• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    hydrophobically associated water-soluble copolymer, and the process of preparing the present invention relates to a hydrophobically associated, water-soluble copolymer comprising a mono-ethylenically unsaturated monomer (a), water-soluble, surfactant and a mono-ethylenically unsaturated hydrophilic monomer (b), different from monomer (a). the copolymer is prepared in the presence of a non-polymerizable surfactant and has marked thickening properties in aqueous systems.
    公开号:BR112012001710B1
    申请号:R112012001710
    申请日:2010-07-30
    公开日:2019-12-24
    发明作者:Guzmann Marcus；Reichenbach-Klinke Roland；Friedrich Stefan；Pfeuffer Thomas
    申请人:Basf Se；
    IPC主号:
    专利说明:

    Descriptive Report on the Invention Patent for WATER-SOLUBLE HYDROPHOBICALLY ASSOCIATED COPOLYMER, AND THE SAME PREPARATION PROCESS.
    Description [001] The present invention relates to a hydrophobically associated copolymer, soluble in water that is obtained in the presence of a non-polymerizable surfactant compound, to processes for its preparation and use.
    [002] Water-soluble polymers with thickening properties are used in various areas of technology, for example, in the field of cosmetics, in food, for the manufacture of cleaners, printing inks, emulsion inks, but in particular also in recovery of mineral oil.
    [003] Several classes of chemically different polymers are known and can be used as thickeners. An important class of thickener polymers is the so-called class of polymers that are hydrophobically associated. This is understood by the person skilled in the art as meaning water-soluble polymers having hydrophobic side or terminal groups, such as, for example, relatively long alkyl chains. In aqueous solution, hydrophobic groups of this type can associate with themselves or with other substances that have hydrophobic groups. As a result, an associative network is formed, through which the medium is thickened.
    [004] An important field of use for these hydrophobically associated copolymers is in the field of mineral oil recovery, in particular for advanced oil recovery (EOR). Details on the use of copolymers that combine hydrophobically for advanced oil recovery are described, for example, in the synthesis article by Taylor, K.C. and Nasr-EI-Din, H.A. in J. Petr. Know. Eng. 1998, 19, 265-280.
    [005] Advanced oil recovery techniques include the injection of hydrophilic polymers. A deposit of mineral oil is not a sea of underground mineral oil, but the mineral oil is contained in the pores di
    Petition 870190032059, of 03/03/2019, p. 9/53
    2/28 minutes of the rock that carries the mineral oil. The diameter of the cavities in the formation is generally only a few micrometers. For the injection of hydrophilic polymers, an aqueous solution of a thickener polymer is injected into a deposit of mineral oil through the injection wells. With the injection of the polymer solution, the mineral oil is forced through said cavities in the formation from the injection well towards the production well and the mineral oil is recovered through the production well.
    [006] The use of an aqueous polymer solution compared to pure water prevents that after the flooding of the underground formations, no channel of variable permeability is formed (fingering), resulting in other underground areas not becoming flooded. The addition of the polymer to the aqueous phase reduces its mobility and induces a more stable flood. In addition, it must be ensured that the aqueous polymer solution does not comprise any type of gel particles. This is because even small particles of gel with dimensions in the micrometric range, can block the tiny pores in the formation and, therefore, lead the advanced oil recovery to a standstill. Therefore, copolymers that combine hydrophobically for advanced oil recovery should have the smallest possible fraction of gel particles. Therefore, the objective is to obtain, through the polymers, an increase in the viscosity of the water, which ideally corresponds to the viscosity of the hydrocarbons to be recovered.
    [007] Copolymers that are hydrophobically associated, soluble in water are generally prepared by the so-called micellar copolymerization. In this process, water-insoluble comonomers are solvated by adding surfactants to the aqueous reaction medium and are reacted with hydrophilic comonomers such as, for example, acrylamide, to give an associated hydrophobically, water-soluble copolymer. So, for example, Macromol. Chem. Phys. 2001, 202, 1384-1397 describes the micellar copolymerization of water-soluble acrylamide comonomers, AMPS (acrylamidomethylpropanesulfonic acid) and MADQUAT ([2 (methacryloyloxy) ethyl] trimethylammonium) with dihexylacrylamide or A / - (4-ethyl ) acrylamide,
    Petition 870190032059, of 03/03/2019, p. 10/53
    3/28 while Polymer 1998, 39 (5), 1025-1033 discusses copolymerization of acrylamide with dihexylacrylamide and Eur. Polym. J. 2007, 43, 824-834 discusses copolymerization of acrylamide with N-octadecylacrylamide. In both cases, the surfactant used is dodecyl sulfonate (SDS). An additional example of a micellar copolymerization is given in J. Colloid Interf. Know. 2009, 333, 152-163. Here, acrylamide is reacted with a propylene glycol methacrylate in the presence of SDS.
    [008] In addition, WO 85/03510 describes hydrophobically, water-soluble copolymers of a water-soluble unsaturated ethyl monomer and an amphiphilic unsaturated ethyl monomer with hydrophobic groups. Such copolymers can be synthesized by reacting water-soluble monomers, such as acrylamide and amphiphilic monomers such as dodecyl-polyoxylene (10) -methacrylate. These amphiphilic comonomers are characterized as water soluble at ambient temperatures but insoluble in water at elevated temperatures such as 60 9 C as used for the synthesis of the copolymers. As a result, a surfactant or emulsifying agent is added if necessary, for example, when polymerization is carried out at elevated temperatures. The addition of the surfactant or emulsifying agent ensures the solubility of amphiphilic comonomers under the conditions of the polymerization process. However, the monomer is no longer soluble in water.
    [009] An additional method for the preparation of hydrophobically associated, water-soluble copolymers is the use of water-soluble comonomers active on the surface. These comonomers have a hydrophobic fraction, which produces the hydrophobic association effect on the copolymer, and a hydrophilic fraction that ensures the solubility of the comonomer in water. An advantage of this process is that no additional surfactants are needed for the solvation of the hydrophobically associated monomer.
    [0010] Examples of the application of this process can be found in EP 705 854 A1, DE 100 37 629 A1 and DE 10 2004 032 304 A1. These applications describe copolymers that are hydrophobically associated,
    Petition 870190032059, of 03/03/2019, p. 11/53
    4/28 water-soluble and its uses, for example, in the field of construction chemistry. As monomers that are hydrophobically associated, the copolymers described in each case comprise monomers of the following type: H 2 C = C (R x ) -COO - (- CH2-CH2-O-) qR y or H2C = C (R x ) -O - (- CH2-CH2-O-) qR y where R x is typically H or CH3 and R y is a relatively large hydrocarbon radical, typically hydrocarbon radicals having 8 to 40 carbon atoms. For example, relatively long alkyl groups or a tristyrylphenyl group are mentioned in the applications.
    [0011] Additionally, J. Appl. Polym. Know. 1999, 74, 211-217 describes the use of a hydrophobic, water-soluble, cationic comonomer that has been obtained by reacting 2-methacryloyloxyethyldimethylamine with 1-bromododecane.
    [0012] Canadian patent application 2,196,908 deals with hydrophobically associated monomers and polymers. In the foreground in this document are emulsion polymers of methacrylic acid, ethyl acrylate and a monomer that has been obtained by the reaction of dimethyl-m-isoprenyl benzyl isocyanate (DMI) and EMI or polybutylene oxide or polybutylene oxide-polybutylene oxide polyethylene. Here, primarily water-soluble monomers and non-hydrophilic monomers, such as, for example, ethyl acrylate, are used.
    [0013] A disadvantage of all the hydrophobically associated polymers described so far and commercially available is their very high gel fraction, which is formed during dissolution and can block porous formations, as a result of which the uniform polymer flood can be appreciably interrupted. This problem had already been partially solved using copolymers according to the unpublished European patent application EP 09 160 799.4; although fractions of gel could be markedly reduced in these, they could not be avoided entirely.
    [0014] Therefore, it was an objective of the present invention to provide copolymers that hydrophobically associate with small or undetectable gel fractions. In addition, copolymers must be capable of being
    Petition 870190032059, of 03/03/2019, p. 12/53
    5/28 prepared in a more profitable way than until now and its effect as a thickener must be at least equal to the current compounds.
    [0015] This objective was achieved with a copolymer that is hydrophobically associated, soluble in water, comprising:
    (a) at least one mono-ethylenically unsaturated, water-soluble, surfactant monomer (a) and (b) at least one mono-ethylenically unsaturated, hydrophilic (b) monomer other than monomer (a).
    [0016] This copolymer is characterized in an essential way for the invention by the fact that, during its synthesis, before the beginning of the polymerization reaction, at least one additional surfactant compound, but not polymerizable, is added as the additional component ( ç).
    [0017] As already mentioned above, an advantage of the process known from the prior art is considered to be that the copolymers that are associated hydrophobically can be prepared without the addition of a surfactant that all the comonomers used are soluble in water.
    [0018] What was more surprising is that, in the case of copolymers according to the invention, through the addition of a surfactant during the aqueous solution polymerization of the hydrophilic monomers with a hydrophobically associated, water-soluble comonomer, an improvement significant of the polymer properties, in particular the thickening effect, can be obtained and, in addition, the gel fraction can be significantly reduced as intended.
    [0019] This effect can presumably be explained as follows:
    [0020] During the known procedure, the hydrophobically associated comonomer, surfactant, forms micelles in the aqueous reaction medium. During polymerization, this leads to regions that are hydrophobically associated to be incorporated en bloc in the polymer. According to the invention, if an additional surfactant compound is present during the preparation of the copolymers, mixed micelles are formed. These micelles
    Petition 870190032059, of 03/03/2019, p. 13/53
    Mixed 6/28 comprise polymerizable and non-polymerizable fractions. Consequently, monomers that are hydrophobically associated are then incorporated into relatively small blocks. At the same time, the number of these small blocks per polymer chain is higher.
    [0021] Consequently, the constitution of copolymers according to the invention differs significantly from copolymers according to the prior art resulting in significantly improved application properties.
    [0022] The hydrophobically associated copolymers according to the invention are water-soluble copolymers that have hydrophobic groups. In aqueous solution, hydrophobic groups can associate with themselves or with other substances that have hydrophobic groups and thicken the aqueous medium as a result of this interaction.
    [0023] It is known to the person skilled in the art that the solubility of (co) polymers that are associated hydrophobically in water may be dependent on a greater or lesser extent of pH, depending on the type of monomers used. A reference point for assessing water solubility should therefore be, in each case, the desired pH for the particular intended use of the copolymer. A copolymer that does not have adequate solubility for its intended use at one particular pH, may have adequate solubility at another pH. The water-soluble expression also includes in particular dispersions of alkali-soluble polymers, that is, polymers that are present in the acid range as dispersions and only in the alkaline pH range dissolve in water and develop their thickening effect.
    [0024] In the ideal case, the copolymers according to the invention should be miscible in water in any desired proportion. According to the invention, however, it is sufficient that the copolymers are soluble in water at the desired concentration of use and at the desired pH. As a rule, the solubility in water at room temperature should be at least 20 g / l, preferably at least 50 g / l and particularly, preferably, at least 100 g / l.
    Petition 870190032059, of 03/03/2019, p. 14/53
    7/28 [0025] In addition to the hydrophobic groups already mentioned, the copolymers that are associated hydrophobically according to the invention therefore comprise hydrophilic groups in an amount such that the desired water solubility is guaranteed at least in the pH ranges contemplated for the particular application.
    [0026] Monomer (a) [0027] The hydrophobically associated copolymer according to the invention comprises at least one mono-ethylenically unsaturated, water-soluble monomer (a) that imparts hydrophobic association properties to the copolymer according to the invention and, therefore, it is referred to below as a monomer that is hydrophobically associated.
    [0028] According to the invention, at least one of the monomers (a) mono-ethylenically unsaturated, soluble in water is preferably a monomer of the general formulas (i), (II) and / or (III)
    H2C = C (R 1 ) -R 4 -O - (- CH2-CH2-O-) k - (- CH2-CH (R 3 ) -O-) iH (I) or H2C = C (R 1 ) - O - (- CH2-CH2-O-) kR 2 (II) or
    H 2 C = C (R 1 ) - (C = O) -O - (- CH2-CH2-O-) kR 2 (III), in which the units - (- CH2-CH2-O-) ke - ( -CH2-CH (R 3 ) -O-) i are arranged in a block structure in the order shown in formula (I) and the radicals and indices have the following meaning:
    k: a number between 6 to 150,
    I: a number between 5 to 25,
    R 1 : H or methyl,
    R 2 : a straight or branched chain aliphatic and / or aromatic hydrocarbon radical having 8 to 40 carbon atoms,
    R 3 : independently of each other, a hydrocarbon radical that has at least 2 carbon atoms,
    R 4 : a single bond or a divalent bond group selected from the group of - (Cnhhn) - [R 4a ], -O- (Cn'H2n ·) - [R 4b ] and -C (O) -O- ( CnH2n) [R 4c ], where n, n1 and n ”is, in each case, a natural number between 1 and 6. [0029] In the monomers (a) of formula (I), an ethylene group H2C = C (R 1 ) - is connected via a divalent link group -R 4 -O- to a
    Petition 870190032059, of 03/03/2019, p. 15/53
    8/28 polyoxyalkylene radical with a block structure - (- CH2-CH2-O-) k - (- CH2CH (R 3 ) -O-) iH, where the two blocks - (- CH 2 -CH 2 -O- ) ke - (- CH 2 -CH (R 3 ) -O-) i are arranged in the order shown in formula (I). The polyoxyalkylene radical has a terminal OH group.
    [0030] In the aforementioned formula, R 1 is H or a methyl group. R 4 is a single bond or a divalent bond group selected from the group of - (CnH2n) - [R 4a ], -O- (Cn-H2n ·) - [R 4b ] and -C (O) -O- ( Cn H2n) - [R 4c ]. In the specified formulas, n, n 'and en are in each case a natural number between 1 and 6. In other words, the linking group is straight or branched chain aliphatic hydrocarbon groups that have 1 to 6 carbon atoms, which are linked to the ethylenic group H2C = C (R 1 ) - directly, through an ether group -O-, or through an ester group -C (O) -O-. The groups - (CnH 2n ) -, - (0ηΉ 2η ·) - and - (0η · Ή 2 η ··) - are preferably linear aliphatic hydrocarbon groups. R 3 is preferably a hydrocarbon radical having at least 3 carbon atoms.
    [0031] Preferably, R 1 is H and R 4 is a group selected from CH 2 - or -O-CH 2 -CH 2 -CH 2 -CH 2 -.
    [0032] Preferably, R 4a is a group selected from -CH 2 -, CH 2 -CH 2 - and -CH 2 -CH 2 -CH 2 -, and is particularly preferably a methylene -CH 2 - group.
    [0033] Preferably, R 4b is a group selected from -O-CH 2 CH 2 -, -O-CH 2 -CH 2 -CH 2 - and -O-CH 2 -CH 2 -CH 2 -CH 2 -, and it is particularly preferably -O-CH 2 -CH 2 -CH 2 -CH 2 -.
    [0034] Preferably, R 4c is a group selected from -C (O) -OCH 2 -CH 2 -, -C (O) O-CH (CH 3 ) -CH 2 -, -C (O) O-CH 2 -CH (CH 3 ) -, -C (O) O-CH 2 -CH 2 CH 2 -CH 2 - and -C (O) O-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - CH 2 -, with preference being given in particular to -C (O) -O-CH 2 -CH 2 - and -C (O) O-CH 2 -CH 2 -CH 2 -CH 2 - and very particular preference being given a -C (O) -O-CH 2 -CH 2 -.
    [0035] The R 4 group is particularly preferably an R 4a or R 4b group , particularly preferably an R 4b group.
    [0036] Additionally, R 4 is particularly preferably a group selected from -CH 2 - or -O-CH 2 -CH 2 -CH 2 -CH 2 -, and is particularly petition 870190032059, from 03/04/2019, p. 16/53
    9/28 and preferably -O-CH2-CH2-CH2-CH2-.
    [0037] Additionally, the monomers (I) have a polyoxyalkylene radical consisting of the units - (- CH2-CH2-O-) ke - (- CH2-CH (R 3 ) -O-) i, where the units are arranged in a block structure in the order shown in Formula (I). The transition between the two blocks can be abrupt or continuous.
    [0038] The number of alkylene oxide units k is a number between 6 to 150, preferably 12 to 100, particularly preferably 15 to 80, very particularly preferably 20 to 30 and, for example, about 22 to 25. For the person well versed in the field of polyalkylene oxides, it is clear that the numbers specified are average values of the distributions.
    [0039] In the second terminal block - (- CH2-CH (R 3 ) -O-) i-, the radicals R 3 , independently of each other, are hydrocarbon radicals with at least 2 carbon atoms, preferably 3 and particularly preferably 3 to 10 carbon atoms. These can be aliphatic and / or aromatic, linear or branched hydrocarbon radicals. These are preferably aliphatic radicals.
    [0040] Examples of suitable R 3 radicals include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and phenyl. Examples of preferred radicals include n-propyl, n-butyl, n-pentyl and particular preference is given to an n-propyl radical.
    [0041] The - (- CH2-CH (R 3 ) -O-) i- block is therefore a block consisting of alkylene oxide units having at least 4 carbon atoms, preferably at least 5 atoms of carbon and / or glycidyl ethers with an ether group of at least 2, preferably at least 3 carbon atoms. Preferably, the R 3 radicals are the specified hydrocarbon radicals; the building blocks of the second terminal block are particularly preferably alkylene oxide units which comprise at least 5 carbon atoms, such as pentene oxide units or higher alkylene oxide units.
    [0042] The number of alkylene oxide units I is a number between 5 to 25, preferably 6 to 20, particularly preferably 8 to 18,
    Petition 870190032059, of 03/03/2019, p. 17/53
    10/28 very particularly preferably 10 to 15, for example, about 12. [0043] In the monomers of the formula (I), a mono-ethylene group, terminal, is therefore attached to a polyoxyalkylene group with block structure and , specifically first, to a hydrophilic block which is composed of at least units of butene oxide, preferably at least units of pentene oxide or units of higher alkylene oxides, such as, for example, dodecene oxide. The second block has a terminal OH group. Therefore, unlike monomers (a) that are hydrophobically associated according to formula (II) and (III), the terminal group is not etherified with a hydrocarbon radical for the hydrophobic association, but the terminal block itself - (- CH2-CH (R 3 ) -O-) i with the radicals R 3 is responsible for the hydrophobic association of the copolymers prepared using the monomers (a).
    [0044] The monomers (a) according to formula (II) are preferably composed of the general formula H2C = CH-O - (- CH2-CH2-O-) kR 2 , where k is a number between 10 and 40 and R 2 is a tristyrylphenyl radical.
    [0045] In the monomers (a) according to formula (III), R 1 is preferably methyl, k is a number between 6 and 30 and R 2 is a C12alkyl radical or a tristyrylphenyl radical.
    [0046] The three representative monomers (I), (II) and (III) can be involved in the synthesis of the copolymer in any desired fractions.
    [0047] For the person skilled in the field of polyalkylene oxide block copolymers, it is clear that the transition between the two blocks can be abrupt or continuous depending on the type of preparation. In the case of a continuous transition, between two blocks there is also a transition zone comprising monomers of the two blocks. If the block boundary is fixed in the middle of the transition zone, correspondingly the first block - (- CH2CH2O-) k may also contain small quantities of units -CH2-CH (R 3 ) O-, and 0 second block - (- CH2 -CH (R 3 ) -O-) i- may have small quantities of -CH2-CH2-O- units, although these units are not randomly distributed over the block, but are arranged in said transition zone.
    Petition 870190032059, of 03/03/2019, p. 18/53
    11/28 [0048] According to the invention, the monomers (a) are soluble in water. As a rule, the solubility of the monomers (a) in water at room temperature should be at least 10 g / l, preferably at least 50 g / l and particularly preferably at least 100 g / l.
    [0049] The amount of monomers (a) which are associated hydrophobically mono-ethylenically unsaturated is governed by the particular intended use of the copolymer according to the invention and is generally 0.1 to 20% by weight, based on the total amount of all monomers in the copolymer. Preferably, the amount is 0.5 to 15% by weight. [0050] Hydrophilic monomers (b) [0051] In addition to the monomers (a), the hydrophobically associated copolymer according to the invention comprises at least one mono-ethylenically unsaturated hydrophilic monomer (b) different from them. It is also possible, of course, to use mixtures of two or more different hydrophilic monomers (b).
    [0052] In addition to an ethylenically unsaturated group, hydrophilic monomers (b) comprise one or more hydrophilic groups. Hydrophilic groups are, in particular, functional groups that comprise O and / or N atoms. They may additionally comprise in particular S and / or P atoms as hetero atoms.
    [0053] The monomers (b) are particularly preferably miscible in water in any desired proportion, although it is sufficient to realize the invention that the hydrophobically associated copolymer according to the invention has the water solubility mentioned at the beginning. Generally, the solubility of the monomers (b) in water at room temperature should be at least 100 g / l, preferably at least 200 g / l and particularly preferably at least 500 g / l.
    Examples of suitable functional groups include carbonyl groups> C = O, ether groups -O-, in particular polyethylene oxide groups (CH2-CH2-O-) n-, where n is preferably a number between 1 to 200 , hydroxyl groups -OH, ester groups -C (O) O-, primary, secondary or tertiary amino groups, ammonia groups, amide groups -C (O) -NH-, carboxamide groups
    Petition 870190032059, of 03/03/2019, p. 19/53
    12/28
    C (0) -NH2 or acid groups such as carboxyl groups -COOH, sulfonic acid groups -SO3H, phosphonic acid groups -PO3H2 or phosphoric acid groups -OP (OH) 3.
    [0055] Examples of preferred functional groups include hydroxyl groups -OH, carboxyl groups -COOH, sulfonic acid groups -SO3H, carboxamide groups -C (O) -NH2, amide groups -C (O) -NH- and oxide groups of polyethylene - (CH2-CH2-O-) nH, where n is preferably a number between 1 to 200.
    [0056] The functional groups can be coupled directly to the ethylene group or otherwise be linked to the ethylene group through one or more hydrocarbon bonding groups.
    [0057] Hydrophilic monomers (b) are preferably monomers comprising acidic groups, where the acidic groups according to the invention are at least one group selected from the group of -COOH, SO3H and -PO3H2. Preference is also given to monomers of the general formula H2C = C (R 7 ) R 8 , where R 7 is H or methyl and R 8 is a hydrophilic group or a group comprising one or more hydrophilic groups.
    [0058] R 8 groups are groups that comprise heteroatoms in an amount such that the solubility in water defined at the beginning is obtained.
    [0059] Examples of suitable monomers (b) include monomers comprising acidic groups, for example, monomers comprising -COOH groups, such as acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic or fumaric acid, monomers comprising sulfonic acid groups, such as vinyl sulfonic acid, allylsulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, 2acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido acid methylbutanesulfonic or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, or monomers comprising phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonic acids or (meth) acryloylalkylphosphonic acids.
    Petition 870190032059, of 03/03/2019, p. 20/53
    13/28 [0060] Also to be mentioned are acrylamide and methacrylamide and also their derivatives, such as, for example, Nmethyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylacrylamide, derivatives of N- vinyl, such as N-vinylformamide, N-vinylacetamide, Nvinylpyrrolidone or N-vinylcaprolactam, and vinyl esters, such as vinyl format or vinyl acetate. N-Vinyl derivatives can be hydrolyzed after polymerization in to vinylamine units, vinyl esters to vinyl alcohol units.
    [0061] Additional examples include monomers comprising hydroxyl groups and / or ether groups, such as, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether, hydroxyvinyl ether butyl or compounds of the formula H 2 C = C (R 1 ) -COO - (- CH2-CH (R 9 ) -O-) bR 10 (IVa) or H2C = C (R 1 ) -O - (- CH2CH ( R 9 ) -O-) bR 10 (IVb), where R 1 is as defined above and b is a number between 2 to 200, preferably 2 to 100. The radicals R 9 are, independently of one another, H, methyl or ethyl , preferably H or methyl, with the proviso that at least 50 mol% of the R 9 radicals are H. Preferably, at least 75 mol% of the R 9 radicals are H, particularly preferably at least 90 mol% and very particularly preferably, exclusively Η. The radical R 10 H, methyl or ethyl, preferably H or methyl. the individual alkylene oxide units can be arranged randomly or in block form. In the case of a block copolymer, the transition between the blocks can be abrupt or gradual.
    [0062] Suitable (b) hydrophilic monomers are also monomers having ammonia groups, in particular ammonia derivatives of N - ((o-aminoalkyl) (meth) acrylamides or esters (o-aminoalkyl (meth) acrylics.
    [0063] In particular, monomers (b) having ammonia groups can be composed of the general formulas H 2 C = C (R 7 ) -CONR 13 -R 11 NR 12 3 + X- (Va) and / or H2C = C (R 7 ) -COO-R 11 -NR 12 3 + X '(Vb), where R 7 has the meaning given above, therefore it is H or methyl, R 11 is preferably a linear C 1 -C 4 alkylene group and R 13 is H or a C 1 -C 4 alkyl group, preferably H or methyl. The radicals R 12 are, independently of each other, C1-C4
    Petition 870190032059, of 03/03/2019, p. 21/53
    14/28 alkyl, preferably methyl or a group of the general formula -R 14 -SO3H, where R 14 is preferably a linear C 1 -C 4 alkylene group or a phenyl group, with the proviso that not more than one of the substituents of R 12 is a substituent that has sulfonic acid groups. The three substituents R 12 are particularly preferably methyl groups, that is, the monomer has a -N (CH3) 3 + group . X 'in the above formula is a monovalent anion, for example Cl'. X 'can also, of course, be a corresponding fraction of a polyvalent anion, although this is not preferred. Examples of suitable monomers (b) of the general formulas (Va) or (Vb) include salts of 3-trimethylammon propylacrylamides or 2-trimethylammon ethyl (meth) acrylates, for example, the corresponding chlorides, such as 3-trimethylammon propylacrylamide chloride (DIMAPAQUAT) and 2-trimethylammonium chloride ethyl (meth) acrylate (MADAME-QUAT).
    [0064] Therefore, monomer (b) can also be a neutral monomer (b1) and here, in particular, a monomer selected from the group of methacrylamide, A / -methyl (meth) acrylamide, A /, A / -dimethyl ( met) acrylamide, Nmethylol (meth) acrylamide, ΛΖ-vinylformamide or A / -vinyl-2-pyrrolidone and the monomer (b2) is at least one selected from the group of (meth) acrylic acid, vinylsulfonic acid, allylsulfonic acid, 2 -acrylamido-2methylpropanesulfonic acid (AMPS), 2-methacrylamido-2methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido3-methylbutanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or vinylphosphonic acid. In addition, the copolymer can also comprise at least one cationic monomer (b3) that has ammonia groups, where the cationic monomer is a salt of 3-trimethylammon propyl (meth) acrylamides and 2trimethylammon ethyl (meth) acrylates.
    [0065] The hydrophilic monomers mentioned above can, of course, be used not only in the form of the acid or base described, but also in the form of corresponding salts. It is also possible to convert acidic or basic groups to the corresponding salts after polymer formation.
    [0066] As already explained, in a preferred embodiment of the invention
    Petition 870190032059, of 03/03/2019, p. 22/53
    15/28, the copolymer according to the invention comprises at least one monomer (b) comprising acidic groups. These are monomers that preferably comprise at least one group selected from the group of -COOH, -SO3H or -PO3H2, with particular preference being given to monomers comprising -COOH groups and / or -SO3H groups. It is also possible that the acid groups are present partially or completely in the form of the corresponding salts.
    [0067] Preferably, at least one of the monomers (b) is a monomer selected from the group of (meth) acrylic acid, vinyl sulfonic acid, allylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid (AMPS), particularly preferably acrylic acid and / or AMPS or its salts.
    [0068] Generally, the monomer component (a) should be present in the polymer in amounts between 0.1 to 20.0% by weight, preferably between 0.1 to 5% by weight, the monomer component (b) should be present in amounts between 25.0 to 99.9% by weight and the component (c) must be present in amounts between 0.1 to 5.0% by weight, in each case based on the total amount of all components in the copolymer. The precise amount is determined by the type and the desired intended use of the copolymers that are associated hydrophobically and is established according to the person skilled in the art.
    [0069] In general, it is considered preferred that the copolymer is a copolymer (A1) comprising at least two different hydrophilic monomers (b) and these are at least • a neutral hydrophilic monomer (b1), preferably acrylamide and • hair at least one anionic hydrophilic monomer (b2) comprising at least one acid group selected from the group of -COOH, -SO3H or -PO3H2, where the amount of the monomers (a) is from 0.1 to 12% by weight and that all the monomers (b) together are 70 to 99.5% by weight, with respect to the amount of all monomers in the copolymer.
    [0070] Additionally, the copolymer is considered to be preferred
    Petition 870190032059, of 03/03/2019, p. 23/53
    16/28 if it is a copolymer (A2) comprising at least two different hydrophilic monomers (b) and these have at least • 5 to 50% by weight of at least one neutral hydrophilic monomer (b1), and • 25 to 94 , 9% by weight of at least one anionic monomer (b2) comprising groups of sulfonic acid, in which the amount of monomers (a) is 0.1 to 12% by weight and all monomers (b) together have 70 to 99.9% by weight, with respect to the amount of all monomers in the copolymer.
    [0071] Component (c) [0072] The copolymers according to the invention must be prepared in the presence of at least one non-polymerizable surfactant compound which is preferably at least one non-ionic surfactant. However, anionic and cationic surfactants are also suitable as long as they do not participate in the polymerization reaction.
    [0073] The non-ionic surfactant is preferably an ethoxylated long chain aliphatic alcohol, which can optionally comprise aromatic fractions.
    [0074] For example, mention may be made of: C12C14 fatty alcohol ethoxylates, CieCie fatty alcohol ethoxylates, C13-OXO alcohol ethoxylates, Cw-oxo alcohol ethoxylates, C13C15-OXO fatty alcohol ethoxylates, Cio alcohol ethoxylates -Guerbet and alkylphenol ethoxylates.
    [0075] a suitable surfactant is, in particular, at least representative that is selected from the series of ethoxylated alkylphenols, ISO-C13 saturated ethoxylated alcohols and / or C10-Guerbet ethoxylated alcohols.
    [0076] Monomers (d) [0077] In special cases, in addition to monomers (a) and (b), the copolymers according to the invention can also optionally comprise monomers (d) which have two or more, preferably two , ethylenically unsaturated groups. As a result, a certain crosslinking of the copolymer can be obtained as long as it has no undesirable negative effects on the intended use of the copolymer. An excessively high degree
    Petition 870190032059, of 03/03/2019, p. 24/53
    17/28 crosslinking, however, should be avoided in any case; in particular, the required solubility of the copolymer in water must not be impaired. Although a discrete crosslinking can be useful in individual chaos, it is governed by the particular application of the copolymer and the person skilled in the art will make the appropriate selection.
    [0078] Examples of suitable (d) monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,3-butylene di (meth) acrylate, di (met) ) neopentyl glycol acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate or oligoethylene glycol di (meth) acrylates such as, for example, bis (met) ) polyethylene glycol acrylate, N, N'methylenobis (meth) acrylamide, ethylene glycol divinyl ether, triethylene glycol divinyl ether, trialylamine, methylammonium trialylamine chloride, tetralylammonium chloride or tr (2-hydroxy) isocyanurate tri (meth) acrylate.
    [0079] Monomer (d) is particularly preferably selected from the group of trialylamine, trialylamine methylammonium chloride, tetralylammonium chloride, N, N'-methylenebis (meth) acrylamide, triethylene glycol bis (meth) acrylate, triethylene glycol bisacrylate , polyethylene glycol bismethacrylate (400) and polyethylene glycol bisacrylate (400).
    [0080] However, if present in any way, the crosslinking monomers (d) are used only in small quantities. Generally, the amount of monomers (d) should not exceed 1% by weight with respect to the amount of all monomers used. Preferably, no more than 0.5% by weight and, particularly preferably, no more than 0.1% by weight should be used. The type and quantity of the crosslinker are established by the person skilled in the art depending on the desired application of the copolymer.
    [0081] Preparation of copolymers that combine hydrophobically, soluble in water:
    [0082] The copolymers according to the invention can be prepared by methods known in principle to the person skilled in the art by polymerizing the free radicals of the monomers (a), (b) and, opcio
    Petition 870190032059, of 03/03/2019, p. 25/53
    18/28 finally (d), for example, by solution polymerization or aqueous phase gel polymerization, although each of the possible polymerization variants must be carried out in the presence of at least one component (c).
    [0083] The synthesis of the monomers (a) of the formula (I) used according to the invention is particularly preferably prepared according to the preparation process described above, by the alkoxylation of alcohols (III), optionally followed by etherification.
    [0084] In a preferred embodiment, the preparation is carried out by means of gel polymerization in aqueous phase. For gel polymerization, initially a mixture of monomers (a), (b) and, optionally (d), initiators, the surfactant (c) and other auxiliaries is prepared with water. The acid monomers can be completely or partially neutralized before polymerization. Preference is given to a pH of about 4 to about 9. The concentration of all components, except for solvents, is generally about 20 to 60% by weight, preferably about 30 to 50% by weight.
    [0085] It is recommended to subject at least one monomer (a) that is hydrophobically associated and at least one monomer (b) hydrophilic to a polymerization in aqueous solution in the presence of at least one surfactant component (c), where preferably, the component of monomer (a) is introduced initially and then, in succession, the monomer component (b) and component (c) are added. In addition, a mixture comprising the monomer component (b) and the component (c) can optionally be added to the monomer component (a). However, it is also contemplated by the invention that component (c) is added to the monomer component (a) and then the monomer component (b) is added to the resulting mixture. Polymerization should be carried out in particular at pH in the range of 5.0 to 7.5 and, preferably, at pH of 6.0.
    [0086] One aspect that is decisive and, therefore, essential to the invention, is the addition of the surfactant (c) to the reaction solution before the start of the powder
    Petition 870190032059, of 03/03/2019, p. 26/53
    19/28 limerization, where the order in which monomers a) and b) and also component c) are added can - as described above - be freely chosen to a large extent.
    [0087] The mixture is polymerized photochemically and / or thermally, preferably at -5 9 C to 50 9 C. If thermal polymerization is carried out, preference is given to the use of polymerization initiators that start even at a comparatively low temperature, such such as, for example, redox initiators. Thermal polymerization can be carried out even at room temperature or by heating the mixture, preferably up to temperatures of no more than 50 9 C. Photochemical polymerization is generally carried out at temperatures between -5 to 10 9 C. Photochemical and thermal polymerization they can be advantageously combined with each other by adding to the mixture of initiators for thermal polymerization and also for photochemistry. Polymerization is initiated, in this case, initially by photochemical means at low temperatures, preferably -5 to +10 9 C. As a result of the reaction heat that is released, the mixture heats up and as a result of this thermal polymerization is additionally initiated. Through this combination, it is possible to achieve a conversion of more than 99%.
    [0088] Gel polymerization generally occurs without stirring. It can occur in a batch form by irradiating and / or heating the mixture in a suitable vessel with a thick layer between 2 to 20 cm. Polymerization produces a solid gel. Polymerization can also be carried out continuously. For this, the polymerization equipment that is used has a conveyor belt to receive the mixture to be polymerized. The treadmill is equipped with devices for heating or irradiating UV radiation. Here, the mixture is poured using a suitable device at one end of the mat, the mixture is polymerized during transport towards the mat and the solid gel can be removed at the other end of the mat.
    [0089] After polymerization, the resulting gel is preferably crushed and dried. Drying should preferably take place at temperatures below 100 C. 9 To prevent adhesion, a suitable separating agent
    Petition 870190032059, of 03/03/2019, p. 27/53
    20/28 can be used for this step. This provides the copolymer that is hydrophobically associated in the form of granules or powder.
    [0090] Additional details on carrying out polymerization in gel are described, for example, in DE 10 2004 032 304 A1, sections [0037] to [0041], [0091] The copolymers according to the invention preferably have a molecular weight numerical mean Mn between 50,000 to 25,000,000 g / mol.
    [0092] As the polymer powder or granules are generally used in the form of an aqueous solution during application at the site of use, the polymer must be dissolved in water at the site. This can lead to unwanted agglutination with the described high molecular weight polymers. In order to avoid this, an auxiliary that accelerates and / or improves the dissolution of the dry polymer in water can be added to the polymers according to the invention during the synthesis. This helper can be, for example, urea.
    [0093] Use of copolymers that combine hydrophobically, soluble in water:
    the hydrophobically associated copolymers according to the invention can be used for thickening aqueous phases. [0094] The selection of the type and quantity of monomers (a) and (b) and, optionally, (c) and / or (d), allows the properties of the copolymers to be adapted to the particular technical needs.
    [0095] The concentration of use is established by the person skilled in the art depending on the type of aqueous phase to be thickened and also on the type of copolymer. As a rule, the concentration of the copolymer is 0.05 to 5% by weight, with respect to the aqueous phase, preferably 0.1 to 2% by weight and particularly preferably 0.15 to 1% by weight.
    [0096] Copolymers can be used alone or in combination with other thickening compounds, for example, other thickening polymers. In addition, they can be formulated, for example, together with surfactants to form micelles and, together with the micelles, copolymers that are associated hydrophobically can form a network of sp
    Petition 870190032059, of 03/03/2019, p. 28/53
    21/28 three-dimensional weighting.
    [0097] 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.
    [0098] The aqueous phases to be thickened may preferably be chemical construction systems such as, for example, construction systems based on hydraulic binders such as cement, lime, plaster and anhydride and water-based coating and paint systems, formulations for the recovery of mineral oil such as, for example, drilling fluids, formulations for acidification or breakage or formulations for advanced oil recovery.
    [0099] In this context, the present invention contemplates as a preferred use of copolymers its use as a thickener, rheological additive for water-based systems, preferably for solutions and, in particular, in the development, exploration and completion of underground deposits of mineral oil and natural gas deposits. If the copolymer according to the invention is used for advanced oil recovery, an aqueous formulation of said copolymers in a concentration between 0.01 to 1% by weight is preferably injected into a mineral oil tank through at least one well injection and the crude oil is removed from the tank through at least one production well.
    [00100] According to the invention, however, the copolymer can also be used as a rheological additive for aqueous construction systems comprising hydraulic binder systems, in which case the copolymer should preferably be in the form of granules or powder . [00101] The aqueous phases to be thickened can, however, also be, for example, liquid detergent and cleaning formulations, such as, for example, detergents, washing aids such as stain removers, fabric softeners, cosmetic formulations, pharmaceutical formulations, food, sliding coating, formulations for textile production, textile printing pastes, printing inks, textile printing pastes, inks, pigment suspensions,
    Petition 870190032059, of 03/03/2019, p. 29/53
    22/28 aqueous formulations for the generation of foam, de-icing mixtures, for example, for aircraft and formulations in general for the construction industry.
    [00102] The following examples are intended to illustrate the invention in more detail.
    [00103] Examples:
    [00104] 1. Preparation process
    1.1 Preparation Example 1 (comparison): without the addition of the surfactant during polymerization
    242.5 g of a 50% Na AMPS solution (AMPS 2405, Lubrizol) was initially introduced into a 3 I vessel equipped with a stirrer and a thermometer. 295.8 g of water was added with stirring. Then, in succession, 1.2 g of Surfynol DF 58 and 0.4 g of Baysilone EN (Bayer) were added as defoamers. After adding 4.6 g of Pluriol A1190V + 12PeO (product developed by BASF consisting of hydroxybutyl vinyl ether with 25 units of ethylene oxide and 12 units of pentene oxide), 228.8 g of a strong acrylamide solution 50 % (Cytec) have been added. After adding 2.4 g of a strong solution of Versenex 5% to destabilize the acrylamide solution, the pH was adjusted to 6.0 using a 20% NaOH solution and / or a strong 20% H2SO4 solution. During inertization by blasting for 30 minutes with nitrogen, the solution was cooled to approximately 20 ° C. The solution was transferred to a plastic container with the dimensions (l * d * a) 15 cm * 10 cm * 20 cm and, in succession, 16.0 g (200 ppm) of 2,2'- dihydrochloride azobis (2-amidinopropane) 10% strong, 0.5 g (10 ppm) of 1% strong bisulfite solution, 8 g (6 ppm) of a strong solution of 0.1% tertbutyl hydroperoxide and 4.0 g ( 5 ppm) of a strong 1% iron (II) sulfate solution was added.
    [00105] Polymerization was initiated by irradiation with UV light (two Phillips tubes; Cleo performance 40 W). After about 2 to 3 h, the cut-resistant gel was removed from the plastic container and cut into cubes of gel measuring about 5 cm * 5 cm * 5 cm using scissors. Before the
    Petition 870190032059, of 03/03/2019, p. 30/53
    23/28 gel cubes were crushed using a conventional meat grinder, they were coated with the separation agent Sitren 595 (polydimethylsiloxane emulsion; Goldschmidt). The separating agent is a polydimethylsiloxane emulsion, which was diluted 1:20 with water.
    [00106] The resulting gel beads were randomly scattered on a sieve drying and dried to a constant weight in a convection drying oven 9 to about 90-120 C in vacuo. About 500 g of white, rigid granules were obtained and converted to a pulverized state with the aid of a centrifugal mill.
    1.2 Preparation of Examples 2-4 (according to the invention): with the addition of a surfactant during gel polymerization [00107] In addition to the monomer solution as described in Comparative Example 2, such as the surfactant, Lutensol TO 15 ( BASF, C13-oxo alcohol ethoxylate + 15 units of ethylene oxide) was dissolved in the following amounts in the monomer solution before polymerization:
    Preparation Example 2: 1% Lutensol TO 15 corresponds to 2.4 g
    Preparation Example 3: 2% Lutensol TO 15 corresponds to 4.8 g
    Preparation Example 4: 3% Lutensol TO 15 correspond to 7.2 g
    1.3 Preparation Examples 5-10 (according to the invention) [00108] Starting with Preparation Example 3, the following polymers were prepared with surfactants alternative to Lutensol TO 15 (viscosity measurement as described in Application Example 1):
    Surfactant Viscosity [mPas] Preparation Example 3 Lutensol TO 15 2% (alcohol ethoxylate C13oxo +15 EO) 230 Preparation Example 5 Lutensol AP 10 2% (alkylphenol + 10 EO) 390 Preparation Example 6 Lutensol XL100 2% (C10-Guerbet alcohol +10 EO) 140 Preparation Example 7 Lutensol XP100 2% (C10-Guerbet alcohol +10 EO) 80 Preparation Example 8 2% sodium dodecyl sulfonate (SDS) 100 Preparation Example 9 dodecyltrimethylammonium chloride 2% 150
    Petition 870190032059, of 03/03/2019, p. 31/53
    24/28
    Preparation Example 10 Lutensol TO 10 2% (C13oxo alcohol ethoxylate + 10 EO) 270
    [00109] As can be seen from the data, it is possible to use not only Lutensol TO 15, but also other non-ionic surfactants and also anionic and cationic surfactants in the synthesis of copolymers according to the invention.
    1.4 Preparation Example 11 (according to the invention) [00110] Analogously to Preparation Example 3, a copolymer was prepared with a hydrophobically associated, water soluble monomer alternative to Pluriol A1190V + 12PeO. This monomer consists of 7 EO ethoxylated C12 alcohol which was then reacted with methacrylic anhydride (Genagen LA070MA from Clariant). The Genagen mass used corresponds to that of Pluriol A1190V + 12PeO in Preparation Example 3.
    [00111] The viscosity measurement as described in Application Example 1 gave a value of 780 mPas.
    [00112] This preparation example shows that different monomers that combine hydrophobically soluble in water can be used.
    1.5 Preparation Example 12 (according to the invention) [00113] Analogously to Preparation example 3, a mixed ionic copolymer was prepared. This copolymer comprises, in addition to AMPS, acrylamide and Pluriol A1190V + 12PeO, the cationic monomer 3-trimethylammonium propylmethacrylamide (DIMAPAQUAT). The molar ratio of the monomers is AMPS: acrylamide: DIMAPAQUAT: Pluriol A1190V + 12PeO = 30: 37: 32: 1.
    [00114] The viscosity measurement, as described in Application Example 1, gave a value of 56 mPas.
    1.6 Preparation Example 13 (according to the invention) [00115] Similarly to Preparation example 3, a copolymer that was prepared comprises, instead of 4.6 g of Pluriol A1190V + 12PeO, the same molar amount of Pluriol A1190V + 16PeO (product developed by BASF consisting of hydroxybutyl vinyl ether with 25 units of ethylene oxide and 16 units of pentene oxide).
    [00116] The measure of viscosity, as described in the Example of
    Petition 870190032059, of 03/03/2019, p. 32/53
    25/28
    Application 1, gave a value of 77 mPas.
    1.7 Preparation Example 14 (according to the invention) [00117] Similarly to Preparation Example 3, a copolymer that has been prepared comprises the sodium salt of acrylic acid instead of AMPS of Na. The weight% of the monomers was 82% Na acrylate, 70% acrylamide and 2% Pluriol A1190V + 12PeO, 4.8 g Lutensol AP 10 (BASF) were added as a surfactant in the solid content of the polymerized gels that had 19.5%.
    [00118] The viscosity measurement, as described in Application Example 1, gave a value of 49 mPas.
    1.8 Preparation Example 15 (according to the invention) [00119] Analogously to Preparation Example 3, a copolymer was prepared, in which the AMPS of Na was partially replaced by the sodium salt of acrylic acid. The% by weight of the monomers had 28% AMPS, 20% Na acrylate, 50% acrylamide and 2% Pluriol A1190V + 12PeO,
    4.8 g of Lutensol TO 15 (BASF) was added as a surfactant. The viscosity measurement, as described in Application Example 1, gave a value of 40 mPas.
    1.9 Preparation Example 16 (according to the invention) [00120] This example represents a polymerization procedure as an alternative to preparation example 5. 121.2 g of Na AMPS (50% solution) were supplied in a plastic bucket containing a magnetic stirrer, a pH meter and a thermometer and then 155 g of distilled water, 0.6 g of Surfynol, 0.2 g of Bisylone, 2.3 g of Pluriol A1190V + 12PeO, 114.4 g of acrylamide (50% solution), 1.2 g of Versenex (5% solution) and 2.4 g of Lutensol AP10 were added successively.
    [00121] After adjusting the pH to 6 by using 20% and 2%, respectively, of a solution of sulfonic acid and the addition of water (total amount of water minus the amount of water added, less the amount of acid used ), the monomer solution was brought to the starting temperature of 20 9 C. Then, the solution was transferred to a flask
    Petition 870190032059, of 03/03/2019, p. 33/53
    26/28 thermal, and a thermal sensor to document the temperature was installed and the solution was bubbled with nitrogen for 30 minutes. At the end of the nitrogen addition, the online temperature measurement was started, the starting temperature was controlled and, if necessary, readjusted and then, 1.6 ml of a 10% V50 solution, 0.2 ml of t solution -BHo and 0.24 ml of a 1% sodium sulfite solution were added. When the monomer solution started to thicken, nitrogen was removed from the monomer solution. After the temperature of the gel block has reached its maximum, the thermal sensor was removed and the thermos flask was placed in a drying chamber for 2 hours at 80 C. 9
    [00122] After the gel block was removed from the thermos and the surface was cut to a depth of 0.5 to 1 cm using scissors and the cut was detached. The remainder of the gel block was divided in two and Comperland COD (coconut oil acid diethanolamide) was applied as a release agent; then the gel blocks were crushed using a meat grinder.
    [00123] The gel granules as manufactured 9 was dried at 55 C for 2 hours in a fluidized bed dryer. The resulting white-colored firm granules were finally made into a powder using a centrifugal mill.
    ΊΟ Preparation Example 17 (according to the invention) [00124] The preparation was analogous to Preparation Example 1.9, but using 6 g of Pluriol A1190V + 12PeO and 6 g of Lutensol AP 10.
    2. Application Examples
    2Ί [00125] The polymers of Preparation Examples 1-4 were dissolved in synthetic seawater according to DIN 50900 (salt content of 35 g / l) such that a polymer concentration of 4000 ppm was obtained. The viscosity of these solutions was measured using a Haake rheometer with a double-gap geometry at 7 s 1 and 60 9 C ·
    Polymer Viscosity [mPa * s] Preparation Example 1 24
    Petition 870190032059, of 03/03/2019, p. 34/53
    27/28
    Preparation Example 2 360 Preparation Example 3 230 Preparation Example 4 80
    [00126] It is clearly seen that, by adding Lutensol TO 15 during polymerization, it is possible to significantly increase the viscosity of the polymers. In addition, the added amount of surfactant has a marked influence on viscosity.
    Z2 [00127] In order to show that the polymers according to the invention are not only a physical mixture of the polymer of Preparation Example 1 and the surfactant, but that the structure of the polymer is decisively influenced during the polymerization reaction, the viscosities of the mixtures of the polymer of Preparation Example 1 with the surfactant Lutensol TO 15 were also measured:
    Viscosity [mPas] Viscosity of the mixture of Preparation Example 1 with the corresponding amount of Lutensol TO 15 [mPas] Preparation Example 2 360 25 Preparation Example 3 230 26 Preparation Example 4 80 20
    [00128] As can be seen from these measurements, a subsequent addition of the surfactant had no positive influence on the viscosity of the polymer.
    [00129] For a more detailed investigation of the mechanism of action, the polymer of Preparation Example 3 was refluxed with toluene in the Soxhlet over a period of 48 h.
    [00130] Here, 90% of the Lutensol TO 15 originally present was extracted from the copolymer. However, the high viscosity of the polymer was maintained even after virtually complete extraction of the surfactant.
    [00131] This indicates that the surfactant is not incorporated and / or grafted covalently into the polymer, but that the addition of the surfactant has a positive influence on the synthesis of the polymer structure. This can be described in such a way that the surfactant forms mixed micelles with the hydrophobically associated monomer.
    2Ό g of the respective copolymer of Preparation Examples 1-4 was stirred
    Petition 870190032059, of 03/03/2019, p. 35/53
    28/28 in 249 g of synthetic seawater according to DIN 50900 (salt content of 35 g / l) for 24 h until complete dissolution. The solution was then filtered through a 200 µm mesh sieve and the volume of the residue remaining on the sieve was measured. The value obtained corresponds to the gel fraction.
    Polymer Gel fraction [ml] Preparation Example 1 (comparison) 45 Preparation Example 2 (invention) 9 Preparation Example 3 (invention) 5 Preparation Example 4 (invention) <1
    [00132] As can be seen from the data, the gel fraction is significantly reduced as a result of the addition of the surfactant. With the increasing amount of the surfactant, the gel fraction can be reduced below the detection limit.
    权利要求:
    Claims (22)
    [1]
    1. Hydrophobically associated, water-soluble copolymer, consisting essentially of (a) at least one mono-ethylenically unsaturated, water-soluble monomer active on the surface (a), and (b) at least two different hydrophilic monomers (b) selected from the group consisting of • a neutral hydrophilic monomer (b1), and • at least one anionic hydrophilic monomer (b2) comprising at least one acid group selected from the group of -COOH, -SO3H or -PO3H2 and / or their salts, in which the amount of monomers (a) is 0.1 to 5% by weight and all monomers (b) together have 70 to 99.5% by weight, with respect to the amount of all monomers in the copolymer, characterized by the fact that the monomer (a) is at least one compound of the general formula (I):
    H2C = C (R 1 ) -R 4 -O - (- CH2-CH2-O-) k - (- CH 2 -CH (R 3 ) -O-) iH (I), where the unit - (- CH2-CH2-O-) ke - (- CH2-CH (R 3 ) -O-) i are arranged in a block structure in the order shown in formula (I) and the radicals and indices have the following meaning:
    k: a number between 6 to 150,
    I: a number between 5 to 25,
    R 1 : H or methyl,
    R 2 : a straight or branched chain aliphatic and / or aromatic hydrocarbon radical having 8 to 40 carbon atoms,
    R 3 : independently of each other, a hydrocarbon radical that has at least 2 carbon atoms,
    R 4 : a single bond or a divalent bond group selected from the group of - (CnH2n) - [R 4a ], -O- (Cn H2 ·) - [R 4b ] and -C (O) -O- (Cn H 2 ) [R 4c ] where n, n 'en ”is, in each case, a natural number between 1 and 6, and where during its synthesis, before the start of the polymerization reaction, at least one surfactant compound additional, but not polymerizable, was used as a component (c), where the copolymer is
    Petition 870190113558, of 11/06/2019, p. 9/12
    [2]
    2/4 a water-soluble hydrophobically associated copolymer.
    2. Copolymer according to claim 1, characterized by the fact that component (c) comprises a nonionic surfactant which is C12-C14 fatty alcohol ethoxylate.
    [3]
    3. Copolymer according to claim 1, characterized in that the monomer component (a) is present in an amount of between 0.1 to 5.0% by weight, the monomer component (b) is present in an amount of between 70.0 to 99.9% by weight and the component (c) is present in an amount of between 0.1 to 5.0% by weight, in each case based on the total amount of all components in the copolymer.
    [4]
    4. Copolymer according to claim 1, characterized by the fact that R 3 is a hydrocarbon radical having at least 3 carbon atoms.
    [5]
    5. Copolymer according to claim 1, characterized by the fact that R 1 is H and R 4 is a group selected from -CH2- or -O-CH2CH2-CH2-CH2-.
    [6]
    6. Copolymer according to claim 1, characterized by the fact that at least one of the monomers (b) is a monomer comprising at least one member selected from the group consisting of an acid group and a salt of an acid group.
    [7]
    Copolymer according to claim 6, characterized in that the acid group is selected from the group consisting of -COOH, -SO3H and -PO3H2 and in which the salt of the acid group is a salt of a member selected from the group consisting of -COOH, -SO3H and -PO3H2.
    [8]
    8. Copolymer according to claim 1, characterized by the fact that the neutral monomer (b1) is a monomer selected from the group of methacrylamide, A / -methyl (meth) acrylamide, N, Ndimethyl (meth) acrylamide, A / -methylol (meth) acrylamide, ΛΖ-vinylformamide or ΛΖ-vinyl2-pyrrolidone and the monomer (b2) is at least one selected from the group consisting of (meth) acrylic acid, vinylsulfonic acid, allylsulfonic acid, acid
    2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2 acid Petition 870190113558, from 11/06/2019, p. 12/10
    3/4 methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido3-methylbutanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid and vinylphosphonic acid.
    [9]
    9. Copolymer according to claim 1, characterized by the fact that the copolymer additionally comprises at least one cationic monomer (b3) having ammonia groups.
    [10]
    10. Copolymer according to claim 9, characterized by the fact that the cationic monomer is a salt of 3-trimethylammon propyl (meth) acrylamide or 2-trimethylammon ethyl (meth) acrylate.
    [11]
    11. Copolymer according to claim 1, characterized in that the copolymer additionally comprises up to 1% by weight of a crosslinker monomer (d), which comprises at least two ethylenically unsaturated groups, where the monomer (d) is at least one selected from the group of trialylamine, trialylamine methylammonium chloride, tetralylammonium chloride, Ν, Ν'-methylenebisacrylamide, bis (meth) triethylene glycol acrylate, triethylene glycol bisacrylate, polyethylene glycol bismethacrylate (400) and polyethylene glycol bisacrylate (400) 400).
    [12]
    12. Copolymer preparation process, as defined in claim 1, characterized by the fact that at least one monomer (a) that is hydrophobically associated and at least one monomer (b) hydrophilic is subjected to polymerization in aqueous solution in the presence of at least one surfactant component (c).
    [13]
    Process according to claim 12, characterized in that the monomer component (a) is introduced initially and then the monomer component (b) and component (c) are added in succession.
    [14]
    Process according to claim 12, characterized in that a mixture comprising the monomer component (b) and the component (c) is added to the monomer component (a).
    [15]
    Process according to claim 12, characterized in that the component (c) is added to the monomer component (a) and then the monomer component (b) is added to the resulting mixture.
    Petition 870190113558, dated 11/06/2019, p. 12/11
    4/4
    [16]
    16. Process according to claim 12, characterized by the fact that the polymerization is carried out at a pH in the range between 5.0 to 7.5.
    [17]
    17. Process according to claim 12, characterized in that the polymerization is initiated under the effect of light in the wavelength range between 100 to 400 nm.
    [18]
    18. Process according to claim 12, characterized in that the product resulting from the polymerization, in the form of a gel, is crushed and finally dried.
    [19]
    19. Copolymer according to claim 1, characterized by the fact that the monomer (b2) is 2-acrylamido-2-methylpropanesulfonic acid (AMPS).
    [20]
    20. Copolymer according to claim 1, characterized by the fact that component (c) comprises a C13oxo alcohol ethoxylates with 15 ethylene oxide units.
    [21]
    21. Copolymer according to claim 1, characterized in that the neutral hydrophilic monomer (b1) is acrylamide.
    [22]
    22. Copolymer according to claim 1, characterized in that the monomer (a) comprises hydroxybutyl vinyl ether with 25 units of ethylene oxide and 12 units of pentene oxide.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012001710B1|2019-12-24|water-soluble hydrophobically associated copolymer, and the process of preparing the same
    ES2448967T3|2014-03-17|Hydrophobic Association Copolymers
    CN103339160B|2016-08-24|Hydrophobic associated copolymer is as additive purposes in concrete field use
    US9163103B2|2015-10-20|Hydrophobically associating copolymers
    JP6567423B2|2019-08-28|Water-soluble hydrophobic associative copolymer containing novel hydrophobic associative monomer
    US9051503B2|2015-06-09|Use of hydrophobically associated copolymer as an additive in specific oilfield applications
    JP2013501112A5|2014-07-31|Hydrophobic associative water-soluble copolymer
    US20210380868A1|2021-12-09|Method for enhanced oil recovery by means of injection of an aqueous polymer composition
    同族专利:
    公开号 | 公开日
    WO2011015520A1|2011-02-10|
    KR20120055624A|2012-05-31|
    ZA201201587B|2014-05-28|
    CN102471415A|2012-05-23|
    CN106749777A|2017-05-31|
    CA2765923C|2014-05-06|
    BR112012001710A2|2016-04-12|
    JP2013501112A|2013-01-10|
    AU2010280846A1|2012-03-01|
    US9315717B2|2016-04-19|
    EA022997B1|2016-04-29|
    JP5847080B2|2016-01-20|
    ECSP12011708A|2012-10-30|
    US20120129739A1|2012-05-24|
    EG26835A|2014-10-20|
    UA108079C2|2015-03-25|
    MX2012000547A|2012-04-30|
    MY160278A|2017-02-28|
    EP2462173A1|2012-06-13|
    EP2287216A1|2011-02-23|
    AR077805A1|2011-09-21|
    CA2765923A1|2011-02-10|
    BR112012001710A8|2016-10-04|
    EP2462173B1|2015-06-10|
    AU2010280846B2|2014-05-29|
    CN106749777B|2021-10-26|
    EA201200245A1|2012-08-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4921902A|1984-02-02|1990-05-01|The Dow Chemical Company|Hydrophobie associative composition containing a polymer of a water-soluble monomer and an amphiphilic monomer|
    JPH02202579A|1989-01-31|1990-08-10|Nippon Shokubai Kagaku Kogyo Co Ltd|Additive for drilling mud|
    CA2196908A1|1993-06-30|1994-12-31|John M. Wilkerson, Iii|Novel associative monomers and polymers|
    US5874495A|1994-10-03|1999-02-23|Rhodia Inc.|Polymers useful as PH responsive thickeners and monomers therefor|
    FR2761690B1|1997-04-04|1999-05-14|Atochem Elf Sa|NOVEL ASSOCIATIVE POLYMERS AND THEIR PREPARATION PROCESS BY REVERSE MICRO-EMULSION|
    US6169058B1|1997-06-05|2001-01-02|Bj Services Company|Compositions and methods for hydraulic fracturing|
    FR2767327B1|1997-08-14|1999-10-29|Atochem Elf Sa|NOVEL ASSOCIATIVE POLYMERS AND THEIR REVERSE EMULSION PREPARATION PROCESS|
    FR2777011B1|1998-04-01|2000-05-19|Atochem Elf Sa|WATER-TO-WATER, STABLE AND LOW-SIZE EMULSIONS OF PARTICLES, THEIR SYNTHESIS PROCESS AND APPLICATION AS THICKENERS|
    JP4655258B2|1999-07-16|2011-03-23|カルゴンコーポレイション|Water-soluble polymer composition and usage|
    DE10037629A1|2000-08-02|2002-02-14|Skw Bauwerkstoffe Deutschland|Water-soluble or water-swellable sulfo-containing associative thickening copolymers, process for their preparation and their use|
    DE102004032304A1|2004-07-03|2006-02-16|Construction Research & Technology Gmbh|Water-soluble sulfo-containing copolymers, process for their preparation and their use|
    DE102005003569A1|2005-01-25|2006-08-03|Basf Ag|Use of aqueous dispersions for tertiary petroleum production involves using water-soluble polymer in form of dispersion of water-soluble polymer and at least one water-soluble polymer stabilizer|
    DE102006038809A1|2006-08-18|2008-02-21|Basf Construction Polymers Gmbh|Water-soluble and biodegradable polyamide-based copolymers and their use|
    US8752624B2|2010-11-24|2014-06-17|Basf Se|Aqueous formulations of hydrophobically associating copolymers and surfactants and use thereof for mineral oil production|US8362180B2|2009-05-20|2013-01-29|Basf Se|Hydrophobically associating copolymers|
    US8939206B2|2010-11-24|2015-01-27|Basf Se|Process for mineral oil production using hydrophobically associating copolymers|
    RU2013128418A|2010-11-24|2014-12-27|Басф Се|METHOD FOR OIL PRODUCTION USING HYDROPHOBIC-ASSOCIATED COPOLYMERS|
    US9051503B2|2010-11-24|2015-06-09|Basf Se|Use of hydrophobically associated copolymer as an additive in specific oilfield applications|
    EA201390770A1|2010-11-24|2013-12-30|Басф Се|WATER PREPARATIVE FORMS OF HYDROPHOBIC-ASSOCIATED COPOLYMERS AND SURFACE, AND THEIR APPLICATION FOR OIL PRODUCTION|
    US8752624B2|2010-11-24|2014-06-17|Basf Se|Aqueous formulations of hydrophobically associating copolymers and surfactants and use thereof for mineral oil production|
    EA201390769A1|2010-11-24|2013-12-30|Басф Се|METHOD OF OIL PRODUCTION BY USING HYDROPHOBIC-ASSOCIATED POLYMERS|
    EP2457973A1|2010-11-24|2012-05-30|Basf Se|Use of a water-soluble, hydrophobically associating copolymer as additive in special oil field applications|
    CA2826635C|2011-04-08|2018-08-28|Basf Se|Process for producing mineral oil from underground formations|
    US8763698B2|2011-04-08|2014-07-01|Basf Se|Process for producing mineral oil from underground formations|
    WO2012156257A1|2011-05-13|2012-11-22|Basf Se|Acrylate-acrylamide-amps terpolymer as dispersant for agrochemical formulations|
    CN102863594A|2012-09-14|2013-01-09|苏州飞翔新材料研究院有限公司|Polymer latex and application thereof|
    WO2014095608A2|2012-12-17|2014-06-26|Basf Se|Process for preparing a macromonomer|
    RU2655389C2|2012-12-17|2018-05-28|Басф Се|Water-soluble, hydrophobically associating copolymers with hydrophobic-associated monomers of new type|
    CN103409125B|2013-06-19|2015-07-29|西南石油大学|A kind of Water-soluble quadripolymer oil-displacing agent and synthetic method thereof|
    CN104693374A|2013-12-09|2015-06-10|中国石油化工股份有限公司|Functional polymer with surface activity as well as preparation method and application thereof|
    EA031462B9|2013-12-13|2019-05-31|Басф Се|Method for recovering petroleum|
    US20190330108A9|2014-11-20|2019-10-31|Basf Se|Rheology modifier for inorganic suspensions|
    EP3098381A1|2015-05-28|2016-11-30|Basf Se|Formulation comprising at least one hydrophobically associating copolymer, a crosslinking agent and a proppant|
    BR112018003430A2|2015-09-02|2018-09-25|Basf Se|use of a hydrophobic association copolymer, and composition for pelletizing metal-containing ore|
    WO2017121669A1|2016-01-13|2017-07-20|Basf Se|Method for tertiary petroleum recovery by means of a hydrophobically associating polymer|
    CN106084144B|2016-05-31|2018-10-26|四川大学|Based on polyether graft modified hot increasing stick polymer and preparation method thereof|
    KR20190018137A|2016-06-10|2019-02-21|에코랍 유에스에이 인코퍼레이티드|Low molecular weight dry powder polymer for use as a drying enhancer for paper|
    WO2019024476A1|2017-08-04|2019-02-07|中国海洋石油集团有限公司|Thickened oil activating agent and preparation method and use thereof|
    BR112020005933A2|2017-10-25|2020-10-06|Basf Se|process to produce hydrophobic association polyacrylamides, hydrophobic association polyacrylamides, and use of hydrophobic association polyacrylamides|
    BR112020021907A2|2018-04-27|2021-03-02|Rohm And Haas Company|rheological modifiers for spray diversion control in agrochemical emulsions|
    CN108822244B|2018-05-07|2021-03-16|常州大学|Preparation method of salt-tolerant thickening agent|
    CA3108176A1|2018-07-30|2020-02-06|Championx Usa, Inc.|Salt-tolerant, fast-dissolving, water-soluble rheology modifiers|
    WO2020084033A1|2018-10-26|2020-04-30|Basf Se|Hydrophobically associating copolymers for enhanced oil recovery, comprising monomers with propylenoxy units|
    WO2020084046A1|2018-10-26|2020-04-30|Basf Se|Process for preparing propylenoxy-containing hydrophobically associating monomers by dmc catalysis|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-05| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-05-07| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-08-20| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-11-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-12-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/07/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09167328A|EP2287216A1|2009-08-06|2009-08-06|Water soluble associative polymers|
    PCT/EP2010/061074|WO2011015520A1|2009-08-06|2010-07-30|Water soluble, hydrophobic associating copolymer|
    [返回顶部]