CA1309552C

CA1309552C - Copolymers of hydrophobic acrylates or methacrylates and hydrophilic comonomers, their preparation and their use as oil demulsifiers

Info

Publication number: CA1309552C
Application number: CA000549642A
Authority: CA
Inventors: Klaus Barthold; Richard Baur; Stefano Carlo Crema; Juergen Lasowski; Knut Oppenlaender; Wilfried Heide
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1986-10-18
Filing date: 1987-10-19
Publication date: 1992-10-27
Anticipated expiration: 2009-10-27
Also published as: EP0264841A2; NO874319L; EP0264841B1; DE3635489A1; NO171682B; NO171682C; NO874319D0; EP0264841A3; DE3783313D1

Abstract

Abstract of the Disclosure: Copolymers of hydrophobic acrylates or methacrylates, whose alcohol component is derived from a mixture of polyglycols and polyglycol ethers, with hydrophilic ethylenically unsaturated co-monomers are suitable as oil demulsifiers, and, in the said copolymers, (i) all or virtually all of the free OH groups are etherified, esterified or converted to urethane groups and/or (ii) the acid used as a catalyst in the esterification is neutralized by adding an amine.

Description

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 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 - 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 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

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
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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 o~ I oa~ .
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_ _ _ . _ _ _ _ _ _ _ _ . _ . _ _ . _ _ _ _ _ . _ _ _ . _ _ ` 1 30"552 - 21 - O.Z. 0050/38739 3) Copolymerization of the hydroPhobic unsaturated esters from A! ~ith romonomers 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.

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.

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 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).

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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.

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~.

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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.

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Claims

1. Use for the demulsification of a water-containing crude oil, of a copolymer of hydrophobic acrylates or methacrylates having an alcohol component derived from a mixture of polyglycols and polyglycol ethers, with hydrophilic ethylenically unsaturated comonomers, wherein, 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 acid used as a catalyst in the esterification is neutralized by adding an amine.

2. Use as claimed in claim 1, wherein the monomeric acrylates or methacrylates used as starting materials in the preparation of the polymer are prepared with the aid of an entraining agent for removal of water, by esterification of acrylic acid or methacrylic acid with an oxyalkylate of the formula , where R1 is a radical of a monohydric or polyhydric alcohol or alkylphenol or a radical of an alkylphenol/formaldehyde or alkylphenol/acetaldehyde condensate, AO is an ethylene oxide, propylene oxide or 1,2-butylene oxide radical or a mixture of these radicals or blocks of these radicals, and x is from 5 to 120.

3. Use as claimed in claim 1, wherein etherification or esterification of some of the free OH
groups or reaction of some of these groups with an isocyanate is carried out prior to the copolymerization.

4. Use as claimed in claim 1, wherein the free OH
groups of the copolymer are converted to ester or urethane groups after the copolymerization.

5. Use as claimed in claim 1, wherein the acid used in the esterification is neutralized by adding an amine.

6. Use as claimed in claim 5, wherein the acid is neutralized by adding a tertiary amine.

7. Use as claimed in claim 1, wherein the copolymer contains A) an acrylate or methacrylate of an oxyalkylate of the formula , where R1 is a radical of a monohydric or polyhydric alcohol or alylphenol or a radical of an alkylphenol/formaldehyde or alkylphenol/acetaldehyde condensate, AO is an ethylene oxide, propylene oxide or 1,2-butylene oxide radical or a mixture of these radicals or blocks of these radicals and x is from 5 to 120, copolymerized with B) a hydrophilic comonomer of the formula where R2 is hydrogen, -COOH, -COOC2H40H, -COOC2H4N(C2H5)2, -CON 2, -CN, , -OCOCH3, -CH20H, -NHCHO, -COOCH3, -COOC2H5, or R3 is hydrogen or -COOH and R4 is hydrogen or -CH3, with the proviso that one or more of the radicals R2 and R3 is a hydrophilic group, the weight ratio of A) to B) being from 300:1 to 1:50, and wherein C) the free OH groups are converted to an unreactive form by etherification, esterification or urethane formation and/or the acid used as a catalyst in the preparation of the esters in A) or in the esterification in C) is neutralized with a tertiary amine.

8. Use as claimed in claim 1, wherein the copolymer is prepared as follows:
A) acrylic acid or methacrylic acid is esterified with an oxyalkylate of the formula where R1 is a radical of a monohydric or polyhydric alcohol or alkylphenol or a radical of an alkylphenol/formaldehyde or alkylphenol/acetaldehyde condensate, AO is an ethylene oxide, propylene oxide or 1,2-butylene oxide radical or a mixture of these radicals or blocks of these radicals and x is from 5 to 120, in the presence of an acidic esterification catalyst and using an entraining agent, and the resulting ester monomer is copolymerized with B) a hydrophilic comonomer of the formula where R2 is hydrogen, -COOH, -COOC2H4OH, -COOC2H4N(C2H5)2, -CONH2, -CN, , -OCOCH3, -CH2OH, -NHCHO, -COOCH3, -COOC2H5, or R3 is hydrogen or -COOH and R4 is hydrogen or -CH3, one or more of the radicals R2 and R3 being the hydrophilic group, in a weight ratio of A) to B) of from 300:1 to 1:50, and C) the remaining free OH groups are esterified or converted to urethane groups and/or the acid used as a catalyst in the preparation according to A) or C) is neutralized with an amine.