US008623979B2

(12) United States Patent (10) Patent N0.: US 8,623,979 B2

Blair et al. (45) Date of Patent: *Jan. 7, 2014

(54) CEMENT DISPERSANT AND METHODS OF 4,652,621 A 3/1987 Kadono et a1.

MAKING AND USING THE SAME 4,674,574 A 6/1987 Savoly et a1.
4,711,731 A 12/1987 Garvey et a1.
4,741,843 A 5/1988 Garvey et a1.
(75) Inventors: Keith A. Blair, Pennsburg, PA (US); 4,744,795 A 5/1988 Savoly et a1.
Arpad Savoly, Martinsville, NJ (US); 4,814,389 A 3/1989 Garvey et a1.
Bennie Veal, Rome, GA (US) 4,870,120 A 9/1989 Tsubakimoto et a1.
5,158,612 A 10/1992 Savoly et a1.
5,180,498 A * 1/1993 Chen et a1. .................. .. 210/697
(73) Assignee: GEO Speciality Chemicals, Inc., 5,714,001 A 2/1998 Savoly et a1.
Cleveland, OH (US) 5,753,744 A 5/1998 Darwin et a1.
5,798,425 A 8/1998 Albrecht et a1.
Notice: Subject to any disclaimer, the term of this 5,866,013 A 2/1999 Kessler et a1.
patent is extended or adjusted under 35 6,140,440 A * 10/2000 Kinoshita et a1. ........ .. 526/3184
U.S.C. 154(b) by 1084 days. 6,174,980 B1 1/2001 Hirata et a1.
6,176,921 B1 1/2001 Kinoshita et a1.
This patent is subject to a terminal dis 6,239,241 B1 5/2001 Yamato et a1.
claimer. 6,264,739 B1 7/2001 Yamato et a1.
6,444,747 B1 9/2002 Chen et a1.
6,451,881 B1 9/2002 Vickers, Jr. et a1.
(21) Appl. N0.: 11/835,441 6,454,850 B2 9/2002 Yamashita et a1.
6,462,014 B1 10/2002 Johnson et a1.
(22) Filed: Aug. 8, 2007 6,486,260 B1 11/2002 Yuasa et a1.
6,548,589 B2 * 4/2003 Widmer et a1. ............. .. 524/457

(65) Prior Publication Data 6,673,885 B1* 1/2004 Shibata et a1. . 526/31841
6,727,315 B2 * 4/2004 Yamamoto et a1. 524/558
US 2007/0270547 A1 Nov. 22, 2007 6,864,337 B2 * 3/2005 Yuasa et a1. ...... .. 526/312
6,869,998 B2 * 3/2005 Bair et a1. ................... .. 524/556
Related US. Application Data 7,271,214 B2 9/2007 Bair et a1.
2003/0052303 A1* 3/2003 Buentello et a1. ........... .. 252/175
(60) Division of application No. 10/874,502, ?led on Jun.
23, 2004, noW Pat. No. 7,271,214, Which is a OTHER PUBLICATIONS
continuation-in-part of application No. 10/602,405, Supplementary European Search Report for EP 04755931 dated May
?led on Jun. 23, 2003, noW Pat. No. 6,869,998.
23, 2006, three pages.
(51) Int. Cl.
* cited by examiner
C08F 22/20 (2006.01)
C08F 20/10 (2006.01)
C08F 16/02 (2006.01) Primary Examiner * Satya Sastri
C08F 16/00 (2006.01) (74) Attorney, Agent, or Firm * Rankin, Hill & Clark LLP
(52) US. Cl.
USPC ...... .. 526/328.5; 526/221; 526/222; 526/223; (57) ABSTRACT
524/556; 524/5
The present invention relates to cement dispersant that is a
(58) Field of Classi?cation Search
copolymer‘iZation product of a ?rst monomer (A) comprising
USPC .......... .. 526/221, 222, 223, 328.5; 524/5, 556
See application ?le for complete search history. a carboxylic acid, a second monomer (B) comprising an
alkoxylated allyl alcohol sulfate, and, optionally, a third
(56) References Cited monomer (C) comprising an alkoxylated allyl alcohol. The
cement dispersant according to the invention provides
U.S. PATENT DOCUMENTS improved slump life properties and Water reduction proper
ties in cement admixtures.
4,457,762 A 7/1984 Papalos et a1.
4,457,874 A 7/1984 Papalos et a1.
4,479,826 A 10/1984 Papalos et a1. 9 Claims, No Drawings
 US 8,623,979 B2
1 2
CEMENT DISPERSANT AND METHODS OF monomer (B) comprising an alkoxylated allyl alcohol sulfate,
MAKING AND USING THE SAME and, optionally, a third monomer (C) comprising an alkoxy
lated allyl alcohol.
CROSS-REFERENCE TO RELATED The foregoing and other features of the invention are here
APPLICATION inafter more fully described and particularly pointed out in
the claims, the folloWing description setting forth in detail
This application is a divisional of commonly oWned appli certain illustrative embodiments of the invention, these being
cation Ser. No. 10/874,502, ?led Jun. 23, 2004, now US. Pat. indicative, hoWever, of but a feW of the various Ways in Which
No. 7,271,214, Which is a continuation-in-part of application the principles of the present invention may be employed.
Ser. No. 10/602,405, ?led Jun. 23, 2003, now US. Pat. No.
6,869,998, all of Which are hereby incorporated herein by DETAILED DESCRIPTION OF THE INVENTION
reference for all purposes.
The cement dispersant according to the present invention
BACKGROUND OF THE INVENTION
comprises a copolymeriZation product of a ?rst monomer (A)
comprising a carboxylic acid, a second monomer (B) com
1. Field of Invention prising an alkoxylated allyl alcohol sulfate, and, optionally, a
The present invention relates to a cement dispersant and third monomer (C) comprising an alkoxylated allyl alcohol.
methods of making and using the same. The polymeriZation of the monomers into a copolymeriZation
2. Description of Related Art product is preferably accomplished using conventional solu
Cement dispersants are often added to cementitious com 20
tion, precipitation or emulsion polymeriZation techniques.
positions such as Portland cement, concrete other hydraulic Conventional polymeriZation initiators such as am com
cement compositions (hereinafter collectively “cement”) to pounds, persulfates, peroxides, UV light, and the like may be
improve the workability or slump properties of the cement, to used. Chain transfer agents such as alcohols (preferably iso
reduce the amount of Water necessary to obtain good Work propanol), amines, hypophosphites or mercapto compounds
ability, Which improves the strength of the resulting cured 25
may be used to regulate or control-the molecular Weight of the
cement. Dispersants, Which are also sometimes referred to as
copolymeriZation product. The backbone of the copolymer
?uidity modi?ers or slump modi?ers, also help control the iZation product preferably comprises a random combination
hardening and curing time of the cement. of the repeat unit remaining after polymerization of the
Cement disspersants have conventionally been based on monomers. The resulting copolymeriZation product may be
polymers and copolymers of naphthalene, aminosulfonic 30
isolated by common isolation techniques including precipi
acids and polycarboxylic acids. Although cement dispersants tation isolation and the like. If polymeriZation is carried out in
of this type do improve the Workability of cement When used Water, the copolymeriZation product may simply be used in its
properly, slump loss still remains a persistent problem in the aqueous solution.
?eld. Unexpected delays in delivering cement to construction The ?rst monomer (A) used to form the copolymeriZation
sites and/ or changes in ambient temperatures can negatively 35
product according to the invention preferably comprises a
impact the quality of the cement and decrease the slump. carboxylic acid, amido carboxylic acid, C1-C6 alkyl ester of
There exists a need for a cement dispersant that provides carboxylic acid, C1-C6 alkyl ester of amido carboxylic acid,
improves slump life properties and Water reduction proper hydroxylated C1-C6 alkyl ester of carboxylic acid, or a
ties. hydroxylated C1-C6 alkyl ester of amido carboxylic acid.
40
Particularly preferred carboxylic acids for use as ?rst mono
BRIEF SUMMARY OF THE INVENTION
mer (A) include acrylic acid, methacrylic acid, acrylamide,
The present invention provides a dispersant for use in
maleic acid, maleic anhydride, fumaric acid, itaconic acid,
2-acrylamido-2-methylpropanesulfonic acid, and Water
cementitious compositions that provides improved slump life soluble salts thereof.
properties and Water reduction properties. The dispersant 45
The second monomer (B) used to form the copolymeriZa
according to the invention comprises a copolymeriZation
tion product according to the invention preferably comprises
product of a ?rst monomer (A) comprising a carboxylic acid
an alkoxylated allyl alcohol sulfate according to Formula (I)
such as, for example, acrylic acid, a second monomer (B)
beloW:
comprising an alkoxylated allyl alcohol sulfate such as, for
example, an allyloxypolyethyleneglycol ammonium sulfate, 50
and, optionally, a third monomer (C) comprising an alkoxy
lated allyl alcohol.
The present invention also provides: (1) a method of
improving the slump properties of cement comprising dis CH;
persing into an admixture comprising cement and Water a 55 0
dispersant comprising a copolymeriZation product of a ?rst
monomer (A) comprising a carboxylic acid, a second mono
mer (B) comprising an alkoxylated allyl alcohol sulfate, and,
optionally, a third monomer (C) comprising an alkoxylated
allyl alcohol; (2) a method of forming a cement dispersaht 60
comprising copolymeriZing a ?rst monomer (A) comprising a Where “R1” is (CH2%H2AD)M, (CH2iCH(CH3)iO)
carboxylic acid, a second monomer (B) comprising an n, or a mixture of both and “n” is an integer from about 1 to
alkoxylated allyl alcohol sulfate, and, optionally, a third about 100; and “M” is sodium, potassium, calcium, ammo
monomer (C) comprising an alkoxylated allyl alcohol to form nium or an organic amine such as triethylamine, morpholine,
a copolymeriZation product; and (3) a cement admixture 65 and the like. As noted in Formula (I) above, the second mono
comprising Water, cement and a copolymeriZation product of mer (B) has a terminal sulfate group covalently bonded
a ?rst monomer (A) comprising a carboxylic acid, a second through an oxygen atom [iC4OiSiO3i], and thus is
 US 8,623,979 B2
3 4
not a sulfonate, Which has a terminal sulfate group covalently the molar ratio of ?rst monomer (A) to second monomer (B)
bonded directly to a carbon atom [iCiS4O3i]. Mono to third monomer (C) in the copolymeriZation product is in a
mer (B) can be prepared by ethoxylation, propoxylation or a range of from about 2.5 to about 6 for ?rst monomer (A), from
combination of the ethoxylation and propoxylation of an allyl about 1 to about 2 for second monomer (B), and from about 0
alcohol followed by an addition of sulfamic acid, Which pro- 5 or 1 to about 3 for third monomer (C) (or about 2.5-6: 1 -2:0 or
duces the monomer unit having a covalently bonded sulfate l-3).
The dispersant according to the invention can be added to
terminated end group bonded through an oxygen atom. freshly mixed cement to disperse and to adjust the Theologi
The optional third monomer (C) used to form the copoly cal properties of the admixture. As noted above, throughout
meriZation product according to the invention preferably the instant speci?cation and in the appended claims, the term
comprises an alkoxylated allyl alcohol according to Formula “cement” refers to all cementitious materials including, for
(II) beloW: example, Portland cement, concrete and other hydraulic
cementitious compositions. The addition of the dispersant to
freshly mixed cement compositions improves, for example,
Formula (II) the slump life of the admixture and also reduces the amount
Of Water needed to obtain desired slump properties. Typi
cally, the dispersant is added into an aqueous cement mixture
in an amount in a range of about 0.1 percent by Weight to
about 1.0 percent by Weight, and more preferably in an
0 20
amount in a range of from about 0.2 percent by Weight to
about 0.32 percent by Weight.
It Will be appreciated that although the dispersant accord
ing to the invention is primarily intended for use in cement
compositions, it can also be used in other compositions Where
dispersants are used. Examples include poWdered inorganic
Where “R2” is H or a loWer (C1 -C4) straight or branched 25 and organic substances, for example clays, porcelain slips,
alkyl chain; “R3” is CH2 or C:O; “R4” is (CHZiCHZiO) silicate meals, chalk, carbon black, poWdered rock, pigments,
m, (CH24CH(CH3)iO)m, or a mixture of both and “m” is talc, synthetic material poWders and hydraulic binding
an integer from about 1 to about 150; and “R5” is H or a agents.Also, the dispersant canbe used in the oil?eld industry
C1 -C1 8 straight or branched alkyl chain. Third monomer (C) for oil Well cementing. Additionally, the polymers can be used
30
is referred to as polyethylene gylcol allyl ether (PEGAE) in the gypsum industry as dispersants or Water reducing
When “R2” and “R5” are H; “R3” is CH2; and “R4” is (CHZi agents. Further, these polymers can be used to disperse SBR
CH24O). Third monomer (C) is referred to as polypropylene and NBR emulsion rubbers during polymeriZation and pro
glycol allyl ether (PPGAE) When “R2” and “R5” are H; “R3” cessing of the rubber. The dispersants according to the inven
is CH2; and “R4” is (CH24CH(CH3)4O). Third monomer tion also ?nd utility in other applications such as, for example,
35
(C) is referred to as polyethyleneglycollprbpylene glycol ally in metal pre-treatment and cooling and boiler Water treatment
ether (PEGPGAE) When “R2” and “R5” are H; “R3” is CH2; applications.
and “R4” is (CH2%H2A)iCH2iCH(CH3)iO). Third
monomer (C) is referred to as hydroxyethyleneglycolmeth EXAMPLES
ylmethacrylate (HEME) When “R2” is CH3; “R3” is C:O;
40
“R4” is (CH24CH24O); and “R5” is H. Third monomer (C) The folloWing examples are intended only to illustrate the
is referred to as methoxyethyleneglycolmethylmethacrylate invention and should not be construed as imposing limitations
(MHEM) When “R2” is CH3; “R3” is C:O; “R4” is (CHzi upon the claims. Unless speci?ed otherWise, all reagents and
CH24O); and “R5” is CH3. It Will be appreciated that “R5” equipment used in the folloWing examples can be obtained
can be sulfonated. from Sigma Aldrich, Inc. (St. Louis, Mo.) and/or Fisher Sci
45
Preferably, the molar ratio of ?rst monomer (A) to second enti?c International, Inc. (Hanover Park, IL). The allyloxy
monomer (B) to third monomer (C) in the copolymeriZation polyethyleneglycol ammonium sulfate monomers used in the
product is in a range of from about 1 to about 10 for ?rst examples are available from Bimax, Inc. (Cockeysville, Md.),
monomer (A), from about 1 to about 4 for second monomer and the allyloxypolyethyleneglycol/propylene glycol ammo
(B), and from about 0 or 1 to about 10 for third monomer (C). nium sulfate monomers used in the examples are available
50
In other Words, the molar ratio of ?rst monomer (A) to second both from Bimax, Inc. and from Rhodia, Inc., (Cranbury,
monomer (B) to third monomer (C) in the copolymeriZation N.J.). The abbreviations shoWn in Table I beloW are used
product is from about l-l0:l-4:0 or l-l0. More preferably, throughout the Examples:
TABLE 1
Abbreviation Monomer Comment

AA acrylic acid i
MAA methacrylic acid i
APES-lO ammonium allylpolyethoxy (l0) alkoxylated With an average of 10 moles
sulphate of ethylene oxide
APES-20 Ammonium allylpolyethoxy (20) alkoxylated With an average of 20 moles
sulphate of ethylene oxide
APES-SO Ammonium allylpolyethoxy (50) alkoxylated With an average of 50 moles
sulphate of ethylene oxide
APES-PSS Ammonium allylpolyethoxy (5) alkoxylated With an average of 5 moles
polypropoxy (5) sulfate of ethylene oxide and 5 moles of
propylene oxide
 US 8,623,979 B2
5
TABLE 1-continued
Abbreviation Monomer Comment

PEGAE-10 polyethyleneglycol (10) allyl alkoxylated With an average of 10 moles

ether of ethylene oxide
PEGAE-ZO polyethyleneglycol (20) allyl alkoxylated With an average of 20 moles
ether of ethylene oxide
PEGAE-SO polyethyleneglycol (50) allyl alkoxylated With an average of 50 moles
ether of ethylene oxide
PEGAE-60 polyethyleneglycol (60) allyl alkoxylated With an average of 60 moles
ether of ethylene oxide
PEGAE-100 polyethyleneglycol (100) allyl alkoxylated With an average of 100
ether moles of ethylene oxide
MHEM16 methoxypolyethylene glycol alkoxylated With an average of 16 moles
monomethacrylate of ethylene oxide

Example 1 Sample 14
The same equipment used to produce Sample 1 Was used to
prepare an acrylic acid/allyloxypolyethyleneglycol sulfate
Sample 1 ammonium salt/allyloxypolyethyleneglycol (AA/APES-10/
A suitable ?ask Was equipped With a condenser, an addition 20 PEGAE-10 terpolymer) copolymeriZation product. Speci?
funnel, a mechanical stirrer, a thermometer and a nitrogen cally, 21.92 g (0.035 mole @95%) ofAPES-10 and 17.45 g
sparger. The ?ask Was charged With 46.3 g (.075 mole @95%) (0.035 mole) of PEGAE-10 and 78.44 g of deionized Water
ofAPES-10 and 90 g of deionized Water. 16.2 g (0.225 mole Were charged to the ?ask. 15.14 g (0.21 mole) ofAA Was
@99%) of AA Was charged to a 20 cc syringe and placed on charged to a 20 cc syringe and placed on a syringe pump. 5.86
a syringe pump. 9.12 g of a 16.6% solution of sodium persul 25 g of a 20% solution of sodium persulfate (“initiator solution”)
Was charged to a separate syringe and placed on a separate
fate (“initiator solution”) Was charged to a separate syringe
and placed on a separate syringe pump. The aqueous APES syringe pump. The aqueous APES-10/PEGAE-10 solution
Was sparged With nitrogen and heated to 85° C. The AA and
10 solution Was sparged With nitrogen and heated to 85° C.
the initiator solution Were pumped into to the aqueous APES
The AA and the initiator solution Were pumped into to the 10/PEGAE-10 solution simultaneously over three hours. The
30
aqueous APES-10 solution simultaneously over three hours. resulting aqueous terpolymer solution Was heated for one
The resulting aqueous copolymer solution Was heated for one more hour at 85° C. then cooled to room temperature. Caustic
more hour at 85° C. then cooled to room temperature. Caustic (50%) Was then added to adjust the pH to 5.3. The resulting
(50%) Was then added to adjust the pH to 6.4. The resulting copolymeriZation product, acrylic acid/allyloxypolyethylene
copolymeriZation product, acrylic acid/allyloxypolyethylene glycol sulfate ammonium salt/allyloxypolyethyleneglycol
35
glycol sulfate ammonium salt (“AA/APES-10”), Was in the glycol (“AA/APES-10/PEGAE-10”), Was in the form of a
form of a clear, light yelloW solution. After diluting the solu clear, light yelloW solution. After diluting the solution to 25%
tion to 25% solids by Weight, a Brook?eld viscosity of 31.7 solids by Weight, a Brook?eld viscosity of 31.5 cps Was
cps Was recorded. The physical properties for the AA/APES recorded. The physical properties for the AA/APES-10/PE
10 copolymeriZation product Were recorded in Table 2 beloW. GAE-10 copolymeriZation product Were recorded in Table 2
40 beloW.
Samples 2-13 Samples 15-26
The same procedure and equipment used to produce The same procedure and equipment used to produce
Sample 1 Was used to prepare the copolymeriZation products Sample 14 Was used to prepare the copolymeriZation prod
identi?ed as Samples 2-13 in Table 2 beloW. The molar ratios ucts identi?ed as Samples 15-26 in Table 2 beloW. The molar
of the monomers used to form the copolymeriZation products ratios of the monomers used to form the copolymeriZation
are also set forth in Table 2 beloW. products are also set forth in Table 2 beloW.
TABLE 2
Sample CopolymeriZation Product Monomer Mole Ratio % Solids Viscosity pH
1 ANAPES-10 3/1 24.3 31.7 cps 5.4
2 ANAPES-10 3/1 24.1 21.8 cps 5.8
3 ANAPES-ZO 2.5/1 25.2 12.3 cps 5.5
4 ANAPES-ZO 3/1 23.7 18.7 cps 5.2
5 ANAPES-ZO 4/1 23.6 21.0 cps 5.1
6 ANAPES 20 5.6/1 25.6 65.9 cps 5.9
7 ANAPES 20 8.9/1 23.1 8850 cps 6.4
8 ANAPES 50 3/1 24.6 19.3 cps 4.7
9 ANAPES 50 3/1 24.6 14.8 cps 4.6
10 ANAPES-PSS 3/1 24.2 13.0 cps 5.5
11 ANAPAES-PSS 3/1 24.8 11.0 cps 6.0
12 MANAPAES-PSS 3/1 25.2 10.6 cps 6.4
13 MANANAPES-lO 1 5/1.5/1 24.0 31.2 cps 6.1
14 ANAPES-lO/PEGAE-lO 3/0.5/0.5 23.8 31.5 cps 5.4
15 ANAPES-ZO/PEGAE-ZO 3/0.5/0.5 25.1 20.3 cps 5.5
16 ANAPES-SO/PEGAE-SO 3/0.5/0.5 24.6 16.5 cps 4.9
17 ANAPES-ZO/PEGAE-SO 3/0.5/0.5 25.0 14.0 cps 5.1
18 ANAPES-ZO/PEGAE-ZO 3/0.27/0 5 23.7 19.0 cps 6.0
19 ANAPES-ZO/PEGAE-ZO 3/0.27/0 5 25.7 50.5 cps 6.1
20 ANAPES-20/PEGAE-60 3/0.5/0.5 24.9 18.3 cps 5.2
 US 8,623,979 B2
7 8
TABLE 2-continued
Sample CopolymeriZation Product Monomer Mole Ratio % Solids Viscosity pH
21 AAJAPES-20/PEGAE5-P5 3/05/05 24.8 14.2 cps 5.5
22 AAJAPAE5-P5 S/PEGAE-50 3/05/05 24.7 17.1 cps 5.2
23 AAJAPES-20/PEGAE-100 3/05/05 40.2 86.3 cps 6.0
24 AAJMHEM-16/APES-20 3/05/05 24.4 19.7 cps 6.6
25 AAJAPES-20/PEGAE5-P5 3/05/05 24.3 14.1 cps 5.8
26 AAJAPES-20/PEGAE5-P5 3/05/05 24.84 14.2 cps 5.5

Several of the samples produced in Example 1 Were sub- TABLE 3_COminued

jected to 13-C NMR testing. The spectra Were characterized
by a broad polyacrylic acid type backbone. Strong resonances Slump Dialn?t?r (cm)
at 61, 70 and 72 ppm correspond to the polyethylene glycol 15 I II I I I I I
moiety andabroad Carbonyl region (179_184 ppm)IAVery Sample Dispersant?i 0min 30min 60min 90min 120m1n
loW level (<3%) of unreacted allylic monomer Was detected in 15 032 185 192 17I6 16I4 152
some ofthe samples. 16 0.32 17.4 18.3 18.3 18.1 17.2
17 0.32 18.8 18.7 19.1 18.7 18.5
Example 2 18 0.32 20.2 17.0 16.6 15.7 15.0
20 19 0.32 15.1 10.7 Thick Thick Thick
Each of the samples of dispersants produced in Example 1 20 0'32 21-6 22-0 22-8 23-0 22-5
Was tested for slump e?icacy using the Cement Mini-slump 8g; 1:‘: i3‘; 333 is)‘; is‘;
testing procedure known as the “Standard Test Method for 23 0:32 17:4 20:7 20:2 19:9 19:4
Slump ofHydraul1c Cement Concrete”ASTM C143-97, Vol. 24 032 164 168 164 160 143
04.02, Which is hereby incorporated by reference in its 25 25 03,2 19I5 20I6 215 2L8 205
entirety. Additional information regarding the Cement Mini- 26 03 2 184 20.7 210 21.4 20.7
slump test is found in D. L. Kantro’s, In?uence of Water
ReducingAdmixlures 0n Properties ofcemenlPasleiA Min
ialure Slump Test, Cement, Concrete and Aggregates, 2,
(1980) pp. 95-102, the entire contents of Which is hereby 30 Example 3
incorporated by reference. Speci?cally, 100 grams (g) of
Type 1 Portland cement Was added to a disposable beaker. 35
g Water Was added to the beaker and the cement and Water Was Each of the samples of dispersants produced in Example 1
mixed for 30 seconds With a metal spatula to produce a slurry. Was tested for slump e?icacy using the same procedure as in
0.32 Weight percent of each of the samples produced: in Example 2, except that 0.20 Weight percent of each of the
Example 1 Was dosed via a disposable syringe into the cement samples produced in Example 1 Was dosed via a disposable
slurry. The slurry Was mixed for an additional 30 seconds. The syringe into the cement slurry. The results of Mini-slump
cement slurry Was poured into a mini-slump cone, Which Was Testing using Samples 1-26 produced in Example 1 is shoWn
sitting on a glass plate. The mini-slump cone Was then ?lled to in Table 4 beloW.
the top With the cement slurry and then the mini-slump cone
40
Was lifted quickly and evenly from the glass plate, alloWing TABLE 4
the cement slurry to How onto the glass plate. The diameter of
the cement slurry patty thus formed Was measured. The mea Slump Diameter (cm)
surement Was the initial slump diameter. The material Was
Sample Dispersant % 0 min 30 min 60 min 90 min 120 min
returned to the disposable beaker, then re-mixed and mea
sured every 30 minutes to monitor slump retention. The 45 1 0 .20 17. 7 Thick Thick Thick Thick
results of Mini-slump Testing using Samples 1-26 produced 2 0.20 18.2 Thick Thick Thick Thick
in Example 1 is shoWn in Table 3 beloW, Where the term 3 0.20 17.3 12.8 12.5 12.0 11.2
4 0.20 20.9 11.4 Thick Thick Thick
“Thick” means that the cement slurry thickened to such an
5 0.20 17.8 9.4 Thick Thick Thick
extent that no meaningful slump data could be obtained. 6 0.20 Thick Thick Thick Thick Thick
50 7 0 .20 13 . 2 Thick Thick Thick Thick
TABLE 3 8 0.20 16.0 14.0 13.4 13.3 12.6
9 0.20 15.8 13.7 13.2 12.9 12.2
Slump Diameter (cm) 10 0.20 20.5 11.7 10.6 9.5 7.6
11 0.20 20.2 Thick Thick Thick Thick
Sample Dispersant % 0 min 30 min 60 min 90 min 120 min 12 0.20 13.5 Thick Thick Thick Thick
55 13 0.20 16.9 Thick Thick Thick Thick
1 0.32 18.0 8.7 Thick Thick Thick 14 0.20 17.6 Thick Thick Thick Thick
2 0.32 16.2 16.6 16.0 13.5 11.9 15 0.20 19.2 12.5 12.2 11.6 10.3
3 0.32 not tested i i i i 16 0.20 15.0 13.0 12.8 12.2 11.6
4 0.32 19.3 21.1 19.0 16.9 15.0 17 0.20 16.9 14.1 14.0 13.5 13.1
5 0.32 17.0 18.4 18.6 18.1 17.6 18 0.20 18.2 8.0 Thick Thick Thick
6 0.32 Thick Thick Thick Thick Thick 19 0.20 13.5 Thick Thick Thick Thick
60
7 0.32 16.5 Thick Thick Thick Thick 20 0.20 20.6 17.9 17.4 16.9 16.0
8 0.32 18.2 18.9 18.8 18.7 18.4 21 0.20 20.4 13.7 12.5 12.3 11.6
9 0.32 17.9 18.1 18.7 18.0 17.9 22 0.20 18.3 16.3 15.6 14.9 14.0
10 0.32 19.5 21.0 21.3 21.0 19.5 23 0.20 18.0 16.0 15.6 14.9 14.0
11 0.32 21.3 13.4 11.1 10.5 9.2 24 0.20 18.0 12.4 7.5 Thick i
12 0.32 18.7 Thick Thick Thick Thick 25 0.20 20.1 13.2 12.2 12.0 11.3
13 0.32 18.8 15.5 12.6 6.3 Thick 65 26 0.20 20.4 13.7 12.5 12.3 11.6
14 0.32 18.1 17.0 17.8 17.1 16.6
 US 8,623,979 B2
9 10
Comparative Example 4 ranging from about 1 to about 100; and “M” is
sodium, potassium, calcium, ammonium or an
To illustrate the relative ef?cacy of the dispersants pro organic amine; and
duced in accordance With the invention With conventional (C) is according to Formula (II):
dispersants, the Mini-slump Test Was repeated using three
different amounts of a conventional calcium naphthalene sul
fonate condensate dispersant available from GEO Specialty Formula (H)
Chemicals as DILOFLO® CA. The results of the compara
tive Mini-Slump Testing are shoWn in Table 5 beloW.

TABLE 5
Slump Diameter (cm)

Sample Dispersant % 0 min 30 min 60 min 90 min 120 min

C1 0.32 17.0 Thick Thick Thick Thick

C2 0.35 16.6 Thick Thick Thick Thick
C3 0.70 19.0 19.2 18.5 16.6 14.6
where “R2” is H or a C1-C4 straight or branched alkyl
chain; “R3” is CH2 or C:O; “R4” is (CHZ-CHZi
Comparative Example 4 demonstrates that nearly tWo 20 O)m or (CH24CH(CH3)iO)m or a mixture of both
times as much of a conventional cement dispersant must be and “m” is an integer ranging from about 1 to about
used in order to achieve the same slump properties as can be 150; and “R5” is H or a C1-C18 straight or branched
obtained With cement dispersants according to the present alkyl chain.
invention. 2. The dispersant composition of claim 1, Wherein (A) is
Additional advantages and modi?cations Will readily 25 one or more selected from the group consisting of acrylic
occur to those skilled in the art. Therefore, the invention in its acid, methacrylic acid, acrylamide, maleic acid, maleic anhy
broader aspects is not limited to the speci?c details and illus dride, fumaric acid, itaconic acid, 2-acrylamido-2-methyl
trative examples shoWn and described herein. Accordingly, propanesulfonic acid, and Water-soluble salts thereof.
various modi?cations may be made Without departing from 3. The dispersant composition of claim 1, Wherein (B)
the spirit or scope of the general inventive concept as de?ned 30 comprises an allyl alcohol that has been ethoxylated, pro
by the appended claims and their equivalents. poxylated, or both, folloWed by the addition of sulfamic acid
What is claimed is: to form an end terminal sulfate group that is covalently
1. A dispersant composition for improving the slump prop bonded through an oxygen atom.
erties of a cement admixture, the dispersant composition 4. The dispersant composition of claim 1, Wherein (B) is an
comprising a terpolymer comprised of a random combination 35 ammonium allylpolyethoxy sulfate alkoxylated With an aver
of structural units (A), (B) and (C) remaining after polymer age of up to about 100 moles of ethylene oxide.
iZation, Wherein: 5. The dispersant composition of claim 1, Wherein (B) is an
(A) is one or more monomers having functional groups ammonium allylpolyethoxy sulfate alkoxylated With an aver
selected from the group consisting of carboxylic acids, age of up to about 50 moles of ethylene oxide.
amido carboxylic acids, C1-C6 alkyl esters of carboxy 40 6. The dispersant composition of claim 1, Wherein (C) is
lic acids, C1-C6 alkyl ester of amido carboxylic acids, one or more selected from the group consisting of polyethyl
hydroxylated C1-C6 alkyl esters of carboxylic acids, ene glycol allyl ether (PEGAE), polypropylene glycol allyl
hydroxylated C1-C6 alkyl esters of amido carboxylic ether (PPGAE), polyethylene glycol/polypropylene glycol
acids and sulfonic acids: allyl ether (PEGPGAE), hydroxyethyene glycol methyl
(B) is according to Formula (1): 45 methacrylate (HEME), and methoxyethyene glycol methyln
nethacrylate (MEME).
7. The dispersant composition of claim 1, Wherein the
Formula (I) molar ratio of (A) to (B) to (C) in the terpolymer is in a range
—l' (CH2—CH) ‘l—
of from about 1 to about 10 for (A), from about 1 to about 4 for
CH; 50 (B), and from about 1 to about 10 for (C).
8. The dispersant composition of claim 1, Wherein the
O
molar ratio of (A) to (B) to (C) in the terpolymer is in a range
of from about 2.5 to about 6 for (A), from about 1 to about 2
for (B), and from about 1 to about 3 for (C).
55 9. The dispersant composition of claim 1, Wherein (A) is
acrylic acid and (B) is an allyloxypolyethylene glycol sulfate
ammonium salt.
Where “R1” is (CH2iCH2iO)n or (CH24CH
(CH3)4O)n or a mixture of both and “n” is an integer