U.S. patent application number 12/552338 was filed with the patent office on 2011-03-03 for formulation and its use.
Invention is credited to Frank Dierschke, Alexander Kraus.
Application Number | 20110054081 12/552338 |
Document ID | / |
Family ID | 43625790 |
Filed Date | 2011-03-03 |
United States Patent
Application |
20110054081 |
Kind Code |
A1 |
Dierschke; Frank ; et
al. |
March 3, 2011 |
FORMULATION AND ITS USE
Abstract
Claimed is a formulation containing a) at least one component
having dispersing properties and being selected from branched comb
polymers having polyether side chains, a naphthalene
sulphonate-formaldehyde condensate and a melamine
sulphonate-formaldehyde condensate, and b) a polycondensation
product. Typical representatives of component a) are
polycarboxylate ether, polycarboxylate ester and uncharged
copolymers. In addition to the main components a) and b) further
additives such as anti-forming agents and tensides or polymers
having a low charge, neutral polymers or polyvinyl alcohol can be
comprised by the formulation that is suitable for controlling the
flowability of aqueous suspensions of construction chemicals.
Inventors: |
Dierschke; Frank;
(Oppenheim, DE) ; Kraus; Alexander; (Evenhausen,
DE) |
Family ID: |
43625790 |
Appl. No.: |
12/552338 |
Filed: |
September 2, 2009 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
61239259 |
Sep 2, 2009 |
|
|
|
Current U.S.
Class: |
524/2 ; 524/147;
525/154 |
Current CPC
Class: |
C04B 2111/0062 20130101;
C04B 24/246 20130101; C04B 28/145 20130101; C04B 28/145 20130101;
C08J 9/0066 20130101; C04B 24/246 20130101; C04B 2103/22 20130101;
C04B 26/02 20130101; C04B 2103/67 20130101; C04B 24/38 20130101;
C04B 38/106 20130101; C04B 2103/12 20130101; C04B 2103/50 20130101;
C04B 40/0028 20130101; C04B 24/223 20130101; C04B 2103/0075
20130101; C04B 28/145 20130101; C04B 2103/50 20130101; C04B 24/226
20130101; C04B 2103/006 20130101; C04B 24/2647 20130101; C04B
24/246 20130101 |
Class at
Publication: |
524/2 ; 525/154;
524/147 |
International
Class: |
C04B 24/26 20060101
C04B024/26; C08L 61/28 20060101 C08L061/28; C08K 5/51 20060101
C08K005/51 |
Claims
1-87. (canceled)
88. A formulation comprising a) at least one component having
dispersing properties and having been selected from the group
consisting of a compound containing a branched comb polymer having
polyether side chains, a naphthalene sulphonate-formaldehyde
condensate and a melamine sulphonate-formaldehyde condensate; and
b) a polycondensation product containing (I) at least one
structural unit with an aromatic or heteroaromatic sub-unit and a
polyether side chain and (II) at least one phosphated structural
unit with an aromatic or heteroaromatic sub-unit and (III) at least
one structural unit with an aromatic or heteroaromatic sub-unit,
structural unit (II) and structural unit (III) differing only in
that the OP(OH).sub.2 group of the structural unit (II) is replaced
by H in structural unit (III), and structural unit (III) is not the
same as structural unit (I).
89. A formulation according to claim 88, wherein the component a)
is a polycarboxylate ether a.sub.1), a polycarboxylate ester
a.sub.2), an uncharged copolymer a.sub.3) or mixtures thereof.
90. A formulation according to either of claim 88, wherein the
component a) is a copolymer a.sub.1) comprising 1) at least one
olefinically unsaturated moncarboxylic acid comonomer, or an ester
or a salt thereof, or an olefinically unsaturated sulphonic acid
comonomer or a salt thereof, and 2) at least one comonomer of the
general formula (I) ##STR00016## in which R.sub.1 is ##STR00017##
and R.sub.2 is H or an aliphatic hydrocarbon radical having from 1
to 5 C atoms; R.sub.3 is an unsubstituted or substituted aryl
radical; and R.sub.4 is H or an aliphatic hydrocarbon radical
having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having
from 5 to 8 C atoms, a substituted aryl radical having 6 to 14 C
atoms or a member selected from the groups consisting of
##STR00018## in which R.sub.5 and R.sub.7 are independently
selected from the group consisting of an alkyl, aryl, aralkyl or
alkaryl radical; and R.sub.6 is an alkylidene, arylidene,
aralkylidene or alkarylidene radical; and p is from 0, 1, 2, 3 or
4, m and n are independently selected from 2, 3, 4 or 5; x and y
are independently selected from an integer .ltoreq.350; and z is
from 0 to 200, wherein (I) in copolymer a.sub.1), comonomer units
which represent components 1) and 2) have no internal molecular
differences or (II) the copolymer a,) is a polymeric mixture of the
components 1) and 2) wherein the comonomer units have internal
molecular differences with respect to at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, m, n, x, y,
z, and the differences the composition and length of the side
chains.
91. A formulation according to claim 89, wherein the copolymer
a.sub.1) contains the comonomer component 1) in a proportion of
from 1 to 70 mol % and the comonomer component 2) in proportions of
99 to 30 mol %.
92. A formulation according to claim 89, wherein the copolymer
a.sub.1) contains the comonomer component 1) in proportions of 5 to
20 mol % and the comonomer component 2) in proportions of 40 to 90
mol %.
93. A formulation according to claim 88, wherein the comonomer
component 1) is an acrylic acid or a salt thereof, and the
comonomer component 2) has a value of with p=0 or 1 and contains a
vinyl or allyl group and R.sub.1 is a polyether.
94. A formulation according to claim 88, wherein the comonomer
component 1) is selected from the group consisting of acrylic acid,
methacrylic acid, crotonic acid, isocrotonic acid, allylsulphonic
acid, vinylsulphonic acid and suitable salts thereof and alkyl or
hydroxyalkyl esters thereof.
95. A formulation according to claim 88, wherein the copolymer
a.sub.1) comprises additional structural groups in copolymerized
form.
96. A formulation according to claim 95, wherein the additional
structural groups are styrenes, acrylamides or hydrophobic
compounds, ester structural units, polypropylene oxide and
polypropylene oxide/polyethylene oxide units being particularly
preferred.
97. A formulation according to claim 95, wherein the copolymer
a.sub.1) contains the additional structural group in proportions up
to 5 mol %.
98. A formulation according to claim 88, wherein the formula (1) is
a polyether containing allyl or vinyl groups.
99. A formulation according to claim 88, wherein the
polycarboxylate ester a.sub.2) is a polymer which is prepared by
polymerization of a monomer mixture (I) containing in an amount of
more than 50 wt. %, a representative of the carboxylic acid monomer
type.
100. A formulation according to claim 99, wherein the
polycarboxylate ester a.sub.2) is an anti-foaming agent, a defoamer
or a surfactant.
101. A formulation according to claim 99, wherein the monomer
mixture (I) contains an (alkoxy)polyalkylene glycol
mono(meth)acrylate monomer (a) of the formula (II) ##STR00019## in
which R.sup.1 is a hydrogen atom or a CH.sub.3 group, R.sup.2O is
one representative or a mixture of at least two oxyalkylene groups
having 2 to 4 carbon atoms, R.sup.3 is a hydrogen atom or an alkyl
group having 1 to 5 carbon atoms and m is a number between 1 and
250 and is the average number of moles of the oxyalkylene group
added, additionally, as monomer (b), a (meth)acrylic acid of the
general formula (III), ##STR00020## in which R.sup.4 is a hydrogen
atom or a CH.sub.3 group and M.sup.1 is a hydrogen atom, a
monovalent metal atom, a divalent metal atom, an ammonium group or
an organic amine group, and optionally a monomer (c) which is
copolymerized with the monomers (a) and (b).
102. A formulation according to claim 101, wherein the monomer (a)
is present in an amount of 5 to 98% by weight, the monomer (b) in
an amount of 2 to 95% by weight and the monomer (c) in an amount of
up to 50% by weight in the monomer mixture (I), the respective
amounts of the monomers (a), (b) and (c) summing to 100% by
weight.
103. A formulation according to claim 99, wherein the monomer (a)
is a hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate,
polyethylene glycol mono(meth)acrylate, polypropylene glycol
mono(meth)acrylate, polybutylene glycol mono(meth)acrylate,
polyethylene glycol polypropylene glycol mono(meth)acrylate,
polyethylene glycol polybutylene glycol mono(meth)acrylate,
polypropylene glycol polybutylene glycol mono(meth)acrylate,
polyethylene glycol polypropylene glycol polybutylene glycol
mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate,
methoxypolypropylene glycol mono(meth)acrylate, methoxypolybutylene
glycol mono(meth)acrylate, methoxypolyethylene glycol polypropylene
glycol mono(meth)acrylate, methoxypolyethylene glycol polybutylene
glycol mono(meth)acrylate, methoxypolypropylene glycol polybutylene
glycol mono(meth)acrylate, methoxypolyethylene glycol polypropylene
glycol polybutylene glycol mono(meth)acrylate, ethoxypolyethylene
glycol mono(meth)acrylate, ethoxypolypropylene glycol
mono(meth)acrylate, ethoxypolybutylene glycol mono(meth)acrylate,
ethoxypolyethylene glycol polypropylene glycol mono(meth)acrylate,
ethoxypolyethylene glycol polybutylene glycol mono(meth)acrylate,
ethoxypolypropylene glycol polybutylene glycol mono(meth)acrylate,
ethoxypolyethylene glycol polypropylene glycol polybutylene glycol
mono(meth)acrylate or a mixture thereof.
104. A formulation according to claim 99, wherein the monomer (b)
is selected from the group consisting of acrylic acid, methacrylic
acid, monovalent metal salts, divalent metal salts, ammonium salts
and organic amine salts thereof and mixtures thereof.
105. A formulation according to claim 99, wherein the monomer (c)
is at least one representative of the esters of an aliphatic
alcohol having 1 to 20 carbon atoms with an unsaturated carboxylic
acid.
106. A formulation according to claim 105, wherein the unsaturated
carboxylic acid is maleic acid, fumaric acid, citraconic acid,
(meth)acrylic acid or monovalent metal salts, divalent metal salts,
ammonium salts or organic amine salts thereof.
107. A formulation according to claim 105, said formula comprising
monoesters or diesters of unsaturated dicarboxylic acids, such as
maleic acid, fumaric acid or citraconic acid, with aliphatic
C.sub.1-C.sub.20-alcohols, C.sub.2-C.sub.4-glycols or
(alkoxy)polyalkylene glycols.
108. A formulation according to either of claim 88, wherein the
component a.sub.2) is a copolymer containing at least one of the
following monomers: A) an ethylenically unsaturated monomer
comprising a hydrolyzable radical, hydrolyzable radical having an
active bonding site for at least one of component a) or b); B) an
ethylenically unsaturated monomer having at least one
C.sub.2-C.sub.4-oxyalkylene side group having a chain length of 1
to 30 units; C) an ethylenically unsaturated monomer having at
least one C.sub.2-C.sub.4-oxyalkylene side group having a chain
length of 31 to 350 units.
109. A formulation according to claim 108, wherein the components
B) and C) are both present in the copolymer a.sub.2).
110. A formulation according to claim 108, wherein the
ethylenically unsaturated monomer of component A) comprises at
least one anhydride, imide, maleic anhydride or maleimide.
111. A formulation according to claim 108, wherein the
ethylenically unsaturated monomer of component A) comprises an
acrylate having an ester functionality which contains the
hydrolyzable radical.
112. A formulation according to claim 111, wherein the ester
functionality is at least one hydroxypropyl or hydroxyethyl
radical.
113. A formulation according to claim 108, wherein the copolymer
a.sub.2) in the component A) has more than one ethylenically
unsaturated monomer with a hydrolyzable radical.
114. A formulation according to claim 113, wherein the
ethylenically unsaturated monomer of component A) has, as a
radical, at least more than one ethylenically unsaturated monomer,
wherein at least one is a hydrolyzable radical or a mixture of the
two.
115. A formulation according to either of claims 113, wherein the
hydrolyzable radical has at least one C.sub.2-C.sub.20-alcohol
functionality.
116. A formulation according to claim 113, wherein the hydrolyzable
radical is at least a C.sub.1-C.sub.20-alkyl ester, a
C.sub.1-C.sub.20-aminoalkyl ester or an amide.
117. A formulation according to claim 108, wherein at least one
ethylenically unsaturated monomer of component B) or C) has a
C.sub.2-C.sub.8-alkyl ether group.
118. A formulation according to claim 117, wherein the
ethylenically unsaturated monomer has a vinyl, allyl, or
(methyl)allyl ether radical, or is derived from an unsaturated
C.sub.2-C.sub.8-alcohol.
119. A formulation according to claim 118, wherein the unsaturated
C.sub.2-C.sub.8-alcohol is at least one representative of the
series consisting of vinyl alcohol, (meth)allyl alcohol, isoprenol
or methylbutenol.
120. A formulation according to claim 108, wherein the
ethylenically unsaturated monomer side groups of the component B)
or C) have at least one C.sub.4-oxyalkylene unit.
121. A formulation according to claim 108, wherein at least one
ethylenically unsaturated monomer of the component B) or C) has a
C.sub.2-C.sub.8-carboxylic ester which in particular is
hydrolyzable.
122. A formulation according to claim 108, wherein the oxyalkylene
side groups have at least one ethylene oxide, one propylene oxide,
one polyethylene oxide, one polypropylene oxide.
123. A formulation according to claim 108, wherein the copolymer
a.sub.2) in the component C) has at least one nonionic or one
non-hydrolyzable monomer radical.
124. A formulation according to claim 88, wherein the nonionic
copolymer a.sub.3) is of formula (IV) ##STR00021## in which Q is an
ethylenically unsaturated monomer having at least one hydrolyzable
radical, G is O, C(O)--O or O--(CH.sub.2).sub.p--O with p is from 2
to 8, mixtures of the variants of G being possible in a polymer;
R.sup.1 and R.sup.2 are independently a C.sub.2-C.sub.8-alkyl;
R.sup.3 comprises (CH.sub.2).sub.c, wherein c is an integer between
2 and 5, wherein mixtures of R.sup.3 may be present in the same
polymer molecule; R.sup.5 is at least one representative selected
from the series consisting of H, a linear or branched saturated or
unsaturated C.sub.1-C.sub.20-aliphatic hydrocarbon radical, a
C.sub.5-C.sub.8-cycloaliphatic hydrocarbon radical or a substituted
or unsubstituted C.sub.6-C.sub.14-aryl radical; m is from 1 to 30;
n is 31 to 350; w is 1 to 40; y is from 0 to 1; and z is from 0 to
1; wherein the sum (y+z) is >0.
125. A formulation according to either of claim 88, wherein the
nonionic copolymer a.sub.3) is a representative of the formula (V)
##STR00022## in which X is a hydrolyzable radical and R is H or
CH.sub.3; G, p, R.sup.1, R.sup.2, R.sup.3, R.sup.5, m, n, w, y, z
and (y+z) are as defined for formula (IV).
126. A formulation according to claim 125, wherein the hydrolyzable
radical is at least one member of the group consisting of alkyl
ester, aminoalkyl ester, hydroxylalkyl ester, aminohydroxyalkyl
ester or amide.
127. A formulation according to either of claim 88, wherein the
nonionic copolymer a.sub.3) is at least one representative of the
formula (VI) ##STR00023## in which R.sup.4 is at least one
C.sub.1-C.sub.20-alkyl or C.sub.2-C.sub.20-hydroxyalkyl radical and
the radicals G, p, R, R.sup.1, R.sup.2, R.sup.3, c, R.sup.4,
R.sup.5 and m, n, w, y, z and (y+z) are as defined for formula
(IV).
128. A formulation according to claim 127, wherein p is 4, R.sup.4
is C.sub.2H.sub.4OH or C.sub.3H.sub.6OH, each of the radicals
R.sup.5 is H, m=5-30, n=31-250, w=1.5-30, y=0 to 1, z=0 to 1 and
(y+z)>0.
129. A formulation according to claim 124, wherein the molar ratio
of w to the sum (y+z) is 1:1 to 20:1 and preferably 2:1 to
12:1.
130. A formulation according to claim 88, wherein the copolymer
a.sub.3) is a nonionic polyether-polyester copolymer.
131. A formulation according to claim 88, wherein the structural
units (I), (II), (III) of component b) have the following formulae
##STR00024## where A are identical or different and are represented
by substituted or unsubstituted aromatic or heteroaromatic compound
having 5 to 10 C atoms, where B are identical or different and are
represented by N, NH or O where n is 2, if B is N, and n is 1, if B
is NH or O where R.sup.1 and R.sup.2 independently of one another,
are identical or different and are represented by a branched or
straight-chain C.sub.1- to C.sub.10-alkyl radical, C.sub.5- to
C8-cycloalkyl radical, aryl radical, heteroaryl radical or H, where
a are identical or different and are represented by an integer from
1 to 300, wherein X are identical or different and are represented
by a branched or straight-chain C.sub.1- to C.sub.10-alkyl radical,
C.sub.5- to C.sub.8-cycloalkyl radical, aryl radical, heteroaryl
radical or H, ##STR00025## for (VIII) and (IX): wherein D are
identical or different and are represented by a substituted or
unsubstituted heteroaromatic compound having 5 to 10 C atoms;
wherein E are identical or different and are represented by N, NH
or O; wherein m is 2, if E is N, and m is 1,if E is NH or O;
wherein R.sup.3 and R.sup.4 are independently selected from a
branched or straight-chain C.sub.1- to C.sub.10-alkyl radical,
C.sub.5- to C.sub.8-cycloalkyl radical, aryl radical, heteroaryl
radical or H, wherein b are identical or different and are
represented by an integer from 0 to 300, wherein M is an alkaline
metal ion, alkaline earth metal ion, ammonium ion, organic ammonium
ion or H; c is 1 or 1/2, wherein if M is an alkaline earth metal
ion, c is 1/2.
132. A formulation according to claim 131, wherein the component b)
contains a structural unit (X) of formula ##STR00026## wherein Y,
independently of one another, are identical or different and are
represented by (VII), (VIII), (IX) or further constituents of the
polycondensation product b), wherein R.sup.5 are identical or
different and are represented by H, CH.sub.3, COOM.sub.c or a
substituted or unsubstituted aromatic or heteroaromatic compound
having 5 to 10 C atoms, wherein R.sup.6 are identical or different
and are represented by H, CH.sub.3, COOM.sub.c or a substituted or
unsubstituted aromatic or heteroaromatic compound having 5 to 10 C
atoms, wherein M is independently of one another an alkaline metal
ion, alkaline earth metal ion, ammonium ion, organic ammonium ion
or H, c is 1 or 1/2, wherein if M is alkaline earth metal ion c is
1/2.
133. A formulation according to claim 132, wherein R.sup.5 and
R.sup.6 in structural unit (X) of component b), independently of
one another, are identical or different and are represented by H,
COOM.sub.c or methyl.
134. A formulation according to claim 88, wherein the molar ratio
of the structural units [(VII)+(VII)+(IX)]:(X) in component b) is
1:0.8 to 3.
135. A formulation according to claim 88, wherein the molar ratio
of the structural units (VII):[(VIII)+(IX)] in component b) is 1:15
to 15:1 and preferably 1:10 to 10:1.
136. A formulation according to claim 88, wherein the molar ratio
of the structural units (VII):(IX) in component b) is 1:0.005 to
1:10.
137. A formulation according to claim 88, wherein the
polycondensation product b) is present in aqueous solution which
contains 2 to 90% by weight of water and 98 to 10% by weight of
dissolved dry matter.
138. A formulation according to claim 88, wherein the component a)
is present in proportions of 5 to 95% by weight based in each case
on the total formulation.
139. A formulation according to claim 88, wherein the component b)
is present in proportions of 5 to 100% by weight based in each case
on the total formulation.
140. A formulation according to claim 88, further comprising at
least one antifoaming agent as component c) or a component d)
having a surface-active effect, wherein the components c) and d)
are structurally different from one another.
141. A formulation according to claim 140, wherein the antifoam
component c) is a member selected from the group consisting of
mineral oil, vegetable oil, silicone oil, silicone-containing
emulsions, fatty acid, fatty acid ester, organically modified
polysiloxane, borate ester, alkoxylate, polyoxyalkylene copolymer,
ethylene oxide (EO)-propylene oxide (PO) block polymer, acetylenic
diol having antifoam properties, phosphoric acid ester of the
formula P(O)(O--R.sub.8).sub.3-x(O--R.sub.9).sub.x wherein P is
phosphorus, O is oxygen and R.sub.8 and R.sub.9 independently of
one another, is a C.sub.2-20-alkyl or an aryl group and x is 0, 1
or 2.
142. A formulation according to claim 140, wherein the antifoaming
component c) is at least one member selected from the group
consisting of trialkyl phosphate, polyoxypropylene copolymer and
glycerol/alcohol acetate.
143. A formulation according to claim 140, wherein the antifoaming
component c) is triisobutyl phosphate.
144. A formulation according to claim 140, wherein the antifoam
component c) is a mixture of a trialkylphosphate and a
polyoxypropylene copolymer.
145. A formulation according to claim 140, wherein the component d)
is at least one representative of the series consisting of ethylene
oxide/propylene oxide block copolymer, styrene/maleic acid
copolymer, fatty acid alcohol alkoxylate, alcohol ethoxylate
R10((EO)(H wherein R10 is an aliphatic hydrocarbon group having 1
to 25 carbon atoms, acetylenic diol, monoalkylpolyalkylene,
ethoxylated nonylphenol, alkyl sulphate, alkyl ether sulphate,
alkyl ether sulphonate or alkyl ether carboxylate.
146. A formulation according to either of claim 140, wherein the
component d) comprises an alcohol having a polyalkylene group, the
polyalkylene group having a carbon chain length of 2 to 20 carbon
atoms.
147. A formulation according to claim 146, wherein the polyalkylene
group has a carbon chain length of 3 to 12 carbon atoms.
148. A formulation according to claim 140, wherein it contains the
antifoaming component c) in free form, bound to the dispersant
component a) or as a mixture of these two forms.
149. A formulation according to claim 140, wherein the antifoaming
component c) is present in an amount of from 0.01 to 10% by weight
or the surface-active component d) is present in an amount of from
0.01 to 10% by weight, based in each case on the total weight of
the formulation.
150. A formulation according to claim 140, wherein the antifoaming
c) or the surface-active component d), independently of one
another, are present in each case in an amount of 0.01 to 5% by
weight, based in each case on the total weight of the
formulation.
151. A formulation according to claim 88, wherein component e) is a
compound selected from the group consisting of a polymer having a
low charge, neutral polymer and polyvinyl alcohol as component
e).
152. A formulation according to claim 151, wherein the component e)
is present in an amount of from 1 to 50% by weight based in each
case on the total weight of the formulation.
153. A formulation according to claim 151, wherein the polymer
having a low charge is branched and the side chain preferably
consists of a polyether or a polyester.
154. A formulation according to claim 151, wherein the polymer
having a low charge is at least one of a polycarboxylate ether or a
polycarboxylate ester.
155. A formulation according to claim 151, wherein the polymer e)
having a low charge is composed of at least one monomer selected
from the series consisting of polyether monoacrylate, polyether
monomethacrylate, polyether monoallyl ether, polyether monomaleate,
monovinylated polyether or mixtures thereof.
156. A formulation according to claim 155, wherein the polyether is
an alkylene oxide polymer having a molecular weight of 500 to
10,000.
157. A formulation according to claim 156, wherein the alkylene
oxide is ethylene oxide, propylene oxide, butylene oxide or a
mixture thereof.
158. A formulation according to claim 151, wherein the polymer e)
having a low charge is composed of at least one monomer selected
from the series consisting of polypropylene glycol acrylate,
polypropylene glycol methacrylates, polyethylene glycol acrylate,
polyethylene glycol methacrylate, polypropylene glycol monovinyl
ether, polyethylene glycol monovinyl ether, alkoxy- or
aryloxypolyethylene glycol acrylate, alkoxy- or aryloxypolyethylene
glycol methacrylates, alkoxy- or aryloxypolyethylene glycol
monovinyl ether, acrylates, methacrylates and monovinyl ethers of
an oxyalkylene or oxypropylene block or random copolymer,
polypropylene glycol allyl ether, polyethylene glycol allyl ether,
polyethylene glycol monomaleate polypropylene glycol monomaleate
and any mixtures thereof.
159. A formulation according to claim 151, wherein the polymer e)
having a low charge carries a carboxylic acid group, preferably
selected from the series consisting of acrylic acid, methacryl
acid, maleic acid, fumaric acid, itaconic acid or anhydrides
thereof.
160. A formulation according to claim 151, wherein the polymer e)
having a low charge carries a sulphonic acid group selected from
the series consisting of 2-acrylamido-2-methylpropanesulphonic acid
(AMPS), vinylsulphonic acid, allyl ether sulphonic acid,
2-sulphoethylmethacrylic acid, styrenesulphonic acid,
methallylsulphonic acid, the sodium, potassium and ammonium salts
thereof and any mixtures thereof, and in particular the AMPS and
vinylsulphonic acid.
161. A formulation according to claim 151, wherein the neutral
polymer e) is composed of neutral monomer building blocks which are
selected in particular from the series consisting of alkyl
acrylates and alkyl methacrylates and hydroxyalkyl esters thereof
having up to 5 carbon atoms, in particular hydroxyethyl acrylate
and hydroxypropyl acrylate or hydroxyethyl methacrylate and
hydroxypropyl methyacrylate, and vinyl acetate, N-vinylpyrrolidone,
N-vinylcaprolactam, styrene and methylstyrene.
162. A formulation according to claim 88, further comprising a
component f) which is a calcium-silicate-hydrate (C-S-H) containing
composition.
163. A formulation according to claim 162, wherein the C-S-H shows
a calcium/silicium (Ca/Si)-molar ratio of 0.5 to 2.0.
164. A formulation according to claim 162, wherein the average
particle size of C-S-H is smaller than 10 .mu.m when measured by
light scattering with the equipment Master Sizer 2000 from the
Malvern Company.
165. A formulation according to claim 162, wherein the average
particle size of C-S-H is greater 0.01 .mu.m.
166. A formulation according to claim 162, wherein the C-S-H
containing composition is prepareble by reaction of a water-soluble
calcium containing compound with a water-soluble silicate
containing compound, the reaction of the water-soluble calcium
containing compound with the water-soluble silicate containing
compound being carried out in the presence of an aqueous solution
preferably containing a water-soluble copolymer that preferably is
a dispersant for hydraulic binders and selected from at least a
representative of at least one of component a) or b).
167. A formulation according to claims 162, wherein the C-S-H
containing composition is prepareble by reaction of a calcium
oxide, a calcium carbonate and/or a calcium hydroxide with a
silicium dioxide during milling, the reaction being carried out in
the presence of an aqueous solution that preferably contains a
water-soluble copolymer that preferably is a dispersant for
hydraulic binders and selected from at least a representative of at
least one of component a) or b).
168. A formulation according to claim 88, wherein it is a liquid or
a powder.
169. A method of controlling the flowability of an aqueous
comprising at least one of hydraulicor latent hydraulic binder
comprising adding a sufficient the formulation of claim 88 to an
aqueous suspension of said hydraulic binder or said latent
hydraulic binder to control the flowability of the aqueous
suspension.
170. A method according to claim 169, wherein the hydraulic binder
is at least one of a cement or a calcium sulphate-based.
171. A method according to claim 169, wherein the formulation is
present in an amount of from 0.001 to 8.0% by weight based on the
total composition of the suspension.
172. A method according to claim 169, wherein the formulation
further comprises an additive, an admixture or a composition with
at least one of flowability controlling or dispersing
properties.
173. A method according to claim 169 wherein the aqueous suspension
comprises a dry mortar composition or a flooring composition.
174. A method according to claim 173, wherein the flooring
composition contains calcium sulphate, cement or a mixture thereof,
and preferably is a self-leveling flooring composition.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to co-pending U.S. Ser. No.
12/______, filed concurrently herewith and entitled "Gypsum
Products Using Additives", incorporated herein by reference in its
entirety.
[0002] The subject of the present invention is a formulation for
the dispersion of hydraulic binder and especially gypsum containing
compositions.
[0003] Conventional dispersants for cementitious and gypsum
compositions typically achieve good water reduction, however, they
are limited in their ability to retain workability over a long
period of time. An alternate method for extended workability
retention is the use of retarding admixtures. In this scenario, the
benefit of workability retention is often achieved at the expense
of setting times and early strength. The usefulness of these
dispersants is therefore limited by their inherent limitations in
molecular architecture.
[0004] Usual dispersants are static in their chemical structure
over time in hydraulic systems. Their performance is controlled by
monomer molar ratio that is fixed within a polymer molecule. A
water reducing effect or dispersing effect is observed upon
dispersant adsorption onto the hydraulic particle surface. As
dispersant demand increases over time due to abrasion and hydration
product formation, which creates more surface area, these
conventional dispersants are unable to respond and workability is
lost.
[0005] Typically, the issue of extended workability is solved by
either re-tempering (adding more water) to the hydraulic
compositions or by adding more high range water reducer. Addition
of water leads to lower strength and thus creates a need for mixes
that are "over-designed" in the way of hydraulic binder
content.
[0006] Various types of organic compounds have been used to
advantageously alter certain properties of wet hydraulic binder
compositions. One class of components, which can collectively be
called "superplasticizers" fluidify or plasticize wet binder
compositions to obtain a more fluid mixture. A controlled fluidity
is desired, such that the aggregate used in mortars and concretes
does not segregate from the binder paste. Alternatively,
superplasticizers may allow the cement composition to be prepared
using a lower water: binder ratio in order to obtain a composition
having a desired consistency which often leads to a hardened
composition having a higher compressive strength development after
setting.
[0007] A good superplasticizer should not only fluidify the wet
hydraulic binder composition to which it is added, but also
maintain the level of fluidity over a desired period of time. This
time should be long enough to keep the wet composition fluid, e. g.
in a ready-mix truck while it is on its way to a job site. Another
important aspect relates to the period for discharging the truck at
the job site and the period needed for the cement composition for
being worked in the desired final form. On the other side, the
hydraulic mixture cannot remain fluid for a too long time, that
means the set must not greatly be retarded, because this will slow
down the work on the job and show negative influences on the
characteristics of the final hardened products.
[0008] Conventional examples of superplasticizers are melamine
sulfonate/formaldehyde condensation products, naphthalene
sulfonate/formaldehyde condensation products and lignosulfonates,
polysaccharides, hydroxycarboxylic acids and their salts and
carbohydrates.
[0009] In most cases, fluidizing agents are multi-component
products with copolymers based on oxyalkylenglykolalkenylethers and
unsaturated dicarboxylic acid-derivatives as most important
species. The European Patent EP 0 736 553 B1 discloses such
copolymers comprising at least three sub-units and especially one
unsaturated dicarboxylic acid derivative, one
oxyalkylenglykolalkenylether and additionally one hydrophobic
structural unit, such as ester units. The third structural unit can
also be represented by polypropylenoxid- and
polypropylenoxid-polyethylenoxid-derivatives, respectively.
[0010] The German published application DE 195 43 304 A1 discloses
an additive for water containing mixtures for the construction
field comprising a) a water-soluble sulfonic acid-, carboxylic- or
sulfate group containing cellulose derivative, b) a sulfonic acid-
and/or carboxylic acid containing vinyl-(co)-polymer and/or a
condensation product based on aminoplast-builders or acryl
containing compounds and formaldehyde. This additive shall show
sufficient water retention ability and rheology-modifying
properties. Therefore, this additive shall be suitable for
construction chemical compositions containing cement, lime, gypsum,
anhydrite and other hydraulic binder components.
[0011] Copolymers based on unsaturated monocarboxylic or
dicarboxylic acid derivatives, oxyalkylenglykolalkenylethers,
vinylic polyalkylenglykol, polysiloxane or ester compounds used as
additives for aqueous suspensions based on mineral or bituminous
binders are described in U.S. Pat. No. 6,777,517 B1. The use of
such additives results in a decrease in the water/binder ratio and
leads to highly fluid building materials without segregation of
individual constituents from the building material mixture. The
copolymers according to this U.S. patent are useful as additives
for aqueous suspensions of inorganic and organic solids and
especially for suspensions that are based on mineral or bituminous
binders such as cement, plaster of paris, lime, anhydrite or other
building materials based on calcium sulfate.
[0012] Disclosed by prior art also are copolymers of ethylenically
unsaturated ethers that can be used as plasticizers for cement
containing mixtures (EP 0 537 870 A1). These copolymers contain an
ether co-monomer and as additional co-monomer an olefinic
unsaturated mono-carboxylic acid or an ester or a salt thereof, or
alternatively an olefinic unsaturated sulfuric acid. These
copolymers show a very short ether side chain with 1 to 50 units.
The short side chain causes a sufficient plasticizing effect of the
copolymers in cement containing masses with a reduced slump loss of
the construction chemicals mass itself.
[0013] U.S. Pat. No. 6,139,623 B1 discloses an emulsion admixture
for use in hydraulic cement compositions formed by emulsifying an
antifoaming agent, a surfactant and a copolymer having a
carbon-containing backbone to which are attached groups that
function as cement-anchoring members by forming ionic bonds and
oxyalkylene groups. This admixture comprising an ethylene
oxide/propylene oxide (EO/PO) type comb polymer and an antifoaming
agent allows a predictable air control in hydraulic cement
compositions such as concrete. The term "cement composition" refers
to pastes, mortars, grouts such as oil well cementing grouts, and
concrete compositions comprising a hydraulic cement binder. Typical
antifoaming agents are phosphate ester, borate ester and
polyoxyalkylene copolymers with defoaming properties. The surface
active component (surfactant) is said to stabilize the emulsion
mixture and is chosen from the group consisting of an esterified
fatty acid ester of a carbohydrate, a C.sub.2 to C.sub.20 alcohol
having polyoxyalkylene groups or a mixture thereof.
[0014] US 2006/0281886 discloses a co-polymer comprising two
monomer components with a component a) being an olefinic
unsaturated monocarboxylic acid co-monomer or an ester or a salt
thereof or an olefinic unsaturated sulfonic acid co-monomer or a
salt thereof, and with component b) preferably represented by an
ether compound. These two monomeric co-polymer can be preferably
used as a superplasticizer in a hydraulic binder containing
composition. There it is alternatively disclosed that the
co-polymer can be used in combination with a defoaming component
that is also an additional structural unit of the co-polymer.
Consequently, the defoaming component can be chemically attached to
the co-polymer or being present in free form in a blend. Under
general aspects the prior art teaches the use of dispersing agents
(plasticizers) such as polycarboxylate ethers (PCE) as typical
additive for calcium sulfate containing binder systems. This
results in a water reduction as well as in an enhancement of
physical properties such as compressive strength. Additionally, the
workability and preferably the rheological behavior of the
construction chemicals composition are improved. On the other hand
the addition of PCE based dispersants causes a distinct air
entrainment to the binder component that worsens the physical
properties of the composition. Another negative aspect is the foam
formation during the preparation of the binder system. For
overcoming these drawbacks defoamer components are used as
additional additive to the dispersing agent. However, defoamers
show a low solubility in aqueous formulations and cause an
insufficient stability. Moreover, the defoaming properties of the
formulation decrease over time due to the resulting phase
separation of the defoamer and the dispersant.
[0015] Based on the different characteristics and the availability
of the superplasticizers mentioned above, it has been further
desired to come up with new formulations suitable as admixtures
which are an improvement over the current state of the art. It is
thus an object of this invention to provide new formulations for
calcium sulfate binder containing compositions which impart to wet
binder compositions excellent fluidizing and water reduction
properties. Furthermore, the properties, the performance and
effects of the provided copolymer shall be arbitrary.
[0016] In the production of gypsum plasterboard, in order to
decrease the drying costs it is necessary to establish as low as
possible a water/gypsum value. In addition, the gypsum mixture
should set as rapidly as possible, so that the necessary cutting
strength of the plate is attained on the conveyor line after as
short a time as possible. For these reasons, dispersants based in
particular on polycarboxylate ethers were developed (DE 10 2006 027
035 A1; U.S. Pat. No. 7,070,648 B1).
[0017] US 2008/017078 teaches a liquid admixture composition for a
calcium sulfate based binder system and a method of use. The
disclosed admixture comprises an aqueous composition of a
copolymeric dispersing component, an antifoaming agent component, a
surfactant component and water. The components may be a blend or
physically or chemically attached and result in a stable liquid
system that can be used as dispersing agent for calcium sulfate
compound containing construction chemicals composition. The
admixture composition disclosed in this document and especially its
application as dispersing agent represent a further improvement of
this state of the art because the admixture with its contained
aqueous composition induces a uniform plasticizing effect all the
time and an improvement of the physical properties due to reduction
of both water and air content in the wet construction chemicals
gypsum mass. Furthermore, the admixture shows an improved storage
stability and homogeneity.
[0018] Gypsum mixtures for foaming, solid and fast drying gypsum
products and a method of making a gypsum slurry by using modifiers
and dispersants are disclosed by US 2009/0101045, US 2006/0281837,
US 2006/0280899, US 2006/0280898, US 2006/0278135, US 2006/0278134,
US 2006/0278130, US 2006/0278127, US 2005/0250888, US 2005/0239924
and US 2006/0280970. The dispersants mentioned in these documents
represent polycarboxylate dispersants, the dispersant having two
repeating units with an olefinic unsaturated mono-carboxylic acid
repeating unit and a vinyl or allyl-group bound to a polyether by
an ether linkage as second repeating unit.
[0019] The results given in any of these documents confirm that
such dispersants can be used to attain advantageous physical
properties known from superplasticizers such as polycarboxylate
ethers.
[0020] It was therefore the object of the present invention to
provide an economical and effective new formulation based on
suitable and well established dispersing components for hydraulic
binders, which dispersant is particularly suitable as a
plasticizer/water reducing agent for concrete and other hydraulic
binder based systems and that can be prepared in a simple manner
and at low costs.
[0021] Provided by this invention therefore is a formulation for
extending workability to a hydraulic binder and preferably a
calcium sulfate containing mixture and water, comprising
introducing into the mixture a combination of dispersing
components. The subject formulation achieves a better workability
and fluidibility of hydraulic setting compositions and establishes
a low water/hydraulic binder value.
DETAILED DESCRIPTION
[0022] The present invention relates to a formulation containing
[0023] a) at least one component having dispersing properties and
selected from the group consisting of a compound at least
containing a branched comb polymer having polyether side chains, a
naphthalene sulphonate-formaldehyde condensate ("BNS") and a
melamine sulphonate-formaldehyde condensate ("MSF"), and [0024] b)
a polycondensation product containing [0025] (I) at least one
structural unit with an aromatic or heteroaromatic sub-unit and a
polyether side chain, and [0026] (II) at least one phosphated
structural unit with an aromatic or heteroaromatic sub-unit, and
[0027] (III) at least one structural unit with an aromatic or
heteroaromatic sub-unit,
[0028] with structural unit (II) and structural unit (III)
differing exclusively in that the OP(OH).sub.2 group of the
structural unit (II) is replaced by H in structural unit (III), and
structural unit (III) is not the same as structural unit (I), the
formulation being suitable as admixture for a hydraulic binder and
preferably a calcium sulfate binder system containing
composition.
[0029] The term "hydraulic binder" according to this invention
means cement and preferably Portland cement represented by CEM I,
CEM II, CEM III, CEM IV and CEM V, white cement, quick lime and
aluminate cement.
[0030] The term "latent hydraulic binder" according to this
invention means at least one representative selected from the group
fly ash, blast furnace slag, metakaoline, microsilica, trass
compounds, alumosilicates, tuff, phomulithe, diatomaceous earth and
oil shell.
[0031] The term "calcium sulfate compound" according to this
invention means calcium sulfate in its anhydrous and hydrate forms,
such as gypsum, anhydrite, calcium sulfate dihydrate and calcium
sulfate hemi-hydrate.
[0032] The term "gypsum" according to this invention is also known
as calcium sulfate, whereby calcium sulfate can be used in its
various anhydrous and hydrate forms with or without crystal water.
Natural gypsum is represented by calcium sulfate dihydrate and the
natural crystal water free form of calcium sulfate is represented
by the term "anhydrite". Besides the natural forms, calcium sulfate
is a typical by-product of technical processes characterized by the
term "synthetic gypsum". One example of such technical processes is
the flue gas desulphurization. Synthetic gypsum may also be a
by-product of phosphorous acid and hydrogen fluoride production
methods for gaining hemi-hydrate forms (CaSO.sub.41/2H.sub.2O).
Gypsum (CaSO.sub.4.2H.sub.2O) may be calcinated by driving off the
water of hydration. Products of the various calcinating procedures
are alpha or beta hemi-hydrate. Beta calcium sulfate hemi-hydrate
results from a rapid heating in open units by a rapid evaporation
of water and by forming cavities. Alpha hemi-hydrate is produced by
a de-watering of gypsum in closed autoclaves. The crystal form in
this case is dense and therefore, this binder needs less amounts of
water than beta hemi-hydrate. On the other hand, gypsum
hemi-hydrate re-hydrates with water to dihydrate crystals. Usually,
the hydration of gypsum needs some minutes to hours indicating a
clearly shortened workability period in contrast to cements that
hydrate in periods over hours or days. These characteristics make
gypsum an attractive alternative to cement as hydraulic binder in
various fields of application, because hardened final gypsum
products show a characteristic hardness and compressive
strength.
[0033] Calcium sulfate hemi-hydrate can produce at least two
crystal forms, whereby .alpha.-calcined gypsum is usually
de-watered (de-hydrated) in closed autoclaves. For various fields
of application, .beta.-calcined gypsum may be selected due to its
availability under economical aspects. However, these advantages
may be reversed because .beta.-calcined gypsum needs higher water
amounts for workability and for making slurries of a given
fluidity. Hardened or dried gypsum tends to a certain weakening
based on the remained water in its crystal matrix. Therefore,
products thereof show less strength than gypsum products that have
been made with smaller amounts of water.
[0034] In general, the workability of gypsum, but also of other
hydraulic binders, can be improved under hydraulic aspects by
adding dispersants. In this connection, the formulation according
to this invention represents a suitable dispersant because of the
dispersing properties of its component.
1. Component a)
[0035] Component a) of the formulation according to the invention
has dispersing properties and is selected from the group consisting
of a compound at least containing a branched comb polymer having
polyether side chains, a naphthalene sulphonate-formaldehyde
condensate ("BNS"), and a melamine sulphonate-formaldehyde
condensate ("MSF"),
[0036] Formulations which contain a branched comb polymer having
polyether side chains as the component a) with dispersant action
have been found extremely effective. It therefore can be seen as
preferred embodiment that the component a) is a polycarboxylate
ether a.sub.1), a polycarboxylate ester a.sub.2), an uncharged
copolymer a.sub.3) or a mixture thereof. In general and
additionally to the dispersing properties of component a)
polycarboxylate ester a.sub.2) are preferred that show anti-foaming
and surface active activities.
1.1 Copolymer a.sub.1:
[0037] Such polyether-containing copolymers, which in the sense of
the present invention are suitable as component a.sub.1), have been
previously described in WO 2006/133933 A2. These copolymers consist
of two monomer components, the first monomer component being an
olefinically unsaturated monocarboxylic acid comonomer or an ester
or a salt thereof and/or an olefinically unsaturated sulphonic acid
comonomer or a salt thereof, and the second monomer component a
comonomer of the general formula (I)
##STR00001##
wherein R.sub.1 represents
##STR00002##
and R.sub.2 represents H or an aliphatic hydrocarbon residue with 1
to 5 C atoms; R.sub.3=unsubstituted or substituted aryl residue and
preferably phenyl, and R.sub.4=H or an aliphatic hydrocarbon
residue with 1 to 20 C atoms, cycloaliphatic hydrocarbon residue
with 5 to 8 C atoms, a substituted aryl residue with 6 to 14 C
atoms or a member of the series
##STR00003##
wherein R.sub.5 and R.sub.7 each represent an alkyl, aryl, aralkyl,
or alkaryl residue and R.sub.6 for an alkylidene, arylidene,
aralkylidene or alkarylidene residue, and [0038] p=0, 1, 2, 3 or 4
[0039] m, n mutually independently mean 2, 3, 4 or 5 [0040] x and y
mutually independently denote an integer.ltoreq.350 and [0041] z=0
to 200.
[0042] In this connection (I) in copolymer a.sub.1) the comonomer
units which represent the components 1) and 2) have in each case no
internal molecular differences and/or (II) the copolymer a.sub.1)
represents a polymeric mixture of the components 1) and 2), in
which case the comonomer units have internal molecular differences
with respect to the radicals R.sub.1 and/or R.sub.2 and/or R.sub.3
and/or R.sub.4 and/or R.sub.5 and/or R.sub.6 and/or R.sub.7 and/or
m and/or n and/or x and/or y and/or z, and the differences
discussed relate in particular to the composition and length of the
side chains.
[0043] With regard to the copolymer the disclosure of WO
2006/133933 A2 is a substantial integral of the present
disclosure.
[0044] In particular, the present invention comprises a formulation
wherein the copolymer a.sub.1) contains the comonomer component 1)
in proportions of 30 to 99 mol. % and the comonomer component 2) in
proportions of 70 to 1 mol. %. A copolymer a.sub.1) which contains
the comonomer component 1) in proportions of 40 to 90 mol. % and
the comonomer component 2) in proportions of 60 to 10 mol. % has
been found particularly advantageous in this connection.
[0045] The comonomer component 1) can preferably be an acrylic acid
or a salt thereof and the comonomer component 2) in the case where
p=0 or 1 a modification which contains a vinyl or allyl group and
as the residue R.sub.1 a polyether.
[0046] Further, in the context of the present invention, it can be
regarded as advantageous if the comonomer component 1) derives from
the group acrylic acid, methacrylic acid, crotonic acid,
isocrotonic acid, allylsulphonic acid, vinylsulphonic acid and
suitable salts thereof and alkyl or hydroxyalkyl esters
thereof.
[0047] In addition, the copolymer a.sub.1) can have additional
structural groups in copolymerized form, which is also taken into
account by the present invention. In this case, the additional
structural groups may be styrenes, acrylamides and/or hydrophobic
compounds, ester structural units, polypropylene oxide and
polypropylene oxide/polyethylene oxide units being particularly
preferred. The copolymer a.sub.1) should contain the said
additional structural groups in proportions up to 5 mol. %,
preferably from 0.05 to 3.0 mol. % and in particular from 0.1 to
1.0 mol. %.
[0048] In addition, it is advantageous if the formula (I) stands
for a polyether containing allyl or vinyl groups.
[0049] With regard to the carboxylate ester modifications a.sub.2)
and the possible forms thereof, reference is in particular made to
EP 0 753 488 B1, the content thereof with regard to the dispersants
described in that document being an integral part of the present
disclosure.
[0050] Concerning the polycarboxylate ester a.sub.2) as preferred
comb polymer, the present invention specifies that this ester
a.sub.2) is a polymer which can be prepared by polymerization of a
monomer mixture (I) containing, as the main component, a
representative of the carboxylic acid monomer type. An important
aspect of component a.sub.2) according to the present invention has
to be seen in the anti-foaming and/or defoaming and/or surface
active properties of such polycarboxylate ester types. This is why
the formulation according to the present invention also comprises a
combination of an antifoaming/surface active agent with dispersing
properties as component a) and the polycondensate component b). In
a more preferred embodiment the monomer mixture (I) contains an
(alkoxy)polyalkylene glycol mono(meth)acrylate monomer (a) of the
general formula (II)
##STR00004##
in which R.sup.1 represents a hydrogen atom or a CH.sub.3 group,
R.sup.2O represents one representative or a mixture of at least two
oxyalkylene groups having 2 to 4 carbon atoms, R.sup.3 represents a
hydrogen atom or an alkyl group having 1 to 5 carbon atoms and m
represents a number between 1 and 250 and represents the average
number of moles of the oxyalkylene group added, additionally, as
monomer (b), a (meth)acrylic acid of the general formula (III),
##STR00005##
[0051] in which R.sup.4 represents a hydrogen atom or a CH.sub.3
group and M.sup.1 represents a hydrogen atom, a monovalent metal
atom, a divalent metal atom, an ammonium group or an organic amine
group, and optionally a monomer (c) which is copolymerized with the
monomers (a) and (b). The monomer (a) can be present in an amount
of from 5 to 98 wt. %, the monomer (b) in a proportion of from 2 to
95 wt. % and the monomer (c) in a proportion up to 50 wt. % in the
monomer mixture (I), wherein the respective proportions of the
monomers (a), (b) and (c) add up to 100 wt. %.
[0052] As typical representatives of the monomer (a),
hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate,
polyethylene glycol mono(meth)acrylate, polypropylene glycol
mono(meth)acrylate, polybutylene glycol mono(meth)acrylate,
polyethylene glycol polypropylene glycol mono(meth)acrylate,
polyethylene glycol polybutylene glycol mono(meth)acrylate,
polypropylene glycol polybutylene glycol mono(meth)acrylate,
polyethylene glycol polypropylene glycol polybutylene glycol
mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate,
methoxypolypropylene glycol mono(meth)acrylate, methoxypolybutylene
glycol mono(meth)acrylate, methoxypolyethylene glycol polypropylene
glycol mono(meth)acrylate, methoxypolyethylene glycol polybutylene
glycol mono(meth)acrylate, methoxypolypropylene glycol polybutylene
glycol mono(meth)acrylate, methoxypolyethylene glycol polypropylene
glycol polybutylene glycol mono(meth)acrylate, ethoxypolyethylene
glycol mono(meth)acrylate, ethoxypolypropylene glycol
mono(meth)acrylate, ethoxypolybutylene glycol mono(meth)acrylate,
ethoxypolyethylene glycol polypropylene glycol mono(meth)acrylate,
ethoxypolyethylene glycol polybutylene glycol mono(meth)acrylate,
ethoxypolypropylene glycol polybutylene glycol mono(meth)acrylate,
ethoxypolyethylene glycol polypropylene glycol polybutylene glycol
mono(meth)acrylate or mixtures thereof are possible.
[0053] For the monomer (b), representatives of the group consisting
of acrylic acid, methacrylic acid, monovalent metal salts, divalent
metal salts, ammonium salts and organic amine salts thereof and
mixtures of at least two of the said representatives are to be
regarded as preferred.
[0054] As regards the monomer (c), the formulation according to the
invention should contain at least one representative of the esters
of an aliphatic alcohol with 1 to 20 carbon atoms with an
unsaturated carboxylic acid. As the unsaturated carboxylic acid, in
particular maleic acid, fumaric acid, citraconic acid (meth)acrylic
acid or monovalent metal salts, divalent metal salts, ammonium
salts or organic amine salts thereof are especially suitable.
Monoesters or diesters of unsaturated dicarboxylic acids such as
maleic acid, fumaric acid or citraconic acid with aliphatic
C.sub.1-C.sub.20 alcohols, C.sub.2-C.sub.4 glycols or with
(alkoxy)polyalkylene glycols are preferred representatives of
monomer (c) according to the present invention.
1.2 Copolymer a.sub.2:
[0055] In the context of the present invention, the component
a.sub.2) can be a copolymer which is made up of at least one of the
following monomers: [0056] A) an ethylenically unsaturated monomer,
containing a hydrolysable residue [0057] B) an ethylenically
unsaturated monomer with at least one C.sub.2-C.sub.4 oxyalkylene
side group with a chain length from 1 to 30 units; [0058] C) an
ethylenically unsaturated monomer with at least one C.sub.2-C.sub.4
oxyalkylene side group with a chain length from 31 to 350
units.
[0059] In a preferred embodiment of the present invention
components B) and C) are simultaneously represented in the
copolymer a.sub.2) of the claimed formulation.
[0060] In this copolymer modification, built up of at least one of
the monomers A), B) and C), according to the invention the
ethylenically unsaturated monomer of the component A) can be at
least one anhydride or imide and/or at least one maleic anhydride
or maleimide. The ethylenically unsaturated monomer of the
component A) can however also include an acrylate ester with an
ester functionality which contains the hydrolysable residue. In
this case, it should be regarded as preferred if the ester
functionality is at least one hydroxypropyl or hydroxyethyl
radical.
[0061] In a further embodiment the copolymer a.sub.2) can however
comprise more than one ethylenically unsaturated monomer with a
hydrolysable radical. Here it is in particular recommended that the
ethylenically unsaturated monomer of the component A) as a residue
has at least more than one representative of the ethylenically
unsaturated monomers, at least one representative of a hydrolysable
radical or a mixture of both. In this connection, the hydrolysable
radical should have at least one C.sub.2-C.sub.20 alcohol
functionality. The present invention also includes the possibility
that the hydrolysable residue is at least one C.sub.1-C.sub.20
alkyl ester, one C.sub.1-C.sub.20 aminoalkyl ester, one
C.sub.2-C.sub.20 alcohol, one C.sub.2-C.sub.20 amino alcohol or one
amide.
[0062] The present invention further comprises that at least one
ethylenically unsaturated monomer of the component B) or C) has a
C.sub.2-C.sub.8 alkyl ether group. In this case, the ethylenically
unsaturated monomer can have a vinyl, allyl or (methyl)allyl ether
residue or else be derived from an unsaturated C.sub.2-C.sub.8
alcohol. In the last-named case of the unsaturated C.sub.2-C.sub.8
alcohol, at least vinyl alcohol, (meth)allyl alcohol, isoprenol or
methylbutenol are especially preferred possibilities as
representatives.
[0063] The ethylenically unsaturated monomer side groups of the
component B) or C) can however also contain at least one C.sub.4
oxyalkylene unit.
[0064] Overall, in connection with the modifications just
described, concerning the comb polymer a.sub.2) it can be stated
that at least one ethylenically unsaturated monomer of the
components B) or C) can have a C.sub.2-C.sub.8 carboxylate ester,
which in particular is hydrolysable. Further, the present invention
includes a modification wherein the oxyalkyl side groups have at
least one ethylene oxide, one propylene oxide, one polyethylene
oxide, one polypropylene oxide or mixtures thereof.
[0065] Finally, the copolymer a.sub.2) in the component C) can have
at least one nonionic ("uncharged") and/or one non-hydrolysable
monomer residue or mixtures thereof.
1.3 Copolymer a.sub.3:
[0066] In addition to the two modifications just described in
detail with regard to the component a), namely its form as
polycarboxylate ethers and polycarboxylate esters, the present
invention also includes a third modification of the comb polymer
a), which then is a nonionic (uncharged) copolymer a.sub.3). Here,
representatives of the general formula (IV) are preferred,
##STR00006##
wherein Q stands for an ethylenically unsaturated monomer with at
least one hydrolysable residue, G means O, C(O)--O or
O--(CH.sub.2)p-O with p=2 to 8, wherein mixtures of the
modifications of G in one polymer are possible; R.sup.1 and R.sup.2
mutually independently mean at least one C.sub.2-C.sub.8 alkyl;
R.sup.3 comprises (CH.sub.2).sub.c, where c is a whole number
between 2 and 5 and where mixtures of the representatives of
R.sup.3 in the same polymer molecule are possible; R.sup.5 means at
least one representative selected from the series H, a linear or
branched, saturated or unsaturated C.sub.1-C.sub.20 aliphatic
hydrocarbon residue, a C.sub.5-C.sub.8 cycloaliphatic hydrocarbon
residue or a substituted or unsubstituted C.sub.6-C.sub.14 aryl
residue; m=1 to 30, n=31 to 350, w=1 to 40, y=0 to 1 and z=0 to 1,
where the sum (y+z)>0.
[0067] However, the nonionic copolymer a.sub.3) can alternatively
also be a representative of the general formula (V),
##STR00007##
wherein X stands for a hydrolysable residue and R for H or
CH.sub.3, and G, p, R.sup.1, R.sup.2, R.sup.3, R.sup.5, m, n, w, y,
z and (y+z) have the meanings stated under the formula (IV).
[0068] In the case where the structure of the non-ionic copolymer
a.sub.3) corresponds to the formula (V), in a preferred embodiment
the hydrolysable residue can be at least one representative of the
series alkyl ester, aminoalkyl ester, hydroxyalkyl ester,
aminohydroxyalkyl ester or amide.
[0069] As a third alternative as regards the nonionic copolymer
a.sub.3), the present invention specifies at least one
representative of the general formula (VI)
##STR00008##
wherein R.sup.4 means at least one C.sub.1-C.sub.20 alkyl or
C.sub.2-C.sub.20 hydroxyalkyl radical and the radicals G, p, R,
R.sup.1, R.sup.2, R.sup.3, c, R.sup.4, R.sup.5 and m, n, w, y, z
and (y+z) have the meanings stated under the formulae (IV) and
(V).
[0070] It is to be regarded as preferred option that in this
formula (VI), p=4, R.sup.4.dbd.C.sub.2H.sub.4OH or
C.sub.3H.sub.6OH, each of the radicals R.sup.5 represents H,
m=5-30, n=31-250, w=1.5-30,y=0 to 1,z=0 to 1 and (y+z)>0.
[0071] Further it is to be regarded as preferred embodiment that in
the said formulae (IV), (V) and (VI), the molar ratio of w to the
sum (y+z) is 1:1 to 20:1 and preferably 2:1 to 12:1.
[0072] The representative of the third modification of the
copolymer a.sub.3) corresponding to formula (VI) should in
particular be a nonionic polyether-polyester copolymer.
[0073] The terms "nonionic" and "uncharged" are to be understood as
synonyms in this context.
[0074] Irrespective of the component a) and its preferred
representatives a.sub.1), a.sub.2) and/or a.sub.3), respectively
contained in the formulation according to the invention, the
present invention specifies that the formulation contain the
component a) in proportions from 5 to 95% by weight, preferably of
10 to 60% by weight and particularly preferably of 15 to 40% by
weight, based in each case on the total formulation.
1.4 Sulphonated Condensates
[0075] Sulphonic acid group containing s-triazines or
naphthalene-formaldehyde condensates are broadly disclosed by prior
art documents and frequently used as water reducing agents or
plasticizers for cement based systems such as concrete.
[0076] .beta.-naphthalene-sulphonate-formaldehyde condensates
("BNS"), also known as naphthalene-formaldehyde sulphonates ("NFS")
disperse cement particles by an electrostatic repulsion that
results from adsorption processes.
[0077] BNS or NFS is suitable for making cement particles with high
dispersion, low foaming and high range water reducing and thereof
it is possible to save the hydraulic binder such as cements or
calcium sulphite based binders to improve the cement mobility and
workability. BNS is a high range admixture for concrete,
cast-in-place, prefabricating, pump and curing and BNS has a good
adaptability to cements and other hydraulic binders and is not
corrosive to reinforcing bar and non poisonous and pollution-free.
Therefore it has been broadly applied to the construction industry
such as highways, bridges, tunnels, industrial buildings,
prestressing force components and high range concretes.
[0078] Usually, such condensates suitable as plasticizer or
dispersants are prepared by the reaction of aromatic sulphonic
acids like naphthalene sulphonic acid with formaldehyde under
ambient pressure and under temperatures up to 100.degree. C.
[0079] The preparation and use of BNS is well known state of the
art and disclosed for example in EP 0 214 412 A1 and DE-PS 2 007
603.
[0080] The effect and properties of BNS can be modified by changing
the molar ratio between formaldehyde and the naphthalene component
that usually is from 0.7 up to 3.5. The ratio between formaldehyde
and the sulphonated naphthalene component preferably is from 0.8 to
3.5 to 1.
[0081] BNS condensates are added to the hydraulic binder containing
composition in amounts from 0.01 up to 6.0 wt. %.
[0082] Melamine-sulphonate-formaldehyde-condensates ("MFS") are
broadly used as flow improving agents in the processing of
hydraulic binder containing compositions such as dry mortar
mixtures, pourable mortars and other cement bonded construction
materials.
[0083] Melamine is used in this connection as representative of the
s-triazine which is why these improving agents are known as MFS
resins. They cause as well as the already mentioned BNS
representatives a strong liquefying effect of the construction
chemicals mixture without any undesired side effects occurring in
the processing or in the functional properties of the hardened
building material.
[0084] It is well known that commercially available flow improving
agents based on melamine-formaldehyde-sulphite such as products of
the Melment series of BASF Construction Polymers GmbH, Germany,
cause an excellent liquefying effect even of low dosages of about
0.3 to 1.2 wt. %, relative to the weight of the hydraulic binder
such as cement.
[0085] The liquefying effect of MFS products is achieved without
lowering the surface tension of the water and binder system which
usually is the case for the example with BNS products or flow
improving agents with a surfactant-like polymers structure. The
advantage of MFS resins is presumed to be due to the fact that no
air avoids are introduced in to mortar during remixing process and
the mortar density and strengths are not adversely effected after
hardening.
[0086] In addition MFS resins provide the fresh mortar mixture with
a good cohesive strength so that even when the flow properties are
extreme separation phenomena within the construction composition do
not occur. This phenomenon, also called as "segregation", is feared
especially in the production of self-flowing smoothing compositions
which especially is the case with self-leveling screeds since its
leads to a non-uniform layer structure of the screed due to
floating of the fine material and sedimentation of the coarse
grain.
[0087] As it is for the BNS technology also for MFS there is a
broad prior art. In this connection as representative documents are
mentioned DE 196 09 614 A1, DE 44 11 797 A1, EP 0 059 353 A1 and DE
195 38 821 A1:
[0088] DE 196 09 614 A1 discloses a water soluble polycondensation
product based on an amino-s-triazine and its use as plasticizer in
aqueous binder containing suspensions based on cement, lime and
gypsum. These polycondensates are capable in two condensation steps
whereby in a pre-condensation step the amino-s-triazine, the
formaldehyde component and the sulphite are condensated at a molar
ratio of 1 to 0.5:5.0 to 0.1:1.5. Melamine is a preferred
representative of amino-s-triazines. Further suitable
representatives are amino plast former selected from the group
urea, thiourea, dicyandiamide or guanidine and guanidine salts.
[0089] According to DE 44 11 797 A1 sulfanilic acid containing
condensation products based on amino-s-triazines that show at least
two amino groups are prepared by using formaldehyde. The sulfanilic
acid is used in amounts of from 1.0 to 1.6 mol per mol
amino-s-triazine and neutralized in aqueous solution with an
alkaline metal hydroxide or in earth alkaline metal hydroxide. In
an additional step the formaldehyde is added in amounts of from 3.0
to 4.0 mol per mol amino-s-triazine at a pH value between 5.0 to
7.0 and at temperatures between 50 and 90.degree. C. The final
viscosity of the solution shall be between 10 and 60 cSt at
80.degree. C.
[0090] According to EP 0 059 353 A1 highly concentrated and low
viscose aqueous solutions of melamine/aldehyde resins are capable
by reacting melamine and an aldehyde in an alkaline medium in a
first step with a component selected from the group comprising
alkali sulphate, earth alkali sulphate or (earth) alkali sulphonate
or other suitable amino compounds to a pre-condensate. This mixture
in an additional process step is reacted with another amino
compound such as amino acids or amino carbonic acids and finally
the resin solution is brought to an alkaline pH value.
[0091] DE 195 38 821 A1 discloses a condensate based on an
amino-s-triazine with at least two amino groups and formaldehyde
and a high content of sulphonic acid groups and a low content of
formate. Such products can be prepared according to this document
by reacting the amino-s-triazine, formaldehyde and a sulphite at a
molar ratio of 1:3.0:6.0:1.51:2.0 in an aqueous solution and at a
temperature between 60 and 90.degree. C. and a pH value between 9.0
and 13.0 until the sulphite is no longer present. In an additional
step the condensation process is conducted at a pH value between
3.0 and 6.5 and at temperatures between 60 and 80.degree. C. until
the condensation product at 80.degree. C. shows a viscosity between
5 and 50 mm.sup.2/s. Finally, the condensation product is to be
brought to a pH value between 7.5 and 12.0 or treated thermally by
a pH.gtoreq.10.0 and a temperature between 60 and 100.degree.
C.
[0092] According to the present invention the BNS and/or MFS
dispersant is used in amounts of from 0.01 to 10 wt. % and
preferably 0.1 to 5 wt. %, related to the hydraulic binder
component. The molar ratio of the sulphonic group and related to
the melamine component is of from 1.0 to 2.0 and the molar ratio of
the formaldehyde related to the melamine component is from 2.5 to
5.0. Preferably the molar ratio melamine to sulphonic acid to
formaldehyde is 1:1.1:1.5:3.3:3.6.
[0093] Concerning the BNS component the molar ratio of formaldehyde
to naphthalene sulphonic acid is from 1.3 to 1:3 to 1.
2. Polycondensation Product b)
[0094] As already discussed as state of the art admixtures in the
form of dispersants are added to aqueous slurries or pulverulent
inorganic or organic substances, such as clays, silicate powder,
chalk, carbon black, crushed rock and hydraulic binders, for
improving their processability, i.e. kneadability, spreadability,
sprayability, pumpability or flowability. Such admixtures are
capable of preventing the formation of solid agglomerates and of
dispersing the particles already present and those newly formed by
hydration and in this way improving the processability. This effect
is utilized in particular in a targeted manner in the preparation
of construction material mixtures which contain hydraulic binders,
such as cement, lime, gypsum, hemihydrate or anhydrite.
[0095] In order to convert these construction material mixtures
based on said binders, into a ready-to-use, processable form, as a
rule substantially more mixing water is required than would be
necessary for the subsequent hydration or hardening process. The
proportion of voids which is formed in the concrete body by the
excess, subsequently evaporating water leads to significantly
poorer mechanical strengths and resistances.
[0096] In order to reduce this excess proportion of water at a
predetermined processing consistency and/or to improve the
processability at a predetermined water/binder ratio, admixtures
are used which are generally referred to as water-reducing agents
or plasticizers. In practice, in particular polycondensates and
copolymers are used as such agents.
[0097] WO 2006/042709 describes polycondensates based on an
aromatic or heteroaromatic compound (A) having 5 to 10 C atoms or
heteroatoms, having at least one oxyethylene or oxypropylene
radical, and an aldehyde (C) selected from the group consisting of
formaldehyde, glyoxylic acid and benzaldehyde or mixtures thereof,
which result in an improved plasticizing effect of inorganic binder
suspensions compared with the conventionally used polycondensates
and maintain this effect over a longer period ("slump retention").
In a particular embodiment, these may also be phosphated
polycondensates. The phosphated monomers used are, however,
relatively expensive since they have to be separately prepared and
purified.
[0098] Alternatively, there has been developed an economical
dispersant, based on a phosphated polycondensate, for hydraulic
binders, which dispersant is particularly suitable as a
plasticizer/water-reducing agent for concrete and can be prepared
in a simple manner and at low costs (non-disclosed prior art filed
provisional as EP 081659155.3 in August 2008).
[0099] This object is achieved by a polycondensate containing
[0100] (I) at least one structural unit having an aromatic or
heteroaromatic and a polyether side chain and [0101] (II) at least
one phosphated structural unit having an aromatic or heteroaromatic
and [0102] (III) at least one structural unit having an aromatic or
heteroaromatic, [0103] structural unit (II) and structural unit
(III) differing exclusively in that the OP(OH).sub.2 group of the
structural unit (II) is replaced by H in structural unit (III), and
structural unit (III) is not the same as structural unit (I).
[0104] The structural units (I), (II) and (III) of component b) of
the claimed formulation can be described in more detail by the
following general formulae
##STR00009##
where [0105] A are identical or different and are represented by a
substituted or unsubstituted aromatic or heteroaromatic compound
having 5 to 10 C atoms where [0106] B are identical or different
and are represented by N, NH or O where [0107] n=2, if B=N and n=1,
if B=NH or O where [0108] R.sup.1 and R.sup.2, independently of one
another, are identical or different and are represented by a
branched or straight-chain C.sub.1- to C.sub.10-alkyl radical,
C.sub.5- to C.sub.8-cycloalkyl radical, aryl radical, heteroaryl
radical or H where [0109] a are identical or different and are
represented by an integer from 1 to 300 where [0110] X are
identical or different and are represented by a branched or
straight-chain C.sub.1- to C.sub.10-alkyl radical, C.sub.5- to
C.sub.8-cycloalkyl radical, aryl radical, heteroaryl radical or
H,
##STR00010##
[0110] for (VIII) and (IX) in each case: where [0111] D are
identical or different and are represented by a substituted or
unsubstituted heteroaromatic compound having 5 to 10 C atoms where
[0112] E are identical or different and are represented by N, NH or
O where [0113] m=2if E=N and m=1 if E=NH or O where [0114] R.sup.3
and R.sup.4, independently of one another, are identical or
different and are represented by a branched or straight-chain
C.sub.1- to C.sub.10-alkyl radical, C.sub.5- to C.sub.8-cycloalkyl
radical, aryl radical, heteroaryl radical or H where [0115] b are
identical or different and are represented by an integer from 0 to
300, where [0116] M is independently of one another an alkaline
metal ion, alkaline earth metal ion, ammonium ion, organic ammonium
ion and/or H, [0117] c is 1 or in the case of alkaline earth metal
ions 1/2.
[0118] In a preferred embodiment, the polycondensate contains a
further structural unit (X) which is represented by the following
formula
##STR00011##
where [0119] Y, independently of one another, are identical or
different and are represented by (VII), (VIII), (IX) or further
constituents of the polycondensate where [0120] R.sup.5 are
identical or different and are represented by H, CH.sub.3,
COOM.sub.c or a substituted or unsubstituted aromatic or
heteroaromatic compound having 5 to 10 C atoms where [0121] R.sup.6
are identical or different and are represented by H, CH.sub.3,
COOM.sub.c or a substituted or unsubstituted aromatic or
heteroaromatic compound having 5 to 10 C atoms.
[0122] Here, R.sup.5 and R.sup.6 in structural unit (X),
independently of one another, are preferably represented by H,
COOM.sub.c and/or methyl.
[0123] The molar ratio of the structural units (VII), (VII), (IX)
and (X) of the phosphated polycondensate according to the invention
can be varied within wide ranges. This has proved to be expedient
if the molar ratio of the structural units [(VII)+(VII)+(IX)]:(X)
is 1:0.8 to 3, preferably 1:0.9 to 2 and particularly preferably
1:0.95 to 1.2.
[0124] The molar ratio of the structural units (VII):[(VIII)+(IX)]
in component b) is usually 1:15 to 15:1, preferably 1:10 to 10:1
and more preferably 1:5 to 3:1.
[0125] In a preferred embodiment, the molar ratio of the structural
units (VIII):(IX) is adjusted to 1:0.005 to 1:10, preferably 1:0.01
to 1:1, in particular 1:0.01 to 1:0.2 and more preferably 1:0.01 to
1:0.1.
[0126] The groups A and D in the structural units (VII), (VIII) and
(IX) of the polycondensate are generally represented by phenyl,
2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl,
3-methoxyphenyl, 4-methoxyphenyl, naphthyl, 2-hydroxynaphthyl,
4-hydroxynaphthyl, 2-methoxynaphthyl, 4-methoxynaphthyl, preferably
phenyl, it being possible for A and D to be chosen independently of
one another and also in each case to consist of a mixture of said
compounds. The groups B and E, independently of one another, are
preferably represented by O.
[0127] The radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can be
chosen independently of one another and are preferably represented
by H, methyl, ethyl or phenyl, particularly preferably by H or
methyl and especially preferably by H.
[0128] A in structural unit (VII) is preferably represented by an
integer from 5 to 280, in particular 10 to 160 and particularly
preferably 12 to 120 and b in structural units (VIII) and (IX) by
an integer from 0 to 10, preferably 1 to 7 and particularly
preferably 1 to 5. The respective radicals, the length of which is
defined by a and b, respectively, may consist here of uniform
building blocks, but a mixture of different building blocks may
also be expedient. Furthermore, the radicals of the structural
units (VII) or (VIII) and (IX), independently of one another, may
each have the same chain length, a and b each being represented by
a number. As a rule, however, it will be expedient if mixtures
having different chain lengths are present in each case so that the
radicals of the structural units in the polycondensate have
different numerical values for a and independently for b.
[0129] Frequently, the phosphated polycondensate according to the
present invention has a weight average molecular weight of 4000
g/mol to 150 000 g/mol, preferably 10 000 to 100 000 g/mol and
particularly preferably 20 000 to 75 000 g/mol.
[0130] As a rule, the phosphated polycondensate according to the
invention is present in the claimed formulation as aqueous solution
which contains 2 to 90% by weight of water and 98 to 10% by weight
of dissolved dry matter, preferably 40 to 80% by weight of water
and 60 to 20% by weight of dissolved dry matter, and more
preferably 45 to 75% by weight of water and 55 to 25% by weight of
dissolved dry matter. The dry matter then substantially comprises
the anhydrous phosphated polycondensate, where further components,
such as antifoams and other auxiliaries, can advantageously also be
present.
[0131] In a further embodiment the polycondensate b) is present in
the formulation in proportions of 5 to 100% by weight, preferably
of 10 to 60% by weight and particularly preferably of 15 to 40% by
weight, based in each case on the total formulation.
[0132] In a particular embodiment, the invention furthermore
envisages a sodium, potassium, ammonium and/or calcium salt and
preferably a sodium and calcium salt, of the phosphated
polycondensate.
[0133] The present invention also relates to a process for the
preparation of a phosphated polycondensate, it being regarded as
essential that the polycondensation and the phosphation be carried
out in a reaction mixture. This is to be understood as meaning that
the phosphated component formed in the reaction solution needs
neither be purified nor isolated. The phosphation can be carried
out before, during or after the polycondensation. It is to be
regarded as being preferred here to carry out both the phosphation
and the polycondensation in the same reaction vessel.
[0134] In a preferred embodiment, the reaction mixture with regard
to the polycondensate component b) contains at least [0135] (Ia) a
monomer having a polyether side chain and an aromatic or
heteroaromatic, [0136] (IIIa) a monomer having an aromatic or
heteroaromatic unit, (IIIa) being partially phosphated during the
reaction and forming the monomer (IIa) and/or, in the
polycondensate, the structural unit (IIa), [0137] (IVa) a monomer
having an aldehyde group and a phosphating agent, [0138] structural
unit (IIIa) not being the same as structural unit (Ia).
[0139] The monomers (Ia), (IIa), (IIIa) and (IVa) and, in the
polycondensate, the structural unit (IIa) are preferably
represented by the following general formulae:
--Monomer (Ia):
##STR00012##
[0140] where [0141] A are identical or different and are
represented by a substituted or unsubstituted aromatic or
heteroaromatic compound having 5 to 10 C atoms where [0142] B are
identical or different and are represented by N, NH or O where
[0143] n=2 if B=N and n=1 if B=NH or O where [0144] R.sup.1 and
R.sup.2, independently of one another, are identical or different
and are represented by a branched or straight-chain C.sub.1- to
C.sub.10-alkyl radical, C.sub.5- to C.sub.8-cycloalkyl radical,
aryl radical, heteroaryl radical or H where [0145] a are identical
or different and are represented by an integer from 1 to 300 where
[0146] X are identical or different and are represented by a
branched or straight-chain C.sub.1- to C.sub.10-alkyl radical,
C.sub.5- to C.sub.8-cycloalkyl radical, aryl radical, heteroaryl
radical or H;
--Monomer (IIa):
##STR00013##
[0147]--Monomer (IIIa):
##STR00014##
[0148] for formulae (VIIIa) and (IXa) in each case: where [0149] D
are identical or different and are represented by a substituted or
unsubstituted heteroaromatic compound having 5 to 10 C atoms where
[0150] E are identical or different and are represented by N, NH or
O where [0151] m=2 if E=N and m=1 if E=NH or O where [0152] R.sup.3
and R.sup.4, independently of one another, are identical or
different and are represented by a branched or straight-chain
C.sub.1- to C.sub.10-alkyl radical, C.sub.5- to C.sub.8-cycloalkyl
radical, aryl radical, heteroaryl radical or H where [0153] b are
identical or different and are represented by an integer from 0 to
300;
--Monomer (IVa):
##STR00015##
[0154] where [0155] R.sup.7 are identical or different and are
represented by H, CH.sub.3, COOH and/or a substituted or
unsubstituted aromatic or heteroaromatic compound having 5 to 10 C
atoms where [0156] R.sup.8 are identical or different and are
represented by H, CH.sub.3, COOH and/or a substituted or
unsubstituted aromatic or heteroaromatic compound having 5 to 10 C
atoms.
[0157] The present invention provides different variants of the
reaction procedure. One possibility consists in first reacting the
monomer (IIIa) with a phosphating agent and subjecting the monomer
(IIa) thus obtained to polycondensation with the monomers (Ia),
(IIIa) and (IVa). The monomer (IIIa) may originate here from an
incomplete reaction during the phosphation reaction or can be
deliberately added to the reaction mixture after the phosphation
reaction.
[0158] However, it is also possible to subject the monomers (Ia),
(IIIa) and (IVa) to a polycondensation and then to react the
polycondensate obtained with a phosphating agent. In a further
embodiment, the monomers (Ia), (IIIa) and (IVa) and the phosphating
agent are reacted simultaneously.
[0159] In particular, polyphosphoric acid and/or phosphorous
pentoxide have proved suitable here as phosphating agents.
[0160] As a rule, the polycondensation is carried out in the
presence of an acidic catalyst, this preferably being sulphuric
acid, methanesulphonic acid, para-toluenesulphonic acid or mixtures
thereof.
[0161] The polycondensation and the phosphation are advantageously
carried out at a temperature between 20 and 140.degree. C. and a
pressure between 1 and 10 bar. In particular, a temperature range
between 80 and 110.degree. C. has proved to be expedient. The
duration of the reaction may be between 0.1 and 24 hours, depending
on temperature, the chemical nature of the monomers used and the
desired degree of crosslinking. Once the desired degree of
crosslinking has been reached, which can also be determined, for
example, by measurement of the viscosity of the reaction mixture,
the reaction mixture is cooled.
[0162] According to a particular embodiment, the reaction mixture
is subjected to a thermal aftertreatment at a pH between 8 and 13
and a temperature between 60 and 130.degree. C. after the end of
the condensation and phosphation reaction. As a result of the
thermal aftertreatment, which advantageously lasts for between 5
minutes and 5 hours, it is possible substantially to reduce the
aldehyde content, in particular the formaldehyde content, in the
reaction solution.
[0163] In a further particular embodiment, the present invention
envisages subjecting the reaction mixture to a vacuum
aftertreatment at pressures between 10 and 900 mbar after the end
of the condensation and phosphation reaction, for reducing the
aldehyde content. Furthermore, however, other methods known to the
person skilled in the art for reducing the formaldehyde content may
also be used. An example is the addition of small amounts of sodium
bisulphite, ethylene urea and/or polyethylenimine.
[0164] The phosphated polycondensates obtained by these processes
can be used directly as component b). In order to obtain a better
shelf life and better product properties, it is advantageous to
treat the reaction solutions with basic compounds. It is therefore
to be regarded as being preferred to react the reaction mixture
after the end of the reaction with a basic sodium, potassium,
ammonium or calcium compound. Sodium hydroxide, potassium
hydroxide, ammonium hydroxide or calcium hydroxide has proved to be
particularly expedient here, it being regarded as being preferred
to neutralize the reaction mixture. However, other alkali metal and
alkaline earth metal salts and salts of organic amine are suitable
as salts of the phosphated polycondensates.
[0165] Furthermore, however, the present invention also provides
the preparation of mixed salts of the phosphated polycondensates.
These can expediently be prepared by reacting the polycondensates
with at least two basic compounds.
[0166] Thus, by a targeted choice of suitable alkali metal and/or
alkaline earth metal hydroxides, it is possible by neutralization
to prepare salts of the polycondensates according to the invention,
with which the duration of the processability of aqueous
suspensions of inorganic binders and in particular of concrete can
be influenced. While a reduction in the processability over time is
observable in the case of the sodium salt, a complete reversal of
this behavior takes place in the case of the calcium salt of the
identical polymer, a smaller water reduction (smaller slump)
occurring at the beginning and increasing with time. As a result of
this, sodium salts of the phosphated polycondensates lead over time
to a decrease in the processability of the binder-containing
material, such as, for example, concrete, mortar or gypsum
slurries, whereas the corresponding calcium salts lead with time to
improved processability. By suitable choice of the amount of sodium
and calcium salts of the phosphated polycondensates used, the
development of the processability of binder-containing materials
can thus be controlled as a function of time. Expediently, the
corresponding phosphated polycondensates, which consist of sodium
and calcium salts, are prepared by reaction with a mixture of basic
calcium and sodium compounds, in particular calcium hydroxide and
sodium hydroxide.
[0167] According to the present invention, the catalyst used can
also be separated off. This can expediently be effected via the
salt formed during the neutralization. If sulphuric acid is used as
a catalyst and the reaction solution is treated with calcium
hydroxide, the calcium sulphate formed can be separated off, for
example, in a simple manner by filtration.
[0168] Furthermore, by adjusting the pH of the reaction solution to
1.0 to 4.0, in particular 1.5 to 2.0, the phosphated polycondensate
can be separated from the aqueous salt solution by phase separation
and can be isolated. The phosphated polycondensate can then be
taken up in the desired amount of water.
[0169] However, other methods known to the person skilled in the
art, such as dialysis, ultrafiltration or the use of an ion
exchanger, are also suitable for separating off the catalyst.
[0170] Surprisingly, with a phosphated polycondensate according to
the invention as component b) of the formulation an improved
efficiency was found in comparison with the polycondensates known
in the prior art. As additional favorable effect a significantly
decreased retardation of the setting and hardening of the various
construction compositions compared to other dispersants is to be
observed, independently from the dosage of component b). This
effect of the polycondensate component b) as well as an expedient
influence on the pore structure surprisingly can be observed also
with the formulation according to the present invention.
[0171] Additionally, it has proved particularly advantageous that
[the phosphated polycondensates according to the invention] can be
prepared by a very economical process, no further purification of
intermediates being required. In particular, no wastes which have
to be disposed of form in the process according to the invention.
Thus, the claimed process also constitutes further progress
compared with the prior art from environmental points of view. The
reaction mixture obtained can be put directly to the intended
formulation optionally after treatment with basic compounds.
3. Additional Components and Aspects
[0172] In a specific embodiment the claimed formulation contains
additionally to the components a) and b) at least one antifoaming
agent c) and/or a component d) having a surface-active effect, the
components c) and d) being structurally different from one
another.
[0173] The antifoaming agent c) is preferably selected from the
group consisting of a mineral oil, a vegetable oil, a silicon oil,
a silicon containing emulsion, a fatty acid, a fatty acid ester, an
organic modified polysiloxane, a borate ester, an alkoxylate, a
polyoxialkylene copolymer, ethylene oxide (EO)-propylene oxide (PO)
block polymer, acetylenic diols having defoaming properties and a
phosphoric ester having the formula P(O)
(O--R.sub.8).sub.3-x(O--R.sub.9).sub.x wherein P represents
phosphorus, O represents oxygen and R.sub.8 and R.sub.9 are
independently a C.sub.2-C.sub.20 alkyl or an aryl group and x=0, 1,
2, whereby an alkyl group with C.sub.2-C.sub.8 is preferred.
[0174] Preferably said antifoaming agent c) comprises
tri-alkylphosphate and more preferably triiso-butylphosphate, a
polyoxypropylen copolymer and a glycerol/alcohol acetate.
[0175] The invention additionally comprises an admixture wherein
said antifoaming agent c) comprises a mixtures of a
tri-alkylphosphate and a polyoxypropylene copolymer.
[0176] The second optional component of the formulation, namely the
surfactant, is preferably selected from the group consisting of a
ethylene oxide/propylene oxide (EO/PO) block copolymer, a
styrene/maleic acid copolymer, a fatty alcohol alkoxylate, an
alcohol ethoxylate R.sub.10-(EO)--H with R.sub.10 being an
aliphatic hydrocarbon group having from 1 to 25 carbon atoms,
acetylenic diols, monoalkylpolyalkylenes, ethoxylated nonylphenols,
alkylsulfates, alkylethersulfats, alkylethersulfonates, alkyl ether
carboxylates.
[0177] More preferably surfactant component d) comprises an alcohol
having a polyalkylene group consisting of a carbon chain length of
2 to 20 carbon atoms, with a specific carbon chain length of
C.sub.3-C.sub.12.
[0178] Advantageously the formulation according to the invention
comprises an aqueous composition that contains the antifoaming
agent component c) in free form or attached to the dispersing
components a), and/or b). If the antifoaming agent is attached to
the dispersing components it can be physically or chemically
attached, and the chemically attached in this case in polymerized
and/or grafted form being preferred. When chemically attached, the
antifoaming agent c) also can be considered as a third co-monomer
of the copolymeric dispersing components a.sub.1), a.sub.2),
a.sub.3). In its free form the antifoaming agent c) is a blend
component of the formulation. Thus, antifoaming agent component c)
is either physically and/or chemically attached to the dispersing
components a.sub.1), a.sub.2) and/or a.sub.3) and/or it is a free
form component and therefore constituent of a blend.
[0179] In a further embodiment the antifoaming component c) is
present in amounts of 0.01 to 10% by weight and/or the
surface-active component d) is present in amounts of 0.01 to 10% by
weight, based in each case on the total weight of the formulation.
According to a preferred embodiment the antifoaming formulation
according to any of Claims 52 to 61, characterized in that the
antifoam c) and/or the surface-active component d), independently
of one another, are present in each case in an amount of 0.01 to 5%
by weight, based in each case on the total weight of the
formulation. The present invention additionally comprises an
embodiment whereby the formulation in addition to the components a)
and b) and optionally c) and/or d), contains at least one further
compound e) selected from the group consisting of a polymer having
a low charge, a neutral polymer or polyvinyl alcohol. This
component e) and particularly its specific role in systems
containing calcium sulfate as hydraulic binder has been teached in
the unpublished provisional European Patent application EP
08171022.0. The component e) plays a major role in gypsum
composition with certain clay contents.
[0180] In the use of clay-containing forms of gypsum, and
particularly natural gypsum, it can be observed that considerable
quantities of the dispersant (fluidizing agent) used are absorbed
or adsorbed by the clay mineral, as a result of which they are no
longer available for the fluidization of the gypsum hemihydrate in
the gypsum mixture.
[0181] To solve this problem, attempts were made to use so-called
sacrificial substances, which in competition with the dispersant
bind more strongly to the surface of the clay particles and in this
way either mask these so that they are no longer accessible to the
dispersant, or largely flocculate the clay particles.
[0182] According to the mentioned European application there has
been provided a formulation based on a branched comb polymer with
ethylene oxide (EO) units in the side-chains for the dispersion of
clay-containing gypsum mixtures. These formulations are capable of
masking clay minerals such as are in particular contained in
natural gypsum to a sufficient extent that the surfaces thereof are
no longer available for the adsorption of dispersants. They have no
adverse effect on the fluidization and consistency of the wet and
unhardened gypsum mixture and they are stable to the temperatures
used in the drying of the gypsum products, so that no odour
problems arise.
[0183] In this connection and with regard to clay-containing gypsum
compositions a copolymer component a.sub.2) is to prefer that is
based on a hydrolysable monomer A having an active binding site for
at least one component of the clay-containing gypsum mixture.
[0184] With component e) according to the present invention, the
surface of the clay particles can be more effectively coated
through the bunching of flexible EO side-chains on a polymer
backbone or the clay particles can themselves be better flocculated
overall. Because of the lower charge density, the component e) can
adsorb mainly on the clay and not on the binder such as gypsum
hemihydrate.
[0185] Evidently a not insignificant role in the effects is played
by the side-chains of the "sacrificial substance". These must
include EO units; however, the side-chains can also in addition
have polyethylene oxide (PO) units. The same applies for the main
substance contained in the formulation according to the invention,
the comb polymer with dispersant properties; this can contain
either EO or PO units or both in its side-chains. Here the mixed
modifications can also each be implemented in at least one, that is
the same, side-chain.
[0186] Overall, it can be stated that from the chemical point of
view the component e) optionally contained in the formulation
according to the invention as a sacrificial substance to some
extent differs only insignificantly from the dispersants a)
commonly used in clay-containing gypsums, since it also consists
inter alia of polycarboxylate ethers. The difference consists
however in the charge state, since only representatives with low or
neutral charge are possible as the sacrificial substance. In other
words, the manufacture of gypsum products in particular can also be
effected with the aid of dispersants which inter alia consist of
copolymer mixtures wherein the low-charge or neutral polymer
fractions predominantly mask the clay minerals and thus enable the
remaining dispersant content to exert its actual fluidizing agent
action.
[0187] The advantageous action of the formulation according to the
present invention and mainly based on component e) is displayed in
essentially all clay-containing gypsum mixtures. However, the
positive action is especially pronounced in gypsum systems which
contain at least one representative of the series calcium sulphate,
calcium sulphate semihydrate or calcium sulphate hemihydrate,
anhydrite and gypsum.
[0188] The clay fraction in the gypsum mixture should preferably be
swellable and in particular water-swellable and derive from the
series of the smectites, montmorillonites, bentonites,
vermiculites, hectorites or from the series of the kaolins,
feldspars and micas such as for example illite and mixtures
thereof.
[0189] Essentially, care should be taken that the clay contents in
the gypsum mixtures do not exceed certain limits. For this reason,
the present invention recommends clay contents in the gypsum
mixtures of .ltoreq.10 wt. %, preferably .ltoreq.6 wt. %,
preferably .ltoreq.4 wt. % and especially preferably between 0.5
and 3 wt. %, each based on the gypsum component.
[0190] For the polymer component e), proportions from 0.01 to 0.40
wt. %, preferably from 0.02 to 0.30 wt. %, preferably from 0.03 to
0.15 wt. % and especially preferably from 0.5 to 0.10 wt. %, each
again based on the gypsum component, are recommended.
[0191] In a further embodiment of the invention the formulation
contains the component e) in amounts of 1 to 50% by weight,
preferably of 5 to 40% by weight and particularly preferably in
amounts of 10 to 30% by weight, based in each case on the total
weight of the formulation.
[0192] In the context of the present invention, the polymer
component e), which reacts with the clay particles in the gypsum
mixture, is of particular significance. In the case of a low-charge
polymer as component e) this should be branched, the side-chain
preferably consisting of a polyether. Polycarboxylate ethers and/or
polycarboxylate esters, preferably with EO side-chains and with a
carboxylate content up to 83 mol. %, and preferably up to 75 mol. %
are to be regarded as especially preferred in this connection.
[0193] As already stated, component a) of the formulation should
advantageously include at least one polycarboxylate derivative
(ether, ester); in particular if this has a low charge content, it
cannot on account of its specific properties adsorb for example
onto gypsum to the necessary extent. For this reason, the generally
known dispersant action of polycarboxylate ethers and esters in
particular does not occur to the necessary extent in this case.
Hence the content of the charge-bearing component is important for
the dispersant action of such representatives. Since the copolymer
components a.sub.1), a.sub.2) and a.sub.3) and, to some extent,
depending on its chemical character, also component e) can compete
with one another as regards the dispersant action, it is
advantageous overall to select the respective contents in the
formulation according to the invention such that the copolymer
component a) can exhibit its dispersant action to the maximum and
the component e) because of its charge properties has as little
dispersant action as possible, but instead is maximally adsorbed on
the clay particles.
[0194] If a low-charge polymer with a polyether side-chain is used
as component e), then this should be made up of at least one
monomer selected from the series polyether monoacrylate, polyether
monomethacrylate, polyether monoallyl ether, polyether monomaleate,
monovinylated polyether or mixtures thereof. In the case of a
polyether, this can be an alkylene oxide polymer with a molecular
weight from 500 to 10 000, preferably from 750 to 7500 and in
particular from 1000 to 5000. As representative alkylene oxide
polymers, those based on an ethylene oxide, propylene oxide,
butylene oxide or mixtures thereof may be mentioned.
[0195] Low-charge polymers which are built up of at least one
monomer selected from the series polypropylene glycol acrylates,
polypropylene glycol methacrylates, polyethylene glycol acrylates,
polyethylene glycol methacrylates, polypropylene glycol monovinyl
ethers, polythylene glycol monovinyl ethers, alkoxy or
aryloxypolyethylene glycol acrylates, alkoxy or aryloxypolyethylene
glycol methacrylates, alkoxy or aryloxy-polyethylene glycol
monovinyl ethers, acrylates, methacrylates and monovinyl ethers of
an oxyethylene and oxypropylene block or randomized copolymer,
polypropylene glycol allyl ether, polyethylene glycol allyl ether,
polyethylene glycol monomaleate, polypropylene glycol monomaleate
and any mixtures thereof have been found especially suitable.
[0196] It can be seen as preferred embodiment that the polymer e)
having a low charge carries a carboxylic acid group, preferably
selected from the series consisting of acrylic acid, methacryl
acid, maleic acid, fumaric acid, itaconic acid or anhydrides
thereof.
[0197] According to the invention, the low-charge polymer can also
bear a carboxylic acid and/or sulphonic acid groups. In this case,
the present invention specifies that the carboxylic acid group is
preferably at least one representative of the series acrylic acid,
methacrylic acid, maleic acid, fumaric acid, itaconic acid or
anhydrides thereof. 2-Acrylamido-2-methylpropanesulphonic acid
(AMPS), vinylsulphonic acid, allyl ether sulphonic acid,
2-sulphoethylmethacrylic acid, styrenesulphonic acid,
methallyl-sulphonic acid, and sodium, potassium and ammonium salts
and any mixtures thereof, are preferred representatives of
compounds which make sulphonic acid groups available. AMPS and
vinylsulphonic acid are to be regarded as especially
preferable.
[0198] In the case of neutral polymers as component e), these
should be made up of neutral monomer building blocks, which are in
particular selected from the series acrylic acid alkyl esters and
methacrylic acid alkyl esters and hydroxyalkyl esters thereof with
up to 5 carbon atoms. Particularly suitable in this case are
hydroxyethyl acrylate and hydroxypropyl acrylate and hydroxyethyl
methacrylate and hydroxypropyl methacrylate. Also possible are
vinyl acetate, N-vinylpyrrolidone, N-vinylcaprolactam, styrene and
methylstyrene.
[0199] In a further embodiment the present invention relates to a
formulation that contains as additional further component f) a
calcium-silicate-hydrate (C-S-H) containing composition.
[0200] It is well known to a skilled person that admixtures for
building material mixtures comprising hydraulic binders typically
also contain hardening accelerators which shorten the setting time
of the hydraulic binder. According to WO 02/070425, calcium
silicate hydrate (C-S-H), in particular present in dispersed
(finely or particularly finely dispersed) form, can be used as such
a hardening accelerator. However, commercially available C-S-H or
corresponding C-S-H dispersions may be regarded only as hardening
accelerators which have little effect.
[0201] By the non-published provisional application EP 08163468.5
of September 2008 a composition acting as a plasticizer and
moreover showing a good performance as a hardening accelerator has
been provided.
[0202] According to the present invention the C-S-H containing
composition is prepareble by reaction of a water-soluble calcium
containing compound with a water-soluble silicate containing
compound, the reaction of the water-soluble calcium containing
compound with the water-soluble silicate containing compound being
carried out in the presence of an aqueous solution preferably
containing a water-soluble copolymer that preferably is a
dispersant for hydraulic binders and selected from at least a
representative of component a) and/or b).
[0203] In principle, only relatively slightly water-soluble
compounds are also suitable in each case as water-soluble calcium
compounds and water-soluble silicate compounds, although readily
water-soluble compounds (which dissolve completely or virtually
completely in water) are preferred in each case. However, it must
be ensured that a reactivity sufficient for the reaction is present
in an aqueous environment with the corresponding reactant (either
water-soluble calcium compound or water-soluble silicate compound).
It is probably to be assumed that the reaction takes place in
aqueous solution but a water-insoluble inorganic compound (C-S-H)
is usually present as a reaction product.
[0204] In the context of the present invention, comb polymers are
to be understood as meaning those polymers which have relatively
long side chains (having a molecular weight of in each case at
least 200 g/mol, particularly preferably at least 400 g/mol) on a
linear main chain at more or less regular intervals. The lengths of
these side chains are frequently approximately equal but may also
differ greatly from one another (for example when polyether
macromonomers having side chains of different lengths are
incorporated in the form of polymerized units).
[0205] In principle, component f) acts as accelerator and in a
preferred embodiment contains an inorganic and an organic
component. The inorganic component may be regarded as modified,
finely disperse calcium silicate hydrate (C-S-H) which may contain
foreign ions, such as magnesium and aluminium. The C-S-H can be
prepared in the presence of the comb polymer plasticizer (organic
component). Usually, a suspension containing the C-S-H in finely
disperse form is obtained, which suspension firstly acts as a
plasticizer and secondly effectively accelerates the hardening
process of hydraulic binders.
[0206] The inorganic component can in most cases be described with
regard to its composition (not with regard to particle size,
specific surface area, etc) by the following empirical formula:
a CaO, SiO.sub.2, b Al.sub.2O.sub.3, c H.sub.2O, d X, e W [0207] X
is an alkali metal [0208] W is an alkaline earth metal
TABLE-US-00001 [0208] 0.1 .ltoreq. a .ltoreq. 2 preferably 0.66
.ltoreq. a .ltoreq. 1.7 0 .ltoreq. b .ltoreq. 1 preferably 0
.ltoreq. b .ltoreq. 0.1 1 .ltoreq. c .ltoreq. 6 preferably 1
.ltoreq. c .ltoreq. 6.0 0 .ltoreq. d .ltoreq. 1 preferably 0
.ltoreq. d .ltoreq. 0.4 0 .ltoreq. e .ltoreq. 2 preferably 0
.ltoreq. e .ltoreq. 0.1
[0209] According to the present invention the C-S-H shows a
calcium/silicium (Ca/Si)-molar ratio of 0.5 to 2.0, preferable 0.7
to 1.8, more preferable 1.6 to 1.7. The average particle size of
C-S-H is smaller than 10 .mu.m, preferable smaller than 1 .mu.m,
more preferable smaller than 0.2 .mu.m, measured by light
scattering with the equipment Master Sizer 2000 from the Malvern
Company. In a further preferred embodiment the average particle
size of C-S-H is greater 0.01 .mu.m, preferable 0.1 .mu.m to 1.0
.mu.m, more preferable 0.2 .mu.m to 0.5 .mu.m.
[0210] With other words the dispersant that is used for this method
of preparation can be identical to the representatives of the
dispersing component a) and/or b) of the formulation. The
dispersing agent in this method of preparation is necessary for
achieving a small particle size distribution of the C-S-H
compound.
[0211] Preferably that C-S-H containing composition is preperable
by reaction of a calcium oxide, a calcium carbonate and/or a
calcium hydroxide with a silicium dioxide during milling, the
reaction being carried out in the presence of an aqueous solution
that preferably contains a water-soluble copolymer that preferably
is a dispersant for hydraulic binders and selected from at least a
representative of component a) and/or b).
[0212] In a further preferred embodiment of the invention, the
water-soluble calcium compound is mixed in a first step, with the
aqueous solution which contains a water-soluble comb polymer
suitable as a plasticizer for hydraulic binders, so that a mixture
preferably present as a solution is obtained, to which the
water-soluble silicate compound is added in a subsequent second
step.
[0213] The aqueous solution may also contain one or more further
solvents in addition to water.
[0214] In a further preferred embodiment, the aqueous solution
containing the dispersant and preferably one that is selected from
component a) and/or b) furthermore has the water-soluble calcium
compound and the water-soluble silicate compound as components
dissolved in it.
[0215] In general, the components used are used in the following
ratios: [0216] i) 0.01 to 75, preferably 0.01 to 5, % by weight of
water-soluble calcium compound, [0217] ii) 0.01 to 75, preferably
0.01 to 5% by weight of water-soluble silicate compound, [0218]
iii) 0.001 to 60, preferably 0.1 to 15% by weight of water-soluble
comb polymer suitable as a plasticizer for hydraulic binders
(preferably component a) and/or b)) [0219] iv) 24 to 99, preferably
90 to 99, % by weight of water.
[0220] Frequently, the aqueous solution also contains, in addition
to silicate and calcium ions, further dissolved ions which are
preferably provided in the form of dissolved aluminium chloride
and/or dissolved magnesium chloride.
[0221] The water-soluble dispersant can be a comb polymer and be
present as a copolymer which contains, on the back bone, side
chains having ether functions and acid functions.
[0222] As a rule, the water-soluble comb polymer is present as a
copolymer which is produced by free radical polymerization in the
presence of acid monomer and polyether macromonomer, so that
altogether at least 45 mol %, preferably at least 80 mol %, of all
structural units of the copolymer are produced by incorporation of
acid monomer and polyether macromonomer in the form of polymerized
units. Acid monomer is to be understood as meaning monomers which
are capable of free radical copolymerization, have at least one
carbon double bond, contain at least one acid function and react as
an acid in an aqueous medium. Furthermore, acid monomer is also to
be understood as meaning monomers which are capable of free radical
copolymerization, have at least one carbon double bond, form at
least one acid function in an aqueous medium as a result of a
hydrolysis reaction and react as an acid in an aqueous medium
(example: maleic anhydride).
[0223] In the context of the present invention, polyether
macromonomers are compounds which are capable of free radical
copolymerization, have at least one carbon double bond, and have at
least two ether oxygen atoms, with the proviso that the polyether
macromonomer structural units present in the copolymer have side
chains which contain at least two ether oxygen atoms.
[0224] For further details reference is made to the description of
the components a) and b) of the claimed formulation hereto.
Often, the water-soluble calcium compound is present as calcium
chloride, calcium nitrate, calcium formate, calcium acetate,
calcium bicarbonate, calcium bromide, calcium carbonate, calcium
citrate, calcium chlorate, calcium fluoride, calcium gluconate,
calcium hydroxide, calcium hypochloride, calcium iodate, calcium
iodide, calcium lactate, calcium nitrite, calcium oxalate, calcium
phosphate, calcium propionate, calcium silicate, calcium stearate,
calcium sulphate, calcium sulphate hemihydrate, calcium sulphate
dihydrate, calcium sulphide, calcium tartrate and/or calcium
aluminate, tricalcium silicate and/or dicalcium silicate.
[0225] The water-soluble calcium compound is preferably present as
calcium chloride, calcium nitrate and/or calcium formate.
[0226] Often, the water-soluble silicate compound is present as
sodium silicate, potassium silicate, waterglass, aluminium
silicate, tricalcium silicate, dicalcium silicate, calcium
silicate, silicic acid, sodium metasilicate and/or potassium
metasilicate.
[0227] The water-soluble silicate compound is preferably present as
sodium metasilicate, potassium metasilicate and/or waterglass.
[0228] In principle, a calcium silicate (provided that it is
soluble) may be used both as a silicate source and as a calcium
source. In many cases, however, this is not preferred. As a rule,
species of different types are used as the water-soluble silicate
compound and as the water-soluble calcium compound.
[0229] According to the present invention the formulation is a
liquid or a powder and preferably a redispersant powder.
[0230] The powder form of the formulation can be achieved by any
method known to a skilled person. Preferred is the spray drying
method that is also suitable for getting the formulation of the
invention as redispersant powder.
4. Method of Use
[0231] Beside the formulation itself a method of use of the
formulation states a further embodiment of the present
invention.
In this connection the use of the formulation for controlling the
flowability of aqueous suspensions used in construction chemistry
and in particular in aqueous suspensions containing hydraulic
and/or latent hydraulic binders is of main interest. The
formulation is used in particular as composition with dispersing
properties. Regarding the aqueous suspensions it is a further
embodiment that these compositions contain, as a hydraulic binder
at least one representative selected from the group consisting of
cements and calcium sulphate-based compounds, in particular calcium
sulphate hemihydrate, anhydrite or gypsum. The aqueous suspension
according to the present invention preferably is based on a dry
mortar composition or a flooring composition. In a further
embodiment the flooring composition contains calcium sulphate or
cement or mixtures thereof, and preferably is a self-leveling
flooring composition.
[0232] Independent from the specific use the formulation according
to the present invention is to be used in amounts of 0.001 to 8.0%
by weight, in particular 0.005 to 5.0% by weight, preferably 0.01
to 2.0% by weight and particularly preferably 0.05 to 1.0% by
weight, based in each case on the total composition of the
suspension.
[0233] Finally, the present invention comprises the option that the
formulation is used together with other admixtures or compositions,
preferably with flowability controlling and/or dispersing
properties, and more preferably together with at least one
dispersant of the type of component a) and/or the polymerisation
product b) of the formulation.
[0234] This means that the combination of component a) and
component b) can be used as formulation according to the present
invention and additionally that this formulation can be used
together with other compounds, additives, admixtures or
compositions. In consequence components a) and b) can be used as
substantial constituents of the formulation and additionally as
single compounds together with such formulation. This kind of use
can be practiced stepwise, that means that either the formulation
or the additional dispersants are added to the hydraulic binder
containing composition in the first step of use and that additional
amounts of the formulation its components are added in up following
process steps.
[0235] The following examples underline the advantages of the
claimed formulation, its comprised components and its use.
EXAMPLE
1. Preparation of Comb Branched Polycondensates (Component b)
Example 1.1
[0236] A reactor equipped with a stirrer and a heating mantle is
filled with 600 parts of poly(ethyleneoxide)monophenylether
(average molecular weight 5000 g/mol), 47.2 parts of concentrated
methane sulfonic acid, 12 parts of water, 110 parts of
.alpha.-phenyl-.omega.-hydroxypoly(oxy-1,2-ethanediyl)phosphate
(average molecular weight 368 g/mol) and 14.7 parts of
paraformaldehyde. This reaction mixture is stirred at 115.degree.
C. for 3 h. After cooling, 830 parts of water are added the
reaction mixture is neutralized with 50% sodium hydroxide solution
to a pH value of 6.5 to 7. The resin is a light yellow colored,
clear and aqueous polymer solution with a solid concentration of
40% by weight. To the stirred solution (500 rpm) of the polymeric
dispersant the antifoaming agent and the surfactant are added at
ambient temperature (25.degree. C.). The amounts of the materials
shown in Table 2 are in percent by weight of the solution.
Example 1.2
[0237] A reactor equipped with a stirrer and a heating mantle is
filled with 26 parts of polyphosphoric acid and heated to
90.degree. C. Within 15 min 44.2 parts of 2-phenoxyethanol are
charged into the reactor. After 1 h, 400 parts of
poly(ethyleneoxide)monophenylether (average molecular weight 5000
g/mol), 31.4 parts of concentrated methane sulfonic acid, 20 parts
of water and 12.6 parts of paraformaldehyde are added. This
reaction mixture is stirred at 105.degree. C. for 6 h. After
cooling, 550 parts of water are added and the reaction mixture is
neutralized with 50% sodium hydroxide solution to a pH value of 6.5
to 7. The resin is a light brown colored, clear and aqueous polymer
solution with a solid concentration of 40% by weight. To the
stirred solution (500 rpm) of the polymeric dispersant the
antifoaming agent and the surfactant are added at ambient
temperature (25.degree. C.). The amounts of the materials shown in
Table 2 are in percent by weight of the solution.
Example 1.3
[0238] A reactor equipped with a stirrer and a heating mantle is
filled with 51.6 parts of polyphosphoric acid and heated to
90.degree. C. Within 15 min 90 parts of 2-phenoxyethanol are
charged into the reactor. After 1 h, 322 parts of
poly(ethyleneoxide)monophenylether (average molecular weight 5000
g/mol), 300 parts of poly(ethyleneoxide)monophenylether (average
molecular weight 2000 g/mol), 42.1 parts of concentrated methane
sulfonic acid, 16.8 parts of water and 28.5 parts of
paraformaldehyde are added. This reaction mixture is stirred at
105.degree. C. for 6 h. After cooling, 800 parts of water are added
and the reaction mixture is neutralized with 50% sodium hydroxide
solution to a pH value of 6.5 to 7. The resin is a light brown
colored, clear and aqueous polymer solution with a solid
concentration of 40% by weight. To the stirred solution (500 rpm)
of the polymeric dispersant the antifoaming agent and the
surfactant are added at ambient temperature (25.degree. C.). The
amounts of the materials shown in Table 2 are in percent by weight
of the solution.
2. Formulation of Dispersant Component a) with Polycondensate
Component b)
[0239] The examples E1 till E20 (see Table 1 and 2) were prepared
by mixing the polycondensate components b) with equivalent amounts
(wt. %) of the dispersants a). Melflux PCE 239 L 35% N.D., Melflux
2500 L 45% N.D., Melflux 2453 L 44% N.D., VP2661/493 L 40% N.D.,
Melflux 2424 L 50% N.D., Melflux AP 120 L 40%, and Sokalan DS5009 X
are a polycarboxylate ether dispersant available from BASF
Construction Polymers GmbH, Germany. Melcrete 500 L is a
naphthalene sulfonate dispersant (BNS) available from BASF
Construction Polymers GmbH. Melment L 15 G is a melamine
sulphonate-formaldehyde condensate (MFS) available from BASF
Construction Polymers GmbH. The non-ionic polymers N1 and N2 are
able to maintain the fluidity of a cement composition and are
synthesized according to the still unpublished application U.S.
Ser. No. 12/477,637.
TABLE-US-00002 TABLE 1 Molar Ratio of Formulation polycondensate
(E: Invention; Polycondensate b) and Solid Stability C: b)
according to Dispersant dispersant content over 3 Comparison)
example a) a) (wt. %) months E1 C7 Melflux PCE 2/1 35 stable 239 L
E2 C8 Melflux PCE 2/1 35 stable 239 L E3 C7 BNS 1/1 25 stable E4 C8
BNS 1/1 25 stable E5 C9 BNS 1/1 25 stable E6 C8 Melflux 2500 L 1/1
40 stable E7-1 C8 VP2661/493 L 3/1 40 stable E7-2 C8 VP2661/493 L
1/3 40 stable E8-1 C8 Melflux PCE 3/1 35 stable 239 L E8-2 C8
Melflux PCE 1/3 35 stable 239 L E9 C8 BNS 2/1 20 stable E10 C8
Sokalan 2/1 35 stable 5009X E11 C8 Melflux AP 2/1 40 stable 120 L
E12 C8 Melment L 15 G 2/1 40 stable E13 C8 N1 2/1 30 stable E14 C8
VP2661/493 L 2/1 40 stable E15 C9 VP2661/493 L 2/1 40 stable E16 C7
BNS 3/1 25 stable E17 C7 Melflux 2500 L 1/1 40 stable E18 C7
Melflux 2453 L 1/1 40 stable E19 C7 Melflux 2424 L 1/1 40 stable
E20 C8 N2 2/1 30 stable C1 -- Melflux 2500 L 40 C2 -- Melflux PCE
35 239 L C3 -- VP2661/493 L 40 C4 -- 1:1 mixture 25 gel of Melflux
formation 2500 L/BNS
3. Formulations of Polycondensates b), with Antifoaming Agents as
Component a)
[0240] In the following admixtures (Test Solution) antifoaming
agent A1 has been a polypropyleneglycol commercially available as
Pluriol.RTM. P2000 and, antifoaming agent A2 an alkoxylated alcohol
commercially available as Degressal.RTM. SD23 and antifoaming agent
A3 a carboxylic ester commercially available as Degressal.RTM. SD30
all from BASF SE (Ludwigshafen, Germany). Surfactant S1 was an
ethoxylated oxo-alcohol commercially available as Lutensol.RTM. TO6
from BASF SE (Ludwigshafen, Germany). Surfactant S2 (as component
a) is a styrene/maleic acid copolymer which was synthesized
according to EP 0306449 A2.
TABLE-US-00003 TABLE 2 Solution Dispersant Stability (E: Invention;
according Antifoaming Surfactant over 3 C: to agent (wt.-%) (wt.-%)
months Comparison) example A1 A2 A3 S1 S2 at RT E21 E1 0.4 0.6 +
E22 1.1 0.2 0.3 + E23 1.1 0.4 0.6 + E24 E2 0.2 0.3 + E25 1.2 0.2
0.3 + E26 1.2 0.4 0.8 + E27 1.2 0.2 0.3 + E28 1.1 0.2 0.3 + E29 1.3
0.2 0.3 + E30 E1 0.2 0.3 + E31 E2 0.2 0.3 + C5 1.1 0.4 -)* C6 1.2
0.4 -)* C7 1.1 none none none none none n.a. C8 1.2 none none none
none none n.a. C9 1.3 none none none none none n.a. )*phase
separation within two days
4. Viscosities of Formulations Consisting of Naphthalene Sulfonate
as Component a) and Polycondensates b)
[0241] The viscosities of the dispersants solutions were measured
with a capillary viscometer at 25.degree. C. The solutions were
prepared by mixing a 25 Wt. % BNS solution with 25 Wt. % solutions
of the dispersants as indicated in Table 1 and 3.
TABLE-US-00004 TABLE 3 Formulation Dispersant:BNS Viscosity in or
dispersant ratio mPas C1 -- 59.1 C4 1:1 529.4 C7 -- 28.0 E3 1:1
137.1 C8 -- 32.9 E4 1:1 188.8 C9 -- 24.5 E5 1:1 83.2
[0242] As can be seen from Table 3, the viscosity of the admixture
E3, E4 and E5 is only slightly higher compared to the viscosity of
the pure condensates C7, C8 and C9. Whereas the admixtures E3, E4
and E5 keep their low viscosity over time, the mixture of BNS and
the polycarboxylate ether starts to form a non pourable gel. Unlike
C4, the admixture E3, E4 and E5 are usable as dispersant agents for
hydraulic binders (see below for application tests).
5. Gypsum based Thin Layer Levelling
TABLE-US-00005 Guide recipe: Alpha hemi hydrate 300 g Sand (0-0.2
mm) 350 g Lime stone filler 150 g Citric acid 0.10 g Starvis 3003 F
0.32 g Water 174.6 g Admixture (Superplasticizer) 0.15%-bws (=by
weight of solids)
Mixing Procedure and Measurement:
[0243] The required amounts of liquid admixture and water were
weighted into a mixing cup. Afterwards the combined solids were
added into the cup and mixed with a kitchen mixer for 60 sec at
level two. The flow value was measured with a Vicat ring after 60
sec.
TABLE-US-00006 TABLE 4 Flow (cm) Admixture 5 min 20 min E26 25.7
27.2 No craters at the surface E25 29.5 30.5 No craters at the
surface C8 28.6 30.2 Defects and crater
As illustrated in Table 4, the admixtures according to the
invention show an excellent antifoaming property. The surface of
thin layer levelling was found to be free of defects and craters
compared to example C8.
6. Gypsum Flow Test
Mixing Procedure and Measurement:
[0244] The required amount of liquid admixture was weighted into
the mixing cup and water was added to reach the water to stucco
ratios given in Table 4. The stucco (400 g from various sources)
together with the accelerator is sifted into water within 15 sec
and afterwards mixed with a Hobart.RTM. mixer for 15 sec at high
speed (285 rpm). After 60 sec the flow value was measured with a
cylinder (height: 10 cm, diameter: 5 cm). The set time was
determined by means of the so-called knife cut test.
TABLE-US-00007 TABLE 5 Natural stucco A Dosage Water to
Accelerator)* Flow Set time Admixture [wt.-%] stucco ratio [g] [cm]
[min:s] E26 0.050 0.63 0.400 20.6 2:20 E26 0.120 0.55 0.300 20.0
2:15 C8 0.055 0.63 0.400 20.1 2:10 C8 0.140 0.55 0.450 20.4 2:15
E31 0.050 0.63 0.400 20.4 2:10 E31 0.140 0.55 0.500 20.5 2:05 C2
0.050 0.63 0.500 20.6 2:10 C2 0.140 0.55 0.700 20.5 2:05 )*finely
ground calcium sulfate dihydrate
[0245] As depicted in Table 5, the admixture E26 according to the
invention show excellent dispersant abilities in comparison to the
polycondensate dispersant C8. Admixture E31, which contains the
polycondensate C8 and the polycarboxylate ether C2, displays a
lower amount of accelerator usage as the pure polycarboxylate ether
C2.
TABLE-US-00008 TABLE 6 Stucco from flue gas desulfurization Dosage
Water to Accelerator)* Flow Set time Admixture [wt.-%] stucco ratio
[g] [cm] [min:s] C8 0.190 0.53 0.060 20.0 2:15 E7-1 0.190 0.53
0.080 19.6 2:15 E7-2 0.190 0.53 0.150 20.1 2:20 C3 0.280 0.53 3.000
20.8 2:10 E8-1 0.190 0.53 0.080 22.6 2:20 E8-2 0.190 0.53 0.120
23.4 2:20 C2 0.190 0.53 0.120 20.2 2:15 E9 0.065 0.63 0.050 19.3
2:20 E10 0.065 0.63 0.060 22.9 2:20 E11 0.065 0.63 0.070 21.1 2:20
E12 0.065 0.63 0.050 19.8 2:20 C8 0.065 0.63 0.070 20.6 2:15
)*finely ground calcium sulfate dihydrate
[0246] As displayed in Table 6, the admixtures E7-1 and E7-2
according to the invention display excellent dispersant abilities
in FGD stucco and in comparison to the polycarboxylate ether
dispersant C3 a significant reduced accelerator demand. Admixtures
E8-1 and E8-2 show higher flow values than the pure polycondensate
C8. The admixtures E9 and E12, which contain the inexpensive
dispersants BNS and MFS, exhibit at the same dosage as the
polycondensate C8 good flow values.
TABLE-US-00009 TABLE 7 Natural clay containing stucco B Dosage
Water to Accelerator)* Flow Set time Admixture [wt.-%] stucco ratio
[g] [cm] [min:s] E26 0.280 0.60 0.230 20.8 2:00 E13 0.240 0.60
0.200 21.1 2:10 C3 0.280 0.60 -- No flow -- C2 0.280 0.755 0.280
20.7 2:15 )*finely ground calcium sulfate dihydrate
[0247] As shown in Table 7, the admixture according to the
invention E26 and E13 possesses fluidity in the natural stucco B.
At the same dosage, the comparison admixture C3 is not fluid
whereas C2 needs a significant higher water to stucco ratio to
reach the same flow value.
TABLE-US-00010 TABLE 8 Natural stucco C Dosage Water to
Accelerator)* Flow Set time Admixture [wt.-%] stucco ratio [g] [cm]
[min:s] C8 0.100 0.60 0.600 21.0 2:05 E26 0.100 0.60 0.800 22.3
2:05 E14 0.100 0.60 1.000 23.2 2:15 E15 0.100 0.60 0.700 23.5 2:20
C3 0.100 0.60 1.600 23.2 2:15 )*finely ground calcium sulfate
dihydrate
[0248] As depicted in Table 8, the admixtures according to the
invention display excellent dispersant abilities in the natural
stucco C and in comparison to the polycarboxylate ether dispersant
C3 reduced accelerator demands. The admixtures E26 and E15 have a
similar low accelerator demand but a higher fluidity as the
polycondensate C8.
7. Application Test:
[0249] Water reduction and change of spread values over time in a
mortar test system
Mixing Procedure and Measurement:
[0250] 600 g of cement powder is homogenized in a RILEM-Mixer. The
required amount of water to reach the water to cement ratios given
in Table 9 is added and mixed in for 30 sec at 140 rpm (level I).
The sand is added during agitation via a funnel and mixed in for 30
sec at 140 rpm (level I). The brims of the bowl will be cleaned and
the required amount of liquid admixture is added after a mixing
break of 1.5 min. The mixing is continued for 60 sec at 285 rpm
(level II) and afterwards the flow value (spread value) is
determined with a Hagermann cylinder according to DIN EN
1015-3.
[0251] The mortar is based on a Karistadt CEM I 42.5 R and has a
sand to cement ratio of 2.2. The sand consists of a mixture of 30%
quartz sand and 70% standardized sand.
TABLE-US-00011 TABLE 9 Spread Dosage value [% solid w/c @ 0 min 15
30 60 90 Example on cement] ratio [cm] min min min min blank --
0.545 24.6 23.5 23.5 23 C7 0.19 0.42 24.7 24.1 22.2 21.5 E16 0.27
0.42 25 23.4 22.2 20.5 BNS 0.50 0.42 24.9 23.6 22.5 21.2 E17 0.20
0.43 24.3 23.4 22.9 E18 0.20 0.40 25.0 25.5 24.9 24.5 E19 0.20 0.41
24.4 24.0 23.4 E13 0.23 0.43 23.5 23.8 25.4 25.2 24.4 E20 0.24 0.43
24.0 24.1 24.3 23.7 23.4
[0252] The admixture E16, that contains the low-cost dispersant
BNS, displays similar fluidity as the condensate C7 at a much lower
dosage level than BNS. As FIG. 9 shows, the admixtures E18 and in
particular E13 and E20 keep the fluidity of the cementious binder
composition for more than 90 min.
* * * * *