Acrylate-PU hybrids for engine oil filter

Abstract

The present invention relates to a composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels, the composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group and an isocyanate component (IC) comprising at least one polyisocyanate. The present invention also relates to a shaped body with improved resistance towards hydrocarbon based fuels, the shaped body comprising said composition, a process for preparing a shaped body and also the use of the composition according to the present invention for the preparation of a shaped body or a part thereof, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter.

Description

[0001] Acrylate-PU hybrids for engine oil filter

[0002] The present invention relates to a composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels, the composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group and an isocyanate component (IC) comprising at least one polyisocyanate. The present invention also relates to a shaped body with improved resistance towards hydrocarbon based fuels, the shaped body comprising said composition, a process for preparing a shaped body and also the use of the composition according to the present invention for the preparation of a shaped body or a part thereof, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter.

[0003] Silicone-, PVC- and polyurethane-based sealant materials are generally used for sealing engine oil filter units. Comparing to the other technologies, polyurethane-based sealants are usually easy to be applied on the parts. However, in some cases, the high service temperature may result in aging of the polyurethane backbone, which leads to poor adhesion. The common polyurethane elastomers do not show a sufficient resistance against liquid chemicals, such as hydrocarbon based fuels, especially at high temperatures. Resistance here, means that the polyurethane material suffers from swelling causing dimensional extension and weakening mechanical properties. Also hybrid materials are used for these applications.

[0004] For example US 5,183,831 discloses a radiation-curable composition containing acrylated urethane and epoxy (meth)acrylate has high temperature oil resistance, used as adhesive in oil filters. JP 2007 254622 A escribed a photosetting composition used as adhesive-agent for engine-oil filter and filter paper, contains urethane acrylate, epoxy acrylate and photoinitiator.

[0005] It has been found, however, that the existing polyurethane-based polymers are not necessarily successful in aggressive environments. The existing polyurethane-based polymers exhibit insufficient chemical and / or permeability resistance when placed into prolonged contact with organic reagents such as fuels and organic solvents. Known materials often undergo an aging process resulting in lower hardness with time. Accordingly, further improvements are warranted in the preparation of polyurethane-based polymers. It was an object of the present invention to provide polyurethane based materials for the application in diesel engines which have improved properties when contacted with hydrocarbon based fuels.

[0006] According to the present invention, this object has been solved by a composition for preparing shaped body with improved resistance towards hydrocarbon based fuels, the composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0007] (i) a composition (PC) comprising at least one polyol (P1 ) and at least one compound (E1) which comprises at least one ethylenically unsaturated group and

[0008] (ii) an isocyanate component (IC) comprising at least one polyisocyanate.

[0009] In particular, this object has been solved by a composition for preparing shaped body with improved resistance towards hydrocarbon based fuels, the composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0010] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, wherein compound (E1) has at least one terminal carbon-carbon double bond, and wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC); and

[0011] (ii) an isocyanate component (IC) comprising at least one polyisocyanate.

[0012] In the context of the present invention, improved resistance to hydrocarbon based fuels, such as for example motor oil or diesel, in particular means that the materials maintain their properties, in particular their mechanical properties when contacted with hydrocarbon based fuels, especially at high service temperatures. Preferably, over the lifetime of a motor part, the properties only decrease about 10%.

[0013] It has been surprisingly found that the compositions used according to the present invention show an extraordinary resistance to diesel. The materials show a significant improvement in hardness after immersing in hot diesel for 55 days, which is especially beneficial for the applications as sealant for diesel filter with a high service temperature.

[0014] The properties of the polyurethane based materials according to the present invention can be adjusted, for example by introducing a higher number of crosslinks and by blending the polyurethane with ethylenically unsaturated compounds. It has been found that a highly crosslinked system can be prepared, with better resistance against hydrocarbon based fuels for the preparation of parts of diesel engines, in particular parts which are in contact with hydrocarbon based fuels or oil, such as for example filters and sealants.

[0015] Polyurethane for the purposes of the present invention comprehends any known polyisocyanate polyaddition products. These include addition products formed from isocyanate and alcohol and also modified polyurethanes which may comprise isocyanurate, allophanate, urea, carbodiimide, uretoneimine or biuret structures and further isocyanate addition products. These polyurethanes of the present invention comprise specifically compact polyisocyanate polyaddition products, such as thermosets, and foamed materials based on polyisocyanate polyaddition products, especially rigid polyurethane foams, as well as polyurethane coatings.

[0016] In a further preferred embodiment, the polyurethane is a compact polyurethane having a density of preferably more than 850 g / L, preferably 900 to 1400 g / L and more preferably 1000 to 1300 g / L. A compact polyurethane is obtained without admixing a blowing agent. Small amounts of blowing agent, for example water comprised in the polyols as a consequence of the production process, shall not be understood as blowing agent admixture for the purposes of the present invention. The reaction mixture for preparing the compact polyurethane preferably comprises less than 2 wt %, more preferably less than 1 wt % of water. The compact polyurethane may also comprise fillers, such as for example fibrous fillers.

[0017] According to the present invention, the elastomer is obtained or obtainable by reacting a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group and an isocyanate component (IC) comprising at least one polyisocyanate.

[0018] Suitable components for the preparation of the elastomers are in principle known to the person skilled in the art.

[0019] Compound (E1) comprises at least one ethylenically unsaturated group and may have further functional groups which are reactive towards isocyanate groups. Compound (E1) may for example be selected from butadiene, isoprene, 1 ,3-pentadiene, 1 ,5-hexadiene, 1 ,7-octadiene, vinyl acrylates, vinyl methacrylate, methoxybutadiene, dipropylene glycol diacrylate, trimethylolpropane triacrylate, polybutadiene. It is also possible according to the present invention that compounds are used which comprise further functional groups which may for example react with isocyanate groups or further functional groups of the components of composition (PC). Preferably, compound (E1) has at least one terminal carbon-carbon double bond. Suitable components may for example be acrylates, methacrylates, and vinylesters.

[0020] Suitable components may for example have a viscosity at 25°C in the range of from 0.05 to 150 Pas, in particular in the range of from 0.5 to 50 Pas, more preferable in the range of from 2 to 20 Pas. The viscosity may for example be determined according to ASTM D4878.

[0021] The double bond functionality of compound (E1) typically is greater than 1 , for example 2 or 3. When a plurality of compounds (E1) are used, the double bond density is the number average double bond density of the components used.

[0022] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein compound (E1) has at least one terminal carbon-carbon double bond.

[0023] According to the present invention, compound (E1) may have further functional groups, in particular functional groups which are reactive towards isocyanate groups. Preferably, the functionality with respect to these further functional groups is in the range of from 1 to 8, in particular in the range of from 2 to 4, more preferable from 2 to 3.

[0024] Useful compounds (E1), comprising at least one carbon-carbon double bond, preferably at least one terminal carbon-carbon double bond, include, for example, compounds comprising one or more vinyl groups. Preferably, the double bonds (i.e., the vinyl groups R — CH=CH2 ) of the compounds of component (E1) have a double bond density of in each case not less than 8%, for example in the range of from 8 to 30%, more preferable in the range of from 11 to 27%. To compute a double bond density for a compound in the manner of the present invention the mass fraction of the terminal double bonds is divided by the entire molecular mass. For the purposes of this computation, a terminal double bond is assumed to have a mass of 27 g / mol ( — CH=CH2; 2 times carbon plus 3 times hydrogen).

[0025] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein compound (E1) is selected from acrylates, methacrylates, and vinylesters.

[0026] Suitable polyols (P1) are in principle also known. Typically, useful compounds having on average not less than 1.5 isocyanate-reactive hydrogen atoms per molecule are used and include any compounds known in polyurethane chemistry and having isocyanate-reactive hydrogen atoms. These have an average functionality of not less than 1.5, preferably from 1.7 to 8, more preferably from 1.9 to 6 and especially from 2 to 4. These include polymeric compounds having isocyanate-reactive hydrogen atoms and a molecular weight of 300 g / mol or more.

[0027] Polymeric compounds suitable as polyol (P1) preferably have a number average molecular weight in the range from 400 to 15 000 g / mol. Useful compounds under this heading may thus be selected from the group of polyether polyols, polycarbonate polyols, polyester polyols or mixtures thereof. Preferably polyol (P1) is selected from polyester polyols.

[0028] Polyesterols are for example prepared from aliphatic or aromatic dicarboxylic acids and polyhydric alcohols, polythioether polyols, polyester amides, hydroxyl-containing polyacetals and / or hydroxyl-containing aliphatic polycarbonates, preferably in the presence of an esterification catalyst. Further possible polyols are for example disclosed in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1.

[0029] Polyol (P1) may also comprise further functional groups, for example hydrophobic groups. These are more preferably hydroxyl-functionalized compounds having hydrophobic groups. Such hydrophobic groups have hydrocarbon groups with preferably more than 6, more preferably more than 8 and fewer than 100 and especially more than 10 and fewer than 50 carbon atoms.

[0030] Suitable hydroxyl-functionalized hydrophobic compounds are in principle known. Preferably polybutadiene diols are used as hydroxyl-functionalized hydrophobic compounds. Also hydroxyl-functionalized oleochemical compounds may be used according to the present invention such as an oleochemical polyol. A whole series of hydroxyl-functional oleochemical compounds which can be used are known.

[0031] Composition (PC) may also include chain extenders and crosslinking agents having an OH functionality of 2 to 6 and a molecular weight of less than 400 g / mol, preferably a functionality of 2 to 4 and more preferably of 2 to 3. Chain extender is the appellation for molecules having two isocyanate-reactive hydrogen atoms, while molecules having more than two isocyanate-reactive hydrogens are termed crosslinkers. These are usable individually or preferably in the form of mixtures. Preference is given to using diamines, diols and / or triols having molecular weights below 300 g / mol, more preferably in the range from 62 g / mol to below 300 g / mol and especially in the range from 62 g / mol to 250 g / mol. Suitable are, for example, aliphatic, cycloaliphatic and / or araliphatic or aromatic diamines and diols having 2 to 14, preferably 2 to 10 carbon atoms, such as diethyltoluenediamines (DEDTA), m-phenylenediamines, ethylene glycol, 1,2-propanediol, 2- methyl-1,3-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1 ,10-decanediol and bis(2-hydroxyethyl)hydroquinone (HQEE), 1,2-, 1,3-, 1,4-dihydroxycyclohexane, bisphenol A bishydroxyethyl (ether), diethylene glycol, dipropylene glycol, tripropylene glycol, triols, such as 1 ,2,4-, 1 ,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane, diethanolamines, triethanolamines, and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene oxide and / or 1,2-propylene oxide and the aforementioned diols and / or triols as starter molecules. Particular preference for use as crosslinkers is given to low molecular weight hydroxyl- containing polyalkylene oxides based on ethylene oxide and / or 1,2-propylene oxide, more preferably 1,2-propylene, and trifunctional starters, especially glycerol and trimethylolpropane. Chain extenders which are particularly preferred are ethylene glycol, 1,2-propanediol, 1,3-pro- panediol, 2-methyl-1,3-propanediol, 1,4-butanediol, diethylene glycol, bis(2-hydroxyethyl)hydro- quinone and dipropylene glycol.

[0032] The proportion of compounds comprising at least one carbon-carbon double bond (E1) is preferably in the range from 5 to 60 wt %, more preferably in the range from 15 to 55 wt % and especially in the range from 20 to 50 wt %, all based on the combined weight of the components of composition (PC).

[0033] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC).

[0034] Preferably, the content of ethylenically unsaturated groups in the elastomer is in the range of from 0.1wt%-25wt%, preferably in the range of from 0.5wt%-20wt%, in particular in the range of from 1wt%-15wt%.

[0035] According to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the content of ethylenically unsaturated groups in the elastomer is in the range of from 0.1wt%-25wt%.

[0036] According to the present invention, isocyanate component (IC) comprising at least one polyisocyanate. Also suitable polyisocyanates used in composition (IC) are in principle known. Useful di- or polyisocyanates include any aliphatic, cycloaliphatic or aromatic isocyanates known for preparation of polyurethanes, and also any desired mixtures of said isocyanates. Examples are 2,2"-, 2,4"- and 4,4"-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and higher-nuclear homologs of diphenylmethane diisocyanate (polymeric MDI), isophorone diisocyanate (IPDI) or its oligomers, 2,4- or 2,6-tolylene diisocyanate (TDI) or mixtures thereof, tetramethylene diisocyanate or its oligomers, hexamethylene diisocyanate (HDI) or its oligomers, naphthylene diisocyanate (NDI) or mixtures thereof.

[0037] Preference for use as di- or polyisocyanates is given to isocyanates based on diphenylmethane diisocyanate, for example 2,4'-MDI, 4,4'-MDI, higher-nuclear homologs of MDI or mixtures of two or more thereof, especially polymeric MDI. The functionality of di- and polyisocyanates (a) is preferably in the range from 2.0 to 2.9 and more preferably in the range from 2.0 to 2.8. The DIN 53019-1 to 3 viscosity of di- or polyisocyanates at 25°C is preferably between 5 and 600 mPas and more preferably between 10 and 300 mPas.

[0038] Di- and polyisocyanates may also be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers are obtainable by above-described polyisocyanates being reacted in excess, for example at temperatures of 30 to 100° C, preferably at about 80° C, with compounds having two or more isocyanate-reactive groups, to form the prepolymer. The NCO content of polyisocyanate prepolymers according to the present invention is preferably in the range from 5 to 50 wt % of NCO, more preferably in the range from 7 to 35 wt % of NCO, in particular in the range from 10 to 33 of NCO, more preferable in the range from 15 to 32 of NCO.

[0039] Furthermore, composition (PC) and / or the isocyanate component (IC) may comprise further additives such as for example catalysts and / or auxiliaries.

[0040] Useful catalysts include polyurethane catalysts of the customary type. These hasten the reaction of compounds having isocyanate-reactive hydrogen atoms with di- and polyisocyanates to a substantial extent. Customary catalysts useful for preparing the polyurethanes include, for example, amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N- cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N'N-tetramethylbutanedia- mine, N,N,N'N-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1 ,2-dimethylimidazole, 1- azabicyclo(3,3,0)octane, and preferably 1,4-diazabicyclo(2,2,2)octane and alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethan- olamine and dimethylethanolamine. Similarly useful are organometallic compounds, preferably organotin compounds, such as tin(ll) salts of organic carboxylic acids, e.g., tin(ll) acetate, tin(ll) octoate, tin(ll) ethylhexoate and tin(ll) laurate and the dialkyltin(IV) salts of organic carboxylic acids, e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also bismuth carboxylates, such as bismuth(lll) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate or mixtures thereof. Also benzopinacol or derivatives thereof such as for example silyl ethers of benzopinacol may be used. Organometallic compounds are usable alone or preferably in combination with strong basic amines. When component (b) is an ester, amine catalysts are preferably used exclusively.

[0041] Catalysts are for example usable in a concentration of 0.001 to 5 wt %, especially 0.05 to 4 wt % as catalyst or catalyst combination, based on the weight of the polyol (P1).

[0042] The double bonds of component (E1) may be free-radically polymerized during the polyurethane reaction of components (PC) and (IC) or in a step subsequent to the polyurethane reaction. Crosslinking the double bonds of the polyurethane material according to the present invention may here be effected via customary free-radical initiators, such as peroxides or AIBN. Crosslinking may further also be effected via irradiation with high-energy radiation, for example UV light, electron beam radiation or p- or y-radiation. A further possible way to effect crosslinking is that of thermal crosslinking at temperatures above 150° C, preferably above 180° C, in the presence of oxygen

[0043] According to a further embodiment, the present invention is also directed to the composition as disclosed above, herein the composition is curable by thermal curing and at a temperature lower than 150 °C.

[0044] It is further possible to employ auxiliaries and / or added-substance materials. Any auxiliary and added-substance materials known for preparing polyurethanes are usable here. Suitable examples include surface-active substances, blowing agents, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, flame retardants, hydrolysis control agents, fungistatic and bac- teriostatically acting substances. Substances of this type are known and for example described in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition 1993, chapters 3.4.4 and 3.4.6 to 3.4.11.

[0045] In contrast, epoxy-containing compounds are not required for preparing the polyurethane materials of the present invention. Preferably, the polyurethane material of the present invention comprises substantially no epoxy-containing compounds. As a result, the proportion of epoxy- containing compounds, based on the combined weight of components, is less than 1 wt % and more preferably below 0.1 wt %.

[0046] In general, in the preparation of the polyurethane material of the present invention, the di- and / or polyisocyanates, the compounds having isocyanate-reactive hydrogen atoms and, if used, further compounds having isocyanate-reactive hydrogen atoms, such as blowing agents for example, are reacted in such amounts that the equivalence ratio between NCO groups of polyisocyanates and the sum total of isocyanate-reactive hydrogen atoms on further components is in the range from 0.8 to 8, preferably in the range from 0.9 to 6 and more preferably in the range from 0.95 to 4, in particular in the range from 1 to 3. A 1 :1 ratio here corresponds to an isocyanate index of 100.

[0047] In one preferred embodiment, the cured polyurethane material of the present invention is obtained in one step. Here “in one step” is to be understood as meaning that the components for preparing the shaped article and, if present, additives, are all mixed together before commencement of the reaction and the reaction is subsequently carried on to obtain a cured polyurethane material without the admixture of further compounds and especially without admixture of further compounds comprising isocyanate-reactive groups.

[0048] This cured polyurethane material of the present invention is a solid. A solid is concerned in the context of the present invention when the Shore hardness of DIN EN ISO 868 is greater than 10 Shore A, preferably greater than 30 Shore A and especially greater than 50 Shore A. The presence of a cured polyurethane material that is in accordance with the present invention shall be independent of the crosslinking reaction of the double bonds of component (E1); that is, the definition of the cured polyurethane material is satisfied as soon as the Shore hardness is attained, irrespective of whether all, some or no double bonds have reacted with one another. The hardness typically continues to rise once the crosslinking reaction of the double bond has taken place.

[0049] The specific starting substances for preparing polyurethanes that are in accordance with the present invention each differ only minimally in quantitative and qualitative terms whether the polyurethane to be prepared as being in accordance with the present invention is a thermoplastic polyurethane, a rigid foam or a thermoset. For instance, no blowing agents are employed for preparing compact polyurethanes and it is strictly difunctional starting substances which are predominantly employed for thermoplastic polyurethane. It is further possible, for example via the functionality and the chain length of the comparatively high molecular weight compound having two or more reactive hydrogen atoms, to vary the elasticity and hardness of the polyurethane that is in accordance with the invention. Modifications of this type are known to the notional person skilled in the art. The reactants are described for example in EP 0989146 or EP 1460094 for preparing a compact polyurethane and in PCT / EP2005 / 010955 for preparing a rigid foam. Compound (E1) is then additionally admixed in each case to the reactants described in these documents.

[0050] According to a further aspect, the present invention is also directed to a shaped body with improved resistance towards hydrocarbon based fuels, the shaped body comprising the composition as disclosed above.

[0051] According to a preferred embodiment, the present invention is also directed to the shaped body as disclosed above, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter.

[0052] According to a further aspect, the present invention is also directed to a process for preparing a shaped body with improved resistance towards hydrocarbon based fuels, the process comprising the steps of

[0053] (a) providing a composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0054] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group and

[0055] (ii) an isocyanate component (IC) comprising at least one polyisocyanate;

[0056] (b) shaping the composition provided in step (a);

[0057] (c) curing the composition.

[0058] According to the present invention, the process comprises steps (a) to (c) but may comprise further steps. Also further components may be included, for example in the shaping step (b). Suitable processes for shaping the composition are in principle known and include for example casting, pressing, injection, extrusion, spraying, printing, in particular casting. Also suitable processes for curing are in principle known and might for example include curing by thermal curing and at a temperature lower than 150 °C.

[0059] According to a further aspect, the present invention is also directed to the use of a composition as disclosed above for the preparation of a shaped body, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter. The present invention includes the following embodiments, wherein these include the specific combinations of embodiments as indicated by the respective interdependencies defined therein.

[0060] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The composition of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The composition of any one of embodiments 1 , 2, 3 and 4". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

[0061] 1 . A composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0062] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, and

[0063] (ii) an isocyanate component (IC) comprising at least one polyisocyanate.

[0064] 2. The composition according to embodiment 1 , wherein compound (E1) has at least one terminal carbon-carbon double bond.

[0065] 3. A composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0066] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, wherein compound (E1) has at least one terminal carbon-carbon double bond, and

[0067] (ii) an isocyanate component (IC) comprising at least one polyisocyanate.

[0068] 4. The composition according to any one of embodiments 1 to 3, wherein compound (E1) is selected from acrylates, methacrylates, and vinylesters. A composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0069] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, wherein compound (E1) is selected from acrylates, methacrylates, and vinylesters, and

[0070] (ii) an isocyanate component (IC) comprising at least one polyisocyanate. The composition according to any one of embodiments 1 to 5, wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC). A composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0071] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, wherein compound (E1) is selected from acrylates, methacrylates, and vinylesters, and

[0072] (ii) an isocyanate component (IC) comprising at least one polyisocyanate, wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC). The composition according to any one of embodiments 1 to 7, wherein the composition is curable by thermal curing and at a temperature lower than 150 °C. A shaped body with improved resistance , towards hydrocarbon based fuels comprising a composition according to any one of embodiments 1 to 8. A shaped body with improved resistance , towards hydrocarbon based fuels comprising a composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0073] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, and

[0074] (ii) an isocyanate component (IC) comprising at least one polyisocyanate. The shaped body according to embodiment 10, wherein compound (E1) has at least one terminal carbon-carbon double bond. The shaped body according to embodiment 10 or 11 , wherein compound (E1) is selected from acrylates, methacrylates, and vinylesters. The composition according to any one of embodiments 10 to 12, wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC). The composition according to any one of embodiments 10 to 13, wherein the composition is curable by thermal curing and at a temperature lower than 150 °C. The shaped body according to any one of embodiments 10 to 14, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter. A process for preparing a shaped body with improved resistance towards hydrocarbon based fuels, the process comprising the steps of

[0075] (a) providing a composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0076] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group and

[0077] (ii) an isocyanate component (IC) comprising at least one polyisocyanate;

[0078] (b) shaping the composition provided in step (a);

[0079] (c) curing the composition. Use of a composition according to any one of embodiments 1 to 8 for the preparation of a shaped body or a part thereof, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter. Use of a composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0080] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, and

[0081] (ii) an isocyanate component (IC) comprising at least one polyisocyanate, for the preparation of a shaped body or a part thereof, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter. The use according to embodiment 18, wherein compound (E1) has at least one terminal carbon-carbon double bond. The use according to embodiment 1 or 19, wherein compound (E1) is selected from acrylates, methacrylates, and vinylesters. The use according to any one of embodiments 18 to 20, wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC). The use according to any one of embodiments 18 to 21 , wherein the composition is curable by thermal curing and at a temperature lower than 150 °C. A composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0082] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, wherein compound (E1) has at least one terminal carbon-carbon double bond, and wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC). and

[0083] (ii) an isocyanate component (IC) comprising at least one polyisocyanate. The composition according to embodiment 23, wherein compound (E1) is selected from acrylates, methacrylates, and vinylesters. The composition according to any one of embodiments 23 or 24, wherein the composition is curable by thermal curing and at a temperature lower than 150 °C. A shaped body with improved resistance towards hydrocarbon based fuels comprising a composition according to any one of embodiments 23 to 25. The shaped body according to embodiment 26, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter. 28. A process for preparing a shaped body with improved resistance towards hydrocarbon based fuels, the process comprising

[0084] (a) providing a composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0085] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group and

[0086] (ii) an isocyanate component (IC) comprising at least one polyisocyanate;

[0087] (b) shaping the composition provided in step (a);

[0088] (c) curing the composition.

[0089] 29. The process according to embodiment 28, wherein compound (E1) has at least one terminal carbon-carbon double bond.

[0090] 30. The process according to any one of embodiments 28 or 29, wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC).

[0091] 31. The process according to any one of embodiments 28 to 30, wherein compound (E1) has at least one terminal carbon-carbon double bond and wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC).

[0092] 32. A process for preparing a shaped body with improved resistance towards hydrocarbon based fuels, the process comprising

[0093] (a) providing a composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting

[0094] (i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, wherein compound (E1) has at least one terminal carbon-carbon double bond, and wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC); and

[0095] (ii) an isocyanate component (IC) comprising at least one polyisocyanate;

[0096] (b) shaping the composition provided in step (a); (c) curing the composition.

[0097] 33. Use of a composition according to any one of embodiments 23 to 25 for the preparation of a shaped body or a part thereof, wherein the shaped body is a part of an engine, in partic- ular for a diesel engine or a part of an oil filter.

[0098] Examples will be used below to illustrate the invention. Examples

[0099] Materials used Typical experimental procedures:

[0100] All raw materials were first tempered at 45 °C. The compounds of the A-component were degassed and mixed at 800 min-1 for 5 minutes, then the A- and B-component were mixed together at 1000 min-1 for 5 seconds and at 1950 min-1 for another 15 seconds. The mixture was poured in an open mold with dimension of 100 mm * 100 mm * 10 mm. After a cure time of 10 min at 45 °C and 5 min at 80 °C, the samples were demolded and subsequently post-cured at 145 °C for 2 hours. Mechanical properties

[0101] Chemical resistance: The samples were first measured for its initial dimensions and hardness, then immersed in different engine oils. The details of each test are summarized in the table below. After a certain period of time, the dimension and hardness were measured after the oil on the surface was removed and the samples were cooled to room temperature. The results are summarized in tables 1a to 1c.

[0102] Table 1 a

[0103]

[0104] Table 1b

[0105] Table 1c

[0106] Conclusion:

[0107] Surprisingly, the systems according to the invention show an extraordinary resistance to diesel.

[0108] Unlike the reference system which undergoes an aging process and behaves lower hardness with time, the both systems according to the invention show a significant improvement in hardness after immersing in hot diesel for 55 days, which is especially beneficial for the applications as sealant for diesel filter with a high service temperature.

[0109] Literature cited:

[0110] US 5,183,831

[0111] J P 2007254622 A “Kunststoffhandbuch, Band 7, Polyurethane”, Carl HanserVerlag, 3rd edition 1993, chapter 3.1. “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition 1993, chapters 3.4.4 and 3.4.6 to 3.4.11

[0112] EP 0989146

[0113] EP 1460094 PCT / EP2005 / 010955

Claims

Claims1. A composition for preparing a shaped body with improved resistance towards hydrocarbon based fuels comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting(i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group, wherein compound (E1) has at least one terminal carbon-carbon double bond, and wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC), and(ii) an isocyanate component (IC) comprising at least one polyisocyanate.

2. The composition according to claim 1, wherein compound (E1) is selected from acrylates, methacrylates, and vinylesters.

3. The composition according to any one of claims 1 or 2, wherein the composition is curable by thermal curing and at a temperature lower than 150 °C.

4. A shaped body with improved resistance towards hydrocarbon based fuels comprising a composition according to any one of claims 1 to 3.

5. The shaped body according to claim 4, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter.

6. A process for preparing a shaped body with improved resistance towards hydrocarbon based fuels, the process comprising(a) providing a composition comprising an elastomer comprising polyurethane units and ethylenically unsaturated units, wherein the elastomer is obtained or obtainable by reacting(i) a composition (PC) comprising at least one polyol (P1) and at least one compound (E1) which comprises at least one ethylenically unsaturated group and(ii) an isocyanate component (IC) comprising at least one polyisocyanate;(b) shaping the composition provided in step (a);(c) curing the composition.

7. The process according to claim 6, wherein compound (E1) has at least one terminal carbon-carbon double bond.

8. The process according to any one of claims 6 or 7, wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC).

9. The process according to any one of claims 6 to 8, wherein compound (E1) has at least one terminal carbon-carbon double bond and wherein the content of compound (E1) in the composition (PC) is in the range of from 5 to 60 % by weight based on the weight of composition (PC).

10. Use of a composition according to any one of claims 1 to 3 for the preparation of a shaped body or a part thereof, wherein the shaped body is a part of an engine, in particular for a diesel engine or a part of an oil filter.

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