There is described the use of monomeric and polymeric N-pyrrolidinone-containing compounds as compatibilizers for plastic compositions, a process for improving the compatibility of plastic compositions, the improved plastic compositions obtainable thereby as well as novel polymeric N-pyrrolidinone-containing compounds.

The invention relates to the use of monomeric and polymeric N-pyrrolidinone-containing compounds as compatibilisers in plastic compositions, to the improved plastic compositions obtainable thereby as well as to novel polymeric N-pyrrolidinone-containing compounds.
Different plastic materials are usually not miscible, i.e. when two different plastic materials are processed, a macroscopic mixture is obtained which has insufficient mechanical properties. This is not only to be observed in mixtures of nonpolar plastics, e.g. polyethylene, and polar plastics, e.g. polyamide, but also even in the case of e.g. HDPE and LDPE. Such mixtures in the simplest case form a dispersion of the one polymer in the matrix of the other, i.e. a two phase system is obtained. Compatibilisers are polymers which preferably attach themselves to the interface between the polymers involved, or which penetrate into the polymers, thereby improving the adhesion between the polymers involved. The improved connection between matrix and dispersed phase enhances the mechanical properties. In addition, compatibilisers can improve the dispersion of the component and reduce the coagulation of the particles. In some cases, the separation of two-component systems or multicomponent systems can be completely inhibited resulting in a homogeneous blend of different plastic materials which has good mechanical properties.
Compatibilisers are used in virgin plastic compositions, but increasingly also in recyclates. Typical examples are polyethylene/polyamide-coextruded films (PE/PA films), which cannot be separated anymore in simple manner by physical methods. Further examples to be mentioned are PE/PET- and PE/PVC-coextruded films.
The known compatibilisers are mainly based on polymers of polar and nonpolar structure which can be prepared by conventional polymerisation reactions (K. Hausmann, Kunststoffe 1993, (83), 820; G. Obieglo and K. Romer, Kunststoffe, 1993, (83), 926; S. Fuzessery, Recycle 91, D 4.1-D 4.13; K. Hausmann, Kunststoffe 1995, (85), 446-451; S. Fuzessery, Recycle 95, Davos, 6-4.3-6-4.9; R. Mxc3xclhaupt et al., Kunststoffe 1994, (84), 1153-1158.
EP-A-0 602 008 discloses poly-N-vinylpyrrolidones as compatibilisers.
There is still a need to provide compatibilisers by means of which the properties of plastic compositions can be improved in simple manner.
This invention solves this task by using N-pyrrolidinone-containing compounds.
Accordingly, the invention relates to the use of 0.5 to 50% by weight of at least one monomeric or polymeric N-pyrrolidinone-containing compound as compatibiliser for plastic compositions, with the proviso that poly-N-vinylpyrrolidones are excluded.
Some of the N-pyrrolidinone-containing compounds used according to this invention are known from the state of the art, while those compounds which are N-pyrrolidinone-containing graft polymers are novel.
One advantage of the present invention is that the compatibility-improving effect is achieved already at low concentrations of monomeric or polymeric N-pyrrolidinone-containing compound.
Monomeric N-pyrrolidinone-containing compounds are preferably those of formula I
wherein
X is a direct bond or xe2x80x94OCH2CH2xe2x80x94, where the carbon atom is bound to the nitrogen,
R is
R1 is hydrogen, C1-C18alkyl, C6-C14aryl, C6-C13aryl which is substituted by 1 to 3 phenyl or C1-C18alkyl groups; C5-C7cycloalkyl, or C5-C7cycloalkyl which is substituted by 1 to 3 C1-C18alkyl groups,
R2 is hydrogen, C1-C18alkyl, C6-C14aryl, C6-C13aryl which is substituted by 1 to 3 phenyl or C1-C18alkyl groups; C5-C7cycloalkyl, or C5-C7cycloalkyl which is substituted by 1 to 3 C1-C18-alkyl groups, and
R3 is hydrogen, C1-C18alkyl, C6-C14aryl, xe2x80x94COOH, C6-C13aryl which is substituted by 1 to 3 phenyl or C1-C18alkyl groups; C5-C7cycloalkyl, or C5-C7cycloalkyl which is substituted by 1 to 3 C1-C18alkyl groups.
Substituents of formula I defined as alkyl of up to 18 carbon atoms are typically radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl or octadecyl as well as corresponding branched isomers.
Substituents of formula I defined as C5-C7cycloalkyl or C5-C7cycloalkyl which is substituted by 1 to 3 C1-C18alkyl groups are suitably radicals such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, ethylcyclohexyl or ethylcycloheptyl.
Substituents of formula I defined as C6-C14aryl or C6-C13aryl which is substituted by 1 to 3 phenyl or C1-C18alkyl groups are suitably radicals such as phenyl, naphthyl or tert-butylphenyl.
R1 and R2 are preferably hydrogen.
R3 is preferably xe2x80x94COOH; phenyl is unsubstituted or substituted by one C1-C12alkyl radical or phenyl radical.
Very particularly preferred compounds of formula I are those, wherein R1 and R2 are hydrogen and R3 is xe2x80x94COOH; phenyl is unsubstituted by one C1-C12alkyl radical or phenyl radical.
The polymeric N-pyrrolidinone-containing compounds are derived from the above-described monomeric compounds, i.e. they contain at least one structural unit of monomeric compounds. The polymeric N-pyrrolidinone-containing compounds can be obtained by linking the monomeric compounds via the ethylenically unsaturated bond by a radically initiated graft polymerisation on organic polymers. In addition to their use as compatibilisers, these polymeric compounds constitute, as novel substances, a further object of the invention. It is not necessary that the monomer is chemically bonded to 100%. It suffices, for example, that only part of the monomer is chemically bonded (e.g. 10 to 40%) and that the remaining monomer is still in reactive form. A compatibiliser is then obtained which contains polymerically bonded groups as well as low-molecular components which only react when used in the blend and which become effective after reaction or as low-molecular compound.
The incorporation of the ethylenically unsaturated compounds of formula (I) in polymers is carried out by grafting on organic polymers. Organic polymers are mainly hydrocarbon polymers which can be saturated or unsaturated. Saturated hydrocarbons include the polyolefins, typically polyethylene, polypropylene, polybutene or polyisobutene. Unsaturated hydrocarbons include the diene polymers and their copolymers with olefines, typically poly-butadiene, polyisoprene, propylene/butadiene or ethylene/propylene/butadiene. It is preferred to graft on polyolefins, in particular on polyethylene and polypropylene.
Besides the cited and preferred polymers, further novel polymeric N-pyrrolidinone-containing compounds are derived from the polymers in the following list:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
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:
a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either xcfx80- or "sgr"-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(II) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
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, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide 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-norbomene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acid copolymers, LLDPE/ethylene-vinylacetate copolymers, LLDPE/ethylene-acrylic acid copolymers 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.
5. Polystyrene, poly(p-methylstyrene), poly(xcex1-methylstyrene).
6. Copolymers of styrene or xcex1-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, 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.
7. Graft copolymers of styrene or xcex1-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. Polymers derived from (xcex1,xcex2-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
9. 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.
10. 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.
11. Polymers selected from the group consisting of the polyurethanes, polyamides, polyesters, polycarbonates and epoxy resins.
12. Blends of the aforementioned polymers (polyblends), typically 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.
The graft reaction can be carried out with or without solvent. The catalysts used are radical formers such as those used for the homo- or copolymerisation of unsaturated compounds. It is preferred to use radical initiators which separate into radicals during heating, typically organic peroxides or hydroperoxides, azo compounds or redox catalysts. The graft polymerisation can also be initiated by energy-rich radiation.
Suitable reaction apparatus for carrying out the graft reaction are those conventionally used in the chemical industry, and grafting is preferably carried out in a kneader or extruder.
The processing conditions suitable for graft polymerisations are known to those skilled in the art.
Preferred graft polymers are those containing at least 1% by weight, preferably at least 2% by weight, of the N-pyrrolidinone-containing compounds in chemically bonded form.
The invention further relates to plastic compositions containing 0.5 to 50% by weight of at least one monomeric N-pyrrolidinone-containing compound of formula I or of a polymeric N-pyrrolidinone-containing compound, obtainable by a radically initiated graft polymerisation of a compound of formula I with an organic polymer. The preferences indicated for the use of the N-pyrrolidinone-containing compounds apply here analogously. Preferred plastic compositions are those containing 1 to 10% by weight of at least one monomeric N-pyrrolidinone-containing compound. Also preferred are plastic compositions containing, depending on the degree of grafting, 1 to 25% by weight of at least one polymeric N-pyrrolidinone-containing compound.
The novel compatibilisers can in principle be used in all incompatible plastic compositions. Said plastic compositions can consist of two or more than two components. The novel compatibilisers are preferably added to compositions of polar and nonpolar plastics.
The nonpolar components of plastic compositions are typically polyolefins such as polyethylene (PE) and polypropylene (PP). To be mentioned here in particular are low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE), and also copolymers such as ethylene/propylene copolymers (EPM) and ethylene/propylene/diene copolymers (EPDM) as well as ULDPE and MDPE. Such nonpolar plastics also include polystyrene (PS, EPS) as well as copolymers with a styrene component (e.g. ABS, ASA, HIPS, IPS) and polyvinyl chloride (PVC), and also copolymers having a predominant component of vinyl chloride (e.g. CPE).
The polar components are typically polyester, e.g. polyethyleneterephthalate (PET) or PBT, polyamides or polycarbonates.
Mixtures of polyethylene and polypropylene, or polyethylene and polyamide, are particularly preferred.
The use of a N-pyrrolidinone-containing compound as compatibiliser for plastic compositions (as well as the plastic composition itself) also includes plastic compositions from scrap materials (recyclates), such as those coming from households and stores (e.g. supermarkets). Such recyclates mainly consist of packaging material. Said material may typically be films, bags, bottles and other containers, or foams. Other utensils may also be included. However, the recyclates also consist of mixtures of plastics predamaged by use, storage and processing. These materials typically come from useful material collections or obligatory returnable originating from, inter alia, the automotive industry, electro/electronic industry, building and agriculture as well as from the textile industry. In certain plastic wastes, minor amounts of foreign materials may also be present, such as paper, pigments and adhesives which are often difficult to remove. These foreign materials may also originate from contact with diverse substances during use or processing, typically fuel residues, paint components, printing inks, metal traces, initiator residues or also water traces.
The invention further relates to a process for enhancing the compatibility of plastic compositions by adding 0.5 to 50% by weight of at least one monomeric or polymeric N-pyrrolidinone-containing compound to the plastic composition, with the proviso that poly-N-vinylpyrrolidones are excluded. The preferences stated for the use of the N-pyrrolidinone-containing compounds and the plastic compositions apply here analogously.
The process, i.e. the incorporation/blending of the monomeric or polymeric N-pyrrolidinone-containing compound, can conveniently be carried out as follows:
as emulsion or dispersion;
as dry mixture during the blending of additional components or polymer mixtures;
by direct addition into the processing apparatus (e.g. calander, mixer, kneader, extruder and the like), or
as solution or melt.
The novel plastic compositions can be prepared in per se known manner by blending the compatibiliser and further optional additives with the plastic composition using per se known apparatus such as the above-mentioned processing apparatus. The further additives can be added singly or as a mixture, or also in the form of so-called masterbatches.
It is also possible to prepare the compatibiliser and the compatible plastic blend in one process step by adding a monomeric N-pyrrolidinone-containing compound and a radical initiator to the plastic blend direct during the processing of the blend, i.e. without prior separate preparation of the compatibiliser.
The plastic compositions of this invention can be brought into the desired shape by known methods. Such methods are, for example, grinding, calandering, extruding, injection moulding, sintering or spinning as well as extrusion blow moulding, or processing according to the plastisol process.
The optional further additives are mainly the conventional stabilisers of plastics processing and are known to the person skilled in the art. The further additives are used in the conventional amounts and combinations described in more detail in the relevant literature (e.g. xe2x80x9cPlastics Additivesxe2x80x9d, Gxc3xa4chter/Mxc3xcller, Hanser Verlag, Mxc3xcnchen/Wien/New York, 3rd edition) and typically include:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 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-(xcex1-methylcyclohexyl)-4,6-di-methylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1xe2x80x2-methylundec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methylheptadec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methyltridec-1xe2x80x2-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butyiphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthio-methyl-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. Chroman derivatives of formula
wherein R is xe2x80x94(CH2)3xe2x80x94CH(CH3)xe2x80x94(CH2)3xe2x80x94CH(CH3)xe2x80x94CH2)3xe2x80x94CH(CH3)2 or xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94C(O)xe2x80x94Z, and Z is C1-C18alkyl, xe2x80x94CH2xe2x80x94CH2xe2x80x94Sxe2x80x94C1xe2x80x94C18alkyl or
wherein Rxe2x80x2 or Rxe2x80x3 is H, CH3 or tert-butyl; e.g. xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, xcex4-tocopherol and mixtures thereof (vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2xe2x80x2-thiobis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-thiobis(4-octylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-3-methylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-2-methylphenol), 4,4xe2x80x2-thiobis(3,6-di-sec-amylphenol), 4,4xe2x80x2-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
1.6. Alkylidenebisphenols, for example 2,2xe2x80x2-methylenebis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-methylenebis(6-tert-butyl-4-ethylphenol), 2,2xe2x80x2-methylenebis[4-methyl-6-(xcex1-methylcyclohexyl)phenol], 2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylenebis(6-nonyl-4-methylphenol), 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(4,6-di-tert-butyl-phenol), 2,2xe2x80x2-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2xe2x80x2-methylenebis[6-(xcex1-methylbenzyl)-4-nonylphenol], 2,2xe2x80x2-methylenebis[6-(xcex1,xcex1-dimethylbenzyl)-4-nonylphenol], 4,4xe2x80x2-methylenebis(2,6-di-tert-butylphenol), 4,4xe2x80x2-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-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)di-cyclopentadiene, bis[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylbenzyl)-6-tert-butyl-4-methyl-phenyl]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 3,5,3xe2x80x2,5xe2x80x2-tetra-tert-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, 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, di-dodecylmercaptoethyl-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. Benzylihosphonates, 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 xcex2-(3,5-di-tert-butyl-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,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
11.14. Esters of xcex2-(5-tert-butyl-4-hydroxy-3-methylphenyl)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,Nxe2x80x2-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of xcex2-(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,Nxe2x80x2-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,Nxe2x80x2-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 xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,Nxe2x80x2-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
2. UV Absorbers and Light Stabilisers
2.1. 2-(2xe2x80x2-Hydroxyphenyl)benzotriazoles, for example 2-(2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-4xe2x80x2-octyloxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-amyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-bis(xcex1,xcex1-dimethylbenzyl)-2xe2x80x2-hydroxyphenyl)benzotriazole, mixture of 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)-carbonylethyl]-2xe2x80x2-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2-dodecyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, and 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-isooctyloxycarbonylethyl)phenyl-benzotriazole, 2,2xe2x80x2-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterifica tion product of 2-[3xe2x80x2-tert-butyl-5xe2x80x2-(2-methoxycarbonylethyl)-2xe2x80x2-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300;
[RCH2CH2COO(CH2)3"Brketclosest"2
xe2x80x83where R=3xe2x80x2-tert-butyl-4xe2x80x2-hydroxy-5xe2x80x2-2H-benzotriazol-2-ylphenyl.
2.2.2-Hydroxybenzophenone, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2xe2x80x2,4xe2x80x2-trihydroxy and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 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 xcex1-cyano-xcex2,xcex2-diphenylacrylate, isooctyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, methyl xcex1-carbomethoxycinnamate, methyl xcex1-cyano-xcex2-methyl-p-methoxycinnamate, butyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate, methyl xcex1-carbomethoxy-p-methoxycinnamate and N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2xe2x80x2-thiobis4-(1,1,3,3-tetra-methylbutyl)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-methylphenyl undecylketoxime, 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-tetramethylpiperidyl)sebacate, bis-(2,2,6,6-tetramethylpiperidyl)succinate, bis(1,2,2,6,6-pentamethylpiperidyl)sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) 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, the condensate of N,Nxe2x80x2-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-butane-tetracarboxylate, 1,1xe2x80x2-(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-pentamethylpipedyl)-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]-decan-2,4-dion, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N,Nxe2x80x2-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)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione.
2.7. Oxamides, for example 4,4xe2x80x2-dioctyloxyoxanilide, 2,2xe2x80x2-diethoxyoxanilide, 2,2xe2x80x2-dioctyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2,2xe2x80x2-didodecyloxy-5,5xe2x80x2-di-tert-butoxanilide, 2-ethoxy-2xe2x80x2-ethyloxanilide, N,Nxe2x80x2-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethoxyanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butoxanilide and mixtures of ortho- and para-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-propyl-oxyphenyl)-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-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine.
3. Metal deactivators, for example N,Nxe2x80x2-diphenyloxamide, N-salicylal-Nxe2x80x2-salicyloyl hydrazine, N,Nxe2x80x2-bis(salicyloyl) hydrazine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N,Nxe2x80x2-diacetyladipoyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)oxalyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) 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) 4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite.
5. Peroxide scavengers, for example esters of xcex2-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(xcex2-dodecylmercapto)propionate.
6. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
7. 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 tin pyrocatecholate.
8. Nucleating agents, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
10. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
11. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 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-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3xe2x80x2-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-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
The following Examples further illustrate the invention. In the Examples as well as throughout the remainder of the description, parts and percentages are by weight, unless otherwise stated.
Preparation of the Compatibilisers


A mobile phone messaging system and method for managing display of messages to mobile phone users. A mobile client application operates at user's mobile phone. Mobile content providers manage the display of messages and related interactions throughout a specific period of time (e.g., daily, weekly, bi-weekly). Phone wakeup time data and message identifying data are transmitted from a mobile content provider server to a mobile phone. The wakeup time data and message identifying data are stored in the phone. The wakeup times are also added to a registry at the phone that facilitates launching of applications at the times indicated in the registry. At the specified wakeup times, the mobile client application determines the message identifying data associated with the wakeup time, connects to the mobile content provider server, and provides the message identifying data. The provider responds with a specific message and the mobile client application displays the message.

As mobile computing services as well as powerful mobile computing devices have proliferated, people increasingly view their cell phones and other mobile devices as their communication medium of choice. Mobile based services are wide ranging and include not only basic telecommunications and text messaging services but also web browsing and information retrieval, games, music, and even movie and television viewing. Although mobile phones may be used for personal activities such as maintaining contact with family and friends as well as for recreational activities such as listening to music and playing games, people also rely on them for important business and emergency communications. As a result, many mobile phone users make certain their phones are always available and always on. The portability of the mobile phone coupled with the variety of features and functionality that are supported have caused many people to choose mobile devices and services over traditional desktop devices and wire services for all kinds of communications.
Because mobile phones are the preferred method of communication for many people, they are using them to receive more and more text-based communications in addition to phone calls and audio messages. To respond to the preference of mobile phone users to receive all communications by phone, mobile content providers are developing applications for transmitting messages that conform to various current messaging standards. One messaging protocol that is commonly used is the Short Message Service (SMS) protocol. The protocol supports transmission of text only messages of a limited size. Messages are transmitted through message centers or gateways and held for delivery to recipients. Typically, users select a messaging icon to access the messages. While most messages are successfully delivered, there are limits associated with the use of SMS protocol for text messaging. There are limits on the size of the messages and sending and responding to such messages requires mobile phone users to use the numeric keypad to enter text. The process of drafting a message is time consuming and error-prone. As a result, many people use shorthand and acronyms that save time but are not necessarily understood or decipherable by the recipient. In addition, a per message cost is typically charged to the sender and the recipient for every SMS message that is transmitted to a mobile phone.
An alternative to SMS protocol for text messaging is the use of the Wireless Application Protocol (WAP). Use of the protocol requires users to install a special WAP browser on their mobile phones. WAP is typically used for transmission of email messages and for access to websites. When accessing websites, data from the site is converted to Wireless Markup Language (WML) and accessed via the WAP browser. Although WAP supports graphics in addition to text, it effectively requires the provider to customize content for delivery to mobile phones and does not support all of the features and functionality of HTML. For many mobile content providers, its appeal as a communications platform is limited because development and maintenance of WAP applications is costly and the protocol has limited features and functionality.
While the use of SMS protocol and WAP are adequate for many applications, they do not provide much more than basic functionality for receiving and delivering messages. As mobile content providers vie for the attention of mobile phone users, they want to be sure that their messages are not only delivered but viewed as well. One way to be sure that a message is viewed is to ask the recipient for confirmation that the message was received and viewed. Because interaction using SMS protocol requires use of the numeric keypad as a typewriter, providing such confirmation is cumbersome. The content of the return message depends upon what the user types and therefore, in some cases, the user's response may not be recognized by the provider's application. From the content provider's standpoint, the message is never acknowledged even though the user may have viewed it.
The use of WAP facilitates more interaction between the mobile phone user and content provider due to the use of graphics that can provide interactivity. Limitations related to use of WML, however, can compromise the interactivity because all of the content must be customized for use in a mobile environment. The standard is specific to mobile devices and therefore, development and maintenance of applications can be costly to a developer.
Even if SMS protocol and WAP are adequate for a mobile content provider's needs, they provide only functionality for delivering messages or content. The protocols are not designed for message management. If the mobile phone is off or unavailable, the messages are not delivered. The message centers or gateways that support the protocols may provide some delivery support and continue trying to deliver a certain message until a specified number of failures occur. Additional support is not provided. In particular, the phone does not have information or data from the mobile content provider that the provider might be trying to deliver a message.
Effective messaging for mobile content providers often involves not only knowing that messages were delivered to and viewed by users but also knowing that the recipients viewed them in a timely manner. For important or urgent communications, mobile content providers would like acknowledgment from their users that a particular message was viewed during a particular timeframe. Although the mobile phone itself can provide some feedback in this regard, in many instances, an explicit acknowledgment from the user is the only way to know that a message was actually communicated to the user. Furthermore, in some instances, the mobile content provider may want the mobile phone user to provide more than an acknowledgment of receipt. In some cases, the mobile content provider may want to know the mobile phone user's response to a particular query. In such instances, the ability to respond with more than a "yes" or "no" answer is important. Therefore, the ability for mobile content providers and mobile phone users to interact in a particular way is important.
There is a need for mobile phone messaging technology that facilitates mobile phone user and mobile content provider interaction. There is a need for a mobile phone messaging system and method that supports highly interactive communications between mobile content providers and mobile phone users. There is a need for a mobile phone messaging system and method that supports graphic-based as well as text-based communication so that users can respond easily to messages provided by mobile content providers. There is a need for a mobile phone messaging system and method that allows mobile content providers to manage timely display of messages and user reactions to messages.

Mobile client application for managing display of messages to users


A premium synthetic lubricating oil base stock having a high VI and low pour point is made by hydroisomerizing a Fischer-Tropsch synthesized waxy, paraffinic feed wax and then dewaxing the hydroisomerate to form a 650-750xc2x0 F.+ dewaxate. The waxy feed has an initial boiling point in the range of about 650-750xc2x0 F., from which it continuously boils up to at least 1050xc2x0 F. and has a T90xe2x88x92T10 temperature difference of at least 350xc2x0 F. The feed is preferably hydroisomerized without any pretreatment, other than optional fractionation. The 650-750xc2x0 F.+ dewaxate is fractionated into two or more base stocks of different viscosity.

The invention relates to premium synthetic lubricant base stocks derived from waxy Fischer-Tropsch hydrocarbons, their preparation and use. More particularly the invention relates to a high VI and low pour point synthetic lubricating oil base stock made by reacting H2 and CO in the presence of a Fischer-Tropsch catalyst to form waxy hydrocarbons boiling in the lubricating oil range, hydroisomerizing the waxy hydrocarbons having an initial boiling point in the range of 650-750xc2x0 F., dewaxing the hydroisomerate, removing light ends from the dewaxate and fractionating to recover a plurality of base stocks from the dewaxate.
Current trends in the design of automotive engines require higher quality crankcase and transmission lubricating oils with high VI""s and low pour points. Processes for preparing lubricating oils of low pour point from petroleum derived feeds typically include atmospheric and/or vacuum distillation of a crude oil (and often deasphalting the heavy fraction), solvent extraction of the lube fraction to remove aromatic unsaturates and form a raffinate, hydrotreating the raffinate to remove heteroatom compounds and aromatics, followed by either solvent or catalytically dewaxing the hydrotreated raffinate to reduce the pour point of the oil. Some synthetic lubricating oils are based on a polymerization product of polyalphaolefins (PAO). These lubricating oils are expensive and can shrink seals. In the search for synthetic lubricating oils, attention has recently been focused on Fischer-Tropsch wax that has been synthesized by reacting H2 with CO.
Fischer-Tropsch wax is a term used to describe waxy hydrocarbons produced by a Fischer-Tropsch hydrocarbon synthesis processes in which a synthesis gas feed comprising a mixture of H2 and CO is contacted with a Fischer-Tropsch catalyst, so that the H2 and CO react under conditions effective to form hydrocarbons. U.S. Pat. No. 4,943,672 discloses a process for converting waxy Fischer-Tropsch hydrocarbons to a lube oil base stock having a high (viscosity index) VI and a low pour point, wherein the process comprises sequentially hydrotreating, hydroisomerizing, and solvent dewaxing. A preferred embodiment comprises sequentially (i) severely hydrotreating the wax to remove impurities and partially convert it, (ii) hydroisomerizing the hydrotreated wax with a noble metal on a fluorided alumina catalyst, (iii) hydrorefining the hydroisomerate, (iv) fractionating the hydroisomerate to recover a lube oil fraction, and (v) solvent dewaxing the lube oil fraction to produce the base stock. European patent publication EP 0 668 342 A1 suggests a processes for producing lubricating base oils by hydrogenating or hydrotreating and then hydroisomerizing a Fischer-Tropsch wax or waxy raffinate, followed by dewaxing, while EP 0 776 959 A2 recites hydroconverting Fischer-Tropsch hydrocarbons having a narrow boiling range, fractionating the hydroconversion effluent into heavy and light fractions and then dewaxing the heavy fraction to form a lubricating base oil having a VI of at least 150.
Lubricant base stocks are produced by (i) hydroisomerizing waxy, Fischer-Tropsch synthesized hydrocarbons having an initial boiling point in the range of 650-750xc2x0 F. and an end point of at least 1050xc2x0 F. (hereinafter xe2x80x9cwaxy feedxe2x80x9d) to form a hydroisomerate having an initial boiling point in said 650-750xc2x0 F. range, (ii) dewaxing the 650-750xc2x0 F.+ hydroisomerate to reduce its pour point and form a 650-750xc2x0 F.+ dewaxate, and (iii) fractionating the 650-750xc2x0 F.+ dewaxate to form two or more fractions of different viscosity as the base stocks. These base stocks are premium synthetic lubricating oil base stocks of high purity having a high VI, a low pour point and are isoparaffinic, in that they comprise at least 95 wt. % of non-cyclic isoparaffins having a molecular structure in which less than 25% of the total number of carbon atoms are present in the branches, and less than half the branches have two or more carbon atoms. The base stock of the invention and those comprising PAO oil differ from oil derived from petroleum oil or slack wax in an essentially nil heteroatom compound content and in comprising essentially non-cyclic isoparaffins. However, whereas a PAO base stock comprises essentially star-shaped molecules with long branches, the isoparaffins making up the base stock of the invention have mostly methyl branches. This is explained in detail below. Both the base stocks of the invention and fully formulated lubricating oils using them have exhibited properties superior to PAO and conventional mineral oil derived base stocks, and corresponding formulated lubricating oils. The present invention relates to these base stocks and to a process for making them. Further, while in many cases it will be advantageous to employ only the base stock of the invention for a particular lubricant, in other cases the base stock of the invention may be mixed or blended with one or more base stocks selected from the group consisting of (a) a hydrocarbonaceous base stock, (b) a synthetic base stock, and mixture thereof Typical examples include base stocks derived from (i) PAO, (ii) mineral oil, (iii) a mineral oil slack wax hydroisomerate, and mixture thereof Because the base stocks of the invention and lubricating oils based on these base stocks are different, and most often superior to, lubricants formed from other base stocks, it will be obvious to the practitioner that a blend of another base stock with at least 20, preferably at least 40 and more preferably at least 60 wt. % of the base stock of the invention, will still provide superior properties in many most cases, although to a lesser degree than only if the base stock of the invention is used.
The waxy feed used in the process of the invention comprises waxy, highly paraffinic and pure Fischer-Tropsch synthesized hydrocarbons (sometimes referred to as Fischer-Tropsch wax) having an initial boiling point in the range of from 650-750xc2x0 F. and continuously boiling up to an end point of at least 1050xc2x0 F., and preferably above 1050xc2x0 F. (105xc2x0F+), with a T90xe2x88x92T10 temperature spread of at least 350xc2x0 F. The temperature spread refers to the temperature difference in xc2x0 F. between the 90 wt. % and 10 wt. % boiling points of the waxy feed, and by waxy is meant including material which solidifies at standard conditions of room temperature and pressure. The hydroisomerization is achieved by reacting the waxy feed with hydrogen in the presence of a suitable hydroisomerization catalyst and preferably a dual function catalyst which comprises at least one catalytic metal component to give the catalyst a hydrogenation/dehydrogenation function and an acidic metal oxide component to give the catalyst an acid hydroisomerization function. Preferably the hydroisomerization catalyst comprises a catalytic metal component comprising a Group VIB metal component, a Group VIII non-noble metal component and an amorphous alumina-silica component. The hydroisomerate is dewaxed to reduce the pour point of the oil, with the dewaxing achieved either catalytically or with the use of solvents, both of which are well known dewaxing processes, with the catalytic dewaxing achieved using any of the well known shape selective catalysts useful for catalytic dewaxing. Both hydroisomerization and catalytic dewaxing convert a portion of the 650-750xc2x0 F.+ matenal to lower boiling (650-750xc2x0 F.xe2x88x92) hydrocarbons. In the practice of the invention, it is preferred that a slurry Fischer-Tropsch hydrocarbon synthesis process be used for synthesizing the waxy feed and particularly one employing a Fischer-Tropsch catalyst comprising a catalytic cobalt component to provide a high alpha for producing the more desirable higher molecular weight paraffins. These processes are also well known to those skilled in the art.
The waxy feed preferably comprises the entire 650-750xc2x0 F.+ fraction formed by the hydrocarbon synthesis process, with the exact cut point between 650xc2x0 F. and 750xc2x0 F. being determined by the practitioner and the exact end point preferably above 1050xc2x0 F. determined by the catalyst and process variables used for the synthesis. The waxy feed also comprises more than 90%, typically more than 95% and preferably more than 98 wt. % paraffinic hydrocarbons, most of which are normal paraffins. It has negligible amounts of sulfur and nitrogen compounds (e.g., less than 1 wppm), with less than 2,000 wppm, preferably less than 1,000 wppm and more preferably less than 500 wppm of oxygen, in the form of oxygenates. Waxy feeds having these properties and useful in the process of the invention have been made using a slurry Fischer-Tropsch process with a catalyst having a catalytic cobalt component.
In contrast to the process disclosed in U.S. Pat. No. 4,943,672 referred to above, the waxy feed need not be hydrotreated prior to the hydroisomerization and this is a preferred embodiment in the practice of the invention. Eliminating the need for hydrotreating the Fischer-Tropsch wax is accomplished by using the relatively pure waxy feed, and preferably in combination with a hydroisomerization catalyst resistant to poisoning and deactivation by oxygenates that may be present in the feed. This is discussed in detail below. After the waxy feed has been hydroisomerized, the hydroisomerate is typically sent to a fractionater to remove the 650-750xc2x0 F.xe2x88x92 boiling fraction and the remaining 650-750xc2x0 F+ hydroisomerate dewaxed to reduce its pour point and form a dewaxate comprising the desired lube oil base stock. If desired however, the entire hydroisomerate may be dewaxed. If catalytic dewaxing is used, that portion of the 650-750xc2x0 F.+ material converted to lower boiling products is removed or separated from the 650-750xc2x0F.+ lube oil base stock by fractionation, and the 650-750xc2x0 F.+dewaxate fractionated separated into two or more fractions of different viscosity, which are the base stocks of the invention. Similarly, if the 650-750xc2x0 F.xe2x88x92 material is not removed from the hydroisomerate prior to dewaxing, it is separated and recovered during fractionation of the dewaxate into the base stocks.
The composition of the base stock of the invention is different from one derived from a conventional petroleum oil or slack wax, or a PAO. The base stock of the invention comprises essentially (xe2x89xa799+wt. %) all saturated, paraffinic and non-cyclic hydrocarbons. Sulfur, nitrogen and metals are present in amounts of less than I wppm and are not detectable by x-ray or Antek Nitrogen tests. While very small amounts of saturated and unsaturated ring structures may be present, they are not identifiable in the base stock by presently known analytical methods, because the concentrations are so small. While the base stock of the invention is a mixture of various molecular weight hydrocarbons, the residual normal paraffin content remaining after hydroisomerization and dewaxing will preferably be less than 5 wt. % and more preferably less than 1 wt. %, with at least 50% of the oil molecules containing at least one branch, at least half of which are methyl branches. At least half, and more preferably at least 75% of the remaining branches are ethyl, with less than 25% and preferably less than 15% of the total number of branches having three or more carbon atoms. The total number of branch carbon atoms is typically less than 25% , preferably less than 20% and more preferably no more than 15% (e.g., 10-15% ) of the total number of carbon atoms comprising the hydrocarbon molecules. PAO oils are a reaction product of alphaolefins, typically 1-decene and also comprise a mixture of molecules. However, in contrast to the molecules of the base stock of the invention which have a more linear structure comprising a relatively long back bone with short branches, the classic textbook description of a PAO is a star-shaped molecule, and in particular, tridecane which is illustrated as three decane molecules attached at a central point. PAO molecules have fewer and longer branches than the hydrocarbon molecules that make up the base stock of the invention. Thus, the molecular make up of a base stock of the invention comprises at least 95 wt. % isoparaffins having a relatively linear molecular structure, with less than half the branches having two or more carbon atoms and less than 25% of the total number of carbon atoms present in the branches.
As those skilled in the art know, a lubricating oil base stock is an oil possessing lubricating qualities boiling in the general lubricating oil range and is useful for preparing various lubricants such as lubricating oils and greases. Fully formulated lubricating oils (hereinafter xe2x80x9clube oilxe2x80x9d) are prepared by adding to the base stock an effective amount of at least one additive or, more typically, an additive package containing more than one additive, wherein the additive is at least one of a detergent, a dispersant, an antioxidant, an antiwear additive, a pour point depressant, a VI improver, a friction modifier, a demulsifier, an antifoamant, a corrosion inhibitor, and a seal swell control additive. Of these, those additives common to most formulated lubricating oils include a detergent or dispersant, an antioxidant, an antiwear additive and a VI improver, with others being optional depending on the intended use of the oil. An effective amount of one or more additives or an additive package containing one or more such additives is added to or blended into the base stock to meet one or more specifications, such as those relating to a lube oil for an internal combustion engine crankcase, an automatic transmission, a turbine or jet, hydraulic oil, etc., as is known. Various manufacturers sell such additive packages for adding to a base stock or to a blend of base stocks to form fully formulated lube oils for meeting performance specifications required for different applications or intended uses, and the exact identity of the various additives present in an additive pack is typically maintained as a trade secret by the manufacturer. Thus, additive packages can and often do contain many different chemical types of additives and the performance of the base stock of the invention with a particular additive or additive package can not be predicted a priori. That its performance differs from that of conventional and PAO oils with the same level of the same additives is itself proof of the chemistry of the base stock of the invention being different from that of the prior art base stocks. As set forth above, in many cases it will be advantageous to employ only a base stock derived from waxy Fischer-Tropsch hydrocarbons for a particular lubricant, while in other cases one or more additional base stocks may be mixed with, added to or blended with one or more of the Fischer-Tropsch derived base stocks. Such additional base stocks may be selected from the group consisting of (i) a hydrocarbonaceous base stock, (ii) a synthetic base stock and mixture thereof By hydrocarbonaceous is meant a primarily hydrocarbon type base stock derived from a conventional mineral oil, shale oil, tar, coal liquefaction, mineral oil derived slack wax, while a synthetic base stock will include a PAO, polyester types and other synthetics. Fully formulated lube oils made from the base stock of the invention have been found to perform at least as well as, and often superior to, formulated oils based on either a PAO or a conventional petroleum oil derived base stock. Depending on the application, using the base stock of the invention can mean that lower levels of additives are required for an improved performance specification, or an improved lube oil is produced at the same additive levels.
During hydroisomerization of the waxy feed, conversion of the 650-750xc2x0 F.+fraction to material boiling below this range (lower boiling material, 650-750xc2x0 F.xe2x88x92) will range from about 20-80 wt. %, preferably 30-70% and more preferably from about 30-60% , based on a once through pass of the feed through the reaction zone. The waxy feed will typically contain 650-750xc2x0 F.xe2x88x92 material prior to the hydroisomerization and at least a portion of this lower boiling material will also be converted into lower boiling components. Any olefins and oxygenates present in the feed are hydrogenated during the hydroisomerization. The temperature and pressure in the hydroisomezization reactor will typically range from 300-900xc2x0 F. (149-482xc2x0 C.) and 300-2500 psig, with preferred ranges of 550-750xc2x0 F. (288-400xc2x0 C.) and 300-1200 psig, respectively. Hydrogen treat rates may range from 500 to 5000 SCFAB, with a preferred range. of 2000-4000 SCF/B. The hydroisomerization catalyst comprises one or more Group VII catalytic metal components, and preferably non-noble catalytic metal component(s), and an acidic metal oxide component to give the catalyst both a hydrogenation/dehydrogenation function and an acid hydrocracking function for hydroisomerizing the hydrocarbons. The catalyst may also have one or more Group VIB metal oxide promoters and one or more Group IB metals as a hydrocracking suppressant. In a preferred embodiment the catalytically active metal comprises cobalt and molybdenum. In a more preferred embodiment the catalyst will also contain a copper component to reduce hydrogenolysis. The acidic oxide component or carrier may include, alumina, silica-alumina, silica-alumina-phosphates, titania, zirconia, vanadia, and other Group II, IV, V or VI oxides, as well as various molecular sieves, such as X, Y and Beta sieves. The elemental Groups referred to herein are those found in the Sargent-Welch Periodic Table of the Elements, (copyright) 1968. It is preferred that the acidic metal oxide component include silica-alumina and particularly amorphous silica-alumina in which the silica concentration in the bulk support (as opposed to surface silica) is less than about 50 wt. % and preferably less than 35 wt. %. A particularly preferred acidic oxide component comprises amorphous silica-alumina in which the silica content ranges from 10-30 wt. %. Additional components such as silica, clays and other materials as binders may also be used. The surface area of the catalyst is in the range of from about 180-400 m2/g, preferably 230-350 m2/g, with a respective pore volume, bulk density and side crushing strength in the ranges of 0.3 to 1.0 mL/g and preferably 0.35-0.75 mL/g; 0.5-1.0 g/rL, and 0.8-3.5 kg/mm. A particularly preferred hydroisomerization catalyst comprises cobalt, molybdenum and, optionally, copper, together with an amorphous silica-alumina component containing about 20-30 wt. % silica. The preparation of such catalysts is well known and documented. Illustrative, but non-limiting examples of the preparation and use of catalysts of this type may be found, for example, in U.S. Pat. No. 5,370,788 and 5,378,348. As was stated above, the hydroisomerization catalyst is most preferably one that is resistant to deactivation and to changes in its selectivity to isoparaffin formation. It has been found that the selectivity of many otherwise useful hydroisomerization catalysts will be changed and that the catalysts will also deactivate too quickly in the presence of sulfur and nitrogen compounds, and also oxygenates, even at the levels of these materials in the waxy feed. One such example comprises platinum or other noble metal on halogenated aluimina, such as fluorided alumina, from which the fluorine is stripped by the presence of oxygenates in the waxy feed. A hydroisomerization catalyst that is particularly preferred in the practice of the invention comprises a composite of both cobalt and molybdenum catalytic components and an amorphous alumina-silica component, and most preferably one in which the cobalt component is deposited on the amorphous silica-alumina and calcined before the molybdenum component is added. This catalyst will contain from 10-20 wt. % MoO3 and 2-5 wt. % CoO on an amorphous alumina-silica support component in which the silica content ranges from 10-30 wt. % and preferably 20-30 wt. % of this support component. This catalyst has been found to have good selectivity retention and resistance to deactivation by oxygenates, sulfur and nitrogen compounds found in the Fischer-Tropsch produced waxy feeds. The preparation of this catalyst is disclosed in U.S. Pat. Nos. 5,756,420 and 5,750,819, the disclosures of which are incorporated herein by reference. It is still further preferred that this catalyst also contain a Group IB metal component for reducing hydrogenolysis. The entire hydroisomerate formed by hydroisomerizing the waxy feed may be dewaxed, or the lower boiling, 650-750xc2x0 F.xe2x88x92 components may be removed by rough flashing or by fractionation prior to the dewaxing, so that only the 650-750xc2x0 F.+components are dewaxed. The choice is determined by the practitioner. The lower boiling components may be used for fuels.
The dewaxing step may be accomplished using either well known solvent or catalytic dewaxing processes and either the entire hydroisomerate or the 650-750xc2x0 F.+ fraction may be dewaxed, depending on the intended use of the 650-750xc2x0 F.xe2x88x92 material present, if it has not been separated from the higher boiling material prior to the dewaxing. In solvent dewaxing, the hydroisomerate may be contacted with chilled ketone and other solvents such as acetone, MEK, MIBK and the like and further chilled to precipitate out the higher pour point material as a waxy solid which is then separated from the solvent-containing lube oil fraction which is the raffinate. The raffinate is typically further chilled in scraped surface chillers to remove more wax solids. Low molecular weight hydrocarbons, such as propane, are also used for dewaxing, in which the hydroisomerate is mixed with liquid propane, a least a portion of which is flashed off to chill down the hydroisomerate to precipitate out the wax. The wax is separated from the raffinate by filtration, membranes or centrifugation. The solvent is then stripped out of the raffinate, which is then fractionated to produce the base stocks of the invention. Catalytic dewaxing is also well known in which the hydroisomerate is reacted with hydrogen in the presence of a suitable dewaxing catalyst at conditions effective to lower the pour point of the hydroisomerate. Catalytic dewaxing also converts a portion of the hydroisomerate to lower boiling, 650-750xc2x0 F.xe2x88x92 materials, which are separated from the heavier 650-750xc2x0 F.+ base stock fraction and the base stock fraction fractionated into two or more base stocks. Separation of the lower boiling material may be accomplished either prior to or during fraction of the 650-750xc2x0 F.+material into the desired base stocks.
The practice of the invention is not limited to the use of any particular dewaxing catalyst, but may be practiced with any dewaxing catalyst which will reduce the pour point of the hydroisomerate and preferably those which provide a reasonably large yield of lube oil base stock from the hydroisomerate. These include shape selective molecular sieves which, when combined with at least one catalytic metal component, have been demonstrated as useful for dewaxing petroleum oil fractions and slack wax and include, for example, ferrierite, mordenite, ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-22 also known as theta one or TON, and the silicoaluminophosphates known as SAPO""s. A dewaxing catalyst which has been found to be unexpectedly particularly effective in the process of the invention comprises a noble metal, preferably Pt, composited with H-mordenite. The dewaxing may be accomplished with the catalyst in a fixed, fluid or slurry bed. Typical dewaxing conditions include a temperature in the range of from about 400-600xc2x0 F., a pressure of 500-900 psig, H2 treat rate of 1500-3500 SCF/B for flow-through reactors and LHSV of 0.1-10, preferably 0.2-2.0. The dewaxing is typically conducted to convert no more than 40 wt. % and preferably no more than 30 wt. % of the hydroisomerate having an initial boiling point in the range of 650-750xc2x0 F. to material boiling below its initial boiling point.
In a Fischer-Tropsch hydrocarbon synthesis process, a synthesis gas comprising a mixture of H2 and CO is catalytically converted into hydrocarbons and preferably liquid hydrocarbons. The mole ratio of the hydrogen to the carbon monoxide may broadly range from about 0.5 to 4, but which is more typically within the range of from about 0.7 to 2.75 and preferably from about 0.7 to 2.5. As is well known, Fischer-Tropsch hydrocarbon synthesis processes include processes in which the catalyst is in the form of a fixed bed, a fluidized bed and as a slurry of catalyst particles in a hydrocarbon slurry liquid. The stoichiometric mole ratio for a Fischer-Tropsch hydrocarbon synthesis reaction is 2.0, but there are many reasons for using other than a stoichiometric ratio as those skilled in the art know and a discussion of which is beyond the scope of the present invention. In a slurry hydrocarbon synthesis process the mole ratio of the H2 to CO is typically about 2.1/1. The synthesis gas comprising a mixture of H2 and CO is bubbled up into the bottom of the slurry and reacts in the presence of the particulate Fischer-Tropsch hydrocarbon synthesis catalyst in the slurry liquid at conditions effective to form hydrocarbons, at portion of which are liquid at the reaction conditions and which comprise the hydrocarbon slurry liquid. The synthesized hydrocarbon liquid is typically separated from the catalyst particles as filtrate by means such as simple filtration, although other separation means such as centrifugation can be used. Some of the synthesized hydrocarbons are vapor and pass out the top of the hydrocarbon synthesis reactor, along with unreacted synthesis gas and gaseous reaction products. Some of these overhead hydrocarbon vapors are typically condensed to liquid and combined with the hydrocarbon liquid filtrate. Thus, the initial boiling point of the filtrate will vary depending on whether or not some of the condensed hydrocarbon vapors have been combined with it. Slurry hydrocarbon synthesis process conditions vary somewhat depending on the catalyst and desired products. Typical conditions effective to form hydrocarbons comprising mostly C5+paraffins, (e.g., C5+-C200) and preferably C10+paraffins, in a slurry hydrocarbon synthesis process employing a catalyst comprising a supported cobalt component include, for example, temperatures, pressures and hourly gas space velocities in the range of from about 320-600xc2x0 F., 80-600 psi and 100-40,000 V/hrNV, expressed as standard volumes of the gaseous CO and H2 mixture (0xc2x0 C., 1 atm) per hour per volume of catalyst, respectively. In the practice of the invention, it is preferred that the hydrocarbon synthesis reaction be conducted under conditions in which little or no water gas shift reaction occurs and more preferably with no water gas shift reaction occurring during the hydrocarbon synthesis. It is also preferred to conduct the reaction under conditions to achieve an alpha of at least 0.85, preferably at least 0.9 and more preferably at least 0.92, so as to synthesize more of the more desirable higher molecular weight hydrocarbons. This has been achieved in a slurry process using a catalyst containing a catalytic cobalt component. Those skilled in the art know that by alpha is meant the Schultz-Flory kinetic alpha. While suitable Fischer-Tropsch reaction types of catalyst comprise, for example, one or more Group VIII catalytic metals such as Fe, Ni, Co, Ru and Re, it is preferred in the process of the invention that the catalyst comprise a cobalt catalytic component In one embodiment the catalyst comprises catalytically effective amounts of Co and one or more of Re, Ru, Fe, Ni, Th, Zr, Hf. U, Mg and La on a suitable inorganic support material, preferably one which comprises one or more refractory metal oxides. Preferred supports for Co containing catalysts comprise titania, particularly. Useful catalysts and their preparation are known and illustrative, but nonlimiting examples may be found, for example, in U.S. Pat. Nos. 4,568,663; 4,663,305; 4,542,122; 4,621,072 and 5,545,674.
As set forth above under the SUMMARY, the waxy feed used in the process of the invention comprises waxy, highly paraffinic and pure Fischer-Tropsch synthesized hydrocarbons (sometimes referred to as Fischer-Tropsch wax) having an initial boiling point in the range of from 650-750xc2x0 F. and continuously boiling up to an end point of at least 1050xc2x0 F., and preferably above 1050xc2x0 F. (1050xc2x0 F.+), with a T90xe2x88x92T10 temperature spread of at least 3500xc2x0 F. The temperature spread refers to the temperature difference in xc2x0 F. between the 90 wt. % and 10 wt. % boiling points of the waxy feed, and by waxy is meant including material which solidifies at standard conditions of room temperature and pressure. The temperature spread, while being at least 350xc2x0 F., is preferably at least 400xc2x0 F. and more preferably at least 450xc2x0 F. and may range between 350xc2x0 F. to 700xc2x0 F. or more. Waxy feed obtained from a slurry Fischer-Tropsch process employing a catalyst comprising a composite of a catalytic cobalt component and a titania component have been made having T10 and T90 temperature spreads of as much as 490xc2x0 F. and even 600xc2x0 F., having more than 10 wt. % of 1050xc2x0 F.+ material and even more than 15 wt. % of 1050xc2x0 F.+ material, with respective initial and end boiling points of 500xc2x0 F.-1245xc2x0 F. and 350xc2x0 F.-1220xc2x0 F. Both of these samples continuously boiled over their entire boiling range. The lower boiling point of 350xc2x0 F. was obtained by adding some of the condensed hydrocarbon overhead vapors from the reactor to the hydrocarbon liquid filtrate removed from the reactor. Both of these waxy feeds were suitable for use in the process of the invention, in that they contained material having an initial boiling point of from 650-750xc2x0 F. which continuously boiled to an end point of above 1050xc2x0 F., and a T90xe2x88x92T10 temperature spread of more than 350xc2x0 F. Thus, both feeds comprised hydrocarbons having an initial boiling point of 650-750xc2x0 F. and continuously boiled to an end point of more than 1050xc2x0 F. These waxy feeds are very pure and contain negligible amounts of sulfur and nitrogen compounds. The sulfur and nitrogen contents are less than 1 wppm, with less than 500 wppm of oxygenates measured as oxygen, less than 3 wt. % olefins and less than 0.1 wt. % aromatics. The low oxygenate content of preferably less than 1,000 and more preferably less than 500 wppm results in less hydroisomerization catalyst deactivation.
The invention will be further understood with reference to the examples below. In all of these examples, the T90xe2x88x92T10 temperature spread was greater than 350xc2x0 F.

Premium synthetic lubricant base stock (Law734) having at least 95% noncyclic isoparaffins

ExxonMobil Research and Engineering Company


In a process for preparing 1,4-butanediol, tetrahydrofuran and xcex3-butyrolactone by oxidation of butane to give a product stream comprising maleic anhydride, absorption of maleic anhydride from the product stream using a high-boiling alcohol to give a liquid absorption product comprising monoesters and diesters of maleic acid and also high-boiling alcohol, after-esterification of the liquid absorption product and subsequent hydrogenation of the after-esterified product in the liquid phase, the high-boiling alcohol is a polyhydric alcohol having a boiling point at atmospheric pressure of above 233xc2x0 C. and the after-esterified product has an acid number of less than 30 mg KOH/g and a water content of less than 1% by weight.

The present invention relates to a process for preparing mixtures comprising 1,4-butanediol, tetrahydrofuran (THF) and xcex3-butyrolactone (GBL) from the product gas stream from a reactor for the oxidation of butane by a) absorption of maleic anhydride (MA) from the product gas stream using a high-boiling alcohol, b) conversion of the maleic monoester formed into the maleic diester and c) hydrogenation of the latter in the liquid phase.
Numerous processes for converting MA into the corresponding monoesters and diesters and hydrogenating the latter are known.
EP-B 0 149 144, EP-B 0 206 194 and EP-B 0 212 121 describe processes for the continuous separation of MA from gaseous reaction mixtures which are obtained in the catalytic oxidation of hydrocarbons. Here, the MA-containing, gaseous reaction mixture is brought into contact with a monohydric alcohol. The gaseous materials formed are brought into contact with dicarboxylic diesters (EP-B 0 206 194 dibutyl fumarate or succinate, EP B 0 212 121 diesters of fumaric, succinic or maleic acid, EP-B 0 149 144 dibutyl maleate) in a countercurrent process and the liquid process product is taken off at the bottom. The liquid process product comprises predominantly the corresponding monoalkyl and dialkyl esters of maleic acid. These are heated at from 110xc2x0 C. to 200xc2x0 C. to complete the esterification and then provide a suitable starting material for the hydrogenation to form 1,4-butanediol.
A disadvantage of this process is that, apart from the alcohol, an additional material (dicarboxylic diester) which transfers the gaseous reaction products formed from alcohol and MA into the liquid phase is circulated. This must not be hydrogenated in a hydrogenation, so that it is always only possible to achieve incomplete conversion, which means complicated control of the hydrogenation. Furthermore, the dibutyl ester of a dicarboxylic acid used as absorption medium has to be separated from butanediol when the product is worked up by distillation, which complicates the work-up.
DE-A 31 06 819, too, describes a process for preparing 1,4-butanediol by catalytic hydrogenation of a mixture which is obtained by treatment of MA-containing, gaseous reaction mixtures with aliphatic alcohols. The absorption of the MA is carried out using monohydric or dihydric alcohols having boiling points above 180xc2x0 C. An additional absorption medium is not necessary. The subsequent after-esterification of the absorption product is carried out at from 120xc2x0 C. to 150xc2x0 C. The diester-containing stream is finally catalytically hydrogenated, but the space-time yield (0.04 kg of butanediol/literxc3x97hour) is low since the acid number after the after-esterification is too high.
Although the abovementioned processes can be carried out industrially, they have disadvantages which lead to high production costs. These disadvantages are, in particular, complicated control of the hydrogenation and a low space-time yield in the catalytic hydrogenation.
It is an object of the present invention to provide a process which requires very little absorption medium, achieves a good space-time yield in the catalytic hydrogenation using inexpensive catalysts and, in the separation of the desired products, forms no mixtures which are difficult to separate.
We have found that this object is achieved by a process for preparing 1,4-butanediol, tetrahydrofuran (THF) and xcex3-butyrolactone (GBL) by oxidation of butane to give a product stream comprising maleic anhydride, absorption of maleic anhydride from the product stream using a high-boiling alcohol to give a liquid absorption product comprising monoesters and diesters of maleic acid and also high-boiling alcohol, after-esterification of the liquid absorption product and subsequent hydrogenation of the after-esterified product in the liquid phase. In the process of the present invention, the high-boiling alcohol is a polyhydric alcohol having a boiling point at atmospheric pressure of above 233xc2x0 C. and the after-esterified product has an acid number of less than 30 mg KOH/g and a water content of less than 1% by weight.
In the context of the present invention, absorption means the separation of MA from a product stream obtained by oxidation of butane using a high-boiling alcohol to carry out this separation. In this absorption step, the MA reacts with the alcohol to give a maleic monoester which constitutes the main product in the absorption product.
In this process, a liquid process product is obtained directly by addition of the esterifying alcohol under the prevailing reaction conditions. The additional use of a high-boiling absorption medium such as a diester of a dicarboxylic acid is not necessary. By this means, a complicated, later separation of the desired products is avoided. Owing to the low acid number, the hydrogenation can be carried out using inexpensive catalysts and in good yields using the after-esterified product. This allows cost savings.
Catalytic oxidation of butane or another hydrocarbon in the gas phase over a vanadium pentoxide catalyst activated with, for example, MoO3 gives a product stream comprising MA and by-products such as carbon dioxide, acetic acid and acrylic acid. In the process of the present invention, this MA-containing, gaseous product stream is brought into contact with a high-boiling alcohol to absorb the MA. In an advantageous embodiment of the invention, the reaction gas is fed in below the surface of the liquid, high-boiling alcohol, e.g. through an immersed tube. Preference is given to a process in which the reaction mixture is introduced directly from below into an absorption column in which the liquid, high-boiling alcohol flows toward the reaction mixture. Carrying out the MA absorption in a column or a plurality of columns connected in series is preferred.
Suitable columns are, for example, bubble cap tray columns, columns containing units of packing or columns packed with loose packing elements, with preference being given to using the latter. These can be provided with intermediate coolers in order to remove the heat of absorption.
The MA content of the product stream from the butane oxidation is not critical for the process of the present invention. In customary processes, it is in the range from 0.5 to 2% by volume. The temperature of the product gas stream is likewise generally not critical. It should, if possible, be not below the dew points and melting points of the individual components in order to avoid caking, i.e. it should preferably be at least 100xc2x0 C.
The by-products occurring in the oxidation of butane, for example CO2, acetic acid and acrylic acid, are likewise not critical for the process. They are either mostly carried away with the waste gas stream or go into the absorption medium. If they do not react with the esterifying alcohol, they are removed in the thermal treatment of the liquid absorption product (partly with the water).
Alcohols used in the process of the present invention are polyhydric alcohols having a boiling point at atmospheric pressure of above 233xc2x0 C., preferably above 250xc2x0 C. As polyhydric alcohols preference is given to using dihydric to tetrahydric alcohols, particularly preferably dihydric alcohols (diols). Examples of alcohols used are polyethylene glycols, xcex1, xcfx89-diols and cyclohexanedimethanols, e.g. 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, neopentyl glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol, very particularly preferably 1,6-hexanediol and 1,4-cyclohexanedimethanol. As trihydric alcohol, it is possible to use glycerol; as tetrahydric alcohol, pentaerythritol. The alcohols can be used in pure form or as mixtures of various alcohols.
In general, the alcohol is used in a molar excess over the MA of up to 30, preferably up to 15, very particularly preferably up to 5.
In the absorption, a monoester of maleic acid is first formed from the MA and the alcohol. This monoester is high-boiling and thus no longer volatile at the reaction temperatures. The absorption can be carried out so that the after-esterification of the monoester to form the diester also takes place in the apparatus used for the absorption of MA. In this reaction, the monoester can react with further free alcohol or with another monoester molecule. The water eliminated in the reaction can, if the temperatures are high enough, be removed with the waste gas stream.
If relatively large amounts of monoester are still present in the liquid product, preference is given to carrying out a thermal after-esterification in a residence time vessel and thus completing the esterification to form the diester. The after-esterification can be carried out with or without addition of an esterification catalyst.
Esterification catalysts which can be used are, in principle, all homogeneous or heterogeneous catalysts known for the esterification of acids. Preference is given to heterogeneous catalysts such as TiO2, ZrO2, Al2O3, SiO2, silicates, zeolites, heteropolyacids or acid ion exchangers.
Particular preference is given to carrying out the esterification without catalyst, purely thermally. The monoester-containing stream is then after-esterified at temperatures of from 160xc2x0 C. to 300xc2x0 C. in general, preferably from 160xc2x0 C. to 250xc2x0 C., particularly preferably from 180xc2x0 C. to 240xc2x0 C. The water of reaction is generally removed continuously by distillation. The residence time usually is a maximum of 3 hours, in general from 0.1 to 3 hours, preferably from 0.2 to 2.5 hours, particularly preferably from 0.3 to 2 hours. To remove the water of reaction, it is also possible to carry out the after-esterification in a stripping column and remove the water liberated as water vapor by means of stripping gas. It is also possible to apply a vacuum to make it easier to remove the water of reaction. Another possibility is to add entrainers for water, e.g. aromatic hydrocarbons. The water content after the esterification is less than 1% by weight, preferably less than 0.5%, particularly preferably less than 0.2%.
Owing to the choice of esterification conditions, the free acid content of the esterification product is low. The free acid content (measured by titration) before the hydrogenation is less than 30 mg KOH/g, preferably less than 20 mg KOH/g, particularly preferably less than 10 mg KOH/g.
The hydrogenation can be carried out in the presence of an inert organic solvent, particularly if only small quantities are to be hydrogenated. For example, the esterification product can be diluted with an inert organic solvent, preferably ethylene glycol dimethyl ether, to make it more pumpable. When carrying out the reaction industrially, an additional solvent is generally dispensed with.
The hydrogenation is carried out batchwise or continuously in the liquid phase over fixed-bed or suspended or homogeneous, soluble catalysts. Preference is given to a continuous procedure. In the case of fixed-bed catalysts, hydrogenation can be carried out in the downflow or upflow mode, with or without product recirculation. One or more reactors can be operated in series or in parallel. For example, it is possible to hydrogenate predominantly the Cxe2x80x94C double bond of the maleic esters in the first reactor, forming succinic esters, and subsequently to continue the hydrogenation in a second reactor to give butanediol, THF and GBL.
The hydrogenation is carried out generally at temperatures of from 70xc2x0 C. to 350xc2x0 C., preferably from 80xc2x0 C. to 300xc2x0 C., particularly preferably from 80xc2x0 C. to 260xc2x0 C., and at pressures of from 20 bar to 350 bar, preferably from 40 bar to 320 bar in general, particularly preferably from 60 bar to 300 bar.
Hydrogenation catalysts which can be used in the process of the invention are, in general, heterogeneous or homogeneous catalysts suitable for the hydrogenation of carbonyl groups. Preference is given to heterogeneous catalysts. Examples are described in Houben-Weyl, Methoden der Organischen Chemie, Volume IV/1c, pp. 16 to 26, Georg Thieme Verlag, 1980.
Among these hydrogenation catalysts, preference is given to those which comprise at least one element of groups Ib, VIb, VIIb and VIII, and IIIa, IVa and Va of the Periodic Table of the Elements, in particular copper, chromium, rhenium, cobalt, rhodium, nickel, palladium, iron, platinum, indium, tin and antimony. Particular preference is given to catalysts comprising copper, cobalt, palladium, platinum or rhenium. Among these, very particular preference is given to those which comprise copper.
One example of a type of catalyst which can be used for the process of the present invention are unsupported catalysts. In these, the catalytically active metals are present essentially without support materials. Examples are the Raney catalysts, e.g. those based on Ni, Cu or cobalt. Other examples are Pd black, Pt black, Cu sponge, alloys or mixtures of, for example, Pd/Re, Pt/Re, Pd/Ni, Pd/Co or Pd/Re/Ag.
The catalysts used in the process of the present invention can also be precipitated catalysts. Such catalysts can be prepared by precipitating their catalytically active components from their salt solutions, in particular from their nitrate and/or acetate solutions, for example by addition of alkali metal hydroxide and/or alkaline earth metal hydroxide and/or carbonate solutions, e.g. as sparingly soluble hydroxides, hydrated oxides, basic salts or carbonates. The precipitates obtained are subsequently dried and then converted into the corresponding oxides, mixed oxides and/or mixed-valence oxides by calcination at generally from 300 to 700xc2x0 C., preferably from 400 to 600xc2x0 C. These oxides are reduced by treatment with hydrogen or hydrogen-containing gases at generally from 50 to 700xc2x0 C., preferably from 100 to 400xc2x0 C., to give the corresponding metals and/or oxidic compounds of lower oxidation states and thus converted into the actual catalytically active form. The reduction is generally carried out until no more water is formed.
In the preparation of precipitated catalysts which comprise a support material, the precipitation of the catalytically active components can be carried out in the presence of the support material concerned. The catalytically active components can also be advantageously precipitated simultaneously with the support material from the salt solutions concerned.
In the process of the present invention, preference is given to using hydrogenation catalysts which comprise the metals or metal compounds which catalyze the hydrogenation deposited on a support material. Apart from the abovementioned precipitated catalysts, which comprise a support material in addition to the catalytically active components, support materials in general in which the hydrogenation-active catalytic components have been applied to a support material by, for example, impregnation are also suitable for the process of the present invention.
The method by which the catalytically active metals are applied to the support is generally not critical and the application can be carried out in various ways. The catalytically active metals can be applied to these support materials by, for example, impregnation with solutions or suspensions of the salts or oxides of the elements concerned, drying and subsequent reduction of the metal compounds to the corresponding metals or compounds of lower oxidation states by means of a reducing agent, preferably using hydrogen or complex hydrides.
Another possible way of applying the catalytically active metals to the supports is to impregnate the supports with solutions of salts which are readily decomposed thermally, e.g. nitrates, or complexes which are readily decomposed thermally, e.g. carbonyl or hydrido complexes, of the catalytically active metals and to heat the support which has been impregnated in this way at from 300 to 600xc2x0 C. so as to effect thermal decomposition of the adsorbed metal compounds. This thermal decomposition is preferably carried out under a protective gas atmosphere. Suitable protective gases are, for example, nitrogen, carbon dioxide, hydrogen or the noble gases.
The catalytically active metals can also be deposited on the catalyst support by vapor deposition or by flame spraying.
The content of the catalytically active metals in the supported catalysts is in principle not critical for the success of the process of the present invention. Higher contents of catalytically active metals in the supported catalysts generally lead to higher space-time yields than lower contents.
In general, use is made of supported catalysts whose content of catalytically active metals is from 0.1 to 90% by weight, preferably from 0.5 to 40% by weight, based on the total catalyst. Since these content figures are based on the total catalyst including support materials but the different support materials have very different densities and specific surface areas, it is possible for the contents to be above or below the ranges specified without this having an adverse effect on the result of the process of the present invention.
It is also possible for a plurality of catalytically active metals to be applied to the respective support material.
Furthermore, the catalytically active metals can be applied to the support by, for example, the methods described in DE-A 25 19 817, EP-A 0 147 219 and EP-A 0 285 420. In the catalysts described in these documents, the catalytically active metals are present as alloys. These are produced, for example, by impregnation with a salt or complex of the abovementioned metals and subsequent thermal treatment and/or reduction.
The activation of both the precipitated catalysts and the supported catalysts can also be carried out in situ at the beginning of the reaction by means of the hydrogen present, but these catalysts are preferably activated separately before use.
Support materials which can be used are, in general, the oxides of aluminum and titanium, zirconium dioxide, silicon dioxide, clay minerals, e.g. montmorillonites, silicates such as magnesium or aluminum silicates, zeolites such as ZSM-5 or ZSM-10 zeolites, and activated carbon. Preferred support materials are aluminum oxides, titanium dioxide, silicon dioxide, zirconium dioxide and activated carbon. Mixtures of various support materials can also serve as support for the catalysts to be used in the process of the present invention.
Examples of heterogeneous catalysts which can be used in the process of the present invention are: cobalt on activated carbon, cobalt on silicon dioxide, cobalt on aluminum oxide, rhenium on activated carbon, rhenium on silicon dioxide, rhenium/tin on activated carbon, rhenium/platinum on activated carbon, copper on activated carbon, copper/silicon dioxide, copper/aluminum oxide, copper chromite, barium copper chromite, copper/aluminum oxide/manganese oxide, copper/aluminum oxide/zinc oxide and the catalysts described in DE-A 39 32 332, U.S. Pat. No. 3 449 445, EP-A 0 044 444, EP-A 0 147 219, DE-A 39 04 083, DE-A 23 21 101, EP-A 0 415 202, DE-A 23 66 264, EP-A 0 552 463 and EP-A 0 100 406.
Preferred catalysts comprise at least one of the metals copper, manganese, rhenium, cobalt, chromium, palladium, platinum or nickel. Particular preference is given to copper, cobalt, palladium, platinum or rhenium.
The ratio of the individual desired products present in the hydrogenation product, viz. 1,4-butanediol, THF and GBL, can vary. For example, the molar ratio of the products may be: butanediol 50-95 mol %, THF 2-40 mol %, GBL 0.1-20 mol %, where the sum of the mole fractions of 1,4-butanediol, THF and GBL is 100 mol %. The ratio of the desired products is determined predominantly by the parameters pressure, temperature, residence time and catalyst in the hydrogenation. Thus, for example, the GBL content can be reduced to virtually 0 if the hydrogenation is carried out at a high pressure, a low temperature and a long residence time. The THF content can be high when the hydrogenation catalyst has acid centers.
Further products which are or can be present in the hydrogenation product are, for example, water, n-butanol, n-propanol and esters of succinic acid and also the absorption alcohol. The alcohol components of the succinic esters can be both the previously used absorption alcohol and butanediol. The succinic esters can be recirculated together with the absorption alcohol.
The work-up of the reaction products can be carried out in a manner with which those skilled in the art are familiar. Preference is given to a work-up by distillation. Here, for example, low boilers such as THF and any water, butanol or propanol present can first be taken off at the top of a distillation column and the remaining products butanediol and GBL can then be distilled off from the bottoms. The bottoms, which consist predominantly of the absorption alcohol, are subsequently recirculated to the MA absorption. If desired, a small bleed stream can be discharged.

Method for producing mixtures of 1,4-butanediol, tetrahydrofuran and xcex3-butyrolactone