EP3353128A1 - Production d'agents dispersants par polymérisation radicalaire vivante - Google Patents

Production d'agents dispersants par polymérisation radicalaire vivante

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Publication number
EP3353128A1
EP3353128A1 EP16775581.8A EP16775581A EP3353128A1 EP 3353128 A1 EP3353128 A1 EP 3353128A1 EP 16775581 A EP16775581 A EP 16775581A EP 3353128 A1 EP3353128 A1 EP 3353128A1
Authority
EP
European Patent Office
Prior art keywords
monomers
mol
copolymer
polymerization
block
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP16775581.8A
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German (de)
English (en)
Inventor
Jürg WEIDMANN
Jörg ZIMMERMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
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Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP3353128A1 publication Critical patent/EP3353128A1/fr
Pending legal-status Critical Current

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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
    • 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
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • 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
    • 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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • 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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
    • 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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
    • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
    • 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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • 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
    • 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
    • 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
    • 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 process for the preparation of a dispersant for solid particles, in particular a dispersant for mineral binder compositions, wherein ionizable monomers m1 and side chain-carrying monomers m2 are polymerized to a copolymer and to correspondingly available copolymers. Further, the invention relates to the use of copolymers and mineral binder composition and moldings formed therefrom containing copolymers. State of the art
  • Dispersants or flow agents are used in particular in the construction industry as plasticizers or water-reducing agents for mineral binder compositions, such as concrete, mortar, cements, plasters 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.
  • PCE Polycarboxylate-based comb polymers
  • 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).
  • copolymer blends such as e.g. in EP 1 1 10 981 A2 (Kao) are mentioned.
  • the copolymer blends are prepared by reacting ethylenically unsaturated monomers in a free radical polymerization reaction wherein the molar ratio of the two monomers is changed at least once during the polymerization process.
  • the comb polymers obtainable by the process are effective, they must, however, be specially adapted or relatively high-dosed with regard to different fields of application in order to achieve the required effect. In particular, the targeted adaptation of the comb polymers designed but consuming and high dosages are uneconomical.
  • the object of the invention is therefore to overcome the disadvantages mentioned above.
  • it is intended to provide improved processes and dispersants, in particular for solid particles and in particular for mineral binder compositions.
  • the process should allow the most flexible and controlled production of the dispersants, so that targeted adaptation to different fields of application or purposes is made possible.
  • the dispersants should enable effective liquefaction and good processing of mineral binder compositions.
  • the effect of the dispersant over the longest possible time should be maintained.
  • the core of the invention is therefore a process for the preparation of a dispersant for solid particles, in particular a dispersant for mineral binder compositions, wherein ionizable monomers m1 and side chain-bearing monomers m2 are polymerized to a copolymer, wherein the method is characterized in that the polymerization by a living free radical polymerization takes place.
  • living, free radical polymerization can effectively calculate, alter and / or control the polymer structure as well as the sequence of the polymer building blocks.
  • copolymers with block and / or gradient structures can be produced in a simple manner.
  • copolymers which have a relatively narrow molecular weight distribution or polydispersity result.
  • the copolymers according to the invention can thus be prepared in an efficient process in a wide variety of modifications in a reliable and flexible manner.
  • dispersants prepared according to the invention have very good liquefaction effects in mineral binder compositions. This also remains relatively long maintained.
  • polymers by living free radical polymerization is basically known, it is surprising that sterically demanding copolymers can be prepared which are suitable as dispersants for solid particles and in particular for mineral binder compositions.
  • a first aspect of the present invention relates to a process for preparing a solid particle dispersant, in particular a mineral binder dispersant, wherein ionizable monomers m1 and side-chain-carrying monomers m2 are polymerized to a copolymer, the process characterized in that the polymerization is carried out by a living free radical polymerization.
  • Another aspect of the present invention relates to a copolymer which is obtainable by the process according to the invention.
  • 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.
  • ionizable monomers and “ionizable monomer units” is meant in particular monomers or polymerized monomers which are present at a pH> 10, in particular at a pH> 12, in anionic form or negatively charged. These are in particular H-donor groups or acid groups.
  • the ionizable groups are particularly preferably acid groups, such as, for example, carboxylic acid, Sulfonic acid, phosphoric acid and / or phosphonic acid groups. Preferred are carboxylic acid groups.
  • the acid groups may also be present as anions in deprotonated form or as a salt with a counterion or cation.
  • 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 is thus 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 contemporaneous 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 feature of the controlled polymerizations makes it possible to produce well-defined structures such as gradient or block copolymers by the sequential addition of different monomers.
  • all three steps initiation, growth and termination
  • 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 preferably carried out by reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP) and / or atom transfer radical polymerization (ATRP).
  • RAFT reversible addition-fragmentation chain transfer polymerization
  • NMP nitroxide-mediated polymerization
  • ATRP atom transfer radical polymerization
  • the control of the polymerization is achieved by a reversible chain transfer reaction.
  • a growing radical chain adds a so-called RAFT agent, resulting in the formation of an intermediate radical.
  • the RAFT agent then fragments, re-forming 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 of 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 side chain-bearing monomers m2 include in particular polyalkylene oxide side chains, preferably polyethylene oxide and / or polypropylene oxide side chains.
  • the ionizable monomers m1 preferably comprise acid groups, in particular carboxylic acid, sulfonic acid, phosphoric acid and / or phosphonic acid groups.
  • the ionizable monomers m1 have a structure according to the formula I:
  • the side chain-carrying monomers m2 preferably have a structure according to the formula II:
  • R 1 in each case independently of one another, is -COOM, -SO 2 -OM, -O-PO (OM) 2 and / or -PO (OM) 2 ,
  • 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 each independently H, -COOM or one
  • X in each case independently of one another, represents -O- or -NH-
  • Cycloalkyl group or alkylaryl group, and n 2-250, especially 10-200.
  • the monomers m1 are each covalently bonded via the carbon atom which carries the groups R 1 and R 2 , and via the carbon atom which carries the groups R 3 and R 4 , with further monomers.
  • the monomers m2 are each covalently bonded via the carbon atom which carries the group R 5 and via the carbon atom which carries the groups R 6 and R 7 with other monomers.
  • a molar ratio of the monomers m1 used to the monomers m2 used is advantageously in the range of 0.5-6, in particular 0.7-4, preferably 0.9-3.8, more preferably 0.1-0.7 or 2-3.5.
  • the copolymer can be prepared on the basis of acrylic or methacrylic acid monomers, which is interesting from an economic point of view.
  • such copolymers have a particularly good dispersing effect in the present context.
  • R 5 H or CH 3
  • X -O-.
  • the copolymers can be prepared, for example, starting from (meth) acrylic 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 1 COOM
  • R 2 H
  • R 5 -CH 3
  • R 1 COOM
  • the R 8 radical in the side-chain-carrying monomers m2 is, based on all R 8 of the monomers, in particular at least 50 mol%, in particular at least 75 mole%, preferably at least 95 mole% or at least 99 mole%, of a polyethylene oxide.
  • a proportion of ethylene oxide units based on 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%.
  • there are no alkylene oxides having three or more carbon atoms or their proportion is 0 mol%.
  • R 1 is COOM
  • 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
  • X is at least 75 mole%, especially at least 90 mole%, especially at least 99 mole% of all monomers m2 is -O-.
  • At least one further monomer ms is present during the polymerization, which is polymerized, in particular a monomer of the formula III:
  • R 5 , R 6 , R 7 , m 'and p' such as R 5 , R 6 , R 7 , m and p are as defined above;
  • Y each independently, is a chemical bond or -O-;
  • Z 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 monomers ms are each covalently bonded via the carbon atom which carries the group R 5 , and via the carbon atom which carries the groups R 6 and R 7 , with further monomers.
  • the further monomer ms is particularly advantageously vinyl acetate, styrene and / or hydroxyalkyl (meth) acrylate, in particular hydroxyethyl acrylate.
  • An azo compound and / or a peroxide as radical initiator is particularly preferably used as initiator for the polymerization, this being at least one member selected from the group consisting of dibenzoyl peroxide (DBPO), di-tert-butyl peroxide, diacetyl peroxide, azobisisobutyronitrile (AIBN), ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride (AAPH) and / or azo-bis-isobutyramidine (AIBA).
  • DBPO dibenzoyl peroxide
  • AIBN azobisisobutyronitrile
  • AAPH ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride
  • AIBA azo-bis-isobuty
  • ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride (AAPH) is advantageously used as the initiator.
  • polymerization in particular one or more representatives from the group consisting of dithioester, dithiocarbamates, trithiocarbonates and / or xanthates can be used. It has also proven to be advantageous if the polymerization takes place at least partially, preferably completely, in an aqueous solution.
  • a copolymer having a polydispersity ( weight average molecular weight M w / number average molecular weight M n ) of the copolymer ⁇ 1 .5, in particular in the range of 1 .0 - 1 .4, especially 1 .1 - 1 .3, prepared.
  • 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 weight average molecular weight M w or number average molecular weight M n are determined by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as the standard. This technique is known per se to the person skilled in the art.
  • a molar ratio of free ionizable monomers m1 to free sidechain-bearing monomers m2 is changed at least temporarily.
  • 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.
  • both a continuous change and a stepwise change in the molar ratio of the free ionizable monomers m1 to the free side chain-carrying monomers m2 occurs.
  • This stepwise change takes place in particular in time before the continuous change is carried out.
  • a copolymer comprises two or more sections of different structure.
  • the ionizable monomers m1 and the side chain-carrying monomers m2 are preferably added at least partially offset in time.
  • 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 ionizable monomers m1 and a subsequent section having a gradient structure can be produced in a simple and cost-effective manner.
  • Step a) is carried out in particular substantially in the absence of ionizable monomers m1.
  • step a) is carried out in particular until 0.1-100 mol%, in particular 1-95 mol%, preferably 10-90 mol%, in particular 25-85 mol%, of the ionizable monomers m1 or the side chain-bearing monomers m2 are reacted or polymerized.
  • the conversion of the monomers m1 and m2 or the progress of the polymerization for example, by means of liquid chromatography, in particular High performance liquid chromatography (HPLC), be controlled in a conventional manner.
  • liquid chromatography in particular High performance liquid chromatography (HPLC)
  • the copolymer is at least 50 mole%, especially at least 75 mole%, especially at least 90 mole% or 95 mole%, of ionizable monomers m1 and side chain bearing monomers m2.
  • the copolymer is prepared as a polymer of substantially linear structure.
  • the copolymer is not prepared with a star-shaped structure and / or the copolymer is not incorporated as part of a branched polymer.
  • the copolymer is not provided as a constituent 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 can be prepared in liquid or solid form.
  • the copolymer is particularly preferably present as a constituent of a solution or dispersion, with a proportion of the copolymer being in particular 10 to 90% by weight, preferably 25 to 65% by weight.
  • the copolymer can be added very well to binder compositions. If the copolymer is prepared in solution, in particular in aqueous solution, it is also possible to dispense with further preparation.
  • a copolymer is prepared in a solid state, in particular in the form of a powder, in the form of pellets and / or plates.
  • a solid state in particular in the form of a powder, in the form of pellets and / or plates.
  • Solutions or dispersions of the copolymers may e.g. be converted by spray drying in the solid state.
  • polymers of predetermined or well-defined structure can be prepared in a controlled manner with the process according to the invention.
  • a mixture of ionizable monomers m1 and side chain-carrying monomers m2 is preferably prepared and these are reacted together by a living free radical polymerization to the copolymer.
  • RAFT reversible addition-fragmentation chain transfer polymerization
  • the mixture of the monomers e.g. heated, added the RAFT agent and the reaction started by addition of an initiator.
  • the reaction may e.g. are terminated when the conversion of the monomers> 90 mol%.
  • the ionizable monomers m1 and the side-chain-carrying monomers m2 are converted into a block-structured copolymer, wherein the side-chain-carrying monomers m2 substantially in substantially at least a first block A and ionizable monomers m1 substantially at least a second block B, are installed.
  • a possibly present proportion of monomers m1 in the first block A is advantageously less than 25 mol%, in particular less than or equal to 10 mol%, based on all monomers m2 in the first block A.
  • a possibly present proportion of monomers m2 is second block B is in particular less than 25 mol%, in particular less than or equal to 10 mol%, based on all the monomers m1 in the second block B.
  • a) At least a portion of the side chain-carrying monomers m2 are reacted or polymerized and after reaching a predetermined conversion in a second step b) the ionizable monomers m1, optionally together with possibly not yet reacted side chain-bearing monomers m2, polymerized.
  • Step a) takes place in particular in the absence of ionizable 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.
  • the sequence of steps a) and b) can, however, in principle also be exchanged.
  • steps a) and b) it is advantageous to react the monomers m1 or m2 in steps a) and b) up to the above-mentioned conversions.
  • steps a) and b) it is advantageous to carry out steps a) and b) directly one after the other regardless of the selected sequence.
  • the polymerization reaction in steps a) and b) can be maintained as best as possible.
  • the process can be carried out, for example, by introducing monomers m2 in a solvent, for example water, in step a) and then polymerizing to give a first block A.
  • a solvent for example water
  • monomers m1 are added without any delay in step b) and the polymerization is continued.
  • the monomers m1 are added in particular to the already formed block A, whereby a second block B is formed.
  • the polymerization is advantageously continued until the desired conversion of monomer m1 (eg 75-95 mol%, in particular 80-92 mol%, see above) is reached.
  • a diblock copolymer comprising a first block A and a second block B connected thereto is obtained.
  • the first step it is also possible in the first step to first convert the ionizable monomers m1 and only in the second step b) the side chain-carrying monomers m2 in an analogous manner.
  • the monomers m2 and any further monomers are present in the first block A of the copolymer, in particular randomly or randomly distributed.
  • the monomers m1 and any further monomers are present in the second block B of the copolymer, in particular randomly or randomly.
  • 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, monomers m2 and / or the at least one second block B comprises 5 to 70, in particular 7 to 50, preferably 20 to 40, Monomers m1.
  • any proportion of monomers m1 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 monomers m2 in the first Block A.
  • a possibly present proportion of monomers m2 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 monomers m1 in the second block B.
  • both conditions are fulfilled at the same time.
  • the monomers m1 and m2 are substantially spatially separated, which benefits the dispersing effect of the copolymer and is advantageous in view of the delay problem.
  • the first block A is based on all monomers 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 monomers m2 of the formula II.
  • the second block B is based on all monomers in the second block B advantageously at least 20 mol%, in particular at least 50 mol%, especially at least 75 mol% or at least 90 mol% of monomers m1 of the formula I.
  • at least one further polymerizable monomer ms is present in step a) and / or in step b).
  • 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.
  • a further step c) of the polymerization of the at least one further polymerizable monomer ms 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 with 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 at least one further monomer 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 monomers in the first block A, up.
  • the at least one further monomer 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 monomers in the second block B, on.
  • the at least one further monomer ms having a proportion of 20-75 mol%, especially 30-70 mol%, based on all monomers in the respective block , available.
  • a particularly advantageous copolymer having a block structure has at least one or more of the following features: (i) Block A has 7 to 40, in particular 10 to 25, monomers m2 and block B has 7 to 50, in particular 20 to 40, monomers m1 , (ii) The first block A is based on all monomers in the first block A to at least 75 mol%, preferably at least 90 mol%, of monomers m2 of the formula II;
  • the second block B is based on all the monomers in the second block B to at least 75 mol%, preferably at least 90 mol%
  • a molar ratio of the monomers m1 to the monomers m2 in the copolymer is in the range of 0.5-6, preferably 0.8-3.5;
  • R 1 is COOM;
  • R 2 and R 5 are H or CH 3 , preferably CH 3 ;
  • a diblock copolymer consisting of blocks A and B which has at least all features (i) - (iv). Further preferred is 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.
  • Block C advantageously comprises monomer ms as described above or block C consists thereof. In a specific embodiment, in these diblock copolymers or triblock copolymers, additionally in block A and B there is additionally contained a further monomer ms as described above.
  • the ionizable monomers m1 and the side chain-carrying monomers m2 are polymerized together at least in a section of the copolymer to form a concentration gradient and / or a gradient structure.
  • concentration gradient means, in particular, a continuous change in the local concentration of a monomer in at least one 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 monomers in at least a portion along the direction of the backbone of the copolymer.
  • 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 monomers.
  • the concentration gradient extends in particular over at least 10, in particular at least 14, preferably at least 20 or at least 40, monomers of the copolymer.
  • abrupt changes in the concentration of monomers e.g. occur in block copolymers, not referred to as concentration gradient.
  • 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 the mean value of the local concentration can be, for example, by Determine the monomer conversion 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 specific monomer converted in the period considered to the total molar amount of monomers reacted in the period under consideration.
  • the conversions of the monomers can e.g. be determined using liquid chromatography, in particular high performance liquid chromatography (HPLC), and taking into account the amounts of monomers used in a conventional manner.
  • HPLC high performance liquid chromatography
  • the copolymer produced may also have more than one section with a gradient structure, in particular two, three, four or even more sections which may be e.g. arranged one behind the other. If present, different gradient structures or concentration gradients may exist in each of the different sections.
  • a local concentration of the at least one ionizable monomer m1 continuously increases along the polymer backbone, while a local concentration of the at least one sidechain-bearing monomer m2 continuously decreases along the polymer backbone, or vice versa.
  • a local concentration of the ionizable monomer m1 at the first end of the at least one gradient structure portion is less than at the second end of the gradient structure portion, while a local concentration of the side chain bearing monomer m2 at the first end of the gradient structure portion is greater than at second end of the section with gradient structure, or vice versa.
  • an increase or decrease in the averaged local concentration of the at least one ionizable monomer 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 in FIG Is also essentially constant.
  • 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 ionizable monomers m1 together with unreacted side chain-carrying monomers m2, polymerized.
  • Step a) takes place in particular in the absence of ionizable monomers m1. It is also possible in a first step a) to react or polymerize at least a portion of the ionizable monomers m1 and after reaching a predetermined conversion in a second step b) the side chain-bearing monomers m2, optionally together with possibly not yet reacted ionizable Monomers m1, to polymerize. Step a) takes place in particular in the absence of ionizable 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.
  • 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 ionizable monomers m1 are reacted or polymerized.
  • At least one further polymerisable monomer ms of the formula III is present in step a) and / or in step b).
  • 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.
  • the at least one section 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 with the gradient structure based on a total number of monomers in the polymer backbone, has a proportion of at least 30%, in particular at least 50%, preferably at least 75% or 90%, of monomers.
  • the at least one section having a gradient structure has a weight fraction of at least 30%, in particular at least 50%, preferably at least 75% or 90%.
  • section with gradient structure with the concentration gradient or the gradient structure in particular mass comes into play.
  • the at least one section having a gradient structure advantageously comprises 5 to 70, in particular 7 to 40, preferably 10 to 25 monomers m1 and 5 to 70, in particular 7 to 40, preferably 10 to 25, monomers m2.
  • 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% of the ionizable monomers m1 are present in the at least one portion having a gradient structure.
  • the copolymer has, in addition to the at least one section, which has a gradient structure, over a further section, wherein over the entire section substantially a constant local concentration of the monomers and / or a random or random distribution of the monomers is present.
  • This section may e.g. consist of monomers of a single variety or of several different monomers, which are randomly distributed. In particular, however, there is no gradient structure or concentration gradient along the polymer backbone in this section.
  • the copolymer may also have more than one other portion, e.g. two, three, four or even more sections, which may differ chemically and / or structurally.
  • the section with the gradient structure preferably directly adjoins the further section with the statistical monomer distribution.
  • the further statistical distribution section comprises ionizable monomers m1 and / or side-chain-carrying monomers m2.
  • the further section with the random monomer distribution in one embodiment of the invention advantageously comprises, for example, 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%, of ionizable monomers m1.
  • a possibly existing proportion of side-chain-carrying monomers m2 in the further section with random monomer distribution is in particular less than 25 mol%, especially less than 10 mol% or less than 5 mol%, based on all monomers m1 in the further section , In particular, no side-chain-carrying monomers m2 are present in the further section with statistical monomer distribution.
  • the further section with statistical monomer distribution based on all monomers contained therein, at least 30 mol%, especially at least 50 mol%, preferably at least 75 mol% in particular at least 90 mol. % or at least 95 mole% side chain-bearing monomers m2.
  • an optional proportion of ionizable monomers m1 in the further section is in particular less than 25 mol%, in particular less than 10 mol% or less than 5 mol%, based on all monomers m2 in the further section with random monomer distribution ,
  • no ionizable monomers m1 are present in the further section with statistical monomer distribution.
  • the further section comprises a total of 5 to 70, in particular 7 to 40, preferably 10 to 25 monomers. These are in particular monomers m1 and / or m2.
  • a ratio of the number of monomer units in the at least one section having a gradient structure to the number of monomers in the at least one further section having a statistical monomer distribution 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.
  • a particularly advantageous gradient-structure copolymer has at least one or more of the following features: (i) the copolymer is at least 75 mole%, especially at least 90 mole% or 95 mole%, of ionizable monomers m1 and side chain-bearing monomers m2;
  • the copolymer comprises or consists of the at least one gradient structure section and another monomer distribution section;
  • the further statistical monomer distribution section comprises side chain-bearing monomers 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 others Monomeric monomer distribution section.
  • a possibly present proportion of ionizable monomers m1 in the further section is less than 25 mol%, in particular less than 10 mol% or less than 5 mol%, based on all monomers m2 in the further section with statistical monomer distribution.
  • a molar ratio of the monomers m1 to the monomers m2 in the copolymer is in the range of 0.5-6, preferably 0.8-3.5;
  • R 1 is COOM
  • R 2 and R 5 are H or CH 3 , preferably CH 3 ;
  • R a H or -CH 3 , preferably CH 3 ;
  • a copolymer consisting of a gradient structure section and a random monomer distribution section having at least all features (i) - (iv). Further preferred is a copolymer which has all the features (i) - (xi). Even more preferred is a copolymer which realizes all features (i) - (xi) in the respectively preferred embodiments.
  • 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, it is 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 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 latent 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 total mineral binder is advantageously at least 5 wt .-%, in particular at least 20 wt .-%, preferably at least 35% by weight, especially 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 latent hydraulic and / or pozzolanic binder is particularly preferably 5 to 65 wt .-%, particularly preferably 15 to 35 wt .-%, while at least 35 wt .-%, in particular at least 65 wt .-%, of the hydraulic Binder present.
  • 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.
  • the proportion of the copolymer refers to the copolymer itself.
  • the solids content is correspondingly decisive.
  • 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 e.g. a bridge, a building, a tunnel, a lane, or a runway. From the following embodiments, further advantageous embodiments of the invention result.
  • Fig.1 The time course of monomer conversions in the
  • Fig. 2 A schematic representation of a possible structure of a
  • Copolymer which can be derived from the sales according to FIG. 1.
  • the solids content of the polymer R1 is about 40 wt .-%.
  • Diblock copolymer P3 was prepared analogously to diblock copolymer P1, but instead of methoxy-polyethylene glycol moo-methacrylate, the corresponding amount of methoxy-PolyethylenglykoUoo-methacrylate (average molecular weight: 400 g / mol; ⁇ 9 ethylene oxide units / molecule) was used. The solids content of the polymer P3 is again about 40% by weight.
  • copolymer P4 As soon as the reaction, based on methoxy-polyethylene glycol methacrylate, is 65 mol%, 4.66 g of methacrylic acid (0.05 mol) dissolved in 20 g of H 2 O are added dropwise within 20 min. After completion, the mixture is allowed to react for a further 4 h and then allowed to cool. What remains is a clear, slightly reddish, aqueous solution with a solids content of around 35%. The Graded-structure copolyne thus obtained is referred to as copolymer P4.
  • Fig. 1 the time course of the monomer conversions in the preparation of the copolymer P4 is shown.
  • the monomer conversions were determined by high performance liquid chromatography (HPLC) in a manner known per se at the times indicated in Figure 1 during the preparation of the copolymer.
  • HPLC high performance liquid chromatography
  • Fig. 2 also shows a possible structure of the copolymer P4 is shown schematically. This can be derived directly from the conversions mentioned in FIG.
  • the ionizable monomers m1 are shown as dumbbell-shaped symbols.
  • copolymer P4 comprises a first section with gradient structure and a further section consisting essentially of side chain-carrying monomers.
  • the polydispersity of the polymers according to the invention is about 1 .2 throughout.
  • the comparative polymer R1 prepared by polymer-analogous esterification has a polydispersity of about 1.5. 3. mortar tests

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Graft Or Block Polymers (AREA)
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Abstract

La présente invention concerne un procédé de production d'un agent dispersant pour des particules de matière solide, en particulier d'un agent dispersant pour des compositions de liant minérales. Selon le procédé, des monomères M1 ionisables et des monomères M2 porteurs de chaînes latérales sont polymérisés afin de former un copolymère, laquelle polymérisation étant réalisée par le biais d'une polymérisation radicalaire vivante.
EP16775581.8A 2015-09-24 2016-09-22 Production d'agents dispersants par polymérisation radicalaire vivante Pending EP3353128A1 (fr)

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EP3353127A1 (fr) * 2015-09-24 2018-08-01 Sika Technology AG Copolymères séquencés comme dispersant pour des liants activés par voie alcaline
US20180265615A1 (en) 2015-09-24 2018-09-20 Sika Technology Ag Production of dispersants by living radical polymerization
US20210040000A1 (en) * 2018-01-24 2021-02-11 Sika Technology Ag Dispersant for reducing the mixing times of mineral binder systems
JP7053297B2 (ja) * 2018-02-13 2022-04-12 株式会社日本触媒 ポリカルボン酸系共重合体およびその製造方法、並びにこれを用いた無機粒子用添加剤およびセメント組成物
EP3940011A1 (fr) * 2018-05-31 2022-01-19 Sika Technology AG Procédé de production de polymères en peigne bien définis

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JP3600100B2 (ja) 1999-12-20 2004-12-08 花王株式会社 コンクリート混和剤
EP1138696A1 (fr) 2000-03-29 2001-10-04 Sika AG, vorm. Kaspar Winkler & Co. Polymères pour compositions dispersantes pour ciment
DE10237286A1 (de) * 2002-08-14 2004-02-26 Degussa Construction Chemicals Gmbh Verwendung von Blockcopolymeren als Dilpergiermittel für wässrige Feststoff-Suspensionen
JP5485494B2 (ja) * 2005-09-26 2014-05-07 株式会社日本触媒 重合体、その重合体の製造方法およびその重合体を用いたセメント混和剤
KR100860370B1 (ko) * 2005-09-26 2008-09-25 니폰 쇼쿠바이 컴파니 리미티드 중합체, 그 중합체의 제조방법 및 그 중합체를 사용한시멘트 혼화제
JP2008291078A (ja) * 2007-05-23 2008-12-04 Kyoto Univ 重合体の製造方法
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
ES2432423T3 (es) * 2009-03-25 2013-12-03 Lafarge Gypsum International Fluidificante para aglutinante basado en el sulfato de calcio
FR2948932B1 (fr) * 2009-08-05 2012-08-17 Lafarge Sa Superplastifiant pour composition hydraulique
JP5779149B2 (ja) * 2012-07-09 2015-09-16 大日精化工業株式会社 インクジェット記録用白色顔料分散液組成物、該組成物に用いるａ−ｂブロックコポリマーの製造方法およびインクジェット記録用白色インク組成物
US10717803B2 (en) * 2014-03-27 2020-07-21 Sika Technology Ag Block copolymer
US20180265615A1 (en) 2015-09-24 2018-09-20 Sika Technology Ag Production of dispersants by living radical polymerization

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BR112018005571B1 (pt) 2022-12-20
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BR112018005571A2 (pt) 2018-10-09
CN108025972A (zh) 2018-05-11
MX2018003597A (es) 2018-08-01
JP2021119215A (ja) 2021-08-12
CO2018004243A2 (es) 2018-07-10
US20180265615A1 (en) 2018-09-20
JP2018529820A (ja) 2018-10-11

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