EP2344557A1 - Procédé de production de substances téléchéliques à une distribution bimodale des masses moléculaires - Google Patents

Procédé de production de substances téléchéliques à une distribution bimodale des masses moléculaires

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Publication number
EP2344557A1
EP2344557A1 EP09736587A EP09736587A EP2344557A1 EP 2344557 A1 EP2344557 A1 EP 2344557A1 EP 09736587 A EP09736587 A EP 09736587A EP 09736587 A EP09736587 A EP 09736587A EP 2344557 A1 EP2344557 A1 EP 2344557A1
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EP
European Patent Office
Prior art keywords
molecular weight
preparation
polymer
weight distribution
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.)
Withdrawn
Application number
EP09736587A
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German (de)
English (en)
Inventor
Sven Balk
Stephan Fengler
Holger Kautz
Karola Dworak
Christine TRÖMER
Lars Zander
Jens LÜCKERT
Johann Klein
Thomas Möller
Volker Erb
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.)
Henkel AG and Co KGaA
Roehm GmbH Darmstadt
Original Assignee
Henkel AG and Co KGaA
Evonik Roehm GmbH
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA, Evonik Roehm GmbH filed Critical Henkel AG and Co KGaA
Publication of EP2344557A1 publication Critical patent/EP2344557A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • 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
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • 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
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the invention relates to a controlled Polymehsations Kunststoffmaschinensky® for producing (meth) acrylate-based telechelics, which have a bimodal molecular weight distribution, and their use as binders in adhesives or sealants.
  • Tailored copolymers with defined composition, chain length, molecular weight distribution, etc. are a broad field of research. One differentiates among other things between gradient and block polymers. For such materials, various applications are conceivable. In the following some of them are briefly presented.
  • Polymers can be prepared for example by ionic polymerization or by polycondensation or addition. In these methods, the presentation of end phenomenonfunktionalinstrumenter products is not a problem. However, a targeted molecular weight buildup is problematic.
  • Polymers obtained by a free radical polymerization process show molecularity indices well above 1, 8. Thus, it is inevitably very short-chain and long-chain polymers in the overall product in such a molecular weight distribution.
  • the short-chain polymer chains show in melt or solution a reduced viscosity and in a polymer matrix increased mobility compared to long-chain components. This leads, on the one hand, to an improved processability of such polymers and, on the other hand, to an increased availability of polymer-bound functional groups in a polymer composition or coating.
  • long-chain by-products lead to a disproportionate increase in the viscosity of the polymer melt or solution. Also, the migration of such polymers in a matrix is significantly reduced.
  • a disadvantage of free-radical-produced binders of this type is a statistical distribution of functional groups in the polymer chain. Besides that is neither a hard-soft-hard triblock architecture nor the targeted synthesis of individual polymer blocks with narrow molecular weight distributions is possible via a free-radical polymerization method.
  • Suitable living or controlled polymerization methods are, in addition to anionic or group transfer polymerization, also modern methods of controlled free-radical polymerization, such as, for example, RAFT polymerization.
  • the atom transfer radical polymerization (ATRP) method was decisively developed in the 1990s by Prof. Matyjaszewski (Matyjaszewski et al., J. Am. Chem. Soc., 1995, 117, p.5614, WO 97/18247; Science, 1996, 272, p. 866).
  • Binders with a defined polymer design can be made available by a controlled polymerization method, for example in the form of atom transfer radical polymerization.
  • ABA triblock copolymers are described which have an unfunctionalized B block and functionalized A outer blocks.
  • EP 1 475 397 describes such polymers with OH groups, in WO 2007/033887 with olefinic, in WO 2008/012116 with amine and in the not yet published DE 102008002016 with silyl groups.
  • all polymers described in these documents have an explicitly narrow molecular weight distribution.
  • the so-called controlled polymerisation processes do not describe any processes with which it would be possible to produce polymers which have one or more blocks with a specifically broad molecular weight distribution.
  • Bimodalities may occur in anionic polymerization. However, these polymerization methods can only produce certain functionalizations. For the ATRP bimodal distributions for systems are described. The bimodality of these polymers, however, results in each case from the presence of block copolymers on the one hand and unreacted macroinitiators on the other hand. Disadvantage of these methods is that the product consists of a mixture of two different polymer compositions.
  • the object was to provide a method for the synthesis of telechelics, which in total have a polydispersity index of at least 1, 8 available.
  • telechelic triblock polymers of structure ABA from poly (meth) acrylates. They are said to be composed of A blocks having a narrow molecular weight distribution of less than 1, 6 and B blocks, which have a bimodal molecular weight distribution with, on the one hand, long polymer chains and, on the other hand, particularly short polymer chains.
  • B blocks which have a bimodal molecular weight distribution with, on the one hand, long polymer chains and, on the other hand, particularly short polymer chains.
  • ABA triblock copolymers whose B-blocks of bimodal molecular weight distribution have a polydispersity index of at least 1.8, and ABA triblock copolymers containing these B blocks having an overall polydispersity index of at least 1.8.
  • ABA triblock copolymers are equated with pentablock copolymers of the composition ACBCA or CABAC.
  • the new process should be cost-effective and quickly feasible.
  • a further object was to realize particularly low residual concentrations of the transition metal complex compounds after only one filtration step.
  • the object has been achieved by providing a new polymerization process based on atom transfer radical polymerization (ATRP).
  • ATRP atom transfer radical polymerization
  • the problem was solved in particular by adding a bifunctional initiator to the polymerization in several portions and stopping the polymerization by adding suitable sulfur compounds.
  • a process for producing (meth) acrylate polymers characterized in that the (meth) acrylate polymer prepared according to the method has a polydispersity index greater than 1.8.
  • the polymer with a bimodal molecular weight distribution is prepared by a process with a two-time initiation.
  • a bimodal molecular weight distribution of a polymer or a mixture of polymers is understood according to the invention to mean a total molecular weight distribution which comprises two different individual molecular weight distributions with different average molecular weights Mn and Mw.
  • the two molecular weight distributions can be completely separated from each other, overlap in that they have two distinguishable maxima or overlap so far that there is a shoulder formation in the total molecular weight distribution.
  • the total molecular weight distribution is determined by gel permeation chromatography.
  • a process is provided in which the addition of suitable functional sulfur compounds causes a termination of the polymerization. By choosing suitable sulfur compounds, the respective chain ends are functionalized. At the same time, the terminal halogen atoms are removed from the polymer and the transition metal needed for the polymerization is almost completely precipitated. This can then be easily separated by filtration.
  • a process for the synthesis of telechelic ABA triblock copolymers having a polydispersity index greater than 1.8 is provided, characterized in that it is a sequentially carried out atom transfer radical polymerization (ATRP) in which a bifunctional Initiator is added to the polymerization solution, and that the block copolymer as a whole and also the block type B has a polydispersity index greater than 1, 8.
  • ATRP atom transfer radical polymerization
  • the process corresponds as far as the production of polymers without block structure.
  • ABA triblock or CABAC pentablock copolymers are built up. Both the initiation, the polymerization of the middle block B and the termination of the polymerization by adding suitable sulfur compounds take place analogously to the preparation of a polymer without a block structure. Therefore, both structures may be considered identical in view of the following description.
  • the block copolymers are prepared by a sequential polymerization process. This means that the monomer mixture for the synthesis of the blocks, for example A, are added to the system only after a polymerization time t 2 when the monomer mixture for the synthesis of the block, for example B, has been converted to at least 90%, preferably at least 95%. This procedure ensures that the B blocks are free of monomers of composition A and that the A blocks are less than 10%, preferably less contained as 5% of the total amount of the monomers of composition B.
  • the block boundaries are according to this definition at the respective point of the chain at which the first repeating unit of the added monomer mixture - in this example, the mixture A - is.
  • a mere 95% conversion has the advantage that the remaining monomers, especially in the case of acrylates, enable a more efficient transition to the polymerization of a second monomer composition, especially of methacrylates. In this way, the yield of block copolymers is significantly improved.
  • the initiator for the polymerization of the monomer mixture or for block copolymers of the monomer mixture B is added to the polymer solution in two batches in a time-delayed manner.
  • the polymerization is started and by a relatively longer polymerization time, relatively high molecular weight polymer chains are formed.
  • the second monomer charge is added.
  • the first initiator charge is 10% to 90%, preferably 25% to 75% of the total amount of initiator.
  • a method is possible in which the initiator is added in more than two batches.
  • macroinitiators of composition B are formed for the sequential construction of block copolymers of composition ABA.
  • These macroinitiators have a molecular weight distribution with a polydispersity index between 1, 8 and 3.0, preferably between 1, 9 and 2.5.
  • the monomer mixture A is finally added after the polymerization time t 2 .
  • the polymerization time t 2 is at least another 60 minutes, preferably at least 90 minutes. Due to the character of the ATRP, both previously initiated polymer species of composition B are available for the polymerization at this time and the polymer blocks A are built up under the already known conditions of ATRP. These segments of the polymer chains accordingly show a close in itself Molecular weight distribution.
  • pentablock polymers it is also possible to construct blocks of type C or D accordingly.
  • Another advantage of the present invention is the further prevention of recombination.
  • the formation of particularly high molecular weights can be suppressed with this method.
  • Such polymer components would contribute disproportionately to an increase in the solution or melt viscosity.
  • the broadly distributed, monomodal polymer produced according to the invention has a novel polymer distribution.
  • the chains are formed which are subject to the longest polymerization time and thus have the highest molecular weight in the end product.
  • a polymer is obtained which, at high molecular weights, still has the characteristics of a polymer produced by controlled polymerization.
  • the total molecular weight distribution of the polymers produced according to the invention has a polydispersity index greater than 1.8.
  • Another component of the present invention is the targeted functionalization of the ABA, CABAC, ACBCA or CDBDC ⁇ Iockcopolymerymere with broad, monomodal molecular weight distribution at the chain ends.
  • the object was achieved in that after completion of ATRP by adding a suitable sulfur compound, the transition metal compound is precipitated and at the same time the chain ends of the polymer be functionalized. In this way, the chain ends are at least 75%, preferably at least 85% functionalized.
  • the reagents added according to the invention after or during the polymerization termination of the polymer solution are preferably compounds which contain sulfur in organically bound form.
  • These sulfur-containing compounds used for precipitation of transition metal ions or transition metal complexes particularly preferably have SH groups and at the same time a second functional group. Most preferably, this second functional group is a hydroxy, acid or silyl group.
  • the particularly preferred compounds are commercially readily available compounds used in free-radical polymerization as regulators. The advantage of these compounds is their easy availability, their low price and the wide range of variations that allow optimal adaptation of the precipitating reagents to the respective polymerization system. However, the present invention can not be limited to these compounds.
  • Very particularly preferred organic compounds are functionalized mercaptans and / or other functionalized or unfunctionalized compounds which have one or more thiol groups and one or more further functional groups and / or form thiol groups corresponding to the solution conditions and / or one or more further functional groups can, listed.
  • the hydroxy-functional sulfur compounds may be, for example, organic compounds such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopentanol or mercaptohexanol.
  • the acid-functional sulfur compounds may be, for example, organic compounds such as thioglycolic acid or mercaptopropionic acid.
  • the silyl-functional sulfur compounds may be, for example, commercially available compounds which, for example, have great industrial significance as adhesion promoters. Advantage of these compounds is their easy availability and their low price.
  • An example of such a compound is 3-mercaptopropyltrimethoxysilane derived from Evonik Industries under the name DYNALYSAN ® -MTMO dar.
  • silanes are 3-mercaptopropyltriethoxysilane or 3-mercaptopropylmethyldimethoxysilane (ABCR). Particularly reactive are the so-called ⁇ -silanes. In these compounds, the mercapto group and the silane group are bonded to the same carbon atom (R 1 is thus usually -CH 2 -). Corresponding silane groups of this type are particularly reactive and can thus lead to a broader range of applications in the later formulation. An example of such a compound would be mercaptomethylmethyldiethoxysilane (ABCR). In the free-radical polymerization, the amount of regulators, based on the monomers to be polymerized, usually with 0.05% by weight to 5% by weight specified.
  • the amount of the sulfur compound used is not related to the monomers but to the concentration of the polymerization-active chain ends in the polymer solution.
  • polymerization-active chain ends is meant the sum of dormant and active chain ends.
  • the sulfur-containing precipitating agents according to the invention are used in this sense in 1, 5 molar equivalents, preferably 1, 2 molar equivalents, more preferably below 1, 1 molar equivalents and most preferably below 1.05 molar equivalents. The remaining amounts of residual sulfur can be easily removed by modification of the following filtration step.
  • the mercaptans described may have no further influence on the polymers when added to the polymer solution during or after termination of the polymerization, with the exception of the substitution reaction described. This applies in particular to the breadth of the molecular weight distributions, the molecular weight, additional functionalities, glass transition temperature or melting temperature in semicrystalline polymers and polymer architectures.
  • the telechelic polymers or block copolymers according to the invention may contain additional functional groups which correspond to the end groups or may differ from these. In block copolymers, these additional functional groups can be incorporated selectively in one or more blocks.
  • additional functional groups can be incorporated selectively in one or more blocks.
  • the following list is only an example to illustrate the invention and is not intended to limit the invention in any way.
  • the telechelic polymers may have additional OH groups.
  • Hydroxy-functionalized (meth) acrylates which are suitable for this purpose are preferably hydroxyalkyl (meth) acrylates of straight-chain, branched or cycloaliphatic diols having 2-36 C atoms, such as, for example, 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl mono (meth ) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,5-dimethyl-1,6-hexanediol mono (meth) acrylate, more preferably 2-hydroxyethyl methacrylate.
  • Amine groups are, for example, by the copolymerization of 2-dimethylaminoethyl methacrylate (DMAEMA), 2-diethylaminoethyl methacrylate (DEAEMA), 2-tert-butylaminoethyl methacrylate (t-BAEMA), 2-dimethylaminoethyl acrylate (DMAEA), 2-diethylaminoethyl acrylate (DEAEA), 2-t / t-butylaminoethyl acrylate (t-BAEA), 3-dimethylaminopropyl-methacrylamide (DMAPMA) and 3-dimethylaminopropyl-acrylamide (DMAPA).
  • DMAEMA 2-dimethylaminoethyl methacrylate
  • DEAEMA 2-diethylaminoethyl methacrylate
  • t-BAEMA 2-tert-butylaminoethyl methacrylate
  • DAEA 2-dimethyla
  • Polymers with allyl groups can be realized, for example, by the copolymerization of allyl (meth) acrylate.
  • Polymers with epoxy groups by the copolymerization of glycidyl (meth) acrylate.
  • Acid groups can be realized by the copolymerization of tert-butyl (meth) acrylate and subsequent saponification or thermal cleavage of isobutene.
  • Examples of (meth) acrylate-bonded silyl radicals are -SiCl 3 , -SiMeCl 2 , -SiMe 2 Cl, -Si (OMe) 3 , -SiMe (OMe) 2 , -SiMe 2 (OMe), -Si (OPh) 3 , -SiMe (OPh) 2 , -SiMe 2 (OPh), -Si (OEt) 3 , -SiMe (OEt) 2 , -SiMe 2 (OEt), -Si (OPr) 3 , -SiMe (OPr) 2 , -SiMe 2 (OPr), -SiEt (OMe) 2 , - SiEtMe (OMe), -SiPh (OMe) 2 , -SiPhMe (OMe), -SiPh 2 (OM (OMe), -SiPh
  • Me are methyl
  • Ph is phenyl
  • Et is ethyl
  • Pr is iso or n-propyl.
  • a commercially available monomer is, for example, Dynasylan ® MEMO from Evonik Degussa GmbH. These are 3-methacryloxypropylthmethoxysilane.
  • the notation (meth) acrylate stands for the esters of (meth) acrylic acid and means here both methacrylate, such as methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, such as methyl acrylate, ethyl acrylate, etc., as well as mixtures of the two.
  • Monomers which are polymerized both in block A and in block B are selected from the group of (meth) acrylates, for example alkyl (meth) acrylates of straight-chain, branched or cycloaliphatic alcohols having 1 to 40 carbon atoms, for example methyl ( meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl ( meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate;
  • Aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate which may each have
  • compositions to be polymerized may also contain further unsaturated monomers which are copolymerizable with the abovementioned (meth) acrylates and with ATRP.
  • further unsaturated monomers which are copolymerizable with the abovementioned (meth) acrylates and with ATRP.
  • these include, inter alia, 1-alkenes such as 1-hexene, 1-heptane, branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methyl-1-pentene, acrylonitrile Vinyl esters such as vinyl acetate, styrene, substituted styrenes having an alkyl substituent on the vinyl group such as ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes having one or more alkyl substituents on the ring such as vinyltoluene and p
  • these copolymers can also be prepared so as to have a hydroxy and / or amino and / or mercapto functionality in a substituent.
  • monomers are vinylpiperidine, 1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpirrolidone, N-vinylpirrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, hydrogenated vinylthiazoles and hydrogenated vinyl oxazoles.
  • Vinyl esters, vinyl ethers, fumarates, maleates, styrenes or acrylonitriles are particularly preferably copolymerized with the A blocks and / or B blocks.
  • the process can be carried out in any halogen-free solvents.
  • Preference is given to toluene, xylene, H 2 O; Acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone; ether; Aliphatic, preferably pentane, hexane; biodiesel; but also plasticizers such as low molecular weight polypropylene glycols or phthalates.
  • the block copolymers of composition ABA are prepared by sequential polymerization.
  • the ATRP can also be carried out as emulsion, miniemulsion, microemulsion, suspension or bulk polymerization.
  • the polymerization can be carried out at atmospheric pressure, underpressure or overpressure.
  • the polymerization temperature is not critical. In general, however, it is in the range of -20 0 C to 200 0 C, preferably from 0 ° C to 130 0 C and particularly preferably from 50 ° C to 120 ° C.
  • the polymer of the invention has a number average molecular weight between 5000 g / mol and 100000 g / mol, more preferably between 7500 g / mol and 50,000 g / mol and most preferably ⁇ 30000 g / mol.
  • 1, 4-butanediol di (2-bromo-2-methylpropionate), 1, 2-ethylene glycol di (2-bromo-2-methylpropionate), 2,5-dibromo-adipic acid di-ethyl ester or 2,3-dibromo-maleic acid di-ethyl ester used. From the ratio of initiator to monomer results in the later molecular weight, if the entire monomer is reacted.
  • Catalysts for ATRP are described in Chem. Rev. 2001, 101, 2921. Copper complexes are predominantly described, but iron, rhodium, platinum, ruthenium or nickel compounds are also used. In general, all transition metal compounds which are compatible with the initiator, or the polymer chain, which has a transferable atomic group, can form a redox cycle.
  • copper can be supplied to the system starting from CU 2 O, CuBr, CuCl, CuI, CuN 3 , CuSCN, CuCN, CuNO 2 , CuNO 3 , CuBF 4 , Cu (CH 3 COO) or Cu (CF 3 COO).
  • a variant of the reverse ATRP represents the additional use of metals in the oxidation state zero.
  • an acceleration of the reaction rate is effected. This process is described in more detail in WO 98/40415.
  • the molar ratio of transition metal to bifunctional initiator is generally in the range of 0.02: 1 to 20: 1, preferably in the range of 0.02: 1 to 6: 1 and more preferably in the range of 0.2: 1 to 4: 1, without this being a restriction.
  • ligands are added to the system.
  • the ligands facilitate the abstraction of the transferable atomic group by the transition metal compound.
  • a list of known ligands can be found, for example, in WO 97/18247, WO 97/47661 or WO 98/40415.
  • the compounds used as ligands usually have one or more nitrogen, oxygen, phosphorus and / or sulfur atoms. Especially preferred are nitrogenous compounds. Very particular preference is given to nitrogen-containing chelate ligands.
  • Examples include 2,2'-bipyridine, N, N, N ', N ", N” - Pentamethyldiethylenthamin (PMDETA), tris (2-aminoethyl) amine (TREN), N, N, N', N '- tetramethylethylenediamine or 1,1,7,7,10,10-hexamethyltriethylenetetramine.
  • PMDETA Pentamethyldiethylenthamin
  • TREN 2,2'-bipyridine
  • TREN 2,2'-bipyridine
  • TREN tris (2-aminoethyl) amine
  • ligands can form coordination compounds in situ with the metal compounds, or they can first be prepared as coordination compounds and then added to the reaction mixture.
  • the ratio of ligand (L) to transition metal is dependent on the denticity of the ligand and the coordination number of the transition metal (M). In general, the molar ratio is in the range 100: 1 to 0.1: 1, preferably 6: 1 to 0.1: 1 and more preferably 3: 1 to 1: 1, without this being a restriction.
  • the transition metal compound is precipitated by adding the described sulfur compound.
  • the chain-terminating halogen atom is substituted to release a hydrogen halide.
  • the hydrogen halide - e.g. HBr protonates the transition metal-coordinated ligand L to an ammonium halide. This process quenches the transition metal-ligand complex and precipitates the "bare" metal, and then allows the polymer solution to be easily purified by simple filtration, with sulfur compounds preferably being SH group compounds This is a known from the free radical polymerization regulator.
  • the selection of the application examples is not suitable for limiting the use of the polymers according to the invention.
  • Preference is given to using telechelics with reactive groups as prepolymers for moisture-curing crosslinking. These prepolymers can be crosslinked with any desired polymers.
  • the preferred applications for the telechelics according to the invention with, for example, silyl groups are in sealants, reactive hot melt adhesives or adhesives Find.
  • sealants for applications in the areas of vehicle, ship, container, machine and aircraft construction, as well as in the electrical industry and in the construction of household appliances.
  • Other preferred applications are sealants for construction applications, heat sealing applications or assembly adhesives.
  • EP 1 510 550 describes a coating composition which consists, inter alia, of acrylate particles and polyurethanes.
  • a polymer according to the invention resulted in an improvement in the processing and crosslinking properties in a corresponding formulation.
  • Conceivable applications are, for example, powder coating formulations.
  • the new binders make it possible to produce crosslinkable one-component and two-component elastomers, for example for one of the listed applications.
  • Typical further constituents of a formulation are solvents, fillers, pigments, plasticizers, stabilizing additives, water scavengers, adhesion promoters, thixotropic agents, crosslinking catalysts, tackifiers, etc.
  • solvents can be used, for.
  • aromatic hydrocarbons such as toluene, xylene, etc.
  • esters such as ethyl acetate, butyl acetate, amyl acetate, Cellosolveacetat, etc.
  • ketones such as.
  • the solvent can be added already in the course of radical polymerization.
  • Crosslinking catalysts for hydrosilylated binders in a formulation with, for example, corresponding polyurethanes are the common organic tin, lead, mercury and bismuth catalysts, e.g. Dibutyltin dilaurate (eg from BNT Chemicals GmbH), dibutyltin diacetate, dibutyltin diketonate (eg Metatin 740 from Acima / Rohm + Haas), dibutyltin dimaleate, tin naphthenate, etc. It is also possible to use reaction products of organic tin compounds, e.g. B.
  • dibutyltin dilaurate with silicic acid esters eg DYNASIL A and 40
  • crosslinking catalysts become.
  • titanates eg, tetrabutyl titanate, tetrapropyl titanate, etc.
  • zirconates eg, tetrabutyl zirconate, etc.
  • amines eg, butylamine, diethanolamine, octylamine, morpholine, 1,3-diazabicyclo [5.4.6] undecene-7 (DBU), etc.
  • DBU 1,3-diazabicyclo [5.4.6] undecene-7
  • An advantage of the block copolymers is the colorlessness and odorlessness of the product produced.
  • Another advantage of the present invention is a limited number of functionalities. A higher proportion of functional groups in the binder leads to a possible premature gelation or at least to an additional increase in the solution or melt viscosity.
  • the number-average or weight-average molecular weights Mn or Mw and the polydispersity index D Mw / Mn as a measure of the molecular weight distributions are determined by gel permeation chromatography (GPC) in tetrahydrofuran versus a PMMA standard.
  • the polymerization is carried out analogously to Comparative Example 1 with the addition of the amounts indicated in Table 1. Termination of the reaction is carried out with the addition of 2.0 g of thioglycolic acid.
  • the polymerization is carried out analogously to Comparative Example 1 with the addition of the amounts indicated in Table 1. Termination of the reaction is carried out with the addition of 5.0 g Dynasylan MTMO.
  • MMA methyl methacrylate
  • n-BA n-butyl acrylate
  • Comparison games 1 to 3 show that with conventional addition of initiator in a batch, polymers with relatively narrow internal blocks and polydispersity indices smaller than 1.4 are formed. After removal of the solvent, the silyl-functionalized products can be stabilized by addition of suitable drying agents. In this way, a good storage stability can be ensured without further increase in molecular weight.
  • a quantity of initiator (see Table 1) 1, 4-butanediol di- (2-bromo-2-methylpropionate) (BDBIB, total initiator dissolved in 26 ml of propyl acetate) is added after a reaction time of two hours the reaction solution a quantity of initiator 2 (see Table 1) 1, 4-butanediol di- (2-bromo-2-methylpropionate) (BDBIB).
  • the polymerization solution is stirred for a further two hours at the polymerization temperature before removing a sample for determining the average molecular weight M n (by SEC) and adding methyl methacrylate (exact amount in Table 1).
  • the mixture is stirred for a further two hours at 75 0 C and then terminated by the addition of 2.1 g of mercaptoethanol.
  • the solution is worked up by filtration through silica gel and subsequent removal of volatiles by distillation. The average molecular weight is finally determined by SEC measurements.
  • Example 3 The polymerization is carried out analogously to Example 1 with the addition of the amounts indicated in Table 2. Termination of the reaction takes place with the addition of 2.3 g of thioglycolic acid.
  • Example 3 The polymerization is carried out analogously to Example 1 with the addition of the amounts indicated in Table 2. Termination of the reaction takes place with the addition of 2.3 g of thioglycolic acid.
  • the polymerization is carried out analogously to Example 1 with the addition of the amounts indicated in Table 2.
  • the reaction is stopped with the addition of 4.9 g of Dynasylan MTMO.
  • the molecular weight distributions of the first polymerization stages are each bimodal and have a molecular index D greater than 1.8.
  • the end products have correspondingly large, although in comparison to the pure B blocks smaller molecularity indices. This effect results from the overall higher molecular weight, but also shows that the polymerization of the A blocks takes place in a controlled manner and the blocks themselves have a narrow molecular weight distribution.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Graft Or Block Polymers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Polymerization Catalysts (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de polymérisation contrôlé pour la production de substances téléchéliques à base de (méth)acrylate, qui présentent une distribution bimodale des masses moléculaires, ainsi que leur utilisation comme liant dans des adhésifs ou des masses d'étanchéité.
EP09736587A 2008-11-12 2009-10-06 Procédé de production de substances téléchéliques à une distribution bimodale des masses moléculaires Withdrawn EP2344557A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008043674A DE102008043674A1 (de) 2008-11-12 2008-11-12 Verfahren zur Herstellung von Telechelen mit einer bimodalen Molekulkargewichtsverteilung
PCT/EP2009/062928 WO2010054894A1 (fr) 2008-11-12 2009-10-06 Procédé de production de substances téléchéliques à une distribution bimodale des masses moléculaires

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EP2344557A1 true EP2344557A1 (fr) 2011-07-20

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DE102008043669A1 (de) * 2008-11-12 2010-05-20 Evonik Röhm Gmbh Verfahren zur Herstellung von ABA-Triblockcopolymeren mit einem breit verteilten B-Block
JP5932142B2 (ja) * 2013-04-25 2016-06-08 株式会社カネカ ビニル系重合体の製造方法
US9587062B2 (en) 2014-12-15 2017-03-07 Henkel IP & Holding GmbH and Henkel AG & Co. KGaA Photocrosslinkable block copolymers for hot-melt adhesives
IT201600129491A1 (it) 2016-12-21 2018-06-21 Piaggio & C Spa Avantreno di motoveicolo rollante con blocco di rollio
IT201600129489A1 (it) 2016-12-21 2018-06-21 Piaggio & C Spa Avantreno di motoveicolo rollante con blocco di rollio
IT201600129510A1 (it) 2016-12-21 2018-06-21 Piaggio & C Spa Avantreno di motoveicolo rollante con controllo di rollio
IT201600129497A1 (it) 2016-12-21 2018-06-21 Piaggio & C Spa Avantreno di motoveicolo rollante con blocco di rollio
IT201600129502A1 (it) 2016-12-21 2018-06-21 Piaggio & C Spa Avantreno di motoveicolo rollante con controllo di rollio

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5807937A (en) 1995-11-15 1998-09-15 Carnegie Mellon University Processes based on atom (or group) transfer radical polymerization and novel (co) polymers having useful structures and properties
EP0906342B2 (fr) 1996-06-12 2015-02-11 Warwick Effect Polymers Limited Catalyseur et procede de polymerisation
US5789487A (en) * 1996-07-10 1998-08-04 Carnegie-Mellon University Preparation of novel homo- and copolymers using atom transfer radical polymerization
TW593347B (en) 1997-03-11 2004-06-21 Univ Carnegie Mellon Improvements in atom or group transfer radical polymerization
US6482900B1 (en) 1997-09-22 2002-11-19 Kaneka Corporation Polymer, process for producing the polymer, and curable composition containing the polymer
US6143848A (en) 1997-10-23 2000-11-07 The B.F.Goodrich Company End-functionalized polymers by controlled free-radical polymerization process and polymers made therefrom
EP1085027B1 (fr) 1998-03-27 2004-11-03 Kaneka Corporation Polymere et procede de production de polymere
DE69933945T2 (de) 1998-09-02 2007-09-13 Kaneka Corp. Polymer, verfahren zu seiner herstellung und zusammensetzung
EP1637550B1 (fr) * 1999-03-23 2017-09-20 Carnegie Mellon University Procédé catalytique pour la polymérisation contrôlée des monomères polymérisables par des radicaux, et leurs systèmes polymériques fonctionnels
EP1475397A1 (fr) 2002-02-13 2004-11-10 Kaneka Corporation Copolymere sequence
AU2003229749B2 (en) * 2002-05-08 2009-02-12 Ciba Specialty Chemicals Holding Inc. Polymers produced by atom transfer radical polymerisation technique with structurally modified terminal groups
US20050234194A1 (en) 2002-05-31 2005-10-20 Asahi Denka Co., Ltd Acrylic sol composition
CN1286869C (zh) * 2005-06-30 2006-11-29 江南大学 原子转移自由基聚合制备聚甲基丙烯酸叔丁酯大分子单体
DE102005045458A1 (de) 2005-09-22 2007-03-29 Röhm Gmbh Verfahren zur Herstellung von ABA-Triblockcopolymeren auf (Meth)acrylatbasis
DE102006035726A1 (de) 2006-07-28 2008-01-31 Evonik Röhm Gmbh Verfahren zur Herstellung von ABA-Triblockcopolymeren auf (Meth)acrylatbasis
DE102008002016A1 (de) 2008-05-28 2009-12-03 Evonik Röhm Gmbh Verfahren zur Herstellung von silyl-funktionalisierten ABA-Triblockcopolymeren auf (Meth)acrylatbasis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010054894A1 *

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AU2009315873A1 (en) 2010-05-20
CN102203152A (zh) 2011-09-28
WO2010054894A1 (fr) 2010-05-20
BRPI0922032A2 (pt) 2015-12-15
JP2012508309A (ja) 2012-04-05

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