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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • 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
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft 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
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate

Definitions

• the invention describes a novel emulsion polymer comprising activator compounds, a two-component or multi-component system with controllable pot life curing by a redox initiator system, which comprises the novel emulsion polymer, and the use of the two-component or multicomponent system.
• the invention relates to emulsion polymers with covalently bonded activators and to two-component or multi-component systems in which in addition to the emulsion polymer containing the activator component also two monomers with different swelling capacity for the emulsion polymer are used.
• the swelling capacity of a first monomer component is insufficient to initiate polymerization of the two- or multi-component system, while the swelling capacity of a second monomer component for the emulsion polymer is sufficiently high to initiate polymerization of the system.
• the polymerization is triggered only by adding this monomer component with sufficiently high swelling capacity.
• the invention also relates to the various applications of the two- or multi-component systems.
• Redox initiation curing two-component systems based on radically polymerizable monomers have long been known.
• the procedure is such that the missing redox system components or all redox system components are added to a liquid monomer or monomer mixture which may contain a redox component prior to use.
• systems are described which additionally contain a polymer dissolved in the monomer or monomer mixture.
• systems are known in which liquid monomer, a Perlpolymehsat and a redox initiator system are mixed before use to a highly viscous mass.
• Exemplary of a variety of publications on the subject are DE 43 15 788, DE OS 1 544 924 and DE 27 10 548 called. All these systems have the disadvantage that, after the components have been mixed together, the time available for processing (pot life) is limited or that energy must be introduced during the application, for example in the form of grinding and friction forces. Although the pot life can be prolonged by reducing the redox component concentration, there are limits to this, since hardening is impaired as the redox component concentration decreases.
• a further disadvantage of the formulations of the prior art is that the maximum concentrations in the workplace (MAK values) of readily volatile monomers, such as, for example, methyl methacrylate, can be exceeded.
• DE 100 51 762 provides monomeric polymer systems based on aqueous dispersions which, in addition to good mechanical properties, offer the advantage of emitting no or only very few monomers and, moreover, being easy to handle and having a high storage stability.
• mixtures of aqueous dispersions are used whose particles are swollen with an ethylenically unsaturated monomer each containing one of the redox components.
• These swollen aqueous systems are virtually unlimited shelf life and cure only after evaporation of the water and the subsequent film formation.
• the disadvantage of these systems is that curing by the required evaporation of the water, especially with thicker layers, takes a long time and disturbs larger amounts of water in a number of applications, such as reactive adhesives.
• WO 99/15592 describes reactive plastisols which, after thermal gelation and curing, lead to films with good mechanical properties.
• These plastisols consist of a known base polymer, preferably in the form of a spray-dried emulsion polymer, a reactive monomer content consisting of at least one monofunctional (meth) acrylate monomer, a plasticizer and optionally further crosslinking monomers, fillers, pigments and excipients.
• Base polymer may have a core / shell structure and contain from 0-20% of polar comonomers.
• the plastisols are stable in storage for weeks and must be heated to high temperatures (eg 130 ° C.) for filming.
• DE 103 39 329 A1 describes a two-component system with controllable pot life curing by a redox initiator system, consisting of an emulsion polymer or more emulsion polymers and an ethylenically unsaturated monomer or a monomer mixture of ethylenically unsaturated monomers, where both the emulsion polymer and the monomer or the monomer mixture may contain one of the components of a redox initiator system.
• the control of the pot life is achieved by absorption of at least one component of the redox initiator system on the polymer.
• the low molecular weight initiator component is physically encapsulated in polymer particles which are prepared by emulsion polymerization.
• concentration of the component encapsulated in the polymer may decrease, for example due to migration.
• the reactivity of the system may deviate from the desired values.
• the components of the redox initiator system essentially the activator component and the peroxidic component, are essential for the rate of cure of the overall system.
• the two specified special constituents have to be stored separately from one another until they are cured, there is always the risk that an incorrectly too slow or too rapid hardening reaction will occur due to incorrect metering of one of the two components.
• the emulsion polymers should allow safe control of the pot life paired with the greatest possible variability of the components that can be stored together.
• the emulsion polymers should also allow the use of a peroxide component in an organic, non-aqueous system.
• two-component or multi-component systems which cure at room temperature are to be made available whose pot life can be adjusted within wide limits and which nevertheless cure rapidly and completely at a defined time without energy input or external mechanical impulse.
• Another object to be solved according to the invention is to minimize odor nuisance and to concentrate the concentration during use
• Another task was to allow a wide variation range of activator concentration.
• the pot life should be made independent of the storage life of the two- or multi-component system. So pot lives are often adjusted by a certain concentration of inhibitors. After prolonged storage under unfavorable conditions, the inhibitors may be partially consumed, so that the pot life is shorter than desired.
• the object of the invention was also to reduce the number of components of the multicomponent system as much as possible, if possible to avoid three or more multicomponent systems and, if possible, to use two-component systems.
• R 1 is hydrogen or methyl
• X is a linear or branched alkanediyl group having 1 to 18 carbon atoms which may be monosubstituted or polysubstituted by hydroxyl groups and / or by C 1 -C 4 alkoxy groups;
• - R 2 is hydrogen or a linear or branched alkyl radical having 1 to 12 carbon atoms, which is optionally substituted one or more times by hydroxyl groups or C 1 -C 4 -alkoxy groups, where the hydroxyl groups may be partially esterified with (meth) acrylic acid;
• - R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen or a linear or branched alkyl or alkoxy group having 1 to 8 carbon atoms, which may be monosubstituted or polysubstituted by hydroxyl groups; and where appropriate, two of the radicals R 3 to R 7 are joined together to form a five- to seven-membered ring and optionally form a fused aromatic ring system with the phenyl radical;
• the activator e) is incorporated into the emulsion polymer via covalent bonds; wherein the emulsion polymer is obtainable by polymerizing the constituents a) to e) in a first stage as a core in the manner of a core-shell polymerization and subsequently in at least one further stage as shell a mixture of the constituents a) to d) ; and wherein the components a) to e) together give 100% by weight of the polymerizable constituents of the emulsion polymer;
• the said emulsion polymer is also referred to below as component A) in connection with the two-component or multicomponent system.
• the notation (meth) acrylate herein and throughout the context of the invention includes both methacrylate, such as methacrylate. Methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, e.g. Methyl acrylate, ethyl acrylate, etc., as well as mixtures of both.
• the emulsion polymer component A) is preferably composed essentially of (meth) acrylate monomers and styrene and / or styrene derivatives and / or vinyl esters.
• Particularly preferred is the structure of at least 80% methacrylate and acrylate monomers, most preferably the structure of exclusively methacrylate and acrylate monomers.
• Examples of monofunctional methacrylate and acrylate monomers having a water solubility ⁇ 2 wt .-% at 20 0 C are in an incomplete list methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, isodecyl methacrylate, lauryl methacrylate, cyclohexyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate,
• styrene derivatives are meant, for example, ⁇ -methylstyrene, chlorostyrene or p-methylstyrene.
• vinyl esters are vinyl acetate and longer chain derivatives such as vinyl versatate.
• Methacrylate monomers in particular methyl methacrylate, are preferably incorporated in order to achieve a higher glass transition temperature, methacrylates having a C number> 4 in the side chain and acrylates in order to lower the glass transition temperature.
• the monomers are combined so that a glass transition temperature above 60 0 C results, preferably above 80 0 C and in particular above 100 C, when the emulsion polymer A) is to be isolated by drying.
• the glass transition temperatures are measured in accordance with EN ISO 11357. If the emulsion polymer A) is to be added to the two-component or multicomponent system as an aqueous dispersion, the glass transition temperature may be lower.
• a glass transition temperature above room temperature is advantageous in some cases.
• it is above 30 ° C, more preferably above 40 0 C, especially above 60 ° C.
• glass transition temperatures below room temperature may be advantageous. This may for example be the case when the dissolving power or the swelling capacity of the monomers used in the two-component or multicomponent system is low, so that the swelling would take too long.
• the glass transition temperatures of the copolymers can be calculated in a first approximation according to the following formula from Fox:
• T 9 is the glass transition temperature of the copolymer (in K), T gA , T gB , T gC , etc., the glass transition temperatures of Homopolymehsate the monomers A, B, C, etc. (in K).
• w A , W B , W C USW. represent the mass fractions of the monomers A, B, C, etc. in the polymer.
• the higher the glass transition temperature of the polymer the greater the swelling resistance compared to the monomers added before the application of the system and thus the pot life.
• increasing the molecular weight / increasing the molecular weight of the polymer generally causes an increase in the swelling resistance.
• particularly preferred emulsion polymers A) are characterized in that a) consists of one or more methacrylate monomers and / or acrylate monomers. Especially useful is a) methyl methacrylate.
• component A b) examples include, among others, maleic anhydride, itaconic anhydride and esters of itaconic and maleic acid.
• Their proportion of the emulsion polymer can be up to 70 wt .-%, preferably from 0 to 30 wt .-%, in particular 0 to 10 wt .-%. Most preferably, component A b) is omitted.
• crosslinker component A c
• the content of polyunsaturated monomers is preferably limited to 20% by weight, based on component A), more preferably less than 10% by weight, more preferably less than 2% by weight, especially less than 0.5 Wt .-% or it is completely dispensed polyunsaturated monomers.
• the swelling resistance of the emulsion polymer for intumescent compounds can also be controlled by the incorporation of polar monomers (component A d)), such as methacrylamide or methacrylic acid, into the emulsion polymer. This increases with increasing amount of methacrylamide or methacrylic acid.
• polar monomers such as methacrylamide or methacrylic acid
• Methylolmethacrylamid and their ethers are conceivable, provided that their proportion is limited so that despite crosslinking of the dispersion particles whose
• the proportion of N-methylolacrylamide or methacrylamide should preferably not exceed 10% by weight, based on component A).
• polar monomers include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, homologues of alkoxy polyethylene glycol methacrylate, alkoxypolypropylene glycol methacrylate, methacryloyloxypolyethylene and polypropylene glycol, and others Vinyloxypolyethylene and polypropylene glycol. All of these monomers can also be used as a mixed form of ethylene and
• Propylene glycol repeating units are present.
• the degree of polymethylation may be from 2 to 150, preferably from 2 to 25.
• Alkoxy is primarily methyl, ethyl and butyl radicals. Longer alkyl chains, e.g. C18, are also possible, but not preferred. Particularly preferred is a methyl radical.
• the proportion of polar monomers depends primarily on the desired pot life of the formulation, but it is also linked to the glass transition temperature of the polymer. The lower the glass transition temperature, the higher the required proportion of polar monomers in order to achieve a specific swelling resistance. Furthermore, the proportion of polar monomers to vote on the dissolving power of the monomers used in the formulation B.
• the proportion of polar monomers in the range of 0 and 20 wt .-%, preferably from 1 to 10 wt .-%, particularly preferably from 2 to 5 wt .-%, in particular from 3 to 5 wt .-% , based on component A). If short pot lives are desired, for example a few minutes, or if the solubility of the monomers in component B) is low, it may be advantageous to limit the content to below 2% or to dispense entirely with polar monomers.
• Methacrylamide and acrylamide as well as methacrylic acid and acrylic acid are particularly effective and are therefore preferred when long pot lives are desired. Particularly preferred is a combination of methacrylamide or acrylamide with methacrylic acid or acrylic acid in the weight ratios of 3 to 1 to 1 to 3.
• the component Ae) to be used successfully in the context of the invention obeys the general formula I.
• linear or branched alkyl radical having 1 to 8
• Carbon atoms are understood for the invention radicals such. Methyl, ethyl, propyl, 1-methylethyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl , or the 1,1,3,3-tetramethylbutyl radical.
• linear or branched alkyl radical having 1 to 12 carbon atoms is meant for the invention radicals having 1 to 8 carbon atoms as described above as well as e.g. the nonyl, isononyl, decyl, undecyl or dodecyl radical.
• C 1 -C 4 -alkoxy groups is understood to mean alkoxy groups for the invention in which the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 4 carbon atoms, such as.
• the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 4 carbon atoms, such as.
• the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 4 carbon atoms, such as.
• the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 4 carbon atoms, such as.
• the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 4 carbon atoms, such as.
• linear or branched alkoxy group having 1 to 8 carbon atoms for the invention is understood to mean alkoxy groups in which the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 8 carbon atoms, such as.
• the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 8 carbon atoms, such as.
• the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 8 carbon atoms, such as.
• the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 8 carbon atoms, such as.
• the hydrocarbon radical is a branched or unbranched hydrocarbon radical having 1 to 8 carbon atoms, such as.
• the possible activator components Ae) are generally (meth) acryloyl-functionalized amine derivatives.
• the activator or accelerator components are based on modified amines, such as 2-N- (ethylanilino) ethanol or 2-N- (ethylanilino) propanol, and these amines are converted to polymerizable accelerator / activator components, preferably by introduction of (meth) acrylate.
• modified amines such as 2-N- (ethylanilino) ethanol or 2-N- (ethylanilino) propanol
• these amines are converted to polymerizable accelerator / activator components, preferably by introduction of (meth) acrylate.
• m-toluidine and Xylidindehvate or other derivatives can be used as a starting point to obtain the activator or accelerator component.
• Preferred activator / accelerator components Ae) include the following compound classes: N - ((meth) acryloyl (poly) oxyalkyl) -
• Particularly advantageous emulsion polymers for the purposes of the invention are methacryloyl-functionalized substances, ie those compounds of the formula (I) in which R 1 is methyl.
• the polymers are characterized in that in the formula (I) X is an ethanediyl, ie an ethylene group -CH 2 -CH 2 -.
• the emulsion polymer is characterized in that X in the formula (I) is a hydroxyl-substituted propanediyl group, namely a 2-hydroxypropylene group -CH 2 -CH (OH) -CH 2 -.
• radical R 2 in the formula (I) is selected from the group consisting of methyl, ethyl and 2-hydroxyethyl.
• e1) contains only one (meth) acryloyl group.
• a content of such crosslinking structures is not critical, as long as it does not affect the usability of the emulsion polymers A) in the two- or multi-component systems, for example by insufficient swellability of the emulsion in monomers due to a too high
• a proportion of polyunsaturated activator monomer below 5% by weight, based on the polymer composition, is not necessarily prohibitive, preferably less than 3, in particular less than 1% by weight. Higher contents are not excluded.
• the person skilled in the art can easily determine whether the monomer is suitable by, for example, testing whether an emulsion polymer A) prepared therewith in the two-component or multicomponent system initiates the polymerization in the desired time interval triggers and whether the polymerization takes place quickly and completely and the polymer has the desired properties.
• those polymers are useful, which are characterized in that in the formula (I) two of the radicals R 3 to R 7 are methyl while the remaining three radicals are hydrogen.
• the proportion of the polymerizable activator Ae) in component A) can be between 0.1 and 95 wt .-%. Preferably, it is chosen as high as possible, for example between 5 and 60 wt .-%, particularly preferably 10 to 60 wt .-%, in particular 20 to 50 wt .-%.
• the upper limit is determined by the behavior of the selected activator in the emulsion polymerization. The skilled person will make sure that not too large amounts of unacceptable amounts of coagulum are formed, or too high residual monomer contents remain. It may also be that the specific activity of the activator decreases with increasing installation quantity. Since the polymerizable activator represents a rather expensive monomer component, the skilled person will strive to find a compromise between the highest possible Einbaumengege and cost-effectiveness.
• the emulsion polymer A) is constructed for the purposes of the invention as a core-shell polymer.
• Core-shell polymer here stands for a polymer which has been prepared by a two- or multi-stage emulsion polymerization, without necessarily having to show the core-shell structure, for example by electron microscopy. If the polymerizable activator is incorporated only in the core, that is to say in the first stage, such a structure contributes to the fact that the Activator is not accessible to the peroxide until sufficient swelling and thus premature polymerization is prevented.
• a particular embodiment of the invention relates to the fact that the polar monomers are confined to the shell, core and shell, apart from the polymehsierbaren activator in the core, but otherwise the same structure.
• the core and the shell may differ significantly in the monomer composition, which has an effect, for example, on the particular glass transition temperature.
• the glass transition temperature of the shell is above that of the core, preferably above 60 0 C, more preferably above 80 0 C, especially above 100 ° C.
• the polar monomers may be confined to the shell.
• the core-shell structure particularly advantageous properties are achieved. Among others, this includes the better protection of the activator against premature contact with the peroxide by a shell or a plurality of shells.
• the activator monomer is preferably incorporated into the core. It may also be necessary to make the cured polymers more flexible.
• the core is set at a relatively low glass transition temperature.
• the shell with a higher glass transition temperature then has the task of ensuring the desired swelling resistance and possibly the insulation as a solid.
• the weight ratio of core to shell depends on how well the activator is to be protected or what effects are expected from this structure. In principle, it may be between 99 and 99: 1, ie it is generally not critical as long as the purpose of the emulsion polymer A) to activate the polymerization of the two-component or multicomponent system in the desired manner is not impaired.
• the shell content is usually limited to the extent necessary to allow a high Aktivatoranteil in the emulsion polymer. If special effects, for example a flexibilization of the cured polymer systems by a core polymer with a low glass transition temperature, are to be achieved by the structure, then the core-shell ratio must be matched to the desired effects. Most of the skilled person will adjust the shell content between 10 and 50 wt .-%, preferably between 20 and 40 wt .-%, in particular between 25 and 35 wt .-%.
• the invention also relates to a process for the preparation of an emulsion polymer according to the invention in which the components a) to e) of component A) are polymerized in aqueous emulsion.
• the emulsion polymerization is carried out in a manner generally known to those skilled in the art.
• the performance of an emulsion polymerization is described by way of example in EP 0376096 B1.
• an initiator is selected which forms no redox system with the polymerizable activator A e).
• azo initiators such as the Na salt of 4,4'-azobis (4-cyanovaleric acid) are suitable.
• the solid A) is required for certain applications, it can be isolated in a known manner.
• the solid of component A) may be recovered from the dispersion by known methods. These include spray drying, freeze coagulation with suction filtration and drying and pressing with an extruder.
• the polymer is preferably obtained as a solid by spray drying.
• component A) is not isolated. Since some amount of water generally does not interfere with the intended applications, component A) may also be added to the system as an aqueous dispersion.
• the molecular weight of component A), expressed as the weight-average molecular weight MW, can be used inter alia to influence the swelling resistance to compounds such as monomers to a certain extent. High weight average molecular weights MW tend to increase the swelling resistance, while lower weight average molecular weights MW lower. Thus, the desired pot life is decisive, inter alia, whether the expert selects a high molecular weight or a rather low.
• the person skilled in the art will generally have a molecular weight MW between 10,000 g / mol and 5,000,000 g / mol, preferably between 50,000 g / mol and 1,000,000 g / mol, and especially preferably set between 100,000 g / mol and 500,000 g / mol.
• the molecular weight is determined by gel permeation chromatography. The measurement takes place in THF, PMMA is used as calibration standard.
• the swelling resistance can also be adjusted by the choice of particle size.
• a smaller average particle diameter provides a higher swelling resistance for monomers.
• the primary particle size of component A) is generally between 50 nm and 2 micrometers, preferably between 100 nm and 600 nm and most preferably between 150 nm and 400 nm.
• the particle size is measured using a Mastersizer 2000 Version 4.00.
• the constituents a) to e) for the core and the constituents a) to d) for the shell are selected so that the glass transition temperature T G s in the resulting polymer is at least a shell is greater than the glass transition temperature T G ⁇ of the core, wherein the glass transition temperatures T G are determined according to EN ISO 11357.
• Yet another process modification provides that the constituents a) to d) are selected for the shell such that in the resulting polymer the glass transition temperature T G s of at least one shell is greater than 80, preferably greater than 100 ° C., the glass transition temperature T G s according to EN ISO 11357 is determined.
• the emulsion polymerization is basically possible batchwise or continuously as a batch or feed polymerization. It is also semi-continuous feasible. Feed polymerization is preferred. Likewise, the preparation of A) via a Miniemulsionspolymerisation is possible. The procedures mentioned are generally known to the person skilled in the art.
• the invention also relates to a two-component or multi-component system with controllable pot life curing by a redox initiator system
• Emulsion polymer does not act or does not swell sufficiently; ii) at least one constituent B 'of component B) for the
• Emulsion polymer A) swelling acts, so that the polymer-fixed activator e) of the polymer A) can be reacted with the component C) to implement; iii) component A) and component B 'are stored together until use of the system; and iv) Component B "is stored separately from component A until use of the system.
• Component A) of the two-component or multi-component system according to the invention is the above-described emulsion polymer with covalently incorporated activator e).
• the two-component or multi-component system of the invention essentially comprises a component B) which has at least two different constituents B 'and B.
• the component B) is distinguished, in particular, by i) at least one constituent B ' of the
• Component B) for the emulsion polymer does not act or does not swell sufficiently; and ii) at least one component B "of component B) for the emulsion polymer A) has a swelling effect, so that the polymer-fixed activator e) of the polymer A) can be reacted with the component C).
• component C which factors influence the swelling capacity of the monomers has in part already been mentioned above in the description of the emulsion polymer.
• methacrylate and acrylate monomers and styrene and mixtures thereof can be used as monomers.
• Subordinate proportions of other monomers such as vinyl acetate, vinyl versatate, vinyloxypolyethylene glycol, maleic and fumaric acid and their anhydrides or esters are possible as long as the copolymerization is not disturbed, but are not preferred. Criteria for the selection of monomers are their dissolving power, polymerization shrinkage, adhesion to the substrate, vapor pressure, toxicological properties and odor.
• (meth) acrylates are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
• (meth) acrylic acid (meth) acrylamide, N-methylol (meth) acrylamide, monoesters of maleic and succinic acid with hydroxyethyl methacrylate and the phosphoric acid ester of hydroxyethyl (meth) acrylate, the proportion of which is usually subordinate.
• component B) is one or a plurality of compounds selected from the group consisting of ethyltriglyl methacrylate, tetrahydrofururyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 1,4-butanediol dimethacrylate, hydroxypropyl methacrylate, trimethylolpropane trimethacrylate, trimethacrylate of an ethoxylated trimethylolpropane with 3-10 moles of ethylene oxide, Dimethacrylate of an ethoxylated bisphenol A with 2-10 moles of ethylene oxide and / or a polyethylene glycol dimethacrylate with 1-10 ethylene oxide units.
• (meth) acrylates having a molecular weight above 140 g / mol, particularly preferably above 165 g / mol and in particular above 200 g / mol.
• Methacrylates are preferred over acrylates for toxicological reasons.
• the peroxide C) is the partner of the activator in the redox system. Its proportion is generally between 0.05 and 10 wt .-%, preferably 0.1 to 5% by weight. Usually, a proportion of 0.5 to 5 wt .-% is selected, preferably 0.5 to 3, in particular 0.5 to 2 wt .-%.
• the decisive factor for the peroxide content is that, in the intended application, a complete curing takes place in the desired time and the cured system has the properties tailored to the intended use.
• the peroxide is often phlegmatized e.g. in plasticizer or water or other medium.
• the peroxide can be present, for example, in an aqueous phase.
• the peroxide initiator in the organic phase for example an organic solvent or in a component of component B).
• Typical peroxide contents of this peroxide formulation are 20-60% by weight.
• Particularly suitable peroxides are dibenzoyl peroxide and dilauryl peroxide.
• the peroxides can be present alone or in a mixture of two or more non-individually mentioned peroxide compounds.
• component C consists in absorbing the peroxide in an emulsion polymer (component C).
• component C thus consists of an emulsion polymer containing a peroxide (component C).
• the emulsion polymer of component C may be identical or different be constructed as component A, but contains no polymerizable activator as a comonomer. Typical peroxide contents in component C are below 20, in particular below 10 wt .-%.
• emulsion polymers A and C are the same or different composition, as long as any incompatibility does not adversely affect.
• oligomers (component D)) of the system unsaturated polyesters and polyurethane (meth) acrylates based on polyether, polyester, or polycarbonate diols, and mixtures thereof can be used. Furthermore, vinyl-terminated prepolymers based on acrylonitrile and butadiene can be used. It is also possible to use epoxide (meth) acrylates and also star-shaped copolymers, as are obtainable, for example, by polymerization of (meth) acrylates in the presence of polyfunctional mercaptans.
• the oligomers are polyunsaturated.
• polymers based on polyacrylates, polyesters, polyethers, polycarbonates or the corresponding copolymers can be both saturated and unsaturated.
• the mixing ratio and the amount used depends on the intended application.
• the polymers or their proportion are usually selected so that the viscosity of the mixture is not adversely affected.
• the molecular weight of the unsaturated oligomers is typically 500 to 20,000, in particular 1,000 to 5,000 g / mol.
• Saturated polymers typically have molecular weights above 20,000, for example 50,000-200,000 g / mole. It is in all cases weight average molecular weight.
• the polymerization inhibitor (component E)) is optional for ensuring a sufficient shelf life of the mixture of
• Components B), D), E) and F are required.
• the effect of the inhibitors is usually that they act as scavengers for the free radicals occurring during the polymerization.
• Suitable inhibitors include u. a. optionally substituted phenols, optionally substituted hydroquinones, such as hydroquinone monomethyl ether (HQME), optionally substituted quinones, optionally substituted pyrocatechols, tocopherol, tert-butylmethoxyphenol (BHA), butylhydroxytoluene (BHT), octyl gallate, dodecyl gallate, ascorbic acid, if appropriate substituted aromatic amines, optionally substituted metal complexes of an aromatic amine, optionally substituted thazines, organic sulfides, organic polysulfides, organic dithiocarbamates, organic phosphites and organic phosphonates, phenothiazine and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 - oxyl.
• hydroquinones such as hydroquinone monomethyl ether (HQME), optionally substituted quinones, optionally substituted pyrocatechols, tocophe
• substituted hydroquinones and optionally substituted phenols are preferably used. Particularly preferred are hydroquinone, hydroquinone monomethyl ether and 4-methyl-2,6-di-tert-butylphenol.
• 0.2 wt .-% inhibitor are sufficient, usually the proportion is significantly lower, for example at 0.05 wt .-% or below.
• the pot life of the system after admixture of the components A and C is controlled according to the invention via the swelling of the component A.
• Higher levels than 0.2 wt% inhibitor, eg, 1 wt% or higher, sometimes used to extend pot life in prior art systems are therefore usually not necessary, but should not be excluded.
• the formulation may in addition to the components described customary particulate fillers (component F), such as titanium dioxide, carbon black or silica, glass, glass beads, glass powder, cement, quartz sand, quartz, sand, corundum, earthenware, clinker, barite, magnesia, calcium carbonate, marble powder or aluminum hydroxide, mineral or organic pigments and auxiliaries (component F)).
• component F customary particulate fillers
• Adjuvants may be, for example: plasticizers, water, leveling agents, thickeners, defoamers, adhesives or wetting agents.
• plasticizers water, leveling agents, thickeners, defoamers, adhesives or wetting agents.
• leveling agents for example: plasticizers, water, leveling agents, thickeners, defoamers, adhesives or wetting agents.
• defoamers for example: plasticizers, water, leveling agents, thickeners, defoamers, adhesives or wetting agents.
• no further plasticizer is included.
• the particulate fillers usually have a particle diameter of about 0.001 mm to about 6 mm.
• the system of the invention is also characterized in that iii) component A) and component B 'are stored together until use of the system; and iv) Component B "is stored separately from component A until use of the system.
• a particularly useful modification of the invention provides that v) the component B "of component B) and component C) are stored together until the application of the system.
• a particular variant of the two-component or multi-component system of the invention is characterized in that vi) the component B "of component B) and component C) are stored together in a non-aqueous system until the system is used.
• the peroxide is stored directly in the monomer B "without further solvent.
• One important advantage of the invention is, inter alia, that one generally manages with a two-component system.
• component B it is particularly expedient to assemble components A), B), C), D), E) and F), with the exception of only one constituent of component B), which has a sufficiently high swelling power to produce the emulsion polymer A ) so far swell that the covalently bonded to the core of the polymer A) activator component e) for the
• Two or more component systems according to the invention can be used with great advantage in adhesives, casting resins, floor coatings, compositions for reactive dowels, dental materials or in sealing compounds.
• compositions according to the invention a broad range of the concentration of the activator (range of variation) can be realized.
• a particular advantage is that at high activator concentrations in component A, less of A must be added to the two or more component system prior to use.
• the possibility of varying the reactivity is also advantageous. With constant addition amount of component A, the reactivity can be varied by A different levels of the activator.
• the pot life of the formulation of components A), B), C), D), E) and F) can be influenced by the swelling power of the monomers used in component B). While methyl (meth) acrylate has high swelling power and thus results in relatively short pot lives, more hydrophobic monomers such as 1,4-butanediol di (meth) acrylate and high molecular weight monomers such as ethyl triglycol (meth) acrylate increase in the Usually the pot life.
• the invention relates to a two-component or multi-component system.
• the particular advantage of the system according to the invention consists in the fact that the components of the redox initiator system together form a storage-stable mixture. Particularly advantageous is the presence of components A) and C) in a storage-stable aqueous phase. Furthermore, a mixture with the components A) and C) also parts of the
• Component B as well as all other components D), E) and F), provided that the monomer component B) stored together with the components A) and C) is not able to swell the component A) to a sufficient extent , The actual curing of the overall system is then achieved only by mixing with a suitable monomer B).
• the application is usually done by mixing all components A) to F) of the system together.
• the polymer A) is swelled by the monomer or the monomers B) within a certain period of time.
• the polymer-fixed activator component Ae) is accessible to the peroxide and thus the polymerization reaction started.
• Is hidden polymer particles Surprising is the rapid and strong increase in temperature at a certain point in time, which shows that a long pot life can be set with the method according to the invention, without the subsequent polymerization being impaired.
• the mixing ratio depends on the intended application. This determines the amount of the components used A - F.
• the mixing ratio of the components used is preferably to be chosen so that a complete polymerization of the given system is achieved. In particular, a sufficient amount of a suitable
• Redoxinitiatorsystems are available, wherein the activator at least predominantly in the form of an emulsion polymer (component A) for Is made available.
• the proportion of polymehsierbaren activator A e) in component A) can be selected within wide limits, there is also a wide margin for the amount of component A).
• the proportion of component A) can be between 0.8 and 69.94 wt .-%, and in turn 0.1 to 95 wt .-% of the polymerizable activator included.
• the amount of activator is adjusted to the proportion of peroxide used.
• the peroxide is the partner of the activator in the redox system. Its proportion is generally between 0.05 and 10 wt .-%, preferably 0.1 to 5 wt .-%.
• a proportion of 0.5 to 5 wt .-% is selected, preferably 0.5 to 3, in particular 0.5 to 2 wt .-%.
• Decisive for the peroxide content and the proportion of component A is that in the intended application, a desired degree of complete polymerization takes place in the desired time and the cured system performs the tuned to the application performance
• the proportion of an ethylenically unsaturated monomer (component B)) can be between 30 and 99.14% by weight. It is preferably 40-94.89% by weight, in particular 40-80% by weight.
• Polymers (component D) is 0-60% by weight, preferably 0-40% by weight, in particular 0-30% by weight.
• the mixture may contain between 0 and 800 parts by weight, based on the sum of A - D to 100 parts by weight, of fillers, pigments and other auxiliaries.
• Preferred two or more component systems according to the invention comprise
• systems are also preferred containing from 5 to 45 wt .-% component
• component C 0.1 to 5% by weight of component C), 0 to 40% by weight of component D);
• component F 0 to 800 parts by weight of component F), the sum of the constituents A) + B) + C) + D) + E) being 100% by weight, and the amount of F) being 100 parts by weight of the sum A) + B) + C) + D)
• component A From 5 to 45% by weight of component A), from 50 to 94.50% by weight of component B),
• component D 0 to 30% by weight of component D
• component E 0.01 to 0.1% by weight of component E) and 0 to 800 parts by weight of component F
• the sum of the constituents A) + B) + C) + D) + E) being 100% by weight
• the amount of F) being 100 parts by weight of the sum A) + B) + C) + D) + E )
• the content of component D) is particularly preferably 0 to 30% by weight.
• the invention comprises a system which is characterized in that component A) and component C) are stored together and at least one component of component B) is stored separately from A) and C) until the application of the system, wherein the swelling capacity of the component B) stored separately for the polymer A) is so high that the polymer-fixed activator of the polymer A) can be reacted with the component C).
• the system is basically suitable for all two-component systems such as adhesives, casting resins, floor coatings and other reactive coatings, sealants, impregnating compounds, investment materials, reactive dowels, dental materials, production of artificial marble or other artificial stones, porous plastic molds for ceramic objects and similar applications. It is also suitable for use in unsaturated polyester resins and their typical applications.
• a high polymer content for example between 30 and 70 wt .-%, may be advantageous.
• the proportion of the activator in component A can then be limited, for example, to 0.1 to 5% by weight, based on component A.
• the components B and D taken together are then between 69.9 and 30 wt .-%.
• the peroxide content is preferably 0.1 to 5 wt .-%.
• the proportion of component A is therefore preferably correspondingly low and is for example between 1 and 10 wt .-%.
• the proportion of the polymer-fixed in component A activator is correspondingly high and can be 10 or even up to 60 wt .-%, in some cases up to 95 wt .-% based on component A.
• Components B and D taken together are then between 98.9 and 90 wt .-%.
• the peroxide content is preferably 0.1 to 5 wt .-%.
• the GELNORM gel timer is an automatic device for determining the
• Test tube test tube holder
• HPMA hydroxypropyl methacrylate
• the blends produced were laced into films.
• the layer thickness varied between 0.85 mm and 0.07 mm. Curing of the films was done in air and was complete within 60 minutes.
• BP-50-FT Benzoyl Peroxide
• Phthalic acid phlegmatized is mixed in equimolar amounts to the activator with the monomers B and component A.
• the polymerization time is defined as the time required from the start of the polymerization (addition of the initiators) until the polymerization peak temperature is reached. As a result, the required time and the peak temperature are indicated.
• the measurement is carried out by means of a contact thermometer recording the temperature profile.
• the storage stability of the samples was visually checked daily. Furthermore, the samples were stirred up again daily to ensure good mixing with the BPO suspension. The final assessment was made after addition of MMA by monitoring swelling and polymerization behavior.
• Dispersions were prepared as described in Tables 1 and 2. Dispersible powders were obtained from the dispersions as described above.
• C13-MA methacrylic acid ester of a mixture of Cio-Ci ⁇ -alcohols
• C17.4-MA methacrylic acid ester of tallow fatty alcohol (mixture of C12-C20-alcohols)
• 6HDDMA 1,6-hexadioldimethacrylate

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• Organic Chemistry (AREA)
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• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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