AU625641B2 - New multiple-constituent mixtures capable of free-radical polymerization and their use - Google Patents

Abstract

Mouldable multiple-constituent mixtures capable of free-radical polymerization, which may also be multicomponent systems with long storage life, containing ethylenically unsaturated polymerizable compounds admixed, if desired, with soluble and/or insoluble fillers or other auxiliary substances, and an activator system which can be initiated by the introduction of oxygen are characterized in that they are applied in the form of at least weakly concentrated material containing an activator system which can be initiated by the introduction of atmospheric air, based on the following main components: N-alkyl-substituted tert.-aryl amines with at least one aliphatic CH bond in the alpha position, metallic compounds which are at least partially soluble in the system and accelerate drying of unsaturated oils, and weak carboxylic acids with pKS values less than approximately 0.9. Preferably, the multiple-constituent mixtures ready for application have a minimum viscosity of at least 50 to 100 mPa.s. The invention also concerns the use of activator systems of these multiple-component mixtures for controlled hardening, at a predetermined pot life, of olefinically unsaturated systems by means of atmospheric air and ambient temperature or only moderately elevated temperatures.

Description

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OPI DATE 23/03/90 APPLN. I D 41825 89 AOJP DATE 26/014/90 PCT NUMBER PCT/EP89/00980 Per INTERNATIONALE ANMELDUNG VEROFFENTLIGHT NACH DEM VERTRAG UI3ER D)IE INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATENTWESENS (PCT) (51) Internationale Patentklassifikation 5 (11) Inter V~al r6 ilc nfe: WO 90/02142 C08F 4/00, C09D 15/00 Al (43) Internatia 5 Verbffentlichungsdatumn 8. Mrz 1990 (08.03.90) (21) Internationales Aktenzeichen: PCT/EP89/00980 (81) Bestimmungsstaa ten -AT (curopaxisches Patent), AU, BE (europiiisch!s Paten!), BR, CH (europaisches Patent), (22) Internationales Anmieldedatumn: 22. August 1989 (22.08.89) DE (europaisches Patent), FR (europaisches Patent), GB (europ~isches Patent), IT (europ~isches Patent), JP, KR, LU (europiiisches Patent), NL (europiiisches Patent), SE Prioritaitsdaten: (europ~isches Patent), US.

P 3829 461.3 3 1. August 1988 (31.08.88) DE Verbffentlicht (71) Anmelder Oftir alle Bestimmungsstaaten ausser US): HEN- Mit international em Recherchenbcricht.

KEL KOM MANDITGESELLSCHAFT AUF AKTIEN [DE/DE]; Henkelstra~e 67, D-4000 D~sseldorf-Holthausen (DE).

(72) Erfinder;und Erf inder/Anmelder (nur fair US) HUVER, Thomas [DE/ DE]; Pfeifferstrale 45, D-4000 Dasseldorf 12 FI- SCHER, Herbert [DE/DE]; Am Nettchesfeld 14, D- 4000 D-.isseldorf 13 EMMERLING, Winfried [DE/DE]; Lfirchenweg 6, D-4006 Erkrath 2 (DE).

(54) Title: NEW MULTIPLE-CONSTITUENT MIXTURES CAPABLE OF FREE-RADICAL POLYMERIZATION AND THEIR USE (54) Bezeichnung: NFUE RADIKALISCH POLYMERISIERBARE MEHRSTOFFGEMISCHE UND 1IRE VERWEN- DUNG (HI) (57) Abstract Mouldable multiple-constituent mixtures capable of free-radical polymerization, which may also be multicomponent systems with long storage life, containing ethylenically unsaturated polymerizable compounds admixed, if desired, with soluble and/or insoluble fillers or other auxiliary substances, and an activator system which can be initiated by the initoduction of oxygen are characterized in that they are applied in the form of at least weakly concentrated material containing an uctivator system whic" can be initiated by the introduction of atmospheric air, based on the following main components N-al kyl -substituted tert.-aryl amines with at least one aliphatic CH bond in the a position, metallic compounds which aire at least partially soluble in the system and accelerate drying of unsaturated oils, and weak carboxylic acids with pKS values less than approximately 0.9.

Preferably, the multiple-constituent mixtures ready for application have a minimum viscosity of at 'least 50 to 100 mPa.s.

The invention also concerns the use of activator systems of these multiple-component mixtures for controlled hardening, at a predetermined pot life, of olefinically unsaturated systems by means of atmospheric air and ambient temperature or only moderately elevated temperatures.

(57) Zusamnmenfassung Beschrieben werden formgebend verarbeitbare radikalisch polymerisierbare Mehrstoffgemische, die auch in Form lagerstabiler Mehrkomponentensystemne vorliegen k6nnen, enthaltend ethylenisch ungesfiv-3te polymerisierbare Verbindungen gewanschtenfalls in Abmischung mit l6slichen und/oder unl6slichen F~ll- und/oder sonstigen Hilfsstoffen sowie emn durch Sauerstoffzutritt initiierbares Aktivatorsystem, die dadurch gekennzeichnet sind, dag sie in Applikationsform als wenigstens schwach angedicktes Material vorliegen und emn durch Zutritt von Umgebungsluft initiierbares Aktivatorsystem auf Basis der nachfolgenden Hauptkomponenten enthalten: N-alkyl .substituierte tert.-Arylamine mit wenigstens einer alpha-stiindigen aliphatischen CH- Bindung i System wenigstens anteilsweise l6sliche MetallIverbindungen filr die Trocknungsbeschleunigung ungesiittigter Ole sowie schwach saure Carbonsliuren mit pKS-Werten nicht kleiner als etwa 0,9. Bevorzugt besitzen die Mehrstoffgemische in Appli kati ons form eine Mindestviskositit von wenigstens etwa 50 bis 100 mPas. Die Erfindung betrifft weiterhin Verwendung der Aktivatorsysteme dieser Mehrstoffgemische fur die zeitgesteuerte Aush~rtung bei vorbestimmbarer Topfzeit mittels Umgebun-,sluft und Raumtemperatur oder nur miilig erhbhten Temperatureii von olefinisch ungeslttigten Systemen.

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ii 4 II -I a ISi) "NEW RADICALLY POLYMERIZABLE MULTIPLE-CONSTITUENT MIXTURES AND USES THEREOF" The invention relates to new mouldable radically polymerizable multiple-constituent mixtures which are present as flowable, spreadable or pasty material, and which then harden under ambient conditions and solution of the polymerization reaction. Considered from the standpoint of technical application, the invention is thus applicable to almost all areas of radically polymerizable or hardenable materials, for example, adhesives, thickeners, the production of mouldings, surface coatings with air-hardening paint systems, particularly with solvent-free paints.

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Hardening initiated by peroxide or hydroperoxide of olefinically unsaturated systems thus requires multipleconstituent activating systems if the reaction is to occur at lower temperatures, particularly at room temperature. It is 1.5 known that specific tertiary amine binders with partial aromatic substitution at the N atom can perform such an activator function. In particular, dimethyl aniline and S dimethyl-p-toluidine are known activators for the polymerisation solution, for example by means of dibenzoylperoxide.

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D 8429 2 A totally different known class of activators for oxidative initiation of the polymerization of certain unsaturated systems, namely drying oils, are metal compounds at least partly soluble in the system of metals which can occur in several valency stages and accelerate the initiating reaction through intermediate shifts in valency Son interaction with other components of the system. Metal compounds such as these sufficiently soluble in organic solvents and/or in binders of metals of the type in question have long been known as so-called driers for the air drying of paints, varnishes and the like based on unsaturated oils. Sufficiently oil-soluble compounds of transition metals, which are capable of occurring in several valency stages, are particularly suitable for this purpose.

The individual components differ in their ability to accelerate hardening, compounds of cobalt and/or manganese being particularly suitable, although iron also accelerates hardening. In addition to and, in particular, in combination with these highly active metallic components, it is pos- "20 sible to use comparable compounds of other metals which may also be capable of forming several valency stages. A detailed description of such systems can be found, for example, in "Ullmann, Encyklopadie der technischen Chemie", 4th Edition, Vol. 23 (1983), 421-424.

25 It is also known that the two types of promoters described here for the radical initiation of polymerization can lead by interaction to an enhanced effect. For example, the Article by L. HORNER et al "Autoxidationsstudien an N,N-dialkylierten Anilinderivaten (Autoxidation Studies on N,N-Dialkylated Aniline Derivatives", in Makromolekulare Chemie 93 (1966), 69 to 108, relates to investigations into the acceleration of the spontaneous autoxidation of Ndialkyl-substituted arylamine compounds in pure, highly dry oxygen gas. In the first stage of the spontaneous autoxidation, the amine hydroperoxide compound is formed at r^ 1 i t71 r j D 8429 3 aliphatic CH groups in the a-position under the effect of dried, superpure oxygen. This spontaneous autoxidation of the N,N-dialkylated arylamines takes place very slowly.

According to the Article in question, the co-use of cobalt(II) compounds and, to a lesser extent, the co-use of iron(III) salts results in activation of the autoxidation process. In further studies reported in this Article, it is shown that acetic acid also has a pronounced accelerating effect on autoxidation at the teriary amine compound whereas stronger acids, such as trichloroacetic acid, or mineral acids form true tertiary ammonium salts which are not autoxidizable. The use of cobalt ions in conjunction with acetic acid leads to the vigorously catalyzed autoxidation of dialkyl aniline compounds under the effect of superpure oxygen.

S" Finally, the Article cited above describes studies into the initiation of the polymerization of vinyl compounds by the dimethyl aniline/superpure oxygen/cobalt salt system. High-purity acrylonitrile, methyl methacrylate, V 20 ethyl acrylate and styrene can be polymerized with this system. The initiating reaction is interpreted as redox catalysis in which molecular oxygen acts as oxidizing agent. There are no references- in the publication in question to the suitability of the multicomponent systems investigated for practical use in the polymerization field.

In fact, however, these theoretical works, which have been available to experts for almost 25 years, have not provided any encouragement for their practical application.

The problem addressed by the invention is to utilize existing knowledge of multicomponent redox systems as described above in developing new possibilities for the practical application of activator systems which may be used in simplified manner for initiating the polymerization of olefinically unsaturated systems. The activator systems are intended to be able, in admixture with radically polyk r

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f D 8429 4 merizable materials or mixtures, to be activated by contact with ambient air. In preferred embodiments, this activation is intended to take place at temperatures as low as room temperature, although a moderate increase in temperature may be applied. In one particularly important embodiment, the invention relates to multicomponent mixtures of the type mentioned which are capable, simply by contact with ambient air at room temperature, of initiating the starting reaction of a radical polymerization of unsaturated systems with time-controlled hardening and a predeterminable pot life.

In a first embodiment, therefore, the present invention relates to the use of activator systems for the radical polymerization of olefinically unsaturated systems containing as principal components of the activator system N-alkyl-substituted tert.-arylamines containing at least one aliphatic CH bond in the a-position metal compounds at least partly soluble in the system 20 to accelerate the drying of unsaturated oils and weakly acidic compounds, more especially monomeric and/or polymeric carboxylic acids, preferably having pKs values no lower than about 0.9 25 for the time-controlled hardening with a predeterminable pot life of moldable mixtures containing the radically polymerizable components, particularly together with dissolved and/or undissolved fillers and/or auxiliaries, by ambient air at room temperature and/or moderately elevated temperatures, preferably during the molding of the mixtures.

In a second embodiment, therefore, the present invention also relates to moldable, radically polymerizable multicomponent mixtures containing ethylenically unsaturated, polymerizable compounds, if P! If, or

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D 8429 210 a.

20 25 a desired in admixture with soluble and/or insoluble fillers and/or other auxiliaries and an activator system initiatable by contact with oxygen, characterized in that, in their in-use form, these multicomponent mixtures are present as at leastly slightly thickened material and contain an activator system based on the following principal components which can be initiated by contact with oxygen and water and, in particular, by contact with ambient air: S N-alkyl-substituted tert.-arylamines containing at least one aliphatic CH bond in the a-position S metal compounds at least partly soluble in the system to accelerate the drying of unsaturated oils and S weakly acidic carboxylic acids having pK, values no lower than about 0.9.

Accordingly, the essence of the teaching according to the invention lies in the choice of the specific reactive system which is being described for the first time in this combination of the required conditions and/or possibilities of use. This system differs from the investigations described by L. HORNER et al in several respects: The invention seeks to create the opportunity to work under practical in-use conditions. One particular requirement to be satisfied in this regard is that the catalyst systems active as so-called "autox" systems should be converted into the active state on contact not with pure and predried oxygen, but with ambient air with its comparatively limited oxygen content and the impurities always present, including moisture. For the purposes of practical application, the components to be polymerized are almost always present in admixture with fillers and/or other auxiliaries.

is! 8 I v D 8429 20 The invention is based on the observation that the problem stated above can be solved taking into account the elements described in detail in the following. Additional freedom in regard to practical application can be created by suitable auxiliary measures which are described in the following. Mere contact with air at ambient temperature or at most moderately elevated temperatures is sufficient to activate the starter system and, hence, to initiate the reaction in the system as a whole for dimensionally stable hardening. The open time of the system required for molding may be varied within wide limits. Practical significance is thus attributed to multicomponent systems having the composition according to the invention in the broadest applicational sense.

The three components of the activator system used in accordance with tI e invention will first be described in detail in the following: N-alkyl-substituted tert. -arylamines All corresponding compounds containing at least one aliphatic CH bond in the a-position are suitable. The amine components used in accordance with the invention correspond in particular to general formula I: S- R

(I)

R2 in which RI is an optionally substituted aryl radical, R 2 has the same meaning as R i or may even be an optionally substituted alkyl radical. This alkyl radical may be linear or branched. R 3 is a linear or branched alkyl radical which may even be substituted and which may be the same as or different from the alkyl radical optionally present in R 2 but is always distinguished by the fact that at least one r, L I II D 8429 7 H atom is present in the a-position to the N.

The preferred aryl radical is the phenyl radical which may even be substituted, more especially alkyl-substituted.

The alkyl radicals present in R 3 and optionally R 2 each preferably contain up to about 10 carbon atoms and, in particular, up to about 6 carbon atcms. Particular significance is attributed to corresponding C 1 3 radicals and again to the methyl radical in particular. In one preferred embodiment, the radicals R 2 and R 3 are corresponding, optionally substituted alkyl radicals while the radical Ri is an optionally substituted phenyl radical, so that N,Ndialkyl-substituted aniline compounds, which may also be alkylated in the phenyl ring, are generally preferred. The most important components in the context of the invention are dimethyl aniline and, in particular, dimethyl-ptoluidine.

Basically, the principles stated by L. HORNER et al, 1loc. cit. apply to the activity and the activatability of .these tertiary amine compounds: nucleus substituents 20 influence the autoxidation rate of the dimethyl aniline.

Electron donors increase the autoxidizability of the amine, electrophilic substituents reduce it. Accordingly, ptoluidine compounds are more reactive than the otherwise structurally identical aniline derivatives. The general S" 25 principles stated by HORNER also apply with regard to the alkyl substitutents in R 3 and R 2 The methyl group is much more accessible to oxidation than all other N-alkyl substituents. Basically, the known results of the action of dibenzoyl peroxide on tertiary amines, as reported in the cited literature reference, also apply here.

Metal compounds at least partly soluble in the system As already mentioned, the most important driers of the type in question are distinguished by the fact that, above all, metal compounds of metal capable of occurring in Oi r

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D 8429 some

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O *r C C. 4 i 0 me.-

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305 !13 several valency stages are used. Selected representatives of the transition metals can be particularly active in this regard. The particular choice of the metal may have inter alia a velocity-determining effect on the initiation of polymerization on account of a certain dependence on temperature of the reactive intervention of this metal component in the process as a whole. Components which are highly active at room temperature are derived in particular from cobalt and/or manganese. Iron also has a certain, albeit weaker, effect in accelerating the reaction at room temperature. The activity of other metal components, for example those based on vanadium, can be increased by increasing the temperature to such an extent that the polymerization reaction can be rapidly initiated.

Cobalt and/or manganese compounds, optionally in admixture with other metallic components, such as compounds of lead, cerium, calcium, barium, zinc and/or zirconium, are particularly suitable for working at room temperature which is of particular advantage for numerous applications.

Reference is made in this regard to the relevant specialist literature, cf. for example the cited publication in "Ullmann" loc. cit. and the literature cited therein.

The metals in question here are used in the form of such compounds that they are at least partly soluble in the system as a whole. Both soap-like metal compounds and also types attached otherwise, particularly in complex form, to organic radicals are suitable. A typical example of working in accordance with the teaching of the invention is the use of corresponding metal naphthenates or metal acetyl acetonates. Providing inorganic salts are sufficiently soluble in the system, it is also possible to use such inorganic systems. A typical example is iron chloride which has a distinctly accelerating effect when used in the system according to the invention.

It may be advisable to use the metal compounds in a

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D 8429 9 low valency stage of the metal, i.e. for example as cobalt(II) or manganese(II). In other cases, it is also suitable to use the metal compound in the higher valency stage of the metal. Thus, iron chloride, for example, is preferably used in the form of the Fe 3 salt.

Carboxylic acid compound(s) A factor of crucial importance in the selection of these components is the acidity of the free carboxylic acid. The pKs value of the free acid should be no lower than about 0.9, the preferred limit being at about 1.

If much more strongly acidic components are used, acceleration of the reaction comes to a stop. This is illustrated by the following examples. The pKs value of trichloroacetic acid is approximately 0.6. The addition of S. trichloroacetic acid to tne system destroys the ability of the multicomponent initiator system used in accordance with the invention to initiate polymerization reactions. By contrast, dichloroacetic acid is a relatively weak 20 carboxylic acid with a pKs value of approximately 1.3. This dichloroacetic acid is eminently suitable for initiating *o polymerization reactions in accordance with the invention.

S. Strongly acidic mineral acids, for example hydrochloric acid, also affect the ability of the activator systems used in accordance with the invention to initiate polymerization reactions. Acetic acid (pK s value of acetic acid approx.

4.76) is eminently suitable for accelerated reaction initiation.

The upper limit to the pKs value may be seen in the region of very weakly acidic compounds determined as free carboxylic acid. In numerical terms, therefore, the upp'er limit is at pKs values of approximately 13 and, preferably, at pKs values of approximately 11.5. However, carboxylic acids which have pKs values in the hydrolyzed state of up to about 8 and preferably of up to about 6 or 7 are particu- *7 V 9 D 8429 larly suitable. Particularly effective components of the type in question here are thus derived from carboxylic acids which have pK s values in the hydrolyzed state in the range from about 1 to 6 or 7.

The carboxylic acids to be used in accordance with the invention may contain one or more carboxyl groups. The constitution of the acid as such is not such a crucial parameter given the correct pKs value. The systems according to the invention may advantageously be based on carboxylic acids containing 1 to 4 carboxyl groups and, more particularly, 1 or 2 carboxyl groups. The choice of the particular carboxylic acid is also largely determined by corresponding expediency considerations. Readily obtainable carboxylic acids, such as lower aliphatic carboxylic acids or corresponding aromatic mono- or polybasic carboxylic acids are suitable components.

Suitable aliphatic carboxylic acids are and preferably

C

1 _1 0 monocarboxylic acids, acetic acid again being particularly important. Suitable aromatic carboxylic acids 20 are benzoic acid or corresponding polycarboxylic acids, for example trimellitic or pyromellitic acid. As shown with reference to the example of dichloroacetic acid, substituted acids of this type are also suitable providing their pK s value is within the stated limits.

In one embodiment of the invention, the free carboxyl- *ic acids or carboxyl groups of the activator system are at least partly formed by COOH groups attached to preformed oligomeric and/or polymeric compounds. These carboxyl groups may thus be utilized in several respects in the context of the teaching according to the invention. In the polymerization initiation phase, these acid components perform the described activating function. Quite apart from this, however, there are the general chemical principles under which free carboxyl groups of the type in question can impart characteristic properties to the reaction prod- 4 7'

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_Ir D 8429 11 uct hardened in particular in dimensionally stable form.

A possible coupling effect with respect to solid surfaces, for example of metal, or the increased possibility of attacking alkaline media are M~eintioned purely by way of example in this regard.

The free carboxyl groups in the oligomeric and/or polymeric components may be reactively bound into the dimensionally stable reaction product formed and/or may be present as non-reactive fillers in the hardened reaction product, depending on the particular structure of the oligomeric or polymeric additives.

However, the invention also encompasses this multifunctionality of acidic components used in a totally different way: Radically initiated polymerization reactions may generally be carried out using ethylenically unsaturated free acids. Such compounds as acrylic acid, methacrylic, crotonic acid, itaconic acid, maleic acid and/or fumaric acid and also olefinically unsaturated compounds of the 20 tetrahydrophthalic acid type and related compounds are particularly well-known as reactive mono- and/or dicarboxylic acids in this regard. Finally, however, it is also known that relatively long-chain, mono- or polyolefinically unsaturated carboxylic acids, particularly unsaturated fatty acids of the type mentioned containing, for example, 10 to 30 carbon atoms and, in particular, 12 to 24 carbon atoms, can be included in radically initiat-d polymerization reactions through their content of ethylenic double bonds.

In the embodiment of the invention under discussion, acid components of the type in question are not only activated as constituents of the reaction mixture hardening by polymerization, they are also able through their free acid groups at least partly to perform the acid function in the activator system used in accordance with the invention

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a i i D 8429 12 of tertiary amine compound, at least partly soluble metal compound and acidic component of limited acitivity. It is clear that this provides for wide variation of the activesubstance mixtures to be used.

Activator systems of the three principal components described in the foregoing, namely aromatic amine compound, at least partly soluble metallic drier and weak acid are able after taking up moisture and oxygen from the ambient air to initiate all the radically polymerizable, olefinically unsaturated systems which, hitherto, have been used with a variety of different, particularly peroxidic, starter systems. To this extent, the other constituents of the radically polymerizable, moldable multicomponent mixtures according to the invention may be as defined in the 15 extensive relevant literature which is concerned with the production and processing of systems based on olefinically S. unsaturated radically polymerizable compounds. A very large number of systems of this type tailored in their properties to the particular application envisaged are 20 currently available to the expert.

Systems distinguished by at least slightly elevated viscosity values at the onset of the polymerization reaction are particularly suitable for the initiation of polymerization by atmospheric oxygen activated in accordance with the invention, particularly at room temperature or nly moderately elevated temperature. Tests have actually Sshown that the us, of ambient air, even where a basically highly active combination of activating agents is used, does not lead to reaction initiation in the right time, if at all, when highly mobile unsaturated systems are used, even where they are known per se for their high reactivity in the polymerization reaction. Typical examples of such systems are conventionally stabilized lower acrylate esters, methacrylate esters or styrene. An activator system of, for example, dimethyl-p-toluidine, soluble cobalt p.

D 8429 13 compounds and acetic acid hardens commercially available, unsaturated components of the type just mentioned on contact with ambient air at room temperature only when the viscosity of the system as a whole is slightly increased.

Generally, therefore, radically polymerizable systems with an initial viscosity of at least about 30 to 100 mPa.s and preferably of at least about 200 or 300 mPa.s should be used in accordance with the invention. Particularly safe initiation of the polymerization reaction can be expected in the case of systems which have an initial viscosity of at least about 500 mPa.s and, more especially, of at least about 1000 mPa.s. All %:hese viscosity values are determined by Brookfield visco!imeter. Commercially available adhesive systems are known to have viscosities of at least 15 about 3,000 mPa.s and, more particularly, viscosity values of up to about 10,000 mPa.s. Materials of this type understandably are eminently suitable for processing in accordance with the invention. However, the invention is by no means limited to such mater.ials. Considerably less viscous 20 systems, for example spreadable paint systems used in particular as solventless systems, are suitable for the reaction-initiating mechanism described herein providing the S: above-mentioned minimum values for t:e initial viscosity of the material to be molded are observed. The same applies to other fields of application, for example the production of plastics moldings based on styrene/unsaturated polyester resins.

The necessary viscosity values may be established in particular by mixtures which have an adequate content of oligomeric and/or polymeric components, optionally in admixture with low molecular weight, unsaturated components liquid at room temperature, such as (meth)acrylates. However, correspondingly viscous materials may also consist solely of precondensates of suitable fluidity. The extensive knowledge of experts on ethylenically unsaturated mixj i* L 71 -v I D 8429 14 tures such as these hardenable by radical polymerization may be applied in this regard.

The multicomponent mixtures to be used in accordance with the invention may be formulated as multicomponent systems. For the practical application of the system, the components are mixed with one another in known manner. The open pot life of the system may be regulated by suitable choice and adaptation of the principal components of the activator system, so that the starting reac- .on may be initiated and, hence, the system ultimately hardened under ambient conditions in air. In one preferred embodiment of the invention, the multicomponent mixtures in question of activator system and polymerizable components are formulated as multicomponent systems which are non-reactive, even on contact with air, two-component systems in particular being present as multicomponent systems. In addition, it is particularly preferred in this regard to separate the three main components of the activator systems used in accordance with the invention from one another in such a 20 way that the tert. N compound is kept separate from the metal compounds and the free carboxylic acids. Both components may thus generally contain ethylenically S:unsaturated reaction product. For processing, these two separately stored components merely have to be mixed, molded during the open pot life of the system and brought into contact with ambient air.

the invention provides for the formulation of optimized active-substance mixtures. Without departing from the principles of the invention, it is possible to use soluble and/or insoluble fillers, elasticizers, thickeners, thixotropic agents, pigments, coupling agents, stabilizdrs and the like without endangering the performance of the activator system according to the invention. This does of course presuppose that disturbances in the interaction of the activator components are precluded through the choice D 8429 of the auxiliaries and fillers. General chemical knowledge may be applied in this regard.

One particular feature of the multicomponent mixtures according to the invention or rather the activator systems used therein is that additional inhibition and hence control of the system as a whole is possible.

Various mechanisms are available for inhibiting the "autox" system used in accordance with the invention, of which the three basic types 1 to 3 are listed below: 1. stabilization against 02, addition of antioxidants 2. stabilization against R-OOH, addition of reducing agent 3. stabilization against radicals, addition of radical inhibitors 15 From general knowledge of chemistry, typical stabilizer components are listed in the following, the numbers in brackets after the particular compound indicating which of the three mechanis :s listed above is to be assigned to the stabilizer: pyrogallol 0 2 -inhibited acrylates hydroquinone hydroquinone monomethyl ether triphenyl phosphine tributyl phosphite butyl hydroxytoluene phenothiazine In the multicomponent mixtures according to the invention, the activator mixtures preferably make up no more than about 25% by weight and, in particular, no more than about 10% by weight, based on the weight of the system as a whole. Depending on the activity of the components used, the weight of the activator mixture can be greatly reduced, for example to about 0.1% by weight or to at least about by weight. Particularly suitable quantities of the activator system are at least about 1% by weight, preferably up to about 8% by weight and more preferably from about 1 to 7% by weight. All these figures are based on the one hand on the total weight of the multicomponent

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D 8429 16 system according to the invention and the total weight of the three principal components of the activator system.

The three principal components of the activator system may advantageously be used in the following quantitative ratios to one another (in by weight, based on the mixture of the three activator constituents): to 20% and preferably 5 to 15% of the metal compound to 60% and preferably 40 to 55% of the teriary amine compound 30 to 60% and preferably 40 to 55% of the masked weak acid.

The particular quantities in which the metal compounds are used may also be defined in particular through the ratio by weight of the weight of the metal to the weight of the multicomponent activator system as follows: Preferred quantities of metal compound are from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight and more preferably from about 0.1i to 1% by weight metal, based .on the total weight of the activator constituents.

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If inhibitors and/or stabilizers of the type mentioned 20 above are used to control the course of the reaction and/or the open pot life, the quantities in which they are used S: will be gauged according to the stated purpose, In each individual case, they may readily be determined by considerations appropriate to the expert and/or by preliminary eel: tests. The regulators used will normally not exceed a few percent, for example about 2 to 5% by weight, of the mixture as a whole and are generally used in quantities of less than 1% by weight.

Mixtures of oligomers and/or polymers together with ethylenically unsaturated monomers of low molecular weight are used as mixtures of radically polmerizable materials suitable and typically used for a variety of applications in practice. The mixture components of relatively high molecular weight are often at least partly dissolved in the monomers. Mixtures of this type are particularly suitable a fli

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D 8429 17 for processing in accordance with the invention. The content of monomers, for example (meth)acrylates, optionally substituted styrene and/or acrylonitrile, is generally at least 10% by weight, preferably at least 20% by weight and, in many applications, at least about 40% by weight, based on the final reactive mixture as a whole. In terms of weight, the monomer component may be by far the predominant component so that, for example, 60 to 80% by weight of the mixture as a whole is formed by the low molecular weight monomers. As mentioned above, however, it is important to ensure that the at least slightly increased initial viscosity of the mixtures for safe reaction initiation on contact with air is guaranteed by the use of an adequate quantity of compounds of relatively high molecular weight and/or by other thickening agents.

i In characteristic examples of application, which fall i: within the scope of the invention as preferred embodiments, these conditions of use are guaranteed in any c-se.

Without any claim to completeness, the following examples are mentioned here: aerobic adhesive systems, spreadable compositions for surface coating with polymerizable, in particular solvent-free lacquers and paints in the form of spreadable air-drying paint systems and the production of moldings with initiation of the reaction involved by contact with ambient air, for example based on styrene/unsaturated polyester resins.

Examp 1 es EXAMPLES 1 TO 9 Solution A MMA (methyl methacrylate) Polyacrylate (Plexigum MB 319, Rohm /soluble filler) Cobalt acetyl acetonate 0.24 Acrylic acid 10 7 D 8429 Solution B

MMA

Plexigum MB 319 N,N-dimethyl-p-toluidine The above quantities are parts by weight.

Solutions A and B were mixed in various quantitative ratios and the adhesive preparations obtained were used to bond PVC.

Example Quantitative No. ratio A:B Pot life Tensile shear strength (mins.) (N/mm 2 15 .0 1 9:1 2 8:2 3 7:5 4 6:4 5 5:5 6 4:6 7 3:7 8 2:8 9 1:9 MF material failure 1.4 1.4 MF (1.7) MF (1.9) MF (3.2) MF MF MF (3.6) To guarantee adequate oxygen uptake, the particular mixture was vigorously stirred in air for 1 minute and the substrates coated with the adhesive preparation were left in air for 2 minutes before being fitted together.

EXAMPLES 10 TO 19 Variation of the amine concentration Mixtures of 6 g MMA 4 g Plexigum MB 319 g acetic acid and mg of a solution of cobalt naphthenete in gasoline

LL

D3 8429 Co) toluidine harden on 19 and different quantities of N,N-dimnethyl-pcontact with atmospheric oxygen.

Example Quantity of No. amine Pot life Tensile shear strength (mins.) (N/mm 2 15 20 3.1 (MF) 8.1 (MF) 7.6 (MB) 4.7 (MB) 7.1 (MB)

(MB)

6.4 (MF) 7.6 (MB) 7.6 (MB) 5.8 (MB) acids and the monomers and 10. 5% initiator EXAMPLES 20 TO 29 Variation of the carboxylic Mixtures of 89.5% monomer (mixture) consisting of N,N-dimethyl 0. 5 cobalt napht] system -p-toluidine hienate solution in gasoline (6% Co) carboxylic acid harden on contact with atmospheric oxygen.

Example Monomer No.

Carboxylic acid Pot life (mins. Y 8 1 '/NI4A it Acetic acid Propionic acid Chloroacetic acid Carboset 515: D 8429 24 Acetic acid Acrylic acid 9 26 "Dichloroacetic acid 12 27 Methacrylate- Acetic acid 2 terminated

PUR

4 28 THF-MA/PMMA 5 Acetic acid 11 29 MMA/PMMA Benzoic acid 1) 1:1 Mixture of MMA and a methacrylate-terminated polyester PUR (reaction product of CAPA 200, a polycaprolactone manufactured by Union Carbide OH value 209, 2 mol), 2,4-tolylene diisocyanate (Desmodur T 100, a product of Bayer AG, 3 mol) b-01/20 (a 15 polypropylene glycol monobutyl ether manufactured by Hoechst, 1 mol), hydroxyethyl methacrylate (HEMA, 1 mol) 2) An acrylic acid copolymer manufactured by B.F.

Goodrich, acid value 60 to .J "20 3 A mixture of 60 parts MMA and 40 parts Plexigum MB 319 (a polyacrylate manufactured by Rbhm) A methacrylate-terminated PUR (reaction product of 1 mol B 01-20, TDI and HPMA) 5 A mixture of 2 parts tetrahydrofurfuryl methacrylate and 1 part Plexigum MB 319 EXAMPLE A mixture of S53 MMA 25 Plexigum MB 319 4 N,N-dimethyl-p-toluidine 4 acetic acid 3 Mn(II) octoate polymerizes 15 minutes after contact with atmospheric S 35 oxygen.

h Ili 4 1 v D 8429 21 EXAMPLES 31 TO 34 Variation of the amines Mixtures consisting of parts MMA 40 parts Plexigum MB 319 3 parts acetic acid 3 parts amine part cobalt naphthenate Example Amine Pot life (mins.) 31 N,N-dimethyl aniline 32 N-ethyl-N-methyl aniline 47 (5 parts amine, parts acid) 33 N,N-dimethyl-m-toluidine 26 34 N,N-dimethyl-p-toluidine 18 EXAMPLE .The following activator system: 5% acetic acid, dimethyl-p-toluidine, 0.5% cobalt solution) was added to the dimethacrylate of bisphenol A x 2 EO (Diacryl 101) Swith no addition of thickener.

The pot life is 1 minute.

25 EXAMPLE 36 The initiator mixture of Example 35 is added to the reaction product of bisphenol-A-diglycidyl ether with methacrylic acid (Ritapox 959, a product of Ritgers) with no addition of thickener.

The pot life is under 1 minute.

EXAMPLE 37 The initiator system of Example 35 is added to Vestopal 150, a commercial product manufactured by Hils (unsaturated polyester resin, 66% in styrene), with no addition of thickener.

y\j D 8429 The pot life is 1.5 minutes.

EXAMPLE 38 The following initiator system: 3% acetic acid, 3-' dimethyl-p--toluidine, 0.5% cobalt solution, i s added to a mixture of cyclohexyl meth&crylate and Plexigum MB 31-9.

The pot life is 16 minutes.

9*

Claims (19)

1. The use of activator systems for the radical polymerization of olefinically unsaturated systems containing as the principal components of the activator system N-alkyl-substituted tert.-arylamines containing at least one aliphatic CH bond in the a-position; metal compounds at least partly soluble in the system to accelerate the drying of unsaturated oils, and weakly acidic compounds, particularly monomeric and/or polymeric carboxylic acids, preferably having pK s values not lower than about 0.9 i for time-controlled curing, by ambient air at room temperature and/or moderately elevated temperatures, with a predetermined pot life, of mouldable substance mixtures which are formulated as a free-flowing, S preferably at least slightly thickened, spreadable to paste-like distributed material, and preferably in the course of their moulding, which contain the components capable of radiacal polymerization especially together with dissolved and/or undissolved fillers and/or auxiliary agents.

2. The use according to claim 1, characterized in that the multicomponent mixtures of activator system and polymerizable components are formulated as a multicomponent system which is non-reactive even on contact with air, the multicomponent systems being in particular two-component systems in which the tertiary N compound is kept separate from the metal compounds and the free carboxylic acids, and the components being combined for moulding and curing.

3. The use according to claims 1 and 2, characterized in that the activator-containing multicomponent mixtures are used with viscosities (Brookfield) of at least about 50 to 100 mPa.s and specifically of at least about 300 mPa.s for moulcing. 4 KEH/364z

4. The use according to claims 1 to 3, characterized in that in the activator system, as N alkyl substituted arylamines there are used compounds of the general formula I R ~N R 3 (I) R 2 in which R1 denotes an optionally substituted aryl radical, more especially an optionally alkyl-substituted phenyl radical, R2 has the same meaning as R or is an optionally substituted, linear or branched alkyl radical, and R 3 denotes a linear or branched alkyl radical which may even be substituted but contains at least one H atom in the a-position relative to the N. r 5. The use according to claims 1 to 4, characterized in that as compounds of the general formula I there are used dialkyl aniline compounds substituted or unsubstituted in the aromatic ring, wherein the alkyl radicals each preferably contain up to 10 and more preferably up to 6 C S atoms, with aniline derivatives optionally alkyl-substituted in the ring, especially those of the structure of dimethyl aniline and/or dimethyl- p-toluidine, being particularly suitable.

6. The use according to claims 1 to 5, characterized in that as the metal-containing drying agents at least partly soluble in the system there are used compounds of metals occurring in several valency stages, more especially compounds of corresponding transition metals, the metal ions preferably being present in their low valency stage. Sf KEH/364z

7. The us- according to claims 1 to 6, characterized in that there are used metal compounds soluble in organic media of cobalt and/or manganese or even iron, the iron even being useable in the form of an 3+ Fe 3 compound.

8. The use according to claims 1 to 7, characterized in that carboxylic acids have pK S values no lower than about 1 and preferably no lower than about 1.3 are used.

9. The use according to claims 1 to 8, characterized in that there are used acid compounds having an upper pKS limit of approximately 13 and preferably of approximately 11.5 and, in particular, corresponding carboxylic acids with an upper pKS limit of the free carboxylic acid of approximately 7.

10. The use according to claims 1 to 9, characterized in that carboxylic acids containing one or more cadboxyl groups and more especially 1 to 4 carboxyl grJps are used.

11. The use according to claims 1 to 10, characterized in that as ethylenically unsaturated polymerizable components there are used acrylate and/or methacrylate compounds or systems, styrene or styrene derivatives and/or acrylonitrile-containing components which may be present, completely or partly, in the form of reactive preformed oligomer and/or polymer compounds.

12. The use according to claims 1 to 11, characterized in that, in the system there are used, in addition, multi-component systems containing fillers, thickeners, elasticizing agents, pigments, adhesion-promoting' agents, stabilizers and/or other auxiliary substances soluble and/or insoluble in the system. i KEH/364z I ^e I TC

13. The use according to claims 1 to 12, characterized in that mixtures containing antioxidants, reducing agents and/or radical inhibitors are us.d for stabilization against unwanted contact with oxygen and/or for adjusting the pot life.

14. The use according to claims 1 to 13, characterized in that there are used and molded multicomponent mixtures in which the activator mixture makes up no more than about 25% by weight and preferably no more than about by weight of the system as a whole and preferably makes up at least 0.1% by weight and, more preferably, about 1 to 8% by weight of the system as a whole. The use according to claims 1 to 14, characterized in that the i: components of the activatc system are used in the following approximate quantitative ratios (in by weight, referred to the mixture of the three constituents of the activator): to 20 and preferably 5 to 15% by weight metal compound or 0.01 to 5 and preferably 0.05 to 2% by weight metal, 30 to 60 and preferably 40 to tert. amine compound, 30 to 60 and preferably 40 to 55% of the weak acid.

16. The use according to claims 1 to 15, characterized in that there are used systems in which 'he concentration of components capable of radical polymerization, parti'ularly the monomer concentration, is at least about by weight and prF,ierably at least about 40% by weight.

17. The use of the activator systems according to claim 1 for curing reactive adhesives by contact with ambient air, particularly at ambient temperature, the reactive adhesives preferably being based on paste-like masses which contain acrylate- and/or methacrylate-based reactive components, particularly in a mixture with polymers at least partly soluble therein, and preferably have viscosity values above 500 mPa.s, specifically in the range from about 3000 to 10,000 mPa.s. 1 EH/364z I i

18. The use of the activator systems claimed according to claim 1 for curing surface coatings, particularly in the form of air-drying paint systems, and for embodying plastics mouldings, in either case by contact with ambient air, and particularly at ambient temperature.

19. Mouldable multicomponent mixtures capable of radical polymerization, which may even be present in the form of multicomponent systems with a stable shelf life, containing ethylenically unsaturated, polymerizable compounds, if desired in a mixture with soluble and/or insoluble fillers and/or other auxiliary agents, and an activator system adapted to be initiated by contact with oxygen, characterized in that, in their in-use form, the multicomponent mixtures are present as an at least slightly thickened material and contain an activator system based on the following principal components which can be initiated by contact with ambient air: S N-alkyl-substituted tert.-arylamines containing at least one r aliphatic CH bond in the a-position, metal compounds at least partly soluble in the system to accelerate the drying of unsaturated oils, and S weakly acidic carboxylic acids having pKS values not lower than I about 0.9. Multicomponent mixtures according to claim 19, characterized in that, in their in-use form, they have a minimum viscosity (Brookfield) of at least about 100 mPa.s, preferably of at least about 300 mPa.s and specifically of at least about 500 mPa.s.

21. Multicomponent mixtures according to claims 19 and 20, characterized in that the free carboxylic acid of the activator system is formed at least partly by ethylenically unsaturated mono- and/or dicarboxylic acids, specifically acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and/or fumaric acid. KE/364z 3 4' iI

22. Multicomponent mixtures according to claims 19 and 20, characterized in that the free carboxyllc acid of the activator system is embodied at least partly by COOH groups bonded to preformed oligomer and/or polymer compounds which are bound preferably into the reaction product during the curing of the multicomponent mixture. i 9/, S.. a a C a.. a.. KH/64 ;id D 8429 Abstract New, radically polymerizable multicomponent mixtures and their use (II) The invention relates to moldable, radically polymerizable multicomponent mixtures, which may even be present in the form of storable multicomponent systems, containing ethylenically unsaturated, polymerizable compounds, if desired in admixture with soluble and/or insoluble fillers and/or other auxiliaries and i" an activator system initiatable by contact with oxygen, characterized in that, in their in-use form, the multi- component mixtures are present as at leastly slightly thickened material and contain an activator system based on the following principal components which can be initiated by contact with ambient air: N-alkyl-substituted tert.-arylamines containing at least one aliphatic CH bond in the a-position metal compounds at least partly soluble in the system to accelerate the drying of unsaturated oils and weakly acidic carboxylic acids having pK, values no lower than about 0.9. In their in-use form, the multicomponent mixtures preferably have a minimum viscosity of at least about 50 to 100 mPa.s. The invention also relates to the use of the activator systems of these mutlicomponent mixtures for the time-controlled hardening with a predeterminable pot-life r ~L V D 8429 of olefinically unsaturated systems by contact with ambient air at room temperature or only moderately elevated temperatures. I INTERNATIONAL SEARCH REPORT International Avolicatlon No PCT/EP 89/00980 1. CLASSIFICATION OF SUBJECT MATTER (it sevorat ciaaalflcstion aimools apply, Indicate all) According to international Patent Classification (IPC) or to both National C44asification and IPC Int.C1 C 08 F 4/00, C 09 D 15/00 II. FIELDS SEARCHED Minimum Documentation Searched7 Classification System IClassification Svrr.ools Int.C1 5 I C 08 F Documentation Searchied other than Minimum Documentation to the Extent that such Documents are Included in the Fields SearchedI Illt. DOCUMENTS CONSIDERED TO BE RELEVANT' Category' Citation of Document, 11 with Indication. wna.. a ooiroornate, of theo relevant pasages 12 IRelevant to Claim No. 13 A Die Makromolekulare Chemi, Vol. 93, 1966 (Basel,CH) L. H-orner et al.: "Autoxidationsstudien an N, N-di- alkylierten Anilinderivaten", pages 69-108 cited in the application A FR,A,1242899 (BAYER) 29 "agust 1960 Special categories oi cited daumeniv: it later document published sfter the international filing date document defining tnio general stats of theo art which is not or, priority atsano not in conflict with the anolicatio but considered to be oi eanicular roeeance citsd to understand tne princioit or theory unoenying the invention earlier document but pubiished on or slir the international document of carticuier relevance: the claimed invention~ filing oats cannot ne considered novel or cannot us considered to document which may throw doubts on priority cilim(s) or involve an Iiventive stop which is cited to establish tre oubication date ot another document of dafliculer relevance: the claimed invention citation or other special reason (as specified) cannot ti. considered to involve an invenive also whien the document referring to an oral disclosure, use, exhibition or document in comoineo with one or more otner sucn oocu- otner means Mentz. such combination osing oovioua to a person acilled document published prior to the international filing date but in ins art. later than ins oriority date claimed document Member ot theo same patent family IV. CERT'IFICATION Date Of the Actual Comoletion oi tio International Search I Date Of Melling oi this international Search Report November 1989 (15.11.89) 13 December 1989 (13.12.89) international Searciting Authority I Signature oi Autnorized Officer IEUROPEAN PATENT OFFICE Form PCT1ISAI21I second enetl lianuary, 191) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8900980 SA 30597 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 06/12/89 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date FR-A- 1242899 BE-A- 581239 CA-A- 637741 GB-A- 871424 S For more details about this annex see Official Journal of the European Patent Office, No. 12/82