Note: Descriptions are shown in the official language in which they were submitted.
CEMENT COMPOSITIONS CONTAINING SET RETARDERS
BASED ON DICYCLOPENTADIENE DERIVATIVES
The invention pertains to aqueous hydraulic
cement slurry compositions containing particular set
retarders which are compounds derived from the
bis(methylamine) of dicyclopentadiene.
Hydrophobic-substituted phosphonic or phos-
phinic 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 75C
to 150C in amounts of 0.1-0.3 perrent by weight is
described in the abstract.
Other organic phosphorous acid derivatives
are taught to be use~ul additives in cement composi-
tions as turbulence-lnducing and flow-property improver
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additives (U.S. 3,964,921 and 4,040,g54, 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. 3,8~5,803)
and are also said to be useful as "cement additives"
without indicating specific uses.
Ultra-rapid hardening Portland cement compo-
sitions 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 manu-
factured by calcining raw materials consisting of
limestone, clay, shale, and slag together at 2,600F
to 2,800F in a rotary kiln.
The resulting material, is cooled and inter-
ground with small percentages of gypsum to form portlandcement. In addition to the above raw materials, other
components such as sand, bauxite, iron oxide, etc., may
be added~to adjust the chemlcal composition depend ng
upon the type of portland cement desired.
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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 sili-
cate, (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 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 ~e taken into
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consideration particularly when pumping cement into
deeper wells since temperature increases as the depth
of the well becomes greater. Temperature also affec-ts
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
such compounds are useful as cement set-retarders.
The products useful as cement set retarders
in the present invention have the following formula:
~/NH2C-- ~ ~ H2 ~
wherein A, B, C and D substituents are each independently
selected from hydrogen; -CH2PO3H2 (methylene phosphonic);
-(CH2)nOH wherein n is 1 to 4; CH2CHOHSO3H (hydroxy-
ethylsulphonic); CH2CHOHCH2SO3H (hydroxypropylsulphonic
-(CH2)nCOOH wherein n is 1 to 3; and the alkali metal,
alkaline earth metal, ammonia, and amine salts of the
.
aforementioned phosphonic, sulfonic or carboxylic acids,
providing that at least one of the above subs-tituents
is a methylenephosphonic acid group or a salt thereof.
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It has been determined that not all dicyclo-
pentadiene bis(methylamine) (DCPD-BMA) derivatives
are useful for the same purposes. Thus, only a limited
few which contain at least one methylenephosphonic
acid group will be effective as set retarders for
cement. Even those which contain the methylene-
phosphonic acid group will be ineffective if certain
other groups are present. Thus, for example the
DCPD-B~ derivative which contains one methylenesul-
fonic acid group and three methylenephosphonic acidgroup does not retard the setting of cement under
conditions of the test.
While the compounds so used must contain at
least one methylenephosphonate group as a substituent
of the amine nitrogen, certain other groups may be
present. Thus, the remaining amine hydrogens may be
unsubstituted. Substituents other than the methylene-
phosphonic group include alkanol radicals, wherein the
alkyl group contains 1 to 4 carbon atoms; alkylcarboxylic
acid radicals, wherein the alkyl group contains 2 to 4
carbons; hydroxyethyl- and hydroxypropylsulfonic acid
radicals; and the alkali metal, alkaline earth metal,
ammonia or amine salts of any of the above phosphonic,
sulfonic or carboxylic ac1d groups.
It should be recognized that when mixed
derivatives are obtainedj it is not usually possible
to direct or predict which amine hydrogens are sub-
stituted. The product, in all probability, contains
a mixture of isomerlc compounds.
When formaldehyde and phosphorus acid are
reacted with DCPD bis(methylamine), hereinafter DCPD-BMA,
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the result is a new compound having the following
structure:
H H H
5 ~HO)2P-CH H2C--~ f ç2 ,CH2P(OH)2
2~N CH2__ 1 ÇH2 t-CH2-~
( HO ) 2 P - CH 2 2 \C/ ~--C~ ~CH 2 P ( OH ) 2
The above compound has been found to have
excellent cement retarding properties.
Other substituents for the hydrogens of the
amine groups of the above DCPD derivatives form useful
chelating agents, but only the compounds having at
least one methylenephosphonic acid group or an
alkali metal, alkaline earth metal, ammonia, or amine
salt derivative are effective as cement set retarding
agents.
Substituents other than methylenephosphonates
give compounds having the following structure:
N~C~2~~ ~ ~ rHz-N
wherein A, B, X, and Y can be hydrogen, C2 to C6
hydroxyalkyl;:hydroxyethyl- and hydroxypropylsul-
fonic, methylene-, ethylene- and propylenesulfonic;
C2 to C~ alkylcarboxylic acid radicals; and the alkali
metal alkaline earth metal,:ammonia, or amine salts
of any of the foregoing acid derivatives; with the
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proviso that at least one of the groups must be a
methylenephosphonic acid group or salt.
The following examples illustrate the
preparation of the compounds useful in the invention.
EXAMPLE 1
Deionized water (100 g) and 49.0 g (0.25
mole) of DCPD-BMA weighed into 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. Approxi-
mately 120 g of concentrated HCl solution and 98.7 g
(1.20 mole) of phosphorous acid were added to the
aqueous amine solution and the reaction mixture heated
to reflux and maintained for one hour. Aqueous 37 percent
formaldehyde solution (85.1 g, 1.05 mole) was added to
the addition funnel and added over a two hour period.
The reaction mixture was heated at reflux for an addi-
tional two hours and then cooled. The product obtained
was the DCPD-BMA derivative in which each amine nitrogen
is replaced by a methylenephosphonic acid
H O
group ~C-P(O~) 2 -
H
EXAMPLE 2
The procedure of Example 1 was followedexcept 0.60 mole of phosphorous acid and 0.53 mole of
aqueous formaldehyde solution were used. The product
obtained was the DCPD-BMA derivative in which there are
two methylenephosphonic acid group substi-tuents with
two hydrogens remaining unsubstituted.
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EXAMPLE 3
Deionized water (40 g) and 24.5 g (0.125
mole) of DCPD-BMA were weighed inko a 500 ml round-
-bottom flask equipped with a water-cooled reflux
condenser, mechanical stirrer, thermometer with a
temperature controller, and an addition funnel.
Caustic solution (10.1 g of 50 percent) and 25.0 g
(0.127 mole) the sodium salt of 3-chloro-2-hydroxy-1-
-propanesulfonic acid, were added with stirring and
the reaction mixture heated at 85C for one hour.
Additional caustic solution (12.0 g of 50 percent)
and 25.0 g of the sodium salt of 3-chloro-2-hydroxy-
-l-propanesulfonic acid, were then added and the
solution heated at 85C for 1-1/2 hours. Approximately
15 60 g of concentrated HCl solution and 24.7 g (0.300
mole) of phosphorous acid were added and the reaction
mixture heated to reflux and maintained for one hour.
A~ueous 37 percent formaldehyde solution (21.3 g, 0.263 mole)
was added to the addition funnel and added over about a
one-hour period. The reaction mixture was heated at
reflux for an additional three hours and then cooled.
The product obtained was the DCPD-BMA derivative contain-
ing two methylenephosphonic acid and two 2-hydroxypropyl-
sulfonic acid groups -H2C-CHOH-CH2-SO3H.
EXAMPLE ~
The procedure of Example 3 was followed
except 0.127 mole of the sodium salt of 3-chloro-2~
hydroxy-1-propanesulfonic acid, 37.0 g (0.450 mole)
of phosphorous acid, and 32.0 g (0.394 mole) of 37
percent formaldehyde solution were used. The product
obtained was the DCPD-BMA derivative containing three
methylenephosphonic acid groups and one 2-hydroxypro-
pylsulfonic acid group~
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EXAMPLE 5
Ethylene oxide (lI.6 y, 0.263 mole) was
reacted with 24.5 g (0.125 mole) of DCPD-BMA and the
reaction product then phosphonomethylated according to
the procedure of Example 1 using 0.300 mole of phosphor-
ous acid and 0.263 mole of formaldehyde solution. The
product obtained was the DCPD-BMA derivative containing
two hydroxyethyl and two methylenephosphonic acid
groups.
EXAMPLE 6
The procedure of Example 5 was followed
except the amine was reacted wi-th 0.132 mole of ethylene
oxide and the reaction product phosphonomethylated
using 0.450 mole of phosphorous acid and 0.394 mole of
formaldehyde solution. The product obtained was the
DCPD-BMA derivative containing one hydroxyethyl group
and three methylenephosphonic acid groups.
EXAMPLE 7
.
Propylene oxide (7.6 g, 0.130 mole) was
reacted with 24.5 g (0.125 mole) of DCPD-BMA and the
reaction product then phosphonomethylated according to
the procedure of Example 1 using 0.450 mole of phosphor-
ous acid and 0.394 r.~le of formaldehyde solution. The
product obtained was the same as that of Example 6
except for a hydroxypropyl group in place of the hydroxy-
ethyl group.
In a similar manner, several more compounds
useful in the invention (Examples 9-11) as well as
several similar compounds which are outside the scope
of the invention (Examples 12-15) were prepared.
Their structures are listed in Table I.
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The following test was used in determiningwhether a given compound was useful as a set retarding
agent:
1. The following ingredients were weighed:
cement - 100 g
water - 38 g
additive - 0.2 g active
2. Water and liquid additive were mixedi
3. Cement was added to liquid, the bottle tightly
closed and shaken to mix;
4. Bottle was placed in a pre-heated 180F (82C)
bathi
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 following table shows the test results of
those compounds indicated.
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TABLE I
Example Substituents(1) Unset at
No. **A B _ D 6 hrs. 24 hrs.
1 MP MP MP MP YesYes
52 MP MP H H YesYes
3 MP MP HPS HPS YesYes
4 MP MP ~P HPS YesYes
MP MP H~ HE YesYes
6 MP MP MP HE YesYes
107 MP MP MP HP YesYes
8 MP MP MP H YesYes
9 MP MP HP HP YesYes
MP MP SA SA YesYes
11 MP MP MP SP YesYes
1512* MP MP MP MS Set --
13* SA SA SA SA Set --
14* SHPS SHPS SHPS SHPS Set --
15* MP MP MS MS Set --
16* NO ADDITIVE Set --
(1) HE = hydroxyethyl; HP = hydroxypropyl; MP = methylene-
phosphonic acid; HPS = hydroxypropylsulfonic acid; SA =
sodium acetate; SP = sodium propionate; MS = methylene-
sulfonic acid; SHPS = sodium hydroxypropylsulfonate.
It should be understood that any one or more of the
isomers of the compound indicated can be present,
i.e. A, B, C and D substituents are interchangeable.
* Not an example Or the invention.
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