EP1196493A1 - Composites de l'ordre du nanometre - Google Patents

Composites de l'ordre du nanometre

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Publication number
EP1196493A1
EP1196493A1 EP00945890A EP00945890A EP1196493A1 EP 1196493 A1 EP1196493 A1 EP 1196493A1 EP 00945890 A EP00945890 A EP 00945890A EP 00945890 A EP00945890 A EP 00945890A EP 1196493 A1 EP1196493 A1 EP 1196493A1
Authority
EP
European Patent Office
Prior art keywords
composition according
component
oil
mixture
layer silicate
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Withdrawn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
EP00945890A
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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 EP1196493A1 publication Critical patent/EP1196493A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/08—Zinc chromate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Definitions

  • the present invention relates to compositions composed of specific resin mixtures and organophilic layer silicates, to a process for the preparation of nanocomposites and to their use.
  • organophilic layer silicates by treatment of layer silicates wfth onium salts, e.g. quaternary ammonium salts, in the presence of a dispersion medium is known from US Patent No. 4 810 734. In that treatment an exchange of ions takes place, the cation of the onium salt being inserted into the interlayer space of the layer silicate. Layer silicates modified in that manner become organophilic as a result of the organic radical of the intercalated amine. When that organic radical contains functional groups, the organophilic layer silicate is capable of forming chemical bonds with suitable monomers or polymers.
  • WO 96/08526 describes the use of such organophilic layer silicates as filler materials for epoxy resins, there being obtained nanocomposites having improved physical and mechanical properties. It is of special interest that there is an increase in rigidity while the toughness at least remains the same. Especially good properties are exhibited by nanocomposites that contain the layer silicate in exfoliated form.
  • organophilic layer silicates gives rise not only to an improvement in rigidity but also to a reduction in tensile strength.
  • a swelling agent selected from sulfonium, phosphonium and ammonium compounds, but in the case where component A1 is an epoxidised oil, salts of melamine compounds and cyclic amidine compounds are excluded as ammonium compounds.
  • component A1 there may be used the epoxidation products of natural or synthetic oils and the reaction products of natural or synthetic oils with maleic acid anhydride.
  • Suitable natural oils are, for example, unsaturated fatty acid esters. It is preferable to use compounds that are derived from mono- and poly-fatty acids having from 12 to 22 carbon atoms and an iodine number of from 30 to 400, for example lauroleic acid, mynstoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic acid, linoleic acid, linolenic acid, elaidic acid, licanic acid, arachidonic acid and clupanodonic acid.
  • mono- and poly-fatty acids having from 12 to 22 carbon atoms and an iodine number of from 30 to 400, for example lauroleic acid, mynstoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic acid, linoleic acid, linolenic acid,
  • Preferred components A1 are derived from triglycerides of formula I
  • R', R" and R'" are each independently of the others saturated or unsaturated fatty acid radicals having from 12 to 25 carbon atoms, but at least one of the radicals R', R" and R'" is an unsaturated fatty acid radical.
  • natural oils are soybean oil, linseed oil, perilla oil, tung oil, oiticica oil, safflower oil, poppyseed oil, hemp oil, cottonseed oil, sunflower oil, rapeseed oil, walnut oil, beet oil, high oleic triglycerides, thglycerides from euphorbia plants, groundnut oil, olive oil, olive kernel oil, almond oil, kapok oil, hazelnut oil, apricot kernel oil, beechnut oil, lupin oil, maize oil, sesame oil, grapeseed oil, Iallemantia oil, castor oil, herring oil, sardine oil, menhaden oil, whale oil, tall oil, palm oil, palm kernel oil, coconut oil, cashew oil and tallow oil and derivatives derived therefrom.
  • Examples of synthetic oils suitable for the preparation of component A1 are polybutadiene oils, polyethylene oils, polypropylene oils, polypropylene oxide oils, polyethylene oxide oils and paraffin oils.
  • component A1 for the preparation of the compositions according to the invention it is also possible to use adducts of epoxy resins with fatty acids and also adducts of epoxy resins with the above-mentioned epoxidised or maleinated oils.
  • component A1 an epoxidised or maleinated oil based on mono- and poly-fatty acids having from 12 to 22 carbon atoms or an epoxidised or maleinated rubber.
  • Especially preferred components A1 are epoxidised or maleinated soybean oil and linseed oil.
  • Suitable as component A2 are monomers or monomer mixtures that can be polymerised to form solid thermoplastics or poiycondensed or polyadded to form crosslinked thermosets, either by irradiation or heating, optionally in the presence of initiators.
  • Preferred components A2 are the monomers or oligomers that can be used for the preparation of thermosetting polymer systems.
  • Thermosetting polymer systems can be used in the form of polycondensates 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 moulding materials), polyimides (PI), bismaleinimide moulding materials (BMI) and polybenzimidazoles (PBI).
  • Thermosetting plastics in the form of polyadducts are, for example, epoxy resins (EP), moulding materials of unsaturated polyester resins (UP moulding materials), DAP resins (polydiallyl phthalate), melamine/formaldehyde resins, e.g. curable melamine/- phenol/formaldehyde moulding materials, and crosslinked polyurethanes (PUR).
  • EP epoxy resins
  • UP moulding materials moulding materials of unsaturated polyester resins
  • DAP resins polydiallyl phthalate
  • melamine/formaldehyde resins e.g. curable melamine/- phenol/formaldehyde moulding materials
  • PUR crosslinked polyurethanes
  • the component A2 is preferably a mixture of a polyisocyanate and a polyol or a mixture of an epoxy resin having more than one 1 ,2-epoxy group in the molecule and a hardener for the epoxy resin.
  • Suitable epoxy resins are:
  • Polyglycidyl and poly( ⁇ -methylglycidyl) esters obtainable by reaction of a compound having at least two carboxyl groups in the molecule with epichlorohydrin and ⁇ -methyl- epichlorohydrin, respectively.
  • the reaction is advantageously carried out in the presence of bases.
  • Aliphatic polycarboxylic acids can be used as the 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 and dimerised or trimerised linoleic acid.
  • cycloaliphatic polycarboxylic acids for example tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
  • Aromatic polycarboxylic acids for example phthalic acid, isophthalic acid or terephthalic acid, may also be used.
  • Polyglycidyl or poly( ⁇ -methylglycidyl) ethers obtainable by reaction of a compound having at least two free alcoholic hydroxy groups and/or phenolic hydroxy groups with epichlorohydrin or ⁇ -methylepichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment.
  • the glycidyl ethers of this kind may be 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 also from polyepi- chlorohydrins, but they may also be derived, for example, from cycloaliphatic alcohols, such as 1 ,4-cyclohexanedimethanol, bis(4-hydroxycyclohexyl)
  • the glycidyl ethers may also be derived from mononuclear phenols, for example from resorcinol or hydroquinone, or they may be based on polynuclear phenols, for example bis(4-hydroxyphenyl)methane, 4,4'-di- hydroxybiphenyl, 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 also on novolaks, obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols, such as phenol, or with phenols substituted in the nucleus by chlorine atoms or C ⁇ -C 9 alkyl groups, for example 4-chlorophenol,
  • Poly(N-glycidyl) compounds obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines that contain at least two amine hydrogen atoms.
  • amines are, for example, aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylene- diamine and bis(4-methylaminophenyl)methane.
  • Poly(N-glycidyl) compounds also include, however, triglycidyl isocyanurate, N,N'-diglycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1 ,3-propyleneurea, and diglycidyl derivatives of hydantoins, such as of 5,5- dimethylhydantoin.
  • Poly(S-glycidyl) compounds for example di-S-glycidyl derivatives, derived from dithiols, for example ethane-1 ,2-dithiol or bis(4-mercaptomethylphenyl) ether.
  • Cycloaliphatic epoxy resins for example bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclo- pentylglycidyl ether, 1 ,2-bis(2,3-epoxycyclopentyloxy)ethane or 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate.
  • epoxy resins in which the 1 ,2-epoxy groups are bonded to different hetero atoms or functional groups; these compounds include, for example, the N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin or 2-glycidyloxy-1 ,3-bis(5,5- dimethyl-1-glycidylhydantoin-3-yl)propane.
  • these compounds include, for example, the N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin or 2-glycidyloxy-1 ,3
  • epoxy resin in the curable mixtures according to the invention a fluid or viscous polyglycidyl ether or ester, especially a fluid or viscous bisphenol diglycidyl ether.
  • Bisphenol A diglycidyl ether and bisphenol F diglycidyl ether are especially preferred.
  • epoxy compounds are known and some of them are commercially available. It is also possible to use mixtures of epoxy resins.
  • All customary hardeners for epoxides can be used; preferred hardeners are amines, carboxylic acids, carboxylic acid anhydrides and phenols. It is also possible to use catalytic hardeners, for example imidazoles. Such hardeners are described, for example, in H.Lee, K. Neville, Handbook of Epoxy Resins, McGraw Hill Book Company, 1982.
  • the amount of hardening agent used is governed by the chemical nature of the hardening agent and by the desired properties of the curable mixture and of the cured product. The maximum amount can readily be determined by a person skilled in the art.
  • the preparation of the mixtures can be carried out in customary manner by mixing the components together by manual stirring or with the aid of known mixing apparatus, for example by means of stirrers, kneaders or rollers.
  • conventionally used additives for example fillers, pigments, colourings, flow agents or plasticisers, may be added to the mixtures.
  • Further preferred components A2 are polyurethane precursors.
  • Structural components for crosslinked polyurethanes are polyisocyanates, polyols and optionally polyamines, in each case having two or more of the respective functional groups per molecule.
  • Aromatic and also aliphatic and cycloaliphatic polyisocyanates are suitable building blocks for polyurethane chemistry.
  • Examples of frequently used polyisocyanates are 2,4- and 2,6- diisocyanatotoluene (TDI) and mixtures thereof, especially the mixture of 80 % by weight 2,4-isomer and 20 % by weight 2,6-isomer; 4,4'- and 2,4'- and 2,2'-methylenediisocyanate (MDI) and mixtures thereof and technical grades that, in addition to containing the above- mentioned simple forms having two aromatic nuclei, may also contain polynuclear forms (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 (
  • polyisocyanates may optionally also have been modified by dimerisation or trimerisation with the formation of corresponding carbodiimides, uretdiones, biurets or allophanates.
  • Especially preferred polyisocyanates are the various methylene diisocyanates, hexamethyl- ene diisocyanate and isophorone diisocyanate.
  • polyols there may be used in the polyurethane production both low molecular weight compounds and oligomeric and polymeric polyhydroxyl compounds.
  • Suitable low molecular weight polyols are, for example, glycols, glycerol, butanediol, trimethylolpropane, erythritol, pentaerythritol; pentitols, such as arabitol, adonitol or xylitol; hexitols, such as sorbitol, mannitol or dulcitol, various sugars, for example saccharose, or sugar and starch derivatives.
  • Low molecular weight reaction products of polyhydroxyl compounds, such as those mentioned, with ethylene oxide and/or propylene oxide are also frequently used as polyurethane components, as well as the low molecular weight reaction products of other compounds that contain sufficient numbers of groups capable of reaction with ethylene oxide and/or propylene oxide, for example the corresponding reaction products of amines, such as especially ammonia, ethylenediamine, 1 ,4-diaminobenzene, 2,4-diaminotoluene, 2,4'-di- aminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1 -methyl-3,5-diethyl-2,4-diamino- benzene and or 1-methyl-3,5-diethyl-2,6-diaminobenzene.
  • amines such as especially ammonia, ethylenediamine, 1 ,4-diaminobenzene, 2,4-diaminotoluen
  • polyester polyols including poly- lactones, for example polycaprolactones, and polyether polyols.
  • the polyester polyols are generally linear hydroxyl polyesters having molar masses of approximately from 1000 to 3000, preferably up to 2000.
  • Suitable polyether polyols preferably have a molecular weight of about from 300 to 8000 and can be obtained, for example, by reaction of a starter with alkylene oxides, for example with ethylene, propylene or butylene oxides or tetrahydrofuran (polyalkylene glycols).
  • Starters that come into consideration are, for example, water, aliphatic, cycloaliphatic or aromatic polyhydroxyl compounds having generally 2, 3 or 4 hydroxyl groups, such as ethylene glycol, propylene glycol, butanediols, hexanediols, octanediols, dihydroxybenzenes or bisphenols, e.g.
  • polyalkylene glycols are polyether polyols based on ethylene oxide and polyether polyols based on propylene oxide, and also corresponding ethylene oxide/propylene oxide copolymers, it being possible for such polymers to be statistical or block copolymers.
  • the ratio of ethylene oxide to propylene oxide in such copolymers may vary within wide limits.
  • the terminal hydroxyl groups of the polyether polyols may have been reacted with ethylene oxide (end capping).
  • the content of ethylene oxide units in the polyether polyols may also, however, have values of e.g. up to 75 or 80 % by weight.
  • the polyether polyols it will frequently be advantageous for the polyether polyols to be at least end-capped with ethylene oxide, since in that case they will have terminal primary hydroxyl groups which are more reactive than the secondary hydroxyl groups originating from the reaction with propylene oxide.
  • polyether polyols that contain solid organic fillers in disperse distribution and chemically partially bonded to the polyether, such as polymer polyols and polyurea polyols.
  • Polymer polyols are, as is known, polymer dispersions that can be prepared by free-radical polymerisation of suitable olefinic monomers, especially acrylonitrile or styrene or mixtures of the two, in a polyether serving as graft base.
  • Polyurea polyols which can be prepared by reaction of polyisocyanates with polyamines in the presence of polyether polyols, are dispersions of polyureas in polyether polyols, there likewise taking place a partially chemical linkage of the polyurea material to the polyether polyols by way of the hydroxyl groups on the polyether chains.
  • Polyols such as those mentioned in this section are described in greater detail, for example, in Becker/Braun "Kunststoffhandbuch", Vol. 7 (Polyurethanes), 2nd edition, Carl Hanser Verlag, Kunststoff, Vienna (1983), pages 76, 77.
  • Polyamines also play an important role as components in the preparation of polyurethanes, especially because they exhibit greater reactivity than comparable polyols.
  • both low molecular weight polyamines e.g. aliphatic or aromatic di- and polyamines
  • polymeric polyamines e.g. poly(oxyalkylene)polyamines
  • Suitable poly(oxyalkylene)polyam ⁇ nes which, for example, in accordance with US Patent 3 267 050 are obtainable from polyether polyols, preferably have a molecular weight of from 1000 to 4000 and are also commercially available, e.g.
  • JEFFAMINE ® such as JEFFAMINE ® D 2000, an ammo-terminated polypropylene glycol of the general formula H 2 NCH(CH3)CH 2 -[OCH 2 CH(CH 3 )] x -NH 2 , wherein x has on average the value 33, resulting in a total molecular weight of about 2000; JEFFAMINE ® D 2001 having the formula H 2 NCH(CH 3 )CH 2 -[OCH 2 CH(CH 3 )] a -[OCH 2 CH 2 ] b -[OCH 2 CH(CH 3 )] c -NH 2 , wherein b is on average about 40.5 and a+c is about 2.5, JEFFAMINE ® BUD 2000, a urea-terminated polypropylene ether of formula H 2 N(CO)NH-CH(CH 3 )CH 2 -[OCH 2 CH(CH 3 )] n -NH(CO)NH 2 , where
  • layer silicates for the preparation of the organophilic layer silicates according to component B of the compositions of the invention there come into consideration especially natural and synthetic smectite clay minerals, more especially bentonite, vermiculite, halloysite, saponite, beidellite, nontronite, hecto ⁇ te, sauconite, stevensite and mont- mo ⁇ llonite.
  • Montmo ⁇ llonite and hecto ⁇ te are preferred.
  • the layer silicate montmo ⁇ llonite for example, corresponds generally to the formula AI 2 [(OH) 2 /S ⁇ 4 O 10 ]. nH 2 O, it being possible for some of the aluminium to have been replaced by magnesium.
  • the composition varies according to the silicate deposit.
  • a preferred composition of the layer silicate corresponds to the formula
  • Synthetic layer silicates can be obtained, for example, by reaction of natural layer silicates with sodium hexafluorosilicate and are commercially available inter alia from the CO-OP Chemical Company, Ltd., Tokyo, Japan.
  • the sulfonium, phosphonium and ammonium compounds required as swelling agents for the preparation of the organophilic layer silicates according to component B of the compositions of the invention are known and some of them are commercially available. They are generally compounds having an onium ion, for example trimethylammonium, trimethyl- phosphonium and dimethylsulfonium, and a functional group that is capable of reacting or bonding with a polymeric compound.
  • Suitable ammonium salts can be prepared, for example, by protonation or quatemisation of corresponding aliphatic, cycloaliphatic or aromatic amines, diamines, polyamines or aminated polyethylene or polypropylene glycols (Jeffamine ® M series, D series or T series).
  • Suitable swelling agents are, for example, salts that contain cations of formulae ll-IV
  • R ⁇ S ⁇ Z-Y (IV), wherein R,, R 2 and R 3 are each independently of the others hydrogen or d-C ⁇ alkyl, Z is the divalent radical of a C 2 -C 30 alkane that is unsubstituted or substituted by one or more phenyl groups, d-C 4 alkoxy groups, hydroxyl groups or halogen atoms and Y is -OH, -COOH, -NH 2 , vinyl, glycidyl or ⁇ -methylglycidyl.
  • ammonium salts that are obtainable by reaction of amino acids with mineral acids.
  • the swelling agent is first advantageously dispersed or dissolved, with stirring, in a dispersion medium, preferably at elevated temperature of about from 40°C to 90°C.
  • the layer silicate is then added and dispersed, with stirring.
  • the organophilic layer silicate so obtained is filtered off, washed with water and dried.
  • Suitable dispersion media are water, methanol, ethanol, propanol, isopropanol, ethylene glycol, 1 ,4-butanediol, glycerol, dimethyl sulfoxide, N,N-dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, acetonitrile, acetone, 2-butanone, chloroform, carbon disulfide, propylene carbonate, 2-methoxyethanol, diethyl ether, tetrachloro- methane and n-hexane.
  • Preferred dispersion media are methanol, ethanol and especially water.
  • the swelling agent brings about a widening of the interlayer spacing of the layer silicate, so that the layer silicate is able to take up monomers into the interlayer space.
  • the subsequent polymerisation, polyaddition or polycondensation of the monomer or monomer mixture results in the formation of a composite material, a nanocomposite.
  • the swelling agent can be inserted into the layer silicate by cation exchange and the resulting organophilic layer silicate can then be incorporated as filler into the resin mass or into one of the components of the resin mass.
  • the quantity ratio of components A and B in the compositions according to the invention may vary within wide limits.
  • the proportion of component B is preferably from 0.5 to 30 % by weight, especially from 2 to 20 % by weight and more especially from 5 to 15 % by weight, based on the weight of component A.
  • compositions according to the invention may contain further customary additives, for example catalysts, stabilisers, propellants, parting agents, fireproofing agents, fillers and pigments, etc..
  • additives for example catalysts, stabilisers, propellants, parting agents, fireproofing agents, fillers and pigments, etc.
  • the invention relates also to a process for the preparation of a nanocomposite, wherein a composition comprising components A and B is solidified by curing or polymerisation of component A.
  • nanocomposites that contain the layer silicate in exfoliated form.
  • compositions according to the invention have a wide variety of uses, inter alia as coatings, paints/varnishes or adhesives.
  • the nanocomposites according to the invention can be processed by customary methods of plastics processing, such as injection moulding or extrusion, or other methods of shaping to form finished mouldings.
  • Epoxy resins can be used as casting resins.
  • the present invention relates also to the use of the compositions according to the invention in the production of paints/varnishes, adhesives, casting resins, coatings, fireproofing agents, thixotropic agents or reinforcing agents.
  • Example 1 Synthesis of 12-aminododecanoic acid hydrochloride and the three-layer silicate organophilically modified therewith 96.96 g of 12-aminododecanoic acid are heated in 4 litres of deionised water in a glass beaker and, with stirring, 48 ml of concentrated hydrochloric acid are added. 200 g of the synthetic three-layer silicate Somasif ME 100 from CO-OP-Chemicals, Japan, are then added, with stirring, to the hot solution, a flocculent cream-coloured precipitate being formed.
  • the precipitate is filtered off and washed with a total of 12 litres of hot deionised water, so that chloride can no longer be detected with 0.1 N silver nitrate solution.
  • the three-layer silicate so modified is dried at 80 5 C for 72 hours in vacuo.
  • the product is referred to as Somasif ADS below.
  • the degree of charge is ascertained by thermogravimetric tests at 78 meq./100 g. Somasif ME 100 has a cation exchange capacity of 70-80 meq./IOO g. Measurement of the layer spacing of the three-layer silicate by means of X-ray tests shows that it has increased from 0.94 nm to 1.6 nm.
  • Examples 2-6 Synthesis of the unmodified nanocomposites and the nanocomposites modified with epoxidised soybean oil (content of Somasif ADS 10 % by weight)
  • epoxidised soybean oil content of Somasif ADS 10 % by weight
  • a mixture of epoxy resin 1 99.71 parts by weight of bisphenol A diglycidyl ether having an epoxy number of 5.00-5.25 eq./kg + 0.29 parts by weight of tetramethylammonium chloride
  • hardener 1 Aldit ® HY 925, methyltetra- hydrophthalic acid anhydride
  • the mixture is modified with the organophilic layer silicate prepared in Example 1.
  • the production of the mouldings is described by way of example below using the example of the 10 % by weight nanocomposite.
  • the modified nanocomposites 1 ; 2.5; 5; 10; 20 % by weight of the epoxy component (epoxy resin 1) are replaced by epoxidised soybean oil (ESO). Again a ratio by weight of the epoxy component mixture (epoxy resin 1 + epoxidised soybean oil) to anhydride hardener (hardener 1 ) of 100 : 80 is selected. Each of the mixtures is then filled with Somasif ADS (10 % by weight).
  • ESO epoxidised soybean oil

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition contenant : (A) un mélange de résine comprenant : (A1) entre 0,5 et 50,0 % en poids, sur la base de la somme des constituants A1 + A2, d'une huile naturelle ou de synthèse époxydée ou maléinée, et (A2) entre 50,0 et 99,5 % en poids, sur la base de la somme des constituants A1 + A2, d'un monomère ou d'un mélange monomère polymérisable ou apte à la cuisson, autre que A1, et (B) un phyllosilicate organophilique obtenu par traitement d'un phyllosilicate naturel ou synthétique avec un agent de gonflement sélectionné parmi les composés sulfonium, phosphonium et ammonium, les sels de composés mélanine et aminide cyclique étant exclus au titre de composés ammonium, si le constituant A1 est une huile époxydée. Cette composition s'utilise pour préparer des composites de l'ordre du nanomètre à haut degré de ténacité et de résistance à la rupture.
EP00945890A 1999-07-13 2000-07-06 Composites de l'ordre du nanometre Withdrawn EP1196493A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH128899 1999-07-13
CH128899 1999-07-13
PCT/EP2000/006422 WO2001004205A1 (fr) 1999-07-13 2000-07-06 Composites de l'ordre du nanometre

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EP1196493A1 true EP1196493A1 (fr) 2002-04-17

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WO2002048270A1 (fr) 2000-12-15 2002-06-20 Agrolinz Melamin Gmbh Particules inorganiques modifiees par un polymere
AT410211B (de) 2000-12-15 2003-03-25 Agrolinz Melamin Gmbh Halbzeuge und formstoffe aus aminoplasten
US7012108B2 (en) 2000-12-15 2006-03-14 Agrolinz Melamin Gmbh Modified inorganic particles
US6887931B2 (en) * 2001-10-23 2005-05-03 Ashland Inc. Thermosetting inorganic clay nanodispersions and their use
EP1448671B1 (fr) 2001-11-19 2007-09-12 AMI Agrolinz Melamine International GmbH Produits, en particulier matieres a mouler, a savoir des polymeres contenant des segments triazine, leur procede de production et leurs utilisations
EP1514843A1 (fr) * 2003-09-15 2005-03-16 Engelhard Corporation Matériau de type organoargile synthétique

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