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    • 专利摘要:
    The present invention relates to lipophilic layered silicates prepared by treating naturally occurring or synthetic layered silicates or mixtures of such silicates with salts of quaternary or other cyclic amidine compounds, or mixtures of such salts; Polymer systems comprising novel lipophilic layered silicates, in particular thermoplastic polymers and thermosetting polymer systems, preferably epoxy resins, polyurethanes and rubbers; And moldable molding materials and finished molded articles in the form of composite materials, in particular in the form of nanocomposites.
    公开号:KR20010024924A
    申请号:KR1020007008967
    申请日:1999-02-10
    公开日:2001-03-26
    发明作者:길크카르스텐；뮐하우프트롤프；핀터위르겐
    申请人:베르너 훽스트；반티코 아게；지크프리트 포트호프；
    IPC主号:
    专利说明:

    Lipophilic layered silicates {Organophilic phyllosilicates}
    [2] Lipophilic layered silicates prepared by ion exchange, for example, are known to be used as fillers for thermoplastics and thermosets to produce nanocomposites. When suitable lipophilic layered silicates are used as fillers, the physical and mechanical properties of the moldings produced therefrom are markedly improved. Of particular interest is the feature of increasing stiffness without reducing toughness. Nanocomposites comprising layered silicates in release form have particularly good properties.
    [3] US-A-4,810,734 discloses the ability to treat layered silicates with quaternary or other ammonium salts of primary, secondary or tertiary linear organic amines in the presence of a dispersion medium. Ion exchange or cation exchange takes place during the treatment and the cations of the ammonium salts are sandwiched in the spaces between the layered silicate layers. Absorbed sub-organic radicals transform the layered silicate to lipophilic as above. If the organic radical contains a functional group, the lipophilic layered silicate may enter a chemical bond with a suitable monomer or polymer. However, the use of the linear amines disclosed in US Pat. No. 4,810,734 has the drawback that the amines are thermally decomposed at temperatures up to 300 ° C. which are commonly used in thermoplastics processing to decolorize the product. The formation of decomposition products is released and therefore impairs mechanical properties such as impact strength.
    [1] The present invention relates to moldable molding materials comprising novel lipophilic layered silicates, their preparations and preferably to the lipophilic layered silicate and to their use in finished shaped articles or composites, in particular nanocomposites.
    [87] 1 shows a WAXS (wide angle X-ray) image of Somasif ME 100 (unmodified),
    [88] 2 shows a WAXS (wide angle X-ray) image of Somasif RDI (unmodified),
    [89] 3 shows the WAXS (Wide-angle X-ray) image of 10 wt% nanocomposite Somasif RDI / 10,
    [90] 4 shows the elastic modulus and tensile strength of nanocomposite Somasif RDI / 2.5-10 and unmodified molding materials,
    [91] 5 shows the elastic modulus and critical stress intensity factor (K1 c ) of the nanocomposite Somasif RDI / 2.5-10 and unmodified molding material,
    [92] 6 shows a WAXS (wide angle X-ray) image of Somasif HEODI (modified),
    [93] FIG. 7 shows the WAXS (Wide-angle X-ray) image of the 10 wt% nanocomposite Somasif HEODI / 10,
    [94] 8 shows the modulus and tensile strength of nanocomposites Somasif HEODI / 2.5-10 and unmodified molding materials,
    [95] 9 shows the elastic modulus and critical stress intensity factor (K1 c ) of the nanocomposite Somasif HEODI / 2.5-10 and the unmodified molding material,
    [96] FIG. 10 shows a WAXS (Wide-angle X-ray) image of Somasif AEODI (modified),
    [97] FIG. 11 shows a WAXS (Wide-angle X-ray) image of 10% by weight nanocomposite Somasif AEODI / 10,
    [98] 12 shows the elastic modulus and tensile strength of nanocomposite Somasif AEODI / 2.5-10 and unmodified molding materials,
    [99] FIG. 13 shows the elastic modulus and critical stress intensity factor (K1 c ) of the nanocomposite Somasif AEODI / 2.5-10 and unmodified molding material,
    [100] FIG. 14 shows a WAXS (wide angle X-ray) image of Somasif W75 (modified),
    [101] FIG. 15 shows a WAXS (Wide-angle X-ray) image of the 10 wt% nanocomposite Somasif W75 / 10,
    [102] FIG. 16 shows the modulus and tensile strength of nanocomposites Somasif W75 / 2.5-10 and unmodified molding materials,
    [103] 17 shows the elastic modulus and critical stress intensity factor (K1 c ) of the nanocomposite Somasif W75 / 2.5-10 and the unmodified molded material,
    [104] FIG. 18 shows WAXS (Wide-angle X-ray) images of the nanocomposites ER (ESO 50) -HEODI / 10 and ER (ESO 50) -AEODI / 10.
    [105] 19 shows the modulus of elasticity of the nanocomposites ER (ESO 1-50), ER (ESO 1-50) -HEODI / 10 and ER (ESO 1-50) -AEODI / 10,
    [106] 20 shows tensile strengths of nanocomposites ER (ESO 1-50), ER (ESO 1-50) -HEODI / 10 and ER (ESO 1-50) -AEODI / 10,
    [107] 21 depicts the critical stress intensity factors (K1 c ) of the nanocomposites ER (ESO 1-50), ER (ESO 1-50) -HEODI / 10 and ER (ESO 1-50) -AEODI / 10,
    [108] FIG. 22 shows WAXS (Wide-angle X-ray) images of the nanocomposites ER (ESO 1-50), ER (ESO 1-50) -HEODI / 10 and ER (ESO 1-50) -AEODI / 10. ,
    [109] FIG. 23 shows the elastic modulus of the nanocomposites ER (DDS 1-50), ER (DDS 1-50) -HEODI / 10 and ER (DDS 1-50) -AEODI / 10,
    [110] 24 shows tensile strengths of nanocomposites ER (DDS 1-50), ER (DDS 1-50) -HEODI / 10 and ER (DDS 1-50) -AEODI / 10,
    [111] FIG. 25 shows critical stress intensity factors (K1 c ) of nanocomposite ER (DDS 1-50), ER (DDS 1-50) -HEODI / 10 and ER (DDS 1-50) -AEODI / 10.
    [4] Surprisingly, lipophilic layer silicates prepared by treating layered silicates with salts of quaternary or other cyclic amidine compounds using cation exchange methods have excellent thermal stability during processing and excellent dispersion and interfacial adhesion. It turned out to have. When the amidinium compound according to the present invention is used in a thermosetting resin, there is no change in the stoichiometry of the reactive component compared with the case of using a linear ammonium salt, which allows an increased amount of filler to be added to the thermosetting material. If the cyclic amidine used contains a reactive group, the lipophilic layer silicate prepared therefrom and used as a filler may be covalently linked to the matrix by grafting. Amidinium ions, for example derived from hydroxystearic acid or hydroxyoleic acid, have surprisingly good layer separation and excellent adhesion to various kinds of polymers and fillers. In contrast to the prior art, especially alkyl substituents having terminal hydroxy groups as well as alkyl groups having non-terminal hydroxy groups are useful. Hydroxy groups in the alkyl side chains can be readily derived to tailor system-specific characteristic spectra. The compounds also create excellent dispersion effects and interfacial adhesion. The heterocyclic amidine salts according to the invention with long-chain substituted or unsubstituted alkyl radicals, despite being bulky, surprisingly effectively exchange cations in space within the layered silicate layer.
    [5] The process according to the invention thus incorporates a cyclic amidine compound in quaternized or, if necessary, protonated form into a layered silicate by cation exchange and then, if necessary, as a filler a thermosetting material or a cyclic amide of a thermosetting epoxy resin material. The addition product to be prepared from the din compound and a part of the epoxy component of the thermosetting material are incorporated into the layered silicate and processed into the rest of the epoxy component to obtain a shaped material.
    [6] The invention is defined in the claims and in particular to lipophilic layered silicates prepared by treating naturally occurring or synthetic layered silicates or mixtures of such silicates with salts of quaternary or other cyclic amidine compounds or mixtures of such salts. It is about.
    [7] The present invention also relates to the preparation of novel lipophilic layered silicates and their use in the production of moldable molding materials comprising the novel lipophilic layered silicates and in the form of finished molded or composite materials, in particular nanocomposites.
    [8] The invention also relates to a composite material, preferably a moldable molding material in the form of a nanocomposite and a finished molded article, preferably comprising a novel lipophilic layered silicate in exfoliated form.
    [9] The invention also relates to the use of novel moldable molding materials for producing coating materials, adhesives, casting resins, coatings, flame retardants, materials with thixotropic effects and / or reinforcing agents.
    [10] The invention also relates to coatings, adhesives, casting resins, coatings, flame retardants, materials having a thixotropic effect and / or reinforcing agents comprising the novel lipophilic layered silicates.
    [11] The invention also relates to the use of an amidine compound of the general formula (I) below for the preparation of a lipophilic layered silicate.
    [12] Layered silicates that can be used in the preparation of lipophilic layered silicates are in particular natural or synthetic smectic clay minerals, in particular montmorillonite, saponite, baydelite, nontronite, hectorite, souconite and stevensite and bentonite, vermiculite Micullite and halosite. Montmorillonite and hectorite are preferred. The layered silicate is preferably at least 1.2 nm in distance, especially when the distance in the layer is about 0.7 to 1.2 nm (nanometer) and in the form of a novel lipophilic layered silicate. The layered silicates used preferably have a cation exchange capacity in the range of 50 to 200 meq / 100 g (milliequivalent / 100 gram). Examples of layered silicates of this type that can be used are described, for example, in A.D. Wilson, H. T. Posser, Developments in Ionic Polymers, London, Applied Science Publishers, Chapter 2, 1986. Synthetic layered silicates are obtained by reacting naturally occurring layered silicates with sodium hexafluorosilicate. Synthetic layered silicates are commercially available from, for example, CO-OP Chemical Company Limited (Tokyo, Japan) and described by the manufacturer.
    [13] In general, the layered silicate montmorillonite has the formula:
    [14] Al 2 [(OH) 2 / Si 4 O 10 ] · nH 2 O
    [15] In the above formula, part of aluminum may be substituted with magnesium. The composition depends on the deposit from which the silicate is obtained. Preferred layered silicate compositions have the formula:
    [16] (Al 3.15 Mg 0.85) Si 8.00 O 20 (OH) 4 X 11.8 · nH 2 O
    [17] Wherein X is a substitutable cation, generally sodium or potassium. Hydroxy groups can be exchanged for example instead of fluoride ions. Substitution with hydroxy groups instead of fluoride ions forms synthetic layered silicates.
    [18] Preferred lipophilic layered silicates are prepared using cyclic amidine compounds of formula (I) or mixtures of these compounds:
    [19]
    [20] In the food,
    [21] R 1 is a straight or branched chain aliphatic radical having 1 to 20 carbon atoms and may contain one or more unsaturated bonds and / or one or more functional groups;
    [22] R 2 contains 1 or more hydrogen or one or more unsaturated bonds and / or one or more functional groups and optionally 1 to 20, which may contain one or more -NH- groups or one or more oxygen atoms in between. Straight or branched aliphatic radicals having 5 carbon atoms;
    [23] R 3 is a straight or branched aliphatic radical having 1 to 8 carbon atoms which may contain hydrogen or one or more unsaturated bonds;
    [24] A is -CH 2 -or -CH 2 -CH 2- ;
    [25] B is -CH 2- ; or
    [26] A and B are combined to be a-(CH = CH)-radical or a formula = CH-CH = or = CH-CH 2 -CH = radical and both of these radicals are part of a cyclic substituted or unsubstituted cyclohexyl ring And again
    [27] X - is any desired anion, for example F -, Cl -, Br - , I -, SO 4 2-, (HCOO) - , or (CH 3 COO) - Im.
    [28] Preferred compounds are
    [29] R 1 is an alkyl radical of a saturated or hydroxy fatty acid having 8 to 20 carbon atoms, preferably 12 to 20 carbon atoms, particularly preferably 14 to 18 carbon atoms, or 8 to 20 carbon atoms, preferably Preferably an alkenyl radical of an unsaturated fatty acid or hydroxy fatty acid having 12 to 20 carbon atoms, particularly preferably 14 to 18 carbon atoms, or by unsubstituted or carboxyl groups or (C 1 -C 3 ) alkoxycarbonyl (C 2 -C 8 ) alkyl substituted by group;
    [30] R 2 is hydrogen or an aliphatic radical having 1 to 8 carbon atoms, containing an unsaturated bond and which may be substituted by a carboxyl group or a (C 1 -C 20 ) alkoxycarbonyl group or a cyclohexylcarbonyl group or a phenylcarboxy group, or Or hydroxyethyl, aminoethyl, tallow or hydrogenated tallow, and may optionally contain -NH- or oxygen in between;
    [31] R 3 is hydrogen or (C 1 -C 4 ) alkyl;
    [32] A and B are each -CH 2- ; or
    [33] A and B combine to form a radical-(CH = CH)-; In addition
    [34] X - is any desired anion, for example F -, Cl -, Br - , I -, SO 4 2-, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) - Lim.
    [35] Particularly preferred compounds have the general formula (I '):
    [36]
    [37] In the food,
    [38] R 1 ′ is an alkenyl radical of 12-hydroxyoleic acid or an alkyl radical of hydrogenated ricinoleic acid (12-hydroxystearic acid);
    [39] R 2 ′ is hydrogen or an unsubstituted or aliphatic radical having 1 to 4 carbon atoms substituted by a (C 1 -C 20 ) alkoxycarbonyl group, or hydroxyethyl, aminoethyl, tallow or hydrogenated tallow;
    [40] R 3 ′ is hydrogen, methyl or ethyl;
    [41] A and B are each -CH 2- ; or
    [42] A and B combine to be a-(CH = CH)-radical; In addition
    [43] X - is any desired anion, for example F -, Cl -, Br - , I -, SO 4 2-, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) - Lim. A and B are each preferably -CH 2- .
    [44] The following compounds and mixtures of these compounds are preferred:
    [45]
    [46] In the food,
    [47] R 2 ″ is hydrogen, methyl, ethyl, propyl or butyl; and
    [48] X - is any desired anion, for example F -, Cl -, Br - , I -, SO 4 2-, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) - ;
    [49]
    [50] In the food,
    [51] Y is -O- or -NH-, preferably -O-;
    [52] Z is a (C 12 -C 20 ) alkyl radical or (C 12 -C 20 ) alkenyl radical of a suitable fatty acid; In addition
    [53] X - is any desired anion, for example F -, Cl -, Br - , I -, SO 4 2-, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) - Lim.
    [54] The procedure for preparing the cyclic amidine compounds of the formula (I) in their respective salt forms is to prepare the cyclic amidine compounds first. The amidine compound is then converted into salt form or quaternary form. Processes for preparing cyclic amidine compounds are known in the art and can be used to prepare cyclic amidine compounds according to the starting materials for preparing the quaternized cyclic amidine compounds or salts according to the invention.
    [55] In order to prepare the salts according to the invention or the quaternized cyclic amidine compounds according to the invention, they can be carried out in a manner analogous to known techniques as described in connection with the salt formation or quaternization of amines.
    [56] The process for producing the novel lipophilic layered silicate converts the amidine compound to the corresponding salt with stirring at an elevated temperature, such as hydrochloric acid in water, preferably in the range from about 60 ° C. to 90 ° C., followed by In addition, to disperse. After sufficient stirring at this temperature, the resulting lipophilic layered silicate is filtered, washed with water and dried.
    [57] The new lipophilic layered silicate is incorporated into a suitable polymer matrix during further processing. Suitable polymers that can be used as the matrix are already known. Preferred polymers for the incorporation process are thermoplastic polymers and thermosetting polymer systems and rubbers.
    [58] The process not only makes it possible to embed the cyclic amidine compound in quaternized or preferably protonated form into the layered silicate by cation exchange but also as a filler in the thermosetting material, preferably the thermosetting epoxy resin material. Allow for incorporation of the cyclic amidine compound and glass product made from a part of the epoxy component of the thermosetting material and insert the resulting product into the layered silicate to process the material into the remaining portion of the epoxy compound to obtain a molding material. .
    [59] Thermoplastic polymers include polyolefins such as polyethylene, polypropylene, polybutylene and polyisobutylene; Vinyl polymers such as poly (vinyl acetate); Polyacrylates, polymethacrylates, polyvinyl chloride, polystyrene, polyacrylonitrile, polyacetals, thermoplastic polyamides, thermoplastic polyesters, thermoplastic polyurethanes, polycarbonates, polysulfonates, poly (alkylene terephthalates ), Polyaryl ethers; Alkylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer, styrene-acrylonitrile copolymer; And mixtures thereof. Preferred polymers are thermoplastic polyesters and thermoplastic polyurethanes, in particular polyurethanes. Thermoplastics and rubbers can be used in mixtures. These polymers may include fillers (such as powdered quartz, wollastonite or chalk), lubricants, release agents, plasticizers, blowing agents, stabilizers, flow agents, dyes, additives such as pigments, or mixtures thereof.
    [60] Examples of rubbers are butadiene copolymers with polybutadiene, polyisoprene, styrene and acrylonitrile, styrene copolymers with acrylonitrile, butadiene and acrylates and / or methacrylates. Such rubber systems are originally known and are described in Ullmanns Encyclopaedie der Technischen Chemie [Ullmann's Encyclopaedia of Industrial Chemistry], Vol. 13, pp. 581 ff, 4th edition, Verlag Chemie Weinheim, New York 1977.
    [61] The thermosetting polymer system used may be a polycondensate or a polyaddition. Examples of polycondensates that are thermoset plastics are curable phenol-formaldehyde resins (PF-casting resins), curable bisphenol resins, curable urea-formaldehyde resins (UF molding materials), polyimides (Pls), BMI molding materials and polybenziimi Doazole (PBIs). Examples of heavy additives that are thermoset plastics are epoxy resins (EPs), molding materials (UP molding materials) made of unsaturated polyester resins, DAP resins (poly (diallyl phthalates)), MF molding materials such as curable melamine-phenol- Formaldehyde molding materials and crosslinked polyurethanes (PUs). Epoxy resins and polyurethanes are preferred.
    [62] Preferred curable thermosetting mixtures comprise (a) an epoxy resin having at least one 1,2-epoxy group in the molecule or an adduct thereof with long chain carboxylic acids and (b) one or more suitable curing agents or mixtures thereof with alkenyl succinates. do. Suitable epoxy resins that can be used in the curable mixtures are conventional epoxy resins of epoxy resin technology. Examples of epoxy resins are as follows:
    [63] I) Polyglycidyl and poly (β-methylglycidyl) esters obtainable by reacting compounds having at least two carboxyl groups in the molecule with epichlorohydrin and β-methylepichlorohydrin. It is advantageous to carry out the reaction in the presence of a base. Compounds having two or more carboxyl groups in the molecule may be aliphatic polycarboxylic acids. Examples of such polycarboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suveric acid, azelaic acid and diolized or trimerized linoleic acid. However, cycloaliphatic polycarboxylic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid can also be used. It is also possible to use aromatic polycarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid.
    [64] II) A compound having at least two free alcoholic hydroxy groups and / or phenolic hydroxy groups is obtained by reacting with epihydrochlorine or β-methyl epichlorohydrin under alkaline conditions or in the presence of an acid catalyst and then treating with alkali. Polyglycidyl or poly (β-methylglycidyl) ether. Glycidyl ethers of this type are, for example, ethylene glycol, diethylene glycol or higher poly (oxyethylene) glycol, 1,2-propanediol or poly (oxypropylene) glycol, 1,3-propanediol, 1,4-butanediol , Poly (oxytetramethylene) glycol, 1,5-pentanediol, 1,6-hexanediol, 2,4,6-hexanetriol, glycerol, 1,1,1, -trimethylolpropane, pentaerythritol or It may be derived from acyclic alcohols such as sorbitol, or polyepichlorohydrin. They are derived from cycloaliphatic alcohols such as for example 1,4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) -propane or they are N, N And aromatic rings such as -bis (2-hydroxyethyl) aniline and p, p'-bis (2-hydroxyethylamino) diphenylmethane. Glycidyl ethers may be derived from mononuclear phenols such as resorcinol or hydroquinone or may be 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 Based on polynuclear phenols such as -4-hydroxyphenyl) propane or aldehydes such as formaldehyde, acetaldehyde, chloral or furfuraldehyde by phenols such as phenols, or by ring chlorine atoms or C 1 From novolaks obtainable by condensation with phenols substituted by -C 9 -alkyl groups such as 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol, or by condensation with bisphenols of the abovementioned type Can be induced.
    [65] III) Poly (N-glycidyl) compounds obtainable by dehydrochlorination of epichlorohydrin with amines having two or more amine hydrogen atoms. Examples of these amines are aniline, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine and bis (4-methylaminophenyl) methane. However, poly (N-glycidyl) compounds include N, N'-diglycidyl derivatives and hydantoins of cycloalkyleneureas such as triglycidyl isocyanurate, ethyleneurea and 1,3-propyleneurea, such as Diglycidyl derivatives of 5,5-dimethylhydantoin.
    [66] IV) Di-S-glycidyl derivatives derived from dithiols such as poly (S-glycidyl) compounds such as 1,2-ethanedithiol or bis (4-mercaptomethylphenyl) ether.
    [67] V) bis (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane and 3,4-epoxycyclohexyl Cycloaliphatic epoxy resins such as methyl-3 ', 4'-epoxycyclohexanecarboxylate.
    [68] VI) A mixture of the above-mentioned epoxy resin and epoxidized oil, such as epoxidized soybean oil.
    [69] However, it is possible to use those in which 1,2-epoxy groups are made of epoxy resins bonded to various heteroatoms or functional groups. Examples of these compounds include N, N, O-triglycidyl derivatives of 4-aminophenol, glycidyl ether-glycidyl esters of salicylic acid, N-glycidyl-N '-(2-glycidyloxypropyl ) -5,5-dimethylhydantoin and 2-glycidyloxy-1,3-bis (5,5-dimethyl-l-glycidylhydantoin-3-yl) propane.
    [70] The epoxy resins preferably used in the curable mixtures according to the invention are liquid or viscous polyglycidyl ethers or polyglycidyl esters, in particular liquid or viscous bisphenol diglycidyl ethers.
    [71] The epoxy compounds described above are originally known and in some cases are commercially available. Mixtures of epoxy resins can also be used. Conventional curing agents for epoxies such as amines, carboxylic acids, carboxylic anhydrides or phenols can also be used. Examples of 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 the desired properties of the curable mixture and the cured product. The maximum amount may be readily determined by one of ordinary skill in the art. The mixture can be prepared by a known method of mixing the components by hand or mixing using a known mixing apparatus such as a stirrer, shaker or roll. It can be mixed with fillers, pigments, dyes, flow control agents or plasticizers depending on the use of commonly used additives.
    [72] The following example using novel lipophilic layered silicates in polyurethanes is preferred. The structural components of the crosslinkable polyurethanes are polyisocyanates, polyols and preferably polyamines, in each case having at least two suitable functional groups per molecule.
    [73] Aromatic or aliphatic, or cycloaliphatic, polyisocyanates are suitable building blocks for polyurethane chemistry. Examples of commonly used polyisocyanates are 2,4- and 2,6-diisocyanatotoluene (TDI) and mixtures thereof, in particular 80% by weight of 2,4- and 20% by weight of 2,6-isomer At least one ring (polymerizable MDIs) in addition to methylene 4,4'-, 2,4'- and 2,2'-diisocyanate (MDI) and mixtures thereof and simple products having the two aromatic rings described above. Product having; Naphthalene 1,5-diisocyanate (NDI); 4,4 ', 4 "-triisocyanatotriphenylmethane and bis (3,5-diisocyanato-2-methylphenyl) methane; hexamethylene-1,6-diisocyanate (HDI) and 1-isocyanato- 3- (isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI) The basic type of polyisocyanate is preferably the corresponding carbodiimide, uretdione, biuret or allopa It can be modified into dimerization or trimerization by the formation of a nate.
    [74] Particularly preferred polyisocyanates are various methylene diisocyanates, hexamethylene diisocyanates and isophorone diisocyanates.
    [75] Polyols used to prepare polyurethanes are low molecular weight compounds or oligomeric or polymerizable polyhydroxy compounds. Examples of suitable low molecular weight polyols are glycol, glycerol, butanediol, trimethylolpropane, erythritol, pentaerythritol; Pentitol, such as arabitol, adonitol or xylitol; Hexitols such as sorbitol, mannitol and dulcitol; Various types of sugars such as sucrose, and sugar derivatives and starch derivatives. Low molecular weight reaction products of polyhydroxy compounds and ethylene oxide and / or propylene oxide as described above are commonly used as polyurethane components and contain other compounds containing a sufficient number of groups to react with ethylene oxide and / or propylene oxide, Amines such as ammonia, ethylenediamine, 1,4-diaminobenzene, 2,4-diaminotoluene, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1-methyl- Low molecular weight reaction products of 3,5-diethyl-2,4-diaminobenzene and / or 1-methyl-3,5-diethyl-2,6-diaminobenzene. Other suitable polyamines are disclosed in EP-A-0 265 781.
    [76] The long chain polyol components used are mainly polyacetones such as polyester polyols such as polycaprolactone and polyether polyols, and polyether polyols.
    [77] Polyester polyols are generally linear hydroxypolyesters having a molecular weight of about 1000 to 3000, preferably 2000 or less.
    [78] Suitable polyether polyols preferably have a molecular weight of about 300 to 8000 (polyalkylene glycol) and are obtained by reacting the starting materials with alkylene oxides such as ethylene, propylene or butylene oxide, or tetrahydrofuran. Can be. Examples of starting materials used herein are water, aliphatic, cycloaliphatic or aromatic polyhydroxy compounds having mostly 2, 3, or 4 hydroxy groups such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, dihydroxy Benzene or bisphenols such as bisphenol A, trimethylolpropane or glycerol or amines (Ullmanns Encyclopadie der technischen Chemie [Ulllmann's Encylopaedia of Industrial Chemistry], 4th edition, Vol. 19, Verlag Chemie GmbH, Weinheim, Germany, 1980, pp. 31 -38 and pp. 304, 305). Particularly preferred types of polyalkylene glycols are polyether polyols based on ethylene oxide, and polyether polyols based on ethylene oxide and suitable ethylene / propylene oxide copolymers which can be random or block copolymers. The ratio of ethylene oxide to propylene oxide in the copolymer varies. For example, only the terminal hydroxy group of the polyether polyol can be substituted with ethylene oxide (terminal capping). However, the content of ethylene oxide in the polyether polyol may be for example 75 to 80% by weight. The polyether polyol may be advantageously end capped with ethylene oxide. It has a primary terminal hydroxy group that is more reactive than a secondary hydroxy group derived from reaction with propylene oxide. Polytetrahydrofuran is the most important and commercially available as above-mentioned polyalkylene glycol (trade name POLYMEG R ). The preparation and properties of such polytetrahydrofuran are described, for example, in Ullmanns Encyclopadie der technischen Chemie [Ulllmann's Encylopaedia of Industrial Chemistry], 4th edition, Vol. 19, Verlag Chemie GmbH, Weinheim, Germany, 1980, pp. It is described in detail in 297-299.
    [79] Polyether polyols, including dispersed solid organic fillers that are chemically bonded to polyethers such as polymerizable polyols and polyurea polymers, are also suitable as components of polyurethanes. As is known, polymerizable polyols are polymerizable dispersions prepared by free radical polymerization with polyethers which serve as graft bases of suitable olefinic monomers, in particular acrylonitrile, styrene or two mixtures thereof. Polyurea polyols (polyurea polyethers) are dispersions of polyurea that can be obtained by reacting polyisocyanates with polyamines in the presence of polyether polyols, and to some extent polyether polyols and polyurea materials, via hydroxy groups on the polyether chain, Can be chemically bonded. Polyols as described above are described, for example, in Becker / Braun "Kunstoffhandbuch" [Plastic Handbook], Vol. 7 (Polyurethanes), 2nd edn, Carl Hanser Verlag, Munich, Vienna (1983), pp. 76, 77.
    [80] Polyamines are likewise major as components for producing polyurethanes, since they have a higher reactivity than the corresponding polyols. Polyamines used with polyols are low molecular weight polyamines such as aliphatic or aromatic di- or polyamines, or polymerizable polyamines such as poly (oxyalkylene) polyamines.
    [81] Suitable poly (oxyalkylene) polyamines which can be obtained from the polyether polyols described in US Pat. No. 3,267,050 and have a molecular weight of 1000 to 4000 are for example JEFFAMINE R such as JEFFAMINE R D 2000 Amino-terminated polypropylene glycol of wherein x has an average value of 33 and has a total molecular weight of about 2000; Chemical formula JEPPAMINE R D 2001 having an average of about 40.5 and a + c of about 2.5; JEPPAMINE R BUD 2000; Chemical formula Commercially available under the trade name JEPPAMINE R T 3000 which is a urea-terminated polypropylene ether of (n is an average value of about 33 and has a molecular weight of about 2075) or a glycerol-derived poly (oxypropylene) triamine having a molecular weight of about 3000.
    [82] Mixtures of one or more polyols and / or one or more polyamines are commonly used to prepare polyurethanes, such as in EP-A-0 512 947, EP-A-0 581 739 and the literature cited in the prior art herein. .
    [83] The material composition for producing the polyurethane may preferably include conventional additives such as catalysts, stabilizers, blowing agents, mold release agents, flame retardants, fillers and pigments and the like, like the epoxy resin composition.
    [84] Novel lipophilic layered silicates may be added to the resin or hardener. The novel lipophilic layered silicates are preferably from 0.5 to 30% by weight, preferably 1 based on the total amount of the matrix, such as based on the total amount of resin and curing agent, or suitably based on the total amount of the thermosetting or thermoplastic matrix. To 30% by weight. As mentioned above, the matrix may further comprise known fillers. The total amount of lipophilic lamellar silicate and filler based on the total amount of the matrix, for example based on the total amount of resin and curing agent or suitably based on the total amount of the thermosetting or thermoplastic matrix, is preferably at most 70% by weight. Examples of preferred fillers for the epoxy system are powdered quartz, wollastonite and chalk.
    [85] Moldable molding compositions comprising the novel layered silicates and, optionally, other additives are processed by conventional plastic processing techniques such as injection molding or extrusion or other molding techniques, ie composite materials, in particular nanocomposites. To form. Epoxy resins can be used as casting resins. The lipophilic layered silicates described can be used in various ways as castings, coating materials or adhesives, as flame retardants, as materials and / or reinforcing agents having a thixotropic effect.
    [86] The novel lipophilic layered silicates can be used in the preparation of various types of casting and crosslinkable compositions. For this purpose, the lipophilic lamellar silicates can be treated with monomers or monomer mixtures, by which the lamellar silicates are swollen due to the penetration of these monomers. After swelling the composition is polymerized. Examples of such monomers are acrylate monomers, methacrylate monomers, caprolactam, laurolactam, aminoundecanoic acid, aminocaproic acid and aminododecanoic acid. The resin component or curing agent component of the epoxy system or component of the polyurethane system may be a monomer of this type.
    [112] Example 1
    [113] (Synthesis of ricinyl-4,5-dihydro-1-H-imidazole from castor oil)
    [114] Refuel 466.7 g (0.5 mole) of castor oil and 135.23 g (2.25 mole) of ethylenediamine at 150 ° C for 4 hours in a two-liter flask equipped with a 250 ml receiving flask with a stirrer, a high performance concentrator and a distillation bridge. Heated to 270 ° C. followed by rapid heating to distill off excess ethylenediamine and water. This reaction was complete after 24 hours of reaction time. This gave 108 g of distillate and 475 g of yellow wax. This wax was slurried in toluene and filtered. The resulting filtrate is concentrated on a rotary evaporator and the residue is 330 g of orange wax as ricinyl-4,5-dihydro-1-H-imidazole (RDI): 1 H NMR: δ (ppm): 6.6 (NH 1), 5.5 (olefin, 14a), 5.3 (olefin, 13a), 3.5 (OH, 17)
    [115] RDI:
    [116]
    [117] Example 2
    [118] (Synthesis of ricinyl-4,5-dihydro-1-H-imidazole of ricinoleic acid)
    [119] 358.16 g (1.2 mole) of castor oil and 180 g (3 mole) of ethylenediamine were refluxed at 150 ° C. for 1 hour in a two-liter flask equipped with a 250 ml receiving flask with a stirrer, a high performance concentrator and a distillation bridge. Heated to 250 ° C. followed by rapid heating to distill off excess ethylenediamine and water. This reaction was complete after 24 hours of reaction time. This gave 142 g of distillate and 367 g of yellow wax. This wax was treated as described in Example 1 to yield the same product.
    [120] Example 3
    [121] (Synthesis of Ricinyl-4,5-dihydro-1-H-imidazolium hydrochloride and lipophilic modified trilayer silicate using the same)
    [122] 154.6 g of purified RDI was heated in 4 liters of deionized water in a glass beaker and mixed with 48 ml of concentrated hydrochloric acid with stirring. 200 g of synthetic three-layer silicate Somasif ME 100 commercially available from CO-OP Chemicals (Japan) was added to the hot solution with stirring to agglomerate a creamy precipitate. This precipitate was filtered and washed with a total of 12 liters of hot deionized water to ensure that no chloride was detected by the 0.1 N silver nitrate solution. This modified three layer silicate was dried in vacuo at 80 ° C. for 72 hours. This product is subsequently referred to as Somasif RDI.
    [123] Thermogravimetric analysis showed a loading of 60 meq / 100g. Somasif ME 100 has a cation exchange capacity of 70 to 80 meq / 100g. X-ray analysis shows that the distance between the layers in the three-layer silicate extends from 0.94 nm to 2.6 nm.
    [124] 1 shows a WAXS (wide angle X-ray) image of Somasif ME 100 (unmodified).
    [125] 2 shows a WAXS (wide angle X-ray) image of Somasif RDI (unmodified).
    [126] Example 4
    [127] Synthesis and Preparation of Epoxy Resin Nanocomposites Filled with Somasif RDI
    [128] To prepare the nanocomposites, the mixture used was a mixture of Araldit CY225 R (epoxy component) and Araldit HY925 R (anhydride hardener) in a 100: 80 weight ratio. The mixtures were each prepared with filler 2.5 prepared in Example 3; 5; Modified using 7.5 and 10% by weight. Examples of the production of the molded article will be described below using 10% by weight of nanocomposites.
    [129] 300 g of Araldit CY225 R and 60 g of Somasif RDI in a metal vessel were stirred for 1 hour in a sawtooth mixer at 80 ° C./13 millibar and then 240 g of Araldit HY925 R was added. The reaction mixture was pre-gelled at 80 ° C./13 millibar to obtain a viscosity of about 20,000 mPas and stirred to prepare a molding which was charged into a 200 × 200 × 4 mm steel mold and cured at 140 ° C. for 14 hours. . Incorporation into the epoxy matrix extended the distance between the layers in the trilayer silicate from 2.6 nm (Somasif RDI) to 3 nm.
    [130] 3 shows the WAXS (wide angle X-ray) image of the nanocomposite Somasif RDI / 10.
    [131] The specimens were cut from the cast moldings and then treated according to ISO 527/95 and then band-notched tested according to PM / 258/90. The mechanical properties obtained are listed in Table 1 below and compared with the values of the unmodified samples.
    [132] Table 1
    [133]
    [134] It can be clearly seen that the epoxy matrix is reinforced by incorporating the filler Somasif RDI. The toughness of the resulting material is increased by slight modifications but not significantly as the filler content increases.
    [135] 4 shows the modulus and tensile strength of nanocomposites Somasif RDI / 2.5-10 and unmodified molding materials.
    [136] FIG. 5 shows the modulus and critical stress intensity factor K1 c of the nanocomposite Somasif RDI / 2.5-10 and the unmodified molding material.
    [137] Example 5
    [138] (Synthesis of hydroxyethyloleyl-4,5-dihydro-1-H-imidazolinium hydrochloride and synthesis of lipophilic modified trilayer silicate using the same)
    [139] 168.3 g of hydroxyethyloleyl-4,5-dihydro-1-H-imidazoline (Servamine KOO 360, Wheels AG, Germany) was heated in 4 liters of deionized water in a glass beaker and 48 ml Mix with concentrated hydrochloric acid. 200 g of synthetic three-layer silicate Somasif ME 100 (manufactured by CO-OP Chemicals, Japan) is added to the hot solution with stirring to agglomerate a creamy precipitate. This precipitate is filtered and washed with a total of 12 liters of hot deionized water to ensure that no chloride is detected using 0.1 N silver nitrate solution. This modified trilayer silicate is dried in vacuo at 80 ° C. for 72 hours. This product is called Somasif HEODI.
    [140] Thermogravimetric analysis showed a load rating of 61 meq / 100g. Somasif ME 100 has a cation exchange capacity of 70 to 80 meq / 100g. X-ray analysis shows that the distance between the layers in the three-layer silicate extends from 0.94 nm to 3.3 nm.
    [141] 6 shows a WAXS (wide angle X-ray) image of Somasif HEODI (modified).
    [142] Example 6
    [143] (Synthesis and Preparation of Epoxy Resin Nanocomposites Filled with Somasif HEODI)
    [144] Nanocomposites were prepared in a manner similar to Example 4 except that Somasif HEODI was used.
    [145] FIG. 7 shows the WAXS (Wide-angle X-ray) phase of the 10 wt% nanocomposite Somasif HEODI / 10.
    [146] Once again, the specimens were cut from the cast moldings and studied. The mechanical properties are listed in Table 2 below and compared with the unmodified samples.
    [147] TABLE 2
    [148]
    [149] 8 shows the modulus and tensile strength of nanocomposites Somasif HEODI / 2.5-10 and unmodified molding materials.
    [150] 9 shows the elastic modulus and critical stress intensity factor K1 c of the nanocomposite Somasif HEODI / 2.5-10 and the unmodified molding material.
    [151] Example 7
    [152] (Synthesis of aminoethyloleyl-4,5-dihydro-1-H-imidazolinium hydrochloride and synthesis of modified three layer silicates therefrom)
    [153] 167.8 g aminoethyloleyl-4,5-dihydro-1-H-imidazoline (Servamine KOO 330, Wheels AG, Germany) was heated in 4 liters of deionized water in a glass beaker and stirred with 48 ml of concentrated Mixed with hydrochloric acid. 200 g of synthetic three-layer silicate Somasif ME 100 (manufactured by CO-OP Chemicals, Japan) is added to the hot solution with stirring to agglomerate a creamy precipitate. This precipitate is filtered and washed with a total of 12 liters of hot deionized water to ensure that no chloride is detected using 0.1 N silver nitrate solution. This modified trilayer silicate is dried in vacuo at 80 ° C. for 72 hours. This product is called Somasif AEODI.
    [154] Thermogravimetric analysis showed a load rating of 61 meq / 100g. Somasif ME 100 has a cation exchange capacity of 70 to 80 meq / 100g. X-ray analysis shows that the distance between the layers in the three-layer silicate extends from 0.94 nm to 3.3 nm.
    [155] 10 shows a WAXS (wide angle X-ray) image of Somasif AEODI (modified).
    [156] Example 8
    [157] (Synthesis and Preparation of Epoxy Resin Nanocomposites Filled with Somasif AEODI)
    [158] Nanocomposites were prepared in a manner similar to Example 4 except that Somasif AEODI was used.
    [159] FIG. 11 shows WAXS (Wide-angle X-ray) images of 10 wt% nanocomposite Somasif AEODI / 10.
    [160] Once again, the specimens were cut from the cast moldings and studied. The mechanical properties are listed in Table 3 below and compared with the unmodified samples.
    [161] TABLE 3
    [162]
    [163] 12 shows the modulus and tensile strength of nanocomposites Somasif AEODI / 2.5-10 and unmodified molding materials.
    [164] FIG. 13 shows the elastic modulus and critical stress intensity factor K1 c of the nanocomposite Somasif AEODI / 2.5-10 and unmodified molding material.
    [165] Example 9
    [166] (Synthesis of 3-layered Silicate Hydrophilically Modified by 1-Methyl-2-Norlowalkyl-3-Uji-fatty Acid Amidoethylimidazolium Methosulfate)
    [167] 357.7 g of 1-methyl-2-nortallowalkyl-3-Uji-fatty acid-amidoethylimidazolinium methosulfate (Rewoquat W 75, manufactured by Wittco Suspectant GmbH, Germany) Heat in deionized water and mix with 48 ml of concentrated hydrochloric acid while stirring. 200 g of synthetic three-layer silicate Somasif ME 100 (manufactured by CO-OP Chemicals, Japan) is added to the hot solution with stirring to agglomerate a creamy precipitate. This precipitate is filtered and washed with a total of 12 liters of hot deionized water to ensure that no chloride is detected using 0.1 N silver nitrate solution. This modified trilayer silicate was dried in vacuo at 80 ° C. for 72 hours. This product is called Somasif W75.
    [168] Thermogravimetric analysis showed a loading of 60 meq / 100g. Somasif ME 100 has a cation exchange capacity of 70 to 80 meq / 100g. X-ray analysis shows that the distance between the layers in the three-layer silicate extends from 0.94 nm to 4.0 nm.
    [169] 14 shows a WAXS (wide angle X-ray) image of Somasif W75 (modified).
    [170] Example 10
    [171] (Synthesis and Preparation of Epoxy Resin Nanocomposites Filled with Somasif W75)
    [172] Nanocomposites were prepared in a manner similar to Example 4 except that Somasif W75 was used.
    [173] FIG. 15 shows the WAXS (Wide-angle X-ray) image of the 10 wt% nanocomposite Somasif W75 / 10.
    [174] Once again, the specimens were cut from the cast moldings and studied. The mechanical properties are listed in Table 4 below and compared with the unmodified samples.
    [175] Table 4
    [176]
    [177] FIG. 16 shows the elastic modulus and tensile strength of nanocomposite Somasif W75 / 2.5-10 and unmodified molding materials.
    [178] FIG. 17 shows the modulus and critical stress intensity factor K1 c of the nanocomposite Somasif W75 / 2.5-10 and unmodified molded material.
    [179] Example 11
    [180] (Synthesis of 10 wt% Nanocomposite Modified with Epoxylated Soybean Oil)
    [181] To prepare these nanocomposites, 1; 2.5; 5; 10; 20 and 50% by weight of the epoxy component (Araldit CY 225 R ) was replaced with epoxidized soybean oil (ESO). Here the selected weight ratio of the epoxy component mixture (Araldit CY 225 R and epoxidized soybean oil) to the anhydride curing agent (Araldit HY 925 R ) was once again 100: 80. Each of these mixtures was charged with 10% by weight of the fillers prepared in Examples 5 and 7 (based on the total weight of the molding to be produced). An example of preparation of these nanocomposites will be described taking the example of preparation of nanocomposites modified with 10% by weight of Somasif HEODI (Example 5) and modified with 50% ESO.
    [182] 150 g Araldit CY225 R , 150 g epoxidized soybean oil and 60 g Somasif HEODI in a metal vessel were stirred for 1 hour in a sawtooth mixer at 80 ° C./13 millibar and then 240 g Araldit HY925 R were added. The reaction mixture was pre-gelled at 80 ° C./13 millibar to obtain a viscosity of about 20,000 mPas and stirred to prepare a molding which was charged into a 200 × 200 × 4 mm steel mold and cured at 140 ° C. for 14 hours. . Additional incorporation of ESO no longer extended the distance in the bed.
    [183] FIG. 18 shows the WAXS (Wide-angle X-ray) images of the nanocomposites ER (ESO 50) -HEODI / 10 and ER (ESO 50) -AEODI / 10.
    [184] Once again, the specimens were cut from the cast moldings and subjected to the mechanical test described above. The mechanical properties obtained are listed in Table 5 below.
    [185] Table 5
    [186]
    [187] Table 5 (continued)
    [188]
    [189] Epoxidized soybean oil may not only prevent the tensile strength of the nanocomposite from dropping but also slightly improve the above characteristics.
    [190] 19 shows the modulus of elasticity of the nanocomposites ER (ESO 1-50), ER (ESO 1-50) -HEODI / 10 and ER (ESO 1-50) -AEODI / 10.
    [191] 20 shows the tensile strengths of the nanocomposites ER (ESO 1-50), ER (ESO 1-50) -HEODI / 10 and ER (ESO 1-50) -AEODI / 10.
    [192] FIG. 21 shows the critical stress intensity factors K1 c of the nanocomposites ER (ESO 1-50), ER (ESO 1-50) -HEODI / 10 and ER (ESO 1-50) -AEODI / 10.
    [193] Example 12
    [194] Synthesis of 10 wt% Nanocomposites Modified with n-dodecenyl succinate
    [195] To prepare the nanocomposite, 1; 2.5; 5; 10; 20 and 50% by weight of the epoxy component (Araldit HY 925 R ) was substituted with epoxidized n-dodecenyl succinate (DDS). Wherein the selected weight ratio of the hardener component mixture (Araldit CY 225 R ) to the anhydride hardener mixture (Araldit HY 925 R and n-dodecenyl succinate) was once again 100: 80. Each of these mixtures was charged with 10% by weight of the fillers prepared in Examples 5 and 7 (based on the total weight of the molding to be produced). Examples of preparation of these nanocomposites will be described with examples of preparation of nanocomposites filled with 10% by weight of Somasif HEODI (Example 5) and modified with 50% DDS.
    [196] 300 g of Araldit CY225 R and 60 g of Somasif HEODI in a metal vessel were stirred for 1 hour in a sawtooth mixer at 80 ° C./13 millibar and then 120 g of Araldit HY925 R and 120 g of DDS were added. The reaction mixture was pre-gelled at 80 ° C./13 millibar to obtain a viscosity of about 20,000 mPas and stirred to prepare a molding which was charged into a 200 × 200 × 4 mm steel mold and cured at 140 ° C. for 14 hours. . Additional incorporation of DDS no longer extended the distance in the layer.
    [197] FIG. 22 shows the WAXS (wide angle X-ray) images of the nanocomposites ER (DDS 50) -HEODI / 10 and ER (DDS 50) -AEODI / 10.
    [198] Once again, the specimens were cut from the cast moldings and subjected to the mechanical test described above. The mechanical properties obtained are listed in Table 6 below.
    [199] It can be clearly seen that the incorporation of n-dodecenylsuccinate not only prevents the reduction in tensile strength of the nanocomposites but also slightly improves these properties.
    [200] Table 6
    [201]
    [202] Table 6 (continued)
    [203]
    [204] FIG. 23 shows the modulus of elasticity of nanocomposite ER (DDS 1-50), ER (DDS 1-50) -HEODI / 10 and ER (DDS 1-50) -AEODI / 10.
    [205] 24 shows tensile strengths of nanocomposites ER (DDS 1-50), ER (DDS 1-50) -HEODI / 10 and ER (DDS 1-50) -AEODI / 10.
    [206] 25 shows the critical stress intensity factors (K1 c ) of the nanocomposites ER (DDS 1-50), ER (DDS 1-50) -HEODI / 10 and ER (DDS 1-50) -AEODI / 10.
    权利要求:
    Claims (26)
    [1" claim-type="Currently amended] A lipophilic layered silicate prepared by treating a naturally occurring or synthetic layered silicate or a mixture of such silicates with a salt of a quaternary or other cyclic amidine compound or a mixture of such salts.
    [2" claim-type="Currently amended] A process according to claim 1, wherein natural or synthetic Smectic clay minerals, bentonite, vermiculite and / or halosite are used in the preparation thereof, and are preferably montmorillonite, saponite, baydelite, nontronite, hector. A lipophilic layered silicate which uses lite, souconite and stevensite, particularly preferably montmorillonite and / or hectorite.
    [3" claim-type="Currently amended] The lipophilic layered silicate according to claim 1 or 2, having an in-layer distance in the range of about 0.7 to 1.2 nm (nanometer) and a cation exchange capacity in the range of 50 to 200 meq / 100 g.
    [4" claim-type="Currently amended] The lipophilic layered silicate according to any one of claims 1 to 3, characterized in that for the preparation thereof a layered silicate of the formula:
    (Al 3.15 Mg 0.85) Si 8.00 O 20 (OH) 4 X 11.8 · nH 2 O
    Wherein X is a substitutable cation, preferably sodium or potassium, and the hydroxy group may be substituted in place of fluoride ions as necessary.
    [5" claim-type="Currently amended] The lipophilic layered silicate according to any one of claims 1 to 4, characterized in that for the preparation thereof a cyclic amidine compound of formula (I) or a mixture of such compounds is used:

    In the food,
    R 1 is a straight or branched chain aliphatic radical having 1 to 20 carbon atoms and may contain one or more unsaturated bonds and / or one or more functional groups;
    R 2 is hydrogen or contains one or more unsaturated bonds and / or one or more functional groups and may optionally include one or more -NH- groups or one or more oxygen atoms in between Straight or branched aliphatic radicals having from 20 to 20 carbon atoms;
    R 3 is a straight or branched aliphatic radical having 1 to 8 carbon atoms which may contain hydrogen or one or more unsaturated bonds;
    A is -CH 2 -or -CH 2 -CH 2- ;
    B is -CH 2- ; or
    A and B are combined to be a-(CH = CH)-radical or a formula = CH-CH = or = CH-CH 2 -CH = radical and both of these radicals are part of a cyclic substituted or unsubstituted cyclohexyl ring And again
    X - is any desired anion, especially F -, Cl -, Br - , I -, SO 4 -2, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) - Lim.
    [6" claim-type="Currently amended] The method of claim 5,
    R 1 is an alkyl radical of a saturated or hydroxy fatty acid having 8 to 20 carbon atoms, preferably 12 to 20 carbon atoms, particularly preferably 14 to 18 carbon atoms, or 8 to 20 carbon atoms, preferably Preferably an alkenyl radical of an unsaturated fatty acid or hydroxy fatty acid having 12 to 20 carbon atoms, particularly preferably 14 to 18 carbon atoms, or by unsubstituted or carboxyl groups or (C 1 -C 3 ) alkoxycarbonyl (C 2 -C 8 ) alkyl substituted by group;
    R 2 is hydrogen or has 1 to 8 carbon atoms and contains unsaturated bonds and may be substituted by a carboxyl group or a (C 1 -C 20 ) alkoxycarbonyl group or a cyclohexylcarbonyl group or a phenylcarboxy group An aliphatic radical which may optionally comprise -NH- or oxygen;
    R 3 is hydrogen or (C 1 -C 4 ) alkyl;
    A and B are each -CH 2- ; or
    A and B combine to form a radical-(CH = CH)-; In addition
    X - is any desired anion, especially F -, Cl -, Br - , I -, SO 4 2-, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) -A lipophilic layered silicate, characterized in that.
    [7" claim-type="Currently amended] A lipophilic layered silicate according to any one of claims 1 to 5, characterized in that for the preparation thereof a cyclic amidine compound of formula (I ') is used:

    In the food,
    R 1 ′ is an alkenyl radical of 12-hydroxyoleic acid or an alkyl radical of hydrogenated ricinoleic acid (12-hydroxystearic acid);
    R 2 ′ is hydrogen or an aliphatic radical having 1 to 4 carbon atoms which is unsubstituted or substituted by a (C 1 -C 20 ) alkoxycarbonyl group;
    R 3 ′ is hydrogen, methyl or ethyl;
    A and B are each -CH 2- ; or
    A and B combine to be a-(CH = CH)-radical; In addition
    X - is any desired anion, for example F -, Cl -, Br - , I -, SO 4 2-, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) - Lim.
    [8" claim-type="Currently amended] The lipophilic layered silicate according to any one of claims 1 to 5, characterized in that for the preparation thereof a cyclic amidine compound of the formula or a mixture of these compounds is used:

    In the food,
    R 2 ″ is hydrogen, methyl, ethyl, propyl or butyl; and
    X - is any desired anion, especially F -, Cl -, Br - , I -, SO 4 2-, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) - ;

    In the food,
    Y is -O- or -NH-, preferably -O-;
    Z is a (C 12 -C 20 ) alkyl radical or (C 12 -C 20 ) alkenyl radical of a suitable fatty acid, and
    X - is any desired anion, especially F -, Cl -, Br - , I -, SO 4 2-, C 6 H 5 SO 3 -, CH 3 SO 4 -, (HCOO) - , or (CH 3 COO ) - Lim.
    [9" claim-type="Currently amended] A thermoplastic polymer comprising the lipophilic layered silicate according to any one of claims 1 to 8 or a mixture of such layered silicates.
    [10" claim-type="Currently amended] A thermosetting polymer system, preferably an epoxy resin system, comprising the lipophilic layered silicate according to claim 1 or a mixture of such layered silicates.
    [11" claim-type="Currently amended] The epoxy resin system of claim 10 comprising (a) an epoxy resin having at least one 1,2-epoxy group in the molecule and (b) at least one curing agent.
    [12" claim-type="Currently amended] 12. Liquid or viscous polyglycidyl ether or polyglycidyl ester or mixtures of these compounds, preferably liquid or viscous bisphenol diglycidyl ether, and epoxidized oils, according to claim 10 or 11. Epoxy resin systems comprising a mixture with epoxidized soybean oil.
    [13" claim-type="Currently amended] 13. A process according to any of claims 10 to 12, comprising a curing agent selected from the group consisting of amines, carboxylic acids, carboxylic anhydrides or phenols, or a mixture of these curing agents or catalytic curing agents, preferably imidazoles. Epoxy resin system.
    [14" claim-type="Currently amended] Polyurethane comprising a lipophilic layered silicate according to any one of claims 1 to 8 or a mixture of such layered silicates.
    [15" claim-type="Currently amended] 15. The polyurethane according to claim 14, which is a crosslinked polyurethane and which comprises polyisocyanates, polyols and optionally polyamines as structural components, each having at least two suitable functional groups per molecule.
    [16" claim-type="Currently amended] Rubber comprising a lipophilic layered silicate according to any one of claims 1 to 8 or comprising a mixture of such layered silicates.
    [17" claim-type="Currently amended] 17. The polymer system of any one of claims 9 to 16 comprising fillers, pigments, dyes, flow regulators and / or plasticizers.
    [18" claim-type="Currently amended] 18. The polymer system according to claim 9, comprising from 0.5 to 30% by weight, preferably from 1 to 30% by weight, of lipophilic layered silicates, based on the total amount of the matrix.
    [19" claim-type="Currently amended] The polymer system according to any one of claims 9 to 18, wherein the total amount of lipophilic layered silicate based on the total amount of the matrix is 70% by weight.
    [20" claim-type="Currently amended] 20. The polymer system according to claim 9, wherein the filler is preferably epoxy or polyurethane and the filler present is powdered quartz, wollastonite and / or chalk.
    [21" claim-type="Currently amended] The process according to claim 1, which has been treated with a polymerizable monomer or a mixture of such monomers, said monomer preferably being an acrylate monomer, methacrylate monomer, caprolactam, laurolactam, aminoundecanoic acid, A lipophilic layered silicate selected from the group consisting of aminocaproic acid and aminododecanoic acid.
    [22" claim-type="Currently amended] A composite material comprising the layered silicate according to claim 1 or a mixture of such layered silicates, in particular a moldable molding material or a finished molded article in the form of a nanocomposite.
    [23" claim-type="Currently amended] Use of the moldable molding material according to claim 22 for producing coating materials, adhesives, casting resins, coatings, flame retardants, materials with thixotropic effects and / or reinforcing agents.
    [24" claim-type="Currently amended] A coating material, an adhesive, a casting resin, a coating, a flame retardant, a substance having a thixotropic effect or a reinforcing agent comprising the lipophilic layered silicate according to any one of claims 1 to 8.
    [25" claim-type="Currently amended] Use of an amidine compound of formula (I) according to claim 5 for producing a lipophilic layered silicate.
    [26" claim-type="Currently amended] Use of the lipophilic layered silicate according to any one of claims 1 to 8 for producing a moldable molding material and a finished molded or composite material, preferably a nanocomposite.
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    同族专利:
    公开号 | 公开日
    ES2195547T3|2003-12-01|
    JP2002504582A|2002-02-12|
    EP1060211A2|2000-12-20|
    EP1060211B1|2003-04-23|
    US6197849B1|2001-03-06|
    CN1297470A|2001-05-30|
    DE69907162D1|2003-05-28|
    WO1999042518A3|1999-10-07|
    DE69907162T2|2004-02-19|
    BR9908120A|2000-10-24|
    WO1999042518A2|1999-08-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-02-20|Priority to CH408/98
    1998-02-20|Priority to CH40898
    1999-02-10|Application filed by 베르너 훽스트, 반티코 아게, 지크프리트 포트호프
    1999-02-10|Priority to PCT/EP1999/000881
    2001-03-26|Publication of KR20010024924A
    优先权:
    申请号 | 申请日 | 专利标题
    CH408/98|1998-02-20|
    CH40898|1998-02-20|
    PCT/EP1999/000881|WO1999042518A2|1998-02-20|1999-02-10|Organophilic phyllosilicates|
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