EP0431026A1 - Nouveaux melanges a plusieurs constituants polymerisables sur le radical et leur utilisation - Google Patents

Nouveaux melanges a plusieurs constituants polymerisables sur le radical et leur utilisation

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Publication number
EP0431026A1
EP0431026A1 EP89909733A EP89909733A EP0431026A1 EP 0431026 A1 EP0431026 A1 EP 0431026A1 EP 89909733 A EP89909733 A EP 89909733A EP 89909733 A EP89909733 A EP 89909733A EP 0431026 A1 EP0431026 A1 EP 0431026A1
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EP
European Patent Office
Prior art keywords
compounds
mixtures according
component
contain
component mixtures
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP89909733A
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German (de)
English (en)
Inventor
Thomas Huver
Herbert Fischer
Winfried Emmerling
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0431026A1 publication Critical patent/EP0431026A1/fr
Pending legal-status Critical Current

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    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08F4/00—Polymerisation catalysts
    • 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
    • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08L2666/28—Non-macromolecular organic substances

Definitions

  • the invention relates to novel, formally processable, free-radically polymerizable multicomponent mixtures which are used, for example, as flowable or spreadable compositions or as pasty compositions and then harden under ambient conditions and triggering the polymerization reaction.
  • the invention relates to almost all areas of the use of free-radically polymerizable or curable compositions. Examples include adhesives, sealing compounds, the targeted structure of plastic molded parts, the surface coating with air-curing, in particular solvent-free, coating systems and the like.
  • the peroxide or. Hydroperoxide-initiated curing of olefinically unsaturated systems requires activator systems composed of several components in particular if the reaction is to be triggered at low temperatures, for example at room temperature or only slightly elevated temperatures. It is known that selected tertiary amine compounds with partial aromatic substitution on the N atom have such an activator function.
  • Known activators for triggering polymerization for example using benzoyl peroxide, are in particular dimethylaniline and dimethyl-p-toluidine.
  • a completely different known class of activator for the oxidative polymerization initiation of certain unsaturated systems namely drying oils
  • Such metal compounds of such metals which are sufficiently soluble in organic solvents and / or in binders have long been known as so-called drying agents for air drying paints, varnishes and the like based on unsaturated oils.
  • Sufficiently oil-soluble compounds of such transition metals which are capable of occurring in several valence stages are particularly suitable here.
  • the cited publication describes some investigations for triggering the polymerization of vinyl compounds by the dimethylaniline / ultrapure oxygen / cobalt salt system.
  • This system can be used to polymerize high-purity acrylonitrile, methyl methacrylate, ethyl acrylate and styrene.
  • the starting reaction is interpreted as redox catalysis, in which molecular oxygen takes over the roiling of the oxidizing agent.
  • the publication mentioned does not contain any indications of a practical usability of the multicomponent systems under investigation for use in polymerization technology. In fact, even these theoretical papers, which have been accessible to experts for almost 25 years, have not given any impetus for their implementation in practice.
  • the object of the invention is to develop a new class of activator systems using the previously known knowledge of more component redox systems, which can be used in a novel and simplified manner to trigger polymerization on olefinically unsaturated systems.
  • the new activator systems are said to lead to non-reactive substance mixtures, which in Do not polymerize the mixture with the olefinically unsaturated polymerizable components and are therefore storable, both in the form of single-component systems and in the form of multi-component systems.
  • the new activator systems should have the ability to be activated by the addition of water and oxygen. In preferred embodiments, this activation should already occur at room temperature; if necessary, a moderate temperature increase is provided.
  • a particularly important aspect of the invention is directed to multi-component systems of the type mentioned, which simply by admission of ambient air with their always present moisture and oxygen content at room temperature or only moderately elevated temperatures to trigger the start reaction of a radical polymerization unsaturated systems.
  • the subject matter of the invention in a first embodiment is to contain free-radically polymerizable nutrient processing tables which can be shaped
  • this multicomponent mixture contains an activator system which can be initiated by the entry of oxygen and water, in particular by the action of ambient air, on the basis of the following main components:
  • hydrolysable compounds of weakly acidic carboxylic acids when moisture enters the free carboxylic acid, hydrolysable compounds of weakly acidic carboxylic acids with pK ⁇ values not less than about 0.9.
  • the essence of the action according to the invention thus lies in the selection of the specific activator system described for the first time in this combination.
  • This system differs from that of L. HORNER et al. described activator systems in particular by the selection of the third component described above.
  • the free carboxylic acid is not present as such, as is the case with the acetic acid investigated by HORNER, rather carboxylic acid derivatives are used which do not have a free carboxyl group as such, but which can be hydrolyzed to form the free carboxylic acid when exposed to moisture.
  • the activation state required to initiate the polymerization in the sense of the invention requires the interaction of the aromatic amine and the metal compound which is at least partially soluble in the system with the free carboxylic acid.
  • the free carboxylic acid By introducing the free carboxylic acid not as such, but rather in capped form, an additional degree of freedom is created with regard to the inhibition of the overall system.
  • the complete exclusion of oxygen or. the corresponding removal of oxygen from multi-component mixtures is known not to be practicable within the scope of practical technical action. Starter systems that convert molecular oxygen into a reaction - triggering intermediate stage - or. polymerizable substance mixtures containing such starter systems - are always comparatively due to undesirable side reactions at risk.
  • This alkyl radical can be straight-chain or branched.
  • the preferred aryl radical is the phenyl radical, which in turn can also be substituted, and in particular can be alkyl-substituted.
  • the alkyl radicals present in R 1 and optionally R_ preferably each contain up to about 10, in particular up to about 6, carbon atoms. Corresponding C, radicals and here in particular the methyl radical are of particular importance.
  • the radicals R ⁇ and R, corresponding optionally substituted alkyl radicals and the radical R- are an optionally substituted phenyl radical, so that N, N-dialkyl-substituted aniline compounds, which may also be alkylated in the phenyl ring, are generally preferred .
  • the most important components in the sense of the invention are dimethylanium and especially dimethyl-p-toluidine.
  • the most important drying substances of the type concerned are characterized in that, above all, metal compounds of such metals. can be used, which can occur in several severity levels. Selected representatives of the transition metals can be particularly active here.
  • the respective selection of the metal can, among other things, have a speed-determining character for initiating polymerization due to a certain temperature dependence of the reactive intervention of this metal component in the overall process.
  • Components that are highly active at room temperature are derived in particular from cobalt and / or manganese. Iron also has a certain - albeit weaker - reaction acceleration in the region of room temperature.
  • Other metal components for example those based on vanadium, can be increased in their activity by increasing the temperature so that the polymerization reaction can be triggered in the short term.
  • Cobalt and / or manganese compounds are particularly suitable for working at room temperature, which is particularly advantageous for many fields of application, optionally in admixture with other metallic components such as compounds of lead, cerium, calcium, barium, zinc and / or zirconium.
  • metallic components such as compounds of lead, cerium, calcium, barium, zinc and / or zirconium.
  • the relevant specialist literature can be referred to here, for example compare the cited publication in "Ullmann” a. O. as well as the pre-literature given there.
  • the metals affected here are used in the form of such compounds that they are at least partially in the overall system are soluble. Both soap-like metal compounds and other types, in particular complexes bonded to organic residues, are possible. Typical examples of working in the sense of the action according to the invention is the use of corresponding metal naphthenates or metal acetyl acetonates. If there is sufficient solubility of inorganic salts in the system, however, the use of such inorganic systems is also possible. A typical example of this is iron chloride, which has a significantly accelerating effect when used in the system according to the invention.
  • metal compounds in each case in a low valence level of the metal - for example as cobalt (I! Or manganese (I I).
  • the use of the metal compound in the higher valence level of the metal is also suitable.
  • iron for example, iron
  • the acidity of the free carboxylic acid is of decisive importance.
  • the pK ⁇ value of the free acid should not be less than about 0.9, the preferred limit is about 1.
  • the pK ⁇ value of trichloroacetic acid is approximately 0.6.
  • the addition of trichloroacetic acid in capped or uncapped form to the system destroys the ability of the initiator multicomponent system used according to the invention to trigger polymerization reactions. reactions.
  • dichloroacetic acid is a weaker carboxylic acid. Their pK_ value is around 1, 3. This dichloroacetic acid is very well suited for triggering polymerization reactions in the sense of the action according to the invention.
  • Strongly acidic mineral acids, for example hydrochloric acid also interfere with the ability to initiate polymerization through the activator systems used according to the invention.
  • Acetic acid or derivatives hydrolyzable to acetic acid - pK ⁇ value of acetic acid about 4.76 - is excellently suited for accelerated reaction initiation.
  • the upper limit of the pK ⁇ value can be seen in the range of very weakly acidic compounds - determined as free carboxylic acid. In terms of numbers, the upper limit is pK ⁇ values of approximately 13, preferably approximately 11.5.
  • carboxylic acids are particularly suitable which, in the hydrolyzed state, have pK_ values of up to about 8, preferably up to about 6 or 7.
  • Particularly effective components of the type concerned here are then derived from carboxylic acids which, in the hydrolyzed state, have pK ⁇ values in the range from about 1 to 5 or 7.
  • the carboxylic acids to be used according to the invention in capped form can have one or more carboxyl groups.
  • the constitution of the acid as such - if the correct pK ⁇ value is exposed - is not so much the decisive parameter.
  • the reliable accessibility of the fully capped form of the respective carboxylic acid is in the foreground of the considerations.
  • care is taken to ensure that there are no free carboxyl groups in the feed mixture, but only form during processing by hydrolytic cleavage of the capping part of the molecule. From a preparative point of view, it can accordingly be advantageous to use carboxylic acids with 1 to 4 carboxyl groups and in particular with 1 or 2 carboxyl groups. groups of the component affected here.
  • masked monocarboxylic acids can be particularly simple because the condition for eliminating free carboxyl groups can be set particularly easily here.
  • the selection of the carboxylic acid concerned is largely determined by appropriate considerations of expediency.
  • Easily accessible carboxylic acids such as lower aliphatic carboxylic acids or corresponding aromatic mono- or polyfunctional carboxylic acids are suitable components.
  • Suitable aliphatic carboxylic acids are the C., preferably C, monocarbon
  • Suitable aromatic carboxylic acids are benzoic acid or corresponding polycarboxylic acids, for example trimellitic or pyromellitic acid. As shown in the example of dichloroacetic acid, substituted acids of this type are also suitable, provided their pK ⁇ value corresponds to the specified boundary conditions.
  • An essential core of the teaching according to the invention is to use these weak carboxylic acids in the form of their hydrolysable derivatives.
  • Corresponding derivatives of weakly acidic carboxylic acids of the general formula II are particularly suitable
  • R y is an optionally substituted alkyl, cycloalkyl or aryl radical and X is a weakly acidic, practically neutral or, at the most, - with simultaneous formation of the free acid R ⁇ COOH - at at least slightly elevated temperatures by hydrolysis by hydrolysis means very weakly basic residue.
  • This restriction in the definition of the radical X ensures that the weak acid R ⁇ COOH can actually fulfill the task to be performed by it when the reaction is triggered.
  • Suitable hydrolysable derivatives of the weak Carboxylic acids are, for example, their anhydrides or their mixed anhydrides with other weak carboxylic acids, these other weak carboxylic acids in particular also meeting the pK, -.- limit value conditions specified above.
  • Mixed anhydrides or esters of the weak carboxylic acids defined according to the invention with hydroxyl compounds of such heteroatoms, which after hydrolysis do not lead to any disturbance of the acidity level in the system according to the invention, can be particularly suitable.
  • Particularly suitable here are the mixed anhydrides or esters, described below, with corresponding compounds of boron and / or silicon.
  • the rate of the course of the reaction can be influenced by the hydrolysis stability of the capped carboxylic acid compound used.
  • reaction-influencing possibilities open up, which make it possible to adapt the polymerization process to the respective application.
  • a masked carboxylic acid compound in the sense of the action according to the invention is acetic anhydride.
  • the acceleration of the reaction when the polymer is triggered by molecular oxygen, in particular by the entry of air is only effected after sufficient hydrolysis by the free acetic acid.
  • Such hydrolysis of the anhydride in situ in the reaction mixture at room temperature and exposure to ambient air with its limited moisture content can be a comparatively lengthy process.
  • radicals of the following general formula I I I radicals of the following general formula I I I
  • the rest R is identical or different from the radical R y from the general formula II and in particular means alkyl, cycloalkyl or aryl, it being possible for all these radicals to be substituted with the proviso that the free carboxylic acid R-COOH formed during the hydrolysis is at least as mentioned corresponds to the lower limit for the pK ⁇ value.
  • radical X from the general formula I I preferably corresponds to the radical of the general formula IV defined below
  • the Z radicals can be the same or different and in particular mean a R ..- CO-0 radical and / or alkyl, cycloalkyl and / or aryl radicals which for their part may also be substituted and / or may also be bonded to the boron via an oxygen atom.
  • R-. has the meaning explained in connection with the general formula III
  • x is 0 or an integer and has in particular the value from 0 to 2.
  • a particularly important masked weak carboxylic acid for the work according to the invention is derived from compounds of the general formula II in which X represents the remainder of the general formula IV, where x is the number 1 and the Z radicals have the meaning of R -CO-0.
  • a characteristic representative of this class of substances is tetraacetoxydiboroxane, which has been shown to be a particularly effective, easily prepared and easily stabilized capped, but nevertheless quickly hydrolyzable by means of ambient air carboxylic acid compound.
  • Z can have the same meaning as given for formula IV, y preferably has a value from 0 to about 10 and in particular a value from 0 to about 5.
  • a portion of the Z radicals is formed by hydrocarbon radicals, in particular by alkyl radicals and here in particular by lower alkyl radicals such as methyl.
  • Components of this type are particularly easy to access and are accordingly accessible the associated capped compounds of general formula II are particularly easily accessible.
  • Activator systems composed of the three main components of aromatic amine compound described here, at least partially soluble metallic drying agent and blocked weak acid capable of hydrolysis are able to initiate all the radically polymerizable olefinically unsaturated systems after absorption of moisture and oxygen from the ambient air which have so far been used with the most diverse, in particular peroxidic starter systems.
  • Polymerizable components and optionally soluble and / or insoluble fillers and mixtures of substances containing the activator systems according to the invention can be designed as a non-reactive 1-component system with the exclusion of air, provided that it is ensured that there are no constituents in the mixture which do little to cause an undesired premature reaction ⁇ lead one of the main components of the system according to the invention. It is particularly important for the formation of 1-component systems that the overall systems are free of reactive groups, in particular in the form of reactive hydrogen atoms such as are present, for example, in the form of hydroxyl and / or carboxyl groups. Such reactive groups with active hydrogen atoms interfere whenever they lead to the premature release of the masked weakly acidic carboxylic acids.
  • the multicomponent mixture to be used according to the invention is provided as a multicomponent system in this embodiment. It should be ensured here that the constituents of the mixture with reactive hydrogen atoms in the multicomponent system are separated from the masked weak carboxylic acids of the activator system according to the invention are kept.
  • the components are mixed with one another in a manner known per se.
  • the open pot life of the system can be regulated by suitable selection and adaptation of the main components of the activator system, so that here too the triggering of the start reaction and thus ultimately the curing of the system under ambient conditions in the air is possible.
  • This principle of the hydrolysis-unstable capping of free carboxy groups can also be used in particular in the following combination: Important olefinically unsaturated and radically polymerizable acids of the type of (meth) acrylic acid (s), crotonic acid, maleic acid and the like can be used in this way capped form are added to the reaction mixture and thus the reaction. If the capping of these acid components is more stable to hydrolysis than that of the capped carboxylic acid component of the activator system used according to the invention to trigger the reaction, the unsaturated carboxylic acids are first included in the capped form in the polymerization process. The hydrolytic cleavage of the capping is possible at a later point in time.
  • unsaturated carboxylic acids in capped but hydrolytically unstable form at least in part as a weakly acidic catalyst component.
  • acrylic acid or methacrylic acid in the reaction mixture has a double function when the reaction is triggered.
  • the free acid formed in cooperation with the other components of the activator systems according to the invention, triggers the reaction, but at the same time this component is included in the polymerization process and incorporated into the resulting polymer molecule.
  • the invention comprises multicomponent systems which are non-reactive even when air is admitted and which trigger the desired starting reaction only after all the components have been mixed.
  • This can be, in particular, the division of the activator system into a 2-component system.
  • Both components of the overall system can, however, contain substantial proportions of the compounds to be polymerized and / or the other fillers and auxiliaries used.
  • the multicomponent mixtures of the invention which contain both the activator system according to the invention and the components to be polymerized in admixture with their fillers and / or auxiliaries are in the form of a flowable but at least slightly thickened to pasty, distributable multicomponent mixture.
  • the particular condition is adapted to the application.
  • Filling or sealing compounds will generally be more pasty than spreadable or. sprayable paints.
  • the systems are free from solvents. Their fluidity is usually adjusted or adjusted using ethylenically unsaturated monomers. regulated.
  • the types of monomers predominantly used in free radical polymerization technology are based today on the type of acrylate and / or methacrylate compounds, styrene or substituted styrenes and / or acrylonitrile.
  • the activator systems according to the invention are effective starters for these types of monomers, in particular in the systems customary in practice today, and can be reactive in particular as at room temperature or only slightly elevated temperatures under the influence of ambient air Starter be trained.
  • the polymerization initiation can be used in the full range of the currently known acrylate or methacrylate systems, the styrene-modified substance mixtures, in particular the systems based on unsaturated polyester resins / styrene.
  • the rapid and effective initiation of polymerization at the system-inherent predetermined point in time is possible in particular if the systems used for the application have at least slightly increased viscosity values.
  • the polymerization in pure unsaturated monomers stabilized in the usual way for example in commercially available pure (meth) acrylate, styrene and the like, can cause difficulties. If, however, these components are only slightly thickened, the polymerisation can be successfully achieved by accessing ambient air without difficulty.
  • the minimum viscosity of the "cured in accordance with the invention, systems in the application state we ⁇ iquess about 30 to 100 Pas (Brookfield).
  • the invention allows the compilation of optimized adhesive mixtures based on acrylic and / or methacrylate in the form of a non-reactive 1-component substance mixture which is activated by application to the surfaces to be bonded and the action of the ambient air taking place here and thus becomes adhesive and subsequently hardens. While maintaining the laws of the invention - in particular inert behavior towards the main components of the activator system - soluble and / or insoluble fillers, elasticizers, thickeners, thixotropic agents, pigments, adhesion promoters, stabilizers and the like can be used without the functionality of the actuator system according to the invention is at risk.
  • the activator systems used according to the invention in these multi-substance mixtures is that double inhibition and thus double control of the overall system is possible.
  • drying agents are preferably incorporated into the multicomponent mixture in predetermined amounts and in active form in a homogeneous distribution.
  • the amount and capacity of the period from which diffusing-in moisture is no longer bound by the desiccant is derived, but instead leads to the hydrolytic cleavage of the blocked weak carboxylic acid with its release.
  • the use of customarily selected reducing agents leads to stabilization against undesired access to oxygen.
  • the amount of reducing agent used can influence the point in time from which the oxygen activation of the system takes place with the formation of hydroperoxide. It is obvious that this double control option gives considerable freedom in individual cases to influence the course of the reaction. For example, it may be desirable to achieve as complete a saturation as possible of an applied lacquer or adhesive with oxygen without premature barrier formation due to premature polymerization initiation on the surface of the reactive material. In this case, it may be desirable to delay the start reaction by delaying hydrolysis of the blocked acid using a larger amount of the drying agent.
  • the activator mixtures preferably make up no more than about 25% by weight and in particular no more than about 10% by weight, in each case based on the weight of the overall system.
  • the weight of the activator mixture can be reduced very sharply and can be reduced, for example, to the range of about 0.1% by weight or at least about 0.5% by weight.
  • Amounts of the activator system of at least about 1% by weight, preferably up to about 8% by weight and particularly from about 1 to 7% by weight, can be particularly suitable. All these Information relates on the one hand to the total weight of the multi-component system according to the invention and the total weight of the three main components of the activator system.
  • the three main components of the activator system can preferably be used in the following proportions to one another - here% by weight based on the mixture of the three activator components:
  • the amounts of metal compounds to be used in each case can also be defined as follows, in particular, via the weight ratio of metal weight to weight of the multicomponent activator system:
  • Preferred amounts of metal are within the range of 0.01 to 5% by weight, particularly 0.05 to 2% by weight. % and in particular within the range from about 0.1 to 1% by weight of metal, in each case based on the total weight of the activator constituents.
  • inhibitors and / or stabilizers of the type specified above are also used to control the course of the reaction and / or the open pot life, their amount is measured according to the stated purpose. In individual cases it can easily be determined by professional considerations and / or by preliminary tests. This is also explained again by way of example using a comparison: if a metal salt which forms water of crystallization, such as copper sulfate, is used for the primary binding of diffusing moisture, then purely in terms of weight, larger amounts are required than with a corresponding one Inhibition of diffusing oxygen by using triphenylphosphine.
  • the regulators used are usually a few percent - z. B. do not exceed about 2 to 5% by weight of the total mixture and are generally below 1% by weight.
  • the subject matter of the invention is the activator systems described in detail at the outset from the three components tertiary amine compound, at least partially soluble metal component and masked compound of the weak acid which can be cleaved by hydrolysis, with pK ⁇ values of the free acid not less than about 0 , 9th All numerical and factual information relating to the definition of these components also apply analogously in this embodiment of the invention.
  • the invention further relates to the use of these activator systems for triggering the reaction by the action of oxygen and water, in particular by the action of ambient air, preferably at room temperature or only slightly elevated temperatures of free-radically polymerizable systems containing ethylenically unsaturated components.
  • the application of the activator systems in acrylate and / or methacrylate-based polymerizable substances or. Mixtures of substances or comparable systems based on compositions containing styrene and / or acrylonitrile, for example of the type of styrene / unsaturated polyester resin mixtures.
  • the invention relates to aerobically curing adhesive systems, which can be present, in particular, in the form of a 1-component adhesive packaged in storage and are characterized by the use of the activator mixtures according to the invention. Further embodiments of the invention relate to the use of these activator systems in the context of surface coating with polymerizable inserts. special spreadable coating materials.
  • the invention provides, in a preferred embodiment, spreadable air-drying lacquer systems which are preferably solvent-free.
  • a further embodiment of the invention finally relates to the use of suitable systems, for example the styrene / unsaturated polyester resin systems mentioned, for the production of moldings by triggering a reaction by the action of ambient air.
  • Systems of the type described above often contain combinations of low molecular weight, ethylenically unsaturated monomers and preformed oligomers and / or polymers which are compatible with the monomers used and in particular are at least partially soluble in them.
  • the content of such multicomponent mixtures of free-radically polymerizable components, in particular their monomer content, is at least about 20% by weight and preferably at least about 40% by weight.
  • Monomer contents can reach the upper limit of 60, 80 or even 90% by weight, taking into account the limiting condition for the at least slightly increased viscosity, in particular the general knowledge of the person skilled in the art applies here.
  • Oligomeric or polymeric components added to the multicomponent mixture can in turn contain reactive groups, in particular ethylenically unsaturated groups, or can also be free thereof.
  • reactive groups in particular ethylenically unsaturated groups
  • the use of low molecular weight monomer compounds can be practically completely dispensed with if the manageability and in particular the shaping processability of a mixture of substances is ensured which consists exclusively of pre-formed oligomer and / or polymer compounds, which at least partly of the radically triggered poly- ..'.- £. risk or Crosslinking reaction are accessible. Examples
  • polyester polyurethane consisting of
  • the adhesive mixture consists of
  • the multicomponent mixture is produced from anhydrous components and, after degassing, is stored in an inert gas atmosphere.
  • the adhesive mixture is applied to the surfaces to be bonded and exposed to the ambient air for 3 to 5 minutes. After the start of the reaction - ascertainable by clouding and beginning skin formation - the parts to be joined are glued and fixed.
  • the commercial product "Diacryl 101" (dimethacrylate of bisphenol A x 2 EO) is used in an amount of 89.5% by weight with an activator system composed of 5% by weight dimethyl-p without the use of further reactive monomer components toluidine, 5% by weight of tetraacetoxy diboroxane and 0.5% by weight of cobalt naphthenate solution.
  • the material After exposure of this mixture of substances to the air, the material is polymerized within 1 hour (surface stickiness) and hardens within a day.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Drying Of Gases (AREA)
  • Polymerization Catalysts (AREA)
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  • Polymerisation Methods In General (AREA)

Abstract

Mélanges à plusieurs constituants polymérisables sur le radical, aptes au façonnage sous une forme déterminée, comprenant des composés polymérisables éthyléniquement insaturés, mélangés de préférence à des charges et/ou à d'autres substances auxiliaires solubles et/ou insolubles, et, un système activateur amorçable par apport d'oxygène, caractérisés en ce que lesdits mélanges à plusieurs constituants comprennent un système activateur amorçable par apport d'oxygène et d'eau, en particulier sous l'action de l'air ambiant, à base des principaux composants suivants: une arylamine tertiaire N-alkyl substituée, ayant au moins une liaison CH aliphatique en position alpha, des composés métalliques au moins partiellement solubles dans le système pour l'accélération du séchage des huiles insaturées, ainsi que des composés d'acides carboxyliques faibles ayant des pKS qui ne soient pas inférieurs à environ 0,9, hydrolysables, par apport d'humidité, en acide carboxylique libre. On décrit en outre l'utilisation de ces mélanges à plusieurs constituants sous la forme d'un système d'une matière adhésive durcissante aérobie, en particulier sous la forme d'une matière adhésive à un constituant, conditionnée de façon stable au stockage, et son utilisation pour le revêtement en surface ou pour le formage de pièces profilées en matière plastique.
EP89909733A 1988-08-31 1989-08-22 Nouveaux melanges a plusieurs constituants polymerisables sur le radical et leur utilisation Pending EP0431026A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3829438A DE3829438A1 (de) 1988-08-31 1988-08-31 Neue radikalisch polymerisierbare mehrstoffgemische und ihre verwendung (i)
DE3829438 1988-08-31

Publications (1)

Publication Number Publication Date
EP0431026A1 true EP0431026A1 (fr) 1991-06-12

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP89909733A Pending EP0431026A1 (fr) 1988-08-31 1989-08-22 Nouveaux melanges a plusieurs constituants polymerisables sur le radical et leur utilisation
EP89115431A Expired - Lifetime EP0356875B1 (fr) 1988-08-31 1989-08-22 Compositions polymérisables par radicaux et leur utilisation

Family Applications After (1)

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EP89115431A Expired - Lifetime EP0356875B1 (fr) 1988-08-31 1989-08-22 Compositions polymérisables par radicaux et leur utilisation

Country Status (15)

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US (1) US5268436A (fr)
EP (2) EP0431026A1 (fr)
JP (1) JP2763810B2 (fr)
KR (1) KR950000035B1 (fr)
AT (1) ATE89011T1 (fr)
AU (1) AU627776B2 (fr)
BR (1) BR8907627A (fr)
CA (1) CA1338498C (fr)
DE (2) DE3829438A1 (fr)
ES (1) ES2041913T3 (fr)
HK (1) HK128694A (fr)
IE (1) IE63522B1 (fr)
MX (1) MX170439B (fr)
WO (1) WO1990002143A1 (fr)
ZA (1) ZA896648B (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5506326A (en) * 1991-03-06 1996-04-09 Loctite (Ireland) Limited Air-activatable polymerizable compositions containing onium salts
DE4112315A1 (de) * 1991-04-16 1992-10-22 Henkel Kgaa Aktivator fuer cyanacrylat-klebstoffe
DE4420151A1 (de) * 1994-06-09 1995-12-14 Henkel Kgaa Einkomponentiger Reaktionsklebstoff
DE19501933A1 (de) * 1995-01-24 1996-07-25 Henkel Kgaa Aerob härtbarer Klebstoff
CA2337187C (fr) 1999-05-29 2011-02-22 Guanghui Zhang Melanges bioabsorbables et articles chirurgicaux constitues desdits melanges
JP4389315B2 (ja) * 1999-12-28 2009-12-24 Ｊｓｒ株式会社 反応性粒子、これを含有する硬化性組成物及び硬化物
EP1201722A1 (fr) 2000-10-23 2002-05-02 Loctite (R & D) Limited Initiateurs de polymérisation, compositions polymérisables et leurs utilisations
AU2003225512A1 (en) 2002-04-19 2003-11-03 Loctite (R And D) Limited Polymerisation initiators based on ammonium tetraalkyl boranes, polymerisable compositions, and uses thereof for bonding low surface energy substrates
US6867271B1 (en) 2002-06-24 2005-03-15 Henkel Corporation Non-flammable and non-combustible adhesive bonding systems having adherence to low energy surfaces
US8202932B2 (en) * 2004-12-03 2012-06-19 Loctite (R&D) Limited Adhesive bonding systems having adherence to low energy surfaces
US7408012B1 (en) 2005-04-18 2008-08-05 Loctite (R&D) Limited Adhesive bonding systems having adherence to low energy surfaces

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE581239A (fr) * 1958-08-05 1900-01-01
US4126504A (en) * 1977-01-27 1978-11-21 Pratt & Lambert, Inc. Adhesive compositions and method employing same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9002143A1 *

Also Published As

Publication number Publication date
IE63522B1 (en) 1995-05-03
JP2763810B2 (ja) 1998-06-11
KR950000035B1 (ko) 1995-01-07
ES2041913T3 (es) 1993-12-01
KR900701854A (ko) 1990-12-04
EP0356875B1 (fr) 1993-05-05
CA1338498C (fr) 1996-07-30
IE892780L (en) 1990-02-28
HK128694A (en) 1994-11-25
BR8907627A (pt) 1991-07-30
DE3829438A1 (de) 1990-03-15
ZA896648B (en) 1990-04-25
US5268436A (en) 1993-12-07
ATE89011T1 (de) 1993-05-15
JPH04500227A (ja) 1992-01-16
DE58904261D1 (de) 1993-06-09
MX170439B (es) 1993-08-23
AU627776B2 (en) 1992-09-03
AU4194389A (en) 1990-03-23
WO1990002143A1 (fr) 1990-03-08
EP0356875A1 (fr) 1990-03-07

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