Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
  • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
  • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide

Definitions

• the present invention relates to a process for the preparation of acrylamido-fe / t-butylsulphonic acid and to a process for the preparation of a copolymer with acrylamide-fe / t-butylsulphonic acid prepared in this way and at least one further unsaturated monomer.
• Acrylamido-fe / t-butyl-sulfonic acid (ATBS, 2-acrylamido-2-methylpropane sulfonic acid, AMPS ®) is an important co-monomer for the production of high molecular weight, thickening polymers based on acrylamide.
• Such polymers may comprise, for example, about 48% by weight of acrylamide, about 50% by weight of ATBS sodium salt and about 2% by weight of a hydrophobically associating monomer.
• WO 2010/133527 A2 describes such ATBS-containing copolymers which can be used inter alia in the development, exploitation and completion of underground oil and natural gas deposits.
• ATBS is crucial for the quality of high molecular weight copolymers containing ATBS for tertiary mineral oil production. Even small amounts of crosslinking components and other by-products can degrade the quality of the polymer.
• ATBS is usually made from acrylonitrile, oleum or sulfur trioxide and isobutene. Acrylamide, Fe / t-butylacrylamide, isobutene sulfonic acid and isobutene disulfonic acid are to be mentioned as frequently occurring by-products in the preparation of ATBS.
• the two latter by-products isobutene sulfonic acid and isobutene disulfonic acid act as chain terminating reagents and affect the quality of the polymer formed accordingly. It is desirable that, in particular, the content of these two components is minimized.
• 8,247,601 B2 describes a direct dependence of the quality of the ATBS as a function of the control of the by-products in the synthesis.
• precise control of the slight excess of SO3 is necessary to reduce the minor components accordingly. This is achieved by extending the reaction time and / or by briefly stopping the SC supply.
• the procedure described is therefore considered to be very expensive in industrial practice, since a constant control and a constant adjustment of the reaction conditions are necessary to achieve the target quality.
• reaction conditions so that by-products are already minimized in the reaction step, whereby a complex purification step could be omitted or at least carried out in a simpler manner.
• the object is achieved by a process for the preparation of acrylamido-fe / t-butylsulphonic acid comprising the steps of (a) determining the water content of a hydrous acrylonitrile and mixing the hydrous acrylonitrile with oleum whose dissolved amount of sulfur trioxide is chosen such that this completely reacts with the water contained in the acrylonitrile to sulfuric acid and a residual water content in the mixture of 0.01 wt .-% to 0.2 wt .-% based on the sum of the amounts of hydrous acrylonitrile and oleum remains;
• the process according to the invention for the preparation of ATBS can achieve this in very high quality if the above-mentioned narrowly chosen water content is maintained.
• the amount of particularly critical by-products isobutene sulfonic acid and isobutene disulfonic acid is greatly reduced, the associated increase in the by-products acrylamide and tert-butylacrylamide surprisingly being small and the overall yield of ATBS is good.
• the usable ATBS in the process according to the invention for the preparation of a copolymer surprisingly gives copolymers of high viscosity and low gel value, so that the copolymers obtained are particularly suitable in formulations for tertiary mineral oil production.
• step (a) of the process according to the invention for the preparation of ATBS the mixing of acrylonitrile and oleum takes place.
• gaseous isobutene is mixed in (step (b)) so that a reaction to ATBS can take place. Accordingly, the simultaneous mixing together of acrylonitrile, oleum and isobutene in a reaction area.
• the downstream mixing can take place in the same reaction area or in one or more other areas.
• a first reaction area the admixing of isobutene a second, of the first range of different reaction area could be provided, and it may be a reaction to the end of the reaction also in this second area or in another third or possibly several other areas.
• the admixing in step (b) takes place subsequently.
• Each of these areas can be driven batchwise or continuously.
• step (a) the mixing of the aqueous acrylonitrile with oleum must be preceded by the determination of the water content of the hydrous acrylonitrile in step (a), since the water content may vary depending on the acrylonitrile used.
• the process according to the invention for the production of ATBS takes place at least partially continuously.
• both the mixing operations and the conversion to ATBS are carried out in a continuous procedure.
• Continuous processes which use stirred tank cascades are described in the prior art, for example in WO 00/34233 A1. ben. Accordingly, the reaction areas may be stirred tank cascades, but other reactor types may be used.
• the method according to the invention can be configured in a first exemplary procedure such that acrylonitrile and oleum are mixed in a first reactor and the mixture is transferred to a second reactor, for example pumped. Isobutene is mixed in this second reactor and the reaction is carried out to ATBS.
• the driving is advantageously carried out continuously.
• acrylonitrile, oleum and isobutene are added simultaneously to a reactor and the reaction is carried out in a single reactor.
• the driving style can also be carried out continuously.
• acrylonitrile and oleum are continuously mixed in a static mixer and transferred to a reactor, in which case mixing and reaction of / with isobutene in this second reactor take place analogously to the first exemplary procedure.
• This mode of operation can be partially run in batch or continuous operation.
• Hydrous acrylonitrile is used in the process of ATBS preparation according to the invention. This makes it possible to use commercially available acrylonitrile, since this is usually not anhydrous. It may, for example, have a water content of from 0.1% by weight to 1% by weight. Normally it has a water content of about 0.4% by weight and typically varies in the range of 0.35% to 0.6% by weight.
• the proportion by weight refers to the sum of all constituents of the acrylonitrile.
• the acrylonitrile used typically has a total purity without water content in the range of 97 wt .-% to 99.9 wt .-%, preferably 98 wt .-% to 99.9 wt .-% to.
• the water content contained in this hydrous acrylonitrile is usually too high to obtain ATBS in high quality. It is therefore necessary to reduce the water content. This is achieved by partial reaction of the water with sulfur trioxide, which is contained in oleum, wherein previously the water content of the hydrous acrylonitrile was determined.
• the amount of SO3 in oleum that is required to adjust the desired residual water content by mixing in step (a) can be determined. If the proportion of water in the acrylonitrile used changes, the amount of SO3 in the oleum must also be adjusted accordingly. Increases, for example, the residual water content, for example, by using another commodity to acrylonitrile or continuous driving by feeding recovered acrylonitrile from the process, the proportion of SO3 can also be increased. With a smaller amount of water, the proportion of SO3 can be reduced accordingly. In this case, however, it is more favorable in terms of process technology to increase the water content by adding water in order to be able to retain the S03 content.
• a S03 proportion in the oleum can always be selected which is so high that always an adjustment of the water content must be made by the addition of water, so that the oleum used in the S03 fraction can remain the same.
• This is process technology favorable, for example, since the then held constant water content can be monitored well, for example by IR measurement.
• Oleum also known as fuming sulfuric acid
• Oleum is a solution of sulfur trioxide in sulfuric acid.
• Oleum is commercially available and often has designations such as "oleum 15", where the numeral “15” indicates the SO 3 component (85% by weight of H2SO4 and 15% by weight of SO3).
• oleum 24, 32 and 65 are commercially available.
• step (a) of the process according to the invention for the preparation of ATBS after determining the water content, mixing of the hydrous acrylonitrile with oleum is carried out. This can be done by methods known to those skilled in the art.
• the mixing of acrylonitrile and oleum should be effected by avoiding side reactions in that oleum is mixed with very good mixing and cooling in a stream of acrylonitrile or in submitted acrylonitrile.
• the amounts of acrylonitrile and fuming sulfuric acid are such that in the reaction mixture, the molar ratio of pure acrylonitrile to pure sulfuric acid in the range of 5: 1 to 25: 1, preferably in the range of 10: 1 to 20: 1, is located.
• pure acrylonitrile is meant the actual proportion of acrylonitrile in the starting material (hydrous acrylonitrile), which can be calculated by the degree of purity of the acrylonitrile, which is indicated either as a commercial product or by conventional methods
• pure sulfuric acid is meant in this case the proportion of sulfuric acid in oleum plus the proportion of sulfuric acid formed by reaction of the sulfur trioxide with water. For this calculation, it can be assumed that 1 mol of sulfur trioxide reacts spontaneously with 1 mol of water to 1 mol of sulfuric acid. A partial back reaction (equilibrium) can be neglected here.
• step (a) of the process according to the invention for the preparation of ATBS oleum (fuming sulfuric acid) is used whose dissolved amount of sulfur trioxide is selected such that it reacts completely with the water containing acrylonitrile to form sulfuric acid and a residual water content in the mixture of 0.01% by weight to 0.2% by weight remains.
• the residual water content is in the range of 0.03 wt% to 0.19 wt%, more preferably in the range of 0.04 wt% to 0.18 wt%, further preferred is a range from 0.05% by weight to 0.17% by weight, more preferred is a range from 0.07% by weight to 0.16% by weight, further preferred is a range of 0.08% by weight.
• the proportion refers to the sum of the amounts of hydrous acrylonitrile and oleum.
• oleum fluoride sulfuric acid
• the dissolved amount of sulfur trioxide in the fuming sulfuric acid of 1 wt .-% to 32 wt .-%, preferably from 8 wt .-% to 24 wt .-% is.
• fuming sulfuric acid for example oleum 24 or 32
• concentrated sulfuric acid for example 96-98% strength
• the mixing which may be required is advantageously obtained after determination of the water content and the manner in which the adjustment of the residual water content is to take place.
• pure sulfur trioxide which is dissolved in concentrated sulfuric acid until the desired concentration of oleum has been reached.
• oleum having a higher than the selected dissolved amount of sulfur trioxide or sulfur trioxide is mixed with concentrated sulfuric acid until the selected dissolved amount of sulfur trioxide is reached.
• Concentrated sulfuric acid typically has a concentration of at least 90% by weight, preferably at least 95% by weight and in particular more than 95% by weight, e.g. 96-98% by weight.
• the desired concentration of dissolved sulfur trioxide can be adjusted firstly by "diluting" oleum having a higher SO3 content with concentrated sulfuric acid
• step (a) of the process according to the invention for the production of ATBS, there are several determination methods.
• a regular or continuous measurement of the water content can take place during the mixing process of oleum and acrylonitrile. This can be done, for example, by appropriate sampling.
• online measurement methods such as IR measurements, are difficult to carry out in the presence of sulfuric acid. Therefore, before mixing oleum and acrylonitrile, the water content in the hydrous acrylonitrile is determined.
• the arithmetic amount of sulfur trioxide is added to the sulfuric acid.
• the proportion of water in the acrylonitrile can vary, there are basically two ways of carrying it out. Firstly, for a given proportion of water, the calculated amount of sulfur trioxide of sulfuric acid can be added. If the water content changes, the sulfur trioxide addition can be increased or decreased. As has already been stated, however, it is more advantageous if, after determining the proportion of water in the acrylonitrile, this is adjusted to a predetermined value, for example to a value of 0.4-0.6% by weight, by appropriate addition of water. This has the advantage that the required amount of dissolved sulfur trioxide in the sulfuric acid can remain constant.
• the setting of a predetermined water content is advantageously carried out before the arithmetic quantity required to adjust the proportion of water in the mixture is added to sulfur trioxide of the sulfuric acid.
• the oleum concentration can be kept constant.
• the determination of the water content in acrylonitrile can be carried out by known methods, such as IR spectroscopy, in the absence of sulfuric acid.
• the water content can also be determined by sampling and Karl Fischer titration.
• this proportion is set to a certain value, so that the calculated amount of sulfur trioxide refers to this particular value.
• This value is preferably in the range from 0.4 to 0.6% by weight of water.
• the temperature in step (a) is preferably in the range of -15 ° C to + 25 ° C, more preferably in the range of -10 ° C to +15 ° C and especially at -5 ° C.
• the temperature control can be done by pre-cooling and appropriate dosage quantity control.
• the mixture is preferably cooled.
• the average residence time of the mixture in a technical apparatus used to carry out step (a) is preferably from 5 seconds to 1 hour.
• a second step (b) of the process according to the invention for the preparation of ATBS the reaction of the mixture with gaseous isobutene is carried out. This can be done for example in a stirred tank reactor.
• steps (a) and (b) can be carried out in one reaction zone.
• step (a) and step occur (b) in different reaction areas.
• the different reaction areas may represent different zones of a reactor or different reactors having a corresponding feed, such as one or more pipelines, eg a stirred tank cascade.
• the gaseous isobutene can even have small amounts of water. However, this does not have to be taken into account when calculating the water content.
• acrylonitrile is used in molar excess.
• the molar ratio of neat acrylonitrile to isobutene is in the range of 10: 1 to 25: 1, more preferably in the range of 13: 1 to 22: 1, more preferably in the range of 15: 1 to 20: 1.
• Step (b) of the process according to the invention for the preparation of ATBS is preferably carried out in a temperature range from +20 ° C to +65 ° C, more preferably in a range from +30 ° C to +45 ° C, especially at +40 ° C.
• the temperature in step (b) is higher than in step (a). Therefore, it is preferable that the mixing of isobutene does not occur simultaneously with step (a).
• a preferred embodiment relates to a method further comprising step (c) after step (b):
• this separation process also includes a washing and drying step to obtain ATBS.
• the washing liquid used is acrylonitrile.
• the resulting ATBS need not be subsequently purified in order to be used for a copolymerization can.
• the acrylonitrile unreacted in the reaction according to step (b) may optionally be purified and reused in the process according to the invention. It should be noted that when re-use of the acrylonitrile in a step (a) upstream step and / or reuse of the acrylonitrile in step (a) and / or reuse of the acrylonitrile in step (b), the desired concentration range of water in the Mixture of acrylonitrile with oleum when adding the gaseous isobutene is maintained.
• the method according to the invention optionally includes the step after step (c) (c + i) recycling at least a portion of the liquid phase containing acrylonitrile from the solid-liquid separation to at least one step selected from steps (a), (b) or a step (a) upstream step.
• the work-up of the excess acrylonitrile is described, for example, in WO 88/01263 A1. If a purification of the unreacted acrylonitrile is to take place, this can take place without prior neutralization. The purification can be carried out in a conventional manner. For example, the separated acrylonitrile can be worked up by distillation, wherein acrylonitrile is distilled off.
• a further aspect of the present invention relates to processes for preparing a copolymer of acrylamido-fe / t-butyl-sulfonic acid and at least one further unsaturated monomer comprising the steps of (a ') preparing acrylamido-fe / t-butyl-sulfonic acid according to above described process according to the invention for the preparation of ATBS and optionally converting the acid into a salt and
• step (a ') no purification, in particular no recrystallization, of acrylamido-fe / t-butyl-sulfonic acid takes place between step (a ') and step (b').
• the at least one further monomer is preferably a monoethylenic monomer, such as acrylamide.
• ATBS is first prepared by a process described therein for its preparation and, if appropriate, converted into its salt. This is expediently carried out by known methods by reaction with a base, preferably in an aqueous medium.
• the bases used are preferably alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide. However, other bases such as amines or the like can be used. Accordingly, the sodium salt of ATBS is preferred. Of course, several different salts of ATBS can be used. In this respect, the term salt also includes a salt in the form of a mixture with different cations and ATBS as anion.
• step (b ') the radical polymerization of ATBS or its salt takes place with at least one further unsaturated monomer.
• This polymerization is known to the person skilled in the art.
• copolymerization of ATBS with acrylamide is preferred, other copolymers can be formed, wherein ATBS or its salt must be used according to the inventive preparation process described herein.
• more hydrophilic monomers (A1) can be used in general.
• the monoethylenic monomers (A1) are hydrophilic.
• hydrophilic in the sense of this invention means that the monomers (A1) should be soluble in the desired use concentration in an aqueous solution which is expediently used for the polymerization, ie a solution containing 25 to 45% by weight of monomers (A1). It is therefore not absolutely necessary that the monomers (A) to be used are completely miscible with water, but it is sufficient if they meet the minimum requirement mentioned .As a rule, the solubility of the hydrophilic monomers (A) in water at room temperature should be at least 50 g / 1, preferably at least 100 g / l and more preferably at least 150 g / l.
• Hydrophilic monoethylenically unsaturated monomers (A1) may be neutral monomers (A1a).
• the monomers (A1 a) comprise hydrophilic groups which give the monomers at least some water solubility.
• (Meth) acrylamide is a monomer (A1 a).
• Examples of further monomers (A1a) include derivatives of (meth) acrylamide, such as N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide or N-methylol (meth) acrylamide.
• hydroxyl and / or ether groups such as, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, hydroxyvinylethyl ether, hydroxyvinylpropyl ether, hydroxyvinyl butyl ether, polyethylene glycol (meth) acrylate, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam and vinyl esters such as vinyl formate or vinyl acetate.
• N-vinyl derivatives can be hydrolyzed after polymerization to vinylamine units, vinyl esters to vinyl alcohol units.
• copolymers to be prepared can be formed from ATBS and one or more further monomers (A1 a).
• Hydrophilic, monoethylenically unsaturated monomers (A1) may be hydrophilic, anionic monomers (A1b) which comprise at least one acidic group or its salts.
• ATBS also belongs to this group. Accordingly, besides ATBS, one or more other monomers (A1b) may also be present in the copolymer, for example with one or more of the monomers (A1a).
• the acidic groups are preferably acidic groups selected from the group of -COOH, -SO3H or -POsl- or their salts. Preference is given to COOH groups and / or -SOsH groups comprising monomers, particularly preferably -SOsH groups comprising monomers. Of course, it may also be the salts of the acidic monomers.
• Suitable counterions include in particular alkali metal ions such as Li + , Na + or K + and ammonium ions such as NH 4 + or ammonium ions with organic radicals.
• Ammonium ions with organic radicals include [NH (CH3) 3] + , [N H2 (CH 3) 2] + , [NH 3 (CH 3)] + , [NH (C 2 H 5 ) 3 ] + , [NH 2 (C 2 H 5 ) 2 ] + , [NH 3 (C 2 H 5 )] + , [NH 3 (CH 2 CH 2 OH)] + , [H 3 N-CH 2 CH 2 -NH 3 ] 2+ or
• COOH group-containing monomers (A1b) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid. Preference is given to acrylic acid.
• sulfonic acid group-containing monomers (A1b) examples include ATBS or its salt, vinylsulfonic acid, allylsulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methyl-butanesulfonic acid or 2-acrylamido-2,4, 4-trimethylpentanesulfonic acid.
• Examples of monomers containing phosphonic acid groups (A1b) include vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonic acids or (meth) acryloyloxyalkylphosphonic acids, preference being given to vinylphosphonic acid.
• monomer (A1b) together with ATBS or its salt can be selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, vinylsulfonic acid, allylsulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3 Acrylamido-3-methylbutanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonic acids and (meth) acryloyloxyalkylphosphonic acids or their salts.
• monoethylenically unsaturated, hydrophilic monomers may be hydrophilic, cationic monomers (A1 c).
• Suitable cationic monomers (A1c) include, in particular, ammonium-containing monomers, in particular ammonium derivatives of N- (co-aminoalkyl) (meth) acrylamides or co-aminoalkyl (meth) acrylic esters.
• H 2 C C (R 1 ) -C (O) O-R 3 -N (R 4 ) 3 + X " (Ib) where R is H or methyl, R 2 is H or d-bis C 4 alkyl group, preferably H or methyl and R 3 is a preferably linear C 1 to C 4 alkylene group, for example a 1, 2-ethylene group -CH 2 -CH 2 - or a 1, 3 Proplyenoli -CH 2 -CH 2 -CH 2 -.
• the radicals R 4 are independently of each other to Cr to C 4 -alkyl, preferably methyl or a group of the general formula -R 5 - SO3H, where R 5 is preferably a linear C to C 4 - Alkylene group or a phenyl group, with the proviso that it is generally not more than one of the substituents R 4 is a sulfonic acid-containing substituent is particularly preferably in the three substituents R 4 to methyl groups, ie, the monomer has a Group -N (CH3) 3 + , X " in the above formula stands for a monovalent anion, for example CK Of course, X- may also represent a corresponding fraction of a multivalent anion, although this is not preferred.
• Examples of preferred monomers (A1c) of the general formula (Ia) or (Ib) include salts of 3-trimethylammonium-propyl (meth) acrylamides or 2-trimethylammoniumethyl (meth) acrylates, for example the corresponding chlorides such as 3-trimethylammoniumpropylacrylamide chloride (DIMAPAQUAT) and 2-trimethylammoniumethyl methacrylate chloride (MADAME-QUAT).
• DIMAPAQUAT 3-trimethylammoniumpropylacrylamide chloride
• MADAME-QUAT 2-trimethylammoniumethyl methacrylate chloride
• amphiphilic Monomers (A2) are monoethylenically unsaturated monomers having at least one hydrophilic group and at least one, preferably terminal, hydrophobic group. Such monomers serve to impart hydrophobically associating properties to the copolymers.
• hydrophobically associating copolymers is understood by the person skilled in the art to mean water-soluble copolymers which, in addition to hydrophilic units (in an amount sufficient to ensure water solubility), have pendant or terminal hydrophobic groups In aqueous solution, the hydrophobic groups can associate with one another. Due to this associative interaction, the viscosity of the aqueous polymer solution increases compared to a similar polymer which has only no associative groups.
• Suitable monomers (A2) have in particular the general formula (IIa), wherein R 5a is H or methyl, R 6 is a linking hydrophilic group and R 7 is a terminal hydrophobic group.
• the linking, hydrophilic group R 6 can be a group comprising alkylene oxide units, for example a group comprising 5 to 50 alkylene oxide units, which can be attached to the group in a suitable manner, for example by means of a single bond or a suitable linking group wherein at least 70 mol%, preferably at least 90 mol% of the alkylene oxide units are ethylene oxide units. Furthermore, it may be a group comprising quaternary ammonium groups.
• the hydrophobic group R 7 is aliphatic and / or aromatic, straight-chain or branched C 8-40 hydrocarbon radicals R 7a , preferably C 12-32 hydrocarbon radicals.
• the hydrophobic group R 7 may be a group R 7b comprising alkylene oxide units having at least 3 carbon atoms, preferably at least 4 carbon atoms.
• the number of alkylene oxide units k is a number from 10 to 80, preferably 12 to 60, particularly preferably 15 to 50 and for example 20 to 40. It is clear to the person skilled in the art of the alkylene oxides that the above-mentioned Values around mean values.
• the radicals R 8a are each independently H, methyl or ethyl, preferably H or methyl, with the proviso that at least 70 mol% of the radicals R 8a is H.
• at least 80 mol% of the radicals R 8a are H, more preferably at least 90 mol% and most preferably exclusively H.
• the block referred to is thus a polyoxyethylene block which optionally contains certain proportions of propylene oxide and / or butylene oxide units, preferably a pure polyoxyethylene block.
• R 7a is an aliphatic and / or aromatic, straight-chain or branched hydrocarbon radical having 8 to 40 carbon atoms, preferably 12 to 32 C atoms.
• it is aliphatic hydrocarbon groups having 8 to 22, preferably 12 to 18 carbon atoms.
• groups include n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl groups.
• these are aromatic groups, in particular substituted phenyl radicals, in particular distyrylphenyl groups and / or tristyrylphenyl groups.
• the monomers (A2) are monomers of the general formula
• H 2 C C (R 5a ) -R 9 -O - (- CH 2 -CH (R 0 ) -O-) x - (- CH 2 -CH (R) -O-) y - (- CH 2 -CH 2 O-) zR 12 (He).
• an ethylenic group H 2 C C (R 5a ) - is linked via a divalent, linking group -R 9 -O- to a block-structured polyoxyalkylene radical, the blocks - ( -CH 2 -CH (R 10 ) -O-) x -, - (- CH 2 -CH (R 11 ) -O-) y -, and optional
• R 5a has the already defined meaning, ie R 5a is H or a methyl group.
• R 9 represents a single bond or a divalent linking group selected from the group consisting of - (C n H 2n ) - [group R 9a ], -O- (C n 'H 2n ') - [group R 9b ] - and -C (O) -O- (C n "H 2n ”) - [group R 9c ].
• n stands for a natural number from 1 to 6, n 'and n "in each case for a natural number from 2 to 6.
• the linking group is straight or branched chain aliphatic hydrocarbon groups having 1 to 6 carbon atoms, which are either directly, via an ether group -O- or via an ester group -C (0) -O- with the ethylenic group
• the groups - (CnFn) -, - (Cn-n) - and - (Cn-1-nn) - are preferably linear aliphatic hydrocarbon groups.
• the group R 9a is a group selected from -CH 2 -,
• the group R 9b is preferably a group selected from -O-CH 2 -CH 2 -, -O-CH 2 -CH 2 -CH 2 - and -O-CH 2 -CH 2 -CH 2 -, particularly preferably -O- CH2-CH2-CH2-CH2.
• the group R 9c is a group selected from
• the group R 9 is particularly preferably a group R 9b , very particularly preferably -O-CH 2 -CH 2 -CH 2 -CH 2 -.
• the radicals R 10 independently of one another are H, methyl or ethyl, preferably H or methyl, with the proviso that at least 70 mol% of the radicals R 10 to H acts.
• at least 80 mol% of the radicals R 10 are H, more preferably at least 90 mol% and most preferably exclusively H.
• the block is thus a polyoxyethylene block which optionally contains certain proportions Propylene oxide and / or butylene oxide units may have, preferably a pure polyoxyethylene block.
• the number of alkylene oxide units x is a number from 10 to 50, preferably from 12 to 40, more preferably from 15 to 35, very preferably from 20 to 30 and for example from about 22 to 25.
• the polyalkylene oxides that these figures are mean values of distributions.
• the radicals R 11 independently represent hydrocarbon radicals of at least 2 carbon atoms, for example 2 to 10 carbon atoms, preferably 2 or 3 carbon atoms. It may be an aliphatic and / or aromatic, linear or branched carbon radical. Preference is given to aliphatic radicals.
• suitable radicals R 11 include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and phenyl.
• Block - (- CH 2 -CH (R 11 ) -O-) y- is thus a block consisting of alkylene oxide units having at least 4 carbon atoms.
• the number of alkylene oxide units y is a number from 5 to 30, preferably 8 to 25.
• z is a number from 0 to 5, for example 1 to 4, ie the terminal block of ethylene oxide units is therefore only optionally present.
• the radical R 12 is H or a preferably aliphatic hydrocarbon radical having 1 to 30 C atoms, preferably 1 to 10 and particularly preferably 1 to 5 C atoms.
• R 12 is preferably H, methyl or ethyl, more preferably H or methyl and most preferably H.
• hydrophobically associating monomers (A2) of the formulas (III), (IId) and (IIe), acrylamide copolymers comprising these monomers and their preparation are known in principle to the person skilled in the art, for example from WO-A 2010/133527 and WO-A 2012 / 069,478th
• R 5a has the meaning defined above.
• R 13 is an alkylene radical, in particular a 1, ⁇ -alkyl radical having 1 to 8 carbon atoms, preferably 2 to 4 carbon atoms and in particular 2 or 3 carbon atoms. Examples include -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - and -CH 2 CH 2 CH 2 CH 2 -. Particularly preferred are -CH 2 CH 2 - and -CH 2 CH 2 CH 2 -.
• R 17 , R 14 and R 15 independently of one another are H or an alkyl group having 1 to 4 carbon atoms, preferably H or methyl.
• R 17 is preferably H and R 14 and R 15 are preferably methyl.
• X - represents a negatively charged counterion, in particular a halide ion selected from F-, Ch, Br or I -, preferably Ch and / or Br.
• R 16 is an aliphatic and / or aromatic, linear or branched hydrocarbon group having 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms.
• R 16 may be aliphatic hydrocarbon radicals having 8 to 18, preferably 12 to 18 carbon atoms.
• examples of such groups include n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, preferred are n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
• Such monomers include N- (meth) acrylamidopropyl-N, N-dimethyl-N-dodecylammonium chloride, N- (meth) acrylamidopropyl-N, N-dimethyl-N-tetradecylammonium chloride, N- (meth) acrylamidopropyl-N, N-dimethyl N-hexadecylammonium chloride or N- (meth) crylamidopropyl-N, N-dimethyl-N-octadecylammonium chloride or the corresponding bromides.
• Such monomers as well as acrylamide copolymers with such monomers are known and described for example in US 7,700,702 B2.
• ATBS copolymers may optionally comprise ethylenically unsaturated monomers other than the monomers (A1) and (A2), preferably monoethylenically unsaturated monomers (A3).
• ethylenically unsaturated monomers other than the monomers (A1) and (A2), preferably monoethylenically unsaturated monomers (A3).
• A3 monoethylenically unsaturated monomers
• A3 monoethylenically unsaturated monomers
• Such monomers can be used to fine tune the properties of acrylamide copolymers.
• the monomers (A3) may be, for example, monoethylenically unsaturated monomers which have a more hydrophobic character than the hydrophilic monomers (A1) and which accordingly are only slightly water-soluble.
• the solubility of the monomers (A3) in water at room temperature is less than 50 g / l, in particular less than 30 g / l.
• Examples of such monomers include N-alkyl and ⁇ , ⁇ '-
• Dialkyl (meth) acrylamides wherein the number of carbon atoms in the alkyl radicals together is at least 3, preferably at least 4.
• examples of such monomers include N-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide or N-benzyl (meth) acrylamide.
• monomers (A3) may also be ethylenically unsaturated monomers having more than one ethylenic group. Such monomers can be used in special cases to achieve easy crosslinking of the acrylamide polymers.
• the monomers (A3) are also particularly preferably exclusively monoethylenically unsaturated monomers.
• ATBS copolymers comprise, in addition to ATBS, at least one further monoethylenically unsaturated monomer other than ATBS. This is at least one monomer selected from the group of non-ATBS hydrophilic monomers (A1), am- phiphilic monomers (A2) or other monomers (A3).
• Preferred ATBS copolymers comprise at least one other-apart from ATBS-hydrophilic monomer (A1).
• Other preferred ATBS copolymers comprise, in addition to ATBS, at least one further - different hydrophilic monomer (A1) and at least one hydrophilic monomer (A2).
• the amount of all hydrophilic monomers (A1) together, i. including ATBS is at least 70 wt .-% with respect to the amount of all monomers, preferably at least 80% by weight and particularly preferably at least 90 wt .-%.
• ATBS copolymers are generally at least 10 wt .-%, in particular at least 15 wt .-%, preferably at least 20 wt .-%, particularly preferably at least 25 wt .-% and for example at least 30 wt .-% of the monoethylenically unsaturated monomer (A) to ATBS, wherein the amount specified refers to the sum of all monomers.
• the amount of amphiphilic monomers (A2) can be up to 15% by weight, based on the total amount of all monomers in acrylamide copolymers, for example 0.1 to 15% by weight, in particular 0.2 to 10% by weight. %, preferably 0.5 to 5 wt .-% and for example 0.5 to 2 wt .-%.
• the amount of optionally present monomers (A3) can be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, based in each case on the total amount of all monomers.
• An upper limit for ethylenically unsaturated monomers having more than one ethylenic group has already been mentioned. Most preferably, no monomers (A3) are present.
• it is a copolymer comprising 85% by weight to 99.9% by weight of hydrophilic monomers (A1) comprising at least ATBS, preferably 90% by weight to 99.8% by weight, especially preferably from 95% by weight to 99.5% by weight and from 0.1% by weight to 15% by weight of amphiphilic monomers (A2), preferably from 0.2% by weight to 10% by weight, more preferably 0 , 5 wt .-% to 5 wt .-%, wherein the sum of all monomers (A1) and (A2) is 100 wt .-%.
• hydrophilic monomers A1 comprising at least ATBS, preferably 90% by weight to 99.8% by weight, especially preferably from 95% by weight to 99.5% by weight and from 0.1% by weight to 15% by weight of amphiphilic monomers (A2), preferably from 0.2% by weight to 10% by weight, more preferably 0 , 5 wt .-% to 5 wt .-%, wherein the sum of all monomers (
• the ATBS polymer is a copolymer comprising ATBS and at least one monoethylenically unsaturated, hydrophilic monomer (A1 a).
• This may in particular be a copolymer which comprises 60 to 80% by weight of (meth) acrylamide and 20 to 40% by weight of ATBS.
• the copolymer may comprise at least one amphiphilic comonomer (A2) in an amount of up to 15% by weight, preferably 0.2 to 10% by weight.
• the residues and indices as well as their preferred ranges have already been defined.
• the (meth) acrylamide polymer is a copolymer comprising (meth) acrylamide and at least two anionic, monoethylenically unsaturated, hydrophilic monomers (A1b), one of these monomers (A1b) being ATBS is.
• the monomers (A1b) are monomers which comprise at least one acidic group selected from the group of -COOH, -SO3H or -PO3H2 or their salts, preferably -COOH and / or -SO3H or salts thereof ,
• Such an acrylamide polymer is preferably a copolymer comprising (meth) acrylamide, ATBS and acrylic acid.
• This may in particular be a copolymer which comprises 40 to 60% by weight of (meth) acrylamide and 20 to 30% by weight of acrylic acid and 20 to 30% by weight of ATBS.
• the copolymer may comprise at least one amphiphilic comonomer (A2) in an amount of up to 15% by weight, preferably 0.2 to 10% by weight.
• the residues and indices as well as their preferred ranges have already been defined.
• the ATBS polymer is a copolymer comprising (meth) acrylamide, at least ATBS and optionally at least one further anionic, monoethylenically unsaturated, hydrophilic monomer (A1b) and at least one amphiphilic monomer (A2) of the general formula
• (Mg) is preferably a monomer of the general formula (IIg)
• the radicals and indices as well as their preferred ranges have already been defined, which may in particular be a copolymer, which comprises 60 to 80% by weight of (meth) acrylamide and 10 to 40% by weight of anionic monomers (A1b) and 0.1 to 10% by weight of said monomer (A2) of the formula (IIf) and / or (Ilg), preferably (Ilg).
• the ATBS-comprising copolymer to be prepared according to the invention has a weight-average molecular weight M w of at least 1 * 10 6 g / mol, in particular from 1 * 10 6 g / mol to 30 * 10 6 g / mol, preferably 5 *. 10 6 g / mol to 30 * 10 6 g / mol, for example 5 to 25 * 10 6 g / mol, for example about 20 * 10 6 g / mol. It is further preferred if the copolymer has a viscosity of more than 1000 mPas according to its inventive production process.
• the copolymer has a gel fraction of less than 7 ml according to its inventive production process.
• Procedure A (stirred tank cascade): Acrylonitrile and oleum were mixed in a first reactor, R1, at the indicated temperature and stoichiometry. This mixture was then pumped into a second reactor, R2, where it was reacted with isobutene at the indicated temperature and stoichiometry. Isobutene was introduced in a gaseous form under the liquid surface.
• Procedure B Acrylonitrile, oleum and isobutene were simultaneously metered into reactor R2 at the indicated temperature and stoichiometry. In this mode, reactor R1 was inoperative.
• Procedure C Acrylonitrile and oleum were mixed in a static mixer at the indicated temperature and stoichiometry. This reactor had a volume of 2 mL. The mixture was then reacted analogously to procedure A in reactor R2 with isobutene at the indicated temperature and stoichiometry. In this mode, reactor R1 was inoperative.
• Mass oleum * S0 3 content / molar weight S0 3 amount S0 3 in moles;
• the adjusted oleum concentration results in a water content of the reaction mixture of 1 1 mmol, corresponding to 198 mg, or 0.09 wt .-% based on the hourly total amount of hydrous acrylonitrile and oleum.
• Isobutene (12.9 g per hour, 230 mmol) was introduced into reactor R2 in this mixture, with ATBS precipitating out of the reaction mixture as a solid. The plant was operated continuously. The average yield of ATBS based on isobutene was 70.1%. After 70 hours, 567 g of solid were filtered off from the product suspension, the filter cake was washed with 250 ml of acrylonitrile and dried at 40 ° C. for 14 h.
• the adjusted oleum concentration results in a water content of the reaction mixture of 15 mmol, corresponding to 270 mg, or 0.12% by weight.
• the system was operated continuously for 20 h.
• ATBS was obtained in 95% yield.
• 479 g of solid were filtered off from the product suspension, the filter cake was washed with 250 ml of acrylonitrile and dried at 40 ° C. for 14 h.
• This mixture was added in the second reactor, R2, at 40 ° C with isobutene (12.3 g per hour, 219 mmol). The system was operated continuously for 24 hours. The average yield was 84%. After 24 h, 547 g of solid were filtered off from the product suspension, the filter cake was washed with 250 ml of acrylonitrile and dried at 40 ° C. for 14 h.
• Example 4 Recycling of the acrylonitrile a) Work-up of the acrylonitrile
• Isobutene (12.8 g per hour, 228 mmol) was introduced into reactor R2 in this mixture, with ATBS precipitating out of the reaction mixture as a solid. The plant was operated continuously for 93 hours. The average yield of ATBS was 76%. After 45 h, 516 g of solid were filtered off from the product suspension, the filter cake was washed with 250 mL of acrylonitrile and dried at 40 ° C. for 14 h.
• ATBS obtained in Examples 1 to 5 were each converted into a 50% strength by weight aqueous sodium salt solution and used in the polymerization described below.
• thermos flask The solution was transferred to a thermos flask, the thermocouple was mounted for temperature recording and purged with nitrogen for 30 minutes and with 4.00 g of a 4% solution of AIBN in methanol, 0.12 ml of a 1% t-BHPO solution and 0.24 ml of a 1% sodium sulfite solution the Polymerization started. With the onset of polymerization, the temperature rose within about 25 minutes at 80 ° C to 90 ° C. A solid polymer gel was obtained.
• the gel block was minced using a meat grinder.
• the resulting gel granules were dried in a fluid bed dryer at 55 ° C for two hours. This gave a white, hard granules, which was converted by means of a centrifugal mill into a powdery state.

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