Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • 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
  • 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
  • C08L53/005—Modified block copolymers
• • 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
  • C09J153/005—Modified block copolymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09K2200/0625—Polyacrylic esters or derivatives thereof

Definitions

• the invention relates to a process for the preparation of (meth) acrylate-based ABA triblock copolymers having a silyl functionalization of the A blocks and their use, for example, 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.
• Block polymers have an abrupt transition between the monomers in the polymer chain, which is defined as the boundary between the individual blocks.
• a common synthesis method for AB block polymers is the controlled polymerization of monomer A and at a later time the addition of monomer B.
• a similar result can also be achieved by adding in a continuous addition of the two monomers whose compositions change at certain points in time. In this case, a gradient copolymer is obtained.
• the ATRP method (atom transfer radical polymerization) was decisively influenced by Prof. Matyjaszewski (Matyjaszewski et al., J. Am. Chenn. Soc., 1995, 117, p.5614, WO 97/18247, Science, 1996, 272, p.866).
• a particular advantage here is that both the molecular weight and the molecular weight distribution are controllable.
• Controlled radical methods are particularly suitable for the targeted functionalization of vinyl polymers.
• silyl functions are of particular interest.
• functionalizations at the chain ends are of particular interest.
• functionalizations at the chain ends are of particular interest.
• functionalizations at the chain ends are of particular interest.
• telechels are functionalizations at the chain ends (so-called telechels) or in the vicinity of the chain ends.
• silyl-telechelic polymers - ie polymers with silyl groups which are located exactly at the two chain ends - is the end-group functionalization of a poly (meth) acrylate with olefinic groups and the subsequent hydrosilylation of these groups.
• a major disadvantage of these products over the invention is the two-stage manufacturing process. While a simple, one-step process is provided by the copolymerization of silyl-functional monomers according to the invention, the described polymer-analogous Implementation not only two stages, but it must also be carried out between the actual polymerization and the hydrosilylation a costly product purification. This must be extremely thorough, since both transition metals - eg from the ATRP process - and in particular the polyvalent, mostly amine ligands used in this process have a deactivating effect on the hydrosilylation catalysts such as the Karstedt catalyst. The resulting multi-stage process is clearly economically and ecologically disadvantageous compared to the inventive single-stage process. Another disadvantage of these products compared to polymers with multiply functionalized, short outer blocks is the higher probability of obtaining unilaterally unfunctionalized products.
• Sealant formulations a lower degree of crosslinking, which counteracts the mechanical stability and chemical resistance of the seal or the adhesive layer.
• EP 1 179 567 and EP 1 197 498 describe three-stage processes for the synthesis of corresponding silyl telechelants. By substitution of the terminal halogen atoms with oxyanions, olefinic groups are introduced at the chain ends. These are finally hydrosilylated in a third process step.
• the disadvantage of free-radically prepared binders of this type would be a statistical distribution of the functional groups in the polymer chain. This leads to a dense network and thus reduced elasticity of the sealant. This can also result in a deterioration of the substrate binding.
• Polymers obtained by a free radical polymerization process often show molecularity indices well above 1.6. With such a molecular weight distribution, therefore, there are inevitably very short-chain and extremely long-chain polymers in the overall product.
• the short-chain by-products may affect the chemical resistance of the product.
• long-chain by-products lead to a disproportionate increase in the viscosity of the polymer melt or solution. This effect is caused by the u.U. as plasticizers effective low molecular weight chains of a broad distribution by no means balanced.
• ATRP-synthesized SiIyI-containing (meth) acrylate copolymers having a random distribution and a narrow molecular weight distribution represent an alternative.
• Disadvantage of such binders compared with the polymers according to the invention is close meshing, which is very advantageous for coating systems, for example
• the formulation in sealants or adhesives can lead to embrittlement of the final product and thus to a higher aging sensitivity.
• other methods are used for the synthesis of functionalized polymer architecture. The two relevant methods will be briefly described below. There will be a distinction from the present invention with regard to the products and also the methodology. In particular, the advantages of ATRP over other methods are highlighted:
• a new development stage are the triblock copolymers described below.
• ABA triblock copolymers are to be equated with 5-block copolymers of the composition ACBCA or CABAC.
• Task was to represent triblock polymers of the structure ABA.
• silyl-terminated poly (meth) acrylates or poly (meth) acrylates which correspond in their properties to silyl-terminated materials or are very similar. This can be achieved for example by the incorporation of one to fewer building blocks with little or no polymerization silyl groups at the chain end. With chain ends, the end segment of a polymer is called, the max. 1 -20 wt .-% of the total weight of the polymer.
• Poly (meth) acrylates which carry silyl-functional chain ends or silyl-terminated poly (meth) acrylates are suitable as prepolymers for moisture-curing formulations, for example in adhesive or sealant applications.
• a further object of the invention is to provide polymers containing reactive silyl functionalities as binders in such a way that the number of silyl groups in the polymer, with good availability for the curing reaction, is kept as low as possible.
• Another object of this invention is the functionalization of short A blocks in ABA triblock copolymers by the incorporation of suitable unsaturated monomers having additional silyl functionality during the last stage of a sequential polymerization.
• Another object is to provide a material with the narrowest possible molecular weight distribution below 1, 6, preferably below 1, 4 available. In this way, both the proportions of higher molecular weight
• Ingredients i.a. contribute to an undesirable increase in the solution or melt viscosity, as well as minimizes the proportions of particularly low molecular weight components that can cause a deterioration of the solvent resistance of the binder. It is therefore an object of the present invention, inter alia, to provide a binding agent for sealing compounds which is either silyl-terminated or has a small number of free silyl groups in the vicinity of the chain ends. Such materials have a higher elasticity when formulated in sealants. This also results in an improvement in adhesion to the substrate.
• Another task was to provide a binder to prevent any premature gelling.
• block copolymers of the composition ABA having at least 1 and a maximum of 4 silyl groups in the individual A blocks characterized in that block A, a copolymer containing silyl-functionalized (meth) acrylates and monomers selected from the Group of (meth) acrylates or mixtures thereof and a block B, containing (meth) acrylates or mixtures thereof, which have no additional silyl function, are polymethylated as ABA block copolymers.
• ABA block copolymers having at least 1 and a maximum of 2 silyl groups in the individual A blocks can also be prepared.
• Both the copolymers of block A and the copolymers of block B can be added with 0-50% by weight of ATRP-polymehsierbare monomers which are not included in the group of (meth) acrylates.
• a preferred embodiment is block copolymers which, with an ABA composition, have ⁇ 4 silyl groups in the individual A blocks and in which case block A is a copolymer comprising silyl-functionalized (meth) acrylates and monomers selected from the group of (meth) acrylates or their Mixtures and optionally further ATRP-polymerizable monomers which are not included in the group of (meth) acrylates and a block B containing (meth) acrylates or mixtures thereof which have no SiIyI function and optionally other ATRP-polymerizable monomers, which are not included in the group of (meth) acrylates, are polymerized as ABA block copolymers, wherein the ATRP-polymerizable monomers can also be copolymerized only in block A or copolymerized only in block B.
• Another performance of the present invention is to provide block copolymers that are specifically functionalized at the ends of the polymer chain.
• the advantage of better crosslinkability can also be seen in the products according to the invention having a relevant higher degree of functionalization. Due to the higher number of reactive groups in the
• Chain end segment a reaction of the silyl groups is more likely and a crosslinking to a comparatively close-meshed elastomer or to flexible sealant runs much faster.
• Targeted control of the crosslink density or the properties of the crosslinked end product is improved by a distribution of the functionalities in the end segments.
• end segments is meant a chain segment which constitutes at most 25% by mass and preferably at most 10% by mass and most preferably at most 5% by mass of the total polymer chain.
• 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 first added to the system 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 process ensures that the B blocks are free of monomers of composition A and that the A blocks contain less than 10%, preferably less than 5% of the total amount of monomers of the monomers
• Composition B included.
• the block boundaries are located at the respective point of the chain at which the first repeat unit of the monomer mixture fed in - in this example mixture A - is located.
• Advantage of the present invention is also a limited number of functionalities in the respective functionalized polymer blocks. 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. This task has been solved by the targeted attachment of the functionalities to the chain end or in the vicinity desselbigen.
• Another advantage of the block copolymers is the colorlessness and odorlessness of the product produced.
• EP 1 510 550 describes a coating composition consisting inter alia of acrylate particles and polyurethanes.
• Conceivable applications would be, for example, powder coating formulations.
• silyl group of the silyl-functional monomer undergoes no or only to a very limited extent a premature crosslinking reaction under polymerization conditions.
• the monomers copolymerized for silyl functionalization are characterized by the following general formula:
• H 2 C CR 3 C (O) OR 4 -Si (OR 1 ) b R 2 aXc
• the organic radicals R 1 and R 2 may each be identical or different from each other. Furthermore, the organic radicals R 1 and R 2 are selected from the group of aliphatic hydrocarbon radicals consisting of 1 to 20 carbon atoms. These groups can be either linear, branched or cyclic. R 1 can also be exclusively hydrogen.
• X is selected from the group of hydrolyzable radicals which are not alkoxy or hydroxy. This includes, inter alia, halo, acyloxy, amino, amido, mercapto, alkenyloxy and like hydrolyzable groups.
• a, b and c are integers between 0 and 3, respectively.
• the sum a + b + c is 3.
• the radical R 3 is hydrogen or an aliphatic hydrocarbon radical consisting of 1 to 20 carbon atoms.
• R 3 is preferably hydrogen (acrylates) or a methyl group (methacrylates).
• R 4 is a divalent group.
• R 4 is preferably divalent aliphatic hydrocarbon radicals consisting of 1 to 20 carbon atoms. Most preferably R 4 is -CH 2 -, - (CH 2 ) 2 - or - (CH 2 ) 3 .
• silyl radicals examples include -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), -SiEt 2 (OMe), -SiPh (OMe) 2 , -SiPhMe (OMe), -SiPh 2 (OMe), -Si
• Me are methyl
• Ph is phenyl
• Et is ethyl
• Pr is iso or n-propyl.
• H 2 C CCH 3 C (O) O-CH 2 -
• H 2 C CHC (O) O- (CH 2 ) 2 -
• H 2 C CCH 3 C (O) O- (CH 2 ) 2 -
• H 2 C CHC (O) O- (CH 2 ) 3 -
• H 2 C CCH 3 C (O) O- (CH 2 ) 3 - listed.
• a commercially available monomer would be, for example, Dynasylan ® MEMO from Evonik Degussa GmbH. This is 3-methacryloxypropyltrimethoxysilane. It is advantageous that the monomers used for the functionalization are polymerized, without resulting in crosslinking reactions.
• the B blocks may in turn have a CDC triblock structure and thus the ABA triblock copolymers would be equivalent to 5-block copolymers of the ACDCA composition.
• the composition of the C blocks corresponds to the composition of the non-silyl-functionalized portion in the A blocks.
• the individual A blocks may in turn have a CA ' diblock structure.
• the blocks A ' are in turn composed of silyl-functionalized (meth) acrylates and monomers selected from the group of (meth) acrylates or mixtures thereof.
• the composition of the C blocks differs from the composition of the A ' blocks in that they contain no silyl-functionalized monomers.
• the C-blocks with respect to the weight fraction in the total polymer - in contrast to the A and A '-Blöcken - not restricted.
• the ABA triblock copolymers with 5 block copolymers of the composition would be equivalent to CA ' BA ' C pentablock copolymers.
• the composition of the C blocks corresponds to the composition of the non-silyl-functionalized portion in the A ' blocks.
• the notation (meth) acrylate stands for the esters of (meth) acrylic acid and here means both methacrylate, such as e.g. Methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, e.g. Methyl acrylate, ethyl acrylate, etc., as well as mixtures of both.
• 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 other unsaturated monomers which are copolymerizable with the abovementioned (meth) acrylates and with ATRP.
• unsaturated monomers 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-methylstyrene, halogenated styrenes such as monoch
• Methylmaleimide and dienes such as e.g. Divinylbenzene, and in the A blocks, the respective hydroxy-functionalized and / or amino-functionalized and / or mercapto-functionalized compounds.
• these copolymers can also be prepared so as to have a hydroxy and / or amino and / or mercapto functionality in a substituent.
• Examples of such 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 according to the invention preferably has a number-average molecular weight between 5000 g / mol and 100 000 g / mol, more preferably between 7500 g / mol and 50 000 g / mol and very particularly preferably ⁇ 30000 g / mol.
• the molecular weight distribution is less than 1, 6, preferably less than 1, 4 and ideally less than 1, 3.
• RO 2 C-CHX- (CH 2 ) n -CHX-CO 2 R RO 2 C-C (CH 3 ) X- (CH 2 ) n -C (CH 3 ) X-CO 2 R, RO 2 C-CX 2 - (CH 2 ) n -CX 2 -CO 2 R, RC (O) -CHX- (CH 2 ) n -CHX-C (O) R, RC (O) -C (CH 3 ) X- (CH 2) n C (CH) 3 XC (O) R, RC (O) -CX 2 - (CH 2) H-CX 2 -C (O) R, XCH 2 -CO 2 - (CH 2) H-OC (O) CH 2 X, CH 3 CHX-CO 2 - (CH 2 ) n - OC (O) CHXCH 3 , (CH 3 ) 2 CX-CO 2 - (CH 2 ) n
• 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 can be used which can form a redox cycle with the initiator, or the polymer chain, which has a transferable atomic group.
• 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,
• ligands can form coordination compounds in situ with the metal compounds, or they can initially be considered as
• Coordination compounds are prepared 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).
• 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 can be precipitated by adding a suitable sulfur compound.
• a suitable sulfur compound By means of addition of, for example, mercaptans, the chain-terminating halogen atom is substituted by release of a hydrogen halide.
• the hydrogen halide - such as 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 also silyl mercaptans may be as used for example 3-Mercaptopropylthmethoxysilan, which can be obtained as Dynasylan MTMO ® from Evonik AG from a known radical polymerization regulators, such as ethylhexyl mercaptan or n-dodecyl mercaptan. to increase the silyl functionalization.
• Block copolymers of the composition ABA, ACBCA, CABAC or CDBDC are preferred as prepolymers for moisture-curing crosslinking.
• the prepolymers can be crosslinked with any desired polymers.
• D blocks are polymer blocks which, on the one hand, correspond in their basic composition to the B block and not the C blocks and, on the other hand, contain silyl-functional building blocks.
• composition ABA, ACBCA, CDBDC or CA ' BA ' C with ⁇ 4 silyl groups in the individual A or D blocks are in sealants,
• Reactive hot melt adhesives or to find in adhesives uses in sealing compounds 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.
• one-component and two-component elastomers can be produced, for example, for one of the listed applications.
• Typical constituents of a formulation are the binder, solvents, fillers, pigments, plasticizers, stabilizing additives, water scavengers, adhesion promoters, thixotropic agents, crosslinking catalysts, tackifiers, etc.
• Aromatic hydrocarbons e.g., toluene, xylene, etc.
• esters e.g., ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, etc.
• ketones e.g., methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc.
• the solvent can be added already in the course of the 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.
• Dibutyltin dilaurate with silicic acid esters can be used as crosslinking catalysts.
• titanates eg tetrabutyl titanate, tetrapropyl titanate, etc.
• zirconates eg tetrabutylzirconate, etc.
• amines eg butylamine, diethanolamine, octylamine, morpholine, 1,3-diazabicyclo [5.4. 6] undezen-7 (DBU), etc.
• DBU 1,3-diazabicyclo [5.4. 6] undezen-7
• the proportion of the crosslinking catalyst in the formulation is preferably 0.01 to 20 parts based on 100 parts of binder, more preferably 0.01 to 10 parts.
• the number-average or weight-average molecular weights Mn or Mw and the molecular weight distributions Mw / Mn are determined by gel permeation chromatography (GPC) in tetrahydrofuran versus a PMMA standard.
• Atmosphere monomer 1 a (exact name and quantity in Table 1), 125 ml of propyl acetate, 0.5 g of copper (l) oxide and 1, 3 g of N, N, N ' , N " , N " - submitted pentamethyldiethylenetriamine (PMDETA) , The solution is left for 15 min. stirred at 80 0 C. Subsequently, initiator 1, 4-butanediol di- (2-bromo-2-methylpropionate) dissolved in 25 ml of propyl acetate (BDBIB, quantity see Table 1) is added dropwise at the same temperature.
• BDBIB 4-butanediol di- (2-bromo-2-methylpropionate
• Example 3 Analogously to Example 1, the monomers 1 b, 2b and 3b (exact name and quantity in Table 1) are used. Example 3
• Example 1 Analogously to Example 1, the monomers 1 c, 2c and 3c (exact name and quantity in Table 1) are used.
• MMA methyl methacrylate
• n-BA n-butyl acrylate
• MEMO Dynasylan MEMO (3-methacryloxypropyltrimethoxysilane) While the molecular weight distributions of the first stage are monomodal, the distributions of the final stages show a more or less pronounced high molecular weight shoulder. These are due to side reactions of the silyl groups under a partial chain dimerization. After removal of the solvent, the products can be stabilized by adding suitable drying agents. In this way, a good storage stability can be ensured without further increase in molecular weight.
• Pentamethyldiethylenetriamine submitted. The solution is left for 15 min. stirred at 80 0 C. Subsequently, initiator 1, 4-butanediol-di- (2-bromo-2-methylpropionate) dissolved in 30 ml of propyl acetate (BDBIB, quantity see Table 1) is added dropwise at the same temperature. After the polymerization time of three hours, a sample for determining the average molecular weight M n (by SEC) is taken and monomer IIa (exact name and quantity in Table 2) is added. After a calculated 95% conversion, a mixture of monomer IIa 'and monomer IIIa (exact name and quantity in Table 2) is finally added.
• initiator 1 4-butanediol-di- (2-bromo-2-methylpropionate
• BDBIB propyl acetate
• MMA methyl methacrylate
• n-BA n-butyl acrylate
• MEMO dynasylan MEMO (3-methacryloxypropyltrimethoxysilane); 1 GPC measurements of the third step before addition of the mercaptan

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