Note: Descriptions are shown in the official language in which they were submitted.
2~0~2
BASFAKTlE- GESELLSCh~FT o.~. ooso/~220~
Use ~f a Copolymer ~ased on Long-chain M~no-olefins
and/or Alkylvinyl Ethers and Ethylenically ~)nsaturated
Dicarboxylic Anhydrides for Hydrophobizing Coll~idal
Sealing Dicarboxyiic Anhydrides for Hydrophobizing
C::olloidal Sealing Compounds, Plas~ers, P~ints and
Building ~dhesives
The invention relates to the use of a copolymer obtained by free-radical
copolymerization of
(a) from 30% to 50% molar of one or more C13-C40-mono-olefins and/or
s C1O-C40-alkylvinyl ethers with
(b) from 50% to 70% molar of one or more ethylenically unsaturated C4-C8- dicarboxylic anhydrides
as a means for rendering colloidal sealing compnunds, plasters, paints, and
building adhesives hydrophobic.
The water resistance of colloidal sealing compounds, plasters, paints, and
building adhesives is frequently improved by the use of hydrophobizing
S agents.
Examples of such hydrophobizing agents are silicones, paraffins, ethylene
wax dispersions, metallic soaps, eg zinc stearate, and distearyl dilcetene. The
use of silicones often leads to surface flaws such as fish eyes due to incom-
20 patability problems, and also it is not always possible to apply a second coatof a paint containing silicones, since the latter migrate to the surface of thefirst coat, where they exert a negative influence on adhesion. Ethylene wax
dispersions do not generally create flow problems, but they reduce the gloss
of sparingly pigmented paints, that is, they frequently act as flatting agents.
25 Their hydrophobizing action is, moreover, only fair; since such ethylene wax
dispersions contain large amounts of emulsifier, which are frequently used in
an amount of from 4% to 15%, based on the wax.
It is very difficult to achieve a homogeneous distribution of metallic soaps.
30 such as zinc stearate, in aqueous paint mixtures, and said soaps also have
a flatting effect. Ion-sensitive dispersions might coagulate due to the
presence of such metallic soaps.
It is not easy to work distearyl diketene, either alone or dissolved in an
;
BAS~AKTIENGEsQLscHAFr 2 0 6 O 8 0 2 o.z.oaso/42208
organic solvent, into aqueous paint formulations.
The water resistance may also be improved by the addition of reactive sub-
stances such as resins based on melamine, urea, or phenol, or alkylamino-
silanes or alkylchlorosilanes. Such resins are only effective at relatively hightemperatures, whilst the silanes shorten the shelf life of aqueous disperse
systems (cf. Rompp, 1983, Vol. 3, ,o. 1796, Frank'sche Ver/agsanstal~
W. Keller & Co., Stuttgart, and ~. Rein~ard, Dispersion~n synthetischer Hoch-
polymerer, Part 2, Springer Ver/ag, Berlin, 1969).
DE-OS 3, 733, 172 describes a fuel for Otto-cycle engines which contains,
inter alia, a small amount of a copolyrner of (a) C1-~30-alkyivinyl ethers or
mixtures of Cl-C30-alkylvinyl ethers with olefins of from 2 to 40 carbon
atoms and (b) maleic anhydride and which have a molar mass of from 500
s to 20,000 g/mole and in which some or all of the anhydride groups of the
copolymer have been reacted with an alkali metal base or alkaline earth
metal base and the remainder of the carboxyl groups have been reacted
with an alcohol and/or amine to form the corresponding ester groups and/or
amide groups, and/or ammonium salts.
It is an object of the invention to provide an improved agent for hydrophobiz-
ing sealing compounds, plasters, paints, and buildinJ adhesives.
According to the invention, this object is achieved by the use of a copoly-
25 mer obtained by free-radical copolymerization of
(a) from 30% to 50% molar of one or more C~3-C40-mono-olefins and/or
C10-C40-alkylvinyl ethers with
30 (b) from 50% to 70% molar of one or more ethylenically unsaturated C4-C8-
dicarboxylic anhydrides
as a means for rendering colloidal sealing compounds, plasters, paints, and
building adhesives hydrophobic.
3;
We have also founcl that copolymers in which the anhydride groups have
been solvolyzed following polymeri7ation are very suitable for rendering seal-
ing compounds, plasters, paints, and building adhesives hydrophobic.
40 We have further found that copolymers in which the anhydride groups have
been solvolyzed and at least 10% of the resulting carboxyl groups have been
-- , , ~ :
~ ' '. . . ~
-
~ .~ .. - . , ~
- 2 0 ~ 2
E~ASFAKTIE~GESE~LScHAFT 3 o.z.ooso/42208
- neutralized with a base are particularly well suited for use as hydrophobizing
agents.
The invention also relates to colloidal sealin~ compounds, plasters, paints,
s and building adhesives containing the aforementioned copolymers.
Said copolyrners are described in, say, DE-OS 3,733,172. They are prepared
by copolymerizing monomer from group (a) with monomer from group (b)
and optionally solvolyzing the anhydride !3roups of the resulting copolymer
10 and partially neutralizing the carboxyl groups produced by said solvolysis.
The monomers in group (a) are C10-C40-al~ylvinyl ethers or mixtures of said
alkylvinyl ethers with C,3-C40-mono-olefins. Examples of said alkylvinyl
ethers are n-decylvinyl ether, dodecylvinyl ether, isododecylvinyl ether, n-tri-15 decylvinyl ether, isotridecylvinyl ether, n-tetradecylvinyl ether, n-hexadecyl-
vinyl ether, n-oc~adecylvinyl ether, n-eicosylvinyl ether, n-docosylvinyl ether,n-tetracosylvinyl ether, n-hexacosylvinyl ether, n-octacosylvinyl ether, oleyl-
vinyl etherJ and mixtures of the above alkylvinyl ethers.
20 Suitable mono-olefins having from 13 to 40 carbon atoms are, for example,
tetradecene-1, hexadecene-1, octadecene-1, C20-olefin-1, C22-olefin-1, C24-
olefin-1, C2~-C24-olefin-l, C24-C28-olefin-~, C30-olefin-l, C35-olefin-~, and
C40-olefin-1. These olefins or olefin mixtures are commercial products. As a
result of the processes involved in their manufacture, the olefins may
25 contain small amounts of inert hydrocarbons, for example up to about
5% w/w. The olefins are usually used in commercial quality and do not
require additional purification. The preferred olefins are C~6-C30-olefins.
When employed as monomers of group (a) for copolymerization, the said
olefins are used either alone or in admixture with the aforementioned alkyl-
vinyl ethers. Alternatively, these alkylvinyl ethers may be used alone as
monomers of group (a). The proportion of alkylvinyl ether and olefin may be
from 0% to 100% w/w in each case, and is preferably from ~0% to 90% w/w.
35 The components (b~ of the copolymers are monoethylenically unsaturated C4-
C8-dicarboxylic anhydrides, for example maleic anhydride, itaconic anhydride,
mesaconic anhydride, citraconic anhydride, methylenemalonic anhydride, and
mixtures thereof. Of these anhydrides, we prefer the C4-C6-dioic anhydrides,
especially maleic anhydride.
The copolymers contain from 30% to 50% molar of monomer units from
c~
., -
-- - : .. - . .
: ' ~
. - .
.~:
2 ~ 9 2
~ASFA~ ENGESELLSC~A~T 4 o.z.ooso/42208
group (a) and from 50% to 70% molar of said dicarboxylic anhydride units,
and their gram-rnolecular Yveight is generally from 500 to 20,000, preferably
from 800 to tO,000, g/mole. They are preferably obtained by polymerizing
monomers from groups (a) and (b) in a molar ratio of from 1:1 to 1:2. It is
s particularly preferred to polymerize the rnonomers (a) and (b) in a molar
ratio of approximately 1:1 or to use an excess of monomer from group (b)
of not more than 10% w/w.
The copolymers may be prepared by any conventional polymerization
process, for example by polymerization in substance, in suspension, or in
solution, or by precipitation. Copolymerization is preferably carried out in thepresence of ~ree-radical compounds. The amount of such compounds
required is generally from 0% to 10% w/w, and preferably from 0.2% to 5%
w/w, based on the weight of monomers involved in the copolymerization. All
of the aforementioned polymerization processes are carried out with the
exclusion of oxygen, preferably under a blanket of nitrogen. All of said
polymerization processes are carried out in conventional apparatus such as
autoclaves and boilers equipped with, say, anchor screws, blade mixers,
impeller mixers, or multistage countercurrent pulse mixers. We particularly
20 prefer to polymerize the monomers from groups (a) and (b) in substance.
This is carried out at a temperature of from 80 to 300C, preferably frGm
120 to 200C, the lower limit of the selected range being at least 20C
above the glass transition temperature of the polymer formed. The
polymerization conditions are adjusted according to the desired molecular
25 weight of the target copolymer. Polymerization at high temperatures results
in copolymers of low molecular weight, whilst low-temperature polymeriza-
tion yields polymers of high molecular weight. The amount of polymerization
initiator also has an influence on the molecular weight. In general, an
amount of from 0% to 10% w/w of free-radical polymerization initiators is
30 required, based on the total weight of monomer used for polymerization.
Larger quantities of initiator lead to copolymers of lower molecular weight.
The monomers of groups (a) and (b) may be polymerized in the absence of
polymerization initiators, if desired, provided the temperature is above 200C.
That is to say, the use of initiators is not obligatory, since said monomers
35 (a) and (b) undergo lFree- radical polymerization at temperatures above
200C in the presence or absence of initiators.
Examples of suitable polymerization initiators are acetylcyclohexane sulfonyl-
peroxide, diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-
40 ethylhexyl peroxydicarbonate, t-butyl peroxyneodecanoate, 2,2'-azo-bis(4-
methoxy-2,4-dimethylvaleronitrile), t-butyl peroxypivalate, t-butyl peroxy-2-
- . . . . .
- -
- ~ ~ :- ~ . ' , ' '
BASFAKTlEr GESELLSCHAFr 5 2 ~ ~ O ~ 0 2 o z.ooso/42208
ethylhexanoate, t-butyl peroxymaleate, 2,2'-azo-bis(isobutyronitrile), bis(t-butyl-
peroxy)cyclohexane, t-butyl peroxyisopropylcarbonate, t-butyl peracetate, di-t-
butyl peroxide, di-t-amyl peroxide, cum0ne hydroperoxide, and t-butyl
hydroperoxide. The said initiators may be used alone or in admixture with
each other. When the monomers are polymerized in substance, the initiator
or mixture of initiators is fed to the polymerization reactor preferably as a
separate stream or dissolved or dispersed in the monomer from group (a).
Redox co-initiators may, of course, be used in the copolymerization process,
examples being benzoin, dimethylaniline, ascorbic acid, and organically
soluble complexes of heavy metals such as copper, cobalt, iron, manganese,
nickel, and chromium. The use of redox co-initiator permits the use of lower
temperatures for the polymerization. The normally used amount of redox co-
initiator is ~rom about 0.1 to ~,000 ppm, preferably from 0.1 to 1,000 ppm,
based on total monomers. If the poiymerization of the monomer mixture is to
be commenced at the lower limit of the temperature range to be used for
polymerization and is to be completed at a higher ternperature, it will be
advantageous to use at least two different initiators which decompose at
different temperatures, so that a sufficient concentration of free radicals willbe present at each temperature level.
When it is desired to manufacture polymers of low molecular weight, it will
often be expedient to carry out the copolymerization in the presence of a
chain stoppage regulator. Conventional regulators may be used for this
purpose, for example C1-C4-aldehydes, formic acid, and compounds con-
Z5 taining organic SH groups, such as 2-mercapto-ethanol, 2-mercaptopropanol,
mercapto-acetic acid, mercaptopropionic acid, t-butyl mercaptan, n-dodecyl
mercaptan, and t-dodecyl mercaptan. These polymerization regulators are
generally used in a concentration of from 0.1% to 10% w/w, based on the
total monomers.
The copolymerization may be carried out batchwise or continuously. For
example, one or more alkylvinyl ethers or one or more olefins or a mixture
of one or more alkylvinyl ethers with at least one olefin may be placed in
the reactor and heated to the desired polymerization temperature with
35 stirring. Once the ~emperature of the monomer(s~ in the reactor has reached
the desired value for polymerization, the ethylenically unsaturated dicarboxylicanhydride is added. If an initiator is used, this is added to the reaction
mixture preferably as a separate stream or dissolved in one of the mono-
mers of group la) to take part in the polymeri7ation. The po~ymerization
40 regulator, if used, is added to the polymerization mixture either as a
separate stream or also dissolved in one of the monomers of group (a). The
. .: ~ . ~
.
.
~A5FAKTIENGEsELLscHAFT 2 3 ~ 2 o.z.ooso/42208
ethylenically unsaturated carboxylic anhydride, in particular maleic anhydride,
is preferably added to the reaction mixtura as molten substanGe. The
temperature of the molten maleic anhydride may be from 60 to 1 00C,
preferably from 70 to 90C.
s
The monomers of groups (a) and (b) rnay, of course, be processed by
methods such as are used in precipitation or suspension polymerization.
In precipitation polymerization, use is made of a solvent in which the
monomers, eg vinyl ether and/or olefin and maleic anhydride, are soluble,
but in which the resultin~ polymer is insoluble, with the result that the latterprecipitates. Examples of such solvents are aromatic hydrocarbons such as
benzene, toluene, o-xylene, m-xylene, p-xylene, and commercial xylene
mixtures, ethylben7ene, cumene, and halohydrocarbons such as methylene
chloride, 1,1- and 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloro-
ethylene, 1,1,2-trichloroethane, perchloroethylene, 1,2-dichloropropane, butyl
chloride, 1,1,2-trichloro-1,2,2-trifluoroethane, 1,~,1,2-tetrachloro-2,2-difluoro-
ethane, 1,1,2,2-tetrachloro-1,2-difluoroethane, and ethers such as diethyl
ether, dipropyl ether, dibutyl ether, methyl-t-butyl ether, diethyleneglycoldi-
20 methyl ether, and mixtures thereof.
In suspension polymerization, solvents are used in which all or at least oneof the monomers and the resulting polymer are insoluble. Suitable solvents
for this purpose are straight-chain and branched-chain aliphatic and
25 cycloaliphatic hydrocarbons. Examples of preferred solvents are pentane,
hexane, heptane, octane, iso-octane, cyclohexane, methylcyclohexane,
ethylcyclohexane, dimethylcyclohexane, diethylcyclohexane, and mixtures
thereof.
30 When polymerization is carried out by the precipitation method, it is
advantageous, particularly if the concentrations of monomer or copolymer
are higher than 40% w/w, to operate in the presence of a protective colloid
in order to avoid aggregation. In the case of suspension polymeri~ation it is
obligatory to operate in the presence of a protective colloid, in order to
35 prevent undesirable agglomeration of the resulting polymer.
Suitable protective colloids are polymeric substances which are readily
soluble in solvents and are inert to the monomers. Examples of suitable
substances are copolymers of maleic anhydride with C~2-C30-alkylvinyl
ethers and/or olefins of from 8 to 20 carbon atoms and preferably their
monoesters with C~0-C20-alcohols, or monoamides or diamides with C10-C20-
.
BASFAKTIENGESELLSCHAFT 7 2 ~ 2 o.z.ooso/42208
alkylamines, and poly(C,-C20-alkyl)vinyl ethers such as polymethylvinyl ether,
polyethylvinyl ether, poly-isobutylvinyl ether, and polyoctadecylvinyl ether. The
amount of protective colloid used is normally between 0.05% to 4% w/w
and is preferably between 0.1% and 2% w/w ~based on totai monomers), and
s it is often an advantage to use a combination of two or more protective
colloids.
To carry out the polymerization, it is advantageous to place the solvent,
protective colloid and one of the monomers in a reactor and, at the desired
lO polymerization temperature, to meter in the comonomer and initiator together
with any co-initiator or regulator used, with vigorous stirring. It is generallyimmaterial whether the maleic anhydride is initially placed in the reactor and
the alkylvinyl ether and/or olefin are metered in or whether the alkylvinyl
ether and/or olefin are initially placed in the reactor and the maleic anhyd-
ride is added. It is, of course, equally possible to place only the solvent and
protective colloid in the reactor and to feed in the monomers ( alkylvinyl
ether and/or olefin and maleic anhydride) concurrently. The feed times for
- monomer and initiator are generally between 1 and 10 hours, preferably
between 2 and 5 hours. Alternatively, all components may be polymerized
zO together in the reactor, but this gives rise to heat removal problems which
make this method less suitable. The concentration of the monomers to be
polymerized is generally from 20% to 80% w/w and preferably from 30% to
70% w/w. The polymer may be directly isolated from the polymer suspension
in an evaporator such as a belt drier, paddle drier, spray drier, or fluidizing
25 drier. Precipitation and suspension polymerization techniques are particularly
suitable for the manufacture of copolymers of maleic anhydride and alkylvinyl
ethers of from 10 to 12 carbon atoms. If longer-chain alkyivinyl ethers
and/or olefins are used, the stage may be reached where the resulting
copolymer is soluble in the aforementioned solvents and the polymerization
30 must therefore be regarded as a solution polymerization.
Solution polymerization is carried out in solvents in which both the
monomers and the resulting copolymer are soluble. All solvents are suitable
for this purpose which fulfil this requirement and which do not react with
35 the monomers. Examples thereof are acetone, methylethyl ketone, diethyl
ketone, methylisobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran,
and dioxane, of which tetrahydrofuran and dioxane are particularly suitahle
for the manufacture of low molecular weight copolymers. As in the case of
polymerization in substance or suspension or by precipitation, it is
40 advantageous to place the solvent and one of the monomeric components in
the reactor and to rneter in the second component together with the initiator
.: ~
. .
- ~ , ., -: - - ,
2~a~2
;FAltTlENGEsELLsc~AFr 8 o.z.ooso/42208
- and any co-initiator or regulator. The solvent and rnaleic anhydride may be
placed in the polymerization reactor and, once the polymerization
temperature has been reached, the alkylvinyl ether and/or olefin plus initiator
and any co-initiator or regulator may be metered in. However, a more favor-
s able technique comprises using the solvent and alkylvinyl ether and/or olefin
as the initial mixture in the reactor and then feeding in the maleic anhydride
plus initiator and any co-initiator or regulator at the desired polymerization
temperature. This method produces less colored polymer solutions. The
concentration of the total monomers is generally from 20% to ~0% w/w and
preferably from 30% to 70~0 w/w. The solid copolymer can be isolated
without any difficulty by evaporating the solvent~ Here again it is
advantageous to select a solvent in which further conversion to the
ammonium salt, alkali metal salt, or alkaline earth metal salt or a reaction
with an alcohol and/or ammonia or an amine can take place.
1~
The first process step produces a copolymer of one or more alkylvinyl
ethers and/or olefins and maleic anhydride or soma other ethylenically
unsaturated carboxylic anhydride as defined above, and this copolymer is
well suited for improving the water resistance of colloidal sealing com-
20 pounds. Solutions of said copolymers are preferably used in plasticizers, forexample chloroparaffins. phthalates, and propoxylated cresols, or in organic
solvents.
The anhydride groups contained in the copolymers may be partially or totally
25 converted to the ammonium salts, alkali metal salts, or alkaline earth metal
salts, and if there is only partial conversion to the ammonium salts, alkali
metal salts, or alkaline earth metal salts, the remainder of said groups may
optionally be reacted with alcohols and/or amines to form esters and/or
amides ancl/or ammonium salts. Alternatively, the said subsequent
30 conversion of the copolymers may be carried out in the reverse order, that
is to say, the copolymers may first be solvolyzed with amines, ammonia
and/or alcohols to Form the corresponding esters and~or amides and/or
arnmonium salts and then conver~ed to, say, the alkali metal salts or alkaline
earth metal salts.
3~;
The copolymers prepared by the aforementioned polymerization techniques
are cooled to room ternperature and then solvolyzed, preferably in molten
form at a temperature ranging from 80 to 180G and preferably from 90
to 150C. The solvolysis of the anhydride groups of the copolyrners consists,
in its simpiest form, of hydrolysis followed by neutralization. It is particularly
advantageous to operate in pressure-tight equipment and to add water
- 2~ 2
B~SFA~TIErlGEsELLscHAFr 9 o.z.ooso/42208
- directly to the molten copolymer as it is produced in said equipment by
polymerization in substance. In this way, the anhydride ~roups o~ the
copolymer are converted to carboxyl groups, after which a base is added to
neutralize at least 10% of the carboxyl gn~ups of the hydrolyzed copolymer.
s However, this hydrolysis and neutralization may be alternatively effected
virtually simultaneously by the addition of a dilute aqueous base to the
molten copolymer. The concentrations of water and neutralizing agent are
adjusted so as to give dispersions or solutions having a solids content of
from 10% to 60% w/w and preferably from 20% to ~5% w/w, which are
marketed as such. From these, working solutions are prepared by dilution to
a solids content of from 0.~% to 50% w/w.
Alternatively, the copolymers obtained by polymerization of monomers from
groups (a) and (b) may be solvolyzed by the addition of primary and/or
secondary amines. Such solvolysis is carried out using an amount ~f amine
such that from 10% to 50% of the carboxyl groups obtained from the
polymerized units of monomer (b) in the copolymer and resultiny ~rom total
hydrolysis are amidated. After half-amide groups have formed in the
copolymer, neutralization is carried out. This is carried to an extent such
20 that at least 10% of ~he carboxyl groups of the copolymer obtained by
polymerization in substance are neutralized.
Another solvolyzing technique is to add an alcohol to the molten copolymer
as obtained by polymerization in substance. The amount of alcohol used is
25 such as to e~Fect esterification of from 10% to 50% of the total carboxyl
groups resulting from the polymerized dicarboxylic acid units contained in the
copolymer. This is followed by neutralization of at least 10% of the total
carboxyl groups formed from the anhydride group-containing copolymer.
30 Preferably, from 20% to 50% of the total carboxyl groups resulting from ~he
polymerized dicarboxylic anhydride groups contained in the copolymer are
amidated or esterified.
Suita~le neutralizing agents are, for example. ammonia, amines, alkali metal
35 bases and alkaline earth metal bases such as caustic soda, caustic potash,
sodium bicarbonate, soda, potassium carbonate, magnesium hydroxide.
calcium hydroxide, barium hydroxide, and all of the amines which may be
used for amidation oF the copolymer. Neutralization is preferably carried out
by adding aqueous caustic soda solution t6 the copolymer. The neutralization
40 of the anhydride group-containing copolymers is carried at least to such an
extent that water-dispersible copolymers are obtained. The degree of
- , `' -
. - ~ . , , ~ . .
.: ,. ~.
~ BAsFAKTIEHGEsELLscHAFT 10 ~ O S ~ ~ ~ 2 o z ooso/42208
neutralization required to achieve this end corresponds to at least 10% of
the total carboxyl ~roups resulting from the anhydride groups. This degree of
neutralization is also dependent on the ~hain length of the alkylvinyl ether
and/or olefin used as component ~a). In order to obtain copolyrners which
are readily dispersible or colloidosoluble in water, a copolymer from, say, a
C10-alkylvinyl ether and maleic anhydride will be neutralized to an extent of
at least 75%, whilst a copolymer from, say, a C20-alkylvinyl ether and
maleic anhydride is readily dispersible in water at a degree of neutralization
corresponding to 50% of the carboxyl groups resulting ~rom said copolymer
In the case of a copolymer from a C~2-alkylvinyl ether and rnaleic
anhydride, a degree of neutralization corresponding to only 20~o of the
carboxyl groups resulting from the polymeri~ed units of rnaleic anhydride
contained in said copolymer is sufficient to make the copolymer dispersible
in water.
Arnidation can be effected using ammonia and primary and secondary
amines. It is preferably carried out in the absence of water by reaction of
the anhydride groups of the copolymer with ammonia or said amines.
Suitable primary and secondary amines may contain from 1 to 40 carbon
20 atoms and preferably from 3 to 30 carbon atoms. Examples of suitable
amines are methylamine, ethylamine, n-propylamine, isopropylamine, n-
butylamine, isobutylamine, hexylamine, cyclohexylamine, methylcyclohexyl-
amine, 2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty amine,
stearylamine, oleylamine, dimethylamine, diethylamine, di-n-propylamine, di-
25 isopropylamine, di-n-butylamine, di-isobutylamine, dihexylamine, di-cyclohexyl-
amine, di-methylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, di-
isotridecylamine, di-tallow fatty amine, distearylamine, di-oleylamine, ethanol-amine, diethanolamine, n-propanolamine, di-n-propanolamine, and morpholine.
Morpholine is preferably used.
In order to effect partial esterification of the anhydride group-containing
copolymer resulting from the polymerization, it is reacted with one or more
alcohols. This esterification is again preferably carried out in the absence of
water. Suitable alcohols may contain from 1 to 40 carbon atoms and
35 preferably from 3 to 30 carbon atoms. lJse may be made of primaly,
secondary, and tertiary alcohols. Both saturated aliphatic alcohols and
unsaturated alcohols, eg oleyl alcohol, can be employed. We prefer to use
monohydric primary or secondary alcohols, for example methanol, ethanol, n-
propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isomers, n-
hexanol and isomers, for example 2-ethylhexanol, n-oc~anol and isomers,
nonanols, decanols, dodecanols, tridecanols, cyclohexanol, tallow fatty
' -:
- B~FAKTI~NGEs~LLscHAFT 11 2 0 g ~ ~ ~ 2 o.z.ooso/42208
alcohol, stearyl alcohol, and the commercially available oxosynthesis-
produced alcohols or alcohol mi~<tures containing from 9 to 19 carbon
atoms, for example Cg/1l-oxoalcohol, C13/15-oxoalcohoi, and Ziegler alcohols
containing from 12 to 24 carbon a~oms and known as "aifols~ e
s particularly prefer to use alcohols containing from 4 to 24 carbon atoms, for
example n-butanol, isobutanol, amyl alcohol, 2-ethyihexanol, tridecanol,
tallow fatty alcohol, stearyl alcohol, Cg/l1-oxoalcohol, C13/15~Ooxoalcohol,
C12/l4sOalfols~ and C16/l8sOalfols
The partial conversion of the anhydride groups to half-amide or half-ester
groups is followed by the hydrolysis of the remaining anhydride groups of
the copolymer. This hydrolysis of the remainder of the anhydride groups of
the copolymer can take place concurrently with the partial neutralization yet
to be carried out, by adding an aqueous base to the partially amidated or
esterified copolymer still containing anhydride groups. The amounts of wa~er
and base are adjusted such that the concentration of the copolymer
dispersion or solution is preferably from 20% to 55% w/w. The pH of this
ready-for-use hydrophobizing agent is in the range of 4 to 10.
20 The aqueous copolymer dispersions thus obtained are stable and have a
good shelf iife. The copolymers of the invention are particularly suitable for
improving the water resistance of colloidal sealing compounds, plasters,
paints, and building adhesives which contain mineral building materials such
as calcium carbonate and/or calcium silicate, magnesium silicate~ or
25 aluminum silicate.
The manufacture of the plasters, paints and sealing compounds is effected in
conventional mixers. One method of incorporating the copolymers of the
invention or their derivatives is to add them to said materials during manu-
30 facture of the latter. Alternatively, they can be added to the dispersionbinder during or after polymerization. The concentration of the copolymers of
the invention or their derivatives in said materials is from 0.01% to 10% w/w
and preferably from 0.01% to 4% w/w, based on the formulation prior to
drying.
Despite their hydrophobic nature, the solutions or dispersions of the invention
show a good dispersing action on inorganic fillers such as calcium
carbonate, aluminum silicate, calcium silicate, or magnesium silicate, and on
finely divided pigments such as titanium dioxide and the various iron oxides.
~ They can partially or completely replace the conventionally used polymeric
- dispersing agents based on polyacrylic acid or diisobutene/maleic anhydride
-~ .: .
: - :
BAsiFA~ E~EseLLscHA~T 12 2 0 ~ ~ ~ 0 2 ~.z.coso/42208
- copolymers and can, like them, be combined with inorganic dispersing
agents such as sodium hexametaphosphate or tetrapotassium pyrophosphate.
If it is desired to make use of this dispersing action during the manufacture
of the paints or plasters, the copolymers of the invention will be added in
s the form of an aqueous solution or dispersion before the pigments or fillers
are stirred in.
The use of the copolymers of the invention considerably improves the wet
abrasion resistance of coatings prepared from heavy emulsion paints. The
10 amount used ranges from 0.01% to 2% W/W and preferably from 0.02% to
1% w/w of copolymer, based on the total weight of the paint formula~ion.
The improved wet abrasion resistance makes it possible to manufacture
coating materials which contain less binder but which satisfy or e~en exceed
the standard requirements as regards resistance to washing and abrasion.
In the following Examples, the percentages are by weight unless otherwise
stated. The molar mass of the copolymers was determined by gel
permeation chromatography using tetrahydrofuran as solvent and using
narrowly distributed fractions of polystyrene for calibration purposes.
(A) Preparation of the copolymers
Example A1
25 1195 g of a C20-C24-olefin-1 mixture (Gulftene 20-24(~), Gulf Oil Chemical
Company, U.S.A. ) were heated to a temperature of 1 90C with constant
stirring under a weak stream of nitrogen in a stainless steel reactor
equipped with a stirrer, feed means and means for working under nitrogen.
Once this temperature had been reached, 329 9 of maleic anhydride having
30 a temperature of 70C and, through a separate inlet, 16 9 of di-t-butyl per-
oxide were added at a constant rate over a period of 4 hours. The
- polymerization temperature was kept in the range of 185 to 1 90C. On
completion of the addition of maleic anhydride and peroxide, the reaction
mixture was heated at a temperature of 190C ~or 2 hours with constant
35 stirring, after which it was cooled to 90C. The viscous melt was poured on
to a metal tray ancl allowed to solidify, after which it was crushed. The
molar mass of the copolymer was 8,900 g/mole.
Example A2
4a
1,195 9 of Gulftene 20-24(~) were placed in the aforementioned reactor
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- E~ASFA~IEr~GEsELLscHAFT 13 2 0 6 ~ ~ 0 2 o.z.ooso/42208
- and heated to a temperature of 150C under a weak stream of nitrogen.
Once ~his temperature had been reached, 392 9 of maleic anhydride having
a temperature of 70C and, through a separate inlet, 16 g o~ di-t-butyl per-
oxide as a liquid were added at a constalnt rate over a period of 6 hours.
s The reaction mixture was then heated at 150C ~or a ~urther 2 hours and
cooled to 90C. Over the next 30 minutes, the following separate streams
were added: 320 g of 50% aqueous caustic soda solution and 5,026 g of
water having a temperature of 90C. The reaction mixture was stirred for a
further 4 hours at a temperature of from '30 to 95:: and then cooled. The
10 aqueous dispersion, which was slightly viscous at room temperature, had a
solids content of 25.2%. The molar mass o~ the unhydrolyzed copolymer was
8,300 g/mole, and 50% molar of the total carboxyl groups ~ormed had been
neutralized.
Examples A3 to A7
The substances listed in Table 1 below were polymerized and subsequently
neutralized and dispersed in the manner described in Example A2.
20 Table 1
Ex. Oiefin or Alkyhlinyl Ether Maleic Di-t-butyl Neutralizing Water
Type Amount AnhydridePeroxide Agent ( )
A3C20-C24-olefin-1 1,195 392 16 103~6 9 of 25% ammonia 6,100
A4octadecylvinyl ether 885 309 23.9 197 9 of 50% NaOH 3,785
A5C24-C28-olefin-1 1,470 392 18.6 323 9 of 50% NaOH 5,965
A6 Cl8-olefin-l 2,100 838.5 29.9 543 9 of 50% NaOH 9,446A7lcl8-olefin-l 756 392 14.2 324 9 of 50% NaOH 4,583
octadecyhlinyl ether 27?
30 The physical data are shown in Table 2 below:
Tab!e 2 _
(g/mole) Solids (C%o)ntent
A38,300 20.8
35 A45,600 24.3
A59,800 25.0
A64,800 24.1
A75000 249
(B) Plasters bonded with synthetic resin
A plaster bonded with a synthetic resin based on a 50% styrene acrylate
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BASF AKTIENGESELLSCHAFT 14 o.z.ooso/42208
dispersion having an MFT of 22C and an average particle size of about
0.1 ~lm was prepared in a conventional mixer using the following recipe. The
parts are by weight.
Parts
Styrene acrylate dispersion (50% strength) 170
methylhydroxypropyl cellulose of high molecular weight (3% s~rength) 21
tetrapotassium pyrophosphate (50% strength in water) 5
defoamer based on silicone 4
preservative 2
white spirit 180/210C 20
mixture of isobutyl glutarate, isobutyl succinate, and isobutyl adipate 20
titanium dioxide (rutile) 32
calcium carbonate 40 ILm 267
calcium carbonate 130 llm 80
aluminum silicate - 79
granulated calcium carbonate 1,500 llm 300
1 ,000
Example B1 (Comparative Example)
The plaster prepared as described under (B) above was trowel-spread into
a metal ring Iying on a glass plate and having an internal diameter of
40 mm and a thickness of 5 mm. The plaster was allowed to dry for 1 day
at 23C and 65% relative humidity, after which the ring was removed and
25 the plaster specimen was dried for 28 days at 23C and 65% relative
humidity while supported on a gauze attached to a wooden frame.
The thus dried plaster specimen was then placed in water for ~4 hours at
23C and the amount of water absorbed was determined by weighing. The
30 result is given in Table 3 below.
Example B2 (Comparative Example)
To 1,000 9 of the plaster described under (B) there were added 3 9 of a
35 65% aqueous paraffin wax emulsion with stirring.
The result of the test is given in Table 3 below.
Example B3 (Comparative E~cample)
To ~,000 9 of the plaster described under (B) there were added 6 9 of a
.
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65Yo aqueous paraffin wax emulsion with stirring.
The result of the lest is given in Table 3 below.
s Example B4
To 1,000 g of the plaster described under ~B) there were added 7.3 9 of a
25% aqueous formulation as described in F~ample A2 above, with stirring.
The result of the test is given in Table 3 below.
Example B5
To 1,000 9 of the plaster described under (B) there were added 8.8 9 of a
~s 20.8% aquenus formulation as described in Example A3 above, with stirring.
The result of the test is given in Table 3 below.
Example B6
To 1,000 9 of the plaster described under (B) there were added 17.6 g of a
20.8% aqueous formulation as described in Example A3 above, with stirring.
The result of the test is given in Table 3 below.
Example B7
To 1,000 9 of the plaster described under (B) there were added 7.5 y of a
24.3% aqueous formulation as described in Example A4 above, with stirring.
. 3~
The result of the test is given in Table 3 below.
Example B8
35 To 1,000 g of the plaster described under (B) there were added 7.3 9 of a
25% aqueous formulation as described in Example A5 a~ove, with stirring.
The result of the test is given in Table 3 below.
2~60~2
BASFAKTI~NGEsELLscHAFr 15 o.z.ooso/42208
Table 3 Water Absorption Data for ~ampies B1 to B8
.
Example B 1 B2 B3 B4 B5 B6 B7 B8
.
AcWitive Arnount added to plaster B (g)
none
wax emulsion (6~%) - 3 6 - - - - -
A2 25.2% strength - - - 7.3 - - - -
A3 20.8% strength -- -- - - 8.8 17.6 - --
M 24.3% strength - - - - - - 7.5
h5 25.0% strength -- -- -- - -- -- - 7.3
10 Wathr absjorption aRer 97 8.8 10.7 2.9 3.92.9 3.5 2.8
A~ ranCe jof speclmen swollen hard
(C) Sealing Compounds
ts
A sealing compound based on a 65% polyacrylate dispersion having a glass
transition temperature of -40C was prepared in a conventional mixer to the
following recipe. The parts are by weight.
Parts
Polymer dispersion (65% strength) 316
Caustic soda solution (10% strength) 3
Plasticizer (propoxilated cresol containing 20 PO units) 70
Titanium dioxide (rutile) 50
Sodium salt of a polyacrylic acid (20% strength)
zs Calcium carbonate 560
1 ,000
Example C1 (Comparative Example)
The sealing compound prepared as described under ~C) was pressed into a
30 groove having a width of 10 mm, a depth of 10 mm and a length of 100 mm.
After drying for 15 minutes at 23C and 65% relative humidity, the
resistance of the compound to premature rainfall was determined. This was
done by placing the compound at an angle of 45 and spraying it with
water from a shower nozie located 35 cm away. The resistance to prema-
35 ture rainfall is taken to be the time which elapses be~ore the off-water
becomes cloudy in appearanceJ ie before ~he sealing compound begins to
wash out.
The result of the test is given in Table 4 below.
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Example C2
To 1,500 g of the sealing compound prepared as described under (C) there
were added 20 9 of the mixture of C2~-C24-olefin/maleic anhydride wax,
' 5 water, and NaOH prepared in Example A2 above.
The result of the test is given in Table 4 below~
Example C3
60 9 of the C20-C24-olefin/maleic anhydride copolymer described in Example
1 were dissolved in the 70~9 of plasticizer listed in the above recipe. This
mixture (1 30~g) was then used when preparing the sealing compound to
said recipe (C) instead of the 70~ of plasticizer.
The result of the test is given in Table 4 below.
Example C4 (Comparative Example)
20 1 9 of ~-aminopropyltriethoxysilane was worked into 1,000 g of the sealing
compound prepared as described under (C).
The result of the test is given in Table 4 below.
zs Table 4
Resistance oF Sea!ing Compounds of Examples C1 to C4 to Premature Rainfall
Examples
C1 C2 C3 C4
Additive Amount added to 1,000 g of sealing compound
none -- - -
A2 -- 20
Al -- -- 60
~--aminopropyltriethoxysilane
. _ .
Resistance to premature rainfall (s) 0 240 180 0
~s
(D) Heavy Interior Pain~ (PVK approx. 83%)
An emulsion paint based on a 50% acrylate/styrene dispersion (MFT app~ox.
22C, average particle size approx. 0.1 llm) was prepared using a dissolver ~!
40 made up of the cornponents in the recipe below (Comparative Example D1~.
The parts are by weight.
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-
Parts
Water 91
Sodium hexametaphosphate, 10% strength 18.25
Ammonium polyacrylate, 30% strength 2.5
s Ammonia, 25% strength 2.5
Preservative 3
Methylhydroxyethyl cellulos~ (high mol. wt.), 2% strength 1~0
White spirit 180-210C 12
Trimethylpentanediol monoisobutyrate 12
Titanium dioxide (rutile) 71
Aluminum silicate 12
Calcium carbonate < 21lm 83
Calcium carbonate 5,um 417
Fatty alcohol ethoxylate, 20% strength 6
Defoamer 0.75
Water 28.3
Acrylate/styrene dispersion, 50% strength 90.7
1 ,000.00
2Q Examples D2 to D8 were carried out in a similar manner. In the Compara-
tive Example D2 there were added 40 parts by weight of calcium stearate,
and in Examples D3 to D8 the ammonia polyacrylate was replaced by
copolymer dispersions of the invention as indicated in Table 5 below.
2s The paints thus obtained were applied to Leneta foil, and the coatings were
subjected to an abrasion test as specified in DIN 53,778, Part 2. The results
of the abrasion tests are listed in Table 5 below.
Table 5
30 Example Additive (Parts by weight)Abrasion Cycles Count
D1 5Comp. E~el2.5 parts of ammorlium polyacrylate 30/O 900
D2 ~Comp. Ex.~ ditto plus 40 parts of calcium stearate <200
D3 3.0 parts of copolymer A1 25.2% 1,600
D4 6.0 parts of copolymer A1 25.2% 2,100
3sD5 6.2 parts of copolymer A6 24.1% 2,600
D6 6.2 parts of copolymer A4 24.3% 2,100
D7 6.0 parts of copolymer A5 25.0% 1,400
D8 6.0 parts of copolymer A7 24.9% 2,200
The use of the copolymers of the invention considerably improved the
abrasion resistance.
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