U.S. patent application number 10/097895 was filed with the patent office on 2002-09-19 for use of polymers containing carboxyl groups and polyalkylene ether side chains as additives in mineral building materials.
This patent application is currently assigned to BASF Aktiengessellschaft. Invention is credited to Hartmann, Markus, Kistenmacher, Axel, Klingelhoefer, Paul, Perner, Johannes, Ruland, Alfred.
Application Number | 20020132946 10/097895 |
Document ID | / |
Family ID | 7815681 |
Filed Date | 2002-09-19 |
United States Patent
Application |
20020132946 |
Kind Code |
A1 |
Kistenmacher, Axel ; et
al. |
September 19, 2002 |
Use of polymers containing carboxyl groups and polyalkylene ether
side chains as additives in mineral building materials
Abstract
The present invention relates to the use of water soluble or
water dispersible polymers containing carboxyl groups, optionally
in latent form, and side-chains of general formula (I)
-X-Y-[-O-(-Alk-O) n -R] k as additives in mineral building
materials, wherein X, Y, Alk, R, n and k have the meanings cited in
claim 1. Said polymers can be obtained by polymerizing
ethylenically unsaturated monomers in the presence of compounds
containing phosphorus and, optionally, by additional
polymer-analogous transformation. The invention further relates to
the production of said polymers and the use thereof. Also described
are polymers, which can be obtained by polymerizing aromatic vinyl
compounds, olefins, cycloolefins and/or dienes, as D monomers and
anhydrides of ethylenically unsaturated dicarboxylic acids as E
monomers and which can be used both as parent compounds for the
above-mentioned polymers and as additives for mineral building
materials.
Inventors: |
Kistenmacher, Axel;
(Ludwigshafen, DE) ; Klingelhoefer, Paul;
(Mannheim, DE) ; Perner, Johannes; (Neustadt,
DE) ; Hartmann, Markus; (Neustadt, DE) ;
Ruland, Alfred; (Schriesheim, DE) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
BASF Aktiengessellschaft
Ludwigshafen
DE
|
Family ID: |
7815681 |
Appl. No.: |
10/097895 |
Filed: |
March 15, 2002 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10097895 |
Mar 15, 2002 |
|
|
|
09331167 |
Jun 21, 1999 |
|
|
|
6384111 |
|
|
|
|
09331167 |
Jun 21, 1999 |
|
|
|
PCT/EP97/07205 |
Dec 19, 1996 |
|
|
|
Current U.S.
Class: |
526/217 ;
526/303.1; 526/319; 526/335; 526/346; 526/348.6 |
Current CPC
Class: |
C04B 24/2647 20130101;
C08F 220/286 20200201; C08F 220/04 20130101 |
Class at
Publication: |
526/217 ;
526/319; 526/303.1; 526/335; 526/346; 526/348.6 |
International
Class: |
C08F 002/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 20, 1996 |
DE |
196 53 524.7 |
Claims
We claim:
1. Use of a water-soluble or water-dispersible polymer containing
carboxyl groups, if desired in latent form, and side chains of the
formula I, -X-Y-OAlk-O).sub.n-R].sub.k (I) where k is 1, 2, 3 or 4,
Y is a single bond or a C.sub.1-C.sub.4-alkylene unit or, when
k.noteq.1, can also be 5X is a single bond or a carbonyl group or,
when Y is not a single bond, can also be O, NR', 6where R' is
hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.5-C.sub.10-cycloalkyl,
C.sub.6-C.sub.20-aryl, C.sub.1-C.sub.20-alkanoyl,
C.sub.7-C.sub.21-aroyl, (Alk-O).sub.n-R or -Alk'-O(Alk-O).sub.n-R,
Alk is C.sub.2-C.sub.4-alkylene, Alk' is C.sub.1-C.sub.4-alkylene
which may also bear an OH group, n is a number in the range from 1
to 300, where n.gtoreq.12 when X is a single bond and n.gtoreq.2
when X is a carbonyl group and Y is a single bond, R is hydrogen,
C.sub.1-C.sub.20-alkyl, C.sub.5-C.sub.8-cycloalkyl,
C.sub.6-C.sub.20-aryl, C.sub.1-C.sub.20-alkanoyl or
C.sub.7-C.sub.21-aroyl, where the polymer is obtainable by
free-radical copolymerization of ethylenically unsaturated monomers
A containing carboxyl groups and ethylenically unsaturated monomers
B having side chains of the formula I and also, if desired, further
monomers C in the presence of from 0.1 to 50% by weight, based on
the monomers to be polymerized, of phosphorus-containing compounds,
or by free-radical copolymerization of ethylenically unsaturated
monomers containing reactive functional groups, if desired together
with monomers A and/or B and, if desired, further monomers C, in
the presence of from 0.1 to 50% by weight, based on the monomers to
be polymerized, of phosphorus-containing compounds and subsequent
conversion of at least part of the reactive functional groups into
side chains of the formula I and/or carboxyl groups, as additives
in mineral building materials.
2. Use as claimed in claim 1, wherein the phosphorus-containing
compound is selected from among phosphinic acid (H.sub.3PO.sub.2),
phosphonic acid (E.sub.3PO.sub.3) and the salts of these.
3. Use as claimed in any of the preceding claims, wherein the
polymer has a weight average molecular weight M.sub.w in the range
from 1000 to 300,000 Dalton, in particular from 5,000 to 150,000
Dalton.
4. Use as claimed in any of the preceding claims, wherein k=1 and X
is a carbonyl function or 7
5. Use as claimed in any of the preceding claims, wherein the
polymer is obtainable by free-radical copolymerization of at least
the monomers A and the monomers B, with the proviso that the
monomers B are selected from among the esters of monoethylenically
unsaturated C.sub.3-C.sub.6-carboxylic acids with alcohols of the
formula II HO).sub.p-Y-OAlk-O).sub.n-R (II) where Y, Alk, n and R
are as defined above and p=1 or, when Y is a single bond, p=0
and/or the amides of monoethylenically unsaturated
C.sub.3-C.sub.6-carboxylic acids with amines of the formulae III,
IIIa H.sub.2N-Alk'-OAlk-O).sub.n-R (III) H.sub.2NAlk-O).sub.n-R
(IIIa) where Alk, Alk', n and R are as defined above.
6. Use as claimed in claim 5, wherein the monomers A are selected
from among ethylenically unsaturated C.sub.3-C.sub.6-monocarboxylic
acids, C.sub.4-C.sub.6-dicarboxylic acids, their anhydrides, their
monoesters with C.sub.1-C.sub.12-alkanols or alcohols of the
formula II, their monoamides with NH.sub.3, with primary
C.sub.1-C.sub.12-alkylamines or with amines of the formulae III and
IIIa, and also the salts of said monocarboxylic and dicarboxylic
acids.
7. Use as claimed in any of claims 1 to 4, wherein the polymer is
obtainable by free-radical copolymerization of at least the
monomers A and the monomers B, with the proviso that the monomers B
are selected from among compounds of the formula IV
R.sup.2HC.dbd.CR.sup.1-YOAlk-O).su- b.n-R].sub.k (IV) where
R.sup.1, R.sup.2 are, independently of one another, hydrogen or
C.sub.1-C.sub.4-alkyl and Y, Alk, R, k are as defined above and
n>12.
8. Use as claimed in claim 7, wherein the monomers A are selected
from among the monomers specified in claim 6.
9. Use as claimed in any of claims 5 to 8, wherein the monomer
mixture to be polymerized comprises from 3 to 50% by weight of
monomers A, from 50 to 97% by weight of monomers B and from 0 to
30% by weight of monomers C.
10. Use as claimed in any of claims 1 to 4, wherein the polymer is
obtainable by free-radical copolymerization of ethylenically
unsaturated monomers containing reactive, functional groups in the
presence of from 0.1 to 50% by weight of phosphorus-containing
compounds and subsequent conversion of at least some of the
reactive, functional groups into side chains of the formula I
and/or carboxyl groups, where the reactive, functional groups are
selected from among cyclic anhydride groups and oxirane groups.
11. Use as claimed in claim 10, wherein the ethylenically
unsaturated monomers containing reactive, functional groups are
selected from among maleic anhydride, citraconic anhydride,
itaconic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, vinyl and
allyl glycidyl ethers and also the glycidyl esters of ethylenically
unsaturated C.sub.3-C.sub.6-monocarboxylic acids.
12. Use as claimed in claim 11, wherein the copolymer is obtainable
by free-radical copolymerization of said anhydrides with
vinylaromatic compounds, C.sub.2-C.sub.12-olefins,
C.sub.5-C.sub.8-cycloolefins and/or dienes and subsequent
conversion of the anhydride groups into carboxyl groups and side
chains of the formula I.
13. Use as claimed in any of the preceding claims, wherein the
polymer comprises structural units derived from maleimide which may
be substituted on the nitrogen by C.sub.1-C.sub.20-alkyl,
C.sub.6-C.sub.20-aryl or C.sub.7-C.sub.20-aralkyl.
14. A polymer as defined in any of claims 1 to 13, wherein
n.gtoreq.5 when X is a carbonyl group and n>12 when X is a
single bond.
15. A copolymer obtainable by polymerization of monomers D selected
from among vinylaromatic compounds, C.sub.2-C.sub.12-olefins,
C.sub.5-C.sub.8-cycloolefins and/or dienes and monomers E selected
from among maleic anhydride, citraconic anhydride, itaconic
anhydride and 1,2,3,6-tetrahydrophthalic anhydride in the presence
of from 0.1 to 50% by weight of phosphorus-containing compounds,
based on the monomers D and E.
16. A copolymer as claimed in any of claims 14 or 15 having a
weight average molecular weight M.sub.w in the range from 1,500 to
30,000.
17. A copolymer as claimed in any of claims 14 to 16, wherein the
monomer E is maleic anhydride.
18. A copolymer as claimed in claim 17, wherein the monomers D are
selected from among 1-butene, isobutene and 1-pentene.
19. A process for preparing the water-soluble or water-dispersible
polymer as claimed in claim 14 by free-radical polymerization of
ethylenically unsaturated monomers A containing carboxyl groups and
ethylenically unsaturated monomers B containing side chains of the
formula I and also, if desired, further monomers C, wherein the
polymerization is carried out in the presence of from 0.1 to 50% by
weight of phosphorus-containing compounds.
20. A process as claimed in claim 19, wherein the polymerization is
carried out in water or in a mixture of water and up to 60% by
weight, based on the mixture, of an OH-containing solvent selected
from among C.sub.1-C.sub.4-alkanols, C.sub.2-C.sub.10-alkylene
glycols, where the alkylene chain may be interrupted by one or more
non-adjacent oxygen atoms, and monoethers of
C.sub.2-C.sub.10-alkylene glycols with
C.sub.1-C.sub.4-alkanols.
21. A process for preparing the water-soluble or water-dispersible
polymer as claimed in claim 14 by free-radical polymerization of
ethylenically unsaturated monomers containing reactive functional
groups, if desired together with monomers A and/or B and, if
desired, further monomers C, wherein the monomers are polymerized
in the presence of from 0.1 to 50% by weight, based on the monomers
to be polymerized, of phosphorus-containing compounds and the
reactive functional groups are subsequently converted into carboxyl
groups and/or side chains of the formula I.
22. A process as claimed in any of claims 19 to 21, wherein the
major part, in particular at least 90%, of the
phosphorus-containing compound is fed continuously into the
reaction vessel during the polymerization.
23. A process for preparing the polymer as claimed in any of claims
15 to 18, which comprises polymerizing monomers D selected from
among vinylaromatic compounds, C.sub.2-C.sub.12-olefins,
C.sub.5-C.sub.8-cycloolefins and/or dienes and monomers E selected
from among maleic anhydride, citraconic anhydride, itaconic
anhydride and 1,2,3,6-tetrahydrophthalic anhydride in the presence
of from 0.1 to 50% by weight of phosphorus-containing compounds,
based on the monomers D and E.
Description
[0001] Use of polymers containing carboxyl groups and polyalkylene
ether side chains as additives in mineral building materials
[0002] The present invention relates to the use of polymers
containing carboxyl groups and polyalkylene ether side chains as
additives in mineral building materials.
[0003] For the purposes of the present invention, mineral building
materials are preparations comprising as essential constituents
mineral binders such as lime and/or, in particular, cement and
also, as aggregates, sands, gravels, crushed rock or other fillers,
eg. natural or synthetic fibers. The mineral building materials are
generally produced by mixing the mineral binders and the aggregates
together with water to convert them into a ready-to-use preparation
which when left to itself hardens with time both in air and under
water to give a stone-like material.
[0004] To obtain the desired processing property profile of the
ready-to-use preparation it is generally necessary to use a larger
amount of water than that required for the subsequent hydration or
curing process. This is the case particularly when a high
flowability of the ready-to-use preparation is desired, for example
when it is to be pumped. The excess water which evaporates later
forms voids in the building component and these lead to a
significant worsening of the mechanical properties and resistances
of the building component.
[0005] To reduce the amount of excess water while maintaining a
prescribed property profile, additives which are generally referred
to as water reducing agents, flow improvers and fluidizers are
generally added to the ready-to-use preparation. According to the
prior art, for example, the following compounds are recommended as
fluidizers for ready-to-use preparations of mineral building
materials:
[0006] Naphthalenesulfonic acid-formaldehyde condensates (EP-A 402
319), melamine-formaldehyde polycondensates (EP-A 402 319),
ligninesulfonates (EP-A 402 319) and also homopolymers and
copolymers of carboxylic acids and dicarboxylic acids with styrene
(EP-A 306 449 and U.S. Pat. No. 3,952,805) or isobutene or
diisobutene (DE-A 37 16 974, EP-A 338 293, DE-A 39 25 306, U.S.
Pat. No. 4,586,960, U.S. Pat. No. 4,042,407 and U.S. Pat. No.
4,906,298). EP 97 513 describes the use of copolymers of
unsaturated carboxylic acids and hydroxyalkyl esters of unsaturated
carboxylic acids as plasticizer additives in cement-containing
compositions.
[0007] The use of copolymers comprising carboxylic acid monomers
and polyalkylene oxide esters of acrylic acid and methacrylic acid
in copolymerized form as fluidizers for cement-containing
compositions is known from DE-A 44 20 444. However, the fluidizers
have to be used together with antifoams based on alkylene
polyethers in order to achieve the desired use properties.
[0008] The use of crosslinked polymers of ethylenically unsaturated
polyoxialkylene ethers, multiply unsaturated alkenyl ethers and
maleic anhydride as fluidizers for cement-containing compositions
is described in EP 619 277. However, the polyfunctional compounds
which are absolutely necessary for the desired properties are
complicated to prepare and make the product more expensive.
[0009] DE-A 195 13 126 describes copolymers based on oxialkylene
glycol-alkenyl ethers and unsaturated dicarboxylic acid derivatives
which comprise at least one further monomer selected from among
multiply unsaturated monomers or diesters of ethylenically
unsaturated carboxylic acids in copolymerized form. Such
terpolymers are likewise suitable for fluidizing cement-containing
compositions.
[0010] DE-A 4304 109 and EP-A 610 699 describe copolymers based on
maleic acid derivatives and vinyl monomers with the maleic acid
derivatives including maleimides and monoamides of maleic acid and
also, as an essential component, a monoester of maleic acid and a
polyalkylene alcohol. Such polymers are likewise suitable as
fluidizers for cement-containing mineral building materials.
However, it appears to be desirable to further reduce the
water/cement ratio of 0.5 given in the examples for flowable
preparations in order to achieve a higher strength of the set
concrete.
[0011] EP-A 537 870 describes copolymers of ethylenically
unsaturated carboxylic acids and/or sulfonic acids with monomers
containing polyether functions. Monomers described are, for
example, allyl ethers of polyethylene glycol having up to 11
ethylene oxide units. The polymers are preferably prepared in the
presence of sodium hypophosphite.
[0012] In summary, it can be said that the additives known from the
prior art for mineral building materials are still in need of
improvement. In particular, their fluidizing action at low
water/binder ratios is generally still not sufficient or is
retained for only a short time. Although a larger amount of the
fluidizer can partially compensate for this deficiency, it not only
makes such a procedure uneconomical but also results in
considerable deterioration of the achievable mechanical strength or
at least unacceptable slowing of the setting rate.
[0013] It is an object of the present invention to provide
additives for mineral building materials which, particularly in
respect of their fluidizing action, have advantages over the known
additives for mineral building materials. In particular, it is
desirable that in the case of low water/binder ratios there is no
need to accept disadvantages in the setting behavior or in respect
of the strength of the set building materials.
[0014] We have found that this object is achieved by a series of
water-soluble or water-dispersible polymers which have carboxyl
groups and side chains having a polyether structure and have
advantageous properties as additives for mineral building materials
if they are obtained by polymerization of ethylenically unsaturated
monomers containing carboxyl groups and/or side chains having a
polyether structure in the presence of phosphorus-containing
compounds. Alternatively, such polymers can be obtained by
polymer-analogous reaction of polymers which have been prepared in
the presence of phosphorus-containing compounds and contain
reactive groups.
[0015] The present invention accordingly provides for the use of
water-soluble or water-dispersible polymers containing carboxyl
groups, if desired in latent form, and side chains of the formula
I,
[0016] -X-YOAlk-O).sub.n-R].sub.k (I),
[0017] where
[0018] k is 1, 2, 3 or 4,
[0019] Y is a single bond or a C.sub.1-C.sub.4-alkylene unit or,
when k.noteq.1, can also be 1
[0020] X is a single bond or a carbonyl group or, when Y is not a
single bond, can also be O, NR', 2
[0021] where R' is hydrogen, C.sub.1-C.sub.20-alkyl,
C.sub.5-C.sub.10-cycloalkyl, C.sub.6-C.sub.20-aryl,
C.sub.1-C.sub.20-alkanoyl, C.sub.7-C.sub.21-aroyl, (Alk-O).sub.n-R
or -Alk'-O(Alk-O).sub.n-R,
[0022] Alk is C.sub.2-C.sub.4-alkylene,
[0023] Alk' is C.sub.1-C.sub.4-alkylene which may also bear an OH
group,
[0024] n is a number in the range from 1 to 300, where n.gtoreq.12
when X is a single bond and n.gtoreq.2 when X is a carbonyl group
and Y is a single bond,
[0025] R is hydrogen, C.sub.1-C.sub.20-alkyl,
C.sub.5-C.sub.8-cycloalkyl, C.sub.6-C.sub.20-aryl,
C.sub.1-C.sub.20-alkanoyl or C.sub.7-C.sub.21-aroyl,
[0026] where the polymers are obtainable by free-radical
copolymerization of ethylenically unsaturated monomers A containing
carboxyl groups and ethylenically unsaturated monomers B having
side chains of the formula I and also, if desired, further monomers
C in the presence of from 0.1 to 50% by weight, based on the
monomers to be polymerized, of phosphorus-containing compounds,
[0027] or by free-radical copolymerization of ethylenically
unsaturated monomers containing reactive functional groups, if
desired together with monomers A and/or B and, if desired, further
monomers C, in the presence of from 0.1 to 50% by weight, based on
the monomers to be polymerized, of phosphorus-containing compounds
and subsequent conversion of at least part of the reactive
functional groups into side chains of the formula I and/or carboxyl
groups,
[0028] as additives in mineral building materials.
[0029] The present invention further provides the polymers used if
n.gtoreq.5 when X is a carbonyl group and n>12 when X is a
single bond. The present invention also provides a process for
preparing these polymers.
[0030] In the following, C.sub.1-C.sub.20-alkyl is a linear or
branched, saturated hydrocarbon chain having up to 20, preferably
from 1 to 10, carbon atoms, eg. methyl, ethyl, n-propyl, i-propyl,
n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, s-pentyl, neopentyl,
1-, 2-, 3-methylpentyl, n-hexyl, 2-ethylhexyl, n-octyl,
3-propylheptyl, 1-decyl, 1-dodecyl, etc.
[0031] C.sub.1-C.sub.4-Alkylene includes, for example, methylene,
1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene,
1,3-butylene, 1,4-butylene and 2,3-butylene. The same applies to
C.sub.2-C.sub.4-alkylene.
[0032] C.sub.5-C.sub.10-Cycloalkyl is a cycloaliphatic radical
having a total of from 5 to 10 carbon atoms and selected from among
cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, each of which
may be unsubstituted or substituted by 1, 2, 3 or 4
C.sub.1-C.sub.4-alkyl groups, in particular by methyl groups.
[0033] C.sub.6-C.sub.20-Aryl is phenyl or naphthyl, each of which
may be unsubstituted or substituted by 1, 2, 3 or 4
C.sub.1-C.sub.10-alkyl groups, C.sub.1-C.sub.4-alkyloxy groups,
hydroxy groups, halogen, eg. chlorine, and can have up to 20 carbon
atoms.
[0034] C.sub.7-C.sub.20-Aralkyl is an aryl group which is bonded
via a C.sub.1-C.sub.4-alkylene unit and can have from 7 to 20
carbon atoms, eg. benzyl or ethylphenyl. C.sub.1-C.sub.20-Alkanoyl
is a radical derived from an aliphatic carboxylic acid and thus
includes formyl and those alkyl radicals which are bonded via a
carbonyl group. C.sub.7-C.sub.21-Aroyl corresponds to
C.sub.7-C.sub.21-arylcarbonyl and is an aryl radical which is
bonded via a carbonyl group and is thus derived from derivatives of
benzoic acid and napthoic acid.
[0035] Carboxyl groups are not only carboxylic acid groups (COOH)
but also neutralized carboxylic acid groups (COO.sup.-). Of equal
utility to the carboxyl groups are anhydride groups since these are
present as carboxyl groups under use conditions (building material
preparations are generally alkaline and promote the hydrolysis of
the anhydride groups). Accordingly, polymers having anhydride
groups as carboxyl groups in latent form in place of the carboxyl
groups are likewise subject matter of the present invention.
[0036] The formulae below are to be interpreted such that the
carbonyl carbon is connected to the polymer chain, possibly via a
methylene group, and the heteroatom is connected to Y: 3
[0037] Reactive functional groups include all groups which can
react with water, ammonia, hydroxyl groups of alcohols and NH.sub.2
groups of primary amines to form a bond. They include, in
particular, oxirane groups and cyclic anhydride groups.
[0038] For the purposes of the present invention,
phosphorus-containing compounds are both inorganic and organic
phosphorus compounds. The inorganic phosphorus compounds to be used
according to the present invention preferably include the oxo acids
of phosphorus and their salts which are soluble or dispersible in
the reaction medium, preferably their alkali metal, alkaline earth
metal or ammonium salts.
[0039] Examples of suitable inorganic phosphorus compounds are:
phosphinic acid (H.sub.3PO.sub.2) and the salts derived therefrom
such as sodium phosphinate (monohydrate), potassium phosphinate,
ammonium phosphinate; hypodiphosphonic acid (H.sub.4P.sub.2O.sub.4)
and the salts derived therefrom; phosphonic acid (H.sub.3PO.sub.3)
and the salts derived therefrom such as sodium hydrogen
phosphonate, sodium phosphonate, potassium hydrogen phosphonate,
potassium phosphonate, ammonium hydrogen phosphonate, ammonium
phosphonate; diphosphonic acid (H.sub.4P.sub.2O.sub.5) and the
diphosphonates derived therefrom; hypodiphosphoric acid
(H.sub.4P.sub.2O.sub.6) and the hypodiphosphates derived therefrom;
phosphoric acid (H.sub.3PO.sub.4) and the dihydrogen phosphates,
hydrogen phosphates and phosphates derived therefrom; diphosphoric
acid (H.sub.4P.sub.2O.sub.7) and the diphosphates derived therefrom
and also polyphosphoric acids and their salts such as sodium
triphosphate.
[0040] The polymers of the present invention are preferably
prepared in the presence of phosphinic acid (H.sub.3PO.sub.2) or
the salts derived therefrom such as sodium phosphinate monohydrate,
potassium phosphinate, ammonium phosphinate and/or phosphonic acid
(H.sub.3PO.sub.3) or the salts derived therefrom, eg. sodium
hydrogen phosphonate, sodium phosphonate, potassium hydrogen
phosphonate, potassium phosphonate, ammonium hydrogen phosphonate
and ammonium phosphonate. Particular preference is given to sodium
phosphinate monohydrate and/or phosphonic acid.
[0041] Phosphorus-containing compounds also include
organophosphorus compounds such as urea phosphate,
methanediphosphonic acid, propane-1,2,3-triphosphonic acid,
butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid,
1-aminoethane-1,1-diphosphonic acid, diethyl
(1-hydroxyethyl)phosphonate, diethyl hydroxymethylphosphonate,
1-amino-1-phenyl-1,1-diphosphonic acid,
aminotrismethylenetriphosphonic acid,
ethylenediaminotetramethylenetetraphosphonic acid,
ethylenetriaminopentamethylenepentaphosphonic acid,
1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic and
phosphonopropionic acids and their salts, diethyl phosphite,
dibutyl phosphite, diphenyl phosphite, triethyl phosphite, tributyl
phosphite, triphenyl phosphite and tributyl phosphate.
[0042] Also suitable are ethylenically unsaturated phosphorus
compounds such as vinyl phosphonate, methyl vinylphosphonate, ethyl
vinylphosphonate, vinyl phosphate, allyl phosphonate or allyl
phosphate.
[0043] Preferred organophosphorus compounds are
1-hydroxyethane-1,1-diphos- phonic acid and its disodium and
tetrasodium salts, aminotrismethylenetriphosphonic acid and its
pentasodium salt and ethylenediaminotetramethylenetetraphosphonic
acid and its salts.
[0044] It is often advantageous to combine a plurality of
phosphorus compounds, for example sodium phosphinate monohydrate
with phosphonic acid, phosphonic acid with disodium
1-hydroxyethane-1,1-diphosphonate and/or
aminotrimethylenetriphosphonic acid and/or 1-hydroxyethane-1,1-dip-
hosphonic acid. They can be mixed with one another in any ratio and
used in the polymerization.
[0045] The amount of phosphorus-containing compound is, based on
the monomers to be polymerized, generally from 0.1 to 50% by
weight, preferably from 0.5 to 25% by weight, in particular from 1
to 20% by weight, particularly preferably from 2 to 15% by weight
and very particularly preferably from 5 to 10% by weight.
[0046] Furthermore, for the action according to the present
invention of the polymers it is advantageous if the side chain of
the formula I has a certain length. Thus, n in the formula I is
preferably a number .gtoreq.5, in particular .gtoreq.10 and
particularly preferably .gtoreq.15.
[0047] The polymers have an activity optimum when n is in the range
from 20 to 60, but polymers of the formula I having shorter or
longer side chains are also suitable as additives for mineral
building materials. It is here generally unimportant whether the
unit -(Alk-O)n- is a uniformly built-up polyalkylene oxide unit or
is built up of different alkylene oxide units. In this case, the
alkylene oxide units can be arranged randomly or in blocks in the
polyalkylene oxide unit -(Alk-O)n-.
[0048] Alk is preferably 1,2-propylene, 1,2-butylene and in
particular 1,2-ethylene. The terminal unit R of the polyalkylene
oxide side chain of the formula I is preferably hydrogen or
C.sub.1-C.sub.4-alkyl, in particular methyl or ethyl. In the
formula I, Y is preferably a single bond, a
C.sub.1-C.sub.4-alkylene unit (Alk'), or possibly also a trivalent
radical derived from glycerol.
[0049] Particular preference is given to polymers in which X is a
carbonyl function or, when Alk' is a C.sub.1-C.sub.4-alkylene unit,
can also be 4
[0050] where R' is as defined above and is particularly preferably
hydrogen, C.sub.1-C.sub.4-alkyl, benzyl or phenyl. Very particular
preference is given to polymers in which X is a carbonyl function
and Y is a single bond.
[0051] It is also advantageous if the weight average molecular
weight of the polymers is in the range from 1,000 to 300,000
Dalton, preferably in the range from 5,000 to 150,000 Dalton, in
particular in the range from 8,000 to 100,000 Dalton and very
particularly preferably in the range from 12,000 to 70,000
Dalton.
[0052] In a preferred embodiment of the present invention, use is
made of polymers which are obtainable by free-radical
copolymerization of from 2 to 95% by weight, preferably from 3 to
50% by weight and in particular from 10 to 40% by weight, based on
the monomers to be polymerized, of ethylenically unsaturated
monomers A containing carboxyl groups and from 5 to 98% by weight,
preferably from 50 to 97% by weight and in particular from 60 to
90% by weight, of ethylenically unsaturated monomers B having side
chains of the formula I, and also, if desired, up to 50% by weight,
preferably up to 30% by weight and in particular up to 20% by
weight, of further monomers C in the presence of from 0.1 to 50% by
weight, preferably from 0.5 to 25% by weight, in particular from 1
to 20% by weight, particularly preferably from 2 to 15% by weight
and very particularly preferably from 5 to 10% by weight, of the
abovementioned phosphorus-containing compounds (Embodiment 1).
[0053] In this embodiment, the monomers A are selected from the
group consisting of ethylenically unsaturated
C.sub.3-C.sub.6-monocarboxylic acids such as acrylic acid,
methacrylic acid, crotonic acid, isocrotonic acid, 2-ethylpropenoic
acid; ethylenically unsaturated C.sub.4-C.sub.6-dicarboxylic acids
such as maleic acid, fumaric acid, itaconic acid, citraconic acid
and also the salts of the monocarboxylic and dicarboxylic acids
mentioned, in particular the sodium, potassium or ammonium salts;
the anhydrides of the ethylenically unsaturated
C.sub.4-C.sub.6-dicarboxylic acids, eg. maleic anhydride, itaconic
anhydride, citraconic anhydride; the monoesters of the
ethylenically unsaturated C.sub.4-C.sub.6-dicarboxylic acids with
C.sub.1-C.sub.12-alkanols or alcohols of the formula II
[0054] HO).sub.p-Y-OAlk-O).sub.n-R (II)
[0055] where p, Y, Alk, R and n are as defined above, eg.
monomethyl maleate, mono-n-butyl maleate, mono-n-butyl fumarate,
mono(methylpolyethylene glycol)maleate; the monoamides of the
ethylenically unsaturated C.sub.4-C.sub.6-dicarboxylic acids with
NH.sub.3, with primary C.sub.1-C.sub.12-alkylamines or with amines
of the formula III or IIIa
[0056] H.sub.2N-Alk'-OAlk-O).sub.n-R (III)
[0057] H.sub.2NAlk-O).sub.n-R (IIIa)
[0058] where Alk, Alk', n and R are as defined above, for example
(methylpolyethylene glycol)maleic monoamide.
[0059] In this embodiment of the present invention, the monomers B
are preferably selected from among the esters of monoethylenically
unsaturated C.sub.3-C.sub.6-monocarboxylic acids with alcohols of
the formula II and the amides of monoethylenically unsaturated
C.sub.3-C.sub.6-monocarboxylic acids with amines of the formula III
or IIIa. Examples of suitable monomers B include: hydroxyethyl
(meth)acrylate, hydroxyethyl(meth)acrylamide, hydroxypropyl
(meth)acrylate, hydroxypropyl(meth)acrylamide, polyethylene glycol
mono(meth)acrylate, polyethylene glycol mono(meth)acrylamide,
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, methoxypolyethylene glycol
mono(meth)acrylamide, methoxypolypropylene glycol
mono(meth)acrylate, methoxypolybutylene 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, ethoxypolyethylene
glycol mono(meth)acrylamide, 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
and ethoxypolyethylene glycol-polypropylene glycol-polybutylene
glycol mono(meth)acrylate.
[0060] Particularly preferred monomers B in this embodiment of the
invention are the esters of acrylic acid and in particular
methacrylic acid with the alcohols of the formula II. Particular
preference is given to the esters of those alcohols in which Y is a
single bond and n is a number .gtoreq.5, in particular .gtoreq.10
and particularly preferably .gtoreq.15. Very particular preference
is given to esters of those alcohols of the formula II in which Y
is a single bond and n is in the range from 20 to 60.
[0061] In this embodiment, the preferred monomers A are acrylic
acid and in particular methacrylic acid and also their sodium,
potassium and ammonium salts.
[0062] Particular preference is given to using polymers which are
built up of methacrylic acid and methylpolyethylene glycol
methacrylate. Very particular preference is given to polymers in
which the methylpolyethylene glycol methacrylate has from 10 to 60,
in particular from 21 to 55, ethylene oxide units. Methacrylic acid
and methylpolyethylene glycol methacrylate are preferably present
in a weight ratio of from 1:9 to 4:6, particularly preferably about
2:8.
[0063] Suitable monomers C include, as monomers C1,
C.sub.1-C.sub.10-alkyl esters of acrylic acid and methacrylic acid,
eg. methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl
(meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate,
i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl
(meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate,
n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl
(meth)acrylate, 2-propylheptyl (meth)acrylate; the vinyl and allyl
esters of C.sub.1-C.sub.12-monocarboxylic acids, eg. vinyl or allyl
formate, acetate, propionate and butyrate; vinyl and allyl ethers
of C.sub.1-C.sub.10-alkanols, eg. methyl vinyl ether, ethyl vinyl
ether, n-propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl
vinyl ether and the corresponding allyl ethers; the amides of
ethylenically unsaturated carboxylic acids, in particular
acrylamides and methacrylamides such as acrylamide, methacrylamide,
N-tert-butylacrylamide, N-methyl(meth)acrylamide.
[0064] The monomers C also include, as monomers C2, N-vinyl
compounds such as vinylacetamide, N-vinylpyrrolidone,
N-vinylimidazole, N-vinylcaprolactam and, as monomers C3,
acrylonitrile, allyl alcohol, vinylpyridine, acrolein and
methacrolein.
[0065] Furthermore, the monomers C include, as monomers C4,
vinylaromatic compounds such as styrene, .alpha.-methylstyrene,
vinyltoluene, vinylchlorobenzene, etc.; linear or branched
C.sub.2-C.sub.12-olefins such as ethene, propene, 1-butene,
2-butene, isobutene, 2-ethylbutene, 1-pentene, 2-methylpentene,
3-methylpentene, 4-methylpentene, 1-hexene, 1-octene and also
.alpha.-C.sub.8-C.sub.10-olefins; C.sub.4-C.sub.12-cycloolefins
such as cyclobutene, cyclopentene, cyclohexene or cyclooctene;
dienes such as butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene
and 1,3-octadiene. Preferred monomers C4 are vinylaromatic
compounds, in particular styrene and C.sub.2-C.sub.12-olefins, in
particular C.sub.2-C.sub.6-olefins and particularly preferably
1-butene, isobutene and 1-pentene.
[0066] In addition, the monomers C also include monomers C5 which
are ionizable in aqueous solution or have an ionic group. These
include ethylenically unsaturated sulfonic acids, eg. vinylsulfonic
acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic
acid, allyloxybenzenesulfonic acid,
2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl methacrylate,
2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 3-sulfopropyl
acrylate, sulfoethoxypolyethylene glycol (meth)acrylate (degree of
ethoxylation from 2 to 100), sulfoethoxypolypropylene glycol
methacrylate and also their salts, eg. their alkali metal or
ammonium salts; ethylenically unsaturated phosphonic acids such as
allylphosphonic acid, isopropenylphosphonic acid, vinylphosphonic
acid and also their salts, eq. their alkali metal or ammonium
salts; and also ethylenically unsaturated amines or ethylenically
unsaturated quaternized ammonium compounds such as
2-(N,N-dimethylamino)ethyl (meth)acrylate,
3-(N,N-dimethylamino)propyl (meth)acrylate,
2-(N,N,N-trimethylammonium)et- hyl (meth)acrylate,
3-(N,N,N-trimethylammonium)propyl (meth)acrylate chloride, and
N,N-diallyl-N,N-dimethylammonium chloride. As monomers C,
preference is given to using the monomers C5, in particular the
ethylenically unsaturated sulfonic acids and phosphonic acids or
their salts.
[0067] Further suitable monomers C are ethylenically unsaturated
siloxane compounds, for example vinylsilanes or
(meth)acryloxyalkylsilanes, as are described, for example, in EP-A
327 006, EP-A 327 376 or EP-A 612 771, and also
polydimethylsiloxane-bis(propylmaleic monoamide) or
polydimethylsiloxane-bis(propyleneaminomaleic monoamide).
[0068] In another preferred embodiment of the present invention,
the monomers B are selected from among compounds of the formula
IV
[0069] R.sup.2HC.dbd.CR.sup.1-YOAlk-O).sub.n-R].sub.k (IV)
[0070] where R.sup.1, R.sup.2 are, independently of one another,
hydrogen or C.sub.1-C.sub.4-alkyl and Y, Alk, R, k are as defined
above and n>12 (Embodiment 2). Preferred compounds B are, in
this case, the vinyl and allyl ethers of the formula V or Va
[0071] R.sup.2HC.dbd.CR.sup.1-OAlk-O).sub.n-R (V)
[0072] R.sup.2HC.dbd.CR.sup.1-CH.sub.2-OAlk-O).sub.n-R (Va)
[0073] where R.sup.1, R.sup.2, Alk, n and R are as defined above.
In particular, R is hydrogen or a C.sub.1-C.sub.4-alkyl group.
[0074] Examples of suitable monomers include: polyethylene glycol
mono(meth)allyl ether, polypropylene glycol mono(meth)allyl ether,
polyethylene glycol-polypropylene glycol mono(meth)allyl ether,
polyethylene glycol-polybutylene glycol mono(meth)allyl ether,
polypropylene glycol-polybutylene glycol mono(meth)allyl ether,
methoxypolyethylene glycol mono(meth)allyl ether,
methoxypolypropylene glycol mono(meth)allyl ether,
methoxypolybutylene glycol mono(meth)allyl ether,
methoxypolyethylene glycol-polypropylene glycol mono(meth)allyl
ether, methoxypolyethylene glycol-polybutylene glycol
mono(meth)allyl ether, methoxypolyethylene glycol-polypropylene
glycol-polybutylene glycol mono(meth)allyl ether,
ethoxypolyethylene glycol mono(meth)allyl ether,
ethoxypolypropylene glycol mono(meth)allyl ether,
ethoxypolybutylene glycol mono(meth)allyl ether, ethoxypolyethylene
glycol-polypropylene glycol mono(meth)allyl ether,
ethoxypolyethylene glycol-polybutylene glycol mono(meth)allyl
ether, ethoxypolypropylene glycol-polybutylene glycol
mono(meth)allyl ether ethoxypolyethylene glycol-polypropylene
glycol-polybutylene glycol mono(meth)allyl ether, polyethylene
glycol monovinyl ether, polypropylene glycol monovinyl ether,
polybutylene glycol monovinyl ether, polyethylene
glycol-polypropylene glycol monovinyl ether, polyethylene
glycol-polybutylene glycol monovinyl ether, polypropylene
glycol-polybutylene glycol monovinyl ether, polyethylene
glycol-polypropylene glycol-polybutylene glycol monovinyl ether,
methoxypolyethylene glycol monovinyl ether, methoxypolypropylene
glycol monovinyl ether, methoxypolybutylene glycol monovinyl ether,
methoxypolyethylene glycol-polypropylene glycol monovinyl ether,
methoxypolyethylene glycol-polybutylene glycol monovinyl ether,
methoxypolypropylene glycol-polybutylene glycol monovinyl ether,
methoxypolyethylene glycol-polypropylene glycol-polybutylene glycol
monovinyl ether, ethoxypolyethylene glycol monovinyl ether,
ethoxypolypropylene glycol monovinyl ether, ethoxypolybutylene
glycol monovinyl ether, ethoxypolyethylene glycol-polypropylene
glycol monovinyl ether, ethoxypolyethylene glycol-polybutylene
glycol monovinyl ether, ethoxypolypropylene glycol-polybutylene
glycol monovinyl ether, ethoxypolyethylene glycol-polypropylene
glycol-polybutylene glycol monovinyl ether.
[0075] In this embodiment too, the monomers B are polymerized in
amounts of from 5 to 98% by weight, preferably from 50 to 97% by
weight and in particular from 60 to 90% by weight. As regards the
type and amount of the phosphorus-containing compounds, what has
been said above applies.
[0076] As monomers A which are copolymerized in amounts of from 2
to 95% by weight, preferably from 3 to 50% by weight and in
particular from 10 to 40% by weight, based on the monomers to be
polymerized, it is possible to use the monomers A of Embodiment 1.
Particularly preferred monomers of this embodiment include maleic
acid, fumaric acid and/or maleic anhydride.
[0077] Very particularly preferred polymers of Embodiment 2 are
copolymers of from 2 to 30% by weight, based on the monomers to be
polymerized, of maleic acid or maleic anhydride and from 70 to 98%
by weight of polyglycol allyl ethers and/or polyglycol vinyl ethers
(mean degree of ethoxylation in each case from 15 to 60).
[0078] In this embodiment too, the abovementioned monomers C can be
present in copolymerized form in amounts of up to 50% by weight,
preferably up to 30% by weight and in particular up to 20% by
weight, based on the monomers to be polymerized.
[0079] In a further preferred embodiment of the present invention,
use is made of polymers which are obtainable by free-radical
copolymerization of ethylenically unsaturated monomers having
reactive, functional groups, if desired, together with the monomers
A and/or B and, if desired further monomers C, in the presence of
from 0.1 to 50% by weight, preferably from 0.5 to 25% by weight, in
particular from 1 to 20% by weight, particularly preferably from 2
to 15% by weight and very particularly preferably from 5 to 10% by
weight, based on the monomers to be polymerized, of the
abovementioned phosphorus-containing compounds and subsequent
conversion of at least part of the reactive functional groups into
side chains of the formula I and/or carboxyl groups (Embodiment
3).
[0080] Preferred reactive groups include cyclic anhydride groups
and oxirane groups. The monomers having reactive, functional groups
are preferably selected from among ethylenically unsaturated
dicarboxylic anhydrides, eg. maleic anhydride, citraconic
anhydride, 1,2,3,6-tetrahydrophthalic anhydride, vinyl and allyl
glycidyl ethers and also the glycidyl ethers of the abovementioned
ethylenically unsaturated C.sub.3-C.sub.6-monocarboxylic acids.
Particular preference is given to the abovementioned anhydrides, in
particular maleic anhydride.
[0081] The conversion of the initially obtainable polymers having
reactive, functional groups is generally carried out by reacting
the reactive, functional groups with alcohols of the formula II or
amines of the formula III or IIIa in the sense of a
polymer-analogous reaction. The reaction conditions required for
this purpose are known in principle to those skilled in the art
(for the alcoholysis of anhydrides see, for example, J. March, 3rd
Edition, John Wiley & Sons, New York, 1985, p. 347 and
literature cited therein; for the aminolysis of anhydrides see
ibid., p. 371 and literature cited therein; for the alcoholysis of
epoxides see ibid., p. 346 and literature cited therein; for the
amination of epoxides see ibid., p. 368 and literature cited
therein). The polymer-analogous reaction of the preferred
polymerized-in anhydride units can be carried out in the manner
described in DE-A 4304 109, DE-A 195 13126 or EP-A 610 699. The
documents mentioned are hereby incorporated in full by
reference.
[0082] Alcohols of the formula II suitable for the
polymer-analogous conversion include alkylpolyalkylene glycols such
as methylpolyethylene glycol having a mean degree of ethoxylation
of 45; alkylpolyethylene glycol-block-polypropylene glycols such as
methylpolyethylene glycol-block-polypropylene glycol having 40
ethylene oxide units and 5 propylene oxide units; alkylpolyethylene
glycol-random-polypropylene glycols, such as methylpolyethylene
glycol-random-polypropylene glycol having a random distribution of
30 ethylene oxide units and 10 propylene oxide units;
butylpolypropylene glycol having a mean degree of propoxylation of
20.
[0083] Polyalkylene glycol amines of the formula III or IIIa
suitable for the polymer-analogous conversion are, for example,
methylpolyethylene glycol amine having a mean degree of
ethoxylation of 8 or methylpolyethylene glycol-block-polypropylene
glycol amine having a mean degree of ethoxylation of 25 and a mean
degree of propoxylation of 5.
[0084] The monomers containing the reactive, functional groups are
preferably used in amounts of from 2 to 95% by weight, in
particular from 30 to 90% by weight and particularly preferably
from 50 to 90% by weight, based on the total amount of monomers to
be polymerized.
[0085] A preferred variant of Embodiment 3 is the use of polymers
which are built up of the abovementioned monomers C4, hereinafter
also referred to as monomers D, and the monomers E' which are
derived from monoesters of ethylenically unsaturated anhydrides
(monomers E). Such polymers can additionally comprise further
monomers C1, C2, C3 and/or C5, as mentioned above, in copolymerized
form.
[0086] Such polymers are in principle obtainable in two different
ways. Thus, on the one hand, the monoesters of the ethylenically
unsaturated dicarboxylic acids (monomers E') can be polymerized per
se together with the monomers D in the presence of the
phosphorus-containing compounds. Preference is given to polymers
which are obtainable by free-radical polymerization of the
abovementioned anhydrides of ethylenically unsaturated dicarboxylic
acids (monomers E) together with said monomers D which are
preferably selected from among vinylaromatic compounds, in
particular styrene and C.sub.2-C.sub.12-olefins, in particular
C.sub.2-C.sub.6-olefins and particularly preferably 1-butene,
isobutene and 1-pentene, in the presence of from 0.1 to 50% by
weight, preferably from 0.5 to 25% by weight, in particular from 1
to 20% by weight, particularly preferably from 2 to 15% by weight
and very particularly preferably from 5 to 10% by weight, based on
the monomers to be polymerized, of the phosphorus-containing
compounds and conversion of the polymerized-in anhydride units into
carboxylate groups and the side chains of the formula I according
to the present invention by reaction with alcohols of the formula
II.
[0087] The conversion of the anhydride units can be carried out
either during the polymerization reaction or after the
polymerization reaction. It is also possible to generate the
monoester in situ by reacting the ethylenically unsaturated
anhydride with the alcohol of the formula II in a reaction
preceding the polymerization and to polymerize this reaction
mixture with the monomers D in the presence of the
phosphorus-containing compounds.
[0088] A particularly preferred variant of this Embodiment 3
comprises the following steps:
[0089] 1. Reaction of the ethylenically unsaturated dicarboxylic
anhydride (monomer E) with an alcohol of the formula II, in the
presence or absence of an esterification catalyst, for example an
organic sulfonic acid,
[0090] 2. polymerization of this reaction mixture together with
monomers D and, if desired, further monomers E and/or further
alcohol of the formula II in the presence of the
phosphorus-containing compounds and free-radical polymerization
initiators,
[0091] 3. if appropriate, completion of the polymer-analogous
conversion of the anhydride units by increasing the reaction
temperature and/or by adding further alcohol of the formula II.
[0092] Preferred polymers of this embodiment are those which are
obtainable by polymer-analogous reaction of copolymers comprising
from 55 to 80% by weight of maleic anhydride and from 20 to 45% by
weight of 1-butene, isobutene or 1-pentene, or of copolymers
comprising from 30 to 60% by weight of maleic anhydride and from 40
to 70% by weight of styrene with alcohols of the formula II.
[0093] Polymers which are obtainable by free-radical polymerization
of the monomers D and the monomers E plus, if desired, further
monomers C in the presence of from 0.1 to 50% by weight of
phosphorus-containing compounds are novel and as starting polymers
for the polymers of the present invention having side chains of the
formula I and carboxyl groups are likewise subject matter of the
present invention.
[0094] Preferred polymers of this class are obtainable by
polymerization of from 5 to 98% by weight, in particular from 10 to
70% by weight and particularly preferably from 10 to 50% by weight,
based on the monomers to be polymerized, of monomers D with from 2
to 95% by weight, in particular from 30 to 90% by weight and
particularly preferably from 50 to 90% by weight, of monomers E and
also, if desired, up to 50% by weight, preferably up to 30% by
weight and particularly preferably up to 20% by weight, of monomers
C1, C2, C3 and/or C5.
[0095] It has now surprisingly been found that such polymers are
likewise suitable as additives for mineral building materials,
particularly when the monomers D are selected from among the
abovementioned olefins and/or cycloolefins. The use of such
polymers is accordingly likewise subject matter of the present
invention. Polymers in which monomer E is maleic anhydride are
particularly suitable. It is likewise advantageous for the use
properties if monomer D is selected from among 1-butene, isobutene
and 1-pentene. Very particular preference is given to polymers of
from 20 to 45% by weight of 1-butene, isobutene and/or 1-pentene
and from 55 to 80% by weight of maleic anhydride. Such copolymers
preferably have a weight average molecular weight M.sub.w in the
range from 1,500 to 35,000.
[0096] All abovementioned polymer classes of Embodiments 1 to 3 can
further comprise polymerized-in structural units derived from
maleimide which may be substituted on the nitrogen by
C.sub.1-C.sub.20-alkyl, C.sub.6-C.sub.20-aryl or
C.sub.7-C.sub.20-aralkyl. Suitable maleimide units are described,
for example, in DE-A 43 04 109, DE-A 195 13 126 and EP-A 610 699,
which are hereby incorporated in full by reference. Such polymers
are in principle obtainable in two different ways: thus, for
example, the abovementioned monomers can be copolymerized by a
free-radical mechanism with suitable derivatives of maleimide, with
the copolymerization being carried out in the presence of
phosphorus-containing compounds. Alternatively, it is possible to
use polymers which are obtainable by
[0097] 1. copolymerization of maleic anhydride with monomers
selected, in particular, from among the monomers of group A, group
B and/or group D, in the presence of phosphorus-containing
compounds,
[0098] 2. and subsequent polymer-analogous reaction of the
copolymerized maleic anhydrides with ammonia, primary
C.sub.1-C.sub.20-alkylamines, C.sub.6-C.sub.20-arylamines or
C.sub.7-C.sub.20-aralkylamines.
[0099] The polymers to be employed according to the present
invention are prepared, as mentioned above, by free-radical
polymerization of ethylenically unsaturated monomers A containing
carboxyl groups and ethylenically unsaturated monomers B having
side chains of the formula I and also, if desired, further monomers
C in the presence of from 0.1 to 50% by weight, preferably from 0.5
to 25% by weight, in particular from 1 to 20% by weight,
particularly preferably from 2 to 15% by weight and very
particularly preferably from 5 to 10% by weight, based on the
monomers to be polymerized, of phosphorus-containing compounds
(method 1)
[0100] or by free-radical copolymerization of ethylenically
unsaturated monomers having reactive, functional groups, if desired
together with monomers A and/or B and, if desired, further monomers
C in the presence of from 0.1 to 50% by weight, preferably from 0.5
to
[0101] 25% by weight, in particular from 1 to 20% by weight,
particularly preferably from 2 to 15% by weight and very
particularly preferably from 5 to 10% by weight, based on the
monomers to be polymerized, of phosphorus-containing compounds and
subsequent conversion of at least part of the reactive, functional
groups into side chains of the formula I and/or carboxyl groups
(method 2).
[0102] The phosphorus-containing compound can either be initially
charged in the reaction vessel or can be fed continuously or a
little at a time into the reaction mixture. Preferably, the major
part and in particular at least 90% of the phosphorus-containing
compound is added during the polymerization reaction.
[0103] The monomers to be polymerized can either be initially
charged in the reaction vessel or be fed into the reaction mixture
a little at a time or preferably continuously. Preferably, the
major part and in particular at least 90% by weight of the monomers
to be polymerized are added continuously to the reaction
mixture.
[0104] The polymerization can be carried out as a bulk
polymerization, solution polymerization or, if the monomers are
sparingly soluble, as an emulsion, dispersion or suspension
polymerization. It is likewise possible, if the polymer is
sufficiently sparingly soluble in the reaction mixture, to carry
out the polymerization as a precipitation polymerization.
[0105] If the polymers are prepared by method 1, the polymerization
is preferably carried out as a solution or precipitation
polymerization in water or in a mixture of water and up to 60% by
weight, based on the mixture, of an OH-containing solvent which is
selected from among C.sub.1-C.sub.4-alkanols,
C.sub.2-C.sub.10-alkylene glycols, in which the alkylene chain may
be interrupted by one or more non-adjacent oxygen atoms and
monoethers of the C.sub.2-C.sub.10-alkylene glycols with
C.sub.1-C.sub.4-alkanols. Examples of suitable OH-containing
solvents are methanol, ethanol, isopropanol, n-butanol, ethylene
glycol, diethylene glycol, methyl diglycol, dipropylene glycol,
butyl glycol, butyl diglycol, triethylene glycol, the methylethers
of said glycols and also oligomers of ethylene oxide containing
from 4 to 6 ethylene oxide units, oligomers of propylene oxide
containing from 3 to 6 propylene oxide units and also polyethylene
glycol-polypropylene glycol cooligomers. Furthermore, the aqueous
reaction medium can further comprise other water-miscible solvents
such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane,
N-methylpyrrolidone, dimethylformamide, etc.
[0106] If the polymers are prepared by method 2, the polymerization
is preferably carried out as a solution or precipitation
polymerization in an inert solvent. Suitable solvents include
cyclic ethers such as tetrahydrofuran or dioxane, ketones such as
acetone, methyl ethyl ketone, cyclohexanone, esters of aliphatic
carboxylic acids with C.sub.1-C.sub.4-alkanols, eg. ethyl acetate
or n-butyl acetate, aromatic hydrocarbons such as toluene, xylenes,
cumene, chlorobenzene, ethylbenzene, industrial mixtures of
alkylaromatics, cyclohexane and industrial mixtures of
aliphatics.
[0107] The polymerization can also be carried out as an emulsion or
suspension polymerization if the monomers are sparingly soluble in
the reaction medium. Such polymerization methods are known to those
skilled in the art and can be carried out in the customary manner
for the preparation of the polymers of the present invention. If
the preparation of the polymers of the present invention is carried
out by free-radical, aqueous emulsion polymerization, it is
advisable to add surfactants or protective colloids to the reaction
medium. A listing of suitable emulsifiers and protective colloids
may be found, for example, in Houben Weyl, Methoden der organischen
Chemie, Volume XIV/1 Makromolekulare Stoffe, Georg Thieme Verlag,
Stuttgart 1961, p. 411 ff.
[0108] The polymerization initiators used for the free-radical
polymerization are preferably soluble in the reaction medium. They
are used in amounts of up to 30% by weight, preferably from 0.05 to
15% by weight, particularly preferably from 0.2 to 8% by weight,
based on the monomers used in the polymerization.
[0109] If the polymerization is carried out in a water-containing
solvent, preference is given to using water-soluble polymerization
initiators such as sodium persulfate, potassium persulfate,
ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide,
2,2'-azobis(2-amidinopropane) dihydrochloride,
2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride and
2,2'-azobis(4-cyanopentanoic acid) The initiators are used either
alone or in admixture, eg. mixtures of hydrogen peroxide and sodium
persulfate.
[0110] The known redox initiator systems can also be used as
polymerization initiators. Such redox initiator systems comprise at
least one peroxide-containing compound in combination with a redox
coinitiator, for example sulfur compounds having a reducing action,
eg. bisulfites, sulfites, thiosulfates, dithionites and
tetrathionates of alkali metals and ammonium compounds, sodium
hydroxymethanesulfinate dihydrate and thiourea. Thus, it is
possible to use combinations of peroxodisulfates with alkali metal
or ammonium hydrogen sulfites, eg. ammonium peroxodisulfate and
ammonium disulfite. The weight ratio of peroxide-containing
compounds to the redox coinitiators is preferably from 30:1 to
0.05:1.
[0111] In combination with the initiators or the redox initiator
systems, it is possible to additionally use transition metal
catalysts such as iron, nickel, cobalt, manganese, copper, vanadium
or chromium salts, eg. iron(II) sulfate, cobalt(II) chloride,
nickel(II) sulfate, copper(I) chloride, manganese(II) acetate,
vanadium(III) acetate, manganese(II) chloride. Based on the
monomers, these transition metal salts are usually used in amounts
of from 0.1 ppm to 1000 ppm. Thus, it is possible to use
combinations of hydrogen peroxide with iron(II) salts, eg. from 0.5
to 30% of hydrogen peroxide and from 0.1 to 500 ppm of Mohr's
salt.
[0112] For the polymerization in a nonaqueous medium, preference is
given to using initiators such as dibenzoyl peroxide, dicyclohexyl
peroxydicarbonate, dilauryl peroxide, methyl ethyl ketone peroxide,
acetylacetone peroxide, tert-butyl hydroperoxide, cumene
hydroperoxide, tert-butyl perneodecanoate, tert-amyl perpivalate,
tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl
per-2-ethylhexanoate, tert-butyl perbenzoate,
azobisisobutyronitrile, 2,2'-azobis(N,N'-dimethyl-
eneisobutyramidine) dihydrochloride, 4,4'-azobis(4-cyanovaleric
acid). In combination with these initiators, it is possible to use
reducing agents such as benzoin, dimethylaniline, ascorbic acid
and, if desired, complexes and salts of transition metals which are
soluble in the reaction medium.
[0113] If the reaction mixture is partially polymerized at the
lower limit of the temperature range which is suitable for the
polymerization and is subsequently fully polymerized at a higher
temperature, it is advantageous to use at least two different
initiators which decompose at different temperatures so that a
sufficient concentration of free radicals is available in each
temperature range.
[0114] The polymerization reaction is preferably carried out at
from 30 to 300.degree. C., preferably from 50 to 160.degree. C. and
very particularly preferably from 80 to 150.degree. C. Preference
is given to carry out the reaction with exclusion of oxygen,
preferably in a stream of nitrogen. The polymerization is generally
carried out at atmospheric pressure, but it is possible to employ
lower or higher pressures, particularly when the polymerization
temperatures employed are above the boiling point of the monomers
and/or the solvent.
[0115] The polymer-analogous conversion of the reactive groups into
side chains of the formula I and/or carboxyl groups which follows
the polymerization in the case of method 2 is carried out in a
manner known per se using a method similar to that described for
Embodiment 3.
[0116] To set the desired molecular weight of the polymers, it may
be necessary to carry out the polymerization in the presence of a
molecular weight regulator, ie. a customary chain-terminating
substance. Suitable molecular weight regulators include, for
example, formaldehyde, acetaldehyde, propionaldehyde,
n-butyraldehyde, isobutyraldehyde, formic acid, ammonium formate,
hydroxylamine and its sulfate, chloride or phosphate; SH-containing
compounds such as thioglycolic acid, mercaptopropionic acid,
mercaptoethanol, mercaptopropanol, mercaptobutanols,
mercaptohexanol, thiomaleic acid, thiophenol,
4-tert-butylthiophenol, n-dodecylmercaptan, tert-dodecylmercaptan.
Further examples of polymerization regulators are allyl alcohol,
butenol, isopropanol, n-butanol, isobutanol, glycol, glycerol,
pentaerythritol.
[0117] If the use of polymerization regulators is required, they
are employed in amounts of up to 20% by weight, based on the
monomers. Polymerization is preferably carried out in the presence
of from 0.5 to 15% by weight of an SH-containing polymerization
regulator, based on the monomers.
[0118] Furthermore, it may be useful for the desired application to
employ crosslinked polymers. Crosslinked polymers are obtainable
either by copolymerization of the monomers mentioned with
ethylenically diunsaturated or polyunsaturated compounds or by
subsequent crosslinking of the carboxyl, anhydride or hydroxyl
groups in the polymer using appropriate polyfunctional compounds.
If crosslinking is carried out by the copolymerization route using
ethylenically polyunsaturated compounds, these are usually used in
proportions of from 0.01 to 20% by weight and preferably in amounts
of from 0.1 to 5% by weight, based on the monomers to be
polymerized. In the case of subsequent crosslinking of the
functional groups in the polymer using polyfunctional reactive
compounds, the latter are usually employed in amounts of from 0.2
to 20% by weight and in particular from 0.5 to 10% by weight, based
on the polymer.
[0119] Suitable ethylenically diunsaturated or polyunsaturated
compounds include: diacrylates or dimethacrylates of at least
dihydric saturated alcohols, eg. ethylene glycol diacrylate,
ethylene glycol dimethylacrylate, 1,2-propylene glycol diacrylate,
1,2-propylene glycol dimethacrylate, 1,4-butanediol diacrylate,
1,4-butanediol dimethacrylate, hexanediol diacrylate, hexanediol
dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol
dimethacrylate, 3-methylpentanediol diacrylate, 3-methylpentanediol
dimethacrylate; acrylic and methacrylic esters of alcohols having
more than 2 OH groups, eg. trimethylolpropane triacrylate,
trimethylolpropane trimethacrylate, glyceryl tri(meth)acrylate;
diacrylates or dimethacrylates of polyethylene glycols or
polypropylene glycols having molecular weights of, in each case,
from 200 to 9000, eg. diethylene glycol diacrylate, diethylene
glycol dimethacrylate, triethylene glycol diacrylate, triethylene
glycol dimethacrylate, tetraethylene glycol diacrylate,
tetraethylene glycol dimethacrylate, polyethylene glycol
(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol
diacrylate, polypropylene glycol (meth)acrylate; vinyl esters of
ethylenically unsaturated C.sub.3-C.sub.6-carboxylic acids, eg.
vinyl acrylate, vinyl methacrylate, vinyl itaconate; vinyl esters
of saturated carboxylic acids containing at least two carboxyl
groups and also divinyl and polyvinyl ethers of at least dihydric
alcohols, eg. divinyl adipate, butanediol divinyl ether,
trimethylolpropane trivinyl ether; allyl esters of ethylenically
unsaturated carboxylic acids, eg. allyl acrylate, allyl
methacrylate; allyl ethers of polyhydric alcohols, eg.
pentaerithritol triallyl ether; triallylsucrose, pentaallylsucrose;
methylenebis(meth)acrylamide, divinylethyleneurea,
divinylpropyleneurea, divinylbenzene, divinyldioxane, triallyl
cyanurate, tetraallylsilane and tetravinylsilane; bis- or
polyacryloylsiloxanes, diallyl phthalate, allyl vinyl ether,
diallyl fumarate.
[0120] Suitable polyfunctional, reactive compounds which can be
used for subsequent crosslinking are, in particular, glycidyl
ethers of polyhydroxy compounds or the glycidyl esters of
dicarboxylic or polycarboxylic acids. Examples of suitable
crosslinking compounds include: ethylene glycol diglycidyl ether,
polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether,
diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether,
sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether,
propylene glycol diglycidyl ether, polypropylene glycol diglycidyl
ether, resorcinol diglycidyl ether, diglycidyl o-phthalate,
diglycidyl adipate.
[0121] Furthermore, it can be advantageous for the use properties
of the polymers if some of the carboxyl groups present in the
polymer or reactive functional groups which may be present are
subsequently further modified by a polymer-analogous reaction. Such
modifications are known in principle to those skilled in the art.
In the case of conversion of the abovementioned reactive groups,
the modification can be carried out by the methods described for
Embodiment 3.
[0122] The polymer-analogous reaction is preferably carried out
using hydroxyl- or amino-containing compounds such as saturated or
unsaturated aliphatic alcohols, eg. methanol, ethanol, n-propanol,
isopropanol, n-butanol, isobutanol, n-pentanol, n-hexanol,
n-octanol, 2-ethylhexanol, nonanol, decanol, tridecanol,
cyclohexanol, tallow fatty alcohol, stearyl alcohol and also
C.sub.9-C.sub.11-oxoalcohols and C.sub.13-C.sub.15-oxoal- cohols;
or primary or secondary amines such as methylamine, ethylamine,
n-propylamine, isopropylamine, n-butylamine, isobutylamine,
hexylamine, cyclohexylamine, methylcyclohexylamine,
2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty
amine, stearylamine, oleylamine, taurine, dimethylamine,
diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,
diisobutylamine, dihexylamine, dicyclohexylamine,
di-methylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine,
di-isotridecylamine, di-tallow fatty amine, distearylamine,
dioleylamine, ethanolamine, diethanolamine, n-propanolamine,
di-n-propanolamine, morpholine and
bis(polydimethylsiloxane-1-prop-3-yl)amine.
[0123] The polymers of the present invention containing carboxyl
groups and side chains of the formula I are very useful as
additives for cement mixtures such as concrete or mortar. For the
purposes of the present invention, cement is, for example, Portland
cement, alumina cement or mixed cement such as pozzolanic cement,
slag cement or other types. Portland cement is preferred. The
copolymers are used in an amount of from 0.01 to 10% by weight,
preferably from 0.05 to 3% by weight, based on the weight of the
cement.
[0124] The polymers can be added in solid form, which is obtainable
by drying, for example by spray-drying, of polymer solutions or
dispersions as are formed in the polymerization, to the
ready-to-use preparation of the mineral building material. It is
also conceivable for the copolymers to be formulated with the
mineral binder and for the ready-to-use preparation of the mineral
building material to be prepared therefrom. Preference is given to
using the copolymer in liquid form, ie. dissolved, emulsified or
suspended form, for example in the form of the polymer solution, in
the preparation of the mineral building material.
[0125] For use in concrete or mortar, it can be advantageous to use
polymers which go over into a water-soluble and thus active form
only in the presence of the alkaline concrete or mortar, for
example polymers containing carboxylic acid or carboxylic anhydride
structures. The slow release of the active polymer results in an
activity which lasts for a longer time.
[0126] The polymers of the present invention can also be used in
combination with the known concrete fluidizers based on
naphthalene-formaldehyde condensate sulfonate,
melamine-formaldehyde condensate sulfonate, phenolsulfonic
acid-formaldehyde condensate and ligninsulfonates. They can also be
used in combination with high molecular weight polyethyleneoxides
(M.sub.w 100,000-8,000,000). Furthermore, they can be used together
with celluloses such as alkylcelluloses or hydroxyalkylcelluloses,
starches or starch derivatives. Moreover, additives such as air
pore formers, expanders, waterproofing agents, setting retarders,
setting accelerators, frost protection agents, sealants, pigments,
corrosion inhibitors, flow improvers, injection aids, stabilizers
and hollow microspheres can be mixed in.
[0127] In principle, the polymers of the present invention can also
be used together with film-forming polymers. These are polymers
having a glass transition temperature (DSC midpoint temperature,
ASTM D 3481-82) of <65.degree. C., preferably <50.degree. C.,
particularly preferably <25.degree. C. and very particularly
preferably <0.degree. C. A person skilled in the art is able to
select suitable polymers with the aid of the relationship between
the glass transition temperature of homopolymers and the glass
transition temperature of copolymers formulated by Fox (T. G. Fox,
Bull. Am. Phys. Soc. (Ser.II) 1, 1956, 123). (Glass transition
temperatures for homopolymers may be found, for example, in
Ullmanns Encyclopedia of Industrial Chemistry, Vol. A21, VCH,
Weinheim 1992, p. 169 or in J. Brandrup, E. H. Immergut, Polymer
Handbook 3rd Ed., J. Wiley, New York 1998).
[0128] Furthermore, it is often advantageous to use the polymers of
the present invention together with antifoams. This prevents, when
preparing the ready-to-use mineral building materials, too much air
being introduced into the concrete in the form of air pores which
would reduce the strength of the set mineral building material.
Suitable antifoams include, in particular, antifoams based on
polyalkylene oxide, for example dialkyl ethers of polyethylene
oxide and polypropylene oxide, eg. diethylene glycol heptyl ether,
polyethylene oxide oleyl ether, polypropylene oxide dibutyl ether,
2-ethylhexyl ethers of polyethylene oxide and polypropylene oxide.
Likewise suitable are the ethoxylation and propoxylation products
of alcohols having from 10 to 20 carbon atoms,
ethoxylated/propoxylated (alkyl)phenol such as propoxylated phenol
(degree of propoxylation from 2 to 40), ethoxylated (alkyl)phenol
(degree of ethoxylation from 2 to 50). Likewise suitable are the
diesters of alkylene glycols or polyalkylene glycols, for example
diethylene glycol dioleate and ethylene glycol distearate, or
aliphatic esters of alkylene oxide sorbitans, for example
polyethylene oxide sorbitan monolaurate and polyethylene oxide
sorbitan trioleate. Other suitable antifoams are phosphoric esters
such as tributyl phosphate or triisobutyl phosphate, phthalates
such as dibutyl phthalate, siloxanes such as polydimethylsiloxane
and their derivatives as are obtained, for example, by
hydrosilylation using allyl alkoxylates. Also suitable are anionic
antifoams such as the sulfuric monoesters of ethoxylated
(alkyl)phenols, eg. methylpolypropylene oxide sulfate sodium salt
and n-dodecylphenol ethoxylate sulfate sodium salt, or phosphates
of ethoxylated fatty alcohols such as polyethylene oxide stearyl
phosphate. Such antifoams are usually used in amounts of from 0.05
to 10% by weight and preferably from 0.5 to 5% by weight, based on
the polymers.
[0129] The antifoams can be combined with the polymer in various
ways. For example, if the polymer is in the form of an aqueous
solution, the antifoam can be added as solid or in dissolved form
to the polymer solution. If the antifoam is not soluble in the
aqueous polymer solution, emulsifiers or protective colloids can be
added to stabilize it.
[0130] If the polymer of the present invention is in the form of a
solid as is obtained, for example, by spray drying or fluidized-bed
spray granulation, the antifoam can be mixed in as solid or else
processed together with the polymer in the spray drying or spray
granulation process.
EXAMPLES
[0131] I. Analytical Methods
[0132] Ia. Determination of the Mean Molecular Weight
[0133] The weight average molecular weight was determined by gel
permeation chromatography (GPC) using aqueous eluents. Calibration
was carried out using a narrow-distribution sodium polyacrylate
standard. Eluents used were an aqueous solution of potassium
dihydrogen phosphate and sodium chloride. Ethylene glycol was used
as internal standard. The chromatography columns were loaded with
TSK PW-XL 3000 and TSK PW-XL 5000 (from TosoHaas) as stationary
phase. A differential refractometer was used as detector.
[0134] Ib. Determination of the K Value
[0135] The K values of the aqueous sodium salt solutions of the
copolymers were determined by the method of H. Fikentscher,
Cellulose-Chemie, Volume 13 (1932), 58-64 and 71-74, in aqueous
solution at a pH of 7, a temperature of 25.degree. C. and a polymer
concentration of the sodium salt of the copolymer of 1% by
eight.
[0136] Ic. Determination of the Solids Content
[0137] A defined amount of the sample (about 0.5-1 g) is weighed
into an aluminum dish (initial weight). The sample is dried for 3
minutes under an IR lamp (160 volt). The mass of the sample is then
determined again (final weight). The percentage solids content SC
is calculated as follows:
[0138] SC=final weight.times.100/initial weight [% by weight]
[0139] II. Methods of Preparation for Copolymers 1 to 10
[0140] Copolymer 1 (According to the Present Invention)
[0141] A 2 l glass reactor fitted with anchor stirrer, 5 automatic
feed metering facilities, reflux condenser and oil bath heating was
charged with 522.85 g of deionized water and the water was heated
to boiling under inert gas. Feed stream 1 consisting of 192 g of
methylpolyethylene glycol methacrylate (having a mean degree of
ethoxylation of 22) and 360 g of deionized water, feed stream 2
consisting of 48 g of methacrylic acid, feed stream 3 consisting of
60 g of a 20% strength solution of sodium phosphinate monohydrate
in deionized water and feed stream 4 consisting of 70.3 g of a 2.5%
strength solution of sodium peroxodisulfate in deionized water
were, commencing simultaneously, metered uniformly into the reactor
over a period of 4 hours. The reaction mixture was subsequently
allowed to polymerize further for 1 hour at the boiling point. The
mixture was then cooled to 30.degree. C. and neutralized using 37 g
of a 50% strength solution of sodium hydroxide in deionized water.
This gave a clear solution of the polymer having a pH of 7.0 and a
solids content of 20.4% by weight. The K value is 31.9, the weight
average molecular weight is 20,300.
[0142] Copolymer 2 (Comparative Example)
[0143] A 4 l glass reactor fitted with anchor stirrer, 4 automatic
feed metering facilities, reflux condenser and oil bath heating was
charged with 1199 g of deionized water and the water was heated to
boiling under inert gas. Feed stream 1 consisting of 403.2 g of
methylpolyethylene glycol methacrylate (having a mean degree of
ethoxylation of 22) and 750 g of deionized water, feed stream 2
consisting of 100.8 g of methacrylic acid and feed stream 3
consisting of 147.6 g of a 2.5% strength solution of sodium
peroxodisulfate in deionized water were, commencing simultaneously,
metered uniformly into the reactor over a period of 4 hours. The
reaction mixture was subsequently allowed to polymerize further for
1 hour at the boiling point. The mixture was then cooled to
30.degree. C. and neutralized using 78 g of a 50% strength solution
of sodium hydroxide in deionized water. This gave a clear solution
of the polymer having a pH of 7.0 and a solids content of 19.8% by
weight. The weight average molecular weight was 40,000, the K value
was 42.2.
[0144] Copolymer 3 (According to the Present Invention)
[0145] A 2 l glass reactor fitted with anchor stirrer, 5 automatic
feed metering facilities, reflux condenser and oil bath heating was
charged with 523 g of deionized water and the water was heated to
boiling under inert gas. Feed stream 1 consisting of 192 g of
methylpolyethylene glycol methacrylate (having a mean degree of
ethoxylation of 22) and 360 g of deionized water, feed stream 2
consisting of 48 g of methacrylic acid, feed stream 3 consisting of
54 g of an 11.1% strength solution of sodium phosphinate
monohydrate in deionized water and feed stream 4 consisting of 70.3
g of a 2.5% strength solution of sodium peroxodisulfate in
deionized water were, commencing simultaneously, metered uniformly
into the reactor over a period of 4 hours. The reaction mixture was
subsequently allowed to polymerize further for 1 hour at the
boiling point. The mixture was then cooled to 30.degree. C. and
neutralized using 44.3 g of a 50% strength solution of sodium
hydroxide in deionized water. This gave a yellow-brown, slightly
turbid solution of the polymer having a pH of 7.0 and a solids
content of 20.2% by weight. The K value is 33.9, the weight average
molecular weight is 25,100.
[0146] Copolymer 4 (According to the Present Invention)
[0147] A 2 l glass reactor fitted with anchor stirrer, 5 automatic
feed metering facilities, reflux condenser and oil bath heating was
charged with 523 g of deionized water and the water was heated to
boiling under inert gas. Feed stream 1 consisting of 192 g of
methylpolyethylene glycol methacrylate (having a mean degree of
ethoxylation of 22) and 360 g of deionized water, feed stream 2
consisting of 48 g of methacrylic acid, feed stream 3 consisting of
72 g of a 33.3% strength solution of sodium phosphinate monohydrate
in deionized water and feed stream 4 consisting of 70.3 g of a 2.5%
strength solution of sodium peroxodisulfate in deionized water
were, commencing simultaneously, metered uniformly into the reactor
over a period of 4 hours. The reaction mixture was subsequently
allowed to polymerize further for 1 hour at the boiling point. The
mixture was then cooled to 30.degree. C. and neutralized using
41.60 g of a 50% strength solution of sodium hydroxide in deionized
water. This gave a yellow-brown solution of the polymer having a pH
of 7.0 and a solids content of 20.8% by weight. The K value is
25.6, the weight average molecular weight is 13,500.
[0148] Copolymer 5 (According to the Present Invention)
[0149] A 2 l glass reactor fitted with anchor stirrer, 5 automatic
feed metering facilities, reflux condenser and oil bath heating was
charged with 523 g of deionized water and the water was heated to
boiling under inert gas. Feed stream 1 consisting of 192 g of
methylpolyethylene glycol methacrylate (having a mean degree of
ethoxylation of 22) and 360 g of deionized water, feed stream 2
consisting of 48 g of methacrylic acid, feed stream 3 consisting of
72 g of a 33.3% strength solution of sodium phosphinate monohydrate
in deionized water and feed stream 4 consisting of 70.3 g of a 2.5%
strength solution of sodium peroxodisulfate in deionized water
were, commencing simultaneously, metered uniformly into the reactor
over a period of 4 hours. The reaction mixture was subsequently
allowed to polymerize further for 1 hour at the boiling point. 3.7
g of diglycidyl ortho-phthalate were then added to the mixture and
the mixture was heated at the boiling point for 3 hours while
stirring. The mixture was subsequently cooled to 30.degree. C. and
neutralized using 42.2 g of a 50% strength solution of sodium
hydroxide in deionized water. This gave a yellow-brown solution of
the polymer having a pH of 7.0 and a solids content of 21.3% by
weight. The K value is 25.5, the weight average molecular weight is
13,100.
[0150] Copolymer 6 (According to the Present Invention)
[0151] A 2 l glass reactor fitted with anchor stirrer, 5 automatic
feed metering facilities, reflux condenser and oil bath heating was
charged with 523 g of deionized water and the water was heated to
boiling under inert gas. Feed stream 1 consisting of 192 g of
methylpolyethylene glycol methacrylate (having a mean degree of
ethoxylation of 22) and 360 g of deionized water, feed stream 2
consisting of 48 g of methacrylic acid, feed stream 3 consisting of
60 g of a 50% strength by weight solution of phosphonic acid in
deionized water and feed stream 4 consisting of 70.3 g of a 2.5%
strength solution of sodium peroxodisulfate in deionized water
were, commencing simultaneously, metered uniformly into the reactor
over a period of 4 hours. The reaction mixture was subsequently
allowed to polymerize further for 1 hour at the boiling point. This
gave a red-brown, clear solution of the polymer having a pH of 7.0
and a solids content of 21.3% by weight. The K value is 40.0, the
weight average molecular weight is 36,400.
[0152] Copolymer 7 (Comparative Example)
[0153] To prepare feed stream 1, 52.26 g of maleic anhydride were
melted under nitrogen in a heatable flask and 120.00 g of
polyethylene glycol having a mean degree of ethoxylation of 12 were
added thereto. While stirring further, the following were
subsequently added thereto: 0.02 g of hydroquinone monomethyl
ether, 1.33 g of dodecyl mercaptan and 2.34 g of
azobisisobutyronitrile. 120.00 g of polyethylene glycol (having a
mean degree of ethoxylation of 12) and 2.6 g of maleic anhydride
were placed in a 2 l glass reactor fitted with anchor stirrer, 5
automatic feed metering facilities, reflux condenser and oil bath
heating. The reactor was heated under a nitrogen atmosphere to an
internal temperature of 100.degree. C. Feed stream 1 (see above)
and feed stream 2 consisting of 53.32 g of styrene were, commencing
simultaneously, metered into the reactor over a period of 1 hour.
The mixture was subsequently stirred further for 1 hour at
100.degree. C., 0.24 g of azobisisobutyronitrile was added and
stirring was continued for another 1 hour at 100.degree. C. The
internal temperature was then increased to 140.degree. C. and 25.66
g of a propylene oxide-ethylene oxide block copolymer containing 30
propylene oxide units and 4 ethylene oxide units were added over a
period of 5 minutes. The mixture was held at 140.degree. C. for two
more hours while stirring. It was then cooled to 65.degree. C. and
470 g of deionized water were added. The mixture was subsequently
cooled to 25.degree..degree.C., 470.00 g of deionized water were
added and the mixture was neutralized using 34.2 g of 50% strength
sodium hydroxide solution. This gave a brown, very turbid solution
of the polymer having a pH of 7.0 and a solids content of 41.5% by
weight. The K value is 20.2, the weight average molecular weight is
18,600.
[0154] Copolymer 8 (According to the Present Invention)
[0155] To prepare feed stream 1, 52.3 g of maleic anhydride were
melted under nitrogen in a heatable flask. 120 g of polyethylene
glycol having a mean degree of ethoxylation of 12 were added
thereto. While stirring further, the following were subsequently
added: 0.02 g of hydroquinone monomethyl ether, 1.33 g of dodecyl
mercaptan, 2.34 g of azobisisobutyronitrile and 17.4 g of
phosphorous acid (98% by weight). 120 g of polyethylene glycol
having a mean degree of ethoxylation of 12 and 2.6 g of maleic
anhydride were placed in a 2 l glass reactor fitted with anchor
stirrer, 5 automatic feed metering facilities, reflux condenser and
oil bath heating. The reactor was heated under a nitrogen
atmosphere to an internal temperature of 100.degree. C. Feed stream
1 (see above) and feed stream 2 consisting of 53.3 g of styrene
were, commencing simultaneously, metered into the reactor over a
period of 1 hour. The mixture was subsequently stirred further for
another 1 hour at 100.degree. C., 0.24 g of azobisisobutyronitrile
was added and stirring was continued for a further 1 hour at
100.degree. C. The internal temperature was then increased to
140.degree. C. and 25.66 g of a propylene oxide-ethylene oxide
block copolymer containing 30 propylene oxide units and 4 ethylene
oxide units were added over a period of 5 minutes. The mixture was
held at 140.degree. C. for two more hours while stirring. It was
then cooled to 65.degree. C. and 470 g of deionized water were
added. The mixture was subsequently cooled to 25.degree. C., 470 g
of deionized water were added and the mixture was neutralized using
34.2 g of 50% strength sodium hydroxide solution. This gave a
yellow-brown, slightly turbid solution of the polymer having a pH
of 7.0 and a solids content of 41.4% by weight. The K value is
23.4, the weight average molecular weight is 21,000.
[0156] Copolymer 9 (According to the Present Invention)
[0157] A 2 l glass reactor fitted with anchor stirrer, 5 automatic
feed metering facilities, reflux condenser and oil bath heating was
charged with 451 g of deionized water and the water was heated to
boiling under inert gas. Feed stream 1 consisting of 172.8 g of
methylpolyethylene glycol methacrylate (having a mean degree of
ethoxylation of 22) and 360 g of deionized water, feed stream 2
consisting of 43.2 g of methacrylic acid, feed stream 3 consisting
of 24 g of 2-acrylamido-2-methylpropanesul- fonic acid and 72 g of
deionized water, feed stream 4 consisting of 60.00 g of a 20%
strength solution of sodium phosphinate monohydrate in deionized
water and feed stream 5 consisting of 70.3 g of a 5% strength
solution of sodium peroxodisulfate in deionized water were,
commencing simultaneously, metered uniformly into the reactor over
a period of 4 hours. The reaction mixture was subsequently allowed
to polymerize further for 1 hour at the boiling point. The mixture
was then cooled 30.degree. C. and neutralized using 49.5 g of a 50%
strength solution of sodium hydroxide in deionized water. This gave
a yellow-brown, slightly turbid solution of the polymer having a pH
of 7.0 and a solids content of 20.7% by weight. The K value is
36.4, the weight average molecular weight is 29,100.
[0158] Copolymer 10 (According to the Present Invention)
[0159] A 2 l glass reactor fitted with anchor stirrer, 5 automatic
feed metering facilities, reflux condenser and oil bath heating was
charged with 526 g of deionized water and the water was heated to
boiling under inert gas. Feed stream 1 consisting of 120 g of
methylpolyethylene glycol methacrylate (having a mean degree of
ethoxylation of 45) and 360 g of deionized water, feed stream 2
consisting of 120 g of methacrylic acid, feed stream 3 consisting
of 60 g a 20% strength solution of sodium phosphinate monohydrate
in deionized water and feed stream 4 consisting of 69.4 g of a 5%
strength solution of sodium peroxodisulfate in deionized water
were, commencing simultaneously, metered uniformly into the reactor
over a period of 4 hours. The reaction mixture was subsequently
allowed to polymerize further for 1 hour at the boiling point. The
mixture was then cooled 30.degree. C. and neutralized using 105.50
g of a 50% strength solution of sodium hydroxide in deionized
water. This gave a brown, clear solution of the polymer having a pH
of 7.0 and a solids content of 21.4% by weight. The K value is
42.8, the weight average molecular weight is 43,200.
[0160] Copolymer 11 (Comparative Example)
[0161] According to copolymer 1 a copolymer was prepared by
polymerizing 192 g of methylpolyethylene glycol methacrylate
(having a mean degree of ethoxylation of 22) and 48 g of
methacrylic acid. Differing from the preparation of copolymer 1
feed stream 1 contained a solution of 1.8 g mercaptoethanol in 8 g
deionized water.
[0162] A clear polymer solution was obtained having a pH of 7.0, a
solids content of 20.2% by weight. The K-value is 31.3, the weight
average molecular weight is 19,900.
[0163] Use Tests
[0164] Test method for concrete fluidizers based on DIN 1048 Part 1
(testing of the fluidizing action of additives for concrete)
[0165] Apparatus:
[0166] Multiflow stirrer, type SE/GB (electric motor)
[0167] Stirred vessel (h=20.7 cm ; d=40.6 cm)
[0168] Table for testing slump (700 mm.times.700 mm with movable
upper plate, see DIN 1048 Part 1, 3.2.1.1)
[0169] Truncated cone mold (internal diameter at top: 130 mm;
internal diameter at bottom: 200 mm; see DIN 1048 Part 1,
3.2.1.1)
[0170] Apparatus for measuring air pore content (see DIN 1048 Part
1, 3.5.1); sample container (h=8.3 cm ; d=12.3 cm) with pressure
measuring apparatus which can be screwed on top
[0171] Shaking table (electric)
[0172] Stopwatch
[0173] Wooden rod (d=1.5 cm; l=55 cm)
[0174] Hand scoop (capacity about 0.6 l)
[0175] Plastic cube mold (internal edge length (L * W * H=15 cm *
15 cm * 15 cm; open at one side)
[0176] Materials Used:
[0177] Mix: Mixing ratio cement/aggregate 1:5.56, grading curve B
16
1 Quartz sand F34 825 g Quartz sand 0.15-0.6 mm 1665 g Quartz sand
0.5-1.25 mm 2715 g Quartz sand 1.5-3.0 mm 1485 g Gravel 3-8 mm 3765
g Gravel 8-16 mm 3330 g Heidelberger cement CEM I 32.5R 2475 g Tap
water 1081 g
[0178] Fluidizer in accordance with Table 1 (% of fluidizer, based
on solid polymer per amount of cement used; "solid-solid")
[0179] Notes:
[0180] The amount of water added with the fluidizer has to be
subtracted from the proportion of tap water. The water/cement ratio
is 0.44. The quality of the cement used is checked by sifting.
[0181] Test Procedure:
[0182] a. Preparation of the Concrete:
[0183] All the aggregates and the cement are weighed into the
stirred vessel and mixed dry for 1 minute using the Multiflow
stirrer. Two thirds of the calculated amount of water is then added
over a period of 30 seconds while stirring. Over the next 30
seconds, the remaining third of water admixed with fluidizer is
added to the mixture. The concrete is then stirred further for
another 3 minutes. The preparation of the concrete mixture is
complete after a total of 5 minutes. After preparation of the
concrete, the first value for determining the slump is
measured.
[0184] b. Slump Test:
[0185] After stirring the finished concrete composition for 5
minutes, the first measurement of the slump is made. (See DIN 1048
Part 1, 3.2.1.2 Procedure for testing slump). After determining the
slump, the concrete from the table for testing slump is returned to
the stirred vessel. After a total of 29 minutes 45 seconds, the
concrete is again mixed for 15 seconds. The second measurement is
carried out after exactly 30 minutes. This procedure is repeated
after total times of 60, 90 and 120 minutes or until the measured
value of the spread in the slump test has been reduced to a
diameter of less than 30 cm.
[0186] c. Air Pore Content:
[0187] The air content of fresh concrete is measured by the
pressure equilibration method using a calibrated test apparatus
having a capacity of 1 l. The air pore content is determined after
the first and last measurement of the slump. For this purpose, the
1 l container of the apparatus for measuring the air pore content
is filled with concrete while the concrete is being compacted for
60 seconds on a shaking table. The container has to be full to the
brim with concrete after the shaking procedure. (For procedure, see
DIN 1048 Part 1, 3.5 Air content). The measurement of the air pore
content is then carried out.
[0188] d. Compressive Strength Test:
[0189] Owing to the influence of the concrete fluidizers to be
tested on the setting capability of the concrete, a compressive
strength test is carried out when required. The compressive
strength is determined on test specimens having an edge length of
15 cm * 15 cm * 15 cm. At least two cubes are produced from the
concrete mixture. The test specimens are produced by half-filling
the cubes with concrete, compacting the concrete for 20 seconds on
the shaking table and then adding sufficient concrete to the cube
mold for the concrete surface to be higher than the brim of the
actual mold after further compaction for 20 seconds. Finally, the
surface of the test specimens is leveled so that the surface is
flush with the height of the cube molds. The test specimens for the
compressive strength test are stored in a closed room at about
23.degree. C. They are first set down in their molds and covered to
protect them from moisture loss. After about 18 hours, the cubes
are removed from the molds and after 24 hours from the time at
which the concrete mixture was prepared a cube is tested by means
of a press. The force value reached in KN is reported in N/mm.sup.2
and indicates the strength of the concrete after 24 hours. After
storage of the second concrete cube for 28 days from the time of
preparation of the concrete, the same test procedure is repeated on
the remaining test specimen and the compressive strength after 28
days is determined.
[0190] Notes:
[0191] Before each new series of tests, a test without addition of
fluidizer (blank value) is to be carried out. Care must also be
taken to ensure that the ambient temperature is constant
(23-25.degree. C.).
2TABLE 1 Results Spread in slump test in cm Anti- Early Fluid-
Amount foam.sup.2) 3 30 60 90 120 AP.sup.4) strength.sup.5) izer
[%].sup.1) [%].sup.3) min min min min min [%] [N/mm.sup.2] None --
20 x.sup.6 x x x 2.5 29 Lignin- 0.75 -- 30 20 x x x 3.0 30 sulfa-
nate Naph- 0.75 -- 37 31 28 x x 2.8 30 thalene- sulfa- nate
Melamine 1.0 -- 35 27 x x x 2.4 30 conden- sate Copo- 0.24 1 55 40
34 31 29 2.6 32 lymer 1 Copo- 0.24 1 47.5 30 x x x 2.9 31 lymer 2
(C) Copo- 0.30 -- 51 41 38 37 x 4.5 30 lymer 3 Copo- 0.24 1 55 40
34 31 29 2.6 32 lymer 3 Copo- 0.20 -- 40 36 33 34 x 4.5 29 lymer 5
Copo- 0.24 -- 26 x x x x 2.5 30 lymer 7 (C) Copo- 0.24 1 49 34 30 x
x 3.1 29 lymer 11 (C) .sup.1) Based on cement (solid-solid) .sup.2)
Tributyl phosphate .sup.3) Based on solid concrete fluidizer
.sup.4) Air pore content .sup.5) After 24 hours .sup.6) Spreading
no longer observed C = Comparative example
[0192] The results show that mineral building material preparations
containing the copolymers of the present invention, even at a
water/cement ratio of 0.44, have a significantly longer time window
in which they are capable of flow than mineral building material
preparations containing the fluidizers of the prior art without a
loss of strength having to be accepted.
* * * * *