Patent Grant
10562999
The invention relates to a copolymer, especially to a dispersant for solid particles, in particular to a dispersant for mineral binder compositions. The invention additionally relates to the use of a copolymer as dispersant for solid particles, to a mineral binder composition and to a shaped body obtainable therefrom.
Dispersants are used in the construction industry as plasticizers or water-reducing agents for mineral binder compositions, for example concrete, mortar, cements, gypsums and lime. The dispersants are generally organic polymers which are added to the makeup water or admixed with the binder compositions in solid form. In this way, it is advantageously possible to alter both the consistency of the binder composition during processing and to alter the properties in the hardened state.
Known particularly effective dispersants are, for example, comb polymers based on polycarboxylate (PCE). Comb polymers of this kind have a polymer backbone and side chains bonded thereto. Corresponding polymers are described, for example, in EP 1 138 697 A1 (Sika AG).
Likewise known as concrete additives are copolymer mixtures as mentioned, for example, in EP 1 110 981 A2 (Kao). The copolymer mixtures are prepared by converting ethylenically unsaturated monomers in a free-radical polymerization reaction, wherein the molar ratio of the two monomers is altered at least once during the polymerization process.
Comb polymers of this kind are indeed effective. Especially in the case of specific applications or under unusual working conditions, the known comb polymers are not always convincing. In such cases, the comb polymers can be combined, for example, with further additions or used in a higher dosage. However, solutions of this kind are usually complicated in their application or costly.
There is therefore still a need for improved dispersants that do not have the disadvantages mentioned.
It is therefore an object of the invention to overcome the aforementioned disadvantages. More particularly, an improved dispersant is to be provided, especially for solid particles and in particular for mineral binder compositions. The dispersant is in particular to enable effective plasticization and good working of mineral binder compositions. In particular, the effect of the dispersant is to be maintained over a maximum period of time. Moreover, what is desired is for the dispersant to be producible in a very flexible and controlled manner.
It has been found that, surprisingly, this object can be achieved by the features of independent claim 1.
The core of the invention is accordingly a copolymer, especially a dispersant for solid particles, in particular a dispersant for mineral binder compositions, having a polymer backbone and side chains bonded thereto, comprising at least one phosphorus group-bearing monomer unit M1 and at least one side chain-bearing monomer unit M2, wherein the copolymer has a nonrandom distribution of the monomer units M1 and/or the monomer units M2 in a direction along the polymer backbone.
As has been shown, copolymers of this kind, by comparison with known dispersants, firstly result in very good plasticizing effects in mineral binder compositions which are additionally maintained for a comparatively longer period. Especially by comparison with conventional dispersants, the copolymers of the invention show significantly better plasticizing performances in some cases. Moreover, the copolymers used in accordance with the invention can be produced in a reliable manner in a wide variety of different modifications in efficient methods.
Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.
A first aspect of the present invention relates to a copolymer, especially a dispersant for solid particles, in particular a dispersant for mineral binder compositions, having a polymer backbone and side chains bonded thereto, comprising at least one phosphorus group-bearing monomer unit M1 and at least one side chain-bearing monomer unit M2, wherein the copolymer has a nonrandom distribution of the monomer units M1 and/or the monomer units M2 in a direction along the polymer backbone.
Copolymer
The terms “phosphorus group-bearing monomer” and “phosphorus group-bearing monomer unit” especially mean monomers or polymerized monomers having at least one phosphorus atom. The phosphorus atom is preferably in the +III and/or +V oxidation state. The phosphorus group-bearing monomer unit particularly comprises a phosphoric acid group and/or a phosphonic acid group. The acid groups may also take the form of anions in deprotonated form or of a salt with a counterion or cation. In addition to the at least one phosphorus atom, the phosphorus group-bearing monomer unit may especially have one or more heteroatoms, one or more alkylene groups and/or one or more alkylene oxide groups. The heteroatom may, for example, be nitrogen, which is especially part of an amine and/or amide group.
A “nonrandom distribution” is understood in the present case to mean a non-statistical distribution of the monomer units M1 and/or the monomer units M2. This means that the phosphorus group-bearing monomer unit M1 and/or the side chain-bearing monomer units M2 are arranged in the copolymer, for example, in an alternating or block-type manner and/or in a gradient structure.
The structure of the copolymers can be analyzed and determined, for example, by nuclear spin resonance spectroscopy (NMR spectroscopy). By 1H and 13C NMR spectroscopy in particular, it is possible in a manner known per se to determine the sequence of the monomer units in the copolymer on the basis of neighboring group effects in the copolymer and using statistical evaluations.
Preferably, the phosphorus group-bearing monomer unit M1 is based, for example, on a (meth)acrylic ester, (meth)acrylamide, vinyl ether, allyl ether, methallyl ether and/or isoprenyl ether, each comprising a phosphoric acid group and/or a phosphonic acid group.
The side chain-bearing monomer unit M2 especially includes polyalkylene oxide side chains, especially polyethylene oxide and/or polypropylene oxide side chains.
More particularly, the phosphorus group-bearing monomer units M1 have a structure of the formula I:
The side chain-bearing monomer units M2 preferably have a structure of the formula II:
where
A molar ratio of the monomer units M1 to the monomer units M2 is advantageously in the range of 0.5-6, especially 0.7-4, preferably 0.9-3.8, further preferably 1.0-3.7 or 2-3.5.
The expression —PO3M2 means a compound of the formula —PO(OM)2, based on a phosphonic acid group.
For R1, it is particularly the case that a+b≥1, and especially, in addition, c=1.
In particular, a≥1 and b=0, and especially, in addition, c=1. Preferably, a=1-2, b=0 and c=1. Also more preferably, a=0 and b≥1, especially a=0, b=1 and c=1.
Preferably, d=1-5 and/or f=1.
In an advantageous embodiment, in the R1 radical of the monomer unit M1, a=0, b=1, c=1, G=—O—, d=1-2, Q=H, e=0 or 1, f=1 and j=0. In particular, R2═H or CH3, R3═R4═H. More preferably, d=2. Especially preferably, in the R1 radical of the monomer unit M1, a=0, b=1, c=1, G=—O—, d=1-2, Q=H, e=1, f=1 and j=0 and, in particular, R2═H or CH3 and R3═R4═H.
Alternatively, it may be advantageous when R1 is —PO(OM)2 and/or —O—PO(OM)2. In this case, a=0, b=0, c=0, d=0, e=0 or 1, f=1 and j=0. More particularly, such a choice of R1 may be advantageous under some circumstances when the copolymer has a gradient structure.
In another advantageous embodiment, in the R1 radical of the monomer unit M1, a=0, b=1, c=1, G=—NH—, d=0-2, Q=H or CH3, e=0, f=1 and j=0. In particular, R2═H or CH3, R3═R4═H.
If j=1, preferably, g=0, i=0, h=1 and K is —CH2— or a chemical bond. In addition, in this case, in particular, e=0 and f=1.
If present, Q is especially hydrogen and/or a methyl group. More preferably, Q is hydrogen.
The X group in the ionizable monomer units M2, advantageously in at least 75 mol %, particularly in at least 90 mol %, especially in at least 95 mol % or at least 99 mol % of all monomer units M2, is —O— (=oxygen atom).
Advantageously, R5═H or CH3, R6═R7═H and X═—O—. It is thus possible to prepare the copolymers, for example, proceeding from (meth)acrylic esters, vinyl ethers, (meth)allyl ethers or isoprenol ethers.
In a particularly advantageous embodiment, R2 and R5 are each mixtures of 40-60 mol % of H and 40-60 mol % of —CH3.
In a further advantageous embodiment, R2═H, R5═—CH3 and R3═R4═R6═R7═H.
In another advantageous embodiment, R2═R5═H or —CH3 and R3═R4═R6═R7═H.
The R8 radical in the side chain-bearing monomer units M2, based on all the R8 radicals in the monomer units, consists of a polyethylene oxide especially to an extent of at least 50 mol %, especially at least 75 mol %, preferably at least 95 mol % or at least 99 mol %. A proportion of ethylene oxide units based on all the alkylene oxide units in the copolymer is especially more than 75 mol %, especially more than 90 mol %, preferably more than 95 mol % and specifically 100 mol %.
More particularly, R8 has essentially no hydrophobic groups, especially no alkylene oxides having three or more carbon atoms. This especially means that a proportion of alkylene oxides having three or more carbon atoms based on all the alkylene oxides is less than 5 mol %, especially less than 2 mol %, preferably less than 1 mol % or less than 0.1 mol %. In particular, there are no alkylene oxides having three or more carbon atoms or the proportion thereof is 0 mol %.
Ra is advantageously H and/or a methyl group. Particularly advantageously, A=C2-alkylene and Ra is H or a methyl group.
More particularly, the parameter n=10-150, especially n=15-100, preferably n=17-70, specifically n=19-45 or n=20-25. In particular, this achieves excellent dispersing effects within the preferred ranges specified.
Particular preference is given to copolymers in which, for R1, a=0, b=1, c=1, G=—O—, d=1-2, Q=H, e=0 or 1, f=1 and j=0; R2 and R5, independently of one another, are H, —CH3 or mixtures thereof; R3 and R6, independently of one another, are H or —CH3, preferably H; R4 and R7, independently of one another, are H or —COOM, preferably H; and where X in at least 75 mol %, particularly in at least 90 mol %, especially in at least 99 mol %, of all monomer units M2 is —O—.
It may further be advantageous when the copolymer comprises at least one further monomer unit MS which especially differs chemically from the monomer units M1 and M2. In particular, multiple different further monomer units MS may be present. In this way, it is possible to further modify the properties of the copolymer and to adjust them, for example, with regard to specific applications.
Particularly advantageously, the at least one further monomer unit MS is a monomer unit of the formula III:
where R5′, R6′, R7′, m′ and p′ are as defined for R5, R6, R7, m and p;
Advantageous examples of further monomer units MS are those where m′=0, p′=0, Z and Y represent a chemical bond and R9 is an alkylaryl group having 6-10 carbon atoms.
Also suitable are especially further monomer units MS in which m′=0, p′=1, Y is —O—, Z represents a chemical bond and R9 is an alkyl group having 1-4 carbon atoms.
Further suitable are further monomer units MS where m′=0, p′=1, Y is a chemical bond, Z is —O— and R9 is an alkyl group and/or a hydroxyalkyl group having 1-6 carbon atoms.
Particularly advantageously, the at least one further monomer unit MS consists of polymerized vinyl acetate, styrene and/or hydroxyalkyl (meth)acrylate, especially hydroxyethyl acrylate.
In particular, the polydispersity (=weight-average molecular weight MW/number-average molecular weight Mn) of the copolymer is <1.5, particularly in the range of 1.0-1.4, especially 1.1-1.3.
A weight-average molecular weight MW of the overall copolymer is especially in the range of 10′000-150′000 g/mol, advantageously 12′000-80′000 g/mol, especially 12′000-50′000 g/mol. In the present context, molecular weights such as the weight-average molecular weight MW or the number-average molecular weight Mn are determined by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as standard. This technique is known per se to the person skilled in the art.
The copolymer is particularly a polymer having essentially linear structure. This particularly means that all monomer units of the copolymer are arranged in a single and/or unbranched polymer chain. Specifically, the copolymer does not have a star-shaped structure and/or the copolymer is not part of a branched polymer. More particularly, the copolymer is not part of a polymer in which there are multiple, especially three or more, polymer chains running in different directions attached to a central molecule.
Copolymers with Gradient Structure
In a preferred embodiment, the copolymer has a gradient structure in at least one section AA in a direction along the polymer backbone with respect to the phosphorus group-bearing monomer unit M1 and/or with respect to the side chain-bearing monomer unit M2.
In other words, in the copolymer of the invention, there is a concentration gradient in the at least one section AA in a direction along the polymer backbone with regard to the phosphorus group-bearing monomer unit M1 and/or with regard to the side chain-bearing monomer unit M2.
The term “gradient structure” or “concentration gradient” in the present case is especially a continuous change in the local concentration of a monomer unit in at least one section in a direction along the copolymer backbone. Another term for “concentration gradient” is “concentration slope”.
The concentration gradient may, for example, be essentially constant. This corresponds to a linear decrease or increase in the local concentration of the respective monomer unit in the at least one section AA in the direction of the copolymer backbone. However, it is possible that the concentration gradient changes in the direction of the copolymer backbone. In this case, there is a nonlinear decrease or increase in the local concentration of the respective monomer unit. The concentration gradient extends especially over at least 10, especially at least 14, preferably at least 20 or at least 40, monomer units of the copolymer.
By contrast, abrupt or sharp changes in concentration of monomers as occur, for example, in the case of block copolymers are not referred to as a concentration gradient.
The expression “local concentration” in the present context refers to the concentration of a particular monomer at a given point in the polymer backbone. In practice, the local concentration or the mean of the local concentration can be ascertained, for example, by determining the monomer conversions during the preparation of the copolymer. In this case, the monomers converted within a particular period can be ascertained. The averaged local concentration especially corresponds to the ratio of the mole fraction of a particular monomer converted within the period of time in question to the total molar amount of the monomers converted within the period of time in question.
The conversions of the monomers can be determined in a manner known per se, for example, with the aid of liquid chromatography, especially high-performance liquid chromatography (HPLC), and taking account of the amounts of monomers used. The structure of the copolymer can be determined as set out above by 1H and 13C NMR spectroscopy.
The copolymer may also have more than one section AA having a gradient structure, especially two, three, four or even more sections AA, which are arranged in succession, for example. If present, different gradient structures or concentration slopes may each be present in the different sections AA.
Preferably, in the at least one section AA, a local concentration of the at least one phosphorus group-bearing monomer unit M1 increases continuously along the polymer backbone, while a local concentration of the at least one side chain-bearing monomer unit M2 decreases continuously along the polymer backbone, or vice versa.
A local concentration of the phosphorus group-bearing monomer unit M1 at the first end of the at least one section AA is especially lower than at the second end of the section AA, while a local concentration of the side chain-bearing monomer unit M2 at the first end of the section AA is greater than at the second end of the section AA, or vice versa.
More particularly, in the case of a division of the at least one section AA into 10 subsections of equal length, the averaged local concentration of the at least one phosphorus group-bearing monomer unit M1 in the respective subsections along the polymer backbone increases in at least 3, especially in at least 5 or 8, successive subsections, while the averaged local concentration of the at least one side chain-bearing monomer unit M2 in the respective subsections along the polymer backbone decreases in at least 3, especially in at least 5 or 8, successive subsections, or vice versa.
Specifically, an increase or decrease in the averaged local concentration of the at least one phosphorus group-bearing monomer unit M1 in the successive subsections is essentially constant, while, advantageously, a decrease or increase in the averaged local concentration of the at least one side chain-bearing monomer unit M2 in the successive subsections is essentially likewise constant.
In an advantageous embodiment, the at least one section AA having the gradient structure, based on a total length of the polymer backbone, has a length of at least 30%, especially at least 50%, preferably at least 75% or 90%.
Advantageously, the at least one section AA, based on a total number of monomer units in the polymer backbone, has a proportion of at least 30%, especially at least 50%, preferably at least 75% or 90%, of monomer units.
In particular, the at least one section AA, based on the weight-average molecular weight of the overall copolymer, has a proportion by weight of at least 30%, especially at least 50%, preferably at least 75% or 90%.
Thus, the section AA with the concentration gradient or the gradient structure is of particular importance.
The at least one section AA having the concentration gradient advantageously comprises 5-70, especially 7-40, preferably 10-25, monomer units M1 and 5-70, especially 7-40, preferably 10-25 monomer units M2.
More particularly, the copolymer consists to an extent of at least 50 mol %, in particular at least 75 mol %, especially at least 90 mol % or 95 mol %, of phosphorus group-bearing monomer units M1 and side chain-bearing monomer units M2.
It is advantageous when at least 30 mol %, especially at least 50 mol %, preferably at least 75 mol %, in particular at least 90 mol % or at least 95 mol %, of the phosphorus group-bearing monomer units M1 are in the at least one section AA having a gradient structure.
Likewise advantageously, at least 30 mol %, especially at least 50 mol %, preferably at least 75 mol %, in particular at least 90 mol % or at least 95 mol %, of the side chain-bearing monomer units M2 are in the at least one section having a gradient structure.
Especially preferably, the two latter aforementioned conditions apply simultaneously.
In another advantageous embodiment, the copolymer, in addition to the at least one section AA having a gradient structure, has a further section AB, wherein there is essentially a constant local concentration of the monomers and/or a statistical or random distribution of the monomers over the entire section AB. Section AB may consist, for example, of a single kind of monomers or of multiple different monomers in statistical distribution. In section AB, however, there is especially no gradient structure and no concentration gradient along the polymer backbone.
The copolymer may also have more than one further section AB, for example two, three, four or even more sections AB, which may differ from one another from a chemical and/or structural point of view.
Preferably, the at least one section AA directly adjoins the further section AB.
It has been found that, surprisingly, copolymers of this kind are even more advantageous under some circumstances with regard to the plasticizing effect and the maintenance thereof over time.
More particularly, the further section AB comprises phosphorus group-bearing monomer units M1 and/or side chain-bearing monomer units M2.
Based on all the monomer units present therein, the further section AB, in one embodiment of the invention, for example, comprises advantageously at least 30 mol %, especially at least 50 mol %, preferably at least 75 mol %, in particular at least 90 mol % or at least 95 mol %, of phosphorus group-bearing monomer units M1. Any proportion of side chain-bearing monomer units M2 present in the further section AB is particularly less than 25 mol %, especially less than 10 mol % or less than 5 mol %, based on all monomer units M1 in the further section. More particularly, there are no side chain-bearing monomer units M2 in the further section AB.
In a further and particularly advantageous implementation of the invention, the further section AB, based on all the monomer units present therein, comprises at least 30 mol %, especially at least 50 mol %, preferably at least 75 mol %, in particular at least 90 mol % or at least 95 mol %, of side chain-bearing monomer units M2. In this case, any proportion of phosphorus group-bearing monomer units M1 present in the further section AB is in particular less than 25 mol %, especially less than 10 mol % or less than 5 mol %, based on all monomer units M2 in the further section AB. More particularly, there are no phosphorus group-bearing monomer units M1 in the further section AB.
It has been found to be appropriate when the further section AB comprises a total of 5-70, especially 7-40, preferably 10-25, monomer units. These are especially phosphorus group-bearing monomer units M1 and/or side chain-bearing monomer units M2.
A ratio of the number of monomer units in the at least one section AA having gradient structure to the number of monomer units in the at least one further section AB having the essentially constant local concentration is advantageously in the range of 99:1-1:99, especially 10:90-90:10, preferably 80:20-20:80, especially 70:30-30:70.
If present, the at least one further monomer unit MS may be part of the at least one section AA and/or of the further section AB. It is also possible that the at least one further monomer unit MS is part of an additional section of the copolymer. More particularly, different further monomer units MS may be present in the different sections.
If present in the at least one section AA, the at least one further monomer unit MS advantageously has a proportion in the at least one section AA of 0.001-80 mol %, preferably 20-75 mol %, especially 30-70 mol %, based on all the monomer units in the first section AA.
If present in the further section AB, the at least one further monomer unit MS especially has a proportion in the further section AB of 0.001-80 mol %, preferably 20-75 mol %, especially 30-70 mol % or 50-70 mol %, based on all the monomer units in the further section AB.
In an advantageous embodiment, the at least one further monomer unit MS is present in the at least one section AA and/or in the further section AB with a proportion of 20-75 mol %, especially 30-70 mol %, based on all monomer units in the respective section.
In an advantageous embodiment, the copolymer consists of the at least one section AA. In another advantageous embodiment, the copolymer consists of the at least one section AA and the further section AB. The latter case in particular results in very good and long-lasting plasticizing effects.
However, it is also possible, for example, that the copolymer contains at least two different sections AA and/or at least two different further sections AB.
A particularly advantageous copolymer has at least one or more than one of the following features:
Especially preferred is a copolymer consisting of sections AA and AB which has at least all the features (i)-(iv). Further preferred is a copolymer having all the features (i)-(xi). Even further preferred is a copolymer which fulfills all the features (i)-(xi) in the executions preferred in each case.
Copolymer with Block Structure
Likewise advantageous is a copolymer comprising at least one first block A and at least one second block B, wherein the first block A has a phosphorus group-bearing monomer unit M1 of the formula I and the second block B has a side chain-bearing monomer unit M2 of the formula II.
More particularly, any proportion of monomer units M2 present in the first block A is less than 25 mol %, especially not more than 10 mol %, based on all the monomer units M1 in the first block A, and where any proportion of monomer units M1 present in the second block B is less than 25 mol %, especially not more than 10 mol %, based on all the monomer units M2 in the second block B.
Multiple different monomer units M1 of the formula I and/or multiple different monomer units M2 of the formula II may be present in the copolymer of the invention.
The monomer units M1 and any further monomer units in the first block A are especially in statistical or random distribution. The monomer units M2 and any further monomer units in the second block B are likewise especially in statistical or random distribution.
In other words, the at least one block A and/or the at least one block B preferably each take the form of a component polymer with random monomer distribution.
The at least one first block A advantageously comprises 5-70, especially 7-40, preferably 10-25, phosphorus group-bearing monomer units M1 and/or the at least one second block B comprises 5-70, especially 7-50, preferably 20-40, side chain-bearing monomer units M2.
Preferably, any proportion of monomer units M2 present in the first block A is less than 15 mol %, particularly less than 10 mol %, especially less than 5 mol % or less than 1 mol %, based on all monomer units M1 in the first block A. In addition, any proportion of monomer units M1 present in the second block B is advantageously less than 15 mol %, particularly less than 10 mol %, especially less than 5 mol % or less than 1 mol %, based on all monomer units M2 in the second block B. Advantageously, both conditions are fulfilled at the same time.
Especially advantageously, for example, any proportion of monomer units M2 present in the first block A is less than 15 mol % (based on all the monomer units M1 in the first block A) and any proportion of monomer units M1 present in the second block B is less than 10 mol % (based on all the monomer units M2 in the second block B).
Thus, the monomer units M1 and M2 are essentially spatially separate, which is to the benefit of the dispersing effect of the block copolymer and is advantageous with regard to the retardation problem.
The first block A, based on all the monomer units in the first block A, consists in particular to an extent of at least 20 mol %, particularly at least 50 mol %, especially at least 75 mol % or at least 90 mol %, of monomer units M1 of the formula I. The second block B, based on all the monomer units in the second block B, consists advantageously to an extent of at least 20 mol %, particularly at least 50 mol %, especially at least 75 mol % or at least 90 mol %, of monomer units M2 of the formula II.
A molar ratio of the monomer units M1 to the monomer units M2 in the block copolymer is especially in the range of 0.5-6, especially 0.7-4, preferably 0.9-3.8, further preferably 1.0-3.7 or 2-3.5. This achieves an optimal dispersing effect in mineral binder compositions.
It may further be advantageous when the block copolymer comprises at least one further monomer unit MS as described above. In particular, multiple different further monomer units MS may be present. In this way, it is possible to further modify the properties of the block copolymer and to adjust them, for example, with regard to specific applications.
The at least one further monomer unit MS may be part of the first block A and/or of the second block B. It is also possible that the at least one further monomer unit MS is part of an additional block of the block copolymer. More particularly, different monomer units MS may be present in the different blocks.
If present in the first block A, the at least one further monomer unit MS advantageously has a proportion in the first block A of 0.001-80 mol %, preferably 20-75 mol %, especially 30-70 mol %, based on all the monomer units in the first block A.
If present in the second block B, the at least one further monomer unit MS especially has a proportion in the second block B of 0.001-80 mol %, preferably 20-75 mol %, especially 30-70 mol % or 50-70 mol %, based on all the monomer units in the second block B.
In an advantageous embodiment, the at least one further monomer unit MS is present in the first block A and/or in the second block B with a proportion of 20-75 mol %, especially 30-70 mol %, based on all the monomer units in the respective block.
In a further advantageous embodiment, there is at least one further block C arranged between the first block A and the second block B, which differs chemically and/or structurally from the first and second blocks.
Advantageously, the at least one further block C comprises or consists of monomer units MS as described above. However, it is also possible for further monomer units to be present in addition to or in place of the monomer units MS.
More particularly, the at least one further block C consists to an extent of at least 50 mol %, especially at least 75 mol %, preferably at least 90 mol % or at least 95 mol %, of monomer units MS as described above.
In a particularly advantageous embodiment, the block copolymer of the invention is a diblock copolymer consisting of a block A and a block B.
Likewise suitable are block copolymers containing at least two blocks of the first block A and/or at least two blocks of the second block B. More particularly, these are block copolymers containing two instances of the first block A and one instance of the second block B, or block copolymers containing one instance of the first block A and two instances of the second block B. Block copolymers of this kind especially take the form of triblock copolymers, tetrablock copolymers or pentablock copolymers, preferably triblock copolymers. There are one or two further blocks present in the tetrablock copolymers and the pentablock copolymers, for example blocks of the C block type as described above.
A particularly advantageous block copolymer has at least one or more than one of the following features:
Especially preferred is a diblock copolymer consisting of blocks A and B which has at least all the features (i)-(iv). Further preferred is a diblock copolymer having all the features (i)-(xi). Even further preferred is a diblock copolymer which fulfills all the features (i)-(xi) in the executions preferred in each case.
Likewise advantageous is a triblock copolymer consisting of the blocks A, B and C, especially in the sequence A-C-B, where the triblock copolymer has at least all the features (i)-(iv). Further preferred is a triblock copolymer having all the features (i)-(xi). Even further preferred is a triblock copolymer which fulfills all the features (i)-(xi) in the executions preferred in each case. Block C advantageously comprises monomer units MS as described above, or block C consists thereof.
In a specific embodiment, these diblock copolymers or triblock copolymers also include, in block A and B, additionally a further monomer unit MS as described above, especially a further monomer unit MS of the formula III.
Preparation of Copolymers
A further aspect of the present invention relates to a process for preparing a copolymer, especially a copolymer as described above, wherein phosphorus group-bearing monomers m1 and side chain-bearing monomers m2 are polymerized together to form a nonrandom distribution of the phosphorus group-bearing monomers m1 and/or the side chain-bearing monomers m2.
The phosphorus group-bearing monomers m1, on completion of polymerization, correspond to the abovementioned phosphorus group-bearing monomer units M1 of the copolymer. The side chain-bearing monomers m2, on completion of polymerization, likewise correspond to the above-described side chain-bearing monomer units M2.
The side chain-bearing monomers m2 especially include polyalkylene oxide side chains, preferably polyethylene oxide and/or polypropylene oxide side chains.
The phosphorus group-bearing monomers m1 are based, for example, on a (meth)acrylic ester, (meth)acrylamide, vinyl ether, allyl ether, methallyl ether and/or isoprenyl ether, each comprising a phosphoric acid group and/or a phosphonic acid group.
More particularly, the ionizable monomers m1 have a structure of the formula IV:
The side chain-bearing monomers m2 preferably have a structure of the formula V:
where the R1-R8 and X groups and the parameters m and p are defined as described above in connection with the copolymer.
In a further advantageous embodiment, there is at least one further monomer ms present during the polymerization, which is polymerized, and this is especially a monomer of the formula VI:
where R5′, R6′, R7′, R9 Y, Z, m′ and p′ are as defined above.
In particular, the phosphorus group-bearing monomer m1 is selected from one or more of the following compounds:
Especially preferred are compound nos. 1, 2, 3, 5, 6, 7, 10, 11, 16 and 17. The acrylates and/or methacrylates are very particularly advantageous. Especially compound nos. 1, 2, 5 and 6.
The copolymer is especially prepared by a living free-radical polymerization.
A free-radical polymerization can basically be divided into three steps: initiation, growth and termination.
“Living free-radical polymerization” is also referred to as “controlled free-radical polymerization” and is known per se to the person skilled in the art in other contexts. The term comprehends chain growth processes in which essentially no chain termination reactions (transfer and termination) take place. Living free-radical polymerization thus proceeds essentially in the absence of irreversible transfer or termination reactions. These criteria can be fulfilled, for example, when the polymerization initiator is already used up at a very early stage during the polymerization and there is exchange between the species of different reactivity that proceeds at least as rapidly as the chain propagation itself. The number of active chain ends especially remains essentially constant during the polymerization. This enables essentially simultaneous growth of the chains that continues over the entire polymerization process. This correspondingly results in a narrow molecular weight distribution or polydispersity.
In other words, controlled free-radical polymerization or living free-radical polymerization is particularly notable for reversible or even absent termination or transfer reactions. After the initiation, the active sites are accordingly conserved over the entire reaction. All polymer chains are formed (initiated) simultaneously and grow continuously over the entire time. The free-radical functionality of the active site is ideally still conserved even after complete conversion of the monomers to be polymerized. This exceptional property of the controlled polymerizations enables preparation of well-defined structures such as gradient or block copolymers through sequential addition of different monomers.
By contrast, in conventional free-radical polymerization as described, for example, in EP 1 110 981 A2 (Kao), all three steps (initiation, growth and termination) proceed in parallel. The lifetime of each of the active, growing chains is very short and the monomer concentration during the chain growth of a chain remains essentially constant. The polymer chains thus formed do not have any active centers suitable for the addition of further monomers. Thus, this mechanism does not permit any control over the structure of the polymers. The preparation of gradient or block structures by means of conventional free-radical polymerization is therefore typically not possible (see, for example,
“Polymere: Synthese, Synthese and Eigenschaften” [Polymers: Synthesis, Synthesis and Properties]; authors: Koltzenburg, Maskos, Nuyken; Verlag: Springer Spektrum; ISBN: 97-3-642-34772-6 and “Fundamentals of Controlled/living Radical Polymerization”; publisher: Royal Society of Chemistry; editors: Tsarevsky, Sumerlin; ISBN: 978-1-84973-425-7).
Thus, there is a clear distinction of “living free-radical polymerization” from conventional “free-radical polymerization” or free polymerization conducted in a non-living or non-controlled manner.
The polymerization is preferably effected by reversible addition-fragmentation chain-transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP) and/or atom transfer radical polymerization (ATRP).
In reversible addition-fragmentation chain-transfer polymerization, control over the polymerization is achieved by a reversible chain transfer reaction. Specifically, a growing free-radical chain adds on what is called a RAFT agent, which leads to formation of an intermediate free radical. The RAFT agent then fragments, in such a way as to reform another RAFT agent and a free radical available for propagation. In this way, the probability of propagation is distributed uniformly over all chains. The average chain length of the polymer formed is proportional to the RAFT agent concentration and to the reaction conversion. RAFT agents used are especially organic sulfur compounds. Particularly suitable are dithioesters, dithiocarbamates, trithiocarbonates and/or xanthates. The polymerization can be initiated in a conventional manner by means of initiators or thermal self-initiation.
In nitroxide-mediated polymerization, nitroxides react reversibly with the active chain end to form what is called a dormant species. The equilibrium between active and inactive chain ends is strongly to the side of the dormant species, which means that the concentration of active species is very low. The probability of two active chains meeting and terminating is thus minimized. An example of a suitable NMP agent is 2,2,6,6-tetramethylpiperidine N-oxide (TEMPO).
In atom transfer radical polymerization (ATRP), the concentration of free radicals is lowered by addition of a transition metal complex and a controlling agent (halogen-based) to such an extent that chain termination reactions, such as disproportionation or recombination, are very substantially suppressed.
In the present context, reversible addition-fragmentation chain-transfer polymerization (RAFT) has been found to be particularly preferable.
The initiator used for the polymerization is more preferably an azo compound and/or a peroxide as free-radical initiator, which may be at least one representative selected from the group consisting of dibenzoyl peroxide (DBPO), ditert-butyl peroxide, diacetyl peroxide, azobisisobutyronitrile (AIBN), α,α′-azodiisobutyramidine dihydrochloride (AAPH) and/or azobisisobutyramidine (AIBA).
If the polymerization is effected in an aqueous solution or in water, α,α′-azodiisobutyramidine dihydrochloride (AAPH) is advantageously used as initiator.
For control of the polymerization, in particular, one or more representatives from the group consisting of dithioesters, dithiocarbamates, trithiocarbonates and/or xanthates are used.
It has additionally been found to be advantageous when the polymerization is effected at least partly, preferably fully, in an aqueous solution.
More particularly, during the polymerization, a molar ratio of free phosphorus group-bearing monomers m1 to free side chain-bearing monomers m2 is at least temporarily altered.
Specifically, the alteration of the molar ratio includes stepwise and/or a continuous alteration. It is thus possible to form, in an efficiently controllable manner, a block structure and/or a concentration gradient or a gradient structure.
Optionally, during the polymerization, either a continuous change or a stepwise change in the molar ratio of the free phosphorus group-bearing monomers m1 to the free side chain-bearing monomers m2 is effected. The stepwise change is especially effected before the continuous change is conducted. In this way, for example, a copolymer comprise two or more sections having different structure is obtainable.
For formation of copolymers having block and/or gradient structures, the phosphorus group-bearing monomers m1 and the side chain-bearing monomers m2 are preferably at least partly added at different times.
In a further preferred embodiment, in the polymerization, in a first step a), a portion of the phosphorus group-bearing monomers m1 is converted or polymerized and, after attainment of a predetermined conversion, in a second step b), the as yet unconverted phosphorus group-bearing monomers m1 are polymerized together with the side chain-bearing monomers m2. Step a) is especially effected essentially in the absence of side chain-bearing monomers m2.
In this way, in a simple and inexpensive manner, a copolymer having a section consisting essentially of polymerized phosphorus group-bearing monomers m1 followed by a section having gradient structure is preparable.
In accordance with a very particularly preferred embodiment, in the polymerization, in a first step a), a portion of the side chain-bearing monomers m2 is converted or polymerized and, after attainment of a predetermined conversion, in a second step b), the as yet unconverted side chain-bearing monomers m2 are polymerized together with the phosphorus group-bearing monomers m1. Step a) is especially effected essentially in the absence of phosphorus group-bearing monomers m1.
In this way, for example, in a simple and inexpensive manner, a copolymer having a section consisting essentially of polymerized side chain-bearing monomers m2 followed by a section having gradient structure is preparable.
It is advantageous here to conduct steps a) and b) in immediate succession. In this way, it is possible to maintain the polymerization reaction in steps a) and b) to the best possible degree.
The polymerization in step a) is especially conducted until 0.1-100 mol %, especially 1-95 mol %, preferably 10-90 mol %, in particular 25-85 mol %, of the phosphorus group-bearing monomers m1 or of the side chain-bearing monomers m2 have been converted or polymerized.
The conversion of the monomers m1 and m2 or the progress of the polymerization can be monitored in a manner known per se, for example, with the aid of liquid chromatography, especially high-performance liquid chromatography (HPLC).
More particularly, the copolymer consists to an extent of at least 50 mol %, in particular at least 75 mol %, especially at least 90 mol % or 95 mol %, of phosphorus group-bearing monomers m1 and side chain-bearing monomers m2.
The copolymer may be prepared in liquid or solid form. More preferably, the copolymer is present as a constituent of a solution or dispersion, wherein a proportion of the copolymer is especially 10-90% by weight, preferably 25-65% by weight. This means that the copolymer can be added, for example, very efficiently to binder compositions. If the copolymer is being prepared in solution, especially in aqueous solution, it is additionally possible to dispense with further processing.
In accordance with another advantageous embodiment, a copolymer is prepared in the solid state of matter, especially in the form of a powder, in the form of pellets and/or sheets. This especially simplifies the transport of the copolymers. Solutions or dispersions of the copolymers can be converted to the solid state of matter, for example, by spray-drying.
According to the reaction regime, it is possible by the process of the invention to prepare polymers having a given or well-defined structure in a controlled manner. More particularly, for example, copolymers having block structure and/or copolymers having gradient structure are obtainable.
Preparation of Copolymers with Gradient Structure
The following procedure has been found to be particularly preferable for preparation of copolymers comprising a gradient structure: in a first step a), at least a portion of the side chain-bearing monomers m2 is reacted or polymerized and, after attainment of a predetermined conversion, in a second step b), the phosphorus group-bearing monomers m1 are polymerized together with as yet unconverted side chain-bearing monomers m2. Step a) is effected in particular in the absence of phosphorus group-bearing monomers m1.
It is also possible, in a first step a), to react or polymerize at least a portion of the phosphorus group-bearing monomers m1 and, after attainment of a predetermined conversion, in a second step b), to polymerize the side chain-bearing monomers m2, optionally together with any as yet unconverted phosphorus group-bearing monomers m1. Step a) is effected in particular in the absence of side chain-bearing monomers m2.
More particularly, by the former process, it is possible in an efficient and inexpensive manner to prepare copolymers having a section consisting essentially of polymerized side chain-bearing monomers m2 followed by a section with gradient structure.
The polymerization in step a) is especially conducted until 1-74 mol %, preferably 10-70 mol %, in particular 25-70 mol %, especially 28-50 mol % or 30-45 mol %, of the side chain-bearing monomers m2 or of the phosphorus group-bearing monomers m1 have been converted or polymerized.
In a further advantageous embodiment, in step a) and/or in step b), there is at least one further polymerizable monomer ms of the formula VI as described above. The at least one further polymerizable monomer ms in this case is especially polymerized together with the monomer m1 and/or the monomer m2.
Alternatively, it is possible, in addition to step a) and step b), to provide a further step c) for polymerization of the at least one further polymerizable monomer ms. In this way, it is possible to prepare a copolymer having an additional section C. More particularly, step c) can be conducted between step a) and step b) in time. Thus, the additional section C is arranged between sections AA and AB in space.
Alternatively, it is possible to conduct step c) before or after steps a) and b). Thus, the additional section C may be arranged after section AA or before section AB.
Advantageous proportions, ratios and configurations of the monomers m1, m2, ms and of any further monomers correspond to the proportions, ratios and configurations already cited above, which have been described in connection with the monomer units M1, M2 and MS.
Preparation of a Copolymer with Block Structure
The following procedure has been found to be particularly preferable for preparation of copolymers comprising a block structure: in a first step a), at least a portion of the side chain-bearing monomers m2 is reacted or polymerized and, after attainment of a predetermined conversion, in a second step b), the phosphorus group-bearing monomers m1 are polymerized, optionally together with any as yet unconverted side chain-bearing monomers m2. Step a) is effected in particular in the absence of phosphorus group-bearing monomers m1.
The polymerization in step a) is especially conducted until 75-95 mol %, preferably 85-95 mol %, especially 86-92 mol %, of the originally charged monomers m2 have been converted/polymerized.
More particularly, the polymerization in step b) is correspondingly conducted until 75-95 mol %, especially 80-92 mol %, of the originally charged monomers m1 have been converted/polymerized.
The sequence of steps a) and b) may, however, in principle also be switched.
Alternatively, it is possible, in addition to step a) and step b), to provide a further step c) for polymerization of the at least one further polymerizable monomer ms. In this way, it is possible to prepare a block copolymer having an additional block C. More particularly, step c) is conducted between step a) and step b) in time. Thus, the additional block C is arranged between the A and B blocks in space.
Advantageous proportions, ratios and configurations of the monomers m1, m2, ms and of any further monomers correspond to the proportions, ratios and configurations already cited above, which have been described in connection with the monomer units M1, M2 and MS.
Uses of the Copolymers
The present invention further relates to the use of a copolymer as described above as dispersant for solid particles.
The term “solid particles” means particles composed of inorganic and/or organic materials. In particular, these are inorganic and/or mineral particles.
Particularly advantageous, the copolymer is used as dispersant for mineral binder compositions. The copolymer can especially be used for plasticization, for water reduction and/or for improvement of the workability of a mineral binder composition.
More particularly, the copolymer can be used for extending the workability of a mineral binder composition.
The copolymer may further be used for increasing the adhesion of a mineral binder composition, especially in the cured state, on a metallic body and/or a metallic substrate. The metallic body or the metallic substrate is especially a body consisting of steel and/or iron on the surface. This may be, for example, a construction of a built structure, for example a building construction or a bridge construction. It has been found that, surprisingly, mineral binder compositions comprising a copolymer of the invention have better adhesion on metallic bodies and/or metallic substrates than an analogous mineral binder composition comprising no copolymer of the invention.
The present invention further additionally relates to a mineral binder composition comprising at least one copolymer as described above.
The mineral binder composition comprises at least one mineral binder. The expression “mineral binder” is especially understood to mean a binder which reacts in the presence of water in a hydration reaction to give solid hydrates or hydrate phases. This may, for example, be a hydraulic binder (e.g. cement or hydraulic lime), a latently hydraulic binder (e.g. slag), a pozzolanic binder (e.g. fly ash) or a nonhydraulic binder (gypsum or white lime).
More particularly, the mineral binder or the binder composition comprises a hydraulic binder, preferably cement. Particular preference is given to a cement having a cement clinker content of 35% by weight. More particularly, the cement is of the CEM I, CEM II, CEM III, CEM IV or CEM V type (according to standard EN 197-1). A proportion of the hydraulic binder in the overall mineral binder is advantageously at least 5% by weight, especially at least 20% by weight, preferably at least 35% by weight, especially at least 65% by weight. In a further advantageous embodiment, the mineral binder consists to an extent of ≥95% by weight of hydraulic binder, especially of cement or cement clinker.
Alternatively, it may be advantageous when the mineral binder or the mineral binder composition comprises or consists of other binders. These are especially latently hydraulic binders and/or pozzolanic binders. Suitable latently hydraulic and/or pozzolanic binders are, for example, slag, fly ash and/or silica dust. The binder composition may likewise comprise inert substances, for example limestone, quartz flours and/or pigments. In an advantageous embodiment, the mineral binder contains 5-95% by weight, especially 5-65% by weight, more preferably 15-35% by weight, of latently hydraulic and/or pozzolanic binders. Advantageous latently hydraulic and/or pozzolanic binders are slag and/or fly ash.
In a particularly preferred embodiment, the mineral binder comprises a hydraulic binder, especially cement or cement clinker, and a latently hydraulic and/or pozzolanic binder, preferably slag and/or fly ash. The proportion of the latently hydraulic and/or pozzolanic binder in this case is more preferably 5-65% by weight, more preferably 15-35% by weight, while at least 35% by weight, especially at least 65% by weight, of the hydraulic binder is present.
The mineral binder composition is preferably a mortar or concrete composition.
The mineral binder composition is especially a workable mineral binder composition and/or one which is made up with water.
A weight ratio of water to binder in the mineral binder composition is preferably in the range of 0.25-0.7, particularly 0.26-0.65, preferably 0.27-0.60, especially 0.28-0.55.
The copolymer is advantageously used with a proportion of 0.01-10% by weight, especially 0.1-7% by weight or 0.2-5% by weight, based on the binder content.
An additional aspect of the present invention relates to a shaped body, especially a constituent of a built structure, obtainable by curing a mineral binder composition comprising a copolymer as described above after addition of water. A built structure may, for example, be a bridge, a building, a tunnel, a roadway or a runway.
The invention further relates to a laminar structure comprising a metallic body and/or a metallic substrate and a mineral binder composition comprising a copolymer of the invention. The mineral binder composition is especially at least partly in direct contact with the metallic body and/or the metallic substrate. The metallic body or the metallic substrate is especially a body consisting of steel and/or iron on the surface, for example a construction of a built structure, for example a building construction or a bridge construction. The mineral binder composition here is in the pasty or cured state.
Further advantageous embodiments of the invention will be apparent from the working examples which follow.
1.1 Copolymer CP1
For preparation of a block copolymer by means of RAFT polymerization, 28.74 g of 50% methoxy polyethylene glycol-1000 methacrylate were weighed into a 3-neck flask and then diluted with 12.59 g of H2O. A gentle nitrogen stream was introduced into the solution. The reaction mixture was heated to 80° C. As soon as the temperature had been attained, 0.252 g of 4-cyano-4-(thiobenzoyl)pentanoic acid was added. After 10 min, 0.045 g of AIBN was then added. From then on, the conversion is determined regularly by means of HPLC. As soon as the conversion, based on methoxy polyethylene glycol methacrylate, has reached about 90%, 10.71 g of MAPC-1-phosphonic acid (CAS: [87243-97-8]) were added. The reaction mixture is left to stir for a further 3 h. After cooling, what remains is an about 40% reddish solution. The copolymer thus obtained is referred to hereinafter as copolymer CP1.
The copolymer thus obtained is referred to as polymer CP1 and, owing to the virtually complete conversion of the methoxy polyethylene glycol methacrylate (90 mol %) has a block structure in which the side chain-bearing monomer units (methoxy polyethylene glycol methacrylate) are present in a first block and the phosphorus-containing monomer units (MAPC-1-phosphonic acid) essentially spatially separately in a second block.
1.2 Copolymer CP2
For preparation of a further block copolymer by means of RAFT polymerization, 28.74 g of 50% methoxy polyethylene glycol-1000 methacrylate were weighed into a 3-neck flask and diluted with 12.59 g of H2O. A gentle nitrogen stream was introduced into the solution. The reaction mixture was heated to 80° C. As soon as the temperature had been attained, 0.252 g of 4-cyano-4-(thiobenzoyl)pentanoic acid was added. After 10 min, 0.045 g of AIBN was then added. From then on, the conversion is determined regularly by means of HPLC. As soon as the conversion, based on methoxy polyethylene glycol methacrylate, had reached about 90%, 7.5 g of 2-(phosphonooxy)ethyl methacrylate (CAS: [24599-21-1]) were added. The reaction mixture is left to stir for a further 3 h. After cooling, what remains is an about 40% reddish solution.
The copolymer thus obtained is referred to as polymer CP2 and likewise has a block structure.
1.3 Copolymer R
For preparation of a comparative polymer, a round-bottom flask equipped with a reflux condenser, stirrer system, thermometer and an inert gas inlet tube is initially charged with 57.4 g of 50% methoxy polyethylene glycol 1000 methacrylate (0.03 mol) and 25.9 g of deionized water, and also 6.21 g (0.07 mol) of methacrylic acid. The reaction mixture is heated to 80° C. with vigorous stirring. A gentle inert gas stream is passed through the solution during the heating and over all the remaining reaction time. 504 mg of 4-cyano-4-(thiobenzoyl)pentanoic acid (1.8 mmol) are then added to the mixture. Once the substance has fully dissolved, 90 mg of AIBN (0.55 mmol) are added. From then on, the conversion is determined regularly by means of HPLC.
The reaction is stopped as soon as the conversion of the two monomers exceeds 85%. What remains is a clear, pale reddish, aqueous solution having a solids content of around 40%. The copolymer thus obtained is referred to as polymer R and has a statistical distribution of the monomer units.
2.1 Production
The cement pastes used for test purposes are based on cement (CEM I 42.5 N; Normo 4; available from Holcim Schweiz) and water.
To make up one of the cement paste the cement dry-mixed in a Hobart mixer for 1 minute. Within 30 seconds, the makeup water (ratio of water to cement
| Number | Date | Country | Kind |
|---|---|---|---|
| 1518676 | Sep 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/072555 | 9/22/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/050905 | 3/30/2017 | WO | A |
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| 20050228142 | Kraus | Oct 2005 | A1 |
| 20120016059 | Faure | Jan 2012 | A1 |
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| Number | Date | Country | |
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| 20180273668 A1 | Sep 2018 | US |
