EP1165438A1 - Phyllosilicates modifies par melanine - Google Patents

Phyllosilicates modifies par melanine

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Publication number
EP1165438A1
EP1165438A1 EP00903610A EP00903610A EP1165438A1 EP 1165438 A1 EP1165438 A1 EP 1165438A1 EP 00903610 A EP00903610 A EP 00903610A EP 00903610 A EP00903610 A EP 00903610A EP 1165438 A1 EP1165438 A1 EP 1165438A1
Authority
EP
European Patent Office
Prior art keywords
contain
organophilic
mixture
acid
phyllosilicates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00903610A
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German (de)
English (en)
Inventor
Carsten Zilg
Rolf Mülhaupt
Jürgen Finter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman Advanced Materials Switzerland GmbH
Original Assignee
Vantico GmbH
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Filing date
Publication date
Application filed by Vantico GmbH filed Critical Vantico GmbH
Publication of EP1165438A1 publication Critical patent/EP1165438A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/20—Mica; Vermiculite
    • C04B14/206—Mica or vermiculite modified by cation-exchange; chemically exfoliated vermiculate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • 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.
  • 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.
  • suitable organophilic phyllosilicates as filling materials, the physical and mechanical properties of the molded parts produced in this way are considerably improved.
  • the increase in rigidity with at least the same toughness is the increase in rigidity with at least the same toughness.
  • Nanocomposites which contain the layered silicate in exfoliated form, have particularly good properties.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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:
  • composition of the layered silicate corresponds to the formula:
  • organophilic layered silicates which, using a cyclic melamine compound of the formula (Ia), (Ib), (Ic):
  • 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
  • R 3 is hydrogen or a linear or branched aliphatic radical with 1-8 C atoms, which may contain one or more unsaturated bonds;
  • 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
  • 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) ⁇
  • 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
  • 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) " .
  • 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.
  • known analogous processes are used, such as those described for the salt formation or quaternization of amines.
  • 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.
  • acid for example with hydrochloric acid
  • 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.
  • polyolefins such as polyethylene, polypropylene, polybutylene or polyisobutylene
  • vinyl polymers such as poly (vinyl acetates), polyacrylates, polymethacrylates, polyviny
  • Thermoplastic polyesters and thermoplastic 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.
  • 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:
  • polyglycidyl and poly ( ⁇ -methylglycidyl) esters obtainable by reacting a compound with at least two carboxyl groups in the molecule and epichlorohydrin or ⁇ -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.
  • 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.
  • Polyglycidyl or poly ( ⁇ -methylglycidyl) ether obtainable by reacting a compound with at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups and epichlorohydrin or ⁇ -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.
  • 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 ,
  • 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 -Ch
  • Poly (N-glycidyl) compounds obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines which contain at least two amine hydrogen atoms.
  • 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.
  • S-glycidyl 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.
  • 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.
  • 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.
  • 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! y
  • 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.
  • the usual additives can be added to the mixtures, such as fillers, pigments, dyes, leveling agents or plasticizers.
  • 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-iso
  • Particularly preferred polyisocyanates are the various methylene diphenyl isocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
  • 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.
  • amines such as, in particular, ammonia, ethylenediamine, 1,4-diaminobenzene, 2,4-diaminotoluen
  • 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).
  • 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.
  • 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.
  • 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.
  • 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 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, Kunststoff 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.
  • 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.
  • 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.
  • compositions for the production of polyurethanes 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the production of the shaped bodies is to be carried out using the example of the 10% by weight nanocomposite:
  • 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.
  • 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.
  • the production of the shaped bodies is to be carried out using the example of the 10% by weight nanocomposite:
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne des phyllosilicates organophiles obtenus par traitement d'un phyllosilicate naturel ou synthétique ou d'un mélange de silicates de ce type, avec un sel, d'un composé mélanine cyclique éventuellement quaternaire ou d'un mélange de sels de ce type. L'invention concerne des systèmes polymères, notamment des polymères thermoplastiques, des systèmes polymères thermodurcissables, de préférence des résines époxy, des polyuréthanes et des caoutchoucs, qui contiennent des phyllosilicates organophiles obtenus selon l'invention, ainsi que des matières de moulage déformables et des pièces moulées produites sous forme de matériaux composites, notamment sous forme de matériaux composites de l'ordre du nanomètre.
EP00903610A 1999-01-28 2000-01-22 Phyllosilicates modifies par melanine Withdrawn EP1165438A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH16099 1999-01-28
CH16099 1999-01-28
PCT/EP2000/000480 WO2000044669A1 (fr) 1999-01-28 2000-01-22 Phyllosilicates modifies par melanine

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EP1165438A1 true EP1165438A1 (fr) 2002-01-02

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EP (1) EP1165438A1 (fr)
JP (1) JP2002535233A (fr)
KR (1) KR20010101734A (fr)
CN (1) CN1339013A (fr)
BR (1) BR0007830A (fr)
WO (1) WO2000044669A1 (fr)

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JP2001040207A (ja) * 1999-08-04 2001-02-13 Emusu Showa Denko:Kk 層状珪酸塩含有複合樹脂組成物及びバリヤー性複合樹脂成形体
SK7482003A3 (en) * 2000-12-15 2004-04-06 Agrolinz Melamin Gmbh Modified inorganic particles
HUP0302595A2 (hu) 2000-12-15 2003-10-28 Agrolinz Melamin Gmbh Polimerrel módosított szervetlen részecskék
AT410211B (de) 2000-12-15 2003-03-25 Agrolinz Melamin Gmbh Halbzeuge und formstoffe aus aminoplasten
KR20020095380A (ko) * 2001-06-14 2002-12-26 (주) 파워테크 산처리 점토를 이용한 고분자-점토 나노복합체 및 이의제조방법
WO2003016370A1 (fr) * 2001-08-10 2003-02-27 Chemiewerk Bad Köstritz GmbH Procede de production de nanocomposites a base d'acide silique/de polyurethane
KR100472574B1 (ko) * 2001-09-04 2005-03-07 금호타이어 주식회사 타이어용 에이팩스 고무조성물
ATE373035T1 (de) 2001-11-19 2007-09-15 Ami Agrolinz Melamine Int Gmbh Erzeugnisse, insbesondere formmassen aus triazinsegmente enthaltenden polymeren, verfahren zu deren herstellung und verwendungen
KR20040022984A (ko) * 2002-09-10 2004-03-18 주식회사 나노코 비할로겐 질소계 화합물 함유 나노복합체형 난연제 조성물및 그 제조 방법
AU2002952373A0 (en) * 2002-10-31 2002-11-14 Commonwealth Scientific And Industrial Research Organisation Fire resistant material
JP2006290723A (ja) * 2004-11-17 2006-10-26 Cci Corp 層間化合物及びその製造方法並びに複合材料
JP4611072B2 (ja) * 2005-03-25 2011-01-12 シーシーアイ株式会社 層間化合物の製造方法
DE102010035103A1 (de) 2010-08-23 2012-02-23 Catena Additives Gmbh & Co. Kg Flammschutzmittelzusammensetzungen enthaltend Triazin-interkalierte Metall-Phosphate
CN102382595A (zh) * 2010-08-31 2012-03-21 杜邦公司 改性的蒙脱石及包含其的粘合剂组合物
CN102504616B (zh) * 2011-09-28 2014-04-09 常州大学 一种磷氮系粘土基复合阻燃剂及其制备方法
CN102659700B (zh) * 2012-03-05 2014-04-09 浙江金科过氧化物股份有限公司 一种颗粒状低含氯量2,4,6-三（氨基己酸基）-1,3,5-三嗪的生产工艺
CN104524920A (zh) * 2014-12-24 2015-04-22 苏州绿科环保新材料有限公司 亲油性硅酸盐的制作方法
CN106365638B (zh) * 2016-08-31 2019-03-05 湖南湖电电力设备有限公司 一种基于纳米蒙特土的高韧陶瓷材料及其制备方法
CN108863967A (zh) * 2018-09-11 2018-11-23 四川格鑫拓科技有限公司 一种三嗪环多季铵盐抗氧缓蚀剂及其制备方法和应用
CN110845217A (zh) * 2019-11-27 2020-02-28 衡阳阳光陶瓷有限公司 一种吸声、减噪的陶瓷加工工艺
CN117263624B (zh) * 2023-11-22 2024-02-06 长沙中科盛联新材料有限公司 一种再生骨料混凝土及其制备方法

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JP2002535233A (ja) 2002-10-22
CN1339013A (zh) 2002-03-06
WO2000044669A1 (fr) 2000-08-03
KR20010101734A (ko) 2001-11-14
BR0007830A (pt) 2002-01-15

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