Note: Descriptions are shown in the official language in which they were submitted.
1 30~52
The present invention relates to the use of
copolymers based on hydrophobic acrylates or methacrylates
as oil demulsifiers for the rapid dehydration of crude
oils.
After an initial phase in which virtually pure
crude oil is recovered, the major part of the crude oil
produced is obtained as a ~ater-in-oil emulsion.
~efore transportation, the water must be separated
off or reduced to an acceptable concentration. This is
generally done by adding oil demulsifiers, separation
being facilitated and accelerated by heating the crude
oil. The compositions of the crude oil emulsions vary
greatLy depending on the source; hence, a large number
of different oil demulsifiers are used ~orld~ide in order
to achieve optimum demulsification results. However,
there is great interest in improved demulsifiers to pro-
vide more rapid separation into oil and water and give
good residual amounts of water and salt when used ~ith a
very ~ide variety ot crude oil emulsions.
The most frequent~y used demulsifiers are ethylene
ox;de/propylene oxide block polymers, oxyalkylated alkyl-
phenol/formaldehyde resins, oxyalkylated polyamines and
in particular crossLinked products of the above basic
cla~ses with multifunctional reagents, egO diisocyanates,
dicarboxylic acids, bisglycldyl ethers and di- and tri-
methylolphenol.
Polymeric oil demulsifiers have also been dis-
closed ~Canadian Patent 1,010,740 and
According to this Canadian patent, oxyalkylated
alcohols and oxyalkylated alkylphenol/formaldehyde res;ns
are etherified ~ith unsaturated gLycidyl comPounds (eg.
glycidyl acrylate), ester;fi~d ~ith~male1c anhydride or
fumar;c acid or transesterified with acrylates or meth-
acrylates in order to introduce unsaturated functions
~? ' ~
1 30q552
-- 2
which can be subjected to free radical polymerization and
are polymerized in a subsequent reaction with other monomers
in solution. DE~Cl 33 38 923 describes products which are
obtained by copolymeri~ing polyoxyalkylene ethers of allyl
or methallyl alcohol with vinyl esters or acrylates or
methacrylates.
All these products have weaknesses with regard to
their activity or arising from the preparation process. For
example, the use of glycidyl compounds for introducing the
unsaturated function during the polymerization frequen-tly
results in the formation of gels and inhomogeneities,
derivatives of allyl alcohol, methallyl alcohol and maleic
acid give rise to poor copolymerization conditions, and
difficulties are encountered in the trans-esterification
with acrylates or methacrylates with regard to complete,
selective esterificatio of the oxyalkylated starting
alcohols, some of which are multifunctional.
Furthermore, the copolymers frequently undergo
reactions leading to gelling and solidification,
particularly where multifunctional starting alcohols are
used in the oxyalkylation. However, products having high
potential activity and a broad spectrum of uses are
obtainable precisely through the use of oxyalkylated
multifunctional alcohols.
It has been found, surprisingly, that copolymers
obtained from hydrophobic acrylates or methacrylates, whose
alcohol component is derived from a mixture of polyglycols
and polyglycol ethers, and from hydrophilic ethylenically
unsaturated comonomers, can be used for the demulsification
of a water-containing crude oil. The copolymers that are so
used have a long shelf life and high efficiency and are
particularly efficient if, in the copolymer, (i) all or
virtually all of the free OH groups are etherified,
esterified or converted to urethane groups and/or (ii) the
,~
1 3nt.~ss2
- 2a -
acid used as a catalyst during the esterification is
neutralized by adding an amine.
The mixture of polyglycols and glycol ethers used
for the esterification consists as a rule of oxyalkylates
`~'
_ 3 _ 130q552
~f the formula
R 1--O~A O~H
~here R1 îs a rad;cal of a monohydric or polyhydric
~lcohol or alkylphenol or a radical of an alkylphenol~
S ~ormaldehyde or alkylphenol/acetaldehyde condensate, AO
~s an ethylene oxide, propylene oxide or 1,2-butylene
oxide radical, a mixture of these radicals or b~ocks of
these radicals, and X is from 5 to 120.
The ~resent invention relates in particular to
the use as oil demulsifiers of copolymers in which
A) acrylates or methacrylates of oxyalkylates of the
formula
R 1--O--EAO~H
vhere R1, AO and x have the above mean;ngsr are copoly-
merized ~ith
B) hydrophilic comonomers of the formula
R~
R 2--N C=~
where R2 is hydrogen, -COOH, -COOC2H~OH -coOc2~4Nlc2H5~2
--CONH2 . --CH . ~ OCOCH3, --CH20H, --N11CHO, --COOCH3, --COOC2H5,
~;~N
-N or ~
o
R3 is hydragen or -COOH and R4 is hydrogen or -CH3, ~ith
the proviso that one or more of the groups R2 and R3 is a
hydrophi~ic group, the ~eight ratio of A) to ~) being
from 300:1 to 1:50, and
C) the free OH groups are converted to an unreactive form
by etherification, esterification or urethane for~ation,
and~or
the acid used as a cata~yst in the preparation of the
.. 1 309552
- 4 - O.Z. 0050/38739
ester in A) and/or in the esterification in C) is neutra-
Lized with a tertiary amine.
The conversion of the free OH groups can also be
carried out before the polymerization, and some of them
may even be converted before the preparation of the ester
comonomer.
The copolymers are prepared in a convent;onal
manner, for example by free radical copoLymerization in
solution, emulsion or suspension.
The esterification of the acrylic acid or meth-
acrylic acid is preferably effected in the presence of an
acidic esterification catalyst and using an entraining
agent.
Suitable esterification catalysts are conventional
inorganic or organic catalysts, such as sulfuric acid,
p-toluenesulfonic acid, dodecylbenzenesulfonic acid,
hydrochloric acid or acidic ion exchangers.
Examples of entraining agents are conventional
organic solvents which form an azeotrope with water~ in
particular xylene or toluene
Examples of suitable agents for the etherification
of the free OH groups are methyl iodide, dimethyl sulfate
and benzyL chloride.
CarboxyLic anhydrides, such as acetic anhydride,
maleic anhydride, phthalic anhydride or succinic anhydride,
are preferably used for esterifying the ~ree OH groups.
The conversion of the free OH groups to urethane
groups, ie. the preferred reaction of the copolymeriza-
tion, is advantageously carried out in a convent;onal
manner by the action of isocyanates, for example using
phenyl isocyanate or stearyl isocyanate.
To neutralize the acids used as an esterification
catalyst, amines, preferably tertiary amines, are added.
Specific example~ of suitable amines are triethylamine,
tributylamine, dimethyl-Cy-amines (where y is C8-C18) and
triethanolamine.
Specifically, the following procedure is adopted,
,, . .... _ ~ _ _ ~ _ .. ~ . ~ _ _ .. _ ... _ _ _ . _ _ _ _ .. . 7 _
1 3~ 2 _ 5 O~Z. 0050/38739
for example, in the preparation of the novel polymers.
Preparation of the oxyalkylates of the formula R1-O-[AO~-H
a) Preparation of the oxyalkylated alcohols
The oxyalkylated alcohols are prepared in a con-
ventional manner by reacting the monofunctional or multi-
functional alcohol with an alkoxide or a mixture of
several alkoxides or blocks of several alkoxides, using
a basic catalyst at from 80 to 160C. Examples of suitable
alcohols are ethanol, butanol, isopropanol, tallo~ fatty
alcohol, stearyl alcohol, alkylphenols of the general
formula
R~3OH
where R is, for example, CgH1g, CH3, CH(CH3)2, C(CH3)3
or CgH17, ethylene glycol, propylene glycol, bisphenol
A, glycerol, trimethylolpropane, pentaerythritol, sorbi-
tol, polyglycerol or the alkylphenollformaldehyde or
acetaldehyde condensates described below.
Preferred alkoxides are ethylene oxide, propylene
oxide and 1,2-butylene ox;de or mixtures of these.
The reaction conditions vary depending on the
type and amount of the alkoxides used. In general, the
reaction temperaturP is from 80 to 160C, and the amount
of basic catalysts var;es from 0.25 to 5%, potass;um hy-
droxide and sod;um hydroxide being preferred. Depending
on the consistency of the starting alcohol and end pro-
duct, an inert solvent which does not influence the re-
action may be added to effect dilution. Xylene is pre-
ferred.
The ratio of alcohol to alkoxide(s) can vary
greatly but is advantageously from 1:120 to 1:5.
b) Oxyalkylated alkylphenol/formaldehyde or acetaldehyde
condensates
The alkylphenol/formaldehyde or acetaldehyde
resins used as alcohols for the oxyalkylation are prepared
in a conventional manner by reacting the aldehyde with
the alkylphenol in a ratio of from 2:1 to 1:2, preferably
. . . . . ~ . ,, . ,,, .. .: , ... , . . , ., . ~ , . . .
" 1 3~)~552- 6 - O.Z. 0050/38739
~ 05, by a base-catalyzed or acid-catalyzed reaction,
preferably the latter, at from 80 to 250C, using a high
boiling solvent for completely removing the resuLting
water of reaction in the form of an azeotrope. The alkyl-
S phenol used is, for example, nonylphenol, tert-butylphenol
or octylphenol, and preferably used aldehydes are formal-
dehyde and acetaldehyde. In general, an alkylsulfonic
acid or alkylbenzenesulfonic acid, eg. dodecylbenzene-
sulfonic acid is preferably used as the catalyst, in an
amount of from 0.2 to 2%, preferably from 0 2 to 0.5%.
At the beginning of the reaction, the temperature
is kept at 90-120C unt;l the major part of the water of
reaction has distilled off. Thereafter, the mixture is
heated to the boiling point of the solvent in order to
complete the reaction, and the residual amount of water
is removed as an azeotrope. The molecules contain on
average from 4 to 12, preferably from 5 to 9, aromatic
nuclei.
The condensates thus obtained are oxyalkylated
as stated under a).
c) Conversion of some of the free OH groups of the alkox-
ides from a) and b)
When the oxyalkylation is complete, the alkoxides
from step a) or b) can be reacted in order to block some
of their terminal groups, blocking of from 20 to 90~ of
the terminal OH groups being preferred. This step can be
carried out by acid-catalyzed esterification with a car-
boxylic anhydride, preferably acetic anhydride, phthalic
anhydride, succinic anhydride or maleic anhydride, at
from 50 to 130C, or by reacting the alcoholates with
dimethyl sulfate, benzyl chloride or methyl iodide, the
alkylat-ng agent being added to the sodium or potassium
alcoholates at from 40 to 80C, and by reaction with iso-
cyanates.
A) Convers;on of the oxyalkylates to monomers
Since the demulsifiers for crude oil emulsions
must be surfactants, the extent of their hydrophilic or
5 5 2
- 7 - O.Z. 005D/38739
hydrophobic nature is adjusted via the ratio of the poly-
ethylene oxide block (hydrophilic) to the polypropylene
oxide block (hydrophobic) to the hydrophilic comonomers
(eg. acrylic acid). Since, in order to achieve maximum
efficiency, these products must be soluble in crude o;l,
it is important that hydrophilic polyacrylic acid moiety
in the copolymer is kept in solution in an aromatic sol-
vent (eg. toluene, xylene or a mixture of aromatics) by
a large hydrophobic radical. This is achieved only by
complete, selective introduction of a functional group
which can be subjected to free radical polymerization
into the hydrophobic oxyalkylated alcohol, some of whose
terminal groups may be blocked, and the use of the said
alcohol in the subsequent free radical copolymerization
with hydrophilic comonomers.
To introduce the unsaturated functional groups
into the said alcohols, the latter are ester;fied with
acrylic acid or methacrylic acid in the presence of an
acidic catalyst (eg. p-toluenesulfonic acid, sulfuric
acid or dodecylbenzenesulfonic acid) at from 8û to 150C,
the necessary complete removal of the water of reaction
being effected by means of an azeotropic entraining
agent, preferably toluene or xylene.
In order to prevent polymerization during the
esterificat;on, it is advisable to use stabili~ers which
are kno~n per se (preferably hydroquinone monomethyl
ether). The ratio of the oxyalkylated alcohol to acrylic
acid or methacrylic acid may be varied from 1:1 to 1:n,
~here n is the functionality (ie. the number of hydroxyl
3û groups) of the starting alcohol. A ratio of 1:1 is pre-
ferred, since other~ise gelling may be observed during
the subseqùent polymerization. Complete esterification
of the acrylic acid or methacrylic acid is advantageously
monitored by analytical methods (eg. the acid number).
~he amount of stabili2er varies from û.3 to 2~ by weight
and is preferably 1% by weight, the percentages being
based on the amount of acrylic acid or methacrylic acid.
.. .. . . . . . .. ..
1 3~955?= 8 - O.Z. 0050/3873~
The acid cata~yst is added in an amount from 0.5 to 5,
preferably from 2 to 3, ~ by weight. Equally good esteri-
ficatio,- results are obtained by using acrylic anhydride
or methacrylic anhydride and acry(oyl chloride or metha-
acryloyl chloride. In this procedure, removal of the waterby azeotropic distillation is dispensed with.
The weight ratio of the solvent to the total amount
of oxyalkylateJ alcohoL and unsaturated carboxylic acid
can vary from 30:70 to ~0:30, a ratio of from 50:50 to
30:70 being preferred.
After esterification with acrylic acid or methacy-
lic acid, any hydroxyl functions still present can be
blocked using carboxylic anhydrides and isocyanates.
Phthalic anhydride, acetic anhydride and maleic anhydride
are preferred. All of the hydroxyl groups can be blocked
by using equimolar amounts of anhydrides, alkylating agents
or isocyanates, or at least some of the hydroxyl groups
can be blocked. Preferably, from 70 to 100% of the ter-
minal hydroxyl groups still present are converted. The
anhydride or isocyanate is added to the solution of the
acrylate or methacrylate, in the presence or absence of a
catalyst, and, depending on the reactivity, the reaction
is complete ;n the course of from 0.5 to 5 hours and from
70 to 1Z0C n
When the ecterification is complete, the added
catalytic amounts of acid can be neutralized by adding
equimolar amounts of amines, eg. triethanolamine, tri-
~thylamine or tributylamine. However, the acids are pre-
ferably neutralized after polymerization and any conden-
sation have been carried out.
~) Copolymerization of the oxyalkylate monomers from A)
~ith hydrophilic comonomers
The copolymers can be prepared by solution, emul-
sion or precipitation polymerization, solution polymer-
ization in a nonpolar solvent (such as toluene or xylene),being preferred. The comonomer or a mixture of several
comonomers is added to, or introduced dropwise to a
1 3 !J ~ 5 5 2
solution of the esterified, oxyalkyLated alcohol in
which the terminal groups may have been blocked, or a
mixture of severaL different esterif;ed oxyalkyLated
alcohols from A) in which the terminal groups may have
been bLocked, and the reaction is carried out with the aid
of known free radical initiators at from 60 to 140C.
Typical comonomers are acryLic acid, methacrylic acid,
maleic anhydride, hydroxyethyl acrylate, N,N-diethylamino-
ethyl acrylate, acrylamide, acrylonitrile, vinyl acetate,
allyl alcohol, vinylformamide, vinylimidazole, vinyl-
pyrrolidone, fumar;c acid, maleic acid, N,N-dimethylacryl-
amide and vinyl methyl ether, acrylic acid, possibly as
a mixture with other comonomers in a ratio of from 10:1
to 1:1, being preferred.
Suitable free radical initiators are, as a rule,
2,2'-azobisisobutyronitrile (AI8N), dibenzoyl peroxide,
tert-butyl peracetate and 2,Z-azobis-2,4-dimethylvalero-
nitrile, AI~N and dib~nzoyl peroxide being preferred. The
amount of free radical initiatnrs used is, as a rule, from
0.1 to 2X ~y weight, based on the tota~ monomer content.
In order to achieve a very Lo~ concentration of residuaL
monomers, a reaction time corresponding to five t;mes the
half life of the initiator at the chosen reaction tem-
perature is preferable. The exothermic copolymerization
can be optimized in respect of the heat of reaction,
molecular weight distribution and residual monomer conSent
by the dropwise addition of the free radicaL initiator,
in the presence or absence of known molecular weight regu-
lators, such as mercaptans or aldehydes, and with or with-
3C out the simultaneous addition of (one part) of the comono-
mer. A single initial addition of from 0.1 to 0.8Z by
weight of AI~N to the solution of the ester and of the co-
monomer and polymeriza~ion at from 60 to 90C in the course
of from Z to 5 houSs, as we~l as a continuous metering of
AIaN to the solution cf the ester and comonomer (with or
without initiaL addition of AlBN to the solution) in the
course from O.S to 3 hours at from 60 to 90C, in the
1 30~552
- 10 -
presence or absence of molecular weight regulators, such
as mercaptans or a~dehydes, in amounts of from 0.05 to
1% by weight, based on the comonomer, are preferred. ~he
simultaneous use of several esterified oxyalkylated al-
cohols in which the terminal groups may be bLocked, and theaddition or metering of several comonomers, are also
possible but do not constitute a preferred procedure. The
polymeri2ation concentrations are from 20 to 70, prefer-
ably from 40 to 60, Z by we;ght. To obtain efficient
1û products, it is sometimes advisable to carry out a pre-
liminary polymerization of the hydrophobic ester of the
oxyaLkylated alcohol and acrylic acid or methacrylic acid,
in which the terminal groups may be blocked, in the course
of from 1 to 2 hours using the above free radical initiators,
and then to add or continuously meter in the comonomer
over from 1/3 to 2/3 of the reaction time, possibly with
additional radical initiator.
The K values of the resulting polymers are in
general from 15 to 60 (measured in 1% strength solution
2a in xyLene). The molecular weight can be influenced by
adding conventional regulators, such as aldehydes or thio
compounds (eg. th;oethanol or thioglycolic acid). Cross-
linking by b;functional comonomers, such as methylenebis-
acrylamide, can also be used to increase the molecular
Z5 weight.
C) Blocking of terminal groups and/or neutrali~ation of
of the catalyt;c amounts of acid after polymerization
is complete
In order to increase the efficiency and in par-
ticular to prolong the shelf life of the copolymers, it;s advisable to carry out partial intramolecular esteri-
fication when polymerization is complete, or final block-
ing of any remaining free hydroxyl functions by reaction
with anhydrides or isocyan~es, and/or neutralization of
any remaining catalytic amounts of acid w;th am;nes ;n
order to avoid transesterification reactions, which may
lead to gelling of the products~
X
1 309552
Partial intramolecular condensation can be ef-
- fected by heating the polymerization solution from ~) to
lOO - 140C in the course of from 1 to 5 hours. Prefer-
ably, the polymerization solution in xylene from a) is
heated for t~o hours at from 11û to 120C. Further con-
densation may result in gelling.
The reaction of the free OH groups with anhydrides
and isocyantes can be carried out directly after the poly-
merization or after partial intramoleeular condensation,
blocking of some of the remaining hydroxyl groups after
the polymerization and subsequent condensation ~ith azeo-
tropic entraining agents ~ith removal of water also being
possible~ A preferred procedure comprises blocking of all
the terminal groups after partial intramolecular conden-
sation at from 110 to 120C and/or blocking of from 60
to 80X of the hydroxyl groups present directly after poly-
merization with subsequent condensation by azeotropic
removal of the uater of reaction ~ith the aid of an en-
train;ng agent, preferably xylene.
~locking of the end groups is effected by adding
or metering the desired amount of anhydride or isocyanate
to the polymerization solution and heating the mixture to
70 - 120C in the course of from O.S to S hours~ in the
presence or absence of a conventional catalyst. Preferred
esterifying agents are acetic anhydride, phthal;c an-
hydride and succinic anhydride.
If the terminal groups have already been blocked
at the stage of the oxyalkylates or of the hydrophobic
acrylates or methacrylates, condensation ~ith the aid of
an azeotropic entraining agent after the polymerization is
preferred.
The neutralization of remaining catalytic amounts
of acid fron the esterification stage ~ith amines is
carried out in addition or alternativeLy to the blocking
of the terminal groups. The neutralizat;on ;s preferably
effected after polymeriza~ionr condensation and any block-
;ng of termina( groups ~ith anhydrides or ;socyanates
1 3 (~ n 5 5 2
- 12 - O.Z. 0050/38739
are complete, with the result that esterification reactions
which proceed to a further stage and may produce gelling
are prevented~
Any catalytic traces of acid from the esterification
reaction which are still present are neutralized by adding
equimolar amounts of amines, eg. triethanolamine, tri-
butylamine or triethylamine, to the solution of the poly-
mer, in which the terminal groups may have been blocked,
and carrying out the reaction for 2 hours at from 20 to
80C. Complete neutralization can be detected via the
amine number.
D) Modification of the polymer from B) and C) (optional)
In order to increase their efficiency and adapt
them to the particular crude oil to be treated, it may
be useful subsequently to modify the copolymers obtained
under B) and C). Depending on the comonomers used in the
copolymerization, the product may be modified in the fol-
lowing ways:
1) Mixing with an oxya~kyLated alcohol or a mixture of
several oxyalkylated alcohols, such as those obtained
as described under a), or with other copolymers trom B)
and C) ;n a ratio of from 10:90 to 90:10, preferably
from SO:S0 to 80:Z0.
Better efficiencies can also be obtained by adding
cosurfactants to the copolymers in amounts of from
5 to 30% by weight. Examples of such cosurfactants
are dodecyl bisulfate, alkylbenzenesulfonates and
alkylnaphthalenesulfonates.
2) The mclecular weight can be increased by subsequent
crosslinking with multifunctional crosslinking reagents
which react with reactive groups of the copolymer.
The crosslinking reactions are carried out (depending
on the type of crosslinking agent) using from 0.1 to
10, preferably from 1 to 4, X by weight of multi-
functional components at from 80 to 140C~ For example,
the following multifunctional crosslinking agents are
used, depending on the comonomers employed: bisglycidyl
1~ ?t- 52
- 13 - O.Z. 0050/38739
ethers (preferably bisglycidyl ethers of bisphenol A),
multifunctional alcohols (eg. sorbitol or ethylene
` glycol), diisocyanate (eg. toluene diisocyanate) and
similar compounds which react with reactive centers
on the copolymer.
3) Subse~uent oxyalkylation with an alkoxide, a mixture
of several alkoxides or blocks containing different
alkoxides. The copolymers from B) and C) are reacted
with the alkoxide(s) using basic catalysts (preferably
sodium hydroxide or potassium hydroxide) in amounts
of from 0.5 to 5% by weight and at from 100 to 150C.
Preferred alkoxides are ethylene oxide, propylene
oxide and 1,2-butylene oxide, the ratio of copolymer
to alkoxide varying from 5:95 to 95:5.
4) Quaternization of ~-containing copolymers ~ith kno~n
quaternizing agents, such as dimethyl sulfate or
methyl iodide, at from 50 to 120C. The amine funtions
present can be completely or only partially quaternized.
Modification of the copolymer from C) is not re-
stricted to the use of a single type of modification. In-
stead, any modifications according to 1) to 4) can be
carried out one after the other.
EXAMPLES
a) Preparation of the oxyalkylated alcohols
Z5 31 9 of trimethylolpropane and 0.3 9 of potassium
hydroxide are initially taken under a nitrogen atmosphere
in an autoclave, and the mixture is reacted with 800 9 of
propylene oxide in the course of 10 hours at from 130 to
140C and under 6 bar. Thereafter, 101 9 of ethylene oxide
are added in a second stage at from 120 to 130C. Toward
the end of the reaction, the temperatùre is kept at 140C
for 1 hour in order to obtain as complete conversion as
possible. The molecular weight calculated from the
measured OH number is 3820. This is Example a5 in the
table below. For the sake of simplicity, a detaiLeddescription of the other examples is dispensed with.
However, the reaction procedures are substantially the
~ -- _ -- '' _ _ _: ~_ .. 7.___.. _ _ ____~_~__~, . ~ ~ _,_,_ _ . ~_ .,,, _ _, ., .. _ _ _ _ _ .. _ . , . , _, _ , , , , _ _ _ ,, _
_ _
` 1 30'~55~
- 14 - O.Z. 0050/38739
same as that o~ the above example. In reactions with
m;xed oxides, the particular aLkoxides are mixed in a
vessel and then metered.
` ` 1 30"552
- 15 0. Z . 0050/38739
._. _
V ~ ,y Y V
J __ _ I O O X O
~ m m m m m m m m m m m m ~ ~n
... .... _ _
o ~C
V~ _ QJ oo ~ ~ ~ ~ ~ ~ ~0 X ~ ~ O U~
~ ~ o
oQc'
Q Q O ~o ~ I
_
C ~ . ~ . ..
o ~ u~ o u~ u~ o o~ ~ O ~ ) o ~t o o ~
ou~ aJ ~ ~ ~ ~ o ~ I' J ~ ~ oo ~ o
CIL Q O
~ .
O 0~
_l O L ~ ~ O O O - O ~ O O O O O ~ I~J --
m O m ~,
_ _
n
1~1 .J I T I I I I I I I I T I I T
_ al o oooooooooooo o y
.
o~o J
u~ 00 ~ O~ ~ o
L 1~ 11~ U~ J Ul O` N 1~ 1~ ~1
__ _
C ~ ~C C .
C ~.C C
O O Q C~ G Q ~ ~ al O
a~ Q
~ ~ L l_ L LO O O L c
c L
J '~ ' _ _ L L J ~ o
, ~ J
~ C O O O O - ~ O >. J ~ O
1. s-- ~ a .c ~:.c ~ L L O O ~ '~:)
_ _O r ~ O D ~
c_ ~ O 0~ E E E E~c ~c ~ 8L C~ ILE E ' a~ O _
OJ L ~ L a~ ~ O O O O L ~ ~ ' ~
aJ
_ ~r~ O
Lel ~~ ~ c~ ~ m ~ n~ C C~ c~ cr
U~ . _ .. __ _
.. ~ ._ .~ _ ~ .~__ ~_ ~_ _ __ ___ _ ~_._ r_~ ~__. ._ ~____ -:~- ~~_~ '~~~~~ ' ' ~ ' ' ~ -
.
1 ~'!'15'ï2
- 16 - O.Z. 0050t38739
b) Preparation of the alkylphenol/formaldehyde or
acetaldehyde-resins
119 9 of xylene are added to 440 9 of nonylphenol,
and 60 9 of paraformaldehyde are metered in at 40C.
Thereafter, 1.5 9 of dodecylbenzenesulfonic acid are ad-
ded at 35C, after ~hich an exothermic condensation
begins. The reaction temperature is kept at 65 - 70C
for 3 hours by cooling. The mixture is then heated at
~0C for 2 hours. In order to complete the reaction,
the mixture is refluxecl for 4 hours at 95 - 100C. There-
after, the water of reaction ;s distilled off, and removal
of water is completed by azeotropic distillation with
xylene for 6 hours. After the mixture has cooled, the
nonylphenol/formaldehyde resin is obtained as the 75 -
80~ strength solution in xylene, having a medium viscosity.This is Example b1 in the table beLo~.
1 33'~552
- 17 - O.Z. 0050t38739
o C o~ ~
~ o
~ .. . . _
o U
U~ ~ ~ U~
,_
L _ N N
~ ~ ~ ~ .
~0 ~
:
~0 _
O
~(1 O CO
~ ~ ~ >~
~ n C -1
~1 ~ N
x D .Q
'' ' 1 ~0q552
- 18 - O.Z. 0050/38739
c) Blocking of terminaL groups of the alkox;des from
a) and b)
200 9 of the alkoxide from Example a 15 are mixed
with 89 of 50~ strength sodium hydroxide solution, and
the alcoholate is prepared under reduced pressure at from
100 to 170C.
Thereafter, 12.6 9 of dimethyl sulfate solution
are added drop~ise at from 50 to 55C, and, when the
addition is complete, the check is made to determine
whether free dimethyl sulfate is present. If necessary,
the reaction is allowed to continue at from 60 to 70C
until the test for free dimethyl sulfate proves negative
This is Example c1.
A) Preparation of the oxyalkylated ester monomers
1) 122 g of the product from Example aS are mixed ~ith
2.4 9 of acrylic acid, 24 mg of hydroquinone mono-
methyl ether, 2.5 9 of para-toluene sulfonic acid and
55 9 of xylene under a nitrogen atmosphere. 0.6 ml
of water is separated off in the course of 3 hours by
heating at 150C. To check for comple~e esteri-
fication, the acid number of the solution ~ie. the
amount of remaining free acrylic acid) is monitored.
This number must drop from the theoretical starting
value of 20 to at least 6 in order to indicate suf-
ficient esterification. The acryLate is obta;ned as
a clear 70% strength solution in xylene. This is
Example A3 in the table below.
2) 609.4 9 of the product from Example a15 are mixed
with 7.9 9 of acrylic acid, 79 mg of hydroquinone mono-
methyl ether, 7.6 9 of para-toluene sulfonic acid and
268 9 of xylene under a nitrogen atmosphere. 1.9 ml
of water are separated off in the course of 3 hours
by heating at 150C. The acid number drops to a
value of about 4.0 after 3 hours. ~hen the esteri-
fication with acrylic acid is complete, the mixture is
allowed to Gool, 14.3 9 of acetic anhydride are added
and the mixture is heated for 2 hours at 100C.
1 30~55~ .
This is Example A14 in the table below.
The procedure in the other exampLes ;s similar.
Longer or shorter reaction times may have to be used in
order to achieve complete esterificat;on and block;ng of
terminal groups.
` ` 1 3~552
- 20 - 0 . Z .0050/38739
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` 1 30"552
- 21 - O.Z. 0050/38739
3) Copolymerization of the hydroPhobic unsaturated esters
from A! ~ith romonomers
EXAMPLE 1
72 9 of acrylic acid~ 284 mg of 2,2'-azobisiso-
S butyron;trile and 307 g of xylene are added, under anitrogen atmosphere, to 587 9 of a solution of the esteri-
fied alcohol prepared under A3, and the mixture is stirred
at 80C for 3 hours and then heated at 110C for 2 hours.
The resulting copolymer has K value of 28.3 (measured as
a 1~ strength solution in xylene). This is Example B1 in
the table below.
EXAMPLE 2
212 mg of 2,2'-azobisisobutyronitrile are added to
764 9 of a solution of the esterified alcohol prepared
under A1, and the mixture is stirred for 2 hours at 90C
under a nitrogen atmosphere. Thereafter, 72 9 of acrylic
acid and 72 9 of xylene are added and st;rring ;s con~inued
for a further 15 hours at 100C. This is Example B2 in
the table below.
EXAMPLE ~
10 9 of acrylic acid, 156 mg of 2,2'-azobisiso-
butyronitrile and 293 9 of xylene are added to 707 9 of
a solution of the esterified alcohol prepared under AS,
under a nitrogen atmosphere, and the solution is heated
to 80C. A solution of 62 9 of acrylic acid and 6Z g
of xylene is then added dropwise in the course of 10 hours.
When the addition is complete, stirring is continued for
S hours at 120C. This is Example ~3 in the table below.
EXAMPLE 4
95.8 9 of acrylic acid, 0.94 9 of n-butyraldehyde
and 350 g of xylene are added to 893 9 of a solution of
the esterified alcohol prepared ~nder A15, under a nitrogen
atmosphere, and the stirred solution ;s heated to 90C.
A solution of 4~6 mg of 2,2'-azobisisobutyronitrile in
103 9 of xylene is added dropwise in the course of 3 hours.
When the addition is compLete, the reaction is allowed to
continue for a further Z hours at-110C. This is
Example ~16 in the ta~le below.
1 30~55~
- ~2 - O.Z. 0050/38739
EXAMPLE 5
95.8 g of acryl;c acicir 436 mg of 2,2'-azobisiso-
butyronitr;le and 453 9 of x, ne are added to 893 9 of
a solution of the esterified alcohol which is prepared as
described under A14 and in which some of the terminal groups
have been blocked, the addition being effected under a
nitrogen atmosphere. The mixture is heated for 3 hours
at 80C, after~which water is separated off as an azeo-
trope under refLux. The product is obtained as a 50X
strength solution in xylene and has a K value of 21.2
(measured as a 1% strength solution in xylene) and an
OH number of less than 1. This is Example ~17 in the
table belo~.
The products below are synthesized similarly to
the above Examples. In the copolymerizations where two
different esters from A) are used, both components are
initially taken at the beginning of the poLymerization
and the procedures descr;bed in Examples 1 to 3 are fol-
lo~ed. In the case of copolymerization with two different
comonomers, both of these are added before the beginning
of the reaction (similarly to Example 1) or the comonomer
mixture is slowly added dropwise during the reaction
(similarly to Example 3).
` ` 1 3a~552
- 23 - O.Z. 0050/38739
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C) Blocking of terminal groups and neutralization of
the catalytic amounts of acid after the polym-ri~ati~
is complete
The Example belo~, in ~hich 70% of the OH groups
still present are blocked with acetic anhydride and sub-
sequently further esterification of the remaining OH groups
by azeotropic esterification and neutralization of the
p-to(uene sulfonic acid w;th tributylamine are carrieJ
out, is only intended to serve as an example of the pos-
sibilities of blocking terminal groups and of neutral-
ization. The higher the proportion of free OH groups
after blocking of the terminal groups, the more sharply
does the K value of the polymer increase in the subsequent
azeotropic esterification.
EXAMPLE 1
95~8 9 of acrylic acid, 453 mg of 2,2'-azobisiso-
butyronitrile and 460 9 of xylene are added to 893 9 of
a solution of the esterified alcohol prepared under A1S,
under a nitrogen atmosphere, and polymerization is carried
out for 3 hours at 80C. The K value of the resulting
copolymer is 13.2 (measured as a 1% strength solution in
xyLene). The solution is allowed to cool, 14.3 9 of
acetic anhydride are added, the mixture is heated at
100C for 3 hours and then at 140 - 145C for 3 hours
and water is separated off as an azeotrope. After the
mixture has been cooled to 40C, 7~7 9 of tributylamine
are added and stirring is continued for a further 2 hours.
The procduct is obtained as a 50% strength solution in
xylene, having a medium viscosity. The K value is 23.8
(measured as a 1~ strength solution in xylene), and the OH
number is less than 1. This is Example Cl in the Tàble
belo~.
_ ,,,,, . .. .......... .. -.. -- ,-
1 30~552
- 26 - O.Z. 0050/38739
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1 3("'552
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- 27 - O.Z. 0050/38739
D) Modification of the copolymers prepared under a) and
C)
The Examples below are ;ntended to serve merely
as examples of the modifications which can be carried
out to the polymers from ~) and C).
a) Mixing ~ith oxyalkylated alcohols and/or cosurfactants
1. 966 9 of a solution of the copolymer prepared
under B1 are mixed with 61 9 of the alcohol oxy-
alkyLated under a14 and 61 9 of xylene.
10 2. 768 9 of a solution of the copolymer prepared
under 89 are mixed with 128 9 of dodecyl bisulfate
and 1613 9 of methanol.
b) Par~ial esterification of the mixtures prepared under
C)
50 9 of a solution o~ the product from B14 are mixed
with 6.5 9 of the oxyalkylated alcohol prepared under
a13 and 6.5 9 of that prepared under a14, and 52 y of
xylene are also added. 0.8 ml of water is separated
off in the course of 4 hours by reflux;ng.
2û c) Subsequent crosslinking of the copolymers from B)
1 9 of a bisglycidyl ether of bisphenol A (Epikote)
is added to 50 9 of a soLution of the product from a10,
and the mixture is heated at 100C for 8 hours.
The viscous solution is diluted by adding 35 9 of
xylene.
d) Subsequent oxyalkylation of the copolymers prepared
under B) and C) w;th ethylene oxide and/or propylene
oxide and/or butyLene ox;de
1 9 of potassium hydroxide is added to 100 9 of a
solution of the copolymers prepared under 87, and the
mixture is reacted with 50 9 of propylene oxide under
6 bar and at 130 - 140C in an autoclave. ~hen the
reaction is complete, 290 9 of ethylene oxide are
metered in a little at a time at from 120 to 130C.
Toward the end of thee reaction, the temperature is
increased to 150C for 2 hours.
-- -- --. ' ._ _----------.V._~ `. ~ .'-- . _ . .__ _ ~ . _~ _ ~v ._ _. .. _ . ._ _ _ _ _ _.
