U.S. patent number RE31,610 [Application Number 06/424,682] was granted by the patent office on 1984-06-26 for modifying mortars of inorganic binding agents with alkylated sulphonated phenol-formaldehyde condensation product.
This patent grant is currently assigned to Bayer Aktiengesellschaft. Invention is credited to Gunther Boehmke, Gunther Reitz, Kurt Schaupp.
United States Patent |
RE31,610 |
Schaupp , et al. |
June 26, 1984 |
Modifying mortars of inorganic binding agents with alkylated
sulphonated phenol-formaldehyde condensation product
Abstract
In a mortar comprising an inorganic binder, water and a
sulphonated phenol condensation product modifier therefor, the
improvement wherein said condensation product comprises a
formaldehyde condensation product of a phenol wherein at least
about 40% of the phenolic OH groups are etherified with an
alkylating agent, the condensation product being present in about
0.05 to 5% by weight of the binder. Advantageously the condensation
product is of the formula ##STR1## in which R is H, C.sub.1-6
-alkyl, C.sub.1-12 -aralkyl, C.sub.1-4 -monohydroxy or dihydroxy
alkyl, of C.sub.3-4 -hydroxy .[.chloralkyl.].
.Iadd.chloroalkyl.Iaddend., less than 40% of the R groups being H,
X is H, CH.sub.2 --SO.sub.3 M, CH.sub.2 OH, CH.sub.2 --R' or
NR'.sub.4, at least about half the X groups being CH.sub.2
--SO.sub.3 M, M is Na, K, Ca/2 or Mg/2, R' is H, C.sub.1-4 -alkyl,
C.sub.2-4 -hydroxy alkyl, or another structural unit of the formula
(I) and n is at least 3. Thereby the mortar is rendered more
plastic and dense while retaining its setting characteristics.
Inventors: |
Schaupp; Kurt (Cologne,
DE), Reitz; Gunther (Cologne, DE), Boehmke;
Gunther (Leverkusen, DE) |
Assignee: |
Bayer Aktiengesellschaft
(Leverkusen, DE)
|
Family
ID: |
6080035 |
Appl.
No.: |
06/424,682 |
Filed: |
September 27, 1982 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
175802 |
Aug 6, 1980 |
04330334 |
May 18, 1982 |
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Foreign Application Priority Data
Current U.S.
Class: |
524/6 |
Current CPC
Class: |
C08L
61/14 (20130101); C04B 28/02 (20130101); C08G
8/18 (20130101); C08G 8/28 (20130101); C08G
8/04 (20130101); C08G 8/36 (20130101); C04B
24/22 (20130101); C04B 28/02 (20130101); C04B
14/02 (20130101); C04B 22/14 (20130101); C04B
24/22 (20130101); C04B 24/302 (20130101) |
Current International
Class: |
C08G
8/36 (20060101); C08G 8/04 (20060101); C08G
8/18 (20060101); C08L 61/14 (20060101); C08L
61/00 (20060101); C04B 24/00 (20060101); C04B
28/02 (20060101); C04B 28/00 (20060101); C08G
8/00 (20060101); C08G 8/28 (20060101); C04B
24/22 (20060101); C04B 007/35 () |
Field of
Search: |
;106/90,97,109,111,315 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Poer; James
Attorney, Agent or Firm: Sprung, Horn, Kramer &
Woods
Claims
We claim:
1. In a mortar comprising an inorganic binder, water and a
sulphonated phenol condensation product modifier therefor, the
improvement wherein said condensation product comprises a
formaldehyde condensation product of a phenol wherein .[.at least
about 40%.]. .Iadd.about 60% to 90% .Iaddend.of the phenolic OH
groups are etherified with an alkylating agent, the condensation
product being present in about 0.05 to 5% by weight of the
binder.
2. A mortar as claimed in claim 1, wherein the sulphonated phenol
condensation product is of the formula ##STR3## in which R is H,
C.sub.1-6 -alkyl, C.sub.1-12 -aralkyl, C.sub.1-4 -monohydroxy or
dihydroxy alkyl, of C.sub.3-4 -hydroxy chloroalkyl, .[.less than.].
.Iadd.10% to .Iaddend.40% of the R groups being H,
X is H, CH.sub.2 --SO.sub.3 M, CH.sub.2 OH, CH.sub.2 --R' or
NR'.sub.4, at least about half the X groups being CH.sub.2
--SO.sub.3 M,
M is Na, K, Ca/2 or Mg/2,
R' is H, C.sub.1-4 -alkyl, C.sub.2-4 -hydroxy alkyl, or another
structural unit of the formula (I) and
n is at least 3.
3. A mortar as claimed in claim 1, wherein the sulphonated phenol
condensation product is present in about 0.1 to 3% by weight of the
binder.
4. A mortar as claimed in claim 2, wherein n is at least 8.
5. A mortar as claimed in claim 2, wherein the sulphonated phenol
condensation product is present in about 0.2 to 2% by weight of the
binder, .[.about 60 to 90% of the phenolic OH groups are
etherified,.]. n is from 10 to 200, and the mortar further contains
at least one aggregate selected from the group consisting of sand,
gravel, perlite, pumice, foamed plastic and solid plastic.
6. A process for improving the processability of mortar comprising
an inorganic binder and water, comprising incorporating therein in
about 0.05 to 5% by weight of the binder a sulphonated phenol
condensation product of a phenol and formaldehyde wherein .[.at
least about 40%.]. .Iadd.about 60% to 90% .Iaddend.of the phenolic
OH groups are etherified with an alkylating agent.
7. A process according to claim 6, wherein the sulphonated phenol
condensation product is of the formula ##STR4## in which R is H,
C.sub.1-6 -alkyl, C.sub.1-12 -aralkyl, C.sub.1-4 -monohydroxy or
dihydroxy alkyl, or C.sub.3-4 -hydroxy chloroalkyl, .[.less than.].
.Iadd.10% to .Iaddend.40% of the R groups being H,
X is H, CH.sub.2 SO.sub.3 M, CH.sub.2 OH, CH.sub.2 --R' or
NR'.sub.4, at least about half the X groups being CH.sub.2
-SO.sub.3 M,
M is Na, K, Ca/2 or Mg2,
R' is H, C.sub.1-4 -alkyl, C.sub.2-4 hydroxy alkyl, or another
structural unit of the formula (I) and
n is at least 3.
8. A process according to claim 6, wherein the sulphonated phenol
condensation product is present in about 0.2 to 2% by weight of the
binder, .[.about 60 to 90% of the phenolic OH groups are
etherified,.]. n is from 10 to 200, and the mortar further contains
at least one aggregate selected from the group consisting of sand,
gravel, perlite, pumice, foamed plastic and solid plastic.
9. A mortar as defined in claim 1, further containing at least one
admix selected from the group consisting of FeSO.sub.4.7H.sub.2 O,
Al.sub.2 (SO.sub.4).sub.3.18H.sub.2 O and
KAl(SO.sub.4).sub.2.12H.sub.2 O.
10. A mortar as defined in claim 1, further containing at least one
aggregate selected from the group consisting of sand, gravel,
perlite, pumice, foamed plastic and solid plastic.
11. A mortar as claimed in claim 1, further containing a
plasticizer.
12. A mortar as claimed in claim 1, further containing a hardening
accelerator.
13. A mortar as claimed in claim 1, further containing a
retarder.
14. A mortar as claimed in claim 1, further containing
air-entraining agent.
15. A mortar as claimed in claim 1, further containing a
diluent.
16. A mortar as claimed in claim 1, further containing an
activator.
17. A mortar as claimed in claim 1, further containing an anti-foam
agent.
Description
This invention relates to mortars containing inorganic binders
which are modified with alkylated phenol condensates and which may
also contain aggregates, admixes and/or additives.
In the production of structural components, such as screeds, wall
boards, walls, ceiling etc., inorganic binders, such as anhydrite
(natural and synthetic), gypsum or cement, are generally mixed and
processed as such, in some cases without leaning, but generally in
conjunction with aggregates, such as sand or gravel, optionally
using additives, such as air-entraining agents or plasticizers. In
order to ensure that the structural components produced with these
mixtures have favorable properties, it is important to work with a
low water-binder factor (WBF), i.e. with as little water as
possible, based on the binder used. In many cases, however, this
makes the mortar viscous. If its water content is reduced any
further, the mortar loses its plasticity and, hence, its favorable
compactibility as well. To be able to produce high quality
structural components from a mortar such as this requires intensive
mechanical compaction by vibration and/or pressing. Since this is
not possible or sufficient for numerous applications, it is often
necessary to use increased quantities of binder in order to achieve
the required properties, such as high strengths, early hardening or
early strippability.
All the measures referred to above involve increased outlay and,
hence, increased costs. Excessive quantities of binder can also
give rise to technical difficulties. For the reason, the measures
in question are frequently not adopted and, instead, easier
processability of the mortar is brought about by increasing the
WBF. However, structural components produced in this way are not of
such high quality.
Accordingly, attempts have been made to improve the processability
of mortars by the use of chemical additives. It is known that
so-called plasticizers may be used with inorganic binders.
Plasticizers of the type in question are generally added to the
binder in relatively small quantities. Larger additions produce no
significant increase in the plasticizing effect, but instead almost
always have a considerable adverse effect upon the properties of
the mortar, as reflected above all in a reduction in the setting
rate, in an increase in the air void content and in a deterioration
in the strength values.
Austrian Pat. No. 263,607 describes the addition of a modified
amino-s-triazine resin to inorganic binders. This addition is said
to provide the building material with good bond, tensile and
compressive strengths and with a high surface quality.
German Offenlegungsschrift No. 2,204,275 describes a
phenol-formaldehyde polycondensation product as a plasticizer for
mortars or concrete based on mineral binders. This condensation
product is nucleus-sulphonated and, in a subsequent reaction, is
etherified with polyhydric alcohols through unreacted methylol
groups.
German Offenlegungsschrift No. 2,405,437 describes condensation
products of formaldehyde with phenol as additives for ceramic
compositions and concrete, which products contain sulpho and/or
sulphomethyl residues, the acid hydrogen atoms being replaced by
sodium, potassium or calcium.
In addition, German Offenlegungsschrift No. 2,421,222 describes a
condensation product of formaldehyde with nucleus-sulphonated
polyhydric phenols as a plasticizer for binders.
However, the compounds disclosed in the abovementioned publications
delay the setting of inorganic binders containing alkaline earth
metals, such as cement or calcium sulphate for example, to a very
considerable extent. In addition, these compounds which fall within
this class and which are directly sulphonated on the nucleus show
more or less pronounced surface-active properties, with the result
that, in aqueous solution, the product tends to foam and, hence,
brings with it the danger of air voids, being introduced into the
binder mass which is undesirable, at least so far as most potential
applications are concerned.
It has now been found that the disadvantages referred to above do
not occur when the phenol group is etherified and the sulpho group
is bound to the nucleus directly or, preferably, through a CH.sub.2
-group.
Accordingly, the present invention provides mortars containing
inorganic binders which are modified with alkylated phenol
condensation products and which may also contain aggregates,
admixes and/or additives, characterized in that the mortars contain
partly sulphonated, preferably partly sulphomethylated condensates
of phenol or phenol derivatives with formaldehyde in quantities of
about 0.05 to 5% by weight, based on the binder used, in which
condensates the phenolic OH-group is etherified with about 0.4 to
1.0 equivalents of alkylating agents.
The present invention also provides a process for the production of
mortars containing inorganic binders and, optionally, aggregates,
admixes and/or additives, characterized in that at least partly
sulphonated, preferably sulphomethylated condensates of phenol or
phenol derivatives, in which the phenolic OH-group is etherified
with from 0.4 to 1.0 equivalents of alkylating agents, are added to
the water-setting mortars in quantities of from 0.05 to 5% by
weight, based on the binder used.
In the context of the present invention, inorganic binders are
understood to be both gypsum having various water contents and in
various modified forms (including anhydrite), lime and ceramic
masses, and also cement which may be processed both into mortars
and also into concrete.
The above-mentioned compounds are at least partly sulphonated,
preferably partly sulphomethylated condensates of phenol or phenol
derivatives which are partly or completely etherified with
alkylating agents on the phenolic hydroxyl group. These condensates
are referred to hereinafter as alkylated phenol condensates.
Alkylating agents are alkyl halides, for example methyl chloride,
ethyl chloride, benzyl chloride or the corresponding bromides or
iodides, and also sulphuric acid esters, such as monomethyl and
dimethyl sulphate, p-toluene sulphonic acid esters and phosphoric
acid esters such as, for example, trimethyl or triethyl phosphate,
formaldehyde and epichlorohydrin. Preferred alkylating agents are
alkylene oxides, for example ethylene oxide or 1,2-propylene
oxide.
The alkylated phenol condensates preferably contain the following
structural elements: ##STR2## In this formula, the letters have the
following meanings:
R.dbd.H, C.sub.1-6 -alkyl, C.sub.1-12 -aralkyl, D.sub.1-4
-monohydroxy or dihydroxy alkyl, C.sub.3-4 -hydroxy chloroalkyl,
less than 40% of the groups being H; R is preferably 2-hydroxy
alkyl and, with particular preference, 2-hydroxy ethyl. X.dbd.H,
CH.sub.2 --SO.sub.3 M, CH.sub.2 --OH or CH.sub.2 --R', where M
represents Na, K, Ca/2, Mg/2 NR'.sub.4 with R'.dbd.H, C.sub.1-4
-alkyl or C.sub.2-4 -hydroxy alkyl, preferably Na, K, Ca/2, Mg/2,
or R' represents another structural element (I), no less than half
of the groups X being CH.sub.2 --SO.sub.3 M;
n=degree of condensation which is at least 3 and preferable at
least about 8, normally amounting to about 10 to 200.
The structural elements (I) are middle groups of the alkylated
phenol condensates. The terminal groups have basically the same
structure, although they may be additionally substituted by H,
(CH.sub.2 --SO.sub.3 M) or methylol groups. The middle groups (I)
are only substituted by methylol groups to a minimal extent.
The alkylated phenol condensates are produced as follows:
Condensates of sulphonated or sulphomethylated phenols or
corresponding phenol derivatives with formaldehyde are produced in
a first step. The sulphonated compounds are obtained, for example,
by reacting phenol or phenol derivatives with H.sub.2 SO.sub.4,
chlorosulphonic acid, oleum or the like. The sulphomethylated
compounds are condensates of phenol or phenol derivatives,
formaldehyde donors or formaldehyde and sulphites or bisulphites,
in which case R in the structural elements (I) is H. These
condensates are then reacted with the abovementioned alkylating
agents in a second step, preferably carried out in an alkaline
medium.
Suitable phenols or phenol derivatives are phenol itself, and also
C.sub.1-10 -alkyl phenols, chlorophenols, bisphenols, such as
bis-(hydroxyphenyl)-propane, bis-(hydroxyphenyl)-sulphone, o- and
p-hydroxy bisphenyl, but preferably phenol. Suitable sulphites are
sodium metabisulphite, preferably Na.sub.2 SO.sub.3, and also
mixtures of both. The sulphites may be used as solids or in the
form of their aqueous solutions. Preferred alkylating agents are
methyl chloride, ethylene oxide, and 1,2-propylene oxide, ethylene
oxide being particularly preferred. Another preferred alkylating
agent is formaldehyde in the form of a 10 to 40% aqueous
solution.
The condensates produced from phenols, formaldehyde and sulphites
are then reacted with the alkylating agents, preferably with
ethylene oxide, in an aqueous medium at pH about 7 to 13 to form
the alkylated phenol condensates containing the structural elements
(I). The reaction is carried out to about 20.degree. to 150.degree.
C. with about 0.4 to 2 moles, preferably about 0.5 to 1.2 moles
and, more particularly, about 0.7 to 1 mole of alkylating agent per
mole of the phenolic compound. The alkylating agent reacts
preferentially with the phenolic hydroxyl group, which may also be
present in the form of a phenolate group, to form the corresponding
alkoxy compound. This may be detected, for example analytically
through the UV-spectra of the condensates in the alkaline aqueous
medium before and after alkylation. Some of the alkylating agent
also reacts with the water or hydroxide anion present in the
reaction mixture. Accordingly, the degree of etherification is
lower than that which corresponds theoretically to the quantity of
alkylating agent used. According to the invention, condensates are
obtained in which the phenolic OH-group is etherified with from 0.4
to 1.0, preferably with about 0.6 to 0.9 equivalents of alkylating
agent per mole of the phenolic compound.
The alkylated phenol condensates thus produced are used in
quantities of from 0.05 to 5% by weight, preferably in quantities
of about 0.1 to 3% by weight and, with particular preference, in
quantities of about 0.2 to 2% by weight, based on the binder
used.
The alkylated phenol condensates described above have a very good
plasticizing effect but do not adversely affect the setting
properties and, in particular, the setting time of the inorganic
binders, as is the case with the non-alkylated condensates of
phenol with formaldehyde. On the other hand, the mortars or binder
sludges according to the invention, to which the products according
to the invention are added as plasticizers, do not undergo rapid
stiffening. In addition, they have an extremely good deflocculating
effect on the binders. This is reflected on the one hand in the
"fat", very plastic consistency and, on the other hand, in the very
good and stable homogeneity of the concretes and mortars produced
therewith.
Surprisingly, the addition of the alkylated phenol condensates
according to the invention does not have a surface-active effect
which would otherwise be the case with the alkyl ethers or their
polymers. An effect such as this would be reflected very clearly in
the introduction of a very large number of air voids (cf. Example
4).
By the addition of the alkylated phenol condensates to the
inorganic binders, structural components or moldings having very
high early strengths are obtained.
An essential feature of the the invention is the etherification of
the phenolic OH-group carried out with the alkylating agents, the
quantity of the etherification molecules per phenol unit being
critical. It has been found that a very good effect is obtained if
preferably from 0.5 to 1.2 moles and, more Particularly, from 0.7
to 1.0 mole of the alkylating agent is reacted per mole of the
phenol compound. Smaller quantities do not sufficiently eliminate
the retarding effect, while larger quantities have a surface-active
effect and, hence, result in the introduction of air voids during
processing of the mortar or concrete and reduce the plasticizing
effect. According to the invention, particularly favorable results
are obtained if not at all the phenolic OH-groups are etherified,
i.e. about 0.2 to 0.4 equivalents of the total quantity are present
in non-etherified form.
The products according to the invention are particularly suitable
for use in the above-mentioned inorganic binders and, particularly
too, in the processing of ceramic compositions. Ceramic slips may
be effectively deflocculated with the alkylated phenol condensates.
In addition, the deflocculated suspensions show outstanding
stability and undergo hardly any sedimentation during the usual
storage periods. These results were surprising because similar,
non-alkylated compounds, although having a deflocculating effect,
give rise to considerable sedimentation, with the result that
products of this type cannot be effectively used.
The mortars according to the invention may be processed with the
usual, conventional additives, such as retarders, accelerators,
anti-foaming agents, foaming agents, sealing compounds,
hydrophobizing agents, synthetic resin dispersions and powders
thereof, plasticizers, air-entraining agents and fluxes, and with
the usual conventional pigments and/or aggregates such as, for
example, sand, gravel.Iadd., .Iaddend.chipping, pumice.Iadd.,
.Iaddend.stone powder, fly ash, perlites, vermiculites, expanded
clays, solid, foamed or .[.exapnded.]. .Iadd.expanded
.Iaddend.plastics and admixes such as Fe-SO.sub.4.7H.sub.2 O,
Al.sub.2 (SO.sub.4).sub.3.18H.sub.2 O,
KAl(SO.sub.4).sub.2.12H.sub.2 O, etc., either individually or in
any combination with one another.
In the process according to the invention for producing the mortars
modified with the alkylated phenol condensates, the above-mentioned
additives and/or aggregates may be added both to the inorganic
binders and also to the aqueous mixture already containing
alkylated phenol condensates, although the constituents may also be
added in a different order. The plasticizer is preferably added to
the mortars mixed with water.
The alkylated phenol condensation products described above may be
very widely used where they are employed as plasticizers for
inorganic binders (including ceramic compositions) in accordance
with the invention. In contrast to other comparable products, the
alkylated phenol condensation products may be produced, for
example, in the form of very stable, highly concentrated aqueous
solutions which, in addition, are still homogeneously liquid at
relatively low temperatures. Thus, a 45% aqueous solution is still
homogeneous and can be effectively poured and pumped at 0.degree.
C., retaining these properties down to -5.degree. C., while
comparable products containing free phenolic OH-groups crystallize
out at least partly at only 0.degree. C. This behavior is a
distinct advantage, particularly during the storage, transportation
and processing of the described condensates in relatively cold
surroundings, because for example fewer difficulties arise through
incorrect dosages, blockages etc. The alkylated phenol condensation
products may be used advantageously in the laying of screeds. The
mortars or concretes produced with the alkylated phenol
condensation products as plasticizers show no tendency towards
bleeding or sedimentation and may be homogeneously produced and
processed.
The process according to the invention is illustrated by the
following examples and tables:
EXAMPLE 1
(Production of Sample A)
376 g of phenol and 36 g of a 45% sodium hydroxide solution were
heated together to 80.degree. C., followed by the dropwise addition
of 800 g of a 30% formaldehyde solution. After the formaldehyde
solution had been added, the mixture was stirred for 10 minutes at
80.degree. to 90.degree. C., after which 1040 g of a 40%
NaHSO.sub.4 solution were slowly added and the mixture was stirred
for 6 hours at a temperature of 140.degree. C. The sample was then
diluted to a solids content of 30%.
EXAMPLE 2
(Production of Sample B)
500 g of a sample produced in accordance with Example 1 were
reacted for 2 hours at 80.degree. C. with 32.5 g of ethylene oxide
in an ethoxylation autoclave.
BUILDING TESTS
The basic mixture used was a concrete of 350 kg of PC 35 F/m.sup.3
concrete which has been produced with a watercement factor (WCF) of
0.56 using 0 to 16 mm aggregate. The zero concrete (no additions)
had been adjusted to a slump (according to DIN 1164) of 40 cm
(after jolting). The increase in slump (also expressed in cm) is
based on this value.
The following additives were used:
A=phenol polycondensed with formaldehyde and sulphonated through
methylol groups according to example 1,
B=same as A, except that 70 to 80% of the phenolic OH groups are
etherified with ethylene oxide=product according to the invention,
example 2
C=standard commercial flux based on ditolyl ether;
D=standard commercial flux based on amino-s-triazine resin.
The plasticizing effect is reflected in the increase in slump.
TABLE 1 ______________________________________ Increase in slump
Mix WCF (cm) ______________________________________ no additions
0.56 0 0.25% A 0.56 17 0.25% B 0.56 18 0.3% C 0.56 16.5 0.3% D 0.56
14.5 ______________________________________
The effect of various additions on the setting times was determined
on non-leaned samples to demonstrate the results more clearly. The
extremely pronounced retarding effect of Sample A is particularly
noticeable.
The additions were made to the mixing water. The setting times were
determined with a Vicat needle.
TABLE 2 ______________________________________ Effect of Fluxes on
the Setting Times Setting Times Mix WBF beginning / end
______________________________________ (a) Cement (PC 35 F) no
addition 0.275 3h 45 mins 4 h 5 mins. +0.75% A 0.275 14 h 30 mins.
20 h 25 mins. +0.75% B 0.275 5 h 20 mins. 7 h 50 mins. (b)
anhydrite binder (AB 20) no additions 0.275 4 h 5 mins. 4 h 55
mins. +0.75% A 0.275 sample only dries, does not set. +0.75% B
0.275 6 h 15 mins. 7 h 10 mins.
______________________________________
Table 3 illustrates the satisfactory setting behavior of cement
where the product according to the invention is added in contrast
to the non-alkylated phenolcondensate A.
The test was carried out as follows:
A thermocurve characterizing the hardening behavior was recorded in
a calorimeter with a temperature recorder connected thereto.
Where the setting time is determined by Vicat's method, the false
hardening can clearly be seen in the case of the conventional
phenol product A, whereas on the other hand the thermocurve shows
the true hardening times. By contrast, the product B according to
the invention shows normal setting behavior.
TABLE 3 ______________________________________ Testing of setting
behavior of PC 45 Setting Time according Thermocurve to Vicat
(mins) beginning/maximum Sample beginning/end (mins.)
______________________________________ 0 180/275 180/380 A 15/30
480/760 B 290/335 240/465
______________________________________
.[.The.]. Table 4 shows the pronounced retarding effect of the
conventional phenol compound A in contrast to product B according
to the invention on the basis of the strengths after different
times. In addition, this table shows the outstanding plasticizing
effect of the product according to the invention on a cement mortar
which had been leaned with 0 to 8 mm sand. Another remarkable
feature in this case is the strength values which, despite the
highly plasticized mortar, show virtually no reduction by
comparison with the non-plasticized 0-mortar.
TABLE 4
__________________________________________________________________________
Zero Sample: PC 35F 1:4 PV* leaned with 0-8 mm sand
__________________________________________________________________________
18 hours 24 hours Mix WBF* Slump UW* BTS* CS* % BTS CS %
__________________________________________________________________________
zero 0.57 10.0/13.5 2.30 0.98 4.15 100 3.57 15.1 100 sample B "
10.0/16.5 2.33 0.85 3.92 90 4.30 17.3 117 A " 10.0/16.0 2.34 0.31
1.15 34 3.40 16.0 100
__________________________________________________________________________
3 days 7 days 28 days Mix BTS CS % BTS CS % BTS CS %
__________________________________________________________________________
zero 5.60 31.0 100 6.42 37.5 100 6.71 48.4 100 sample B 5.40 30.3
97 6.50 38.3 102 7.08 46.7 101 A 5.17 31.6 97 6.22 39.9 101 7.87
49.9 110
__________________________________________________________________________
*PV = parts by volume WBF = water binder factor UW = unit weight
(kg/l) BTS = bending tension strength (N/mm.sup.2) CS = compressive
strength
The positive effect of the product according to the invention was
also in evidence where it was used in conjunction with gypsums.
Despite very good plasticization, an improvement in the strength
values was obtained in this case, too.
TABLE 5 ______________________________________ Effect of
plasticizers on fluidity, setting time and strength values in the
case of gypsum Setting time(mins.) Strengths/n/mm.sup.2 Sam- Slump
bending ple (cm) beginning end tension compressive
______________________________________ 0 18.5 17 .25 6.38 19.5 A 30
13 21 5.07 16.8 B 28 6 15 6.32 20.3
______________________________________ Agypsum was used.
EXAMPLE 3
The following tests were carried out to determine the effect of the
degree of alkylation on plasticization and setting times:
500 g of a sample produced in accordance with Example 1 were
reacted at 80.degree. C. in an ethoxylation autoclave with
______________________________________ (a) 16.8 g of ethylene oxide
= 0.43 mole per mole of phenol (b) 24.2 g of ethylene oxide = 0.62
mole per mole of phenol (c) 31.2 g of ethylene oxide = 0.8 mole per
mole of phenol (d) 38.7 g of ethylene oxide = 0.99 mole per mole of
phenol (e) 46.[.,.]..9 g of ethylene oxide = 1.2 mole per mol of
phenol (f) g of ethylene oxide ( = 1.54 mole per mole of phenol (g)
78.2 g of ethylene oxide = 2.0 mole per mole of phenol
______________________________________
The determination of slump, trace time and setting time where the
products are used for anhydrite is a very good indicator for the
activity test. The relevant data are given in Table 6.
1 kg of anhydrite, 250 g of water and 4 g of the particular sample
were intensively mixed, followed by determination of the degree of
slump, the trace time (in a dish) and the setting time according to
Vicat (in a ring). The trace time is understood to be that period
of time which passes before a trace drawn in the mix remains
intact.
As can be seen from table 6, products 3c and 3d are particularly
suitable.
Identical tests with non-leaned cement give similar results:
TABLE 6 ______________________________________ Slump Trace time
Setting time cm mins. hours/mins.
______________________________________ no additions 20.5 0 4 h 50'
Example 1 42.5 200 infinite Example 3a 42.5 190 infinite 3b 41.5
180 approximately 36 h 3c 41.0 100 12 h 3d 38.5 45 7 h 50' 3e 34 17
7 h 10' 3f 28 7 7 h 3g 26 4 6 h 50'
______________________________________
A mixture of 1 kg of cement, 300 g of water and, optionally, 5 g of
plasticizer produced the following result:
Without the plasticizer, the slump amounted to 10 cm and the
setting time to 5 hours. Where the product of Example 1, i.e. not
reacted with ethylene oxide, was used the slump increased to 33 cm,
but the setting time was too long, i.e. 14 hours. With the product
of Example 3 g, i.e. after reaction with 2 moles of ethylene oxide
per mole of phenol, the slump is very poor at only 11.5 cm,
although the setting time is good (4 hours 40 minutes). The
products of Example 3c and 3d, i.e. reacted with 0.8 and 0.99
moles, respectively, of ethylene oxide per mole of phenol, are
again the most suitable, giving a high slump of 30 cm and a good
setting time of 6.5 hours, i.e. only slightly higher than that of
the sample without added plasticizer.
EXAMPLE 4
This example demonstrates the outstanding properties of the
plasticizers according to the invention in regard to the
introduction of air and the resulting undesirable reduction in unit
densities.
800 g of cement, 4 kg of sand, 460 g of water and 4 g of the
plasticizer indicated below were mixed, and the resulting mixture
was introduced into a measuring vessel of granulated volume,
briefly compacted and then weighed out. The following densities
were measured:
______________________________________ Density
______________________________________ no addition 2.261 Example 1
2.261 Example 3a 2.261 3b 2.260 3c 2.259 3d 2.259 3e 2.259 3f 2.245
3g 2.237 ______________________________________
Up to Example 3e, the unit densities remained substantially
unchanged by comparison with the mixture containing no added
plasticizer, so that no air was introduced. With larger proportions
of reacted oxide (Example 3f and 3g), the unit densities fell
distinctly because air was introduced.
It will be appreciated that the instant specification and examples
are set forth by way of illustration and not limitation, and that
various modifications and changes may be made without departing
from the spirit and scope of the present invention.
* * * * *