CA2061174A1 - Reaction products of alkoxylates and vinyl monomers, their preparation and their use as demulsifiers for crude oil emulsions - Google Patents
Reaction products of alkoxylates and vinyl monomers, their preparation and their use as demulsifiers for crude oil emulsionsInfo
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- CA2061174A1 CA2061174A1 CA002061174A CA2061174A CA2061174A1 CA 2061174 A1 CA2061174 A1 CA 2061174A1 CA 002061174 A CA002061174 A CA 002061174A CA 2061174 A CA2061174 A CA 2061174A CA 2061174 A1 CA2061174 A1 CA 2061174A1
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- formula
- alkoxylates
- vinyl monomers
- polymerization
- vinyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
O.Z. 0050/42219 Abstract of the Disclosure: Reaction products are prepared from predominantly hydrophilic vinyl monomers of the general formula I
I
and predominantly hydrophobic alkoxylates of the general formula II
R8-O-[R9-O]x-H II
and are used as demulsifiers for crude oil emulsions.
I
and predominantly hydrophobic alkoxylates of the general formula II
R8-O-[R9-O]x-H II
and are used as demulsifiers for crude oil emulsions.
Description
2 ~
O.z. 0050/42219 Reaction p~roducts of alkoxylates and vinyl monomers, their preparation and their use as demulsifiers for crude oil emulsions The pre~ent invention relates to reaction pro-ducts of predominantly hydropho~ic alkoxylates and pre~dominantly hydrophilic vinyl monomers, a process for their preparation and their use as mineral oil demul-sifiers for rapidly dewatering crude oils.
In the production of crude oils, an increasing amount of water is simultaneously obtainsd with increas-ing exploitation of the deposits. Surfactants prssent in the crude oils emul~ify the major part of the water, stable water-in-oil emulsions being formed. Salts which may lead to corrosion problems during the further pro-ces~ing of the crude oil in the refinery may be presentin solution in the emulsion water. The emulsion water must therefore be separated off or reduced below an acceptable concentration prior to transport. Thi~ is ~enerally effected by adding mineral oil demulsifiers, heating of the crude oil facilitating and accelerating the separation.
The crude oils differ in their composition, depending on their origin. The natural emulsifier~
present in the crude oils furthermore have a complicated chemical composition, ~o that il: i nece~sary to develop selective min ral oil demulsifiers to overcome their e~fect. Owing to the opening up of the new oil fields and the changed production conditions in old fields, thQre i5 a constant need for novel demulsifier which effect more rapid separation into oil and water and result in very small amounts of residual water and residual salt.
The most frequently used demulsifiers are ethylene oxide/propylene oxide block copolymers, alkoxylated alkylphenol/formaldehyde resin~, alkoxylated polyamines and crosslinking product~ of the a~ove ba~ic classes with multifunctional reagents, for example 2 ~
- 2 - O.Z. 0050/42219 diisocy~nates, dicarboxylic acids, bisglycidyl ethers and di- and trimethylolphenolO
Polymeric mineral oil demulsifiers are also known (Canadia~ Patent 1,010,740 and DE-C1 33 38 923). Accord-ing to this Canadian Patent, un~aturated functions whichcan be subjected to free radical polymerization and which are polymerized in a subsequent reaction with other monomers in solution are introduced into alkoxylated alcohols and alkoxylated alkylphenol/formaldehyd~ resins by etherification with unsaturated diglycidyl compounds (eg. glycidyl acrylate), by esterification with maleic anhydride or fumaric acid or by transesterification with acrylates or methacrylates. DE-Cl 33 38 923 describes product~ which are obtained by copolymerization of lS polyoxyalkylene ethers of allyl or methallyl alcohol with vinyl esters or acrylates or methacrylates. All of these products have weaknesses ~pecific to their activity or relating to their production. For example, when glycidyl compounds are used for introducing the unsaturated functions, the formation of gel~ and inhomogeneities frequently occurs during the polymerization, while derivatives of allyl alcohol, methallyl alcohol and maleic acid result in poor copolymerization conditions.
Furthermore, gelling and solidification reactions fre-quently take place, particularly as a result of the useof multifunctional s~arting alcohols in the alkoxylation.
DE 36 35 489-A1 describes copolymers of hydro-phobic acrylates or methacrylates and hydrophilic mono-mers. The hydrophobic esters are prepared by acid-catalyzed azeotropic esterification of alkoxylates ofmonohydric or polyhydric alcohols or alkylphenol/aldehyde condensate~ with (meth)acrylic acid. After the copoly-merization of the hydrophobic esters with hydrophilic monomers, th~ free O~ group~ are converted into a form which is no longer reactive and/or the catalyst acid is neutralized with a tertiary amine. The preparation of these products is tLme-consuming since the esterification - 3 - O.Z. 0050/42219 of the alkoxylate with (meth)acrylic acid requires several hours. In the esterification of alkoxylates of polyhydric alcohols, it is impos~ible selectively to prepare the monoester, so that, owing to the pre~ence of multifunctional acrylates during the copolymerization with hydrophilic monomers~ insoluble gels readily form.
EP 0 331 323-A~ di~closes demulsifiers which, however, are based on nitrogen compounds and for whose preparation long reaction time~ are required.
It is an object of the present invention to provide demulsifiers which permit very rapid separation into water and oill give very small amount~ of residual water, have a long shelf life and can be prepared in a simple manner and in short reaction times.
We have found that this object is achieved and that~ surprisingly, product~ having better demulsifier activity and a longer shelf life are obtained in a short reaction time if vinyl monomers are polymerized in the presence of one or more alkoxy:Lates without unsaturated functional groups capable of free radical polymerization having been introduced beforehand into the alkoxylates, and a condensation step i~ carried out after the polyme-rization i~ complete, or if the alkoxylates are condensed with polymers prepared from vinyl monomers.
The pre~ent invention therefore relate~ to reaction product~ o alkoxylate~ and vinyl monomers, obtained by a) polymerization of one or more vinyl monomers of the general formula I
Rl 3 0 C=CH--R 2 where Rl i9 hydrogen, -COOH, -COOC2H5O~, -COOC3~70H~
-Coo-R4-N(R5)2, -Co-~H-R4-N~R5)2, -CONH2, -CNr -phenyl, -o-Co-R4, -pyridyl, -N-C~-R6, -COCH3, -CooR7, -o-R7, -o-R7-oH, -R7, -imidazoyl or 2~
- ~ - O.Z. 0050/~2219 -COOCH2-c\-/H2 o R2 i3 hydrogen or -COOH, and Rl and R2 together may form an anhydride ring, R3 is hydrogen or CH3, and Rl, R2 and R3 are not simultaneously hydrogen, R4 is an alkyl or alkylene group of 1 to 4 carbon atoms, R5 and R6 independently of one another are each hydrogen or Cl-C4-alkyl, and R5 and R6 together may furthe~more form a 5-membered or 6-membered rin~, and R7 is an alkyl, hydroxyalkyl or alkylene group of 1 to 30 carbon atoms, in the presence of one or more alkoxylates of the general formula II
R8-O-~Rg-O]X-H II
where R~ is a radical of a monohydric or polyhydric alcohol, a phenol or alkylphenol of 1 to 30 carbon atoms or a radical of an alkylphenol/formaldehyde or alkylphenol/acetaldehyde condensate, R9 i5 ethylene, propylene, 1,2-butylene or 1,4-butylene and x is from 5 to 120, and within the polyalkylene oxide chains different units [R9-O] according to the above meaning of R3 may be present in the form of blocks or as random mixture~ and x relates to the total number of all units [R9-O], and subsequent condensation or b) polymerization of one or more vinyl monomers of the abovementioned general formula I and condensa~ion of the resulting copolymer with one or more alkoxylates of the abovementioned general ormula II, where in each case 7~
- 5 - O.Z. 0050/4~219 the vinyl monomer~ carry not les~ than 20~ by weight of functional groups capable of undergoing a chemi-cal reaction with the hydroxyl groups of the alk-oxylates after the polymerization is complete, the condensation i3 carried out so ~ha~ not all hydro~yl group~ are converted, and the weight ratio of alkoxylate~ II to the 8um of the vinyl monomers I i from 300 : 1 to 1 : 50.
Preferred reaction products are those which are prepared using, as vinyl monomer~ of the general formula I, acrylic acid, methacrylic acid, esters or amides of these acids, vinyl ethers, acrylonitrile, vinyl-pyrrolidone or mixture~ of the~e monomers. Acrylic acid in an amount of from 50-lO0~ by weight, based on the total amount of vinyl monomer~, is particularly prefer-ably used.
The alkoxylates suitable for ~he preparation of the novel reaction products do not con~ain any nitrogen.
Block copolymers which are obtained from poly-hydric alcohols by reaction with propylene oxide and then with ethylene oxide are preferred, the weight ra~io of propylene oxide to ethylene oxide being from 10 : 1 ~o l : 10, particularly preferably from 5 : 1 to 1 : 8.
For the preparation of the novel polymer~, one or more alkoxylates and one or more vinyl monomers may be used. Hydrophilic vinyl monom~r~ are preferably used, and not moxe than 60% by weight of hydrophobic monomers may furthermore be present in the monomer mixture when a plurality of monomer is used. The hydrophilic monom~rs must carry not les~ than 20, preferably 40, particularly preferably 60, ~ by weight of functional group~ capable of undergoing a chemical reaction wi~h the hydroxyl groups of the alkoxylatPs after pol~merization is comple~e.
ExampleY of suitable vinyl monomsrs are acrylic acid, methacrylic acid, mathyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth~acrylate, lau~yl acrylate, 2 ~ 7 ~
~ 6 - o.Z. 0050/42219 hydroxyethyl (meth)acrylate, di.ethylaminoethyl acrylate, diethylaminoethyl methacrylamicle, glycidyl methacrylate, vinylformamide, vinyl acetate, vinyl propionate, styrene, isobutener trimethylpentene, allyl alcohol, ~inyl methyl S ether, vinyl 4-hydroxybutyl ether, vinylimidazole, vinylpyrrolidone, maleic acid and fumaric acid. Acrylic acid or monomer mixtures which contain not less than 50%
by weight of acrylic acid are particul~rly preferred.
The weight ratio of alko~ylate ~o the sum of the vinyl monomers i9 from 300 : 1 to 1 : S0, preferably from 100 : 1 to 1 : 10, particularly preferably from 30 : 1 to 1 : 1.
A) Preparation of the alko~ylates (DE 36 35 489-Al, pages 5, 32-67) The alko~ylated alcohols are prepared in a known manner by reacting thP monofunctional or polyfunctional alcohol with an alXoxide or with a mixture of a plurality of alkoxide~ or block by block with a plurality of alkoxides with the aid of ba~ic catalysts at from 80 to 160C. Example~ of suitable alcohols are ethanol, butan-ol, isopropanol, tallow fatty alcohol, stearyl alcohol, alkylphenol~ o the general formula R~30H
wh~re R is, for example, C~Hl9, CH3, CH(CH3)2, C(CH3)3 or C~HL7, ethylene glycol, bi3phsnol A, glycerol, trimethyl-olpxopane, pentaerythritol, sorbitol, polyglycerol or the alkylphenol/formaldehyde or ace~aldehyde condensates de cribed below.
Preferred alko~idec are ethylene oxide, propylene oxide and 1,2-butylene oxide or mixtures thereof.
The reaction conditions vary depending on the type and amount of the alkoxide~ usedO In general, the reaction temperature is from 80 to 160C and the amount of basic catalys~ varies from 0.25 to 5~, po~assium hydroxide and sodium hydroxide being preferredO
7'~ ~;
- 7 - o.Z. 0050/~2219 Depending on the consistency of the starting alcohol or of thP end product, an inert solvent which does not influence the reaction may be added for dilution. Xylene i 5 pref~rred.
The ratio of alcohol to alkoxide(s) may vary greatly but is advantageously from 1 : 120 to 1 : 5.
Alkoxylated alkylphenolJformaldehyde or ac~taldehyde condensates The alkylphenol/for~aldehyde or acetaldehyde resins used as alcohols for the alkoxylation are prepared in a conventional manner by reacting the aldehyde with ~he alkylphenol in a ratio of from 2 : 1 to 1 : 2, preferably 1 : 1.05, with base or acid catalysi~, prefer-ably acid catalysis, at from 80 to 250C, with the aid of a high boiling ~olvent for complet2 azeotropic removal of the resulting water of reaction. For example, nonyl-phenol, tert-butylphenol or octylphenol is used as the alkylphenol, while preferably used aldehydes are formal-dehyde and acetaldehyde. In general, an alkylsulfonic acid or alkylbenzenesulfonic acid, for example dodecyl-benzenesuLfonic acid, is used a~ the ca~aly~t, in amounts of from 0.2 to 2%, preferably from 0.2 to 0.5%.
Ak the beginning of the reaction, the temperature is kept at from 90 to 120C until the ma~or part of the water of reaction ha~ been distillsd off. Thereafter, the mixture i~ heated to the boiling point of the solvent to en~ure complete conversion, and residual amount~ of water are removed azeotropically. The molecules con~ain on avera~e from 4 to 12, preferably from 5 to 9, aromatic nuclei.
The conden~ates thus obtained are alkoxylated as stated above.
The pure alkoxylates have, as a rule, very little or no activity as mineral oil demulsifiers. Highly effec~ive products are obtained only as a result of the copolymerization with the vinyl monomers and the subse-quent condensa~ion step or condensation of the . ' t7 l.,~
- 8 - O.~. 0050/42219 alkoxylates with the polymer~ prepared from vinyl monomer~O
B) Preparation of the novel polymers The prepaxation of the no~el polymer3 can be carried out in principle by two method~:
a~ by effecting the polymerization of the vinyl mono-mers in the presence of the alkoxylate and effecting condensation step af~er polymerization is complete, or 0 b) by polymerizing ths vinyl monomer~ separately from the alkoxylate and not adding the alkoxylate until before the conden3ation step.
Proces~ a) is, a~ a rule, preferred. In this process, some of the vinyl monomer~ are grafted onto the alkoxylateO The degree of grating depend~ to a very great extent on the polymerization conditions and on the type of alkoxylate a4 the grafting base. The pre~encP of graft copolymer has proven advantageou~ in many cases.
Proce~s b) i~ preferably chosen when vinyl monomers which do not dissolve in the alkoxylate or in solvents in which the alkoxylate dicsolve~ are to be polymerized or when, even before the polymerization is complete, the monomers would undergo with the alkoxylate the chemical reaction similar to that when, for example, 2S maleic anhydride is used as a comonomer.
The polymerization of th.e vinyl monomer~ accord-ing to variant a) or b) i~ carried out by the known batchwi~e or continuous methods of free radical polyme-rization, such a~ mas~, suspension, precipitation or solution polymerization, and initiation with conventional free radical donors, such a~ acetylcyclohexane~ulfonyl pexoxide, diacetyl peroxydi~arbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl perneodecanoats, 2,2'-azobis-(4-methoxy~2,4-dimathylvaleronitrile~, ~ert-butyl perpivalate, tert-butyl per-2~e~hylhexanoate, tert-butyl penmalaate, 2,2'-azobisisobutyronitrile/ bi3 (tert-butylperoxy3cyclo-- 9 O.Z. 0050/42219 he~ane, tert-butyl peroxyi opropyl carbonate, tert-butyl peracetate, dicumyl pero~ide, di-tert~amyl peroxide, di-tert-butyl pero~ide, p-menthane hydropProxide, cumyl hydroperoxide or ~er~-butyl hyd~operoxide and mixture~
S with one another. In general, the~e initiatorq are used in amounts of from 0.1 to ~0, preferably from 0.2 to 15, % by weight, based on the monomers.
The polymexization is carried out as a rule at from 40 to 200C, preferably from 60 to 150C, in the course of from 0.5 to 10, preferably from 1 to 6, par-ticularly preferably from 2 to 3, hour~, and advan-tageously under superatmo~pheric pressure when solvents having boiling points below the polymeriæation ~emperature are used. The polymerization is advan-lS tageously carried out in the ab~ence of air, ie. when it is not po~ible to work under boiling conditions, for example under nitrogen or carbon dioxide, since oxygen inhibits the polymerization. The reaction can be ac-celerated by the presence of redox coinitiators, such as benzoin, dLmethylaniline, a~corbic acid and soluble organic complexe~ of chromium. The amount~ u~ually used are from 0.1 to 2,000, preferably from 0.1 to l,000, ppm by weight.
To obtain low molecular weight copolymers, it is often advantageous to work in the presence of regulator~.
Example of suitable regulators are allyl alcohols t such a~ but-1-en-3-ol, organic mercapto compounds, such as 2-mercaptoethanol, 2~mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, which are generally used in amounts of from 0.1 to 10~ by weight.
Apparatu~e~ suitable for the polymerization are~
for example, conventional ~tirred kettle~ having, for example, anchor~ paddle or Lmpeller ~tirrers or multi-~taye impul~e countercurrent agitator~ and, for con-tinuou~ preparation, stirred kettle ca~cade~ tubular - 10 - O.Z. 0050/42219 reactors and static mixers.
The simplest polymerization method is mass polymerization. Here, the monomers are polymerized in the presence of an initiator and in the absence of solvents. Advantageously, all monomers are mixed to gi~e the desired composition, and a ~mall portion, for example from about 5 to 10%, is initially taken in ths reactor together with the alkoxylate ~according to process a~) and heated to the desired polymerization temperature with stirring, and the remaining monomer mixture and the initiator and, if required, coinitiator and regulator are metered in uniformly in the course of from 1 to 10, preferably from 2 to 5, hours. It is ad~antageous to meter in ~he initiator and the coinitiator separately in the form of solutions in a small amount of suitable solvent. The condensation step can then be carried out in the melt. The end product can then be added to the crude oil emulsion directly as solidified melt or after being taken up in a suitable so].vent.
A further sLmple me~hod for the preparation of the novel polymers is solution polymerization. It is carried out in solvents in which the monomers and the resul~ing copolymers are soluble. All solvents which meet thi~ precondition and wh:Lch do not undergo any reaction with the monomers are suitable for this purpose.
Examples are toluene, xylene, ethylbenzene, cum~ne, high boiling mixture of aromatics, such as Solves~o~ 100, 150 and 200, aliphatic and cycloaliphatic hydrocarbons, eg. n-hexane, cyclohexane, me~hylcyclohexane, n-octane, isooctane, liquid paraffins, Shellsol TD, T and K and acetone, cyclohexanone, tPtrahydrofuran and dioxane, tetrahydrofuran and dioxane being particularly suitable for obtaining low molecular weight copolymers.
Sinc~ the d~mulsifier~ for crude oil em~lRions are surfactants which ~hould be ~oluble in the continuous phase (oil phase) of the crude oil emul~ion, it is s~
~ O.Z. 0050/~219 advantageous to choo~a, for the polymerization, a ~olv~nt which i~ compatible with the emulsion, ~o that the demul~ifier ~olution can be added directly to the emul sion. Solution pol~merization i4 the preferred method of preparation for the novel copolymer~
In carrying out ~he solution polymerization, it i8 advantageous initially to take the solvent, the alkoxylate and some of the monomer mixture (for example from about 5 to 20~) and to mPter in ~he remainder of the monomer mixture with the initiator and, if required, coinitiator, regulator and solvent. The monomerR may also be metered in individually at different rates. This is advisable in the case of monomers having greatly different reactivitie~ and if particularly uniform distribution of ths less reactive monomer i~ desired.
The less reactive monomer is metered in more rapidly and the more reacti~e monomer more slowly. It is also po~sible initially to take th~ total amount of the monomer, preferably of the the les~ reactive monomer, and to meter in only the more reactive one. Finally, it i8 also possible initially to take the total monomers, the alkoxylate and the solvent and to meter in only the initiator and, if required, coinitiator and regulator (batchwise procedure). When thi~ procedure i~ carried out on a larger scale, however~ problems may be encoun~ered with heat xemoval, ~o that thi~ procedure should be u~ed only at low concentration~ of the monomers to b~ polymerized. The concentrations of said monomers are from 5 to 80, preferably from 10 to 50, ~ by weight.
C) The condensation step In the condensation ~tep, some of the free hydroxyl group~ of the alkoxylate are reacted with some of the reactive group~ of the polymer of the vinyl monomer~ ~for example acrylic acid or ester~ thereof).
This resul~ in bridging, ~o that VQry effecti~e demul~
sifiers are formed. The compo~ition of the alkoxylate and of the vinyl monomers and the reaction conditions J~ J~
- 12 - O.Z. 0050/4~219 must be choRen so that completely oil-soluble end products are obtained. Hence~ all of the hydroxyl groups of the alkoxylate must not be converted in the condens~tion step since insoluble products would form;
instead, low con~ersions are generally sufficient to obtain the desired efect.
The preferred reaction in the condensation step is esterification The condensation is carried out as a rule at from 80 to 250C, preferably from 100 to 200C, particularly preferahly at from 120 to 180C, in the course of from 0.5 to 10, preferably from 1 to 8, particularly preferab-ly from 2 to 6, hours, in the melt or in solu~ion. If the boiling point of the solvent is below th~ desired lS condensation temperature, the condensation is carried out under superatmospheric pressure.
To carry out the condensation step, the reaction mixture, consisting of alkoxylate and polymer of vinyl monomers and, if required, ~olvent, is brought to the desired temperature. In some cases, it is advantageous to remove the low molecular weis~st reaction produc~s (for e~ample water or low molecular weight alcohols) from the reaction vessel. Thi~ may be effected, for example, by passing in an inert gas over the polymer melt or by using an entraining agent. If it is intended to remove, for example, water from the reaetion mixture, suitable entraining age~ts are the conventional organic solvents which form an azeotropic mi*ture with water, in par-ticular xylene or toluene. The conden~ation can be accelerated by adding catalyst~, in particular acidic catalysts, such as sulfuric acid, p-toluene~ulfonic acid/
dodecylbenzene~ulfonic acid, hydrochloric acid or acidic ion exchangers. If a cataly~t acid i~ added, it must be neutralized after the end of the condencation ~tep. All ba~ic compounds are in principle suitable for this purpose. However~ amine~ such a~ triethylamine, ethyl-hexylamine, tributylamine, morpholine, piperidine or 7.~1 - 13 - O.Z. 0050/42219 ethanolamine are preferably used. Not less than the stoichiometric amount of base required for neutralizing ~he catalyst acid i5 added. However, it is also possible to add a larger amount of base. In this case, the remaining acidic groups introduced by the vinyl monomers, especially carboxyl groups which originate from the ac~ylic acid, axe also partially or completely neutral-ized. The activity of the demulsifiers can be ad~pted to the crude oil emul~ions by the correct choice of the base and of the degree of neutralization.
The novel polymers possess both better activity and a longer shelf life compared with the demul~ifiers - described in German Laid-Open Application DOS 3,365,489, without i~ being necessary to convert the free hydroxyl groups of the alkoxylate into ether, ester or urethane groups. Such a conversion can also be carried out in the case of the novel polymers but has no further advantages with regard to activity or sta~ility.
D) Modification of the polymer of B) and C) (optional) For increasing the activity and tailoring to the particular crude oil to be treated, subsequent modifica-tion of the copolymers obtained under B) and C) may be useful. The following modification of the product may be carried out, depending on the comonomers used in the copol~merization:
1) Mixing with an alkoxylated alcohol or a mixture of a plurality of alkoxylated alcohols obtained as de~cribed under A) or with other copolymers of B) and C) in a ratio of rom 10 : 9~ to 90 : 10, preferably from 50 : 50 to 80 : 20.
Better activities can also bs achieved by adding cosurfactan~s to the copolymer in amounts of from 5 to 30% by weight. Such cosurfac~ant3 may be, for example, dodecyl bisulfa~Q, alkylbenzene~ulfonate~ or alkylnaph-thalenesulfonate~.
2) The molecular weigh~ can be increased by subse-quent crosslinking with polyfunctional crosslinXing 2~ 7 - 14 - O.Z. 0050/42219 reagents which react with reactive groups in the copoly-mer. Depending on the type of cro~slinking agent, crosslinking is carried out using from O.1 to lO, prefer-ably from l to 4, % by weight of polyfunctional com-ponents at from 80 to 140C. Depending on the comonomers used, suitable polyfunctional crosslinking agent3 are, for example, bisglycidyl ethers (p2sferably bisglycidyl ether of bisphenol A), polyfunctional alcohols (eg.
~orbi~ol or ethylene glycol), diisocyanates (eg. toluene diisocyanate) and comparable compound which react with reactive centers in the copolymer.
3) Subsequent oxyalkylation with an alkoxide or a mixture of a plurality of alkoxides or block by block with different alkoxides. The copolymers of B) and C) are reacted with tha alkoxide(s) in the presence of ba~ic catalyst (pxef2rably sodium hydroxide or potas~ium hydroxide) in amounts of from 0.5 to 5~ by weight at from lO0 to 150C. Preferably used alkoxide~ are ethylene oxide, propylene oxide or l,2-butylene oxide, ~he ratio of copolymer to alkoxide varying from 5 : 95 to 9S : 5.
O.z. 0050/42219 Reaction p~roducts of alkoxylates and vinyl monomers, their preparation and their use as demulsifiers for crude oil emulsions The pre~ent invention relates to reaction pro-ducts of predominantly hydropho~ic alkoxylates and pre~dominantly hydrophilic vinyl monomers, a process for their preparation and their use as mineral oil demul-sifiers for rapidly dewatering crude oils.
In the production of crude oils, an increasing amount of water is simultaneously obtainsd with increas-ing exploitation of the deposits. Surfactants prssent in the crude oils emul~ify the major part of the water, stable water-in-oil emulsions being formed. Salts which may lead to corrosion problems during the further pro-ces~ing of the crude oil in the refinery may be presentin solution in the emulsion water. The emulsion water must therefore be separated off or reduced below an acceptable concentration prior to transport. Thi~ is ~enerally effected by adding mineral oil demulsifiers, heating of the crude oil facilitating and accelerating the separation.
The crude oils differ in their composition, depending on their origin. The natural emulsifier~
present in the crude oils furthermore have a complicated chemical composition, ~o that il: i nece~sary to develop selective min ral oil demulsifiers to overcome their e~fect. Owing to the opening up of the new oil fields and the changed production conditions in old fields, thQre i5 a constant need for novel demulsifier which effect more rapid separation into oil and water and result in very small amounts of residual water and residual salt.
The most frequently used demulsifiers are ethylene oxide/propylene oxide block copolymers, alkoxylated alkylphenol/formaldehyde resin~, alkoxylated polyamines and crosslinking product~ of the a~ove ba~ic classes with multifunctional reagents, for example 2 ~
- 2 - O.Z. 0050/42219 diisocy~nates, dicarboxylic acids, bisglycidyl ethers and di- and trimethylolphenolO
Polymeric mineral oil demulsifiers are also known (Canadia~ Patent 1,010,740 and DE-C1 33 38 923). Accord-ing to this Canadian Patent, un~aturated functions whichcan be subjected to free radical polymerization and which are polymerized in a subsequent reaction with other monomers in solution are introduced into alkoxylated alcohols and alkoxylated alkylphenol/formaldehyd~ resins by etherification with unsaturated diglycidyl compounds (eg. glycidyl acrylate), by esterification with maleic anhydride or fumaric acid or by transesterification with acrylates or methacrylates. DE-Cl 33 38 923 describes product~ which are obtained by copolymerization of lS polyoxyalkylene ethers of allyl or methallyl alcohol with vinyl esters or acrylates or methacrylates. All of these products have weaknesses ~pecific to their activity or relating to their production. For example, when glycidyl compounds are used for introducing the unsaturated functions, the formation of gel~ and inhomogeneities frequently occurs during the polymerization, while derivatives of allyl alcohol, methallyl alcohol and maleic acid result in poor copolymerization conditions.
Furthermore, gelling and solidification reactions fre-quently take place, particularly as a result of the useof multifunctional s~arting alcohols in the alkoxylation.
DE 36 35 489-A1 describes copolymers of hydro-phobic acrylates or methacrylates and hydrophilic mono-mers. The hydrophobic esters are prepared by acid-catalyzed azeotropic esterification of alkoxylates ofmonohydric or polyhydric alcohols or alkylphenol/aldehyde condensate~ with (meth)acrylic acid. After the copoly-merization of the hydrophobic esters with hydrophilic monomers, th~ free O~ group~ are converted into a form which is no longer reactive and/or the catalyst acid is neutralized with a tertiary amine. The preparation of these products is tLme-consuming since the esterification - 3 - O.Z. 0050/42219 of the alkoxylate with (meth)acrylic acid requires several hours. In the esterification of alkoxylates of polyhydric alcohols, it is impos~ible selectively to prepare the monoester, so that, owing to the pre~ence of multifunctional acrylates during the copolymerization with hydrophilic monomers~ insoluble gels readily form.
EP 0 331 323-A~ di~closes demulsifiers which, however, are based on nitrogen compounds and for whose preparation long reaction time~ are required.
It is an object of the present invention to provide demulsifiers which permit very rapid separation into water and oill give very small amount~ of residual water, have a long shelf life and can be prepared in a simple manner and in short reaction times.
We have found that this object is achieved and that~ surprisingly, product~ having better demulsifier activity and a longer shelf life are obtained in a short reaction time if vinyl monomers are polymerized in the presence of one or more alkoxy:Lates without unsaturated functional groups capable of free radical polymerization having been introduced beforehand into the alkoxylates, and a condensation step i~ carried out after the polyme-rization i~ complete, or if the alkoxylates are condensed with polymers prepared from vinyl monomers.
The pre~ent invention therefore relate~ to reaction product~ o alkoxylate~ and vinyl monomers, obtained by a) polymerization of one or more vinyl monomers of the general formula I
Rl 3 0 C=CH--R 2 where Rl i9 hydrogen, -COOH, -COOC2H5O~, -COOC3~70H~
-Coo-R4-N(R5)2, -Co-~H-R4-N~R5)2, -CONH2, -CNr -phenyl, -o-Co-R4, -pyridyl, -N-C~-R6, -COCH3, -CooR7, -o-R7, -o-R7-oH, -R7, -imidazoyl or 2~
- ~ - O.Z. 0050/~2219 -COOCH2-c\-/H2 o R2 i3 hydrogen or -COOH, and Rl and R2 together may form an anhydride ring, R3 is hydrogen or CH3, and Rl, R2 and R3 are not simultaneously hydrogen, R4 is an alkyl or alkylene group of 1 to 4 carbon atoms, R5 and R6 independently of one another are each hydrogen or Cl-C4-alkyl, and R5 and R6 together may furthe~more form a 5-membered or 6-membered rin~, and R7 is an alkyl, hydroxyalkyl or alkylene group of 1 to 30 carbon atoms, in the presence of one or more alkoxylates of the general formula II
R8-O-~Rg-O]X-H II
where R~ is a radical of a monohydric or polyhydric alcohol, a phenol or alkylphenol of 1 to 30 carbon atoms or a radical of an alkylphenol/formaldehyde or alkylphenol/acetaldehyde condensate, R9 i5 ethylene, propylene, 1,2-butylene or 1,4-butylene and x is from 5 to 120, and within the polyalkylene oxide chains different units [R9-O] according to the above meaning of R3 may be present in the form of blocks or as random mixture~ and x relates to the total number of all units [R9-O], and subsequent condensation or b) polymerization of one or more vinyl monomers of the abovementioned general formula I and condensa~ion of the resulting copolymer with one or more alkoxylates of the abovementioned general ormula II, where in each case 7~
- 5 - O.Z. 0050/4~219 the vinyl monomer~ carry not les~ than 20~ by weight of functional groups capable of undergoing a chemi-cal reaction with the hydroxyl groups of the alk-oxylates after the polymerization is complete, the condensation i3 carried out so ~ha~ not all hydro~yl group~ are converted, and the weight ratio of alkoxylate~ II to the 8um of the vinyl monomers I i from 300 : 1 to 1 : 50.
Preferred reaction products are those which are prepared using, as vinyl monomer~ of the general formula I, acrylic acid, methacrylic acid, esters or amides of these acids, vinyl ethers, acrylonitrile, vinyl-pyrrolidone or mixture~ of the~e monomers. Acrylic acid in an amount of from 50-lO0~ by weight, based on the total amount of vinyl monomer~, is particularly prefer-ably used.
The alkoxylates suitable for ~he preparation of the novel reaction products do not con~ain any nitrogen.
Block copolymers which are obtained from poly-hydric alcohols by reaction with propylene oxide and then with ethylene oxide are preferred, the weight ra~io of propylene oxide to ethylene oxide being from 10 : 1 ~o l : 10, particularly preferably from 5 : 1 to 1 : 8.
For the preparation of the novel polymer~, one or more alkoxylates and one or more vinyl monomers may be used. Hydrophilic vinyl monom~r~ are preferably used, and not moxe than 60% by weight of hydrophobic monomers may furthermore be present in the monomer mixture when a plurality of monomer is used. The hydrophilic monom~rs must carry not les~ than 20, preferably 40, particularly preferably 60, ~ by weight of functional group~ capable of undergoing a chemical reaction wi~h the hydroxyl groups of the alkoxylatPs after pol~merization is comple~e.
ExampleY of suitable vinyl monomsrs are acrylic acid, methacrylic acid, mathyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth~acrylate, lau~yl acrylate, 2 ~ 7 ~
~ 6 - o.Z. 0050/42219 hydroxyethyl (meth)acrylate, di.ethylaminoethyl acrylate, diethylaminoethyl methacrylamicle, glycidyl methacrylate, vinylformamide, vinyl acetate, vinyl propionate, styrene, isobutener trimethylpentene, allyl alcohol, ~inyl methyl S ether, vinyl 4-hydroxybutyl ether, vinylimidazole, vinylpyrrolidone, maleic acid and fumaric acid. Acrylic acid or monomer mixtures which contain not less than 50%
by weight of acrylic acid are particul~rly preferred.
The weight ratio of alko~ylate ~o the sum of the vinyl monomers i9 from 300 : 1 to 1 : S0, preferably from 100 : 1 to 1 : 10, particularly preferably from 30 : 1 to 1 : 1.
A) Preparation of the alko~ylates (DE 36 35 489-Al, pages 5, 32-67) The alko~ylated alcohols are prepared in a known manner by reacting thP monofunctional or polyfunctional alcohol with an alXoxide or with a mixture of a plurality of alkoxide~ or block by block with a plurality of alkoxides with the aid of ba~ic catalysts at from 80 to 160C. Example~ of suitable alcohols are ethanol, butan-ol, isopropanol, tallow fatty alcohol, stearyl alcohol, alkylphenol~ o the general formula R~30H
wh~re R is, for example, C~Hl9, CH3, CH(CH3)2, C(CH3)3 or C~HL7, ethylene glycol, bi3phsnol A, glycerol, trimethyl-olpxopane, pentaerythritol, sorbitol, polyglycerol or the alkylphenol/formaldehyde or ace~aldehyde condensates de cribed below.
Preferred alko~idec are ethylene oxide, propylene oxide and 1,2-butylene oxide or mixtures thereof.
The reaction conditions vary depending on the type and amount of the alkoxide~ usedO In general, the reaction temperature is from 80 to 160C and the amount of basic catalys~ varies from 0.25 to 5~, po~assium hydroxide and sodium hydroxide being preferredO
7'~ ~;
- 7 - o.Z. 0050/~2219 Depending on the consistency of the starting alcohol or of thP end product, an inert solvent which does not influence the reaction may be added for dilution. Xylene i 5 pref~rred.
The ratio of alcohol to alkoxide(s) may vary greatly but is advantageously from 1 : 120 to 1 : 5.
Alkoxylated alkylphenolJformaldehyde or ac~taldehyde condensates The alkylphenol/for~aldehyde or acetaldehyde resins used as alcohols for the alkoxylation are prepared in a conventional manner by reacting the aldehyde with ~he alkylphenol in a ratio of from 2 : 1 to 1 : 2, preferably 1 : 1.05, with base or acid catalysi~, prefer-ably acid catalysis, at from 80 to 250C, with the aid of a high boiling ~olvent for complet2 azeotropic removal of the resulting water of reaction. For example, nonyl-phenol, tert-butylphenol or octylphenol is used as the alkylphenol, while preferably used aldehydes are formal-dehyde and acetaldehyde. In general, an alkylsulfonic acid or alkylbenzenesulfonic acid, for example dodecyl-benzenesuLfonic acid, is used a~ the ca~aly~t, in amounts of from 0.2 to 2%, preferably from 0.2 to 0.5%.
Ak the beginning of the reaction, the temperature is kept at from 90 to 120C until the ma~or part of the water of reaction ha~ been distillsd off. Thereafter, the mixture i~ heated to the boiling point of the solvent to en~ure complete conversion, and residual amount~ of water are removed azeotropically. The molecules con~ain on avera~e from 4 to 12, preferably from 5 to 9, aromatic nuclei.
The conden~ates thus obtained are alkoxylated as stated above.
The pure alkoxylates have, as a rule, very little or no activity as mineral oil demulsifiers. Highly effec~ive products are obtained only as a result of the copolymerization with the vinyl monomers and the subse-quent condensa~ion step or condensation of the . ' t7 l.,~
- 8 - O.~. 0050/42219 alkoxylates with the polymer~ prepared from vinyl monomer~O
B) Preparation of the novel polymers The prepaxation of the no~el polymer3 can be carried out in principle by two method~:
a~ by effecting the polymerization of the vinyl mono-mers in the presence of the alkoxylate and effecting condensation step af~er polymerization is complete, or 0 b) by polymerizing ths vinyl monomer~ separately from the alkoxylate and not adding the alkoxylate until before the conden3ation step.
Proces~ a) is, a~ a rule, preferred. In this process, some of the vinyl monomer~ are grafted onto the alkoxylateO The degree of grating depend~ to a very great extent on the polymerization conditions and on the type of alkoxylate a4 the grafting base. The pre~encP of graft copolymer has proven advantageou~ in many cases.
Proce~s b) i~ preferably chosen when vinyl monomers which do not dissolve in the alkoxylate or in solvents in which the alkoxylate dicsolve~ are to be polymerized or when, even before the polymerization is complete, the monomers would undergo with the alkoxylate the chemical reaction similar to that when, for example, 2S maleic anhydride is used as a comonomer.
The polymerization of th.e vinyl monomer~ accord-ing to variant a) or b) i~ carried out by the known batchwi~e or continuous methods of free radical polyme-rization, such a~ mas~, suspension, precipitation or solution polymerization, and initiation with conventional free radical donors, such a~ acetylcyclohexane~ulfonyl pexoxide, diacetyl peroxydi~arbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl perneodecanoats, 2,2'-azobis-(4-methoxy~2,4-dimathylvaleronitrile~, ~ert-butyl perpivalate, tert-butyl per-2~e~hylhexanoate, tert-butyl penmalaate, 2,2'-azobisisobutyronitrile/ bi3 (tert-butylperoxy3cyclo-- 9 O.Z. 0050/42219 he~ane, tert-butyl peroxyi opropyl carbonate, tert-butyl peracetate, dicumyl pero~ide, di-tert~amyl peroxide, di-tert-butyl pero~ide, p-menthane hydropProxide, cumyl hydroperoxide or ~er~-butyl hyd~operoxide and mixture~
S with one another. In general, the~e initiatorq are used in amounts of from 0.1 to ~0, preferably from 0.2 to 15, % by weight, based on the monomers.
The polymexization is carried out as a rule at from 40 to 200C, preferably from 60 to 150C, in the course of from 0.5 to 10, preferably from 1 to 6, par-ticularly preferably from 2 to 3, hour~, and advan-tageously under superatmo~pheric pressure when solvents having boiling points below the polymeriæation ~emperature are used. The polymerization is advan-lS tageously carried out in the ab~ence of air, ie. when it is not po~ible to work under boiling conditions, for example under nitrogen or carbon dioxide, since oxygen inhibits the polymerization. The reaction can be ac-celerated by the presence of redox coinitiators, such as benzoin, dLmethylaniline, a~corbic acid and soluble organic complexe~ of chromium. The amount~ u~ually used are from 0.1 to 2,000, preferably from 0.1 to l,000, ppm by weight.
To obtain low molecular weight copolymers, it is often advantageous to work in the presence of regulator~.
Example of suitable regulators are allyl alcohols t such a~ but-1-en-3-ol, organic mercapto compounds, such as 2-mercaptoethanol, 2~mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, which are generally used in amounts of from 0.1 to 10~ by weight.
Apparatu~e~ suitable for the polymerization are~
for example, conventional ~tirred kettle~ having, for example, anchor~ paddle or Lmpeller ~tirrers or multi-~taye impul~e countercurrent agitator~ and, for con-tinuou~ preparation, stirred kettle ca~cade~ tubular - 10 - O.Z. 0050/42219 reactors and static mixers.
The simplest polymerization method is mass polymerization. Here, the monomers are polymerized in the presence of an initiator and in the absence of solvents. Advantageously, all monomers are mixed to gi~e the desired composition, and a ~mall portion, for example from about 5 to 10%, is initially taken in ths reactor together with the alkoxylate ~according to process a~) and heated to the desired polymerization temperature with stirring, and the remaining monomer mixture and the initiator and, if required, coinitiator and regulator are metered in uniformly in the course of from 1 to 10, preferably from 2 to 5, hours. It is ad~antageous to meter in ~he initiator and the coinitiator separately in the form of solutions in a small amount of suitable solvent. The condensation step can then be carried out in the melt. The end product can then be added to the crude oil emulsion directly as solidified melt or after being taken up in a suitable so].vent.
A further sLmple me~hod for the preparation of the novel polymers is solution polymerization. It is carried out in solvents in which the monomers and the resul~ing copolymers are soluble. All solvents which meet thi~ precondition and wh:Lch do not undergo any reaction with the monomers are suitable for this purpose.
Examples are toluene, xylene, ethylbenzene, cum~ne, high boiling mixture of aromatics, such as Solves~o~ 100, 150 and 200, aliphatic and cycloaliphatic hydrocarbons, eg. n-hexane, cyclohexane, me~hylcyclohexane, n-octane, isooctane, liquid paraffins, Shellsol TD, T and K and acetone, cyclohexanone, tPtrahydrofuran and dioxane, tetrahydrofuran and dioxane being particularly suitable for obtaining low molecular weight copolymers.
Sinc~ the d~mulsifier~ for crude oil em~lRions are surfactants which ~hould be ~oluble in the continuous phase (oil phase) of the crude oil emul~ion, it is s~
~ O.Z. 0050/~219 advantageous to choo~a, for the polymerization, a ~olv~nt which i~ compatible with the emulsion, ~o that the demul~ifier ~olution can be added directly to the emul sion. Solution pol~merization i4 the preferred method of preparation for the novel copolymer~
In carrying out ~he solution polymerization, it i8 advantageous initially to take the solvent, the alkoxylate and some of the monomer mixture (for example from about 5 to 20~) and to mPter in ~he remainder of the monomer mixture with the initiator and, if required, coinitiator, regulator and solvent. The monomerR may also be metered in individually at different rates. This is advisable in the case of monomers having greatly different reactivitie~ and if particularly uniform distribution of ths less reactive monomer i~ desired.
The less reactive monomer is metered in more rapidly and the more reacti~e monomer more slowly. It is also po~sible initially to take th~ total amount of the monomer, preferably of the the les~ reactive monomer, and to meter in only the more reactive one. Finally, it i8 also possible initially to take the total monomers, the alkoxylate and the solvent and to meter in only the initiator and, if required, coinitiator and regulator (batchwise procedure). When thi~ procedure i~ carried out on a larger scale, however~ problems may be encoun~ered with heat xemoval, ~o that thi~ procedure should be u~ed only at low concentration~ of the monomers to b~ polymerized. The concentrations of said monomers are from 5 to 80, preferably from 10 to 50, ~ by weight.
C) The condensation step In the condensation ~tep, some of the free hydroxyl group~ of the alkoxylate are reacted with some of the reactive group~ of the polymer of the vinyl monomer~ ~for example acrylic acid or ester~ thereof).
This resul~ in bridging, ~o that VQry effecti~e demul~
sifiers are formed. The compo~ition of the alkoxylate and of the vinyl monomers and the reaction conditions J~ J~
- 12 - O.Z. 0050/4~219 must be choRen so that completely oil-soluble end products are obtained. Hence~ all of the hydroxyl groups of the alkoxylate must not be converted in the condens~tion step since insoluble products would form;
instead, low con~ersions are generally sufficient to obtain the desired efect.
The preferred reaction in the condensation step is esterification The condensation is carried out as a rule at from 80 to 250C, preferably from 100 to 200C, particularly preferahly at from 120 to 180C, in the course of from 0.5 to 10, preferably from 1 to 8, particularly preferab-ly from 2 to 6, hours, in the melt or in solu~ion. If the boiling point of the solvent is below th~ desired lS condensation temperature, the condensation is carried out under superatmospheric pressure.
To carry out the condensation step, the reaction mixture, consisting of alkoxylate and polymer of vinyl monomers and, if required, ~olvent, is brought to the desired temperature. In some cases, it is advantageous to remove the low molecular weis~st reaction produc~s (for e~ample water or low molecular weight alcohols) from the reaction vessel. Thi~ may be effected, for example, by passing in an inert gas over the polymer melt or by using an entraining agent. If it is intended to remove, for example, water from the reaetion mixture, suitable entraining age~ts are the conventional organic solvents which form an azeotropic mi*ture with water, in par-ticular xylene or toluene. The conden~ation can be accelerated by adding catalyst~, in particular acidic catalysts, such as sulfuric acid, p-toluene~ulfonic acid/
dodecylbenzene~ulfonic acid, hydrochloric acid or acidic ion exchangers. If a cataly~t acid i~ added, it must be neutralized after the end of the condencation ~tep. All ba~ic compounds are in principle suitable for this purpose. However~ amine~ such a~ triethylamine, ethyl-hexylamine, tributylamine, morpholine, piperidine or 7.~1 - 13 - O.Z. 0050/42219 ethanolamine are preferably used. Not less than the stoichiometric amount of base required for neutralizing ~he catalyst acid i5 added. However, it is also possible to add a larger amount of base. In this case, the remaining acidic groups introduced by the vinyl monomers, especially carboxyl groups which originate from the ac~ylic acid, axe also partially or completely neutral-ized. The activity of the demulsifiers can be ad~pted to the crude oil emul~ions by the correct choice of the base and of the degree of neutralization.
The novel polymers possess both better activity and a longer shelf life compared with the demul~ifiers - described in German Laid-Open Application DOS 3,365,489, without i~ being necessary to convert the free hydroxyl groups of the alkoxylate into ether, ester or urethane groups. Such a conversion can also be carried out in the case of the novel polymers but has no further advantages with regard to activity or sta~ility.
D) Modification of the polymer of B) and C) (optional) For increasing the activity and tailoring to the particular crude oil to be treated, subsequent modifica-tion of the copolymers obtained under B) and C) may be useful. The following modification of the product may be carried out, depending on the comonomers used in the copol~merization:
1) Mixing with an alkoxylated alcohol or a mixture of a plurality of alkoxylated alcohols obtained as de~cribed under A) or with other copolymers of B) and C) in a ratio of rom 10 : 9~ to 90 : 10, preferably from 50 : 50 to 80 : 20.
Better activities can also bs achieved by adding cosurfactan~s to the copolymer in amounts of from 5 to 30% by weight. Such cosurfac~ant3 may be, for example, dodecyl bisulfa~Q, alkylbenzene~ulfonate~ or alkylnaph-thalenesulfonate~.
2) The molecular weigh~ can be increased by subse-quent crosslinking with polyfunctional crosslinXing 2~ 7 - 14 - O.Z. 0050/42219 reagents which react with reactive groups in the copoly-mer. Depending on the type of cro~slinking agent, crosslinking is carried out using from O.1 to lO, prefer-ably from l to 4, % by weight of polyfunctional com-ponents at from 80 to 140C. Depending on the comonomers used, suitable polyfunctional crosslinking agent3 are, for example, bisglycidyl ethers (p2sferably bisglycidyl ether of bisphenol A), polyfunctional alcohols (eg.
~orbi~ol or ethylene glycol), diisocyanates (eg. toluene diisocyanate) and comparable compound which react with reactive centers in the copolymer.
3) Subsequent oxyalkylation with an alkoxide or a mixture of a plurality of alkoxides or block by block with different alkoxides. The copolymers of B) and C) are reacted with tha alkoxide(s) in the presence of ba~ic catalyst (pxef2rably sodium hydroxide or potas~ium hydroxide) in amounts of from 0.5 to 5~ by weight at from lO0 to 150C. Preferably used alkoxide~ are ethylene oxide, propylene oxide or l,2-butylene oxide, ~he ratio of copolymer to alkoxide varying from 5 : 95 to 9S : 5.
4) Quaternization of N-containing copolymers with known quaternizing agents, such as dimethyl sulfate or methyl iodide, at from 50 to 121)C. Complete or partial qua~ernization of the amine fl1nctions present may be effected.
Modification of copolymer C) is not restricted to tha u8e of only one method of modification. Ins~ead, any mod~fications according to l~ to 4) may be carried out in succes3ion.
The novel polymers may also be used as a mixture with other demulsifiers, for example those based on alkoxylated amines.
The R ~-alues (according to H. Fikentscher, Cellulosechemie 13 (1932), 58-64 and 71-74, determined in 2~ (w/v) solution in xylen4) o the novel polymers are fxom lO to 50, preferably from lO to 40, particularly preferably from 13 ~o 30.
- lS - O.Z. 0050/~2219 The novel additives are added to the mineral oil emul~ions in amounts of from O . 5 to 1, 000, preFerably f rom 1 to 2 0 0, ppm .
The Example~ which follow illustrate the invention.
The alko~ylates can be prepared, for example, as described in D~ 36 35 489-Al. In the Examples, the meanings are as follows:
Al: Block copolymer of 1 mol of propylene glycol reacted with (on average) 30.0 mol of propylene oxide and then with (on a~erage) 10.4 mol of ethylene oxide.
A2: Block copolymer o~ 1 mol of propylene glycol reacted with (on average) 47.4 mol of propylene oxide and then with (on average) 20.0 mol of et~ylene oxide ~= Example a3 from German Laid-Open Application DOS
3,365r489)o A3: Block copolymer of 1 mol of propylene glycol reacted with (on average) 20.5 mol of propylene oxide and then with (on average) 11.6 mol of ethylene oxide. 0 A4: Block copolymer of 1 mol of trimethylolpropane reacted with (on average) 80.0 mol of propylene oxide and then with ~on average) 30.3 mol of ethylene oxide (- Example al5 from German Laid-Open Application DOS 3,365,48g). 5 AS: Polytetrahydrofuran having a molecular waight of about 2,000 g~mol.
Preparation of the ns~el pol~mers In a reactor provided with a stirrer, a heating mean~ and a feed apparatus, a solution of 152 g of alkoxylate Al in 126 g of xylene was heated to 70C in a gentle stream of nitrogen, and a solution of 30 g of acrylic acid in 30 g of xylene and simultaneously a solution of 0.6 g of AIBN tazobi~i obutyronitrile) in 26 g of xylene were metered in uniformly in the course of 2 hours. Heating was then carried out for a further hour at 70C. ~ whitish turbid polym~r solution of about 50~
- 16 - O.Z. 0050/42219 ~trangth and having a K value of 20.3 was obtained.
0,8 g of p-toluene~ulfonic acid was added to this polymer 901ution and the mixture was refluxed (140C) for two hours. It was then cooled to 40C and 0.7 g of morpholine was added.
EXAMPL~ 2 The procedure was a in Example 1, except that alkoxylate A2 was used. A milky transparent polymer solution of abou~ 50% strength by weight and having a K
value of 21.5 wa~ obtained. The condensation wa~ carried out similarly to Example 1.
~he procedure was a~ in Example 1, except tha~
alkoxylate A3 was usa~. A ~ranslucent polymer solution o about 50% strength by weight and having a ~ value of 19.8 was obtained. The condensation was carried out after the addition of p-tolueneYulfonic acid by distilling off water azeotropically in the course of two hours The catalyst acid wa~ neutralized by adding an equimolar amount of triethanolamine.
The procedure was as in Example 1, except that polyether ~S waq employed instead of alkoxylate ~1, and 54 g of acrylic acid and 1.3 g of AIBN were llsed for the polymerization. A whi~i~h turbid polymer solution of about 50% strength by weight and having a ~ value of ~4.2 wa~ obtained. The condensation and n~utralization were carried out similarly to Example 1.
In a reactor according to Example 1, 190 g of alXoxylate ~4, 159 g of xylene, 27 g of acrylic ~cid and 1 g of p-toluenesulfonic acid were initially taken and were heated to 70C while stirring and passing through nitrogen. Thereafter, 1.5 g o AIBN in 60 g of xylene were metered in uniformly in the oourse of 2 hours, heating wa~ continued for on~ hour at 70C and rafluxing 2 ~
- 17 - O.Z. 0050/42219 was carried out for a fur~her 3 hours. After the mixture had cooled to room temperature, 1.5 g of tri-n-~utylamine were added. A brownish, transparent polymer solution of about 50% strength and having a ~ value of l9.Z was S obtained.
In a reactor according to Example 1, 100 g of alkoxylate A4, 14.2 g of acrylic acid and 0.53 ~ of p~
toluenesulfonic acid were heated to 65C while stirring and pa~sing through nitrogen, and 100 mg of AIBN were added. After a few minutes, the temperature increased to 77C. After the exothermic reaction had died down, the mixture was kept at 70~ and a further 200 mg of AIBN were added. The mixture was kept at 70C for a further hour and then heated at 135-140C for 1 hour. The viscous pol~mer melt was cooled to 50C and then taken up in the same amount of Solvesso~ 150 (high boiling mixture of aromatics) and 2 g of morpholine.
The procedure wa~ similar to that of Example 1, but with alkoxylate A4 and Solvesso~ 150 as a solvent.
For condensation, the mixture was heated at 160C for 2 hours.
In Examples 8 to 21, the procedure~ were similar to those of the Example~ shown in the last column of ~able 1.
2,9~ t.~7l~
1~ - O.Z. 0050/42219 Ex~- Alko~c- Part~ Mono~or~ P~rt~ Or T~p. Inltl~tor ~ogul4tor 31 pl~ yl~te ~. 2. monom~r~ C Typ~ 0 ) Typ~ 4 ) to Z ~X~pl~
_ . .
9 A4 190 AA - 13. ~ - 70AI2N 5.5 - - 5 9 A4 190 ~A - 53.6 - 70 AI3N 2.0 A4 190 AA - ao.~ - 70 l~Ia~; 2.0 - - 1 11 A4 190 A~ 0.2 - 70 AI~I~2.0 ~3 2.0 0 12 A4 190 AA - 53.6 - 90 l~lP01.3 - - 3 13 A4 190 AA - 26.B - 110 ~P0 2.0 3~2 .4A 2A 57.914.5 70AI~N 2.0 A4 190 M ~EA36.24.070AI3N 2.0 16 A4 342 A~ VP 57.914.5 70A~N2.0 1517 A4 190 AA ~A 36.24.0 70AIall 2.0 18 A4 190 AA AN 36.24.0 70AI~2.0 19 A4 190 AA V4-OE136.~ 4.0 70AI~II 2.0 A~S 190 AA ~A 36.24.0 70A~3N 2.0 21 A4 342 A~9 ~ 65.27.2 70A~iN 2.0 - - 1 ~ ~ by weight, ba~ed on the vinyl monomers AA Acrylic acid EA Ethyl acrylate VP Vinylpyrrolidone LA Lauryl acrylate (mixture of n-dodecyl and n-tetradecyl acrylate) AN Acrylonitrile V4-OEI 4-Hydroxybutyl vinyl ethe3r N~A Methacrylic acid S Styrene EX~MPLE 22 In a reactor according to Example 1, 65 g oE
alko~ylate A4, 81 g of xylene, 0.35 g of p-toluene-sulfonic acid and 32.2 g of a 50.5~ stren~th by weight aqueous ~olution of a copolymer of 50 parts of acrylic acid and 50 parts of maleic acid, having a molecular weight o 3,000 g/mol, were heated to the boil and about 16.5 g of water were separated off azeotropically in the course of 2 hour. The mixture was diluted to 35~ by weight wi~h ~ylene, and water wa~ qeparated off for a 7 ~
- 19 - O.Z. 0050/~2219 further hour. A clear, yellowish solution was obtained by dilution with xylene to about 10% by weLght.
COMPARATIVE EXAMPLE (EXAMPLE B18 from DE 36 35 489-A1) 1. Preparation of the e~er (Example Al5) S In a reactor according to Example 1, 426.3 g of alkoxylate A4, 5.53 g of acrylic ac~d, 5.53 g of p-toluenesulfonic acid, 85 mg of hydroquinone monomethyl ether and 187.6 g of xylene were heated to the boil for three hours, the water of reaction ~hen being removed by azeotropic di~tillation. A clear, brown solution was obtained. The acid number waR 3.9 mg of KOH~g.
2. Copolymerization with acrylic acid (Example B18) In a reactor according to Example 1, 223.3 g of the ester from 1., 23.95 g of acrylic acid, 113 mg of AIBN and 113.2 g of xylene were heated to 80C ~hile passing through nitrogen and were kept at thi~ tempera-ture for three hours. ~hereafter, heating was continued for two hour~ at 110C, the mixture was cooled to 30C and 1.96 g of tri-n-butylamine were addad. A yellowish-brown, clear, viscous polymer solut.ion having a K value of 28.5 was obtained.
The novel polymers were tested using various crude oil emulsions. For this purpose, the corresponding amount of demulsifier was added to the emulsion while stirring, and removal of water was monitoxed ~s a func-tion of timQ in a measuring cylinder. The temperature required for optLmum demul~ification was achieved by placing the measuring cylinder in a thermostated water bath. The numerical values shown in Tables 2 and 3 correspond to the percentage of water removed, based on the total water content of the emulsion (= 100%).
Crude oil emulsion ~
Origina Ruhlermoor/Geoxgsdorf Water content: 47% by volume Demulsification temperature: 50C
2`1~
- 20 - o.Z. 0050/42219 Product Dose Amount of water removed in ~ after from Example (ppm) minutes ¦ hours l ~ 0 0 0 7 24 4970 S 6 210 28 74 88 981~0 . Comp. Exclmple 10 0 0 0 0 3 5 8 : Crude oil emulsion II
Origin: Adorf/Scherhorn Water content: 51% by volume Demulsification temperature: 50C
Product Dose Amount of water removed in ~ after from Example (ppm) minutes ¦ hours 10203Cl 45 1 1 2 4 2 20 821 3~ 63 94 99100 ~5 1520 2~ 35 59 ~899 7 15 812 21 31 ~0 69100 4 6 1~ 25 52 9298 11 10 41? 21 33 63 94100 14 15 421 38 67 9~ 99100 Comp~ Exampl~ 25 0 0 0 5 914 21 The v~lues ~hown in Table~ 2 and 3 indicate the good activity of the novel polymers as demulsifier~ for rrude oil emulsion~. The low dose and tha 3hort demulsification time are typical. The comparative 2 ~ 7 !~
- 21 - O. Z . 0050/42219 p:roduct ha~ sub~:tantially poorer activity in a s;~ilar do~e ~
Modification of copolymer C) is not restricted to tha u8e of only one method of modification. Ins~ead, any mod~fications according to l~ to 4) may be carried out in succes3ion.
The novel polymers may also be used as a mixture with other demulsifiers, for example those based on alkoxylated amines.
The R ~-alues (according to H. Fikentscher, Cellulosechemie 13 (1932), 58-64 and 71-74, determined in 2~ (w/v) solution in xylen4) o the novel polymers are fxom lO to 50, preferably from lO to 40, particularly preferably from 13 ~o 30.
- lS - O.Z. 0050/~2219 The novel additives are added to the mineral oil emul~ions in amounts of from O . 5 to 1, 000, preFerably f rom 1 to 2 0 0, ppm .
The Example~ which follow illustrate the invention.
The alko~ylates can be prepared, for example, as described in D~ 36 35 489-Al. In the Examples, the meanings are as follows:
Al: Block copolymer of 1 mol of propylene glycol reacted with (on average) 30.0 mol of propylene oxide and then with (on a~erage) 10.4 mol of ethylene oxide.
A2: Block copolymer o~ 1 mol of propylene glycol reacted with (on average) 47.4 mol of propylene oxide and then with (on average) 20.0 mol of et~ylene oxide ~= Example a3 from German Laid-Open Application DOS
3,365r489)o A3: Block copolymer of 1 mol of propylene glycol reacted with (on average) 20.5 mol of propylene oxide and then with (on average) 11.6 mol of ethylene oxide. 0 A4: Block copolymer of 1 mol of trimethylolpropane reacted with (on average) 80.0 mol of propylene oxide and then with ~on average) 30.3 mol of ethylene oxide (- Example al5 from German Laid-Open Application DOS 3,365,48g). 5 AS: Polytetrahydrofuran having a molecular waight of about 2,000 g~mol.
Preparation of the ns~el pol~mers In a reactor provided with a stirrer, a heating mean~ and a feed apparatus, a solution of 152 g of alkoxylate Al in 126 g of xylene was heated to 70C in a gentle stream of nitrogen, and a solution of 30 g of acrylic acid in 30 g of xylene and simultaneously a solution of 0.6 g of AIBN tazobi~i obutyronitrile) in 26 g of xylene were metered in uniformly in the course of 2 hours. Heating was then carried out for a further hour at 70C. ~ whitish turbid polym~r solution of about 50~
- 16 - O.Z. 0050/42219 ~trangth and having a K value of 20.3 was obtained.
0,8 g of p-toluene~ulfonic acid was added to this polymer 901ution and the mixture was refluxed (140C) for two hours. It was then cooled to 40C and 0.7 g of morpholine was added.
EXAMPL~ 2 The procedure was a in Example 1, except that alkoxylate A2 was used. A milky transparent polymer solution of abou~ 50% strength by weight and having a K
value of 21.5 wa~ obtained. The condensation wa~ carried out similarly to Example 1.
~he procedure was a~ in Example 1, except tha~
alkoxylate A3 was usa~. A ~ranslucent polymer solution o about 50% strength by weight and having a ~ value of 19.8 was obtained. The condensation was carried out after the addition of p-tolueneYulfonic acid by distilling off water azeotropically in the course of two hours The catalyst acid wa~ neutralized by adding an equimolar amount of triethanolamine.
The procedure was as in Example 1, except that polyether ~S waq employed instead of alkoxylate ~1, and 54 g of acrylic acid and 1.3 g of AIBN were llsed for the polymerization. A whi~i~h turbid polymer solution of about 50% strength by weight and having a ~ value of ~4.2 wa~ obtained. The condensation and n~utralization were carried out similarly to Example 1.
In a reactor according to Example 1, 190 g of alXoxylate ~4, 159 g of xylene, 27 g of acrylic ~cid and 1 g of p-toluenesulfonic acid were initially taken and were heated to 70C while stirring and passing through nitrogen. Thereafter, 1.5 g o AIBN in 60 g of xylene were metered in uniformly in the oourse of 2 hours, heating wa~ continued for on~ hour at 70C and rafluxing 2 ~
- 17 - O.Z. 0050/42219 was carried out for a fur~her 3 hours. After the mixture had cooled to room temperature, 1.5 g of tri-n-~utylamine were added. A brownish, transparent polymer solution of about 50% strength and having a ~ value of l9.Z was S obtained.
In a reactor according to Example 1, 100 g of alkoxylate A4, 14.2 g of acrylic acid and 0.53 ~ of p~
toluenesulfonic acid were heated to 65C while stirring and pa~sing through nitrogen, and 100 mg of AIBN were added. After a few minutes, the temperature increased to 77C. After the exothermic reaction had died down, the mixture was kept at 70~ and a further 200 mg of AIBN were added. The mixture was kept at 70C for a further hour and then heated at 135-140C for 1 hour. The viscous pol~mer melt was cooled to 50C and then taken up in the same amount of Solvesso~ 150 (high boiling mixture of aromatics) and 2 g of morpholine.
The procedure wa~ similar to that of Example 1, but with alkoxylate A4 and Solvesso~ 150 as a solvent.
For condensation, the mixture was heated at 160C for 2 hours.
In Examples 8 to 21, the procedure~ were similar to those of the Example~ shown in the last column of ~able 1.
2,9~ t.~7l~
1~ - O.Z. 0050/42219 Ex~- Alko~c- Part~ Mono~or~ P~rt~ Or T~p. Inltl~tor ~ogul4tor 31 pl~ yl~te ~. 2. monom~r~ C Typ~ 0 ) Typ~ 4 ) to Z ~X~pl~
_ . .
9 A4 190 AA - 13. ~ - 70AI2N 5.5 - - 5 9 A4 190 ~A - 53.6 - 70 AI3N 2.0 A4 190 AA - ao.~ - 70 l~Ia~; 2.0 - - 1 11 A4 190 A~ 0.2 - 70 AI~I~2.0 ~3 2.0 0 12 A4 190 AA - 53.6 - 90 l~lP01.3 - - 3 13 A4 190 AA - 26.B - 110 ~P0 2.0 3~2 .4A 2A 57.914.5 70AI~N 2.0 A4 190 M ~EA36.24.070AI3N 2.0 16 A4 342 A~ VP 57.914.5 70A~N2.0 1517 A4 190 AA ~A 36.24.0 70AIall 2.0 18 A4 190 AA AN 36.24.0 70AI~2.0 19 A4 190 AA V4-OE136.~ 4.0 70AI~II 2.0 A~S 190 AA ~A 36.24.0 70A~3N 2.0 21 A4 342 A~9 ~ 65.27.2 70A~iN 2.0 - - 1 ~ ~ by weight, ba~ed on the vinyl monomers AA Acrylic acid EA Ethyl acrylate VP Vinylpyrrolidone LA Lauryl acrylate (mixture of n-dodecyl and n-tetradecyl acrylate) AN Acrylonitrile V4-OEI 4-Hydroxybutyl vinyl ethe3r N~A Methacrylic acid S Styrene EX~MPLE 22 In a reactor according to Example 1, 65 g oE
alko~ylate A4, 81 g of xylene, 0.35 g of p-toluene-sulfonic acid and 32.2 g of a 50.5~ stren~th by weight aqueous ~olution of a copolymer of 50 parts of acrylic acid and 50 parts of maleic acid, having a molecular weight o 3,000 g/mol, were heated to the boil and about 16.5 g of water were separated off azeotropically in the course of 2 hour. The mixture was diluted to 35~ by weight wi~h ~ylene, and water wa~ qeparated off for a 7 ~
- 19 - O.Z. 0050/~2219 further hour. A clear, yellowish solution was obtained by dilution with xylene to about 10% by weLght.
COMPARATIVE EXAMPLE (EXAMPLE B18 from DE 36 35 489-A1) 1. Preparation of the e~er (Example Al5) S In a reactor according to Example 1, 426.3 g of alkoxylate A4, 5.53 g of acrylic ac~d, 5.53 g of p-toluenesulfonic acid, 85 mg of hydroquinone monomethyl ether and 187.6 g of xylene were heated to the boil for three hours, the water of reaction ~hen being removed by azeotropic di~tillation. A clear, brown solution was obtained. The acid number waR 3.9 mg of KOH~g.
2. Copolymerization with acrylic acid (Example B18) In a reactor according to Example 1, 223.3 g of the ester from 1., 23.95 g of acrylic acid, 113 mg of AIBN and 113.2 g of xylene were heated to 80C ~hile passing through nitrogen and were kept at thi~ tempera-ture for three hours. ~hereafter, heating was continued for two hour~ at 110C, the mixture was cooled to 30C and 1.96 g of tri-n-butylamine were addad. A yellowish-brown, clear, viscous polymer solut.ion having a K value of 28.5 was obtained.
The novel polymers were tested using various crude oil emulsions. For this purpose, the corresponding amount of demulsifier was added to the emulsion while stirring, and removal of water was monitoxed ~s a func-tion of timQ in a measuring cylinder. The temperature required for optLmum demul~ification was achieved by placing the measuring cylinder in a thermostated water bath. The numerical values shown in Tables 2 and 3 correspond to the percentage of water removed, based on the total water content of the emulsion (= 100%).
Crude oil emulsion ~
Origina Ruhlermoor/Geoxgsdorf Water content: 47% by volume Demulsification temperature: 50C
2`1~
- 20 - o.Z. 0050/42219 Product Dose Amount of water removed in ~ after from Example (ppm) minutes ¦ hours l ~ 0 0 0 7 24 4970 S 6 210 28 74 88 981~0 . Comp. Exclmple 10 0 0 0 0 3 5 8 : Crude oil emulsion II
Origin: Adorf/Scherhorn Water content: 51% by volume Demulsification temperature: 50C
Product Dose Amount of water removed in ~ after from Example (ppm) minutes ¦ hours 10203Cl 45 1 1 2 4 2 20 821 3~ 63 94 99100 ~5 1520 2~ 35 59 ~899 7 15 812 21 31 ~0 69100 4 6 1~ 25 52 9298 11 10 41? 21 33 63 94100 14 15 421 38 67 9~ 99100 Comp~ Exampl~ 25 0 0 0 5 914 21 The v~lues ~hown in Table~ 2 and 3 indicate the good activity of the novel polymers as demulsifier~ for rrude oil emulsion~. The low dose and tha 3hort demulsification time are typical. The comparative 2 ~ 7 !~
- 21 - O. Z . 0050/42219 p:roduct ha~ sub~:tantially poorer activity in a s;~ilar do~e ~
Claims (8)
1. A reaction product of alkoxylates and vinyl monomers, obtained by a) polymerization of one or more vinyl monomers of the formula I
I
where R1 is hydrogen, -COOH, -COOC2H5OH, -COOC3H7OH, -COO-R4-N(R5)2, -CO-NH-R4-N(R5)2, -CONH2, -CN, -phenyl, -O-CO-R4, -pyridyl, , -COCH3, -COOR7, -O-R7, -O-R7-OH, -R7, -imidazoyl or R2 is hydrogen or -COOH, and R1 and R2 together may form an anhydride ring, R3 is hydrogen or CH3, and R1, R2 and R3 are not simultaneously hydrogen, R4 is an alkyl or alkylene group of 1 to 4 carbon atoms, R5 and R6 independently of one another are each hydrogen or C1-C4-alkyl, and R5 and R6 together may furthermore form a 5-membered or 6-membered ring, and R7 is an alkyl, hydroxyalkyl or alkylene group of 1 to 30 carbon atoms, in the presence of one or more alkoxylates of the formula II
R8-O-[R9-O]x-H II
where R8 is a radical of a monohydric or polyhydric alcohol, a phenol or alkylphenol of 1 to 30 carbon atoms or a radical of an alkylphenol/formaldehyde or alkylphenol/acetaldehyde condensate, R9 is ethylene, propylene, 1,2 butylene or 1,4-butylene and x is from 5 to 120, and within the polyalkylene oxide - 23 - O.Z. 0050/42219 chains different units [R9-O] according to the above meaning of R9 may be present in the form of blocks or as random mixtures and x relates to the total number of all units [R9-O], and subsequent condensation or b) polymerization of one or more vinyl monomers of the abovementioned formula I and condensation of the resulting copolymer with one or more alkoxylates of the abovementioned formula II, where in each case the vinyl monomers carry not less than 20% by weight of functional groups capable of undergoing a chemi-cal reaction with the hydroxyl groups of the alk-oxylates after the polymerization is complete, the condensation is carried out so that not all hydroxyl groups are converted, and the weight ratio of alkoxylates II to the sum of the vinyl monomers I is from 300 : 1 to 1 : 50.
I
where R1 is hydrogen, -COOH, -COOC2H5OH, -COOC3H7OH, -COO-R4-N(R5)2, -CO-NH-R4-N(R5)2, -CONH2, -CN, -phenyl, -O-CO-R4, -pyridyl, , -COCH3, -COOR7, -O-R7, -O-R7-OH, -R7, -imidazoyl or R2 is hydrogen or -COOH, and R1 and R2 together may form an anhydride ring, R3 is hydrogen or CH3, and R1, R2 and R3 are not simultaneously hydrogen, R4 is an alkyl or alkylene group of 1 to 4 carbon atoms, R5 and R6 independently of one another are each hydrogen or C1-C4-alkyl, and R5 and R6 together may furthermore form a 5-membered or 6-membered ring, and R7 is an alkyl, hydroxyalkyl or alkylene group of 1 to 30 carbon atoms, in the presence of one or more alkoxylates of the formula II
R8-O-[R9-O]x-H II
where R8 is a radical of a monohydric or polyhydric alcohol, a phenol or alkylphenol of 1 to 30 carbon atoms or a radical of an alkylphenol/formaldehyde or alkylphenol/acetaldehyde condensate, R9 is ethylene, propylene, 1,2 butylene or 1,4-butylene and x is from 5 to 120, and within the polyalkylene oxide - 23 - O.Z. 0050/42219 chains different units [R9-O] according to the above meaning of R9 may be present in the form of blocks or as random mixtures and x relates to the total number of all units [R9-O], and subsequent condensation or b) polymerization of one or more vinyl monomers of the abovementioned formula I and condensation of the resulting copolymer with one or more alkoxylates of the abovementioned formula II, where in each case the vinyl monomers carry not less than 20% by weight of functional groups capable of undergoing a chemi-cal reaction with the hydroxyl groups of the alk-oxylates after the polymerization is complete, the condensation is carried out so that not all hydroxyl groups are converted, and the weight ratio of alkoxylates II to the sum of the vinyl monomers I is from 300 : 1 to 1 : 50.
2. A reaction product as claimed in claim 1, wherein the vinyl monomer of the formula I is acrylic acid, methacrylic acid, an ester or amide of acrylic acid or methacrylic acid, vinyl ether, acrylonitrile, vinyl-pyrrolidone or a mixture of these monomers.
3. A reaction product as claimed in claim 1, wherein the vinyl monomer of the formula I contains from 50 to 100% by weight of acrylic acid.
4. A reaction product as claimed in claim 1, where in, in the formula II, R9 is ethylene and propylene.
5. A mixture containing a reaction product as claimed in claim 1 and, if required, surfactants, sol-vents or further demulsifiers.
6. Process for the preparation of a reaction product as claimed in claim 1, comprising a) polymerization of one or more vinyl monomers of the formula I as claimed in claim 1 or 2 or 3 in the presence of one or more alkoxylates of the formula - 24 - O.Z. 0050/42219 II as claimed in claim 1 or 4 and subsequent conden-sation or b) polymerization of one or more vinyl monomer of the formula I as claimed in claim 1 or 2 or 3 and condensation of the resulting copolymer with one or more alkoxylates of the formula II as claimed in claim 1 or 4, where in each case the vinyl monomers carry not less than 20% by weight of functional groups capable of undergoing a chemi-cal reaction with the hydroxyl groups of the alk-oxylates after the polymerization is complete, the condensation is carried out so that not all hydroxyl groups are converted, and the weight ratio of alkoxylates II to the sum of the vinyl monomers I is from 300 : 1 to 1 : 50.
7. A method for using a reaction product as claimed in claim 1, wherein the reaction product is employed as a demulsifier in crude oil emulsions.
8. A method for using a mixture as claimed in claim 5, wherein the mixture is employed as a demulsifier in crude oil emulsions.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4104610A DE4104610A1 (en) | 1991-02-15 | 1991-02-15 | ACTION PRODUCTS OF ALKOXYLATES AND VINYLIC MONOMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE AS DEMULGATORS FOR CRUDEOULULULULULAR POWERS |
| DEP4104610.2 | 1991-02-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2061174A1 true CA2061174A1 (en) | 1992-08-16 |
Family
ID=6425078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002061174A Abandoned CA2061174A1 (en) | 1991-02-15 | 1992-02-13 | Reaction products of alkoxylates and vinyl monomers, their preparation and their use as demulsifiers for crude oil emulsions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0499068B1 (en) |
| CA (1) | CA2061174A1 (en) |
| DE (2) | DE4104610A1 (en) |
| NO (1) | NO300780B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7671098B2 (en) | 2003-06-04 | 2010-03-02 | Clariant Produkte (Deutschland) Gmbh | Alkoxylated, cross-linked polyglycerols and use thereof as biodegradable demulsifier |
| US9296957B2 (en) | 2007-10-08 | 2016-03-29 | Basf Se | Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions |
| US10323215B2 (en) | 2013-07-03 | 2019-06-18 | Basf Se | Solid polymer composition obtained by polymerization of an acid group containing monomer in the presence of a polyether compound |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4326772A1 (en) * | 1993-08-10 | 1995-02-16 | Basf Ag | Reaction products from olefinically unsaturated carboxylic acids and polyetherols and their use as demulsifiers for crude oil emulsions |
| DE102005006030A1 (en) | 2005-02-09 | 2006-08-10 | Basf Ag | Hyperbranched polymers as demulsifiers for cracking crude oil emulsions |
| BRPI0923766A2 (en) | 2008-12-29 | 2019-09-24 | Basf Se | hyperbranched polyesters and polycarbonates as demulsifiers for dividing crude oil emulsions |
| DE102009019179A1 (en) * | 2009-04-28 | 2010-11-11 | Clariant International Ltd. | Alkoxylated (meth) acrylate polymers and their use as crude oil emulsion breakers |
| WO2015180873A1 (en) | 2014-05-28 | 2015-12-03 | Basf Se | Coated mesh and its use for oil-water separation |
| US20170203235A1 (en) | 2014-05-28 | 2017-07-20 | Basf Se | Mesh comprising a surface of hydrated aluminum oxides and their use for oil-water separation |
| EP3554666A1 (en) | 2016-12-16 | 2019-10-23 | Basf Se | Coated meshes and their use, especially for oil-water separation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4138381A (en) * | 1975-04-14 | 1979-02-06 | E. I. Du Pont De Nemours And Company | Polymeric thickeners, processes for their preparation and uses thereof |
| US4626379A (en) * | 1983-05-02 | 1986-12-02 | Petrolite Corporation | Demulsifier composition and method of use thereof |
| DE3513550C1 (en) * | 1985-04-16 | 1986-11-06 | Th. Goldschmidt Ag, 4300 Essen | Use of copolymers of polyoxyalkylene ethers of allyl and / or methallyl alcohol and acrylic or methacrylic esters as demulsifiers for petroleum containing water |
| DE3635489A1 (en) * | 1986-10-18 | 1988-04-21 | Basf Ag | COPOLYMERISATE MADE OF HYDROPHOBIC ACRYLIC ACID OR METHACRYLIC ACID ESTERS AND HYDROPHILIC COMONOMERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PETROLEUM EMULSION SPLITTER |
| US4968449A (en) * | 1989-03-17 | 1990-11-06 | Nalco Chemical Company | Alkoxylated vinyl polymer demulsifiers |
-
1991
- 1991-02-15 DE DE4104610A patent/DE4104610A1/en not_active Withdrawn
-
1992
- 1992-01-24 DE DE59206721T patent/DE59206721D1/en not_active Expired - Fee Related
- 1992-01-24 EP EP92101120A patent/EP0499068B1/en not_active Expired - Lifetime
- 1992-02-13 CA CA002061174A patent/CA2061174A1/en not_active Abandoned
- 1992-02-14 NO NO920601A patent/NO300780B1/en not_active IP Right Cessation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7671098B2 (en) | 2003-06-04 | 2010-03-02 | Clariant Produkte (Deutschland) Gmbh | Alkoxylated, cross-linked polyglycerols and use thereof as biodegradable demulsifier |
| US9296957B2 (en) | 2007-10-08 | 2016-03-29 | Basf Se | Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions |
| US9303215B2 (en) | 2007-10-08 | 2016-04-05 | Basf Se | Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions |
| US10323215B2 (en) | 2013-07-03 | 2019-06-18 | Basf Se | Solid polymer composition obtained by polymerization of an acid group containing monomer in the presence of a polyether compound |
| US10344249B2 (en) | 2013-07-03 | 2019-07-09 | Basf Se | Gel-like polymer composition obtained by polymerizing a monomer containing acid groups in the presence of a polyether compound |
| US10647945B2 (en) | 2013-07-03 | 2020-05-12 | Basf Se | Use of a gel-like polymer composition which can be obtained by polymerizing an acid group-containing monomer in the presence of a polyether compound in formulations for automatic dishwashing |
| US10655088B2 (en) | 2013-07-03 | 2020-05-19 | Basf Se | Solid polymer composition obtained by polymerization of an acid group-containing monomer in the presence of a polyether compound |
Also Published As
| Publication number | Publication date |
|---|---|
| NO920601L (en) | 1992-08-17 |
| NO300780B1 (en) | 1997-07-21 |
| EP0499068A1 (en) | 1992-08-19 |
| EP0499068B1 (en) | 1996-07-10 |
| NO920601D0 (en) | 1992-02-14 |
| DE59206721D1 (en) | 1996-08-14 |
| DE4104610A1 (en) | 1992-08-20 |
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