Patent Application
20080153948
The present invention relates to compositions comprising an organic material subject to oxidative, thermal or light-induced degradation, in particular a synthetic polymer, and at least one product obtainable by reacting a nano-scaled filler with an additive that is linked to a reactive group. The present invention relates also to new products obtainable by reacting a nano-scaled filler with an additive that is linked to a reactive group, to the use of these products as nonvolatile stabilizers or flame retardants for nanocomposite organic materials which are subject to oxidative, thermal or light-induced degradation, in particular to synthetic nanocomposite polymers or coatings, or as photoinitiators for the in-situ polymerization of pre-polymeric nanocomposites or sols to nanocomposite materials. The present invention relates also to a process for stabilizing or flame-retarding a nanocomposite organic material, which is subject to oxidative, thermal or light-induced degradation, in particular a synthetic nanocomposite polymer or coating, or to photoinitiating in-situ polymerization of a pre-polymeric nanocomposite or sol to a nanocomposite material.
The addition of fillers to organic materials, especially polymers, is known and is described for example in R. Gächter/H. Müller (eds.), Plastics Additives Handbook, 3rd ed., pages 525-591, Hanser Publishers, Munich 1990. The use of fillers in polymers has the advantage that it is possible to bring about improvement in, for example, the mechanical properties, especially the density, hardness, rigidity or impact strength of the polymer.
Using extremely small filler particles (<200 nm), so-called nano-scaled fillers, mechanical properties, long term stability or flame retardant property of the polymers can be improved at a much lower concentration of 5 to 10% by weight compared to 20 to 50% by weight with the micro-scaled normal filler particles. Polymers containing nano-scaled fillers show improved surface qualities like gloss, lower tool wear at processing and better conditions for recycling. Coatings and films comprising nano-scaled fillers show improved stability, flame resistance, gas barrier properties and scratch resistance.
Nano-scaled fillers possess an extremely large surface with high surface energy. The deactivation of the surface energy and the compatibilization of the nano-scaled fillers with a polymeric substrate is therefore even more important than with a common micro-scaled filler in order to avoid aggregation and to reach an excellent dispersion of the nano-scaled filler in the polymer. The nano-scaled fillers like the phyllosilicates are made organophilic by ion exchange, for example with alkylammonium salts. Such nano-scaled organophilic phyllosilicates are better swellable and easier to disperse (exfoliate) into a polymer matrix [for example Nanomer® form Nanocor or Closite® from Southern Clay Products].
In the case of precipitated calcium carbonate, organophilization can be achieved by a treatment with an organophilic carboxylic acid [e.g. Socal® (from Solvay), see M. Avella et al, Nano Lett., 1 (4), 2001].
Colloidal silica can be suspended in neutral, reactive (crosslinking) or pre-polymeric diluents resp. monomers or mixtures of all [e.g. Highlink® OG or Klebosol® from Clariant, see C. Vu et al, RadTech'2000, Baltimore], as so called sols.
U.S. Pat. No. 6,020,419 discloses a transparent coating composition containing a binder and 0.5 to 25 weight %, based on resin solids, of a material consisting of nano-scaled particles obtained by jet dispersion of the nano-scaled particles in the coating composition.
WO-A-01/05897 discloses binding agents modified with nano-scaled particles.
Photoinitiators may be covalently coupled to silica gel to initiate the polymerization of for example acrylates, methacrylates or styrene from the silica gel surface [see for example M. Koehler; J. Ohngemach, ACS Symp. Ser. 1990, 417 (Radiat. Curing Polym. Mater.), 106-24, “coreactive photoinitiators for surface polymerization”]. p-Substituted 2-hydroxy-2-methylpropiophenone photoinitiators are disclosed, and the photoinitiators are covalently coupled to silica gel via the p-substituted groups; the anchored photoinitiators were then used to initiate polymerization from the silica gel surface. The p-substituted groups included triethoxysilyl, epoxy, or azido groups. The initiators are used to polymerize either acrylates, methacrylates, styrene, or N-vinylpyrrolidone. The influences of monomer type, monomer concentration and initiator type on polymerisation kinetics are examined.
Hybrid type of photoinitiators containing polysiloxane groups have been described to be used for scratch-resistant radiocurable coatings.
It has now been found that specifically modified, especially organophilic, nano-scaled fillers which contain an additive selected from the group of radical scavengers, hydroperoxide decomposers, UV-absorbers or flame retardants are especially useful as stabilizers or flame retardants for nanocomposite organic materials which are subject to oxidative, thermal or light-induced degradation. Modified nano-scaled fillers which contain a photoinitiator are especially useful for the in-situ polymerization of pre-polymeric nanocomposites or sols to nanocomposite materials.
This invention therefore relates to a composition comprising
AD-L-RG (I)
Of interest are also products obtainable by reacting a nano-scaled filler with a compound of the formula I, wherein
AD is an additive selected from the group of radical scavengers, hydroperoxide decomposers, UV-absorbers, light stabilizers, flame retardants or photoinitiators,
L is a direct bond, —R—O— with the proviso that the oxygen atom is attached to AD,
C1-C25alkylene, C2-C25alkylene interrupted by —O—, —S—, —SO—, —SO2—,
phenylene or C5-C8cycloalkylene;
or a maleic anhydride-grafted polypropylene,
wherein
R1 is C1-C18alkylene,
R2 is a direct bond or C1-C18alkylene,
R3 is hydrogen or C1-C8alkyl,
R4 is hydrogen or C1-C4alkyl,
R5, R6 and R7 are each independently of the others hydrogen, C1-C25alkyl, phenyl or C7-C25phenylalkyl,
R8, R9 and R10 are each independently of the others hydroxyl,
R11 is hydrogen or C1-C25alkyl,
R12 is hydrogen or C1-C25alkyl, C3-C25alkyl interrupted by oxygen, sulfur or by or
C2-C24alkenyl,
R13, R14 and R15 are each independently of the others halogen, amino, C1-C25alkoxy or C1-C25alkyl, with the proviso that at least one radical of R13, R14 and R15 is different from C1-C25alkyl,
R16, R17 and R18 are each independently of the others C1-C12alkoxy or C2-C25alkanoyloxy,
R19, R20 and R21 are each independently of the others C1-C12alkoxy, C2-C25alkanoyloxy or benzoyloxy,
R22, R23, R24 and R25 are each independently of the others hydrogen, C1-C25alkyl or hydroxyl-substituted C2-C24alkyl,
M is a r-valent metal cation,
X− is fluoride, chloride, bromide, iodide, nitrite, nitrate, hydroxide, acetate, hydrogen sulfate, sulfate, methyl sulfate or mixtures thereof, and
r is 1, 2 or 3.
C1-C25Alkylene is a branched or unbranched radical, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. A preferred definition for L, R1 and R2 is C1-C12alkylene, especially C1-C8alkylene, for example C2-C8alkylene.
C2-C25alkylene interrupted by —O—, —S—, —SO—, —SO2—,
phenylene or C5-C8cycloalkylene is, for example,
—CH2—O—CH2—, —CH2—S—CH2—, —CH2—N(CH3)—CH2—, —CH2—O—CH2CH2—, —CH2CH2—O—CH2CH2—, —CH2CH2—O—CH2CH2—O—CH2CH2—, —CH2CH2—(O—CH2CH2—)2O—CH2CH2—, —CH2CH2—(O—CH2CH2—)3O—CH2CH2—, —CH2CH2—(O—CH2CH2—)4O—CH2CH2
Alkyl having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl.
C7-C9-Phenylalkyl is, for example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl and α,α-dimethylbenzyl.
C3-C25Alkyl interrupted by oxygen, sulfur or by
is, for example, CH3—O—CH2CH2—, CH3—S—CH2CH2—, CH3—N(CH3)—CH2CH2—, CH3—O—CH2CH2—O—CH2CH2—, CH3—(O—CH2CH2—)2O—CH2CH2—, CH3—(O—CH2CH2—)3O—CH2CH2— or CH3—(O—CH2CH2—)4O—CH2CH2—.
Alkenyl having 2 to 24 carbon atoms is a branched or unbranched radical such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having 3 to 18, especially 3 to 12, for example 3 to 6, especially 3 to 4 carbon atoms.
Halogen is, for example, chlorine, bromine or iodine. Preference is given to chlorine and bromine.
Alkoxy having up to 25 carbon atoms is a branched or unbranched radical, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given to alkoxy having from 1 to 12, especially from 1 to 8, e.g. from 1 to 6, carbon atoms.
Alkanoyloxy having up to 25 carbon atoms is a branched or unbranched radical, for example acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, icosanoyloxy or docosanoyloxy. Preference is given to alkanoyloxy having from 2 to 18, especially from 2 to 12, e.g. from 2 to 6, carbon atoms.
Hydroxyl-substituted C2-C24alkyl is a branched or unbranched radical which contains preferably 1 to 3, in particular 1 or 2, hydroxyl groups, such as, for example, hydroxyethyl, 3-hydrooxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexyl, 5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxyheptyl, 4-hydroxyheptyl, 3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl, 7-hydroxyoctyl, 6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl, 2-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxyoctadecyl, 20-hydroxyeicosyl or 22-hydroxydocosyl. A preferred definition of R22, R23, R24 and R25 is hydroxyl-substituted C2-C12alkyl, especially hydroxyl-substituted C4-C8alkyl.
A mono-, di- or tri-valent metal cation is preferably an alkali metal cation, alkaline earth metal cation or aluminium cation, for example Na+, K+, Mg++, Ca++ or Al+++.
Block-graft copolymers are for example maleic anhydride-grafted polypropylene (PP-g-MA), ithaconic acid-grafted polypropylene, acrylic acid-grafted polypropylene or polyethyleneoxide-block-polystyrene (PEO-bl-PS). Preferably, block-graft copolymers have molecular weights of Mn 1000 to 10000, and for the maleic anhydride modified polypropylene oligomers (PP-g-MA) the maleic anhydride content is from 1 to 10% [for example Epolene® E43, MA content 2.9 weight %, Mn 8800 (Eastman); Hostaprime® HC5, MA content 4.2 weight %, Mn 4000].
The nano-scaled filler have a particle size below 200 nm, preferably below 100 nm and more preferably below 50 nm.
Nano-scaled fillers of special interest are nano-scaled oxides made by gas-phase or sol-gel processes, for example SiO2, SiO2 [e.g. Aerosil® from Degussa; Ludox® from DuPont; Snowtex® from Nissan Chemical; Levasil® from Bayer; or Sylysia® from Fuji Silysia Chemical], TiO2 [e.g. NanoTek® from Nanophase], ZrO2, SnO2, MgO, ZnO [e.g. Activox® B or Durhan® TZO from Elementis], CeO2, Al2O3, In2O3 or mixed oxides, including colloidal silica [e.g. Klebosol®], or organosols [e.g. Hilink® OG from Clariant], or polyhedral oligomeric silsesquioxanes [e.g. POSSE from Hybrid Plastics] with compatibilizing or reactive organic modifications like hydrocarbon, silane or siloxane chains, with or without functional groups such as hydroxyl, amino, mercapto, epoxy or ethylenic groups, or natural or modified semi-synthetic or synthetic [e.g. Somasif® from CO-OP Chemicals] phyllosilicates, organophilic precipitated calcium carbonate [e.g. Socal® from Solvay] or anion exchanging hydrotalcite [e.g. Hycite®713 from Ciba Specialty Chemicals].
Preferred fillers are organophilically modified natural or synthetic phyllosilicates or a mixture of such phyllosilicates. Especially preferred fillers are organophilically modified montmorillonites [e.g. Nanomer® from Nanocor or Nanofil® from Suedchemie], bentonites [e.g. Cloisite® from Southern Clay Products], beidellites, hectorites, saponites, nontronites, sauconites, vermiculites, ledikites, magadiites, kenyaites or stevensites.
Of special interest are products obtainable by reacting a nano-scaled filler with a compound of the formula I, wherein AD is an additive selected from the group of phenolic antioxidants, benzofuran-2-ones, sterically hindered amines, aminic antioxidants, 2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-1,3,5-triazines, phosphites, phosphonites, thioethers, benzophenones, α-activated acetophenones, bisacylphosphin-oxides (BAPO), monoacylphosphinoxides (MAPO), alkoxamines, thioxanthones, benzoins, benzil ketals, benzoin ethers, α-hydroxy-alkylphenones or α-aminoalkylphenones.
Of very special interest are products obtainable by reacting a nano-scaled filler with a compound of the formula I, wherein AD is
wherein
R26 is hydrogen or methyl,
R27 is hydrogen or methyl,
R28 is hydrogen or
R29 is C1-C4alkylene,
R30 and R31 are each independently of the other hydrogen, C1-C18alkyl, C7-C9phenylalkyl, phenyl or C5-C8cycloalkyl,
R32 and R33 are each independently of the other hydrogen, C1-C18alkyl, C7-C9-phenylalkyl, phenyl or C5-C8cycloalkyl,
R34 and R35 are each independently of the other hydrogen, halogen, C1-C4alkyl, —CN, trifluoromethyl or C1-C4alkoxy,
R36 is a direct bond or —O—,
R37 is hydrogen, —O′, C1-C20alkyl, C2-C20alkenyl, C2-C20alkinyl, C1-C20alkoxy, C5-C12cycloalkoxy, C7-C25aralkoxy, C6-C12aryloxy, C7-C9phenylalkyl, C5-C12cycloalkyl, phenyl, naphthyl, hydroxyethyl, C2-C25alkanoyl, benzoyl, naphthoyl or C2-C20alkoxyalkanoyl,
R38 is hydrogen or an organic radical,
R39 and R40 are each independently of the other hydrogen, C1-C18alkyl, C7-C9phenylalkyl or phenyl,
R41 is hydrogen, halogen or C1-C18alkyl,
R42 is hydrogen, C1-C18alkyl or C7-C9phenylalkyl,
R43 and R44 are each independently of the other hydrogen, C1-C18alkyl, C1-C18alkoxy, di(C1-C4alkyl)amino, hydroxyl or
R45 is hydrogen, C1-C18alkyl, C1-C18alkoxy or
R46 and R47 are each independently of the other hydrogen, hydroxyl, C1-C18alkyl, phenyl, C1-C18alkoxy or C7-C9phenylakyl,
R48 is a direct bond or oxygen,
R49 and R50 are each independently of the other C1-C18alkyl, C7-C9phenylalkyl, cyclohexyl, phenyl, or phenyl substituted by 1 to 3 alkyl radicals having in total 1 to 18 carbon atoms,
R51, R52 and R53 are each independently of the others hydrogen, halogen C1-C4alkyl or C1-C4alkoxy,
R54 is C1-C20alkyl, C5-C8cycloalkyl, C7-C9phenylalkyl or phenyl,
R55 is C1-C25alkyl,
R56 is methylene or ethylene,
R57 is methylene or ethylene,
R62 is hydrogen or C1-C18alkyl,
R63 and R64 are each independently of the other hydrogen, C1-C18alkyl, C1-C18alkoxy, C1-C4alkylthio, morpholinyl, C7-C9phenylalkyl of phenyl,
R65 and R66 are each independently of the other C1-C18alkyl,
R67 is C2-C4alkylene,
R68 is hydrogen or C1-C18alkyl,
R69 is C3-C7alkylene,
R70 and R71 are each independently of the other C1-C8alkyl or C7-C9phenylalkyl,
R72 and R73 are each independently of the other C1-C8alkyl or R72 and R73 are together —CH2CH2—O—CH2CH2— thus forming with the nitrogen atom to which they are attached a morpholinyl ring,
R74 is hydrogen, C1-C18alkyl or C7-C9phenylalkyl, and
x is 1, 2 or 3.
Especially preferred compounds of the formula I are:
Many of the compounds of the formula I are known in the literature like for example the above mentioned compounds (108) to (148). The new compounds of the formula I may be prepared in analogy to the preparation of the known compounds (108) to (148).
The preparation of component (b) by the reaction of a compound of the formula I with a nano-scaled filler, in its unmodified state or after an organophilic modification, is preferably carried out in a well stirred suspension or solution in a suitable protic or aprotic solvent, such as water, ethanol or xylene.
The pH is preferably adjusted in the range of pH 11 and pH 3, in particular between pH 9 and 4.
The reaction is preferably carried out at temperatures of from 20 to 150° C., for example, in particular at from 50 to 150° C., e.g. at from 50 to 100° C.
During the reaction it is preferable that the compound of formula I is used in excess in respect to the calculated amount to be covalently bound, complexingly coordinated or adsorbed to the nano-scaled filler, e.g. in a molar excess to the cationic respectively anionic exchange capacity in case of phyllosilicates respectively hydrotalcites.
After the reaction the product is preferably isolated, for example, by filtration or centrifugation and, especially preferred, by additional washing steps to extract the non reacted excess of the compound of the formula I.
The amount of covalently bound, complexingly coordinated or adsorbed compound of the formula I is preferably calculated indirectly by subtraction of the extracted amount. In cases of colloidal suspensions of nano-scaled fillers in neutral, reactive or pre-polymeric diluents respectively monomers, or mixtures of all, the compounds of the formula I are preferably directly added and reacted, before further utilization of the such functionalized colloidal suspensions or sols. A specifically preferred molar ratio of the compound of the formula I to the nano-scaled filler is from 1.05:1 to 1.5:1.
The compound of the formula I can also be reacted with a nano-scaled filler during the organophilic modification of the filler [see e.g. P. Reichert, et al, Macromol. Mat. Eng. 275, 8-17 (2000)].
When the compound of formula I is of the character of a modified block-graft copolymer, like for example a functionalized maleic acid anhydride modified polypropylene oligomer (for example Epolene® E43 or Hostaprime® HC5) compatibilizer it can also be added during (melt)processing of the nanocomposite polymeric material.
The products obtainable by reacting a nano-scaled filler with a compound of the formula I are suitable for stabilizing or flame-retarding nanocomposite organic materials, which are subject to oxidative, thermal or light-induced degradation, in particular synthetic nanocomposite polymers or coatings, or for photoinitiating in-situ polymerization of pre-polymeric nanocomposites or sols to nanocomposite materials.
Examples of such materials are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethyllene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethyleneacrylic acid copolymers (EM), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
Homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).
6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polyketones.
21. Polysulfones, polyether sulfones and polyether ketones.
22. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
23. Drying and non-drying alkyd resins.
24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
25. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
28. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
29. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
30. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
31. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
32. Pre-polymeric monomers or oligomers of the aforementioned polymers or blends.
33. Sols, especially organosols, as stable liquid suspensions of colloidal nano-particles in a diluent, a reactive (e.g. crosslinking) diluent or in a polymerizable or crosslinking monomer, or in a mixture of all.
Preferred organic materials are polymers, for example a pre-polymer for a nanocomposite material, in particular synthetic polymers, for example thermoplastic polymers. Polyamides and polyolefins are particularly preferred. Examples of preferred polyolefins are polypropylene or polyethylene.
Preferably, component (b) is added to the material to be stabilized, compatibilized, flame-retarded and/or polymerization regulated in an amount from 0.01 to 10%, in particular 0.01 to 2%, for example 0.1 to 2%, relative to the weight of the organic material to be stabilized, compatibilized, flame-retarded and/or polymerization regulated.
The compositions according to the invention can contain, in addition to components (a) and (b), additional additives, for example the ones listed below:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylhenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
1.4. Tocopherols, for example α-tocopherol, α-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2, 2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
1.6. Alkylidenebisphenols, for example 2, 2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di-tert-butylphenol), 4,4′-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. O—, N- and S-benzyl compounds, for example 3, 5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard®XL-1, supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyidiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyidiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.
2. UV Absorbers and Light Stabilizers
2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R—CH2CH2—COO—CH2CH22, where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, a reaction product of maleic acid anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
2.7. Oxamides, for example 4, 4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
3. Metal deactivators, for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], 2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxyylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octylalpha-heptyinitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.
9. Polyamide stabilisers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
11. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.
12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one, 3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.
The costabilizers are added, for example, in concentrations of 0.01 to 10%, relative to the total weight of the material to be stabilized and/or compatibilized.
Incorporation of component (b) and, if desired, further additives into the polymeric, organic material is carried out by known methods, for example before or during moulding or else by applying the dissolved or dispersed compounds to the polymeric, organic material, if appropriate with subsequent slow evaporation of the solvent. Component (b) can also be added to the materials to be stabilized in the form of a masterbatch or a colloidal sol or organosol containing for example 5 to 50% by weight of component (b).
Component (b) can also be added before or during polymerisation or before crosslinking.
Component (b) can be incorporated into the material to be stabilized and/or compatibilized in pure form or encapsulated in waxes, oils or polymers.
Component (b) can also be sprayed onto the material to be stabilized, compatibilized, flame-retarded and/or polymerized.
The materials thus treated as mentioned above can be used in various forms, for example as films, fibres, ribbons, moulded materials, profiles, coatings or as binders for paints, adhesives or cement.
The invention also relates to novel products obtainable by reacting a nano-scaled filler with a compound of the formula I
AD-L-RG (I)
wherein
AD is an additive selected from the group of radical scavengers, hydroperoxide decomposers, UV-absorbers, light stabilizers, flame retardants or photoinitiators,
L is a direct bond, —R1—O— or
with the proviso that the oxygen atom is attached to AD; C1-C25alkylene, C2-C25alkylene interrupted by —O—, —S—, —SO—, —SO2—,
phenylene or C5-C8cycloalkylene; or a block-graft copolymer,
wherein
R1 is C1-C18alkylene,
R2 is a direct bond or C1-C18alkylene,
R3 is hydrogen or C1-C8alkyl,
R4 is hydrogen or C1-C4alkyl,
R5, R6 and R7 are each independently of the others hydrogen, C1-C25alkyl, phenyl or C7-C25-phenylalkyl,
R8, R9 and R10 are each independently of the others hydroxyl,
R11 is hydrogen or C1-C25alkyl,
R12 is hydrogen or C1-C25alkyl, C3-C25alkyl interrupted by oxygen, sulfur or by
C2-C24alkenyl,
R13, R14 and R15 are each independently of the others halogen, amino, C1-C25alkoxy or C1-C25alkyl, with the proviso that at least one radical of R13, R14 and R15 is different from C1-C25alkyl,
R16, R17 and R18 are each independently of the others C1-C12alkoxy or C2-C25alkanoyloxy,
R19, R20 and R21 are each independently of the others C1-C12alkoxy, C2-C25alkanoyloxy or benzoyloxy,
R22, R23, R24 and R25 are each independently of the others hydrogen, C1-C25alkyl or hydroxyl-substituted C2-C24alkyl,
M is a r-valent metal cation,
X− is fluoride, chloride, bromide, iodide, nitrite, nitrate, hydroxide, acetate, hydrogen sulfate, sulfate, methyl sulfate or mixtures thereof, and
r is 1, 2 or 3.
Of special interest of novel products obtainable by reacting a nano-scaled filler with a compound of the formula I are those, wherein
AD is an additive selected from the group of radical scavengers, hydroperoxide decomposers, UV-absorbers, light stabilizers, flame retardants or photoinitiators,
L is a direct bond, —R1—O— with the proviso that the oxygen atom is attached to AD,
C1-C25alkylene, C2-C25alkylene interrupted by —O—, —S—, —SO—, —SO2—,
phenylene, C5-C8cycloalkylene; or a maleic anhydride-grafted polypropylene,
wherein
R1 is C1-C18alkylene,
R2 is a direct bond or C1-C18alkylene,
R3 is hydrogen or C1-C8alkyl,
R4 is hydrogen or C1-C4alkyl,
R5, R6 and R7 are each independently of the others hydrogen, C1-C25alkyl, phenyl or C7-C25-phenylalkyl,
R8, R9 and R10 are each independently of the others hydroxyl,
or
R11 is hydrogen or C1-C25alkyl,
R12 is hydrogen or C1-C25alkyl, C3-C25alkyl interrupted by oxygen, sulfur or by
C2-C24alkenyl,
R13, R14 and R15 are each independently of the others halogen, amino, C1-C25alkoxy or C1-C25alkyl, with the proviso that at least one radical of R13, R14 and R15 is different from C1-C25alkyl,
R16, R17 and R18 are each independently of the others C1-C12alkoxy or C2-C25alkanoyloxy,
R19, R20 and R21 are each independently of the others C1-C12alkoxy, C2-C25alkanoyloxy or benzoyloxy,
R22, R23, R24 and R25 are each independently of the others hydrogen, C1-C25alkyl or hydroxyl-substituted C2-C24alkyl,
M is a r-valent metal cation,
X− is fluoride, chloride, bromide, iodide, nitrite, nitrate, hydroxide, acetate, hydrogen sulfate, sulfate, methyl sulfate or mixtures thereof, and
r is 1, 2 or 3.
Preferred groups of the novel products conform to the preferences given above for the compositions according to the invention.
The present invention further provides a process for stabilizing, flame-retarding and/or compatibilizing an organic material which is subject to oxidative, thermal or light-induced degradation, which comprises incorporating therein, or applying thereto, at least one product obtainable by reacting a nano-scaled filler with a compound of the formula I.
The present invention also provides a process for photoinitiating in-situ polymerization or hardening of a pre-polymeric nanocomposite or sol to a nanocomposite material, which comprises incorporating therein, or applying thereto, at least one product obtainable by reacting a nano-scaled filler with a compound of the formula I.
A further embodiment of the present invention is the use of a product obtainable by reacting a nano-scaled filler with a compound of the formula I as stabilizer and/or flame-retarder and/or compatibilizer for organic materials which are subject to oxidative, thermal or light-induced degradation.
The present invention also provides the use of a product obtainable by reacting a nano-scaled filler with a compound of the formula I as photoinitiator for the in-situ polymerization or hardening of pre-polymeric nanocomposites or sols to nanocomposite materials.
The preferred products and organic materials for the process and use are the same as those for the compositions according to the invention.
The following Examples illustrate the invention in more detail. Parts or percentages are by weight.
35.3 g (0.10 mole) of Tinuvin 1130®, Ciba Specialty Chemicals Inc.), 21.5 g (0.12 mole) of 3-aminopropyl-trimethoxysilane and 0.50 g (2.0 mmole) of dibutyltinoxide are mixed and heated to 130° C. The formed methanol is distilled off during 5 hours. The excess 3-aminopropyl-trimethoxysilane is distilled off under reduced pressure using a vacuum rotary evaporator. The residue yields 50 g of the compound of the formula (101) as a clear yellow, viscous oil. 1H-NMR (300 MHz, CDCl3, ppm): 1.49 (s, 9H, tert-butyl); 3.53 (s, 9H, Si(OCH3)3).
120 g of a nano-scaled organophilic montmorillonite [Nanomer® 1.42E] is suspended in 2.4 l of ethanol (95%) and heated under vigorous stirring to 75° C. Then, a solution of 4.2 g of the compound of the formula (101), prepared according to Example 1a, in 50 ml of ethanol is added dropwise during 10 minutes. Then the pH was adjusted with acetic acid (35 ml) to a pH of 5.3. The reaction mixture is refluxed for 24 hours. The reaction mixture is cooled to room temperature and the product isolated by filtration. The residue is washed with water and ethanol and afterwards dried under vacuum to a constant weight. The slightly yellowish powder (106 g) is homogenized in a mortar. It contains 3.2% by weight of (2′-hydroxyphenyl)benzotriazol type UV absorber.
29.3 g (0.10 mole) of Metilox®, Ciba Specialty Chemicals Inc.), 21.5 g (0.12 mole) of 3-aminopropyl-trimethoxysilane and 0.5 g (2.0 mmole) of dibutyltinoxide are mixed and heated to 130° C. The formed methanol is distilled off during 2 hours. The excess 3-aminopropyl-trimethoxysilane is distilled off under reduced pressure using a vacuum rotary evaporator. The residue yields 43 g of the compound of the formula (107) as a slightly yellowish, viscous oil. 1H-NMR (400 MHz, CDCl3, ppm): 1.43 (s, 18H, tert-butyl); 3.54 (s, 9H, Si(OCH3)3).
120 g of a nano-scaled organophilic montmorillonite [Nanomer 1.42E®] is suspended in 2.4 l of ethanol (95%) and heated under vigorous stirring to 75° C. Then, a solution of 4.2 g of the compound of the formula (107), prepared according to Example 2a, in 50 ml of ethanol is added dropwise during 10 minutes. The pH is adjusted to 5.3 with acetic acid (33 ml). The suspension is then heated at reflux for 24 hours. Then the reaction mixture is cooled to room temperature, and after standing for 20 minutes the ethanol is decanted. After washing the precipitated product with ethanol and water it is isolated by filtration and dried in an oven at 80° C. till constant weight. The slightly yellowish powder (106 g) is homogenized in a mortar and contains 3.1% by weight of phenolic antioxidant.
116.2 (1.0 mole) of 1,6-diaminohexane are dissolved in 200 ml of toluene. Then a solution of 58.4 g (0.20 mole) of Metilox®, Ciba Specialty Chemicals Inc.) in 100 ml of toluene is added within 5 hours while toluene and generated methanol are continuously distilled off at an inner temperature of approximately 160° C. The reaction mixture is heated for another 14 hours at a bath temperature of 170° C., with methanol and a part of 1,6-diaminohexane distilling. Then the remaining excess of 1,6-diaminohexane is distilled off under reduced pressure. The residue is dissolved in 200 ml of toluene and washed with water. The organic phase is concentrated at reduced pressure using a vacuum rotary evaporator. 61 g of a clear, viscous oil is chromatographically purified on silicagel to yield 33 g of a white solid (yield 44%) of formula (202) with mp 102-104° C. (beside 5.1 g of the bisphenolic product as a white solid with mp 157-158° C.). Analysis, calculated: C, 73.36; H, 10.71; N, 7.44%. Analysis, found. C, 73.12; H, 10.53; N, 7.34%.
3.8 g (0.010 mole) of the compound of the formula (202) is added to a solution of 7.1 g (0.020 mole) of sodium carbonate in 14 ml of water. After the addition of 10 g (0.070 mole) of methyl iodide the reaction mixture is refluxed at 45° C. for 6 hours. The reaction mixture is cooled and the excess methyl iodide distilled off under reduced pressure using a vacuum rotary evaporator. The residue is dissolved with dichloromethane. The organic phase is washed with water, filtered and concentrated using a vacuum rotary evaporator. The residue is suspended in 50 ml of hexane. The product is collected by filtration and dried under reduced pressure at 70° C. to yield 4.7 g (85%) of the compound of the formula (102), m.p. 123-130° C.
To vigorously stirred solution of 3.5 g (0.0064 mole) of the compound of the formula (102) in 1200 ml of ethanol (95%) is added 120 g of a nano-scaled organophilic montmorillonite [Nanomer 1.42E®]. The suspension is then heated at reflux for 2 hours. The reaction mixture is cooled to room temperature and the product is isolated by filtration. The residue is washed twice with 200 ml of ethanol, twice with 200 ml of water and then dried in an oven at 90° C. for 24 hours. The off-white powder (111.5 g) is homogenized in a mortar and contains 2.3% by weight of phenolic antioxidant.
2 kg of unstabilized polyamide 6.6 granules [Zytel 101L® of Du Pont] is dried under vacuum at 80° C. over night. The nano-scaled fillers are dried at 80° C. for 4 hours. 102 g (5% by weight) of the nano-scaled fillers are then dry blended with the polyamide 6.6 and compounded in a twin-screw extruder (type Berstorff) at a maximum of 300° C. and then pelletized. The granules obtained are injection moulded in an injection moulding apparatus at a maximum of 240° C. to 2 mm thick plaques. These plaques are aged in a circulating air oven at 150° C. The yellowness index (YI) of these plaques is determined in accordance with ASTM D 1925-70 as a function of oven ageing time. Low YI values denote little discoloration, high YI values strong discoloration of the plaques. The less discoloration, the more effective the additive functionalized nano-scaled filler. The results are compiled in Table 1.
a)Comparison Example.
b)Example of this invention.
c)Nanomer I.42E (RTM) is a nano-scaled organophilic montmorillonite.
d)Compound A is an antioxidant which does not possess a RG (reactive group) and therefore does not react with the nano-scaled filler.
It has to be noted that the amount of antioxidant in Examples 4a, 4b and 4c is identical. In the comparison Example 4a, 2 g of the compound of formula A which does not possess a reactive group was added to 100 g of the pure nano-scaled filler [Nanomer 1.42E®]. In Examples 4b and 4c the used amount of the product of Examples 2b and 3b is such that that the antioxidant content corresponds to the amount of antioxidant used in the comparative Example 3a.
Examples A-D disclose the preparation of further compounds of the formula I which are useful as starting materials for the preparation of component (b) of the instant invention.
25.8 g (0.3 mol) γ-butyrolactone and 105 g (0.9 mol) of 1,6-diaminohexane are diluted with 45 g of tetrahydronaphthalene. The suspension is heated to 200° C. Then the clear and colorless solution is stirred at 185 to 200° C. for another 24 hours at reflux. Then tetrahydronaphthalene and excess of 1,6-diaminohexane is distilled off under reduced pressure. 17 g (31%) of a clear colorless oil is distilled at 190° C. under reduced pressure (ca. 0.05 mbar) to give the compound of the formula (203).
b) A mixture of 14.6 g (0.05 mol) of Metilox®, Ciba Specialty Chemicals Inc.), 11.0 g (0.06 mol) of the compound of the formula (203) [prepared according to Example Aa] and 0.25 g dibutyl tin oxide is heated to 130° C. and methanol is distilled off continuously. Within 5 hours all the Metilox has reacted. The raw product is a transparent, yellow melt. It is chromatographically purified on silicagel to yield 14 g (63%) of the compound of the formula (105) as clear, colorless, highly viscous liquid. Analysis, calculated: C, 72.93; H, 9.97; N, 6.30%. Analysis, found. C, 72.70%; H, 9.95; N, 6.12%.
To a suspension of 33.9 g (0.3 mol) of 6-caprolactame and 20.0 g (0.33 mol) of ethylene diamine is added ca. 30 g of gaseous HCl within 1.5 hours. Without heating, the temperature raises from room temperature to 160° C. After heating to 200° C. for 15 minutes addition of HCl is stopped. Then, at 230° C. and slightly reduced pressure (ca. 200 mbar) 2.4 g of water is separated (50%). Cooling the raw product to 100° C. leaves a glassy mass. Addition of 30 ml of hot water leads to a clear solution. After cooling to 10° C. 80 g of NaOH (45% solution) is added within 10 minutes. The clear solution with some precipitate is concentrated to dryness. The resulting yellow oil with some white solid particles is re-dissolved/suspended and stirred in 200 ml ethanol, then filtered and reconcentrated to give a highly viscous oil. Distillation of the raw-product (ca. 120° C./0.03 mmbar) yields 15.7 g 34% of the compound of the formula (204), white solid, mp 78-80° C. Analysis, calculated: C, 61.90; H, 11.04; N, 27.07%. Analysis, found. C, 61.77; H, 10.87; N, 26.74%.
b) A mixture of 14.6 g (50 mmol) Metilox®, Ciba Specialty Chemicals Inc.), 7.8 g (50 mmol) of the product from example Ba and 0.25 g dibutyl tinoxide is heated to 140° C. and methanol is distilled off continuously. Within 4 hours all the Metilox has reacted. The raw-product is a very viscous yellow oil. Purification by column chromatography on silicagel yields as the main product 13.4 g (65%) of the compound of the formula (104) as highly viscous yellowish oil. Analysis, calculated: C, 72.07; H, 10.16; N, 10.09%. Analysis, found. C, 70.36; H, 9.90; N, 9.59% (some methanol present according to 1H-NMR spectra).
To a solution of 1.6 g sodium carbonate (15 mmol) in 10 ml water is added 10.6 g (75 mmol) methyl iodide and 6.2 g (15 mmol) of the compound of the formula (104) [prepared according to Example Bb]. The reaction mixture is heated to reflux temperature (45° C.) for 6 hours. Then the excess of methyl iodide is distilled off. The residue is dissolved in 50 ml dichloromethane. This solution is washed with some water, filtered and concentrated under reduced pressure. The highly viscous yellow oil crystallizes from 100 ml hexane over night and yields 7.4 g (86%) of the compound of the formula (103) as a yellowish solid. Analysis, calculated: C, 56.64; H, 8.27; N, 7.34; 122.16%. Analysis, found. C, 56.36; H, 8.12; N, 6.95; 121.35%.
To a solution of 2.9 g (10 mmol) tetraisopropyl orthotitanate in 5 ml toluene is added 2.8 g (10 mmol) of ‘Metilox acid’ (the corresponding carboxylic acid of Metilox). The suspension is heated to 40° C. for 30 minutes. Then 2.9 g of stearic acid is added and the clear solution is heated to 60° C. for another hour. The reaction mixture is concentrated in vacuo and dried at 80° C./0.05 mbar to yield 7.0 g (96%) of the compound of formula (106) as a clear orange viscous oil. Analysis, calculated: C, 67.56; H, 10.51; Ti 6.57%. Analysis, found. C, 67.45; H, 9.96; Ti 7.41%.
| Number | Date | Country | Kind |
|---|---|---|---|
| 01810634.4 | Jun 2001 | EP | regional |
This application is a divisional of U.S. application Ser. No. 10/481,964, which is a 371 of international app. No. PCT/EP02/06848, filed Jun. 20, 2002, the contents of which applications are incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10481964 | Dec 2003 | US |
| Child | 11982561 | US |
