PROCESS FOR THE PREPARATION OF A WATER SOLUBLE HYDROPHOBIC ASSOCIATION COPOLYMER AND THE USE OF COPO

专利摘要:
water soluble hydrophobic association copolymer, process for preparing a water soluble hydrophobic association copolymer, and use of the copolymers. The present invention relates to water-soluble hydrophobically-associated copolymers which are obtained in the presence of a non-polymerizable surface-active compound and which comprise novel hydrophobically-associated monomers. the monomers comprise an ethylene unsaturated group and a polyether block, the polyether block comprising a hydrophilic polyethyleneoxy block and a hydrophilic polyalkyleneoxy block consisting of alkyleneoxy units having at least 4 carbon atoms. the monomers may optionally have a polyethyleneoxy terminal block. the invention further relates to processes for preparing the copolymers and the use thereof.
公开号:BR112015014069B1
申请号:R112015014069-6
申请日:2013-12-13
公开日:2021-08-31
发明作者:Benjamin Wenzke；Roland Reichenbach-Klinke；Björn Langlotz；Christian Spindler；Christian Bittner
申请人:Basf Se；
IPC主号:

专利说明:

Description
[001] The present invention relates to hydrophobic association copolymers soluble in water which are obtained in the presence of a non-polymerizable surface active compound and which comprise new association monomers in a hydrophobic manner. The monomers comprise an ethylene unsaturated group and a polyether block, the polyether block comprising a hydrophilic polyethyleneoxy block and a hydrophobic polyalkyleneoxy block consisting of alkyleneoxy units having at least 4 carbon atoms. The monomers optionally can have a terminal polyethyleneoxy block. The invention further relates to processes for preparing copolymers and their use.
[002] Water-soluble thickening polymers are used in many fields of industry, for example, in the cosmetics sector, in food, for the production of cleaning products, printing inks and emulsion inks, and in mineral oil production.
[003] Many chemically different classes of polymers useful as thickeners are known. An important class of thickening polymers is what hydrophobic association polymers are called. This is understood by the person skilled in the art as water-soluble polymers having hydrophobic side or end groups, for example relatively long alkyl chains. In aqueous solution, such hydrophobic groups may associate with each other or with other substances having hydrophobic groups. This forms an associative network that thickens the medium.
[004] EP 705 854 A1, DE 100 37 629 A1 and DE 10 2004 032 304 A1 describe association copolymers in a hydrophobic manner and their use, for example, in the construction chemistry sector.
[005] It is known that association copolymers in a hydrophobic manner can be used in the mineral oil production sector, especially for the production of tertiary mineral oil (enhanced oil recovery, EOR). Details of this are described, for example, in the article reviewed by Taylor, K.C. and Nasr-El-Din, H.A. in J. Petr. Sci. Eng. 1998, 19, 265 to 280.
[006] One of the tertiary mineral oil production techniques is the so-called “polymer flooding”. A mineral oil deposit is not an underground “mineral oil sea”, in fact, mineral oil is kept in small pores in the rock that carries mineral oil. The diameter of the cavities in the formation is typically only a few micrometers. For polymer flooding, an aqueous solution of a thickening polymer is injected through the injection wells into a mineral oil deposit. The injection of the polymer solution forces mineral oil through said cavities in the formation from the injection well proceeding towards the production well, and mineral oil is produced through the production well. It is important for this application that the aqueous polymer solution does not comprise any particles in general whatsoever. Even small gel particles that have dimensions in the micrometer range can block the fine pores in formation and thus stop the production of mineral oil. Association copolymers hydrophobically for the production of tertiary mineral oil, therefore, must have a minimum proportion of gel particles.
[007] An additional technique in the production of mineral oil is the so-called "hydraulic fracturing". “Hydraulic fracturing” typically involves injecting a high-viscosity aqueous solution under high pressure into the stratum of the formation that carries oil or gas. The high pressure causes cracks in the rock, which facilitate the production of oil or gas. The thickeners used herein are particularly guar and the more thermally stable derivatives thereof, for example hydroxypropyl guar or carboxymethyl hydroxypropyl guar (J.K. Fink, Oil Field Chemicals, Elsevier 2003, p.240ff). These biopolymers, however, like most polymers in general, have a distinct decrease in viscosity with increasing temperature. As, however, elevated temperatures prevail in underground formations, it may be advantageous to use in “hydraulic fracturing” to use thickeners where the viscosity does not decrease or even increase with increasing temperature.
[008] Additional fields of use of hydrophobic association copolymers in the field of mineral oil production is the thickening of drilling muds and completion fluids. This is described, for example, in the revised article by Taylor, Ann. Transactions of the Nordic Rheology Society, Vol. 11, 2003.
[009] WO 2010/133527 describes the preparation of hydrophobic association copolymers of the type H2C=C(R1)-R4-O-(-CH2-CH(R2)-O-)k-(-CH2-CH( R3)-O-)i-R5 and subsequent reaction with additional hydrophilic monomers to form copolymers. The described macromonomers have an ethylene unsaturated group and a polyether group with a block structure consisting of a hydrophilic polyalkyleneoxy block consisting essentially of ethyleneoxy units and a terminal hydrophobic polyalkyleneoxy block consisting of alkyleneoxy units having at least 4 carbon atoms.
[0010] The document WO 2011/015520 describes the copolymerization of association monomers in a hydrophobic manner and hydrophilic monomers unsaturated by monoethylene in the presence of nonionic surfactants and the use of copolymers formed by polymer flooding.
[0011] CN 102146159 A likewise describes a process for preparing a polyvinyl ether monomer, the polyether monomer having the general formula H2C=C(R2)-O-R1-O-CaH2aO)n-(CbH2bO)mH where a and b are each integers from 2 to 4, a is not equal to b, and R1 is a C1 to C8 alkylene group. The monomers described in the document have a polyalkyleneoxy group formed from ethylene oxide, propylene oxide and/or butylene oxide. The alkoxylation is preferably carried out at a temperature in the range 120 to 160 °C with the addition of an alkyd catalyst, eg potassium methoxide.
[0012] For the preparation of the monomers, the process according to WO 2010/133527 proceeds from alcohols unsaturated by monoethylene, which are subsequently alkoxylated in a two-stage process, such that the mentioned block structure is obtained. The alkoxylation is carried out first with ethylene oxide, optionally in a mixture with propylene oxide and/or butylene oxide, and, in a second step, with alkylene oxides having at least 4 carbon atoms. The examples in WO 2010/133527 describe the performance of alkoxylation using KOMe (potassium methoxide) as a catalyst at a reaction temperature of 140 °C, the concentration of the potassium ions being above 3 mol%.
[0013] The alkoxylation reaction is often carried out under base catalysts. For this purpose, the alcohol used as the starting material typically is mixed with alkali metal hydroxides or alkali metal alkoxides in a pressure reactor and converted to the corresponding alkoxide. Then, commonly under an inert gas atmosphere, the alkylene oxides are measured, for example, in a plurality of steps. In order to control the reaction and to avoid oversaturation of the reaction mixture with alkylene oxide, it is commonly necessary to maintain particular pressure and temperature ranges in alkoxylation.
[0014] The process according to WO 2010/133527 is said to avoid the formation of crosslinking by-products, and then the preparation of copolymers with a low gel content is said to be possible.
[0015] However, it has been found that prior art preparation processes are not a reliable method for preparing hydrophobic association copolymers with a low gel content. Floating copolymer qualities were found, for example, in the event of pressure and reaction time variation in the alkoxylation steps, such that sometimes highly crosslinked copolymer products were obtained.
[0016] In prior art processes it has been found that monomers having two ethylene unsaturated groups are likely to be formed as a by-product. These bifunctional by-products have a cross-linking effect and lead to increased gel formation in copolymerization. It has been found that the occurrence of these unwanted side reactions increases with the temperature and duration of the reaction. Copolymers with a gel content in general can no longer be filtered and are no longer useful for injection into porous matrices in mineral oil deposits.
[0017] Typically there is a preference for KOMe (potassium methoxide) as a basic catalyst than for NaO-Me (sodium methoxide), as KOMe is more strongly basic than NaOMe, and therefore the alkoxylation reaction proceeds faster. However, the more strongly basic KOMe was found to promote the formation of the crosslinking monomers described above. Butylene oxide and pentylene oxide react much more slowly than ethylene oxide or propylene oxide; therefore, the side reactions in the case of alkoxylation with butylene oxide or pentylene oxide have a more distinct effect.
[0018] Therefore, it was an objective of the invention to provide association copolymers in a hydrophobic manner with lower or undetectable gel contents compared to those already known copolymers, proceeding from new crosslinking free monomers. The copolymers were also prepared more economically than the current ones and their action as thickeners was at least equal compared to that of existing compounds.
[0019] Surprisingly, it has now been found that the formation of bifunctional crosslinking compounds and thus the gel content in the resulting copolymers can be reduced or virtually completely avoided when a critical amount of potassium ions is less than or equal to 0.9% in mol based on the alcohol to be alkoxylated and a temperature less than or equal to 135 °C is observed in the second alkoxylation step (reaction with butylene oxide or pentylene oxide). Additionally it was found that the preparation process according to the invention, with the given safety demands relating to chemistry and operation (more particularly a pressure of less than 210,000 Pa (2.1 bar) in the alkoxylation with pentylene oxide and more particularly a pressure of less than 310,000 Pa (3.1 bar) in the alkoxylation with butylene oxide) guarantees good reproducibility with reasonable reaction time.
[0020] Suitably, water-soluble hydrophobically associating copolymers comprising the following monomers have been found: (a) 0.1 to 20% by weight of at least one hydrophobically associating monomer (a), and ( b) 25 to 99.9% by weight of at least one hydrophilic monomer (b) other than monomer (a), with the use of at least one more non-polymerizable surface active component (c) in the course of its synthesis, before the start of the polymerization reaction, where each of the stated amounts is based on the total amount of all monomers in the copolymer, and at least one of the monomers (a) being a monomer of general formula (I)
where the units (CH2-CH2-O)k, (CH2-CH(R3)-O-)i, and optionally (-CH2-CH2-O-)m are arranged in the block structure in the sequence shown in formula (I ) and each of the radicals and indices is defined as in the sequence: k: is a number from 15 to 35, preferably from 20 to 28, more preferably from 23 to 26; 1: is a number from 5 to 30, preferably from 5 to 28, more preferably from 5 to 25; m: is a number from 0 to 15, preferably from 0 to 10; R1: is H or methyl; R2: is independently a single bond or bivalent bond group selected from the group of -(CnHn)- and -O-(Cn'H2n')-, where n is a natural number from 1 to 6 and n' is a natural number from 2 to 6; R3: is independently a hydrocarbyl radical having at least two carbon atoms or an ether group of the general formula -CH2-O-R3' where R3' is a hydrocarbyl radical having at least two carbon atoms; with the proviso that the sum total of carbon atoms in all hydrocarbyl radicals R3 and R3' is in the range from 15 to 60, preferably from 15 to 56, more preferably from 15 to 50; R4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms; and the hydrophobically associating monomer (a) of the general formula (I) which can be obtained by a process comprising the following steps: a) reacting an unsaturated alcohol with monoethylene A1 of the general formula (II)
with ethylene oxide, where the radicals R1 and R2 are as defined above; with the addition of a C1 alkaline catalyst comprising KOMe and/or NaOMe to obtain an alkoxylated alcohol A2; b) reacting the alkoxylated alcohol A2 with at least one alkylene oxide Z of the formula (Z)
where R3 is as defined above; with the addition of a C2 alkaline catalyst; where the concentration of potassium ions in the reaction in step (b) is less than or equal to 0.9% by mol, preferably from 0.01 to 0.9% by mol, more preferably from 0.01 to 0.5 % by mol, based on alcohol A2 used; and where the reaction in step b) is carried out at a temperature less than or equal to 135°C, to obtain an alkoxylated alcohol A3 of formula (III)
where R4 = H, where the radicals Ri, R2 and R3 and the kel indices are as defined above; c) optionally reacting at least a portion of the alkoxylated alcohol A3 with ethylene oxide to obtain the alkoxylated alcohol A4 which corresponds to monomer (a) of formula (I) where R4 = H and >0; d) optionally etherifying the alkoxylated alcohol A3 and/or A4 with a compound R4-X where R4 is as defined above and X is a leaving group, preferably selected from the group of Cl, Br, I, -O-SO2-CH3 (mesylate), -O-SO2-OR4 to obtain a monomer (a) of the formula (I) and/or (III) where R4 = hydrocarbyl radical having 1 to 4 carbon atoms.
[0021] In a preferred embodiment the invention relates to water-soluble hydrophobically association copolymers, wherein the radicals and indices in the monomers (a) of formula (I) are as defined in the sequence: k: is a number of 23 to 26; 1: is a number from 5 to 30, preferably from 5 to 28, more preferably from 5 to 25; m: is a number from 0 to 15, preferably from 0 to 10; R1: is H or methyl; R2: is independently a single bonding or bivalent bonding group selected from the group of -(CnHn)- and -O-(Cn'H2n')-, where n is a natural number from 1 to 6 and n' is a natural number from 2 to 6; R3: is independently a hydrocarbyl radical having at least two carbon atoms or an ether group of the general formula -CH2-O-R3' where R3' is a hydrocarbyl radical having at least two carbon atoms; with the proviso that the sum total of carbon atoms in all hydrocarbyl radicals R3 and R3' is in the range from 15 to 60, preferably from 15 to 56, more preferably from 15 to 50; R4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms.
[0022] In a preferred embodiment, the sum total of all monomers in the copolymer is equal to 100% by weight.
[0023] Monomer a) preferably is exclusively a monomer of general formula (I) as described above. In a preferred embodiment, water-soluble hydrophobically associating copolymers comprising the following monomers have been found: (c) 0.1 to 20% by weight of at least one hydrophobically associating monomer (a), and (b) 25 to 99.9% by weight of at least one hydrophilic monomer (b) other than monomer (a), with the use of at least one more non-polymerizable surface active component (c) in the course of its synthesis, before the beginning of the polymerization reaction, where each of the stated amounts is based on the total amount of all monomers in the copolymer, and at least one of the monomers (a) being a monomer of general formula (I)
where the units (CH2-CH2-O)k, (CH2-CH(R3)-O-)i, and optionally (-CH2-CH2-O-)m are arranged in the block structure in the sequence shown in formula (I ) and each of the radicals and indices is defined as in the sequence: k: is a number from 23 to 26; l: is a number from 8.5 to 17.25; m: is a number from 0 to 15, preferably from 0 to 10; R1: is H or methyl; R2: is independently a single bond or bivalent bond group selected from the group of -(CnHn)- and -O-(Cn'H2n')-, where n is a natural number from 1 to 6 and n' is a natural number from 2 to 6; R3: is independently a hydrocarbyl radical having at least two carbon atoms or an ether group of the general formula -CH2-O-R3' where R3' is a hydrocarbyl radical having at least two carbon atoms; with the proviso that the sum total of carbon atoms in all hydrocarbyl radicals R3 and R3' is in the range of 25.5 to 34.5; R4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms; and the hydrophobically associating monomer (a) of the general formula (I) which can be obtained by a process comprising the following steps: a) reacting an unsaturated alcohol with monoethylene A1 of the general formula (II)
with ethylene oxide, where the radicals R1 and R2 are as defined above; with the addition of a C1 alkaline catalyst comprising KOMe and/or NaOMe to obtain an alkoxylated alcohol A2; b) reacting the alkoxylated alcohol A2 with at least one alkylene oxide Z of the formula (Z)
where R3 is as defined above; with the addition of a C2 alkaline catalyst; where the concentration of potassium ions in the reaction in step (b) is less than or equal to 0.9% by mol, preferably from 0.01 to 0.9% by mol, more preferably from 0.01 to 0.5 % by mol, based on alcohol A2 used; and where the reaction in step b) is carried out at a temperature less than or equal to 135°C, to obtain an alkoxylated alcohol A3 of formula (III)
where R4 = H, where the radicals R1, R2 and R3 and the kel indices are as defined above; c) optionally reacting at least a portion of the alkoxylated alcohol A3 with ethylene oxide to obtain the alkoxylated alcohol A4 which corresponds to monomer (a) of formula (I) where R4 = H and >0; d) optionally etherifying the alkoxylated alcohol A3 and/or A4 with a compound R4-X where R4 is as defined above and X is a leaving group, preferably selected from the group of Cl, Br, I, -O-SO2-CH3 (mesylate), -O-SO2-CF3 (triphylate) and -O-SO2-OR4 to obtain a monomer (a) of the formula (I) and/or (III) where R4 = hydrocarbyl radical having 1 to 4 carbon atoms .
[0024] In a preferred embodiment, the sum total of all monomers in the copolymer is 100% by weight.
[0025] Monomer a) preferably is exclusively a monomer of general formula (I) as described above.
[0026] In addition, the preparation of such copolymers was discovered, as the use of them for the development, exploration and completion of underground mineral oil and natural gas deposits.
[0027] Specific details of the invention are as follows:
[0028] The hydrophobic association copolymers of the invention are water-soluble copolymers having hydrophobic groups. In aqueous solution, hydrophobic groups can associate with each other or with the hydrophobic groups of other substances and thicken the aqueous medium as a result of these interactions.
The person skilled in the art is aware that the solubility of hydrophobic association (co)polymers in water can be more or less strongly pH dependent, depending on the nature of the monomers used. The reference point for the assessment of water solubility, therefore, will be in each case the desired pH for the respective end use of the copolymer. Monomer (a)
[0030] The association copolymer hydrophobically comprises at least one monomer unsaturated by monoethylene (a) which imparts association properties hydrophobically to the copolymer of the invention and is therefore referred to hereinafter as association monomer hydrophobically .
[0031] According to the invention, at least one of the hydrophobically associating monomers (a) is a monomer of the general formula (I) H2C=C(R1)-R2-O-(CH2-CH2-O)k -(CH2-CH(R3)-O-)i-(-CH2-CH2-O-)m-R4(I)
[0032] In the monomers (a) of the general formula (I), an ethylenic group H2C=C(Ri)- is linked through a bivalent linking group -R2-O- to a polyalkyleneoxy radical having the block structure (CH2 -CH2-O)k-(CH2-CH(R3)-O-)1-R4, where the blocks -(CH2-CH2-O)k and -(CH2-CH(R3)-O-)i are arranged in the sequence shown in formula (I). Optionally, monomer (a) of formula (I) may have an additional polyethyleneoxy block -(-CH2-CH2-O-)m. The polyalkyleneoxy radical has both a terminal OH group and a terminal ether group OR4.
[0033] In the formula mentioned above, R1 is H or a methyl group. Preferably Ri is H.
[0034] R2 is a single bonding or bivalent bonding group selected from the group of -(CnHn)- and -O-(Cn‘H2n’)-. In the mentioned formulas, n is a natural number from 1 to 6 and n' is a natural number from 2 to 6. In other words, the linking group comprises straight-chain or branched-chain aliphatic hydrocarbyl groups having from 1 to 6 carbon atoms or from 2 to 6 carbon atoms and are attached either directly or through an ether group -O- to the ethylenic group H2C=C(R1)-. The groups -(CnH2n)- and -O-(Cn'H2n')- preferably are linear aliphatic hydrocarbyl groups.
[0035] Preferably, the group R2 = -(CnH2n)- is a group selected from -CH2-, -CH2-CH2- and -CH2-CH2-CH2-, particular preference being given to a methylene group -CH2- .
[0036] Preferably, the group R2 = -O-(Cn'H2n')- is a group selected from -O-CH2-CH2-, -O-CH2-CH2-CH2- and -O-CH2-CH2 -CH2-CH2-, particular preference being given to -O-CH2-CH2-CH2-CH2-.
[0037] More preferably, the R2 group is an -O-(Cn'H2n')- group.
[0038] In addition, R2 is more preferably a group selected from -CH2- and -O-CH2-CH2-CH2-CH2-, very particular preference being given to -O-CH2-CH2-CH2-CH2-.
[0039] Monomers (a) additionally possess a polyalkyleneoxy radical consisting of -(CH2-CH2-O)k, -(CH2-CH(R3)-O-)i and optionally -(-CH2-CH2-O-) units and optionally -(-CH2-CH2-O-). )m, the units being arranged in the block structure in the sequence shown in formula (I). The transition between blocks can be abrupt or even continuous.
[0040] The number of ethyleneoxy units k is a number from 15 to 35, preferably from 20 to 28, more preferably from 23 to 26.
[0041] Preferably, the number of ethyleneoxy units k is a number from 23 to 26. It will be apparent to the person skilled in the art in the field of polyalkylene oxides that the numbers mentioned are mean values of distributions.
[0042] In the second block -(CH2-CH(R3)-O-)i, each of the R3 radicals is independently a hydrocarbyl radical having at least 2 carbon atoms, preferably having 2 to 14 carbon atoms, preferably 2 to 4 carbon atoms and more preferably having 2 or 3 carbon atoms. This can be a linear or branched, aliphatic and/or aromatic carbon radical. Preference is given to aliphatic radicals. Particular preference is given to an aliphatic unbranched hydrocarbyl radical having 2 or 3 carbon atoms. The block mentioned preferably is a polybutyleneoxy block or a polypentyleneoxy block.
Examples of suitable R3 radicals comprise ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl and phenyl.
Examples of suitable R3 radicals comprise ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and phenyl. Examples of preferred radicals comprise n-propyl, n-butyl, n-pentyl, particular preference being given to an ethyl radical or an n-propyl radical.
[0045] The radicals R3 may additionally be ether groups of the general formula -CH2-O-R3' where R3' is a linear or branched, aliphatic and/or aromatic hydrocarbyl radical having at least 2 carbon atoms, preferably from 2 to 10 carbon atoms and more preferably at least 3 carbon atoms. Examples of R3' radicals comprise n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n- tetradecyl or phenyl.
[0046] The block -(-CH2-CH(R3)-O-)l- thus is a block consisting of an alkyleneoxy moiety having at least 4 carbon atoms, preferably having 4 or 5 carbon atoms, and/or glycidyl ethers having an ether group of at least 2 carbon atoms, preferably at least 3 carbon atoms. Preferred R3 radicals are the hydrocarbyl radicals mentioned; the units in the second block are more preferably alkyleneoxy units comprising at least 4 carbon atoms, such as butyleneoxy or pentyleneoxy units or higher alkylene oxide units, even more preferably butylene oxide or pentyleneoxy units.
[0047] It will be apparent to the person skilled in the art in the field of polyalkylene oxides that the orientation of the hydrocarbyl radicals R3 may depend on the conditions in the alkoxylation, for example, in the catalyst selected for the alkoxylation. Alkyleneoxy groups can thus be incorporated into the monomer in the -(-CH 2 -CH(R 3 )-O-)- orientation or alternatively the reverse orientation - (-CH(R 3 )-CH 2 -O-) 1-. The representation in formula (I) therefore should not be considered to be restricted to a particular orientation of the R3 group.
The number of alkyleneoxy units l is a number from 5 to 30, preferably from 5 to 28, preferably from 5 to 25, preferably from 7 to 23, preferably from 7 to 18, especially preferably from 8.5 to 17, 25 with the proviso that the sum total of carbon atoms in all hydrocarbyl radicals R3 and R3' is in the range from 15 to 60, preferably from 15 to 56, preferably from 15 to 50, preferably from 25.5 to 34, 5. If the radicals R3 are an ether group -CH2-O-R3', the condition applies that the sum total of the hydrocarbyl radicals R3' is in the range from 15 to 60, preferably from 15 to 56, preferably from 15 to 50, preferably from 25.5 to 34.5, not including the carbon atom in the linking group -CH2-O- in -CH2-O-R3'.
[0049] A preferred embodiment relates to a copolymer described above comprising a monomer (a) where R3 is ethyl and l is a number from 7.5 to 28, preferably from 7.5 to 25, more preferably from 12.75 to 25, especially preferably from 13 to 23, especially preferably from 12.75 to 17.25, for example 14, 16 or 22.
[0050] In a preferred embodiment the number of alkyleneoxy units l is a number from 8.5 to 17.25 with the proviso that the sum total of carbon atoms in all hydrocarbyl radicals R3 and R3' is in the range of 25 .5 to 34.5. If the radicals R3 are an ether group -CH2-O-R3', the condition applies that the sum total of the hydrocarbyl radicals R3' is in the range of 25.5 to 34.5, not including the carbon atom in the group. linking -CH2-O- into -CH2-O-R3'. A preferred embodiment refers to a copolymer described above comprising a monomer (a) where R 3 is ethyl and l is a number from 12.75 to 17.25, especially preferably from 13 to 17, eg 14 or 16. A preferred embodiment refers to a copolymer described above comprising a monomer (a) where R3 is n-propyl and l is a number from 8.5 to 11.5, especially preferably from 9 to 11, for example 10 or 11. It will be apparent to the skilled in the art in the field of polyalkyleneoxy oxides that the numbers mentioned above are mean values of distributions.
[0051] The optional -(-CH2-CH2-O-)m block is a polyethyleneoxy block. The number of ethyleneoxy units m is a number from 0 to 15, preferably from 0 to 10, more preferably from 0.1 to 10, more preferably from 0.1 to 5, especially preferably from 0.5 to 5 and even more preferably from 0.5 to 2.5. It will be apparent to one skilled in the art in the field of polyalkylene oxides that the numbers mentioned above are mean distribution values.
[0052] In a preferred embodiment of the invention, m is greater than 0 (ie, optional step c) is performed). In particular in this embodiment m is a number from 0.1 to 15, preferably from 0.1 to 10, more preferably from 0.5 to 10, especially preferably from 1 to 7, further preferably from 2 to 5. It will be apparent to the skilled in the art in the field of polyalkylene oxides that the numbers mentioned above are mean distribution values.
The radical R4 is H or a hydrocarbyl radical preferably aliphatic having from 1 to 4 carbon atoms, R4 is preferably H, methyl or ethyl, more preferably H or methyl and most preferably H.
[0054] In the monomers of formula (I), a terminal monoethylenic group is thus joined to a polyalkyleneoxy group with block structure, more specifically first to a hydrophilic block having polyethyleneoxy units and the last in turn to a second hydrophobic block formed to from alkyleneoxy units, preferably at least butyleneoxy units or higher alkylene oxide units, and more preferably from butyleneoxy or pentyleneoxy units. The second block can have a terminal group -OR4, especially an OH group. The end group need not be etherified with a hydrocarbyl radical for hydrophobic association; instead, the second block -(-CH2-CH(R3)-O-)i itself having the radicals R3 and R3' is responsible for the hydrophobic association of the copolymers prepared using the monomers (a). etherification is only one option that can be selected by the person skilled in the art according to the desired properties of the copolymer.
[0055] It will be apparent to the person skilled in the art in the field of polyalkyleneoxy block copolymers that the transition between the two blocks, according to the method of preparation, can be abrupt or even continuous. In the case of a continuous transition, there is a transition zone comprising monomers from both blocks between the blocks. If the block boundary is set in the middle of the transition zone, the first -(-CH2-CH2-O-)k block correspondingly may still have small amounts of -(-CH2-CH(R3)-O-) units and the second block -(-CH2-CH(R3)-O-)i may still have small amounts of -(-CH2-CH2-O-) units, in which case these units, however, are not distributed from random way by the block, but they are arranged within the mentioned transition zone. More particularly, the optional third block -(-CH2-CH2-O-)m may have small amounts of the -(-CH2-CH(R3)-O-)- units.
[0056] The present invention relates to a process for preparing a macromonomer M of formula (I) wherein the units -(CH2-CH2-O)k, -(CH2-CH(R3)-O-)l and optionally -( -CH2-CH2-O-)m are arranged in block structure in the sequence shown in formula (I). "Block structure" in the context of the present invention means that blocks are formed from corresponding units to an extent of at least 85% by mol, preferably to an extent of at least 90% by mol, more preferably to an extent of at least 95% by mol, based on the total amount of the respective block. This means that the blocks, as well as the corresponding units, can have small amounts of other units (especially other polyalkyleneoxy units). More particularly, the optional polyethyleneoxy block -(-CH2-CH2-O-)m comprises at least 85% by mol, preferably 90% by mol, based on the total amount of the block, the -(-CH2-CH2-O unit) -). More particularly, the optional polyethyleneoxy block -(-CH2-CH2-O-)m consists of 85 to 95 mol% of the unit the optional polyethyleneoxy block -(-CH2-CH2-O-) comprises and from 5 to 15% in mol of the unit the optional polyethyleneoxy block -(-CH2-CH(R3)-O-).
[0057] The invention preferably relates to a copolymer in which the radicals and indices are as defined in the sequence: k: is a number from 15 to 35, preferably from 20 to 28, more preferably from 23 to 26; 1: is a number from 5 to 30, preferably from 5 to 28, more preferably from 5 to 25; m: is a number from 0 to 15, preferably 0 or preferably from 0.5 to 10; n: : is H; o: : is independently a bivalent linking group -O- (Cn’H2n’)-, where n’ is 4; p: : is independently a hydrocarbyl radical having two carbon atoms; especially ethyl; q: : is H.
[0058] The invention preferably relates to a copolymer in which the radicals and indices are as defined in the sequence: k: is a number from 15 to 35, preferably from 20 to 28, more preferably from 23 to 26; 1: is a number from 5 to 30, preferably from 5 to 28, more preferably from 5 to 25; m: is a number from 0 to 15, preferably from 0.5 to 10, especially preferably 2 to 5; R1: is H; R2: is independently a bivalent linking group -O- (Cn’H2n’)-, where n’ is 4; R3: is independently a hydrocarbyl radical having two carbon atoms; especially ethyl; R4: is H.
[0059] The invention preferably relates to a copolymer in which the radicals and indices are as defined in the sequence: k: is a number from 15 to 35, preferably from 20 to 28, more preferably from 23 to 26; 1: is a number from 7.5 to 28, preferably from 7.5 to 25, more preferably from 12.75 to 25, especially preferably from 13 to 23, for example 14, 16 or 22; m: is a number from 0 to 15, preferably 0 or preferably from 0.5 to 10; n: : is H; o: : is independently a bivalent linking group -O- (Cn’H2n’)-, where n’ is 4; p: : is independently a hydrocarbyl radical having two carbon atoms; especially ethyl; q: : is H.
[0060] The invention preferably relates to a copolymer in which the radicals and indices are as defined in the sequence: k: is a number from 15 to 35, preferably from 20 to 28, more preferably from 23 to 26; 1: is a number from 7.5 to 28, preferably from 7.5 to 25, more preferably from 12.75 to 25, especially preferably from 13 to 23, for example 14, 16 or 22; m: is a number from 0 to 15, preferably from 0.5 to 10, more preferably from 2 to 5; R1: is H; n: : is independently a bivalent linking group -O- (Cn’H2n’)-, where n’ is 4; o: : is independently a hydrocarbyl radical having two carbon atoms; especially ethyl; p: : is H.
[0061] The invention preferably relates to a copolymer in which the radicals and indices are as defined in the sequence: q: is a number from 23 to 26; r: is a number from 12.75 to 17.25; s: is a number from 0 to 15, preferably 0 or preferably from 0.5 to 10; t:: is H; u: : is independently a bivalent linking group -O- (Cn’H2n’)-, where n’ is 4; v: : is independently a hydrocarbyl radical having two carbon atoms; especially ethyl; w: : is H.
[0062] The invention preferably relates to a copolymer in which the radicals and indices are as defined in the sequence: x: is a number from 23 to 26; y: is a number from 8.5 to 11.5; z: is a number from 0 to 15, preferably 0 or preferably from 0.5 to 10; R1: is H; aa: is independently a bivalent linking group -O- (Cn’H2n’)-, where n’ is 4; bb: is independently a hydrocarbyl radical having 3 carbon atoms; especially n-propyl; cc: is H.
[0063] In addition, the invention preferably relates to a copolymer in which the monomer (a) of the formula (I) is a mixture of a monomer (a) of the formula (I) where m = 0 and a monomer (a) of formula (I) where m = 1 to 15, preferably from 1 to 10. In addition, the invention preferably relates to a copolymer wherein the weight ratio of monomer (a) of formula (I) where m = 0 and the monomer (a) of formula (I) where m = 1 to 15, preferably 1 to 10, is in the range of 19:1 to 1:19, preferably in the range of 9:1 to 1:9. This mixture of monomer (a) of formula (I) where m = 0 and monomer (a) of formula (I) where m = 1 to 15 more preferably gives an average value (with the average of all monomers (a) in the mixing) in the range of m = 0.1 to 10, preferably from 0.1 to 5, more preferably from 0.5 to 5, most preferably from 0.5 to 2.5.
[0064] Additionally, the mixture of the monomer (a) of the formula (I) where m = 0 and the monomer (a) of the formula (I) where m = 1 to 15 more preferably gives an average value (with the average over all the monomers (a) of the mixture) in the range of m = 0.1 to 10, preferably from 0.1 to 5, more preferably from 0.5 to 5, more preferably from 0.5 to 3.5, most preferably from 0.5 to 2.5.
[0065] In general, an ethoxylation of the alkoxylated alcohol A3 in step c) will preferably be carried out in chains already ethoxylated, since the primary alkoxide group is more active compared to the secondary alkoxide group of alcohol A3. Thus, more particularly, after step c), there may be a mixture of chains having a terminal ethyleneoxy block -(-CH2-CH2-O-)m comprising at least one unit (monomers of formula (I)), and chains which they do not have a terminal ethyleneoxy block -(-CH2-CH2-O-)m (monomers of formula (III)). Preparation of monomers (a) of formula (I)
[0066] The monomers (a) of the general formula (I)
are prepared in the steps described above. Preferred embodiments of monomer (a) correspond to those already specified above.
[0067] Step a) of the process according to the invention comprises the reaction of an alcohol unsaturated by monoethylene A1 with ethylene oxide, with the addition of a C1 alkaline catalyst comprising KOMe (potassium methoxide) and/or NaOMe (methoxide sodium) to obtain the alkoxylated alcohol A2.
[0068] The preferred conditions specified hereinafter (e.g. temperature and pressure ranges) in the reactions in step a), b) c) and/or d) mean that the respective step is performed completely or partially under the given conditions.
[0069] Step a) preferably comprises first the reaction of the unsaturated alcohol by monoethylene A1 with the alkaline catalyst C1. Typically, the alcohol A1 used as the starting material for this purpose is mixed in a pressure reactor with an alkaline catalyst C1. Reduced pressure typically of less than 10,000 Pa (100 mbar), preferably in the range of 5,000 to 10,000 Pa (50 to 100 mbar) and/or elevated temperature typically of 30 to 150°C allow water and/or products to enter boiling at low temperature are present in the mixture to be removed. Next, the alcohol is essentially present in the form of the corresponding alkoxide. Subsequently, the reaction mixture is typically treated with an inert gas (eg nitrogen).
[0070] Step a) preferably comprises first the reaction of the unsaturated alcohol by monoethylene A1 with the alkaline catalyst C1. Typically, the alcohol A1 used as the starting material for this purpose is mixed in a pressure reactor with an alkaline catalyst C1. Reduced pressure typically less than 10,000 Pa (100 mbar), preferably in the range 3,000 to 10,000 Pa (30 to 100 mbar) and/or elevated temperature typically 30 to 150°C allow water and/or products to enter boiling at low temperature are present in the mixture to be removed. Next, the alcohol is essentially present in the form of the corresponding alkoxide. Subsequently, the reaction mixture is typically treated with an inert gas (eg nitrogen).
[0071] Step a) preferably comprises the addition of ethylene oxide to the above-described mixture of alcohol A1 with the alkaline catalyst C1 (as described above). After the addition of ethylene oxide is complete, the reaction mixture typically is allowed to react further. The addition and/or further reaction is typically carried out for a period of 2 to 36 hours, preferably 5 to 24 hours, especially preferably 5 to 15 hours, more preferably 5 to 10 hours.
[0072] Step a) preferably comprises the addition of ethylene oxide to the above-described mixture of alcohol A1 with the alkaline catalyst C1 (as described above). After the addition of ethylene oxide is complete, the reaction mixture typically is allowed to react further. The additional reaction is typically carried out for a period of 0.1 to 1 hour. Addition including optional decompression (intermediate pressure reduction, for example, from 600,000 to 300,000 Pa (6 to 3 bar absolute)) and including the additional reaction will be carried out, for example, for a period of 2 to 36 hours, preferably 5 to 24 hours, especially preferably 5 to 15 hours, more preferably 5 to 10 hours.
[0073] Step a) is typically carried out at temperatures from 60 to 180 °C, preferably from 130 to 150 °C, more preferably from 140 to 150 °C. More particularly, step a) comprises adding ethylene oxide to the mixture of alcohol A1 with catalyst C1 at a temperature from 60 to 180 °C, preferably from 130 to 150 °C, more preferably from 140 to 150 °C .
[0074] Ethylene oxide is preferably added to the mixture of alcohol A1 and alkaline catalyst C1 at a pressure in the range of 100,000 to 700,000 Pa (1 to 7 bar), preferably in the range of 100,000 to 500,000 Pa (1 to 5 bar) . In order to satisfy safety regulations, the addition in step a) is typically carried out at a pressure in the range of 100,000 to 310,000 Pa (1 to 3.1 bar). More particularly, the addition of ethylene oxide and/or further reaction is carried out under the conditions mentioned above.
[0075] Ethylene oxide is preferably added to the mixture of alcohol A1 and alkaline catalyst C1 at a pressure in the range of 100,000 to 700,000 Pa (1 to 7 bar), preferably in the range of 100,000 to 600,000 Pa (1 to 6 bar) . In order to satisfy safety regulations, the addition in step a) is typically carried out at a pressure in the range of 100,000 to 400,000 Pa (1 to 4 bar), preferably 100,000 to 390,000 Pa (1 to 3.9 bar), more preferably from 100,000 to 310,000 Pa (1 to 3.1 bar) or in a further embodiment of the invention from 300,000 to 600,000 Pa (3 to 6 bar). More particularly, the addition of ethylene oxide and/or further reaction is carried out under the conditions mentioned above.
[0076] Step a) preferably comprises the addition of ethylene oxide to the above-described mixture of alcohol A1 with the alkaline catalyst C1 for a period of less than or equal to 36 hours, preferably less than or equal to 32 hours , more preferably for a period of 2 to 32 hours, and at a pressure of less than or equal to 500,000 Pa (5 bar), preferably 100,000 to 310,000 Pa (1 to 3.1 bar). More particularly, the period specified above comprises the addition of ethylene oxide and/or the further reaction.
[0077] Step a) preferably comprises the addition of ethylene oxide to the above-described mixture of alcohol A1 with the alkaline catalyst C1 for a period of less than or equal to 36 hours, preferably less than or equal to 32 hours , more preferably for a period of 2 to 32 hours, and at a pressure of less than or equal to 500,000 Pa (5 bar), preferably less than 100,000 to 400,000 Pa (1 to 4 bar), especially preferably 100,000 Pa at 390,000 Pa (1 to 3.9 bar), preferably from 100,000 to 310,000 Pa (1 to 3.1 bar). More particularly, the period specified above comprises the addition of ethylene oxide and/or the further reaction.
[0078] More particularly, the reaction of an unsaturated alcohol by monoethylene A1 with ethylene oxide, with the addition of a C1 alkaline catalyst comprising KOMe (potassium methoxide) and/or NaOMe (sodium methoxide), in step a) of the process according to the invention can be carried out in one or more of the ethoxylation steps. Preference is given to a process as described above in which step a) comprises the following steps: reaction of the unsaturated alcohol by monoethylene A1 with the alkaline catalyst C1, reaction of the mixture of alcohol A1 with catalyst C1 with a portion of the ethylene oxide, especially from 10 to 50% by weight, especially from 10 to 30% by weight, of the total amount of ethylene oxide, an intermediate step comprising a rest phase and/or a decompression and reaction with the remaining portion of the ethylene oxide.
[0079] Preference is additionally given to a process as described above in which step a) comprises the following steps: reaction of unsaturated alcohol by monoethylene A1 with alkaline catalyst C1, reaction of the mixture of alcohol A1 with catalyst C1 with a portion of ethylene oxide, especially from 50 to 98% by weight, especially from 80 to 98% by weight, of the total amount of ethylene oxide, a step for the removal of components with a low boiling point, with decompression to a lower pressure than that 10,000 Pa (100 mbar), preferably 5,000 to 10,000 Pa (50 to 100 mbar), and/or elevated temperature, typically within the range of 30 to 150°C, reaction of the resulting ethoxylation product with the alkaline catalyst C1 and reaction of the remaining portion of ethylene oxide with the mixture of the ethoxylation product and the alkaline catalyst C1.
[0080] Preference is additionally given to a process as described above in which step a) comprises the following steps: reaction of unsaturated alcohol by monoethylene A1 with alkaline catalyst C1, reaction of the mixture of alcohol A1 and catalyst C1 with a portion of ethylene oxide, especially from 50 to 98% by weight, especially from 80 to 98% by weight, of the total amount of ethylene oxide, a step for the removal of components with a low boiling point, with decompression to a lower pressure than that 10,000 Pa (100 mbar), preferably 3,000 to 10,000 Pa (30 to 100 mbar), and/or elevated temperature, typically within the range of 30 to 150°C, reaction of the resulting ethoxylation product with the alkaline catalyst C1 and reaction of the remaining portion of ethylene oxide with the mixture of the ethoxylation product and the alkaline catalyst C1.
[0081] The alkaline catalyst C1 especially comprises from 10 to 100% by weight of KOMe and/or NaOMe, preferably 20 to 90% by weight. The C1 catalyst may comprise, as well as KOMe and/or NaOMe, additional alkaline compounds and/or a solvent (especially a C1 to C6 alcohol). For example, a compound selected from alkali metal hydroxides, C2 to C6 sodium alkoxides, preferably ethoxide), alkaline earth metal alkoxides (especially C1 to C6 alkoxides, preferably methoxide and/or ethoxide) may be present, or catalyst C1 preferably comprises, as well as KOMe and/or NaOMe, at least one more alkaline compound selected from sodium hydroxide and potassium hydroxide. In another preferred embodiment, the alkaline catalyst C1 consists of KOMe or a mixture of KOMe and methanol (MeOH). Typically, it is possible to use a solution of 20 to 50% by weight of KOMe in methanol (MeOH).
[0082] In an additional preferred embodiment, the alkaline catalyst C1 consists of NaOMe or a mixture of NaOMe and methanol (MeOH). Typically, a solution of 20 to 50% by weight of NaOMe in methanol (MeOH) can be used.
[0083] In a further preferred embodiment, the alkaline catalyst C1 consists of a mixture of KOMe and NaOMe or a solution of KOMe and NaOMe in methanol.
[0084] If the basic C1 catalyst used in the reaction in cap a) is KOMe, it is advantageous to use C1 in such an amount that an upper limit of 2500 ppm (approximately 0.4 mol%) of KOMe is maintained relative to the alcohol A1 used in order to avoid decomposition of unsaturated alcohol by monoethylene A1. The concentration of potassium ions in step a) preferably is less than or equal to 0.4% by mol based on the total amount of alcohol A1 used, more preferably it is from 0.1 to 0.4% by mol.
[0085] If the KOMe is added in such an amount that the concentration is greater than 0.9% mol based on the ethoxylated alcohol A2 (product of step a) of the process), the KOMe needs to be completely or partially removed before the step b), in order to obtain a potassium ion concentration lower than 0.9% in mol in step c) of the process. This can be done, for example, by isolating and optionally purifying the ethoxylated alcohol A2 after step a).
[0086] In a further preferred embodiment, KOMe is used in such an amount that the concentration of potassium ions after the reaction in step a) is already less than or equal to 0.9% mol based on A2.
[0087] Step b) of the process according to the invention comprises the reaction of the ethoxylated alcohol A2 with at least one alkylene oxide Z, with the addition of an alkaline catalyst C2, to obtain an alkoxylated alcohol A3 corresponding to the monomer (a ) of formula (III)

[0088] Step b) preferably comprises first the reaction of the unsaturated alcohol by monoethylene A2 with the alkaline catalyst C2. Typically, alcohol A2 for this purpose is mixed in a pressure reactor with an alkaline catalyst C2. Reduced pressure typically of less than 10,000 Pa (100 mbar), preferably in the range of 5,000 to 10,000 Pa (50 to 100 mbar) and/or elevated temperature typically of 30 to 150°C allow water and/or products to enter boiling at low temperature are present in the mixture to be removed. Next, the alcohol is essentially present in the form of the corresponding alkoxide. Subsequently, the reaction mixture is typically treated with an inert gas (eg nitrogen).
[0089] Step b) preferably comprises first the reaction of the unsaturated alcohol by monoethylene A2 with the alkaline catalyst C2. Typically, alcohol A2 for this purpose is mixed in a pressure reactor with an alkaline catalyst C1. Reduced pressure typically less than 10,000 Pa (100 mbar), preferably in the range 3,000 to 10,000 Pa (30 to 100 mbar) and/or elevated temperature typically 30 to 150°C allow water and/or products to enter boiling at low temperature are present in the mixture to be removed. Next, the alcohol is essentially present in the form of the corresponding alkoxide. Subsequently, the reaction mixture is typically treated with an inert gas (eg nitrogen).
[0090] Step b) preferably comprises the addition of at least one alkylene oxide Z to the above-described mixture of alcohol A2 with the alkaline catalyst C2. After the addition of alkylene oxide Z is complete, the reaction mixture typically is allowed to react further. The addition and/or further reaction is typically carried out for a period of 2 to 36 hours, preferably 5 to 24 hours, especially preferably 5 to 20 hours, more preferably 5 to 15 hours.
[0091] Step b) preferably comprises the addition of alkylene oxide Z to the above-described mixture of alcohol A2 with the alkaline catalyst C2. After the addition of alkylene oxide Z is complete, the reaction mixture typically is allowed to react further. The addition including the optional decompression and including the additional reaction will be carried out, for example, for a period of 2 to 36 hours, preferably 5 to 30 hours, especially preferably 10 to 28 hours, more preferably 11 to 24 hours.
[0092] According to the invention, the concentration of potassium ions in step b) is less than or equal to 0.9% in mol, preferably less than 0.9% in mol, preferably from 0.01 to 0 .9 mol%, more preferably 0.1 to 0.6% mol, based on the alcohol A2 used. Preferably, the concentration of potassium ions in the preparation of monomer (a), in the reaction in step b), is 0.01 to 0.5% by mol based on the alcohol A2 used.
[0093] In a particularly preferred embodiment, the concentration of potassium ions in the reaction in step b) is from 0.1 to 0.5% in mol and the reaction in step b) is carried out at temperatures from 120 to 130 °C.
[0094] The C2 alkaline catalyst preferably comprises at least one alkaline compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal hydroxides (especially C1 to C6 alkoxides, preferably methoxide and/or ethoxide), hydroxides of alkaline earth metal (especially C1 to C6 alkoxides, preferably methoxide and/or ethoxide). The catalyst preferably comprises at least one basic sodium compound, especially selected from NaOH, NaOMe and NaOEt, more preferably NaOMe or NaOH. The catalyst C2 used can be a mixture of the mentioned alkaline compounds; catalyst C2 preferably consists of one of the mentioned basic compounds or mixtures of the mentioned alkaline compounds. Often an aqueous solution of the alkaline compounds is used. In another preferred embodiment, the alkaline catalyst C1 consists of NaOMe or a mixture of NaOMe and methanol. Typically, a 20 to 50% by weight solution of NaOMe in methanol can be used. Catalyst C2 preferably does not comprise any KOMe.
[0095] Preferably, the preparation in step b) involves using a C2 catalyst comprising at least one basic sodium compound, specially selected from NaOH, NaOMe and NaOEt, the concentration of sodium ions in the reaction in step b) being 3 .5 to 12% by mol, preferably from 3.5 to 7% by mol, more preferably from 4 to 5.5% by mol, based on the alcohol A2 used.
[0096] According to the invention, the reaction of step b) is carried out at a temperature less than or equal to 135 °C. Preference is given to carrying out the reaction in step b) at temperatures from 60 to 135 °C, preferably from 100 to 135 °C, more preferably from 120 to 130 °C. More particularly, step b) comprises the addition of at least one alkylene oxide Z to a mixture of alcohol A2 with alkaline catalyst C3 at a temperature less than or equal to 135 °C, preferably at temperatures from 60 to 135 °C , more preferably from 100 to 135 °C, more preferably from 130 to 135 °C.
[0097] Preference is given to carrying out step b) at a pressure in the range from 100,000 to 310,000 Pa (1 to 3.1 bar), preferably from 100,000 to 210,000 Pa (1 to 2.1 bar). In order to satisfy the safety conditions, the reaction in step b) is preferably carried out at a pressure in the range of less than or equal to 310,000 Pa (3.1 bar) (preferably from 100,000 to 310,000 Pa (1 to 3, 1 bar)) if R3 is a hydrocarbyl radical having 2 carbon atoms. Especially, the addition of alkylene oxide Z and/or the additional reaction is carried out under the pressures mentioned above.
[0098] More particularly, the present invention relates to a copolymer where R3 is a hydrocarbyl radical having 2 carbon atoms and step c) in the preparation of the monomer (a) is carried out at a pressure in the range of 100,000 to 310,000 Pa ( 1 to 3.1 bar); or where R3 is a hydrocarbyl radical having at least 3 carbon atoms (preferably having 3 carbon atoms) and step b) in preparing the monomer (a) is carried out at a pressure of 100,000 to 210,000 Pa (1 to 2.1 Pub).
[0099] More particularly, the addition of alkylene oxide Z and/or the additional reaction are carried out at the pressure mentioned above. Step b) preferably comprises adding at least one alkylene oxide Z to a mixture of alcohol A2 and alkaline catalyst K2 at a pressure in the range of less than or equal to 310,000 Pa (3.1 bar) (preferably 100,000 to 310,000 Pa (1 to 3.1 bar)) if R3 is a hydrocarbyl radical having 2 carbon atoms, or at a pressure of less than or equal to 210,000 Pa (2.1 bar) (preferably from 100,000 to 210,000 Pa (1 to 2.1 bar)) if R3 is a hydrocarbyl radical having at least 3 carbon atoms.
[00100] Step b) preferably comprises the addition of at least one alkylene oxide Z to a mixture of alcohol A2 with alkaline catalyst C2 for a period of less than or equal to 36 hours, preferably less than or equal to 32 hours, more preferably for a period of 2 to 32 hours, even more preferably for a period of 5 to 24 hours, and at a pressure of less than or equal to 310,000 Pa (3.1 bar), preferably 100,000 to 210,000 Pa (1 to 2.1 bar) (additional preferably at the pressures mentioned above).
[00101] Step b) also preferably comprises the addition of at least one alkylene oxide Z to a mixture of alcohol A2 with alkaline catalyst C2 for a period of less than or equal to 36 hours, preferably less than or equal to 32 hours, more preferably for a period of 2 to 32 hours, even more preferably for a period of 11 to 24 hours, and at a pressure of less than or equal to 310,000 Pa (3.1 bar) (additional preferably at pressures mentioned above).
[00102] Preference is given to carrying out step b) at a pressure in the range of 100,000 to 310,000 Pa (1 to 3.1 bar) (preferably at the pressures mentioned above) and at a temperature of 120 to 130 °C.
[00103] The process according to the invention may optionally comprise step c), wherein at least a portion of the alkoxylated alcohol A3 is reacted with ethylene oxide to obtain an alkoxylated alcohol A4 corresponding with a monomer (a) of the formula (I) where R4 = H at > 0, preferably from 0 to 15, preferably from 0 to 10, more preferably 0.1 to 10, more preferably from 0.1 to 5, especially preferably around 0.5 to 5 and even more preferably around 0.5 to 2.5. In a preferred embodiment, step c) comprises reacting all of the alkoxylated alcohol A3 with ethylene oxide.
[00104] According to a preferred embodiment of the invention, the process comprises step c), wherein at least a portion of the alkoxylated alcohol A3 (preferably all of the alkoxylated alcohol A3) is reacted with ethylene oxide to obtain an alkoxylated alcohol A4 which corresponds with the macromonomer M of the formula (I) where R4 = H and m is a number from 0.1 to 15, preferably from 0.1 to 10, more preferably from 0.5 to 10, especially preferably from 1 to 7, additionally preferably from 2 to 5.
[00105] Optional step c) especially is carried out without additional addition of an alkaline catalyst. Optional step c) is especially carried out at a pressure in the range of 100,000 to 700,000 Pa (1 to 7 bar), preferably 100,000 to 500,000 Pa (1 to 5 bar), and a temperature in the range of 60 to 140 °C, preferably from 120 to 140 °C, more preferably from 125 to 135 °C. The ethoxylation in optional step c) is especially carried out for a period of 0.5 to 7 hours, especially 0.5 to 5 hours, preferably 0.5 to 4 hours.
[00106] Optional step c) especially is carried out without additional addition of an alkaline catalyst. Optional step c) is especially carried out at a pressure in the range 100,000 to 700,000 Pa (1 to 7 bar), preferably 100,000 to 600,000 Pa (1 to 6 bar), and a temperature in the range 60 to 140 °C, preferably from 120 to 140 °C, more preferably from 120 to 135 °C. The ethoxylation in optional step c) is especially carried out for a period of 0.5 to 7 hours, especially 1 to 5 hours, preferably 1 to 4 hours.
[00107] Optional step c) preferably comprises adding ethylene oxide to the reaction mixture after step b), comprising the alkoxylated alcohol A3 of formula (III) without further work and/or decompression. After the ethylene oxide addition is complete, the reaction mixture typically is allowed to react further. The addition and/or further reaction is typically carried out for a period of 0.5 to 10 hours, especially 0.5 to 7 hours, especially 0.5 to 5 hours, preferably 0.5 to 4 hours.
[00108] Optional step c) preferably comprises adding ethylene oxide to the reaction mixture after step b), comprising the alkoxylated alcohol A3 of formula (III) without further work and/or decompression. After the ethylene oxide addition is complete, the reaction mixture typically is allowed to react further. The addition and/or further reaction is typically carried out for a period of 0.5 to 10 hours, especially 2 to 10 hours, especially 4 to 8 hours.
[00109] The particular intended effect of the performance of optional step c), ie of a final ethoxylation, is that the alkylene oxide Z possibly still present in the reaction mixture after step b) is depleted and removed.
[00110] Additionally it is possible to remove the Z alkylene oxide which has not been depleted after step b) by a decompression and/or temperature increase after step b).
[00111] The process according to the invention may optionally comprise step d), wherein the alkoxylated alcohol A3 and/or A4 is etherified with a compound R4-X where X is a leaving group, preferably selected from the group of Cl, Br, I, -O-SO2-CH3 (mesylate), -O-SO2-CF3 (triphylate) and -O-SO2-OR4.
[00112] If the alkoxylated alcohol A3 of formula (III) and/or A4 of formula (I) is to be etherified with a terminal OH group (i.e. R4 = H), this can be achieved with the usual known alkylating agents in principle by those skilled in the art, for example, alkyl sulfates and/or alkyl halides. Compound R4-X typically can comprise alkyl halides. For etherification, it is also possible to use especially dimethyl sulphate or diethyl sulphate. Etherification is just one option that can be selected by the person skilled in the art according to the desired properties of the copolymer. Hydrophilic Monomers (b)
[00113] Through and above the monomers (a), the association copolymer in a hydrophobic manner of the invention comprises at least one hydrophilic monomer unsaturated by monoethylene (b). it will be appreciated that it is also possible to use mixtures of a plurality of different hydrophilic monomers (b).
[00114] The hydrophilic monomers (b) comprise, as well as an ethylenic group, one or more hydrophilic groups. These impart sufficient water solubility to the copolymer of the invention due to their hydrophilicity. Hydrophilic groups are especially functional groups comprising oxygen and/or nitrogen atoms. Additionally they can especially comprise sulfur and/or phosphorus atoms as heteroatoms.
[00115] The monomers (b) are most preferably miscible with water in any ratio, but it is sufficient for carrying out the invention that the hydrophobically association copolymer of the invention has the solubility in water mentioned in the definition. In general, the solubility of the monomers (b) in water at room temperature should be at least 100 g/l, preferably 200 g/l and more preferably at least 500 g/l.
[00116] Examples of suitable functional groups comprise carbonyl groups >C=O, ether groups -O-, especially polyethyleneoxy groups -(CH2-CH2-O-)n- where n is preferably a number from 1 to 200, hydroxyl groups - OH, -C(O)O- ester groups, primary, secondary or tertiary amino groups, ammonium groups, amide groups -C(O)-NH-, carboxamide groups -C(O)-NH2- or acid groups such as groups carboxyl -COOH, sulfo groups -SO3H, phosphonic acid groups -PO3H2 or phosphoric acid groups -OP(OH)3.
[00117] Examples of preferred functional groups comprise hydroxyl groups -OH, carboxyl groups -COOH, sulfo groups -SO3H, carboxamide groups -C(O)-NH2-, amide groups -C(O)-NH- and polyethyleneoxy groups - ( CH2-CH2-O-)n- where n is preferably a number from 1 to 200.
[00118] Functional groups can be attached directly to the ethylenic group, or further joined to the ethylenic group through one or more hydrocarbyl linking groups.
[00119] The hydrophilic monomers (b) are preferably monomers of the general formula H2C=C(R5)R6 (IV) where R5 is H or methyl and R6 is a hydrophilic group or a group comprising one or more hydrophilic groups.
[00120] The R6 groups are groups that comprise heteroatoms in such an amount that the water solubility defined in the disclosure is achieved.
[00121] Examples of suitable monomers (b) comprise monomers comprising acidic groups, for example monomers comprising -COOH groups such as acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, monomers comprising groups sulfo such as vinyl sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2-methacrylamido-2-methylpropane sulfonic acid, 2-acrylamidobutane sulfonic acid, 3-acrylamido-3-methylbutane sulfonic acid or 2-acrylamido-2,4,4-trimethylpentane sulfonic acid or monomers comprising phosphonic acid groups such as vinyl phosphonic acid, allyl phosphonic acid, N-(meth)acrylamido alkyl phosphonic acids or (meth)acyloyloxy alkyl phosphonic acids.
[00122] Mention should additionally be made of acrylamide and methacrylamide and derivatives thereof, for example, N-methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide and N-methylolacrylamide, N-vinyl derivatives such as N-vinyl formamide, N-vinyl acetamide, N-vinyl pyrrolidone or N-vinyl caprolactam, and vinyl esters such as vinyl formate or vinyl acetate. N-vinyl derivatives can, after polarization, be hydrolyzed to vinylamine units and vinyl esters to vinyl alcohol units.
[00123] Additional examples comprise monomers comprising hydroxyl and/or ether groups, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether, hydroxyvinyl butyl ether or compounds of the formula H2C= C(R1)-O-(-CH2-CH(R7)-O-)b-R8(V) where R1 is as defined above and b is a number from 2 to 200, preferably 2 to 100. Each of the radicals R7 is independently H, methyl, ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the R8 radicals are H. Preferably, at least 75 mol% of the R7 radicals are H, more preferably at least 90 mol% of the radicals mol, and they are even more preferably exclusively H. The radical R8 is H, methyl or ethyl, preferably H or methyl. The individual alkyleneoxy units can be arranged randomly or in blocks. In the case of a block copolymer, the transition between blocks can be abrupt or gradual.
[00124] Additional suitable hydrophilic monomers (b) are described in WO 2011/133527 (page 15 lines 1 to 23).
[00125] It is clear that the hydrophilic monomers mentioned above can be used not only in the acidic and basic form described, but also in the form of the corresponding salts. It is also possible to convert acidic or basic groups to the corresponding salts after polymer formation. Preferably, the corresponding salts are alkali metal salts or ammonium salts, more preferably organic ammonium salts and especially preferably water-soluble organic ammonium salts.
[00126] Preference is given to a copolymer in which at least one of the monomers (b) is a monomer comprising acid groups, the acid groups being at least one group selected from the group of -COOH, -SO3H and -PO3H, and salts thereof.
[00127] At least one of the monomers (b) is preferably a monomer selected from the group of (meth)acrylic acid, vinyl sulfonic acid, allyl sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid (AMPS), more preferably acrylic acid and/or APMS or salts thereof.
[00128] The invention preferably relates to a copolymer comprising at least two different hydrophilic monomers (b) which are: - at least one uncharged hydrophilic monomer (b1), and - at least one hydrophilic anionic monomer (b2) comprising at least an acid group selected from the group of -COOH, -SO3H and -PO3H2 and salts thereof
[00129] Examples of suitable monomers (b1) comprise acrylamide and methacrylamide, preferably acrylamide and derivatives thereof, for example N-methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide and N-methylolacrylamide. Mention should additionally be made to N-vinyl derivatives such as N-vinyl formamide, N-vinyl acetamide, N-vinyl pyrrolidone or N-vinyl caprolactam. Mention should additionally be made of monomers having OH groups such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether or hydroxyvinyl butyl ether. Monomer (b1) in the copolymer of the invention preferably is acrylamide and derivatives thereof, more preferably acrylamide.
[00130] Examples of anionic monomers (b2) comprise acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, monomers comprising sulfo groups such as vinyl sulfonic acid, allyl sulfonic acid, 2-acrylamido-2 acid -methylpropane sulfonic acid (AMPS), 2-methacrylamido-2-methylpropane sulfonic acid, 2-acrylamidobutane sulfonic acid, 3-acrylamido-3-methylbutane sulfonic acid or 2-acrylamido-2,4,4-trimethylpentane sulfonic acid or monomers comprising groups phosphonic acid such as vinyl phosphonic acid, allyl phosphonic acid, N-(meth)acrylamido alkyl phosphonic acids or (meth)acyloyloxy alkyl phosphonic acids.
[00131] Examples of preferred anionic monomers (b2) comprise acrylic acid, vinyl sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2-acrylamidobutane sulfonic acid, 3-acrylamido-3-methylbutane acid sulfonic acid or 2-acrylamido-2,4,4-trimethylpentane sulfonic acid, very particular reference being given to 2-acrylamido-2-methylpropane sulfonic acid (AMPS).
[00132] The copolymer preferably is one comprising acrylamide as the monomer (b1) and a monomer comprising acid groups as the monomer (b2).
[00133] The copolymer preferably is one comprising acrylamide as the monomer (b1) and a monomer comprising acid groups as the monomer (b2), the acid group being -SO3H. The copolymer is especially preferably one comprising acrylamide as the monomer (b1) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) as the monomer (b2).
[00134] The copolymer is preferably one comprising acrylamide as the monomer (b1) and acrylic acid as the monomer (b2).
[00135] The copolymer is additionally preferably one comprising acrylamide as the monomer (b1) and at least two different additional monomers (b2) comprising acidic groups. The copolymer is especially preferably one comprising acrylamide as the monomer (b1) and a monomer comprising the -SO3H group and a monomer comprising the -COOH group as the monomer (b2) comprising acidic groups.
[00136] The copolymer is additionally preferably one comprising acrylamide as the monomer (b1), and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and a monomer comprising the -COOH group as the monomer (b2). The copolymer is additionally preferably one comprising acrylamide as the monomer (b1), and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and acrylic acid as the monomer (b2).
[00137] The amount of the monomers (b) in the copolymer of the invention is from 25 to 99.9% by weight based on the total amount of all monomers in the copolymer, preferably from 25 to 99.5% by weight. The exact amount is guided by the nature and desired end use of the hydrophobic association copolymers and is appropriately fixed by the person skilled in the art.
[00138] The invention preferably relates to a copolymer comprising (a) 2% by weight of at least one hydrophobically associating monomer (a), and (b) 50% by weight of acrylamide as an uncharged hydrophilic monomer ( b1), and (c) 48% by weight of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) as an anionic hydrophilic monomer (b2), where the stated amounts are each based on the total amount of all monomers in the copolymer . Non-polymerizable surface active components (c)
[00139] The copolymers of the invention are prepared in the presence of at least one non-polymerizable surface active compound which is preferably at least one non-ionic surfactant. However, anionic and cationic surfactants are also suitable as long as they do not take part in the polymerization reaction.
[00140] Component (c) preferably is at least one non-ionic surfactant.
[00141] Component (c) especially may comprise surfactants, preferably nonionic surfactants of the general formula R10-Y' where R10 is a hydrocarbyl radical having 8 to 32, preferably 10 to 20 and more preferably 12 to 18 carbon atoms and Y1 is a hydrophilic group, preferably a hydrophilic group, especially a polyalkyloxy group.
[00142] The nonionic surfactant preferably is an ethoxylated long chain aliphatic alcohol having from 10 to 20 carbon atoms and optionally may comprise aromatic moieties.
[00143] Examples include: C12C14 fatty alcohol ethoxylates, C16C18 fatty alcohol ethoxylates, C13 oxo alcohol ethoxylates, C10 oxo alcohol ethoxylates, C13C15 oxo alcohol ethoxylates, C10 Guerbet alcohol ethoxylates, and alkyl phenol ethoxylates. Especially useful compounds have been found to be those having 5 to 20 ethyleneoxy units, preferably 8 to 18 ethyleneoxy units. Optionally it is also possible for small amounts of higher alkyleneoxy units, especially propyleneoxy and/or butyleneoxy units, to be present, in which case, however, the amount as ethyleneoxy units in general should be at least 80% by mol based on all. the alkyleneoxy units.
[00144] Especially suitable surfactants are those selected from the group of ethoxylated alkyl phenols, ethoxylated iso-C13 saturated alcohols and/or C10 Guerbet alcohols, with the presence in each case of 5 to 20 ethyleneoxy units, preferably 8 to 18 ethyleneoxy units in the alkoxy radicals. Preparation of association copolymers in a hydrophobic manner
[00145] Copolymers can be prepared by methods known to the person skilled in the art, by free radical polymerization of monomers (a) and (b), for example, by volumetric polymerization, in solution, in gel, in emulsion, in dispersion or in suspension, preferably in the aqueous phase, although each of the possible polymerization variants must be carried out in the presence of at least one component (c).
[00146] The present invention relates to a process for preparing a copolymer of the invention described above in which at least one hydrophobically associating monomer (a) and at least one hydrophilic monomer (b) are subjected to a polymerization in aqueous solution in the presence of at least one surface active component (c), and wherein the monomer (a) of the general formula (I) is prepared by the process described above.
[00147] With regard to the process for preparing the copolymer of the invention, the preferred embodiments which were described above together with the copolymers of the invention apply.
[00148] The present invention preferably relates to a process for preparing the copolymer of the invention, wherein the solution polymerization is carried out at a pH of 5.0 to 7.5.
The monomers (a) of the formula (I) used according to the invention are provided by the preparation process detailed above, by multistage alkoxylation of the alcohols (II), optionally followed by an etherification. With regard to the process for preparing monomer (a), the preferred embodiments which were described above together with the copolymers of the invention apply.
[00150] In a preferred embodiment, the preparation of the copolymer is taken by means of gel polymerization in the aqueous phase, provided that all the monomers used have sufficient water solubility. For gel polymerization, a mixture of the monomers, initiators and other assistants with water or an aqueous solvent mixture is provided first. Suitable aqueous solvent mixtures comprise water and water miscible organic solvents, the proportion of water in general being at least 50% by weight, preferably at least 80% by weight and more preferably at least 90% by weight. Organic solvents which should be mentioned here are especially water miscible alcohols such as methanol, ethanol and propanol. Acidic monomers can be completely or partially neutralized prior to polymerization.
[00151] The concentration of all components except for solvents typically is from 25% to 60% by weight, preferably from 30 to 50% by weight.
[00152] The mixture is subsequently polymerized photochemically and/or thermally, preferably from -5°C to 50°C. If polymerization is carried out thermally, preference is given to the use of polymerization initiators which start at a comparatively low temperature, eg redox initiators. Thermal polymerization can be carried out at room temperature or by heating the mixture, preferably to temperatures of not more than 50 °C. photochemical polymerization typically is carried out at temperatures from -5 °C to 10 °C. It is particularly advantageously possible to combine photochemical and thermal polymerization by adding initiators for both the thermal and photochemical polymerization of the mixture. The polymerization, here first, is initiated photochemically at low temperatures, preferably from -5°C to 10°C. The heat of reaction released heats the mixture and this additionally initiates thermal polymerization. Through this combination, it is possible to achieve a conversion of more than 99%.
[00153] The gel polymerization in general is carried out without stirring. It can be carried out in batch, by irradiating the mixture in a suitable vessel with a path length of 2 to 20 cm and/or heating it. Polymerization gives a firm gel. Polymerization can also be continuous. For this purpose, a polymerization apparatus having a conveyor belt to accommodate the mixture to be polymerized is used. The conveyor belt is equipped with devices for heating or radiating with UV radiation. In this method, the mixture is poured by means of a suitable apparatus at one end of the belt, the mixture is polymerized on the conveyor path towards the belt, and the firm gel can be removed at the other end of the belt.
[00154] After polymerization, the gel is comminuted and dried. Drying should preferably be carried out at temperatures below 100 °C. To avoid conglutination, a suitable separating agent can be used for this step. The hydrophobically associating copolymer is obtained as a powder.
[00155] Further details regarding the performance of a gel polymerization are disclosed, for example, in DE 10 2004 032 304 A1, paragraphs [0037] to [0041] of the original version.
[00156] The copolymers of the invention in the form of alkali-soluble aqueous dispersions can preferably be prepared by means of emulsion polymerization. The performance of an emulsion polymerization using association monomers in a hydrophobic manner is disclosed, for example, in WO 2009/019225, page 5, line 16 to page 8, line 13 of the original version.
[00157] The copolymers of the invention preferably have a number average molecular weight Mn of 1,000,000 to 30,000,000 g/mol. Use of association copolymers in a hydrophobic manner
[00158] The hydrophobically associating copolymers of the invention can, as already mentioned in the disclosure, be used according to the invention to thicken aqueous phases.
[00159] The present invention relates to the use of copolymers of the invention in the development, exploration and completion of underground mineral oil and natural gas deposits. More particularly, the use refers to the preferred embodiments which have been described above in conjunction with the copolymers of the invention.
[00160] The copolymers can be used alone here, or even in combination with other thickening components, for example, together with other thickening polymers. They can additionally be formulated, for example, together with surfactants to form a thickening system. Surfactants can form micelles in aqueous solution, and hydrophobically associating copolymers together with micelles can form a three-dimensional thickening network.
[00161] For use, the copolymer can be dissolved directly in the aqueous phase to be thickened. It is also conceivable to pre-dissolve the copolymer and then add the formed solution to the system to be thickened.
[00162] By selecting the type and amount of monomers (a) and (b), and component (c), it is possible to adjust the properties of the copolymers to the respective technical demands.
[00163] The copolymers of the invention can be used, for example, in the mineral oil production sector as an additive for thickening drilling muds and completion fluids.
[00164] In addition, the copolymers of the invention find use as a thickener in hydraulic fracturing. This typically involves injecting a high-viscosity aqueous solution under high pressure into the formation stratum carrying oil or gas.
[00165] The invention preferably relates to the use of the copolymers of the invention for the production of tertiary mineral oil, wherein an aqueous formulation of said copolymers in a concentration of 0.01 to 5% by weight is injected into a mineral oil deposit through at least one injection well and crude oil is withdrawn from the deposit through at least one production well.
[00166] The concentration of the copolymer in general should not exceed 5% by weight based on the sum of all constituents in the formulation and typically is from 0.01 to 5% by weight, especially 0.1 to 5% by weight, preferably from 0.5 to 3% by weight and more preferably from 1 to 2% by weight.
[00167] The formulation is injected into the mineral oil deposit through at least one injection well, and the crude oil is withdrawn from the deposit through at least one production well. The term "crude oil" in this context is of course not only meaning single-phase oil, rather the term also encompasses crude oil-in-water emulsions. In general, a deposit is provided with several injection wells and with several production wells. The injected formulation, called “polymer flood”, generates a pressure that causes the mineral oil to flow towards the production well and be produced through the production well. The viscosity and flooding medium must be matched as closely as possible with the viscosity of the mineral oil in the mineral oil tank. The viscosity especially can be adjusted through the concentration of the copolymer. Polymer flooding involves using an aqueous formulation comprising not only water, but also at least one association copolymer in a hydrophobic manner. Of course, it is also possible to use mixtures of different copolymers. In addition, of course, additional components can also be used. Examples of additional components comprise biocides, stabilizers or inhibitors. The formulation preferably can be prepared by initially charging water and spraying the copolymer as a powder. The aqueous formulation must be subjected to a minimum level of shear forces.
[00168] To increase mineral oil yield, polymer flooding can advantageously be combined with other tertiary mineral oil production techniques.
[00169] To increase mineral oil yield, polymer flooding can advantageously be combined with other tertiary mineral oil production techniques.
[00170] The invention preferably relates to the use of the copolymers of the invention in the development, exploration and completion of underground mineral oil and natural gas deposits, especially for the production of tertiary mineral oil, the aqueous formulation of said components comprising at least one surfactant .
[00171] In a further preferred embodiment of the invention, "polymer flooding" using the association copolymers in a hydrophobic manner may be combined with a prior "surfactant flooding". This involves, prior to polymer flooding, first injecting an aqueous surfactant formulation to form mineral oil. This reduces the interfacial tension between the formation water and the actual mineral oil, and thus increases the mobility of the mineral oil in the formation. The combination of the two techniques allows an increase in mineral oil yield.
[00172] Examples of surfactants suitable for surfactant flooding comprise surfactants having sulfate groups, sulfonate groups, polyoxyalkylene groups, anionic-modified polyoxyalkylene groups, betaine groups, glucoside groups or amine oxide groups, e.g., alkylbenzene sulfonates, sulfonates of olefin or amidopropyl betaines. It is preferable to use anionic and/or betaine surfactants.
The person skilled in the art is aware of the industrial performance details of polymer flooding and surfactant flooding, and employs an appropriate technique according to the type of deposit.
[00174] It will be appreciated that it is also possible to use surfactants and the copolymers of the invention in a mixture.
[00175] The following examples are intended to illustrate the invention in detail: Part I: Synthesis I-a Preparation of monomers (a)
[00176] Unless explicitly mentioned, reactions are conducted in such a way that the target filling level at the end of the alkoxylation was about 65% of the reactor volume. Example Ml HBVE - 22 EO (0.4 mol% potassium ions)
[00177] A 2-liter pressure autoclave with anchor stirrer was initially charged with 135.3 g (1.16 mol) of hydroxybutyl vinyl ether (HBVE) (stabilized with 100 ppm potassium hydroxide (KOH)) and the shaker was turned on. 1.06 g of potassium methoxide solution (KOMe) (32% KOMe in methanol (MeOH), corresponding to 0.0048 mol of potassium) was fed and the stirrer vessel was evacuated at a pressure less than 1000 Pa ( 10 mbar), heated to 80 °C and operated at 80 °C and a pressure of less than 1000 Pa (10 mbar) for 70 minutes. MeOH was distilled.
[00178] According to an alternative procedure in potassium methoxide solution (KOMe) (32% KOMe in methanol (MeOH)) were fed and the stirred vessel was evacuated to a pressure of 1000 to 2000 Pa (10 to 20 mbar ), heated to 65 °C and operated at 65 °C and a pressure of 1000 to 2000 Pa (10 to 20 mbar) for 70 minutes. MeOH was distilled.
[00179] The mixture was purged three times with N2 (nitrogen). Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C. The mixture was decompressed to 100,000 Pa (1 bar) absolute and 1126 g (25.6 mol) of ethylene oxide (EO) were measured until pmax was 390,000 Pa (3.9 bar) absolute and Tmax was 150 °C . After 300 g and EO were added, the metered addition was stopped (about 3 hours after start) for a holding period of 30 minutes and the mixture decompressed to 130,000 Pa (1.3 bar) absolute. Then the rest of the EO was measured. The measured addition of EO including decompression took a total of 10 hours.
[00180] Stirring was continued to constant pressure at approximately 145 to 150 °C (1 hour), and the mixture was cooled to 100 °C and released from products with low boiling point at a pressure of less than 1000 Pa ( 10 mbar) for 1 hour. The material was transferred at 80°C under N2.
Analysis (OH number, GPC, 1H NMR in CDCl3, 1H NMR in MeOD) confirmed the structure. Example M2 HBVE - 22 EO - 10.6 PeO (0.4 mol% potassium ions, 4.6 mol% sodium ions), addition of PeO at 140 °C at 320,000 Pa (3.2 bar)
[00182] A 2 liter pressure autoclave with anchor stirrer was initially charged with 135.3 g (1.16 mol) of hydroxybutyl vinyl ether (HBVE) (stabilized with 100 ppm potassium hydroxide (KOH)) and the shaker was turned on. 1.06 g of potassium methoxide solution (KOMe) (32% KOMe in methanol (MeOH), corresponding to 0.0048 mol of potassium) was fed and the stirrer vessel was evacuated at a pressure less than 1000 Pa ( 10 mbar), heated to 80 °C and operated at 80 °C and a pressure of less than 1000 Pa (10 mbar) for 70 minutes. MeOH was distilled.
[00183] According to an alternative procedure in potassium methoxide solution (KOMe) (32% KOMe in methanol (MeOH)) were fed and the stirred vessel was evacuated to a pressure of 1000 to 2000 Pa (10 to 20 mbar ), heated to 65 °C and operated at 65 °C and a pressure of 1000 to 2000 Pa (10 to 20 mbar) for 70 minutes. MeOH was distilled.
[00184] The mixture was purged three times with N2 (nitrogen). Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C. The mixture was decompressed to 100,000 Pa (1 bar) absolute and 255 g (5.8 mol) of ethylene oxide (EO) was measured until pmax was 390,000 Pa (3.9 bar) absolute and Tmax was 150 °C . Stirring was continued to constant pressure at approximately 145 to 150 °C (1 hour), and the mixture was cooled to 100 °C and freed from low boiling products at a pressure of less than 1000 Pa (10 mbar) for 1 hour. The material (HBVE-5 EO) was transferred at 80°C under N2.
A 2 liter pressure autoclave with anchor stirrer was initially charged with 180 g (0.54 mol) of the above HBVE-5 EO and the stirrer was turned on. Next, 4.32 g of 30% solution of NaOMe (sodium methoxide) in MeOH (0.024 mol of NaOMe, 1.30 g of NaOMe) were added, a reduced pressure less than 1000 Pa (10 mbar) was applied , and the mixture was heated to 100 °C and kept that way for 80 minutes, in order to distill off the MeOH. The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 150 °C. the mixture was decompressed to 100,000 Pa (1.0 bar) absolute. 398g (9.04 mol) of EO were measured to a pressure of 200,000 Pa (2 bar) absolute and the reaction was allowed to continue for 1 hour. The mixture was cooled to 140°C and 502 g (5.83 mol) of PeO (pentylene oxide) were measured within two hours. The mixture was cooled to 80 °C, and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm of BHT (butyl hydroxy toluene) was added. The transfer was carried out at 80°C under N2.
[00186] Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M3 HBVE - 22 EO - 10.5 PeO (0.4 mol% potassium ions, 3.3 mol% sodium ions), addition of PeO at 140 °C at 210,000 Pa (2.1 bar)
[00187] A 2 liter pressure autoclave with anchor stirrer was initially charged with 135.3 g (1.16 mol) of hydroxybutyl vinyl ether (HBVE) (stabilized with 100 ppm potassium hydroxide (KOH)) and the shaker was turned on. 1.06 g of potassium methoxide solution (KOMe) (32% KOMe in methanol (MeOH), corresponding to 0.0048 mol of potassium) was fed and the stirrer vessel was evacuated at a pressure less than 1000 Pa ( 10 mbar), heated to 80 °C and operated at 80 °C and a pressure of less than 1000 Pa (10 mbar) for 70 minutes. MeOH was distilled.
[00188] According to an alternative procedure in potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH)) were fed and the stirred vessel was evacuated to a pressure of 1000 to 2000 Pa (10 to 20 mbar ), heated to 65 °C and operated at 65 °C and a pressure of 1000 to 2000 Pa (10 to 20 mbar) for 70 minutes. MeOH was distilled.
[00189] The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C. The mixture was decompressed to 100,000 Pa (1 bar) absolute and 255 g (5.8 mol) of EO was measured until pmax was 390,000 Pa (3.9 bar) absolute and Tmax was 150 °C. The mixture was released from products with low boiling point at a pressure of less than 1000 Pa (10 mbar) for 1 hour. The material (HBVE-5 EO) was transferred at 80°C under N2.
[00190] A 2 liter pressure autoclave with anchor stirrer was initially charged with 180 g (0.54 mol) of the above HBVE-5 EO and the stirrer was turned on. Next, 3.18 g of 30% NaOMe solution in MeOH (0.018 mol NaOMe, 0.95 g NaOMe) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated to 100 °C and kept that way for 80 minutes in order to distill the MeOH. The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 150 °C. the mixture was decompressed to 100,000 Pa (1.0 bar) absolute. 398g (9.04 mol) of EO was measured to a pressure of 200,000 Pa (2 bar) absolute and the reaction was allowed to continue for 1 hour, then the mixture was cooled to 100 °C and freed from low boiling products at a pressure less than 1000 Pa (10 mbar) for 1 hour. The material (HBVE-22 EO) was transferred at 80°C under N2.
A 1 liter autoclave with anchor stirrer was initially loaded with 450 g (0.425 mol) of the above HBVE-22 EO and the stirrer was turned on. The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 140 °C. The mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00192] Then, at 140,000 Pa (1.4 bar) absolute and 140 °C, 384 g (5.83 mol) of PeO was measured at 48 g/l until the pressure increased to 210,000 Pa (2.1 bar ) absolute. Two interruptions were required. The mixture was allowed to react at 140°C until the pressure dropped again. PeO was measured within two days. The mixture was cooled to 80 °C and the residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M4 HBVE - 22 EO - 10.5 PeO (0.4 mol% potassium ions, 4.6 mol% sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00194] The starting material used was the M1 monomer. A 2 liter pressure autoclave with anchor stirrer was initially charged with 745 g (0.69 mol) of HBVE-22 EO and the stirrer was turned on. Next, 5.36 g of NaOMe solution in 32% MeOH (0.0317 mol NaOMe, 1.71 g NaOMe) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated to 80 °C and held for 80 minutes in order to distill off the MeOH.
[00195] The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 127 °C and then the pressure was set to 100,000 Pa (1.0 bar) absolute.
[00196] 591 g (6.9 mol) of PeO were measured at 127 °C; pmax was 210,000 Pa (2.1 bar) absolute. Two intermediate decompressions were required due to the increase in the filling level. The PeO measurement was stopped, and the mixture was allowed to react for 2 hours until the pressure was constant and decompressed to 100,000 Pa (1.0 bar) absolute. Thereafter, the measured addition of PeO was continued. Pmax was still 210,000 Pa (2.1 bar). After the measured addition of PeO had finished, the reaction was allowed to continue at constant pressure for 4 hours. The mixture was cooled to 110°C and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 110°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
[00197] Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M5 HBVE - 22 EO - 11 PeO (0.4 mol% potassium ions, 4.6 mol% sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00198] The preparation was analogous to example M4, except that 11 instead of 10 eq (molar equivalents) of PeO were added. Example M6 HBVE - 24.5 EO - 11 PeO (0.4 mol% potassium ions, 4.6 mol% sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00199] The starting material used was monomer M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 650 g (0.60 mol) of HBVE-22 EO and the stirrer was turned on. Next, 5.96 g of NaOMe solution in 25% MeOH (0.0276 mol of NaOMe, 1.49 g of NaOMe) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated to 100 °C and held for 80 minutes in order to distill off the MeOH.
The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 100,000 Pa (1.0 bar) absolute. 66 g (1.577 mol) of EO were measured at 127°C; pmax was 210,000 Pa (2.1 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00201] 567 g (6.6 mol) of PeO were measured at 127 °C; pmax was 210,000 Pa (2.1 bar) absolute. Two intermediate decompressions were required due to the increase in the filling level. The PeO measurement was stopped, and the mixture was allowed to react for 2 hours until the pressure was constant and decompressed to 100,000 Pa (1.0 bar) absolute. Thereafter, the measured addition of PeO was continued. Pmax was still 210,000 Pa (2.1 bar). After the measured addition of PeO had finished, the reaction was allowed to continue at constant pressure for 4 hours. The mixture was cooled to 110°C and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 110°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M7 HBVE - 24.5 EO - 10 PeO (0.4 mol% potassium ions, 4.6 mol% sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00203] The preparation was analogous to example M6, except that 10 instead of 11 eq of pentene oxide were added. Example M8 HBVE - 24.5 EO - 10 PeO (0.9 mol% potassium ions, 4.1 mol% sodium ions), addition of PeO at 127°C at 210,000 Pa (2.1 bar)
[00204] The preparation was analogous to example M6, except that the catalyst concentration was 0.9% mol of potassium ions and 4.1% mol of sodium ions and 10 instead of 11 eq of PeO were added. Example M9 HBVE - 24.5 EO - 10 PeO (1.5% by mol of potassium ions, 4.6% by mol of sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00205] The preparation was analogous to example M6, except that the catalyst concentration was 1.5% mol of potassium ions and 4.1% mol of sodium ions and 10 instead of 11 eq of PeO were added. Example M10 HBVE - 24.5 EO - 11 PeO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
The starting material used was monomer M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 684g (0.631 mol) of HBVE-22 EO and the stirrer was turned on. Next, 2.78 g of 50% NaOH (sodium hydroxide) solution (0.0348 mol of NaOH, 1.39 g of NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was added. applied, and the mixture was heated to 100 °C and held for 80 minutes in order to distill the water.
The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 69.4 g (1.577 mol) of EO were measured at 127°C; pmax was 210,000 Pa (2.1 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
542.5 g (6.03 mol) of PeO were measured at 127 °C; pmax was 210,000 Pa (2.1 bar) absolute. Two intermediate decompressions were required due to the increase in the filling level. The PeO measurement was stopped, and the mixture was allowed to react for 1 hour until the pressure was constant and decompressed to 100,000 Pa (1.0 bar) absolute. Thereafter, the measured addition of PeO was continued. Pmax was still 210,000 Pa (2.1 bar) (first decompression after 399 g PeO, total PeO measurement time 7 hours including decompression break). After the measured addition of PeO was finished, the reaction was allowed to continue at constant pressure for 3 hours. The mixture was cooled to 110°C and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 110°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M11 HBVE - 24.5 EO - 9 PeO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00210] The preparation was analogous to example M10, except that 9 instead of 10 eq of PeO were added. Example M12 HBVE - 24.5 EO - 9 PeO (5.8 mol% potassium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
The starting material used was monomer M1 from example M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 889.2 g (0.820 mol) of HBVE-22 EO and the stirrer was turned on. Next, 9.69 g of KOMe solution in 32% MeOH (0.0443 mol of KOMe, 3.11 g of KOMe) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated to 100°C and held for 80 minutes in order to distill the water.
[00212] The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 100,000 Pa (1 bar) absolute. 90.2 g (2.050 mol) of EO were measured at 140°C. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute at 120 °C.
[00213] A relatively large sample was taken, such that 789 g (0.66 mol) of HBVE-24.5 EO remained in the reactor. For safety, the mixture was left inert again with N 2 , set to 100,000 Pa (1.0 bar) absolute and heated to 127 °C. 511 g (5.95 mol) of PeO were measured at 127°C; pmax was 210,000 Pa (2.1 bar) absolute. An intermediate decompression was required due to the increased filling level. The PeO measurement was stopped, and the mixture was allowed to react for 2 hours until the pressure was constant and decompressed to 100,000 Pa (1.0 bar) absolute. Thereafter, the measured addition of PeO was continued. Pmax was still 210,000 Pa (2.1 bar). After the measured addition of PeO had finished, the reaction was allowed to continue at constant pressure for 3 hours. The mixture was cooled to 110°C and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 110°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M13 HBVE - 24.5 EO - 8 PeO (0.4 mol% potassium ions, 4.6 mol% sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00215] The preparation was analogous to example M10, except that 8 instead of 11 eq of PeO were added. Example M14 HBVE - 26.5 EO - 10 PeO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
The preparation was analogous to example M10, except that, prior to HBVR-22 EO, 4.5 eq of EO instead of 2.5 eq of EO were added. Example M15 HBVE - 24.5 EO - 10 PeO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00217] The preparation was analogous to example M10, except that PeO was added at 122 °C instead of 127 °C. Example M16 HBVE - 24.5 EO - 10 PeO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of PeO at 127 °C at 210,000 Pa (2.1 bar)
[00218] The preparation was analogous to example M10, except that PeO was added at 132 °C instead of 127 °C. Example M17 HBVE - 24.5 EO - 10 BuO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 210,000 Pa (2.1 bar)
[00219] The starting material used was monomer M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 730.8 g (0.674 mol) of HBVE-22 EO and the stirrer was turned on. Next, 2.97 g of 50% NaOH (sodium hydroxide) solution (0.0371 mol of NaOH, 0.85 g of NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was added. applied, and the mixture was heated to 100 °C and held for 80 minutes in order to distill the water.
The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 74.1 g (1.685 mol) of EO were measured at 127 °C; pmax was 390,000 Pa (3.9 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00221] 485.3 g (6.74 mol) of BuO (butylene oxide) were measured at 127 °C; pmax was 210,000 Pa (2.1 bar) absolute. Two intermediate decompressions were required due to the increase in the filling level. Measurement of BuO was stopped, and the mixture was allowed to react for 1 hour until the pressure was constant and decompressed to 100,000 Pa (1.0 bar) absolute. Next, the measured addition of BuO was continued. Pmax was still 210,000 Pa (2.1 bar) (first decompression after 246 g BuO, total BuO measurement time of 10 hours including decompression break). After the measured addition of BuO was complete, the reaction was allowed to continue at constant pressure for 3 hours. The mixture was cooled to 110°C and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 110°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M18 HBVE - 24.5 EO - 14 BuO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 210,000 Pa (2.1 bar)
[00223] The preparation was analogous to example M17, except that 12 instead of 10 eq of BuO were added. Example M19 HBVE - 24.5 EO - 14 BuO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 210,000 Pa (2.1 bar)
[00224] The preparation was analogous to example M17, except that 14 instead of 10 eq of BuO were added. Example M20 HBVE - 24.5 EO - 16 BuO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 210,000 Pa (2.1 bar)
[00225] The preparation was analogous to example M17, except that 16 instead of 10 eq of BuO were added. Example M21 HBVE - 24.5 EO - 18 BuO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 210,000 Pa (2.1 bar)
[00226] The preparation was analogous to example M17, except that 18 instead of 10 eq of BuO were added. Example M22 HBVE - 24.5 EO - 16 BuO (5.8 mol% potassium ions), addition of BuO at 127 °C at 310,000 Pa (3.1 bar)
[00227] The starting material used was monomer M1 from example M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 622.8 g (0.575 mol) of HBVE-22 EO and the stirrer was turned on. Next, 6.92 g of KOMe solution in 32% MeOH (0.0316 mol of KOMe, 2.21 g of KOMe) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated to 100°C and held for 80 minutes in order to distill the water.
The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 50.3 g (1.144 mol) of EO were measured at 127°C; pmax was 390,000 Pa (3.9 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00229] 662 g (9.19 mol) of BuO were measured at 127 °C; pmax was 310,000 Pa (3.1 bar) absolute. After the measured addition of BuO was complete, the reaction was allowed to continue at constant pressure for 5 hours. The mixture was cooled to 110°C and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 110°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
[00230] Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M23HBVE - 24.5 EO - 16 BuO (0.4 mol% potassium ions, 11 mol% sodium ions), addition of BuO at 127 °C at 310,000 Pa (3.1 bar)
[00231] The starting material used was monomer M1 from example M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 595.1 g (0.549 mol) of HBVE-22 EO and the stirrer was turned on. Next, 4.83 g of 50% NaOH solution (0.060 mol NaOH, 2.41 g NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated. up to 100 °C and kept that way for 80 minutes in order to distill the water.
The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 60.4 g (1.373 mol) of EO were measured at 127 °C; pmax was 390,000 Pa (3.9 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
632.2 g (8.748 mol) of BuO were measured at 127°C; pmax was 310,000 Pa (3.1 bar) absolute. An intermediate decompression was required due to the increased filling level. Measurement of BuO was stopped, and the mixture was allowed to react for 1 hour until the pressure was constant and decompressed to 100,000 Pa (1.0 bar) absolute. Then the measured addition of BuO was continued, Pmax was still 310,000 Pa (3.1 bar) (first decompression after 334 g BuO, total BuO measurement time 5 hours including decompression break). After the measured addition of BuO was complete, the reaction was allowed to continue at constant pressure for 3.5 hours. The mixture was cooled to 100°C, and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 110°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M24 HBVE - 24.5 EO - 17 BuO - 2.5 EO (0.4 mol% potassium ions, 11 mol% sodium ions), addition of BuO at 127 °C at 310,000 Pa (3.1 Pub)
[00235] The starting material used was monomer M1 from example M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 576.7 g (0.532 mol) of HBVE-22 EO and the stirrer was turned on. Next, 2.33 g of 50% NaOH solution (0.029 mol NaOH, 1.17 g NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated. up to 100 °C and kept that way for 80 minutes in order to distill the water.
[00236] The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 23.4 g (0.532 mol) of EO were measured at 127°C; pmax was 390,000 Pa (3.9 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00237] 651.2 g (9.044 mol) of BuO were measured at 127 °C; pmax was 310,000 Pa (3.1 bar) absolute. After the measured addition of BuO was complete, the reaction was heated to 135°C and the reaction was allowed to continue for 2 hours. Next, 58.5 g (1.331 mol) of EO were measured at 135 °C; pmax was 320,000 Pa (3.2 bar) absolute. After the measured addition of EO had finished, the reaction was allowed to continue for 2 hours.
[00238] The mixture was cooled to 100°C, and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 120°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
[00239] Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M25 HBVE - 24.5 EO - 16 BuO - 3.5 EO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 310,000 Pa (3 .1 bar)
[00240] The starting material used was monomer M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 588.6 g (0.543 mol) of HBVE-22 EO and the stirrer was turned on. Next, 2.39 g of 50% NaOH solution (0.030 mol NaOH, 1.19 g NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated. up to 100 °C and kept that way for 80 minutes in order to distill the water.
[00241] The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 59.7 g (1.358 mol) of EO were measured at 127 °C; pmax was 390,000 Pa (3.9 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00242] 625.5 g (8.688 mol) of BuO were measured at 127 °C; pmax was 310,000 Pa (3.1 bar) absolute. An intermediate decompression was required due to the increased filling level. Measurement of BuO was stopped, and the mixture was allowed to react for 1 hour until the pressure was constant and decompressed to 100,000 Pa (1.0 bar) absolute. Then the measured addition of BuO was continued, Pmax was still 310,000 Pa (3.1 bar) (first decompression after 610 g BuO, total BuO measurement time 8 hours including decompression break). After the measured addition of BuO was complete, the reaction was heated to 135°C and the reaction was allowed to continue for 2 hours. Next, 83.6 g (1.901 mol) of EO were measured at 135 °C; pmax was 320,000 Pa (3.2 bar) absolute. After the measured addition of EO had finished, the reaction was allowed to continue for 4 hours. The mixture was cooled to 100°C, and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 120°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
[00243] Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M26 HBVE - 24.5 EO - 16 BuO - 3.5 EO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 310,000 Pa (3 .1 bar)
[00244] The starting material used was monomer M1 from example M1. The preparation was analogous to example M25, except that 5 instead of 3.5 eq of EO were added after addition of BuO and polymerization, ie 119.5 g (2.715 mol) of EO were measured at 135 °C.
Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M27 HBVE - 24.5 EO - 10 BuO - 3.5 EO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 310,000 Pa (3 .1 bar)
[00246] The starting material used was monomer M1 from example M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 685.2 g (0.632 mol) of HBVE-22 EO and the stirrer was turned on. Next, 2.78 g of 50% NaOH solution (0.035 mol NaOH, 1.39 g NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated. up to 100 °C and kept that way for 80 minutes in order to distill the water.
[00247] The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 69.8 g (1.587 mol) of EO were measured at 127°C; pmax was 390,000 Pa (3.9 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00248] 455.2 g (6.322 mol) of BuO were measured at 127 °C; pmax was 310,000 Pa (3.1 bar) absolute. After the measured addition of BuO was complete, the reaction was allowed to continue for 7 hours. Next, 97.4 g (2.213 mol) of EO were measured at 135 °C; pmax was 310,000 Pa (3.1 bar) absolute. After the measured addition of EO had finished, the reaction was allowed to continue for 2 hours. The mixture was cooled to 100°C, and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 120°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
[00249] Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M28 HBVE - 24.5 EO - 5 BuO - 3.5 EO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 310,000 Pa (3 .1 bar)
The starting material used was monomer M1 from example M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 822.0 g (0.758 mol) of HBVE-22 EO and the stirrer was turned on. Next, 3.34 g of 50% NaOH solution (0.042 mol of NaOH, 1.67 g of NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated. up to 100 °C and kept that way for 80 minutes in order to distill the water.
[00251] The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 127 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 83.4 g (1.895 mol) of EO were measured at 127°C; pmax was 390,000 Pa (3.9 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00252] 273.0 g (3.792 mol) of BuO were measured at 127 °C; pmax was 310,000 Pa (3.1 bar) absolute. After the measured addition of BuO was complete, the reaction was allowed to continue for 15 hours. Next, 116.8 g (2.654 mol) of EO were measured at 127°C; pmax was 310,000 Pa (3.1 bar) absolute. After the measured addition of EO had finished, the reaction was allowed to continue for 4 hours. The mixture was cooled to 100°C, and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 120°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M29 HBVE - 24.5 EO - 22 BuO - 3.5 EO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 310,000 Pa (3 .1 bar)
The starting material used was monomer M1 from example M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 493.3 g (0.455 mol) of HBVE-22 EO and the stirrer was turned on. Next, 2.00 g of 50% NaOH solution (0.025 mol NaOH, 1.00 g NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated. up to 100 °C and kept that way for 80 minutes in order to distill the water.
The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 127 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 50.0 g (1.138 mol) of EO were measured at 127°C; pmax was 390,000 Pa (3.9 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 100,000 Pa (1.0 bar) absolute.
[00256] 720.9 g (10.012 mol) of BuO were measured at 127 °C; pmax was 310,000 Pa (3.1 bar) absolute. After the measured addition of BuO was complete, the reaction was allowed to continue for 9 hours. The mixture was heated to 135°C. Next, 70.1 g (1.593 mol) of EO were measured at 135 °C; pmax was 310,000 Pa (3.1 bar) absolute. After the measured addition of EO had finished, the reaction was allowed to continue for 2 hours. The mixture was cooled to 100°C, and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. Then 0.5% water was added at 120°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
[00257] Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Example M30 HBVE - 24.5 EO - 16 BuO - 3.5 EO (0.4 mol% potassium ions, 5.5% mol sodium ions), addition of BuO at 127 °C at 400,000 to 600,000 Pa (4 to 6 bar)
[00258] The starting material used was monomer M1 from example M1. A 2 liter pressure autoclave with anchor stirrer was initially charged with 568.6 g (0.525 mol) of HBVE-22 EO and the stirrer was turned on. Next, 2.31 g of 50% NaOH solution (0.029 mol of NaOH, 1.16 g of NaOH) was added, a reduced pressure of less than 1000 Pa (10 mbar) was applied, and the mixture was heated. up to 100 °C and kept that way for 80 minutes in order to distill the water.
[00259] The mixture was purged three times with N2. Next, the vessel was checked for pressure retention, 50,000 Pa (0.5 bar) relative (150,000 Pa (1.5 bar) absolute) was set and the mixture was heated to 120 °C and then the pressure was set to 160,000 Pa (1.6 bar) absolute. 57.7 g (1.311 mol) of EO were measured at 127 °C; pmax was 600,000 Pa (6 bar) absolute. After waiting 30 minutes for the establishment of constant pressure, the mixture was decompressed to 400,000 Pa (4.0 bar) absolute.
[00260] 640.2 g (8.392 mol) of BuO were measured at 127 °C; pmax was 600,000 Pa (6 bar) absolute. An intermediate decompression was required due to the increased filling level. Measurement of BuO was stopped, and the mixture was allowed to react for 1 hour until the pressure was constant and decompressed to 100,000 Pa (1.0 bar) absolute. Then the measured addition of BuO was continued, Pmax was still 600,000 Pa (6 bar) (first decompression after 505 g BuO, total BuO measurement time 11 hours including decompression break). After the measured addition of BuO was complete, the reaction was allowed to continue for 6 hours at 127 °C. it has been decompressed to 400,000 Pa (4 bar) absolute.
[00261] Next, 80.8 g (1.836 mol) of EO were measured at 127 °C; pmax was 600,000 Pa (6 bar) absolute. After the measured addition of EO had finished, the reaction was allowed to continue for 4 hours. The mixture was cooled to 100°C, and residual oxide was removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. About 1400 ppm of volatile components were removed. Then 0.5% water was added at 120°C and volatiles were subsequently removed until the pressure was below 1000 Pa (10 mbar) for at least 10 minutes. The vacuum was broken with N2 and 100 ppm BHT was added. The transfer was carried out at 80°C under N2.
[00262] Analysis (mass spectrum, GPC, 1 H NMR in CDCl 3 , 1 H NMR in MeOD) confirmed the structure. Ic Preparation of copolymers based on monomers (M2 to M30) Example C1 General preparation of a copolymer from 2% by weight of monomer M, 50% by weight of acrylamide and 48% by weight of 2-acrylamido-2-acid sulfonic methylpropane
[00263] A plastic bucket with a magnetic stirrer, pH meter and thermometer was initially charged with 121.2 g of 50% aqueous solution of NaATBS (2-acrylamido-2-methylpropane sulfonic acid, Na salt), followed by addition successive 155 g distilled water, 0.6 g defoamer (Surynol® DF-58), 0.2 g silicone defoamer (Baysilon® EM), 2.3 g monomer M, 114.4 g of an aqueous solution of acrylamide, 1.2 g of pentasodium diethylene triamine pentaacetate (complexing agent, as a 5% aqueous solution) and 2.4 g of a nonionic surfactant (isotridecanol, alkoxylated with 15 units of oxide ethylene).
[00264] After adjusting the pH with a 20% or 2% sulfuric acid solution to a value of 6 and adding the remainder of the water, the monomer solution was adjusted to the initial temperature of 5 °C. the total amount of water was such that - after polarization - a solids concentration of approximately 30 to 36 % by weight was reached. The solution was transferred to a thermos flask, a temperature sensor was provided to record the temperature and the solution was purged with N2 for 30 minutes. Polymerization was subsequently initiated by the addition of 1.6 ml of a 10% aqueous solution of a water-soluble cationic azo initiator 2,2'-azobis(2-amidinopropane) dihydrochloride (Wako V-50), 0, 12 ml of a 1% aqueous solution of tert-butyl hydroperoxide and 0.24 ml of a 1% sodium sulphite solution. After the initiators are added, the temperature rise to approximately 80 °C within 15 to 30 minutes. After 30 minutes, the reaction vessel was placed in a drying cabinet at approximately 80 °C for approximately 2 hours to complete the polymerization. Total polymerization time was about 2 hours to 2.5 hours.
[00265] A gel block was obtained, which, after the polymerization had ended, was comminuted with a meat grinder. The gel granules thus obtained were dried in a fluid bed dryer at 55 °C for two hours. Rigid white granules were obtained, which were converted to a powdery state by means of a centrifugal mill. A copolymer was obtained having a mass average molecular weight of about 1,000,000 g/mol to 30,000,000 g/mol. Example C2 Copolymer based on M2 monomer
[00266] The copolymer was obtained according to the general preparation method above using monomer 2 from comparative example M2. Examples C3 to C30
[00267] Copolymers C3 to C30 were prepared by the general method above using the respective monomers M3 to M30. Part II: Performance Tests
[00268] The resulting copolymers based on the monomers were used to conduct the tests that follow, in order to assess the suitability for the production of tertiary mineral oil. Description of Test Methods a) Determination of solubility
[00269] The copolymers were dissolved in synthetic seawater to DIN 50900 (salt content 35 g/l) in order to give a polymer concentration of 2000 ppm: 0.5 g of the respective copolymer was stirred into 249 g of synthetic seawater (DIN 50900) for 24 hours until complete dissolution (the precision glass stirrer used should preferably be a paddle stirrer, the polymer has been gradually spread to the apex it forms). b) Determination of viscosity
[00270] The viscosities of the copolymer solutions mentioned above were determined using a Haake rheometer with double gap geometry at 7 Hz and 60 °C. After approximately 5 minutes, a plateau value was established for viscosity, which was read. Very good values were considered as viscosities greater than or equal to 150 mPa.s (2000 ppm copolymer in synthetic seawater at 60 °C 7 Hz). Good values were considered as viscosities greater than 120 mPa.s to 149 mPa.s. Moderate viscosity values were considered from 80 to 119 mPa.s. Viscosities less than 80 mPa.s were considered poor. c) Determination of filtration capacity
[00271] Prior to the actual filtration test, the polymer solution was filtered through a 200 µm Retsch sieve to determine its gel content.
[00272] The filtration test to determine the MPFR value - the ratio of the flow rate of the first quarter to that of the fourth quarter is called the "millipore filter ratio" (MPFR) - was conducted by means of a cell of Sartorius 16249 pressure filtration (filter diameter 47 mm) and an Isopore polycarbonate membrane filter (diameter 47 mm, pore size 3 μm) at room temperature and pressure 100,000 Pa (1 bar). 210 to 220 g of polymer solution were used. In the test, at least 180 g of the filtrate must pass through for 30 minutes. Good values were considered to be MPFR of less than or equal to 1.3. If they are between 1.3 and 1.6, the filtering capacity was considered moderate. If less than 30 g of the filtrate passed, the sample was considered non-filterable. d) Determination of gel content
[00273] 1 g of the respective copolymer from preparation examples 2 to 30 was stirred in 249 g of synthetic seawater to DIN 50900 (salt content 35 g/l) until complete dissolution for 24 hours. Subsequently, the solution was filtered through a 200 µm mesh size sieve and the volume of the residue remaining on the sieve being measured. The value obtained corresponds to the gel content. Test Results:



[00274] Examples 2 and 3 show that the pressure window for measuring PeO at 140 °C has a large influence on product quality. A larger pressure window allows for fast measurement and a short cycle time (2 hours per PeO). However, if the pressure window required by the safety specifications is observed, as in example 3, the reaction is prolonged (2 days for PeO). As a result of the high temperature, there are side reactions and formation of crosslinkers, the effect of which is that of further copolymerization forms a thickening copolymer that is no longer filterable, and this can no longer be employed for users in a porous matrix (by example, rock strata carrying mineral oil, thickeners in mineral oil production).
[00275] Example 4 shows that decreasing the reaction temperature while maintaining the small pressure window can produce crosslinker-free copolymers. As can be seen from the examples, the concentration of potassium ions is of central significance. As examples 9 to 12 show, above 0.9 mol% potassium ions, the polymer is no longer filterable despite temperatures of 127 °C in the PeO measurement. A potassium ion concentration greater than 0.9% mol apparently leads to the formation of crosslinking compounds that lead to a copolymer that is no longer filterable. In addition, the exact content of sodium ion catalyst also appears to play an important role.
[00276] Surprisingly, it is further observed that the hydrophilic/hydrophobic ratio of the monomer is also of great significance. Despite the crosslinker-free operation, the copolymer according to example 5 somehow has worse filterability than copolymers based on monomers with only 1 eq of PeO less (example 4). If monomers with 24.5 EO units are used, the variation in PeO units has no influence on the filterability of the copolymers (comparison of examples 6 and 7 and comparison of examples 10 and 11). The specific selection of a hydrophilic/hydrophobic ratio, i.e. ratio of EO and PO units, leads to the surprising robustness of the process. In examples 10 and 11 (24.5 EO units), no variation in PeO content was noticeable. This provides good stability for industrial scale production, where variations of less than 1 eq of alkylene oxide are not easy to guarantee. Deviations in process and structure are thus much better tolerated in further copolymer synthesis or application.
[00277] A similar picture is found in the case of copolymers based on monomers with terminal BuO groups. A comparison of examples 20 and 22 shows that, also in the case of preparing copolymers based on monomers with terminal BuO groups, a potassium ion concentration of less than 0.9% by mol surprisingly leads to improved copolymers. Excessively high values for potassium ions in the copolymer lead to unfilterable structures.
[00278] Examples 19 and 20 show that optimal product properties (good viscosities and good filterability) can be especially achieved at a butoxylation level above 12 and below 18. A comparison of the results that refer to monomers with terminal PeO groups and refer to monomers with terminal BuO groups further showed that the total number of carbon atoms in the side chains of the monomers, especially in the terminal alkylene oxide blocks, is of crucial significance for the property of the resulting copolymers . For example, the total number of carbon atoms in the side chains of the terminal alkylene oxide block from examples 19 and 20 (total of 28 to 32 carbon atoms) coincides with the total number range in examples 6, 10 and 11 (total of 27 to 33 carbon atoms in the side chains) which refers to monomers with terminal PeO groups. Other levels of butoxylation as in examples 17, 18 and 21 lead to monomer properties that are no longer optimal in all ranges.
[00279] Additionally, it has been shown that monomers with BuO blocks, in particular with blocks having 16 to 22 BuO units, can advantageously be modified with a terminal EO block. Thus, copolymers with very good viscosity properties and good filterability can be obtained (example 24 to 26 and 29). On the contrary, it appears that the introduction of a terminal EO block in monomers having a BuO block with less than 12 BuO units does not result in an advantageous effect (Examples 27 and 28).
[00280] Example 23 shows that the sodium ion concentration can be up to at least 11 mol% during the addition of butylene oxide.
[00281] Example 30 shows that the addition of butylene oxide can also be carried out advantageously at a pressure in the range of 400,000 to 600,000 Pa (4 to 6 bar).

权利要求:
Claims (17)
[0001]
1. Process for preparing a water-soluble hydrophobically associating copolymer consisting of (a) 0.1 to 20% by weight of at least one hydrophobically associating monomer (a), and (b) 25 a 99.9% by weight of at least one hydrophilic monomer (b) different from monomer (a), by means of a polymerization reaction, in the presence of at least one more non-polymerizable surface active component (c) in the course of the synthesis of the even before the start of the polymerization reaction, where each of the stated amounts is based on the total amount of all monomers in the copolymer, and at least one of the monomers (a) being a monomer of general formula (I)
[0002]
2. Process according to claim 1, characterized in that each of the radicals and indices are as defined in the sequence: k: is a number from 23 to 26; l: is a number from 5 to 25; m: is a number from 0 to 15; R': is H or methyl; R²: is independently a single-bond or bivalent-bond group selected from the group of –(CnH2n)– and –O–(Cn'H2n')–, where n is a natural number from 1 to 6 and n' is a natural number from 2 to 6; R³: is ethyl; R4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms.
[0003]
3. Process according to claim 1 or 2, characterized in that each of the radicals and indices are as defined in the sequence: k: is a number from 23 to 26; l: is a number from 8.5 to 17.25; m: is a number from 0 to 15; R': is H or methyl; R²: is independently a single-bond or bivalent-bond group selected from the group of –(CnH2n)– and –O–(Cn'H2n')–, where n is a natural number from 1 to 6 and n' is a natural number from 2 to 6; R³: is ethyl; R4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms.
[0004]
4. Process according to any one of claims 1 to 3, characterized in that each of the radicals and indices are as defined in the sequence: k: is a number from 23 to 26; l: is a number from 12.75 to 17.25; m: is a number from 0 to 15; R¹: is H; R²: is a bivalent linking group –O–(Cn’H2n’)–, where n’ is 4; R³: is ethyl; R4: is H.
[0005]
5. Process according to any one of claims 1 to 4, characterized in that the weight ratio of the monomer of formula (I) where m = 0 and the monomer of formula (I) where m = 1 to 15 is in range from 19:1 to 1:19.
[0006]
6. Process according to any one of claims 1 to 5, characterized in that the concentration of potassium ions in the preparation of the monomer (a), in the reaction in step b), is from 0.01 to 0.5% in mol based on the A2 alcohol used.
[0007]
7. Process according to any one of claims 1 to 6, characterized in that the preparation of monomer a) involves using a C2 catalyst comprising at least one basic sodium compound in step b), the concentration of sodium ions in the reaction in step b) being in the range of 3.5% by mol to 12% by mol, based on the alcohol A2 used.
[0008]
8. Process according to any one of claims 1 to 7, characterized in that step b) in the preparation of the monomer (a) is carried out at a pressure in the range of 100,000 to 310,000 Pa (1 to 3.1 bar) and a temperature of 120 to 135 °C.
[0009]
9. Process according to any one of claims 1 to 8, characterized in that R3 is ethyl and step b) in the preparation of the monomer (a) is carried out at a pressure in the range of 100,000 to 310,000 Pa (1 to 3 .1 bar).
[0010]
10. Process according to any one of claims 1 to 9, characterized in that at least one of the monomers (b) is a monomer comprising acid groups, the acid groups being at least one group selected from the group of - COOH, -SO3H and -PO3H2 and salts thereof.
[0011]
11. Process according to any one of claims 1 to 10, characterized in that it comprises at least two different hydrophilic monomers (b) which are - at least one uncharged hydrophilic monomer (b1), and - at least one anionic monomer hydrophilic (b2) comprising at least one acid group selected from the group of -COOH, -SO3H and -PO3H2 and salts thereof.
[0012]
12. Process according to any one of claims 1 to 11, characterized in that it comprises (a) 2% by weight of at least one hydrophobic association monomer (a), and (b) 50% by weight of acrylamide as an uncharged hydrophilic monomer (b1), and (c) 48% by weight of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) as an anionic hydrophilic monomer (b2), where the stated amounts are each based on total amount of all monomers in the copolymer.
[0013]
13. Process according to any one of claims 1 to 12, characterized in that component (c) is at least one non-ionic surfactant.
[0014]
14. Process for preparing a copolymer according to claim 13, characterized in that the solution polymerization is carried out at a pH in the range of 5.0 to 7.5.
[0015]
15. Use of copolymers as defined in any one of claims 1 to 13, characterized in that it is in the development, exploration and completion of underground mineral oil and natural gas deposits.
[0016]
16. Use of the copolymers according to claim 15, for the production of tertiary mineral oil, characterized in that an aqueous formulation of said copolymers in a concentration of 0.01 to 5% by weight is injected into an oil deposit mineral through at least one injection well and crude oil is withdrawn from the deposit through at least one production well.
[0017]
17. Use of copolymers according to claim 16, characterized in that the aqueous formulation of said copolymers comprises at least one surfactant.

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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