WO2017050905A1 - Copolymere mit phosphorgruppen-tragenden monomereinheiten - Google Patents
Copolymere mit phosphorgruppen-tragenden monomereinheiten Download PDFInfo
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- WO2017050905A1 WO2017050905A1 PCT/EP2016/072555 EP2016072555W WO2017050905A1 WO 2017050905 A1 WO2017050905 A1 WO 2017050905A1 EP 2016072555 W EP2016072555 W EP 2016072555W WO 2017050905 A1 WO2017050905 A1 WO 2017050905A1
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- 0 C*(**)C(*(C)C(C)(C)CC(C)(C)C(*)(C(*)(*)N)N)=O Chemical compound C*(**)C(*(C)C(C)(C)CC(C)(C)C(*)(C(*)(*)N)N)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0061—Block (co-)polymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0063—Polymers chosen for their physico-chemical characteristics obtained by an unusual polymerisation process, e.g. by changing the molar ratio of the different monomers during the polymerisation process
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Definitions
- the invention relates to a copolymer, in particular a dispersant for solid particles, in particular a dispersant for mineral binder compositions. Furthermore, the invention relates to the use of a copolymer as a dispersant for solid particles, a mineral binder composition and a molded article obtainable therefrom.
- Dispersants are used in the construction industry as liquefiers or water reducing agents for mineral binder compositions, e.g. Concrete, mortar, cement, plaster and lime.
- the dispersants are generally organic polymers which are added to the make-up water or added as a solid to the binder compositions. As a result, both the consistency of the binder composition during processing and the properties in the cured state can be advantageously changed.
- Polycarboxylate-based comb polymers for example, are known as particularly effective dispersants. Such comb polymers have a polymer backbone and side chains attached thereto. Corresponding polymers are described, for example, in EP 1 138 697 A1 (Sika AG). Also known as concrete admixtures are copolymer blends as mentioned, for example, in EP 1 1 10 981 A2 (Kao). The copolymer blends are prepared by reacting ethylenically unsaturated monomers in a free radical polymerization reaction, wherein the molar Ratio of the two monomers during the polymerization process is changed at least once.
- the object of the invention is therefore to overcome the disadvantages mentioned above.
- an improved dispersant especially for solid particles and in particular for mineral binder compositions should be provided.
- the dispersant should enable effective liquefaction and good processing of mineral binder compositions.
- the effect of the dispersant over the longest possible time should be maintained. It is further desirable that the dispersant can be produced as flexibly and as controlled as possible.
- the core of the invention is therefore a copolymer, in particular a dispersant for solid particles, in particular a dispersant for mineral binder compositions, having a polymer backbone and side chains attached thereto, comprising at least one phosphorus group-bearing monomer unit M1 and at least one side chain-carrying monomer unit M2, wherein the Copolymer in one direction along the polymer backbone has a non-random distribution of the monomer units M1 and / or the monomer units M2.
- such copolymers give, on the one hand, very good liquefaction effects in mineral binder compositions compared with known dispersants, which also remain relatively longer.
- the copolymers according to the invention show in some cases significantly better liquefaction performance.
- the copolymers used according to the invention can be prepared in an efficient manner in a wide variety of modifications in a reliable manner.
- a first aspect of the present invention relates to a copolymer, in particular a dispersant for solid particles, in particular a mineral binder dispersing agent having a polymer backbone and side chains attached thereto, comprising at least one phosphorus group-carrying monomer unit M1 and at least one side chain-carrying monomer unit M2 wherein the copolymer has a non-random distribution of the monomer units M1 and / or the monomer units M2 in one direction along the polymer backbone.
- phosphorus group-carrying monomers and "phosphorus group-carrying monomer unit” is meant, in particular, monomers or polymerized monomers which have at least one phosphorus atom. This is preferably present in the oxidation state + III and / or + V.
- the phosphoric group-carrying monomer unit comprises a phosphoric acid group and / or a phosphonic acid group.
- the acid groups may also be present as anions in deprotonated form or as a salt with a counterion or cation.
- the phosphoric group-carrying monomer unit may in particular contain one or more heteroatoms, one or more alkylene groups and / or one or more heteroatoms. have more alkylene oxide groups.
- the heteroatom may be, for example, nitrogen, which is in particular part of an amine and / or amide group.
- a "non-random distribution” is understood to mean a non-statistical distribution of the monomer units M1 and / or the monomer units M2. This means that the phosphorus group-carrying monomer unit M1 and / or the side chain-carrying monomer units M2 are arranged in the copolymer, for example, alternately, block-wise and / or in a gradient structure.
- the structure of the copolymers can be analyzed and determined, for example, by nuclear magnetic resonance spectroscopy (NMR spectroscopy).
- NMR spectroscopy nuclear magnetic resonance spectroscopy
- 1 H and 13 C NMR spectroscopy can be determined in a conventional manner due to neighboring group effects in the copolymer and based on statistical evaluations, the sequence of the monomer units in the copolymer.
- the phosphorus group-carrying monomer unit M1 is preferably 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-carrying monomer unit M2 contains in particular polyalkylene oxide side chains, in particular polyethylene oxide and / or polypropylene oxide side chains.
- the phosphoric group-carrying monomer units M1 have a structure according to formula I:
- the side chain-carrying monomer units M2 preferably have a structure according to the formula II:
- each G is independently, -O- or -NH-; and each Q, each independently of the others, is hydrogen, an alkyl group of 1-5 carbon atoms and / or PO3M2; each K, independently of the others, is hydrogen, a chemical bond or an alkylene group of 1-3 carbon atoms;
- R 2 , R 3 , R 5 and R 6 are H or an alkyl group having 1 to 5 carbon atoms,
- R 4 and R 7 are H, -COOM or an alkyl group having 1 to 5 carbon atoms,
- a molar ratio of the monomer units M1 to the monomer units M2 is advantageously in the range from 0.5 to 6, in particular 0.7 to 4, preferably 0.9 to 3.8, more preferably 1 .0 to 3.7 or 2 to 3.5.
- -PO 3 M 2 stands for a compound of the formula -PO (OM) 2 , which is based on phosphonic acid group.
- R 1 is -PO (OM) 2 and / or -O-PO (OM) 2 .
- R 1 may be advantageous in some instances when the copolymer has a gradient structure.
- R 2 H or CH 3
- Q is in particular hydrogen and / or a methyl group. More preferably, Q is hydrogen.
- the copolymers can be prepared, for example, starting from (meth) acrylic acid esters, vinyl, (meth) allyl or isoprenol ethers.
- R 2 and R 5 are each mixtures of 40-60 mol% H and 40-60 mol% -CH 3 .
- R 2 H
- R 5 -CH 3
- the radical R 8 in the side chain-carrying monomer units M2 consists, based on all the radicals R 8 of the monomer units, in particular at least 50 mol%, in particular at least 75 mol%, preferably at least 95 mol% or at least 99 mol% %, from a polyethylene oxide.
- a proportion of ethylene oxide units relative to all alkylene oxide units in the copolymer is in particular more than 75 mol%, in particular more than 90 mol%, preferably more than 95 mol% and in particular 100 mol%.
- R 8 has substantially no hydrophobic groups, especially no alkylene oxides having three or more carbon atoms.
- a proportion of alkylene oxides having three or more carbon atoms, based on all alkylene oxides, is less than 5 mol%, in particular less than 2 mol%, preferably less than 1 mol% or less than 0.1 mol% is.
- there are no alkylene oxides having three or more carbon atoms or their proportion is 0 mol%.
- R a is advantageously H and / or a methyl group.
- A C2-alkylene and R a is H or a methyl group.
- excellent dis - achieved pergier moralen in particular in the preferred ranges mentioned, excellent dis - achieved pergier moralen.
- R 2 and R 5 independently of one another, are H, -CH 3 or mixtures thereof;
- R 3 and R 6 independently of one another, are H or -CH 3 , preferably H;
- the copolymer comprises at least one further monomer unit MS, which differs in particular from the monomer units M1 and M2 chemically.
- at least one further monomer unit MS is a monomer unit of the formula III:
- R 5 , R 6 , R 7 , m 'and p' are the same as R 5 , R 6 , R 7 , m and p are defined;
- Y each independently, is a chemical bond or -O-;
- Z each independently, is a chemical bond, -O- or -NH-;
- R 9 in each case independently of one another, represents an alkyl group, cycloalkyl group, alkylaryl group, aryl group, hydroxyalkyl group or an acetoxyalkyl group, each having 1 to 20 C atoms.
- the at least one further monomer unit MS consists of copolymerized vinyl acetate, styrene and / or hydroxyalkyl (meth) acrylate, in particular hydroxyethyl acrylate.
- a weight average molecular weight M w of the entire copolymer is in particular in the range of 10 ⁇ 00 - 150 ⁇ 00 g / mol, advantageously 12 ⁇ 00 - 80 ⁇ 00 g / mol, especially 12 ⁇ 00 - 50 ⁇ 00 g / mol.
- molecular weights such as the weight-average molecular weight M w or the number-average molecular weight M n are determined by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as a standard. This technique is known per se to the person skilled in the art.
- the copolymer is a polymer of substantially linear structure. This means in particular that all monomer units of the copolymer are arranged in a single and / or unbranched polymer chain.
- the copolymer does not have a star-shaped structure and / or the copolymer is not part of a branched polymer.
- the copolymer is not part of a polymer in which a plurality of, in particular three or more, extending in different directions polymer chains are attached to a central molecule.
- 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-carrying monomer unit M1 and / or with respect to the side chain-carrying monomer unit M2.
- the copolymer according to the invention has a concentration gradient in at least one section AA in one direction along the polymer backbone with respect to the phosphoric group-carrying monomer unit M1 and / or with respect to the side chain-carrying monomer unit M2.
- concentration gradient is used here in particular for a continuous change in the local concentration of a Monomer unit in at least a portion in a direction along the backbone of the copolymer.
- concentration gradient is “concentration gradient”.
- the concentration gradient may e.g. be essentially constant. This corresponds to a linear decrease or increase in the local concentration of the respective monomer unit in at least a portion AA along the direction of the backbone of the copolymer. However, it is possible that the concentration gradient changes along the direction of the backbone of the copolymer. In this case, there is a nonlinear decrease or increase in the local concentration of the respective monomer unit.
- the concentration gradient extends in particular over at least 10, in particular at least 14, preferably at least 20 or at least 40, monomer units of the copolymer.
- the term "local concentration" as used herein refers to the concentration of a particular monomer at a given site of the polymer backbone.
- the local concentration or mean of the local concentration e.g. by determining the monomer conversions during the preparation of the copolymer. In this case, the monomers reacted in a certain period of time can be determined.
- the average local concentration corresponds in particular to the ratio of the molar fraction of a certain monomer converted over the period under consideration to the total molar amount of monomers reacted in the period considered.
- the conversions of the monomers can be determined, for example, by means of liquid chromatography, in particular high-performance liquid chromatography (HPLC), and taking into account the amounts of monomers used, in a manner known per se.
- the structure of the copolymer can be determined as described above by 1 H and 13 C NMR spectroscopy.
- the copolymer can also have more than one section AA with a gradient structure, in particular two, three, four or even more sections AA, which are arranged, for example, behind one another. If available, different gradient structures or concentration gradients can exist in each of the different sections AA.
- a local concentration of the at least one phosphorus group-carrying monomer unit M1 continuously increases 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-carrying monomer unit M1 at the first end of the at least one section AA is in particular lower than at the second end of the section AA, while a local concentration of the side chain-carrying monomer unit M2 at the first end of the section AA is greater than at the second end of section AA, or vice versa.
- the average local concentration of the at least one phosphorus group-carrying monomer unit M1 in the respective subsections along the polymer backbone in at least 3, in particular in at least 5 or 8, successive subsections increases as the average 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, in particular at least 5 or 8, successive subsections, or vice versa.
- an increase or decrease in the averaged local concentration of the at least one phosphorus group-carrying monomer unit M1 in the successive subsections is substantially constant while, advantageously, a decrease or increase in the averaged local concentration of the at least one sidechain-bearing monomer unit M2 in the successive Subsections is also essentially constant.
- the at least one section AA with the gradient structure based on a total length of the polymer backbone, has a length of at least 30%, in particular at least 50%, preferably at least 75% or 90%.
- the at least one section AA based on a total number of monomer units in the polymer backbone, a proportion of at least 30%, in particular at least 50%, preferably at least 75% or 90% of monomer units.
- the at least one section AA based on the weight-average molecular weight of the entire copolymer, has a weight fraction of at least 30%, in particular at least 50%, preferably at least 75% or 90%.
- the section AA with the concentration gradient or the gradient structure in particular mass comes into play.
- the at least one concentration gradient section AA advantageously comprises 5 to 70, in particular 7 to 40, preferably 10 to 25 monomer units M1 and 5 to 70, in particular 7 to 40, preferably 10 to 25, monomer units M2.
- the copolymer is at least 50 mole%, more preferably at least 75 mole%, especially at least 90 mole% or 95 mole%, of phosphoric group-bearing monomer units M1 and side chain-carrying monomer units M2.
- the last two aforementioned conditions apply simultaneously.
- the copolymer has, in addition to the at least one section AA, which has a gradient structure, over a further section AB, wherein over the entire section AB substantially a constant local concentration of the monomers and / or a random or random distribution the monomers are present.
- Section AB may e.g. consist of monomers of a single variety or of several different monomers, which are randomly distributed. In section AB, however, in particular there is no gradient structure or no concentration gradient along the polymer backbone.
- the copolymer may also have more than one further portion AB, e.g. two, three, four or more sections AB, which may differ chemically and / or structurally.
- the at least one section AA connects directly to the further section AB.
- the further section AB comprises phosphoric group-carrying monomer units M1 and / or side-chain-carrying monomer units M2.
- the further section AB in one embodiment of the invention advantageously comprises at least 30 mol%, in particular at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mol %, Phosphoric group-carrying monomer units M1.
- a possibly existing proportion of side-chain-carrying monomer units M2 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 M1 in the further section , In particular, there are no side chain-carrying monomer units M2 in the further section AB.
- the further section AB comprises, based on all the monomer units contained therein, at least 30 mol%, in particular at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mole percent, side chain bearing monomer units M2.
- an optional proportion of phosphoric group-carrying monomer units M1 in the further section AB is in particular less than 25 mol%, in particular less than 10 mol% or less than 5 mol%, based on all monomer units M2 in the further section FROM.
- the further section AB comprises a total of 5 to 70, in particular 7 to 40, preferably 10 to 25 monomer units. These are, in particular, phosphorus-carrying monomer units M1 and / or side-chain-carrying monomer units M2.
- a ratio of the number of monomer units in the at least one section AA with gradient structure to the number of monomer units in the at least one further section AB with the substantially constant local concentration is advantageously in the range from 99: 1 to 1:99, in particular 10:90 to 90:10 , preferably 80:20 - 20:80, especially 70:30 - 30:70.
- the at least one further monomer unit MS may be part of the at least one section AA and / or 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. In particular, different further monomer units MS can be present in the different sections.
- the at least one further monomer unit MS in the at least one section AA advantageously has a proportion of 0.001-80 mol%, preferably 20-75 mol%, especially 30-70 mol%, based on all monomer units in the first section AA, on.
- the at least one further monomer unit MS in the further section AB has in particular a proportion of 0.001-80 mol%, preferably 20-75 mol%, especially 30-70 mol% or 50-70 mol% , based on all monomer units in the further section AB, on.
- the at least one further monomer unit MS with a proportion of 20-75 mol%, especially 30-70 mol%, based on all monomer units in the respective Section, present.
- the copolymer consists of the at least one section AA.
- the copolymer consists of the at least one section AA and the further section AB. Especially in the latter case, very good and long-lasting liquefaction effects result.
- the copolymer may contain 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 of the following characteristics: i) The copolymer consists of at least 75 mol%, especially at least 90 mol% or 95 mol%, of phosphoric group-carrying monomer units M1 and side chain-carrying monomer units M2 ; ii) the copolymer comprises or consists of at least a section AA and a further section AB; iii) The further section AB comprises side chain-carrying monomer units M2, in particular at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mol%, based on all the monomer units contained in section AB , A possibly present proportion of phosphorus group-carrying monomer units M1 in the further section AB is less than 25 mol%, in particular less than 10 mol% or less than 5 mol%, based on all monomer units M2 in the further section AB.
- a molar ratio of the monomer units M1 to the monomer units M2 in the copolymer is in the range of 0.5-6, preferably 0.8-3.5; v)
- R 2 and R 5 are H or CH 3 , preferably CH 3 ;
- X -O- x)
- R a H or -CH 3 , preferably CH 3 ;
- a copolymer consisting of sections AA and AB which has at least all of the features (i) - (iv). Furthermore, a copolymer which has all the features (i) - (xi) is preferred. Even more preferred is a copolymer which realizes all features (i) - (xi) in the respectively preferred embodiments.
- a copolymer comprising at least a first block A and at least one second block B, wherein the first block A has a phosphoric group-carrying monomer unit M1 of the formula I and the second block B and a side chain-carrying monomer unit M2 of the formula II having.
- an optional fraction of monomer units M2 in the first block A is less than 25 mol%, in particular less than or equal to 10 mol%, is based on all monomer units M1 in the first block A and where at most any fraction of monomer units M1 in the second block B less than 25 mol%, in particular less than or equal to 10 mol%, based on all the monomer units M2 in the second block B.
- monomer units M1 of the formula I and / or several different monomer units M2 of the formula II can be present in the copolymer according to the invention.
- the monomer units M1 and any further monomer units in the first block A are distributed in particular statistically or randomly.
- the monomer units M2 and any further monomer units are present in the second block B in particular statistically or randomly distributed.
- the at least one block A and / or the at least one block B is preferably present in each case as a partial polymer with random monomer distribution.
- the at least one first block A advantageously comprises 5 to 70, in particular 7 to 40, preferably 10 to 25, monomer unit M1 carrying phosphoric groups and / or the at least one second block B comprises 5 to 70, in particular 7 to 50, preferably 20 - 40, side chain-carrying monomer units M2.
- any fraction of monomer units M2 present in the first block A is less than 15 mol%, in particular 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.
- any existing proportion of monomer units M1 in the second block B is advantageously less than 15 mol%, in particular 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.
- both conditions are fulfilled at the same time.
- a possibly present proportion of monomer units M2 in the first block A is particularly advantageously less than 15 mol% (based on all the respective monomer units M1 in the first block A) and a possibly existing proportion of monomer units M1 in the second block B is less than 10 Mol%, (based on all monomer units M2 in the second block B).
- the monomer units M1 and M2 are essentially spatially separated, which benefits the dispersing effect of the block copolymer and is advantageous in view of the delay problem.
- the first block A is based on all monomer units in the first block A in particular at least 20 mol%, in particular at least 50 mol%, especially at least 75 mol% or at least 90 mol%, of monomer units M1 of formula I.
- Der second block B based on all the monomer units in the second block B, advantageously comprises at least 20 mol%, in particular 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 in particular in the range from 0.5 to 6, in particular 0.7 to 4, preferably 0.9 to 3.8, more preferably 1 .0 to 3.7 or 2 to 3.5. This achieves an optimum dispersing effect in mineral binder compositions.
- the block copolymer comprises at least one further monomer unit MS as described above.
- several different further monomer units MS can be present.
- the properties of the block copolymer can be further modified and adapted, 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 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. In particular, different monomer units MS can be present in the various blocks.
- the at least one further monomer unit MS in the first block A advantageously has a proportion of 0.001-80 mol%, preferably 20-75 mol%, especially 30-70 mol%, based on all monomer units in the first block A, up.
- the at least one further monomer unit MS in the second block B has in particular a proportion of 0.001-80 mol%, preferably 20-75 mol%, especially 30-70 mol% or 50-70 mol% , based on all monomer units in the second block B, on.
- the at least one further monomer unit MS in the first block A and / or in the second block B, has a proportion of 20-75 mol%, especially 30-70 mol%, based on all monomer units in the respective block , available.
- at least one further block C is arranged, which differs chemically and / or structurally from the first and from the second block.
- the at least one further block C comprises monomer units MS as described above or consists thereof.
- monomer units MS as described above or consists thereof.
- further monomer units it is also possible for further monomer units to be present.
- the at least one further block C comprises at least 50 mol%, in particular at least 75 mol%, preferably at least 90 mol% or at least 95 mol% of monomer units MS as described above.
- the block copolymer according to the invention is a diblock copolymer consisting of a block A and a block B.
- block copolymers which contain at least two blocks of the first block A and / or at least two blocks of the second block B.
- block copolymers which contain the first block A twice and the second block B once or block copolymers which contain the first block A once and the second block B twice.
- block copolymers are in particular triblock copolymers, tetrablock copolymers or pentablock copolymers, preferably triblock copolymers.
- Block A has 7 - 40, in particular 10 - 25, monomer units M1 and block B has 7 - 50, in particular 20 - 40, monomer units M2.
- the first block A is based on all monomer units in the first block A to at least 75 mol%, preferably at least 90 mol%, of monomer unit M1 of the formula I; iii)
- the second block B is based on all monomer units in the second block B to at least 75 mol%, preferably at least 90 mol%, of monomer units M2 of the formula II; iv)
- a molar ratio of the monomer units M1 to the monomer units M2 in the block copolymer is in the range from 0.5 to 6, preferably 0.8 to 3.5; v)
- R 2 and R 5 are H or CH 3 , preferably CH 3 ; vii)
- a diblock copolymer which has all the features (i) - (xi). Even more preferred is a diblock copolymer which realizes all features (i) - (xi) in the respectively preferred embodiments.
- a triblock copolymer consisting of the blocks A, B and C, in particular in the sequence ACB, wherein the triblock copolymer at least all features (i) - (iv).
- a triblock copolymer which has all the features (i) - (xi). Even more preferred is a triblock copolymer which has all the features (i) - (xi) in realized the respective preferred embodiments.
- Block C advantageously comprises monomer units MS as described above or block C consists thereof.
- block A and B additionally contain a further monomer unit MS as described above, in particular a further monomer unit MS of the formula III.
- a further aspect of the present invention relates to a process for preparing a copolymer, in particular a copolymer as described above, wherein monomers carrying phosphorous group m1 and side chain-carrying monomers m2 to form a non-random distribution of the phosphorus group-carrying monomers m1 and / or the side chain-carrying monomers m2 are polymerized together.
- the monomers carrying phosphorous groups m1 correspond after polymerization to the abovementioned phosphorus group-carrying monomer units M1 of the copolymer.
- the side chain-carrying monomers m2 correspond to the side-chain-carrying monomer units M2 described above after polymerization.
- the side chain-carrying monomers m2 include in particular polyalkylene oxide side chains, preferably polyethylene oxide and / or polypropylene oxide side chains.
- the phosphorous group-carrying monomers m1 are based, for example, on a (meth) acrylic ester, (meth) acrylamide, vinyl ethers, allyl ethers, methyl thealyl ethers, and / or isoprenyl ethers, each comprising a phosphoric acid group and / or a phosphonic acid group.
- the ionizable monomers m1 have a structure according to the formula IV:
- the side chain-carrying monomers m2 preferably have a structure according to the formula V:
- At least one further monomer ms is present during the polymerization, which is polymerized, which is in particular a monomer of the formula VI:
- R 5 , R 6 , R 7 , R 9 , Y, Z, m 'and p' are as defined above.
- the phosphorus group-carrying monomer m1 is selected from one or more of the following compounds:
- the preparation of the copolymer takes place in particular by a living free radical polymerization.
- 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 those skilled in the art in other contexts.
- the term is used for chain growth processes in which essentially no chain termination reactions (transfer and termination) take place.
- the living free radical polymerization thus takes place essentially in the absence of irreversible transfer or termination reactions.
- These criteria can be met, for example, if the polymerization initiator is already consumed very early during the polymerization and there is an exchange between the different reactive species, which proceeds at least as fast as the chain propagation itself.
- the number of active chain ends remains in the polymerization during the polymerization Essentially constant. This allows a substantially simultaneous growth of the chains throughout the polymerization process. This results in a corresponding narrow molecular weight distribution or polydispersity.
- controlled radical polymerization or living-radical polymerization is characterized in particular by reversible or even absent termination or transfer reactions. After initiation, therefore, the active sites are retained throughout the reaction. All polymer chains are formed (initiated) simultaneously and grow continuously over the entire time. The radical functionality of the active center is ideally retained even after complete conversion of the monomers to be polymerized. This special property of controlled polymerizations makes it possible, by sequential addition of various monomers to produce well-defined structures such as gradient or block copolymers.
- the "living free radical polymerization” clearly differs from the conventional "free radical polymerization” or the non-living or uncontrolled carried out free polymerization.
- the polymerization is carried out by reversible addition
- RAFT Fragmentation Chain Transfer Polymerization
- NMP Nitroxide Mediated Polymerization
- ATRP Atom Transfer Radical Polymerization
- RAFT agent a growing radical chain adds a so-called RAFT agent, resulting in the formation of an intermediate radical.
- the RAFT agent then fragments in such a way as to rebuild a RAFT agent and a radical available for propagation. In this way, the propagation probability is distributed equally over all chains.
- the average chain length the polymer formed is proportional to the RAFT-agent concentration as well as the reaction conversion.
- organic sulfur compounds are used as RAFT agents.
- Particularly suitable are dithioesters, dithiocarbamates, trithiocarbonates and / or xanthates.
- the initiation of the polymerization can be carried out conventionally by means of initiators or thermal self-initiation.
- nitroxides react reversibly with the active chain end to form a so-called dormant species.
- the equilibrium between active and inactive chain ends is strongly on the side of the dormant species, whereby the concentration of active species is very low. The probability that two active chains meet and cancel is thus minimized.
- Suitable as NMP agent is e.g. 2,2,6,6-tetramethylpiperidine N-oxide (TEMPO).
- the free radical concentration is reduced by the addition of a transition metal complex and a controlling agent (halogen-based) to the extent that chain termination reactions, such as disproportionation or recombination, are largely suppressed.
- RAFT reversible addition fragmentation chain transfer polymerization
- the initiator used for the polymerization is particularly preferably an azo compound and / or a peroxide radical initiator, which is at least one member selected from the group consisting of dibenzoyl peroxide (DBPO), di-tert-butyl peroxide, diacetyl peroxide and azobisisobutyronitrile (AIBN), ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride (AAPH) and / or azo-bis-isobutyramidine (AIBA).
- DBPO dibenzoyl peroxide
- AIBN azobisisobutyronitrile
- AAPH ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride
- AIBA azo-bis-isobutyramidine
- ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride (AAPH)
- AAPH ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride
- a molar ratio of free phosphorus group-carrying monomers m1 to free side chain-carrying monomers m2 is at least temporarily changed.
- the change in the molar ratio includes stepwise and / or continuous change.
- a block structure and / or a concentration gradient or a gradient structure can be formed in a manner which is easy to control.
- the stepwise change takes place in particular in time before the continuous change is performed.
- a copolymer comprises two or more sections of different structure.
- the monomers carrying the phosphorous groups m1 and the side chain-carrying monomers m2 are preferably added at least partially offset in time.
- the polymerization in a first step a) converts or polymerizes a portion of the monomers carrying the phosphorous groups and, after reaching a predetermined conversion in a second step b), combines the not yet reacted phosphorous group-carrying monomers m1 polymerized with the side chain-carrying monomers m2.
- Step a) takes place in this case in particular essentially in the absence of side-chain-carrying monomers m2.
- a copolymer having a section which consists essentially of polymerized phosphorus group-carrying monomers m1 and a subsequent section having a gradient structure can be produced in a simple and cost-effective manner.
- Step a) a part of the side chain-carrying monomers m2 reacted or polymerized and after reaching a predetermined conversion in a second step b) the unreacted side chain-carrying monomers m2 together with the Phos - Phor weakness-carrying monomers m1 polymerized.
- Step a) is carried out in particular substantially in the absence of phosphorous group-carrying monomers m1.
- step a) is carried out in particular until 0.1 to 100 mol%, in particular 1 to 95 mol%, preferably 10 to 90 mol%, in particular 25 to 85 mol%, of the monomers carrying the phosphorous groups m1 or the side chain-carrying monomers m2 reacted or polymerized.
- the conversion of the monomers m1 and m2 or the progress of the polymerization can e.g. be controlled by means of liquid chromatography, in particular high-performance liquid chromatography (HPLC), in a conventional manner.
- the copolymer is at least 50 mole%, more preferably at least 75 mole%, especially at least 90 mole% or 95 mole% Phosphorus group-carrying monomers m1 and side chain-carrying monomers m2.
- the copolymer can be prepared in liquid or solid form.
- the copolymer is present as part of a solution or dispersion, with a proportion of the copolymer being in particular 10-90% by weight, preferably 25-65% by weight.
- the copolymer can be added very well to binder compositions.
- a copolymer is prepared in a solid state, in particular in the form of a powder, in the form of pellets and / or plates. As a result, in particular the transport of the copolymers is simplified. Solutions or dispersions of the copolymers may e.g. be converted by spray drying in the solid state.
- polymers with a predetermined or well-defined structure can be prepared in a controlled manner with the process according to the invention.
- e.g. Block structure copolymers and / or graded-structure copolymers are available.
- a first step a at least part of the side chain-carrying monomers m2 are reacted or polymerized and after reaching a predetermined conversion in a second step b) the phosphorus groups are reacted.
- Step a) takes place in particular in the absence of phosphorous group-carrying monomers m1.
- a first step a it is also possible, in a first step a), to react or polymerize at least some of the phosphoric group-carrying monomers m1 and, after reaching a predetermined conversion, in a second step b) the side chain-carrying monomers m2, optionally together with any not yet reacted phosphorus group-carrying monomers m1 to polymerize.
- Step a) takes place in particular in the absence of side chain-bearing monomers m2.
- copolymers having a gate consisting essentially of polymerized side-chain-carrying monomer monomers m2 and having a subsequent gradient-type section can be prepared in an efficient and cost-effective manner.
- step a) the polymerization in step a) is carried out in particular 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 the phosphoric group-carrying monomers m1 are reacted or polymerized.
- step a) and / or in step b) at least one further polymerisable monomer ms of the formula VI as described above is present.
- the at least one further polymerizable monomer ms is polymerized in this case, in particular together with the monomer m1 and / or the monomer m2.
- step a) and step b) it is also possible, in addition to step a) and step b), to provide a further step c) of the polymerization of the at least one further polymerizable monomer ms.
- a copolymer having an additional portion C can be prepared.
- step c) can be performed in time between step a) and step b).
- the additional section C is spatially arranged between sections AA and AB.
- step c) before or after steps a) and b).
- the additional section C can be arranged after section AA or before section AB.
- a first step a at least part of the side-chain-carrying monomers m2 are reacted or polymerized and after reaching a predetermined conversion in a second step b) the phosphorus groups are reacted.
- Step a) takes place in particular in the absence of phosphorous group-carrying monomers m1.
- step a) The polymerization in step a) is carried out in particular until 75-95 mol%, preferably 85-95 mol%, in particular 86-92 mol%, of the initially charged monomers m2 have been reacted or polymerized.
- step b) the polymerization in step b) is carried out correspondingly until 75 to 95 mol%, in particular 80 to 92 mol%, of the originally introduced monomers m1 are reacted or polymerized.
- step a) and step b) it is also possible, in addition to step a) and step b), to provide a further step c) of the polymerization of the at least one further polymerizable monomer ms.
- a block copolymer having an additional block C can be produced.
- step c) is performed temporally between step a) and step b).
- the additional block C is spatially arranged between the blocks A and B.
- the present invention relates to the use of a copolymer as described above as a dispersant for solid particles.
- solid particles stands for particles of inorganic and / or organic materials. In particular, these are inorganic and / or mineral particles.
- the copolymer is particularly advantageously used as a dispersant for mineral binder compositions.
- the copolymer can be used in particular for liquefaction, for water reduction and / or for improving the processability of a mineral binder composition.
- the copolymer can be used to extend the processability of a mineral binder composition.
- the copolymer may be used to increase the adhesion of a mineral binder composition, particularly in the cured state, to a metallic body and / or a metallic substrate.
- the metallic body or the metallic substrate is in particular a body which consists of iron and / or steel on the surface. This may be, for example, a building construction such as e.g. a building construction or a bridge construction, act. It has surprisingly been found that mineral binder composition containing a copolymer according to the invention on metallic bodies and / or metallic substrates adhere better than an analogous mineral binder composition which contains no inventive copolymer. Further, the present invention further relates to a mineral binder composition containing at least one copolymer as described above.
- the mineral binder composition contains at least one mineral binder.
- mineral binder is meant in particular a binder which reacts in the presence of water in a hydration reaction to solid hydrates or hydrate phases. This may be, for example, a hydraulic binder (eg cement or hydraulic lime), a latently hydraulic binder (eg slag), a pozzolanic binder (eg fly ash) or a non-hydraulic binder (gypsum or white lime).
- the mineral binder or binder composition contains a hydraulic binder, preferably cement. Particularly preferred is a cement having a cement clinker content of> 35 wt .-%.
- the cement is of the type CEM I, CEM II, CEM III, CEM IV or CEM V (according to standard EN 197-1).
- a proportion of the hydraulic binder in the entire mineral binder is advantageously at least 5% by weight, in particular at least 20% by weight, preferably at least 35% by weight, in particular at least 65% by weight.
- the mineral binder consists of> 95 wt .-% of hydraulic binder, in particular cement or cement clinker.
- the mineral binder or the mineral binder composition contains or consists of other binders. These are in particular latent hydraulic binders and / or pozzolanic binders.
- Suitable latent hydraulic and / or pozzolanic binders are, for example, slag, fly ash and / or silica fume.
- the binder composition may contain inert substances such as limestone, quartz flours and / or pigments.
- the mineral binder contains 5 to 95% by weight, in particular 5 to 65% by weight, particularly preferably 15 to 35% by weight, of latently hydraulic and / or pozzolanic binders.
- Advantageous latent hydraulic and / or pozzolanic binders are slag and / or fly ash.
- the mineral binder contains a hydraulic binder, in particular cement or cement clinker, and a latent hydraulic and / or pozzolanic binder, preferably slag and / or fly ash.
- the proportion of the latent hydraulic and / or pozzolanic binder is particularly preferably 5-65% by weight, more preferably 15-35% by weight, while at least 35% Wt .-%, in particular at least 65 wt .-%, of the hydraulic binder.
- the mineral binder composition is preferably a mortar or concrete composition.
- the mineral binder composition is, in particular, a processable and / or waterborne mineral binder composition.
- a weight ratio of water to binder in the mineral binder composition is preferably in the range from 0.25 to 0.7, in particular 0.26 to 0.65, preferably 0.27 to 0.60, in particular 0.28 to 0.55.
- the copolymer is advantageously used in a proportion of 0.01-10% by weight, in particular 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 molded article, in particular a component of a building, obtainable by curing a mineral binder composition as described above comprising a copolymer after the addition of water.
- a building can be eg a bridge, a building, a tunnel, a roadway, or a runway.
- the invention further relates to a layer structure comprising a metallic body and / or a metallic substrate and a mineral binder composition comprising a copolymer according to the invention.
- the mineral binder composition is in particular at least partially in direct contact with the metallic body and / or the metallic substrate.
- the metallic body or the metallic substrate is, in particular, a body which is made of iron and / or steel on the surface, for example a building structure such as a building construction or a bridge construction.
- the mineral binder composition is present in pasty or hardened state. From the following embodiments, further advantageous embodiments of the invention result.
- copolymer CP1 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 allowed to stir for a further 3 hours. After cooling, an approximately 40% reddish solution remains. The copolymer thus obtained is hereinafter referred to as copolymer CP1.
- the copolymer thus obtained is referred to as polymer CP1 and has a block structure in which the side chain-carrying monomer units (methoxy-polyethylene glycol-methacrylate) in a first block and the phosphorus-containing monomer units (MAPC-1 - phosphonic acid) are substantially spatially separated in a second block.
- side chain-carrying monomer units methoxy-polyethylene glycol-methacrylate
- MAC-1 - phosphonic acid phosphorus-containing monomer units
- copolymer CP2 The copolymer thus obtained is referred to as polymer CP2 and also has a block structure. 1 .3 Copolymer R
- the reaction is stopped as soon as the conversion of both monomers exceeds 85%. What remains is a clear, slightly reddish, aqueous solution with 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.
- Table 1 gives an overview of the cement paste tests carried out and the results achieved.
- Experiment V1 is a comparative experiment carried out without addition of a polymer.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Graft Or Block Polymers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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EP16775582.6A EP3353130A1 (de) | 2015-09-24 | 2016-09-22 | Copolymere mit phosphorgruppen-tragenden monomereinheiten |
JP2018515772A JP6916170B2 (ja) | 2015-09-24 | 2016-09-22 | リン基担持モノマー単位を有するコポリマー |
BR112018005579-4A BR112018005579B1 (pt) | 2015-09-24 | 2016-09-22 | Copolímero, seu uso e composição aglutinante |
MX2018003601A MX2018003601A (es) | 2015-09-24 | 2016-09-22 | Copolimeros que tienen unidades monomericas que portan grupos fosforo. |
US15/763,425 US10562999B2 (en) | 2015-09-24 | 2016-09-22 | Copolymers having phosphorus group-carrying monomeric units |
CN201680055527.1A CN108025974A (zh) | 2015-09-24 | 2016-09-22 | 具有带磷基的单体单元的共聚物 |
CONC2018/0004244A CO2018004244A2 (es) | 2015-09-24 | 2018-04-20 | Copolímeros que tienen unidades monoméricas que portan grupos fósforo |
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EP15186761 | 2015-09-24 | ||
EP15186761.1 | 2015-09-24 |
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PCT/EP2016/072555 WO2017050905A1 (de) | 2015-09-24 | 2016-09-22 | Copolymere mit phosphorgruppen-tragenden monomereinheiten |
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US (1) | US10562999B2 (de) |
EP (1) | EP3353130A1 (de) |
JP (1) | JP6916170B2 (de) |
CN (1) | CN108025974A (de) |
BR (1) | BR112018005579B1 (de) |
CO (1) | CO2018004244A2 (de) |
MX (1) | MX2018003601A (de) |
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WO2017050907A1 (de) * | 2015-09-24 | 2017-03-30 | Sika Technology Ag | Copolymere mit gradientenstruktur |
JP2022188314A (ja) * | 2019-11-29 | 2022-12-21 | デンカ株式会社 | 樹脂組成物改質用ブロック共重合体、その製造方法、及び樹脂組成物 |
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EP1110981A2 (de) | 1999-12-20 | 2001-06-27 | Kao Corporation | Betonzusatzmittel |
EP1138697A1 (de) | 2000-03-29 | 2001-10-04 | Sika AG, vorm. Kaspar Winkler & Co. | Polymer-Zementdispergierzusammensetzungen |
FR2949777A1 (fr) * | 2009-09-09 | 2011-03-11 | Lafarge Gypsum Int | Fluidifiant pour liant hydraulique. |
WO2015144886A1 (de) * | 2014-03-27 | 2015-10-01 | Sika Technology Ag | Blockcopolymer |
Family Cites Families (10)
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KR100479628B1 (ko) * | 1996-07-10 | 2005-04-06 | 이.아이,듀우판드네모아앤드캄파니 | 리빙 특성을 갖는 중합 방법 |
KR100551524B1 (ko) * | 2002-01-22 | 2006-02-13 | 아르끄마 | 니트록사이드 존재하에 조절된 라디칼 중합에 의해 수득된 블락 코폴리머를 함유하며 충격 강화된 물질의 제조 및 사용 방법 |
DE10237286A1 (de) * | 2002-08-14 | 2004-02-26 | Degussa Construction Chemicals Gmbh | Verwendung von Blockcopolymeren als Dilpergiermittel für wässrige Feststoff-Suspensionen |
CN1948206A (zh) * | 2005-10-14 | 2007-04-18 | 建筑研究及技术有限责任公司 | 混凝土的加速混合物 |
JP5733608B2 (ja) * | 2008-07-28 | 2015-06-10 | 大日精化工業株式会社 | 高分子分散剤の製造方法 |
PL2411346T3 (pl) * | 2009-03-25 | 2014-05-30 | Siniat Int | Środek upłynniający do spoiwa na bazie siarczanu wapnia |
FR2957072B1 (fr) * | 2010-03-02 | 2012-02-17 | Lafarge Sa | Procede d'inertage d'argiles non gonflantes |
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- 2016-09-22 BR BR112018005579-4A patent/BR112018005579B1/pt active IP Right Grant
- 2016-09-22 EP EP16775582.6A patent/EP3353130A1/de active Pending
- 2016-09-22 WO PCT/EP2016/072555 patent/WO2017050905A1/de active Application Filing
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- 2016-09-22 MX MX2018003601A patent/MX2018003601A/es unknown
- 2016-09-22 US US15/763,425 patent/US10562999B2/en active Active
- 2016-09-22 CN CN201680055527.1A patent/CN108025974A/zh active Pending
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BR112018005579B1 (pt) | 2023-01-10 |
JP2018529818A (ja) | 2018-10-11 |
MX2018003601A (es) | 2018-08-01 |
EP3353130A1 (de) | 2018-08-01 |
US20180273668A1 (en) | 2018-09-27 |
US10562999B2 (en) | 2020-02-18 |
BR112018005579A2 (de) | 2018-10-02 |
CN108025974A (zh) | 2018-05-11 |
CO2018004244A2 (es) | 2018-08-21 |
JP6916170B2 (ja) | 2021-08-11 |
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