalcium aluminate, (3CaO Al2O3), tetracalcium al~lmino-ferrite, (4CaO Alz03 Fe2O3), tricalcium silicate, (3CaO-SiO2), and dicalcium silica-te, (2CaO SiO23.
31,888-F -2-)8(~i When water is added to cement, setting and hardening reactions begin immediately. The chemical compounds in the cement undergo the processes of hydra-tion and recrystallization which results in a set prGduct. 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 partic-ular 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.
31,888 F -3-Because of this temperature effect, it is important to retard the setting of the cemen-t employed in the deeper wells.
It has now been discovered that certain new compounds are useful in aqueous cemen-t slurries as set retarding additives.
These compounds have the Eormula B C
A-N-~CH2CH2Nt~l) wherein substituents A, B, C and D are each independ-ently selected from hydrogen; methylenephosphonic acid or salts thereof; 2-hydroxy-3(trialkylammonium halide) propyl wherein each alkyl moiety contains from 1 to 5 carbon atoms; a moiety of the formula o -R-C-OH
wherein R is an unsubstituted or inertly sub-stituted alkyl group having l to 6, preferably 1 to 3, more preferahly 1 carbon atoms, or salts thereof; n is 0 to 15; and wherein said substituents include at least one methylenephosphonic acid group, or salt thereof, and at least one 2-hydroxy-3(tri-alkylammonium halide~ propyl group.
The compounds useful in the present inventionare substitllted ammonia and amines in which at least one of the amine hydrogens is substituted witn a methyi-enephosphonic acid group or salts thereof and at: least one with a quaternary ammonium radical.
3l,888-F -~-~LZ~:~30~3 It has now been discovered that such a functionality when attached -to a diamine or polyamine which also contains a methylenephosphonic acid group will when added to an aqueous cemen-t slurry retard the setting of the cement.
The following describes a typical preparation of the compounds useful in the present invention.
Example 1 Ethylenediamine (EDA) (15 g, 0.25 mole) and 10 94 g (0.25 mole) of a 50 percent aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride were added to 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 mixture was heated to 9GC and digested ~or about one hour and cooled. Approximately 60 g of concen-trated hydrochloric acid solution and 67.5 g (0.82 mole) of phosphorous acid were added to the reaction flask and heated to reflux and maintained for one hour.
Aqueous 37 percent formaldehyde solution (67.4 g, 0.83 mole) was weighed into the addition funnel and added over a two-hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the derivative of EDA
in which one hydrogen had been replaced with a
2-hydroxypropyltrimethylammonium chloride group and the remaining hydrogens with methylenephosphonic acid groups.
31,888-F -5-~x~
Ethyleneamine E-100* (12.5 g) and 12.5 g of deionized water were added to a 500-mi round-bottom reaction flask as in Example 1 and heated to 90C. A
50 percent aqueous solution of 3-chloro-2-hydroxypropyl-trimethylammonium chloride (12.0, 0.032 mole) was weighed into the addition funnel and added over about a 10-minute period. The reaction mixture was heated for an additional hour at 90C and cooled. Approximately 110 g of concentrated hydrochloric acid solution and 28.5 g (0.35 mole) of phosphorous acid were added to the reaction flask and heated to reIlux and maintained for one hour. Aqueous 37 percent formaldehyde solution (24.5, 0.30 mole) was weighed into the addition funnel and added over a one-hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the E-lO0 derivative in which ~10 percent of the amine hydrogens had been replaced with hydroxypropyltrimethylammonium chloride groups, the remainder being replaced with methylenephosphonic acid groups.
The above and other related compounds were determined to be useful as cement retarders by employing the following -test.
1. The following ingredients were weighed:
cement - 100 g water - 38 g additive - 0.2 g (active ingredient mass) *Ethyleneamine E-100 is a product of The Dow Chemical Company and is described as a mixture of pentaethylene-hexamine plus heavier ethyleneamines with an avera~e molecular weight of 250-300.
31,888-F -6-~LZZ~308~!
2. Water and liquid additive were mixed;
31,888-F -5-~x~
Ethyleneamine E-100* (12.5 g) and 12.5 g of deionized water were added to a 500-mi round-bottom reaction flask as in Example 1 and heated to 90C. A
50 percent aqueous solution of 3-chloro-2-hydroxypropyl-trimethylammonium chloride (12.0, 0.032 mole) was weighed into the addition funnel and added over about a 10-minute period. The reaction mixture was heated for an additional hour at 90C and cooled. Approximately 110 g of concentrated hydrochloric acid solution and 28.5 g (0.35 mole) of phosphorous acid were added to the reaction flask and heated to reIlux and maintained for one hour. Aqueous 37 percent formaldehyde solution (24.5, 0.30 mole) was weighed into the addition funnel and added over a one-hour period. The reaction mixture was heated at reflux for an additional three hours and then cooled. The product was the E-lO0 derivative in which ~10 percent of the amine hydrogens had been replaced with hydroxypropyltrimethylammonium chloride groups, the remainder being replaced with methylenephosphonic acid groups.
The above and other related compounds were determined to be useful as cement retarders by employing the following -test.
1. The following ingredients were weighed:
cement - 100 g water - 38 g additive - 0.2 g (active ingredient mass) *Ethyleneamine E-100 is a product of The Dow Chemical Company and is described as a mixture of pentaethylene-hexamine plus heavier ethyleneamines with an avera~e molecular weight of 250-300.
31,888-F -6-~LZZ~308~!
2. Water and liquid additive were mixed;
3. Cement was added to liquid, the bottle tightly closed and shaken to mixi
4. Bottle was placed in a pre-heated 180F 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.
The compounds listed in Table I were prepared and tested using the above procedure. Results of these tests on retarding cement setting are given in Table I.
31, &88-F -7---8~
U~
r~
~a o = - = = = =
h ~.q ~ d' ~ ~ O= = = - _ =
o ~1 O .
a~ ~ ~ ~
~ ,C ~a)-= =_==
.~ ~ Ul E~ ~
a~ o = = = = = = ~
-~1 0 ~ O
a) ~ a~ o O II ~
I I ,a ~ I I I I I
O V _ C~
~
O O O O
~1 ~1 ~') N ~ ~ ~
O C~ Lr~ O U~ I
1-1 ~) C~ OD
Z
_l O O
O O ~ ~ I
O ~1r~
. ~ O U~
Z ~ 'o ~ a ~ rl O O O
h ~ ,~ ¢ E~ o ~
O O
~1 ~) ~r:m c~ v U~
~ 1~
O ~ ~1 ~ Z
~ X
31, 888-E' -8-o~
In a manner similar to Examples 1 and 2, another compound useful in the invention is prepared.
EXAMPL~ 3 An a~ueous polymeric polyalkylenepolyamine (PAPA) solution (66.4 g of 36 percent), prepared from ethyleneamine E-100 and ethylene dichloride, was added to a 500-ml round-bottom reaction flask equipped as in Example 1. Approximately 40 g of concentrated hydro-chloric acid solution and 49.3 g (0.60 mole) of phos-phorous acid were added to the reaction flask andheated to reflux and maintained for one hour. Aqueous 37 percent formaldehyde solution (51.1 g, 0.63 mole) was weighed into the addition funnel and added over a one-hour period. The reaction mixture was heated at reflux for an additional one and one-half hours and cooled. The intermediate product was the PAPA in which all amine hydrogens had been substituted with methylenephosphonic acid groups. The polymeric polyalkylenepolyamine intermediate product was modified by reacting te~ mole percent of the avail-able aminohydrogens with 3-chloro-2-hydroxypropyl-trimethylammonium chloride in a similar manner as described in Example 3. The resultant reaction product was then phosphonomethylated with phosphorous acid and formaldehyde in the presence of hydrochloric acid. The product was the PAPA in which ~10 percent of the amine hydrogens had been replaced with hydroxypropyltrimethyl-ammonium chloride groups, the remainder being r~placed with methylenephosphonic acid groups.
31,88~-F -9-
A blank (no additive) was run for comparison with each of the additives.
The compounds listed in Table I were prepared and tested using the above procedure. Results of these tests on retarding cement setting are given in Table I.
31, &88-F -7---8~
U~
r~
~a o = - = = = =
h ~.q ~ d' ~ ~ O= = = - _ =
o ~1 O .
a~ ~ ~ ~
~ ,C ~a)-= =_==
.~ ~ Ul E~ ~
a~ o = = = = = = ~
-~1 0 ~ O
a) ~ a~ o O II ~
I I ,a ~ I I I I I
O V _ C~
~
O O O O
~1 ~1 ~') N ~ ~ ~
O C~ Lr~ O U~ I
1-1 ~) C~ OD
Z
_l O O
O O ~ ~ I
O ~1r~
. ~ O U~
Z ~ 'o ~ a ~ rl O O O
h ~ ,~ ¢ E~ o ~
O O
~1 ~) ~r:m c~ v U~
~ 1~
O ~ ~1 ~ Z
~ X
31, 888-E' -8-o~
In a manner similar to Examples 1 and 2, another compound useful in the invention is prepared.
EXAMPL~ 3 An a~ueous polymeric polyalkylenepolyamine (PAPA) solution (66.4 g of 36 percent), prepared from ethyleneamine E-100 and ethylene dichloride, was added to a 500-ml round-bottom reaction flask equipped as in Example 1. Approximately 40 g of concentrated hydro-chloric acid solution and 49.3 g (0.60 mole) of phos-phorous acid were added to the reaction flask andheated to reflux and maintained for one hour. Aqueous 37 percent formaldehyde solution (51.1 g, 0.63 mole) was weighed into the addition funnel and added over a one-hour period. The reaction mixture was heated at reflux for an additional one and one-half hours and cooled. The intermediate product was the PAPA in which all amine hydrogens had been substituted with methylenephosphonic acid groups. The polymeric polyalkylenepolyamine intermediate product was modified by reacting te~ mole percent of the avail-able aminohydrogens with 3-chloro-2-hydroxypropyl-trimethylammonium chloride in a similar manner as described in Example 3. The resultant reaction product was then phosphonomethylated with phosphorous acid and formaldehyde in the presence of hydrochloric acid. The product was the PAPA in which ~10 percent of the amine hydrogens had been replaced with hydroxypropyltrimethyl-ammonium chloride groups, the remainder being r~placed with methylenephosphonic acid groups.
31,88~-F -9-
Claims (7)
1. In a process for retarding the setting of an aqueous cement slurry which comprises adding to said slurry an organic phosphonate, the improvement which comprises employing as the organic phosphonate a compound of the formula wherein (a) n is 0 to 15;
(b) A, B, C, and D are each independently selected from (i) hydrogen;
(ii) methylenephosphonic acid and salts thereof;
(iii) 2-hydroxy-3(trialkylammonium halide) propyl moieties wherein each alkyl moiety has from 1 to 5 carbon atoms; and (iv) a moiety of the formula 31, 888-F -10-wherein R is an unsubstituted or inertly substituted alkyl group having 1 to 6 carbon atoms, or salts thereof;
such that at least one of A, B, C, and D
is (ii) and at least one is (iii).
(b) A, B, C, and D are each independently selected from (i) hydrogen;
(ii) methylenephosphonic acid and salts thereof;
(iii) 2-hydroxy-3(trialkylammonium halide) propyl moieties wherein each alkyl moiety has from 1 to 5 carbon atoms; and (iv) a moiety of the formula 31, 888-F -10-wherein R is an unsubstituted or inertly substituted alkyl group having 1 to 6 carbon atoms, or salts thereof;
such that at least one of A, B, C, and D
is (ii) and at least one is (iii).
2. The process of Claim 1 wherein the compound employed has the formula in which n is 0 or 1 and at least two of A, B, C, and D are (ii).
3. The process of Claim 1 wherein the compound employed has the formula in which n is 0, 1 or 2; one of A, B, C, and D is (iii), one is (iv), and any other of A, B, C, and D is (ii).
4. The process of Claim 1 wherein the compound employed is a polyamine having an average molecular weight of 250-300.
5. The process of Claim 4 wherein from 5 to 15 mole percent of the substituent groups are (iii) and the remainder are (ii).
6. The process of Claim 5 wherein the substituent acid groups are in the form of the alkali metal or phosphoric alkaline earth metal salt.
7. The process of Claim 6 wherein the alkali metal salt is the sodium salt.
31,888-F -11-
31,888-F -11-
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000457393A CA1228080A (en) | 1984-06-26 | 1984-06-26 | Set retarding additives for cement from aminomethylenephosphonic acid derivatives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000457393A CA1228080A (en) | 1984-06-26 | 1984-06-26 | Set retarding additives for cement from aminomethylenephosphonic acid derivatives |
Publications (1)
Publication Number | Publication Date |
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CA1228080A true CA1228080A (en) | 1987-10-13 |
Family
ID=4128172
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA000457393A Expired CA1228080A (en) | 1984-06-26 | 1984-06-26 | Set retarding additives for cement from aminomethylenephosphonic acid derivatives |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114685797A (en) * | 2020-12-31 | 2022-07-01 | 南京博特新材料有限公司 | Water reducing agent containing carboxyl and phosphonic acid group and preparation method thereof |
-
1984
- 1984-06-26 CA CA000457393A patent/CA1228080A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114685797A (en) * | 2020-12-31 | 2022-07-01 | 南京博特新材料有限公司 | Water reducing agent containing carboxyl and phosphonic acid group and preparation method thereof |
CN114685797B (en) * | 2020-12-31 | 2023-08-08 | 南京博特新材料有限公司 | Water reducer containing carboxyl and phosphonic acid groups and preparation method thereof |
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