EP1165438A1

EP1165438A1 - Melamine-modified phyllosilicates

Info

Publication number: EP1165438A1
Application number: EP00903610A
Authority: EP
Inventors: Carsten Zilg; Rolf Mülhaupt; Jürgen Finter
Original assignee: Vantico GmbH
Current assignee: Huntsman Advanced Materials Switzerland GmbH
Priority date: 1999-01-28
Filing date: 2000-01-22
Publication date: 2002-01-02
Also published as: BR0007830A; KR20010101734A; WO2000044669A1; CN1339013A; JP2002535233A

Abstract

The invention relates to organophilic phyllosilicates which are produced by treating a natural or synthetic phyllosilicate or a mixture of such silicates with a salt of a cyclic, optionally quaternary, melamine compound or a mixture of such salts. The invention also relates to polymer systems, especially thermoplastic polymers, duroplastic polymer systems, preferably epoxy resins, polyurethanes and caoutchoucs which contain the inventive organophilic phyllosilicates and moldable molding and extrusion materials and finished molded parts in the form of composite materials, especially in the form of nano composite materials.

Description

Melamine-modified layered silicates

The present invention relates to new organophilic layered silicates, their production and their use in deformable molding compositions and in finished molded parts or composite materials, in particular in nano-composite materials (nanocomposites), which preferably contain the organophilic layered silicates according to the invention in exfoliated form.

It is known to use organophilic layered silicates, which have been produced, for example, by means of ion exchange, as fillers for thermoplastic materials and for thermosets, nanocomposites being obtained. When using suitable organophilic phyllosilicates as filling materials, the physical and mechanical properties of the molded parts produced in this way are considerably improved. Of particular interest is the increase in rigidity with at least the same toughness. Nanocomposites, which contain the layered silicate in exfoliated form, have particularly good properties.

From DE-A-38 10 006 it is known to treat layered silicates with an, optionally quaternary, ammonium salt of a primary, secondary or tertiary linear organic amine in the presence of a dispersion medium. An ion exchange or cation exchange takes place, the cation of the ammonium salt being embedded in the interlayer space of the layered silicate. Layered silicates modified in this way become organophilic as a result of the organic residue of the amine taken up. If this organic radical contains functional groups, the organophilic layered silicate is able to form a chemical bond with a suitable monomer or polymer. However, the use of the linear amines mentioned in DE-A-38 10 006 has the disadvantage that they thermally decompose at the high temperatures of up to 300 ° C. customarily used for processing thermoplastics and can discolor the product. The formation of decomposition products can lead to emissions and deterioration of the mechanical properties, e.g. impact resistance.

It has now surprisingly been found that organophilic phyllosilicates, which are obtained by treating phyllosilicates, ie by means of cation exchange with salts of optionally quaternary, melamine compound were produced, show a higher temperature stability during processing combined with excellent dispersing action and interfacial adhesion. In thermosets, an increased addition of the organophilic three-layer silicates according to the invention is possible as is customary without affecting the processing by increasing the viscosity. If the cyclic melamines used contain reactive groups, the organophilic phyllosilicates produced therewith and used as fillers can be covalently linked to the matrix by grafting. Melaminium ions, which are derived, for example, directly from melamine or from aminopropionic acid and 12-aminododecanoic acid, are distinguished by surprisingly good layer separation, combined with excellent adhesion to a large number of polymers and fillers. In contrast to the prior art (Giannelis), it turned out to be surprising that the melaminium salts according to the invention with long and optionally substituted alkyl radicals efficiently exchange cations within the interlayer spaces of the layered silicates despite the high steric space filling. It is further surprising that the organophilic three-layer silicates according to the invention are not only excellent fillers for improving the mechanical properties of polymers, but also act as flame retardants, the disadvantage of increased water absorption in melamine composites not occurring here.

The present invention is defined in the claims. In particular, the present invention relates to organophilic phyllosilicates, which are characterized in that they have been prepared by treating a natural or synthetic phyllosilicate or a mixture of such silicates with a salt of an optionally quaternary, cyclic melamine compound or a mixture of such salts.

The present invention furthermore relates to the production of the organophilic layered silicates according to the invention and their use in deformable molding compositions and in finished molded parts or composite materials, in particular in the production of nano-composite materials (nanocomposites), which preferably contain the organophilic layered silicates according to the invention in exfoliated form.

The present invention further relates to deformable molding compositions and manufactured molded parts in the form of composite materials, in particular in the form of nano- Composite materials (nanocomposites) which contain the organophilic phyllosilicates according to the invention, preferably in exfoliated form.

The present invention further relates to the use of the deformable molding compositions according to the invention for the production of lacquers, adhesives, casting resins, coatings, flame retardants, thixotropic agents and / or reinforcing agents.

The present invention further relates to lacquers, adhesives, cast resins, coatings, flame retardants, thixotropic agents and / or reinforcing agents which contain an organophilic layered silicate according to the invention.

The present invention also relates to the use of the melamine compounds of the formula (I) given below for the production of organophilic phyllosilicates.

Layer silicates for the production of organophilic layer silicates are primarily natural or synthetic smectite clay minerals, in particular montmorillonite, saponite, beidelite, nontronite, hectorite, sauconite and stevensite, and also bentonite, vermiculite and halloysite. Montmorillonite and hectorite are preferred. In particular, layered silicates are preferred whose layers have a layer spacing of approximately 0.7 nm-1.2 nm (nanometers) and in the form of the organophilic layer silicates according to the invention have a layer spacing of at least 1.2 nm. The layered silicates used preferably have a cation exchange capacity in the range of 50-200 meq / 100 g (milliequivalents per 100 grams). Such sheet silicates that can be used are described, for example, in A.D. Wilson, H.T. Posser, Developments in lonic Polymers, London, Applied Science Publishers, Chapter 2, 1986. Synthetic layered silicates are obtained, for example, by reacting natural layered silicates with sodium hexafluorosilicate. Synthetic layered silicates are commercially available, for example, from CO-OP Chemical Company, Ltd., Tokyo, Japan and have also been described by this company.

The layered silicate montmorillonite, for example, generally corresponds to the formula:

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] nH ₂ O where part of the aluminum can be replaced by magnesium. The composition varies depending on the silicate deposit. A preferred one The composition of the layered silicate corresponds to the formula:

(AI ₃ .i5Mgo.B5) SiB.ooθ ₂ o (OH) ₄ Xιi _Λ . nH ₂ O where X is an exchangeable cation, usually sodium or potassium. The specified hydroxyl groups are interchangeable with fluoridones, for example. By exchanging hydroxyl groups for fluoridones, for example, the synthetic layered silicates are obtained.

Preferred are organophilic layered silicates which, using a cyclic melamine compound of the formula (Ia), (Ib), (Ic):

or a mixture of such compounds have been prepared in which Ri is a linear or branched aliphatic radical having 1-20 C atoms, which may contain one or more unsaturated bonds and / or one or more functional groups; R _{2 is} hydrogen or a linear or branched aliphatic radical having 1-20 C atoms, which has one or more unsaturated bonds and / or one or more functional

Contain groups and optionally interrupted by one or more -NH groups or by one or more oxygen atoms;

R _{3 is} hydrogen or a linear or branched aliphatic radical with 1-8 C atoms, which may contain one or more unsaturated bonds; and

X ^"the same or different, any anions of the charge [m-], where m is preferably 1 or 2, for example: F ^" , Cl ^" , Bf, I ^" , SO ₄ ^{2 "} , CH ₃ SO ₄ ^" , C ₆ H ₆ SO ₄ ^" , (HCOO) ^' , or (CH ₃ COO) ^" .

Preferably mean:

Ri is the alkyl radical of a saturated or the alkenyl radical of an unsaturated fatty acid,

Hydroxy fatty acid or an amino carboxylic acid with 8-20 C atoms, preferably with 12-20

C atoms, preferably with 14-18 C atoms, or (C ₂ -C ₈ ) alkyl, which is optionally substituted by a carboxyl group or a (CrC ₃ ) alkoxycarbonyl group,

R _{2 is} hydrogen or an aliphatic radical with 1-8 C atoms, which is an unsaturated

Contain bond and can be substituted with a carboxyl group or a (CrC ₂ o) alkoxycarbonyl group or a cyclohexylcarbonyl group or a phenylcarboxyl group, and is optionally interrupted by -NH- or by oxygen,

R _{3 is} hydrogen or (CC ₄ ) alkyl;

X ^{m "the} same or different, any anions of the charge [m-], where m is preferably 1 or 2, for example: F ^" , Cl ^' , Br \ I ^" , SO ₄ ^2" , CH ₃ SO ₄ ^' , C ₆ H ₆ SO ₄ ^" , (HCOO) ^" , or (CH ₃ COO) \

Compounds of the formulas (Ia ¹ ), (Ib ') or (Ic') are particularly preferred:

wherein

Ri 'the alkenyl radical of 12-hydroxyoleic acid or the alkyl radical of aminocaproic acid (3-

Aminopropionic acid) and 12-aminododecanoic acid,

R ₂ 'is hydrogen, or an aliphatic radical having 1 -4 C atoms, which is optionally substituted by a (CrC ₂₀ ) alkoxycarbonyl group;

R ₃ 'is hydrogen, methyl or ethyl; and

X ^{m "the} same or different, any anions of the charge [m-], where m is preferably 1 or 2, for example: F ^" , Cl ^" , Br ^" , I ^" , SO ₄ ^2" , CH ₃ SO ^" , C ₆ H ₆ SO ₄ ^" , (HCOO) ^" , or (CH ₃ COO) ^" .

For the preparation of the cyclic melamine compounds of the formula (I), which are each in salt form, the procedure is that the cyclic melamine compound is prepared beforehand and then converted or quaternized into the salt form. The methods of producing cyclic melamine compounds are known per se and can also be used for the preparation of the cyclic melamine compound, which are used as starting materials for the preparation of the salts according to the invention or of the quaternized cyclic melamine compounds. For the preparation of the salts according to the invention or of the quaternized cyclic amidine compounds according to the invention, known analogous processes are used, such as those described for the salt formation or quaternization of amines.

To prepare the organophilic phyllosilicates according to the invention, the melamine compound is converted into the corresponding salt with acid, for example with hydrochloric acid, in water, preferably at an elevated temperature in the range from about 60 ° C. to 90 ° C., the layered silicate is added with stirring and dispersed. After sufficient stirring at the specified temperature, the organophilic phyllosilicate obtained is filtered off, washed with water and dried.

In further processing, the organophilic phyllosilicates according to the invention are incorporated into a suitable polymer matrix. Suitable polymers which can be used as a matrix are known per se. Thermoplastic polymers and thermosetting polymer systems as well as rubbers are preferred for incorporation.

Thermoplastic polymers are selected, for example, from the group comprising polyolefins such as polyethylene, polypropylene, polybutylene or polyisobutylene, vinyl polymers such as poly (vinyl acetates), polyacrylates, polymethacrylates, polyvinyl chlorides, polystyrenes, polyacrylonitriles, polyacetals, thermoplastic polyamides, thermoplastic polyesters, thermoplastic polyurethanes, polycarbonates Polysulfones, poly (alkylene terephthalates), polyaryl ethers, alkylene inyl ester copolymers, such as ethylene-vinyl acetate copolymers, styrene / acrylonitrile copolymers and mixtures thereof. Thermoplastic polyesters and thermoplastic polyurethanes, in particular polyurethanes, are preferred. Thermoplastics and rubbers can also be present in a mixture. These polymers can contain additives such as fillers (e.g. quartz powder, wollastonite, chalk), lubricants, mold release agents, plasticizers, foaming agents, stabilizers, flow agents, dyes, pigments and mixtures thereof.

Rubbers are, for example, polybutadiene, polyisoprene, butadiene copolymers with styrene and acrylonitrile, styrene copolymers with acrylonitrile, butadiene and acrylate and / or methacrylates. Such rubber systems are known per se and in Ulimann's Encyclopaedie der Technical Chemistry, Volume 13, pages 581 ff, 4th edition, Verlag Chemie Weinheim, New York, 1977.

Thermosetting polymer systems can be used in the form of polyconsensates or polyadducts. Thermosetting plastics in the form of polycondensates are, for example, curable phenol / formaldehyde plastics (PF casting resins), curable bisphenol resins, curable urea / formaldehyde plastics (UF molding compounds), polyimides (PI), BMI molding compounds and polybenzimidazoles (PBI). Thermosetting plastics in the form of polyadducts are, for example, epoxy resins (EP), molding compounds made from unsaturated polyester resins (UP molding compounds), DAP resins (polydiallyl phthalate), MF molding compounds, e.g. curable melamine / phenol / formaldehyde molding compounds, or cross-linked polyurethanes (PUR). Epoxy resins and polyurethanes are preferred.

Preference is given to thermosetting curable mixtures comprising (a) an epoxy resin with more than one 1,2-epoxy group in the molecule and their adducts with long-chain carboxylic acids and (b) at least one suitable hardener, pure or in a mixture with alkenyl succinates. The epoxy resins which are customary in epoxy resin technology are suitable as epoxy resins which can be used in the curable mixtures. Examples of epoxy resins are:

I) polyglycidyl and poly (β-methylglycidyl) esters, obtainable by reacting a compound with at least two carboxyl groups in the molecule and epichlorohydrin or β-methylepichlorohydrin. The reaction is conveniently carried out in the presence of bases. Aliphatic polycarboxylic acids can be used as a compound having at least two carboxyl groups in the molecule. Examples of such polycarboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid or dimerized or trimerized linoleic acid. However, cycloaliphatic polycarboxylic acids can also be used, such as, for example, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid. Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid can also be used.

II) Polyglycidyl or poly (β-methylglycidyl) ether, obtainable by reacting a compound with at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups and epichlorohydrin or β-methylepichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment. The glycidyl ethers of this type are derived, for example, from acyclic alcohols, such as from ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol or poly- (oxypropylene) glycols, propane-1,3-diol , Butane-1, 4-diol, poly- (oxytetramethylene) glycols, pentane-1, 5-diol, hexane-1, 6-diol, hexane-2,4,6-triol, glycerol, 1, 1, 1 -Trimethylolpropane, pentaerythritol, sorbitol and polyepichlorohydrins. However, they are also derived, for example, from cycloaliphatic alcohols, such as 1,4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane, or they have aromatic nuclei, such as N. , N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane. The glycidyl ethers can also be derived from mononuclear phenols, such as, for example, from resorcinol or hydroquinone, or they are based on multinuclear phenols, such as, for example, bis- (4-hydroxyphenyl) methane, 4,4'-dihydroxybiphenyl, bis- (4-hydroxyphenyl) -sulfone, 1, 1, 2,2-tetrakis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl ) -propane and novolaks, obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols, such as phenol, or with phenols which are essentially substituted with chlorine atoms or C _r C ₉ -alkyl groups, such as 4 -Chlorphenol, 2-methylphenol, or 4-tert-butylphenol or by condensation with bisphenols, such as those of the type mentioned above.

III) Poly (N-glycidyl) compounds, obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines which contain at least two amine hydrogen atoms. These amines are, for example, aniline, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane. The poly (N-glycidyl) compounds also include triglycidyl isocyanurate, N.N'diglycidyl derivatives of cycloalkyleneureas, such as ethylene urea or 1,3-propyleneurea, and diglycidyide derivatives of hydantoins, such as of 5,5-dimethylhydantoin.

IV) Poly (S-glycidyl) compounds, for example di-S-glycidyl derivatives, which are derived from dithiols, such as, for example, ethane-1, 2-dithiol or bis (4-mercaptomethylphenyl) ether. V) Cycloaliphatic epoxy resins, for example bis-2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane, or 3,4-epoxycyclohexylmethyl-3 ', 4 '-epoxycyclohexancyrboxylate.

VI) Mixtures of the above epoxy resins with epoxidized oils, for example epoxidized soybean oil

However, epoxy resins can also be used in which the 1,2-epoxy groups are bonded to different heteroatoms or functional groups; these compounds include, for example, the N, N, O-triglycidyl derivative of 4-aminophenol, the glycidyl ether glycidyl esters of salicylic acid, N-glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethylhydantoin or 2-G! ycidyloxy- 1,3-bis (5,5-dimethyl-l-glycidylhydantoin-3-yl) propane.

A liquid or viscous polyglycidyl ether or ester, in particular a liquid or viscous bisphenol diglycidyl ether, is preferably used as the epoxy resin in the curable mixtures according to the invention.

The epoxy compounds mentioned above are known and some of them are commercially available. Mixtures of epoxy resins can also be used. All usual hardeners for epoxies can be used, such as amines, carboxylic acids, carboxylic acid anhydrides or phenols. Catalytic hardeners, such as imidazoles, can also be used. Such hardeners are described, for example, in H. Lee, K. Neville, Handbook of Epoxy Resins, McGraw Hill Book Company, 1982. The amount of curing agent used depends on the chemical nature of the curing agent and on the desired properties of the curable mixture and the cured product. The maximum amount can easily be determined by a specialist. The mixtures can be prepared in the customary manner by mixing the components by hand stirring or with the aid of known mixing units, for example using a stirrer, kneader or rollers. Depending on the application, the usual additives can be added to the mixtures, such as fillers, pigments, dyes, leveling agents or plasticizers.

The use of the organophilic phyllosilicates according to the invention in polyurethanes is further preferred. Construction components for cross-linked polyurethanes are Polyisocyanates, polyols and optionally polyamines, each with two or more of the corresponding functional groups per molecule.

Aromatic as well as aliphatic and cycloaliphatic polyisocyanates are suitable building blocks for polyurethane chemistry. Examples of commonly used polyisocyanates are 2,4- and 2,6-diisocyanatoluene (TDI) and their mixtures, in particular the mixture of 80% by weight of 2,4- and 20% by weight of 2,6-isomer; 4,4'- as well as 2,4 'and 2,2'-methylenediphenyl isocyanate (MDI) and their mixtures and technical forms, which can optionally contain polynuclear forms in addition to the simple forms mentioned above with two aromatic nuclei (polymer MDI); Naphthalene-1,5-diisocyanate (NDI); 4,4 ', 4 "-triisocyanatotriphenylmethane and 1, 1-bis (3,5-diisocyanato-2-methyl) -1-phenylmethane; 1, 6-hexamethylene diisocyanate (HDI) and 1-isocyanato-3- (isocyanatomethyl) - 3,5,5-Trimethyicyclohexane (isophorone diisocyanate, IDPI). Such basic types of polyisocyanates can optionally also be modified by dimerization or trimerization to form corresponding carbodiimides, uretdiones, biurets or aliophanates.

Particularly preferred polyisocyanates are the various methylene diphenyl isocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

Both low molecular weight compounds and oligomeric and polymeric polyhydroxyl compounds are used as polyols in the production of polyurethane. Suitable low molecular weight polyols are, for example, glycols, glycerol, butanediol, trimethylolpropane, erythritol, pentaerythritol; Pentites such as arabite, adonite or xylitol; Hexites, such as sorbitol, mannitol or dulcitol, the most varied types of sugar, for example sucrose, or also sugar and starch derivatives. Low molecular weight reaction products of polyhydroxyl compounds, such as those mentioned, with ethylene and / or propylene oxide as polyurethane components are also often used, as are the low molecular weight reaction products of other compounds which contain groups capable of reacting with ethylene and / or propylene oxide in sufficient numbers, for example the corresponding reaction products of amines, such as, in particular, ammonia, ethylenediamine, 1,4-diaminobenzene, 2,4-diaminotoluene, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1-methyl-3,5-diethyl-2, 4-diaminobenzene and / or 1-methyl-3,5- diethyl-2,6-diaminobenzene. Other suitable polyamines are listed in EP-A-0 265 781.

The long-chain polyol components used are mainly polyester polyols, including polylactones, for example polycaprolactones, and polyether polyols.

The polyester polyols are generally linear hydroxyl polyesters with molecular weights from about 1000 to 3000, preferably up to 2000.

Suitable polyether polyols preferably have a molecular weight of about 300 to 8000 and can be obtained, for example, by reacting a starter with alkylene oxides, for example with ethylene, propylene or butylene oxides or tetrahydrofuran (polyalkylene glycols). Examples of starters here are water, aliphatic, cycloaliphatic or aromatic polyhydroxyl compounds with usually 2, 3 or 4 hydroxyl groups, such as ethylene glycol, propylene glycol, butanediols, hexanediols, octanediols, dihydroxybenzenes or bisphenols, e.g. B. bisphenol A, trimethylolpropane or glycerol, or amines (see Ulimann's Encyclopedia of Industrial Chemistry, 4th ed. Vol. 19, Verlag Chemie GmbH, Weinheim 1980, pages 31-38 and pages 304, 305). Particularly preferred types of polyalkylene glycols are polyether polyols based on ethylene oxide and polyether polyols based on propylene oxide, and corresponding ethylene / propylene oxide copolymers, which can be both statistical and block copolymers. The ratio of ethylene oxide to propylene oxide can vary within wide limits in these copolymers. For example, only the terminal hydroxyl groups of the polyether polyols can be reacted with ethylene oxide (end-capping). The content of ethylene oxide units in the polyether polyols can e.g. B. but also assume values up to 75 or 80 wt .-%. It will often be expedient if the polyether polyols are at least end-capped with ethylene oxide. They then have terminal primary hydroxyl groups which are more reactive than the secondary hydroxyl groups resulting from the reaction with propylene oxide. Also to be emphasized are polytetrahydrofurans, which, like the polyalkylene glycols already mentioned above, are also commercially available (trade name, for example, POLYMEG ^® ). Production and properties of such polytetrahydrofurans are e.g. B. in Ulimann's Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 19, Verlag Chemie GmbH, Weinheim 1980, pp. 297-299. Polyether polyols which contain solid organic fillers in disperse distribution and chemically bound to the polyether, such as polymer polyols and polyurea polyols, are also suitable as components of polyurethanes. As is known, polymer polyols are polymer dispersions which are prepared by radical polymerization of suitable olefinic monomers, in particular acrylonitrile, styrene or mixtures of the two, in a polyether which serves as a graft base. Polyurea polyols (PHD polyethers) are a dispersion of polyureas which can be obtained by reacting polyisocyanates with polyamines in the presence of polyether polyols, and also where the polyurea material is partially chemically linked to the polyether polyols via the hydroxyl groups on the polyether chains. Polyols such as those mentioned in this section are e.g. B. in Becker / Braun "Plastic Handbook", Vol. 7 (Polyurethane), 2nd ed., Carl Hanser Verlag, Munich Vienna (1983), p.76, 77 described in more detail.

Polyamines also play an important role as components for the production of polyurethanes, in particular because they show a higher reactivity than comparable polyols. As with the polyols, both low molecular weight polyamines, e.g. B. aliphatic or aromatic di- and polyamines, as well as polymeric polyamines for use, for. B. Poly (oxyalkylene) polyamines.

Suitable poly (oxyalkylene) polyamines, which are obtainable, for example, from polyether polyols in accordance with US Pat. No. 3,267,050, preferably have a molecular weight of 1000 to 4000 and are also commercially available, e.g. B. under the name JEFFAMINE ^® , such as. B. JEFFAMINE ^® D 2000, an amino-terminated polypropylene glycol of the general formula H ₂ NCH (CH3) CH2- [OCH ₂ CH (CH3)] _x -NH ₂ , where x has the value 33 on average, so that a total molecular weight of approx. 2000 results; JEFFAMINE ^® D 2001 with the following formula H ₂ NCH (CH ₃ ) CH2- [OCH ₂ CH (CH ₃ )] _a - [OCH ₂ CH ₂ ] _b - [OCH ₂ CH (CH ₃ )] ₀ - NH ₂ , where b averages about 40.5 and a + c is about 2.5; JEFFAMINE ^® BUD 2000, a urea-terminated polypropylene ether of the formula H ₂ N (CO) NH-CH (CH ₃ ) CH ₂ - [OCH ₂ CH (CH ₃ )] _n -NH (CO) NH ₂ , where n averages about 33 is such that a molecular weight of about 2075 results; or JEFFAMINE ^® T 3000, a glycerol-initiated poly (oxypropylene) thamine with a molecular weight at about 3000. Mixtures of one or more polyols and / or enem or more polyamines are often used for the production of polyurethanes, for example in EP-A-0 512 947, EP-A-0 581 739 or the prior art cited in these documents described.

The compositions for the production of polyurethanes, like the epoxy resin compositions, can, if desired, contain other customary additives, such as, for example, catalysts, stabilizers, blowing agents, mold release agents, flame retardants, fillers and pigments, etc.

The organophilic layered silicates according to the invention can be added to both the resin and the hardener. The organophilic phyllosilicates according to the invention are preferably used in amounts of 0.5-30 percent by weight, preferably 1-30 percent by weight, based on the total weight of the matrix, that is to say on the total weight of resin and hardener or on the total weight of the thermosetting or thermoplastic matrix. As mentioned, the matrix can contain fillers known per se. The total amount of organophilic layered silicate and filler, based on the total weight of the matrix, that is to say on the total weight of resin and hardener or on the total weight of the thermosetting or thermoplastic matrix, is preferably at most 70 percent by weight. Preferred fillers, in particular for epoxy systems and polyurethanes, are, for example, quartz powder, wollastonite and chalk.

The deformable molding compositions, which contain the layered silicates according to the invention and, if appropriate, further additives, can be processed into custom molded parts, that is to say composite materials, in particular nanocomposites, using customary plastic processing methods, such as injection molding or extrusion or other shaping methods. Epoxy resins can be used as casting resins. The organophilic layered silicates described can also be used in a variety of ways in coatings, in paints or adhesives, as flame retardants, thixotropic agents and / or reinforcing agents.

Numerous pourable and cross-linkable compositions can be produced with the organophilic layered silicates according to the invention. It is possible to do this to treat organophilic layered silicates with a monomer or a mixture of such monomers, the layered silicates swelling as a result of the penetration of these monomers. After swelling, the compositions are polymerized. Such monomers are, for example, acrylate monomers, methacrylate monomers, caprolactam, laurolactam, aminoundecanoic acid, aminocaproic acid or aminododecanoic acid. The resin component or the hardener component of an epoxy system or the components of a polyurethane system can also be such monomers.

example 1

(Synthesis of the melamine hydrochloride and the organophilically modified

Layered silicate)

60.53 g of melamine are heated in a beaker in 4 liters of deionized water and 48 ml of concentrated hydrochloric acid are added with stirring. 200 g of the synthetic sheet silicate Somasif ME 100 from CO-OP-Chemicals, Japan, are then added to this hot solution with stirring, a white precipitate flocculating. This precipitate is filtered off and washed with a total of 12 liters of hot deionized water, so that chloride can no longer be detected with 0.1 N silver nitrate solution. The layered silicate modified in this way is dried in vacuo at 80 ° C. for 72 hours. The product is called Somasif MLA in the following.

The degree of loading results from thermogravimetric studies of 61 meq / 100g. Somasif ME 100 has a cation exchange capacity of 70-80 meq / 100g. X-ray examinations (WAXS x-ray wide-angle images) show that the layer spacing of the layered silicate has widened from 0.94 nm (unmodified Somasif ME 100) to 1.2 nm (Somasif MLA).

Example 2

(Synthesis of the epoxy resin nanocomposites filled with Somasif MLA and production of the

Molded body)

A mixture of Araldit CY225 (liquid, solvent-free bisphenol A epoxy resin) and hardener HY925 (anhydride hardener) in a weight ratio of 100: 80 is always used to produce the nanocomposites. This mix comes with 2.5 each; 5; 7.5; 10; 20 and 30 wt .-% of the filler Somasif MLA produced in Example 1 modified. In the following, the production of the shaped bodies is to be carried out using the example of the 10% by weight nanocomposite:

300 g Araldit CY225 and 60 g Somasif MLA are stirred in a planetary stirrer at 80 ° C / 13 mbar for 1 hour in a tin can and then 240 g Araldit HY925 are added. This reaction mixture is pre-gelled at 80 ° C./13 mbar to a viscosity of approx. 20,000 mPas with stirring and then poured into steel molds of the dimensions 200 × 200 × 4 mm for the production of moldings and cured at 140 ° C. for 14 hours. Incorporation into the epoxy matrix resulted in a renewed widening of the layer spacing of the three-layer silicate from 1.2 nm (Somasif MLA) to 1.5 nm (WAXS wide-angle X-ray image).

Test specimens are milled from the cast moldings, which are subjected to a tensile test in accordance with ISO 527/95 and a bend notch test in accordance with PM / 258/90. The mechanical properties obtained from this are summarized in Table 1 below and compared with those of an unmodified sample.

Table 1

It can clearly be seen that the incorporation of the filler Somasif MLA strengthens the epoxy matrix. The toughness of the resulting material also increases as a result of slight modification and continues to increase sharply with increasing filler content. Example 3

(Synthesis of the substituted melaminium hydrochloride and the organophilically modified layered silicate)

224.93 g of Irgacor L 190 are heated in a beaker in 4 liters of deionized water and 48 ml of concentrated hydrochloric acid are added with stirring. 200 g of the synthetic layered silicate Somasif ME 100 from CO-OP-Chemicals, Japan, are then added to this hot solution with stirring, a white precipitate flocculating. This precipitate is filtered off and washed with a total of 12 liters of hot deionized water, so that chloride can no longer be detected with 0.1 N silver nitrate solution. The layered silicate modified in this way is dried in vacuo at 80 ° C. for 72 hours. The product is called Somasif L 190 in the following.

The degree of loading results from thermogravimetric studies of 63 meq / 100g. Somasif ME 100 has a cation exchange capacity of 70-80 meq / 100g. X-ray examinations (WAXS wide-angle X-ray images) show that the layer spacing of the layered silicate has widened from 0.94 nm (Somasif ME 100) to 1.36 nm (Somasif L 190).

Example 4

(Synthesis of the epoxy resin nanocomposites filled with Somasif L 190 and production of the

Molded body)

A mixture of Araldit CY225 (liquid, solvent-free bisphenol A epoxy resin) and hardener HY925 (anhydride hardener) in a weight ratio of 100:80 is used to produce the nanocomposites. This mixture is with 2.5; 5; 7.5; 10; 20 and 30 wt .-% of the filler produced in Example 3 Somasif L 190 modified. In the following, the production of the shaped bodies is to be carried out using the example of the 10% by weight nanocomposite:

300g Araldit CY225 and 60g Somasif L 190 are stirred in a planetary stirrer at 80 ° C / 13mbar for 1 hour in a tin can and then 240g Araldit HY925 are added. This reaction mixture is pre-gelled at 80 ° C./13 mbar up to a viscosity of approximately 20,000 mPas with stirring and then for the production of moldings in Steel molds of the dimensions 200x200x4 mm filled and hardened at 140 ° C for 14 hours. Incorporation into the epoxy matrix results in a renewed widening of the layer spacing of the three-layer silicate from 1.36 nm (Somasif L 190) to 1.5 nm. (WAXS wide-angle X-ray image)

Test specimens are milled from the cast moldings, which are then subjected to a tensile test in accordance with ISO 527/95 and a bend notch test in accordance with PM / 258/90. The mechanical properties obtained from this are summarized in Table 2 below and compared with those of an unmodified sample.

Table 2

It can be clearly seen that the incorporation of the filler Somasif L190 strengthens the epoxy matrix. The toughness of the resulting material also increases as a result of slight modification and continues to increase sharply with increasing filler content.

Claims

claims

1. Organophilic phyllosilicates, characterized in that they have been prepared by treating a natural or synthetic phyllosilicate or a mixture of such silicates with a salt of an optionally quaternary, cyclic melamine compound or a mixture of such salts.

2. Organophilic layered silicates according to claim 1, characterized in that for their production natural or synthetic smectite clay minerals, bentonite, vermiculite and / or halloysite, preferably montmorillonite, saponite, beidelite, nontronite, hectorite, sauconite and stevensite, preferably montmorillonite and / or Hectorite have been used.

3. Organophilic phyllosilicates according to claim 1 or 2, characterized in that they have a layer spacing of about 0.7 nm - 1.2 nm (nanometers) and a cation exchange capacity in the range of 50-200 meq / 100 g.

4. Organophilic phyllosilicates according to one of claims 1 to 3, characterized in that a phyllosilicate of the formula:

(AI ₃ .i5Mgo.85) Si8.oo0 ₂ o (OH) ₄ X ₁₁ . ₈ . nH ₂ O was used, in which X is an exchangeable cation, preferably sodium or potassium, and the specified hydroxyl groups have optionally been replaced by fluorine ions.

5. Organophilic phyllosilicates according to one of claims 1 to 4, characterized in that they are used using a cyclic melamine compound of the formula (Ia), (Ib), (Ic):

or a mixture of such compounds in which

Ri is a linear or branched aliphatic radical with 1-20 C atoms, which may contain one or more unsaturated bonds and / or one or more functional groups;

R _{2 is} hydrogen or a linear or branched aliphatic radical having 1-20 C atoms, which has one or more unsaturated bonds and / or one or more functional

X ^{m "the} same or different, any anions of the charge [m-], where m is preferably 1 or 2, in particular: F ^" , Cl ^" , Br ^" , I ^" , SO ₄ ^2" , CH ₃ SO ₄ ^" , C ₆ H ₆ SO ^" , (HCOO) ^" , or

(CH ₃ COO) ^" .

6. Organophilic phyllosilicates according to claim 5, characterized in that R 1 is the alkyl radical of a saturated or the alkenyl radical of an unsaturated fatty acid, hydroxy fatty acid or an aminocarboxylic acid with 8-20 C atoms, preferably with 12-20 C atoms, preferably with 14-18 C atoms, or (C ₂ -C ₈ ) alkyl, which is optionally substituted by a carboxyl group or a (C ₁ -C ₃ ) alkoxycarbonyl group, R _{2 is} hydrogen or an aliphatic radical with 1 -8 carbon atoms, which contain an unsaturated bond and can be substituted by a carboxyl group or a (CrC ₂ o) alkoxycarbonyl group or a cyclohexylcarbonyl group or a phenylcarboxyl group, and optionally by -NH- or by Oxygen is interrupted, R _{3 is} hydrogen or (CC ₄ ) alkyl;

X ^{m "the} same or different, any anions of the charge [m-], where m is preferably 1 or 2, in particular: F ^" , Cl ^" , Br ^" , I ^" , SO ₄ ^2" , CH ₃ SO ₄ ^" , C ₆ H ₆ SO ₄ ^" , (HCOO) ^" , or (CH ₃ COO) ^" .

7. Organophilic phyllosilicates according to claim 5 of the formula n (la ¹ ), (Ib ') or (Ic'):

wherein Ri 'the alkenyl radical of 12-hydroxyoleic acid or the alkyl radical of aminocaproic acid (3-

Aminopropionic acid) and 12-aminododecanoic acid,

R ₂ 'is hydrogen, or an aliphatic radical with 1 -4 C atoms, which is optionally substituted by a (CC ₂ o) alkoxycarbonyl group;

R ₃ 'is hydrogen, methyl or ethyl; and

X ^{m "the} same or different, any anions of the charge [m-], where m is preferably 1 or 2, preferably: F ^" , Cl ^" , Br ^' , I ^" , SO ₄ ^{2 "} , CH ₃ SO ₄ ^" , C ₆ H ₆ SO ₄ ^" , (HCOO) ^" , or

(CH ₃ COO) ^' .

8. Thermoplastic polymers which contain an organophilic phyllosilicate according to one of claims 1 to 7 or a mixture of such phyllosilicates.

9. Thermosetting polymer systems, preferably epoxy resin systems, which contain an organophilic phyllosilicate according to one of claims 1 to 7 or a mixture of such phyllosilicates.

10. epoxy resin systems according to claim 9, characterized in that these (a) contain an epoxy resin with more than one 1, 2-epoxy group in the molecule and (b) at least one hardener.

11. Epoxy resin systems according to claim 9 or 10, characterized in that they contain a liquid or viscous polyglycidyl ether or polyglycidyl ester or a mixture of such compounds, preferably a liquid or viscous bisphenol diglycidyl ether.

12. Epoxy resin systems according to one of claims 9 to 11, characterized in that they contain a hardener, which is preferably selected from the group of amines, carboxylic acids, carboxylic anhydrides or phenols or contain a catalytic hardener, preferably an imidazole.

13. Polyurethanes which contain an organophilic sheet silicate according to one of claims 1 to 7 or a mixture of such sheet silicates.

14. Polyurethanes according to claim 13, characterized in that they represent crosslinked polyurethanes and contain as structural components polyisocyanates, polyols and optionally polyamines, each with two or more of the corresponding functional groups per molecule.

15. Rubbers which contain an organophilic sheet silicate according to one of claims 1 to 7 or a mixture of such sheet silicates.

16. Polymer systems according to one of claims 8 to 15, characterized in that they contain fillers, pigments, dyes, leveling agents and / or plasticizers.

17. Polymer systems according to one of claims 8 to 16, characterized in that they contain the organophilic phyllosilicates in amounts of 0.5-30 percent by weight, preferably 1-30 percent by weight, based on the total weight of the matrix.

18. Polymer systems according to one of claims 8 to 17, characterized in that the total amount of organophilic phyllosilicate and filler based on the total weight of the matrix is up to 70 percent by weight.

19. Polymer systems according to one of claims 8 to 18, preferably epoxy resin systems and polyurethanes, characterized in that they contain quartz powder, wollastonite and / or chalk as fillers.

20. Organophilic phyllosilicates according to one of claims 1 to 7, characterized in that they have been treated with a polymerizable monomer or a mixture of such monomers, these monomers preferably being selected from the group of acrylate monomers, methacrylate monomers, caprolactam, laurolactam , Aminoundecanoic acid, aminocaproic acid and aminododecanoic acid.

21. Deformable molding compositions and molded parts in the form of composite materials, in particular in the form of nano-composite materials, which contain a layered silicate according to one of claims 1 to 7 or a mixture of such layered silicates.

22. Use of the deformable molding compositions according to claim 21 for the production of paints, adhesives, casting resins, coatings, flame retardants, thixotropic agents and / or reinforcing agents.

23. Varnishes, adhesives, casting resins, coatings, flame retardants, thixotropic agents and / or reinforcing agents which contain an organophilic layered silicate according to one of claims 1 to 7.

24. Use of the amidine compounds of formula (I) according to claim 5 for the preparation of organophilic phyllosilicates.

25. Use of the organophilic phyllosilicates according to one of claims 1 to 7 in deformable molding compositions and in finished molded parts or composite materials, preferably in the production of nano-composite materials.