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    • 专利摘要:
    FILLED TIRE, AND, REACTION SYSTEM AND PROCESS TO MAKE A POLYURETHANE ELASTOMER. Elastomeric polyurethane compositions for making tires, methods for making said tires and tires made from said polyurethane elastomers. Said tires are in particular suitable for use as tires for low speed vehicles such as bicycle tires
    公开号:BR112016014373B1
    申请号:R112016014373-6
    申请日:2014-09-15
    公开日:2020-12-29
    发明作者:Johan Van Dyck；Dieter Niclaes；Siddharth Sahu
    申请人:Huntsman International Llc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to methods for improving the dynamic performance of tires, in particular bicycle tires, made of an elastomeric cellular polyurethane material. More specifically, reducing the rolling resistance of the polyurethane elastomer. Therefore, the invention relates to a specific developed polyurethane elastomer.
    [002] The present invention relates to methods for making polyurethane tires with enhanced dynamic performance while maintaining good resistance to hydrolysis and water resistance.
    [003] The present invention further relates to a method for making polyurethane elastomers suitable for use as tires, thereby controlling phase separation problems while using rotary molding to manufacture the tires.
    [004] The present invention further relates to a reactive composition comprising polyisocyanates and products reactive with polyisocyanate to make the polyurethane tire elastomer according to the invention.
    [005] The present invention additionally relates to tires, preferably bicycle tires made of a polyurethane elastomer. BACKGROUND OF THE INVENTION
    [006] Tires are commonly used in road vehicles such as automobiles and trucks. Tires have the advantages of being light in weight and providing a smooth and comfortable ride, as the tire casing is filled with gas or air. The main disadvantage of tires is the risk of deflation due to punctures, separation of the tire wrap from the rim, or another failure of the tire wrap or rim.
    [007] US6303060 describes a non-deflatable tire assembly having a hollow toroid shaped flanged insert and a flexible body molded around the insert to form a tire, and at least one rim on which the tire is mounted. The flexible body is made of a polyurethane foam formed from a combination of polyol and polyisocyanate, while the insert is made of another material such as high density polyethylene. The hollow insert itself is necessary to provide load transport rigidity for the tire, thus contributing to a cushioned ride. Although the hollow internal area is reduced in size, the tire cannot be completely deflated and hollow areas are still necessary to achieve acceptable mechanical properties.
    [008] For the above reasons, inflated tires are more attractive than pneumatics. A filled tire contains a solid or semi-solid material instead of a compressed gas. This eliminates the risk of deflation, as a puncture or other failure of the tire casing will not lead to a gas leak.
    [009] However, a tire filling material must satisfy several requirements to compete with the good dynamic properties of tires. For example, the tire inflation material should allow the tire to absorb shock and provide good traction. Therefore, the tire filling material must be soft and flexible. In addition, the tire filler must be such that the tire does not accumulate excessive heat during use, as heat can damage the filler material or the casing and thus shorten the tire's life. In addition, cost is a more important concern.
    [0010] Soft polyurethane / urea elastomers have been used as a tire filler material in the past and several approaches have been tried. In some cases, the polyurethane / urea polymer was foamed using carbon dioxide that is generated in a reaction between water and an organic isocyanate. Such an approach is described in US 3605848. These foams have the advantages of light weight due to their cellular nature, and being very soft and the foams tend to exhibit high hysteresis and high heat build-up.
    [0011] Soft phases containing polyester lead to the highest level of dynamic properties in cellular PU elastomers having a rigid urea phase. Products of this type are also well known. For example, WO 2001018086 describes the use of polyester polyetherol which can be obtained by polycondensation of polyoxytetramethylene glycol in which the average molar mass is 220 to 270 g / mol and adipic acid, for the production of cellular polyurethane elastomers with good properties dynamic and with high flexibility at low temperature. However, the ester bonds make the resulting foam susceptible to hydrolysis.
    [0012] DE-A 3613964 describes the production of products based on soft phases of pure polyester and, respectively, soft phases of polyester - polyetherol. The test specimens based on polytetrahydrofuran (M = 2000 g / mol) as a soft phase in the comparative example in DE-A 3613964 had only comparatively low flexural strength.
    [0013] The global disadvantage of cellular polyurethane elastomers known in the prior art and used for tires is the fact that they do not retain the desired shape if the polyurethane elastomer is subjected to an increased temperature and they cannot withstand contact with moisture and / or the high pressure action on the elastomer.
    [0014] For all the reasons indicated above there is a need to develop a new elastomeric polyurethane material that has very good dynamic properties and is able to retain the desired shape if the polyurethane elastomer is subjected to an increased temperature and to withstand the contact with humidity and / or with high pressure action on the elastomer. OBJECTIVE OF THE INVENTION
    [0015] It is an objective of the invention to improve the properties of a polyurethane elastomer such that its dynamic performance and resistance (more specific hydrolysis resistance and water resistance) are satisfactory for use as bicycle tires and become comparable with tires .
    [0016] It is an additional object of the present invention to develop a reactive composition and a method for making solid tires, more particularly bicycle tires, made of an elastomeric material of cellular (foamed) polyurethane. SUMMARY OF THE INVENTION
    [0017] This invention relates to an elastomer of polyurethane compositions for making tires, to methods for making said tires and to tires made of said polyurethane elastomers. Said tires in particular are suitable for use as tires for low speed vehicles such as bicycle tires, however the invention is not limited to bicycle tires (such as tires for wheelchairs, pushchairs, pushchairs, pushchairs to pin, ...).
    [0018] Surprisingly we have discovered an elastomeric material of cellular polyurethane (foamed) that has satisfactory dynamic performance and in this way maintains excellent performance of resistance to hydrolysis and water resistance. The polyurethane composition elastomer according to the invention makes it possible to compete with the properties of tires. In this respect, the polyurethane tire elastomer according to the invention are solid tires (made of cellular polyurethane) which reduces the risk of deflation due to punctures, separation of the tire casing from the rim, or other failure of the tire casing or rim to almost zero.
    [0019] According to a first aspect, a inflated tire made of an elastomeric material of polyurethane-urea or cellular polyurethane is described, said elastomeric material having the following properties: - Shore A hardness (according to ASTM D2240) minus 45 and less than 85, preferably in the range of 45 to 80; - Compression set at room temperature less than 10% and at 70 ° C less than 40% (according to ASTM D395); - Ball rebound (according to ASTM D3574) of at least 40%, preferably from 40 to 70%.
    [0020] According to the modalities of the invention, the tire is a low speed vehicle tire such as a bicycle tire.
    [0021] According to the modalities of the invention, the tire is made of an elastomeric material of cellular polyurethane having a molded density in the range of 400 to 700 kg / m3, preferably in the range of 500 to 600 kg / m3 and an elevation density free in the range of 250 to 350 kg / m3, preferably in the range of 300 to 320 kg / m3 (according to ISO 845)
    [0022] According to a second aspect, a reaction system for making the cellular polyurethane elastomer according to the invention is described, said reaction system comprising at least: - a polyisocyanate composition having an NCO value free from 15 to 25% by weight comprising an isocyanate-terminated prepolymer which is the reaction product of an excess of an organic polyisocyanate and a polyether polyol having an average nominal hydroxyl functionality of 2 to 6, a weight numerical average molecular weight from 2000 to 6000 and an ethylene oxide content of 20 to 35% by weight, in which at least 50% of the ethylene oxide groups are present at the end of the polyether polyol, and - at least one polyol of polymer polyether having a molecular weight in the range of 2000 to 7000 and having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol; and - chain extenders, and - catalysts, and - blowing agents.
    [0023] According to the modalities of the invention, the organic polyisocyanates used in the reaction system for the preparation of polyisocyanates according to the invention are selected from aliphatic, cycloaliphatic and / or araliphatic polyisocyanates, preferably selected from aromatic polyisocyanates, more preferably from polyisocyanates based on diphenylmethane diisocyanate (MDI), even more preferably polyisocyanates based on diphenylmethane diisocyanate (MDI) having> 95% by weight 4 , 4'-MDI calculated on the total weight of the organic polyisocyanate mixture.
    [0024] According to embodiments of the invention, the polyether polyols used to prepare the prepolymer in the reaction system for the preparation of the polyisocyanate composition according to the invention contain from 20 to 35% by weight of groups of ethylene oxide in which at least 50%, preferably at least 75% and more preferably all (100%) of these ethylene oxide groups are present at the end of the polyether (tip) polyol and wherein said polyether polyols have an average nominal functionality of 2 to 6, preferably 2 to 4, a numerical average molecular weight of 2000 to 6000 and preferably 2000 to 5000 and even more preferably 3000 to 5000.
    [0025] According to the modalities of the invention, the polyether polyols used to prepare the prepolymer in the reaction system for the preparation of the polyisocyanate composition according to the invention are selected from poly (oxyethylene-oxypropylene) diols and triols.
    [0026] In accordance with embodiments of the invention, the at least one polymer polyether polyol in the reaction system according to the invention is selected from a filled polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol and is having a maximum ethylene oxide content of 20% by weight, preferably in the range of 10 to 20% by weight and where ethylene oxide groups are present at the end of the polyether polyol (cutting edge).
    [0027] According to embodiments of the invention, the at least one polymer polyether polyol in the reaction system according to the invention is selected from a filled polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol and wherein said polymer polyol is a dispersion of solid polymer particles such as styrene-based polymer particles, preferably styrene-acrylonitrile particles.
    [0028] According to embodiments of the invention, the at least one polymer polyether polyol in the reaction system according to the invention is a mixture of a first polyether polyol and a second polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol mixture and where - the first polyether polyol is having a molecular weight in the range of 5000 to 7000 and an ethylene oxide content of 10 to 20% by weight and the groups of ethylene oxide are present at the end of the polyether (tip) polyol - the second polyether polyol is having a molecular weight in the range of 4000 to 6000, preferably around 5000 and an ethylene oxide content of 10 to 20 % by weight and where the ethylene oxide groups are present at the end of the polyether (tip) polyol, and - the molecular weight of the mixture is preferably in the range of 4000 to 7000 and where the ratio of the first polyether polyol for the second pre-polyether polyol ferably it is in the range of 20/80 to 40/60.
    [0029] According to embodiments of the invention, the at least one polymer polyether polyol in the reaction system according to the invention is a mixture of a first polyether polyol and a second polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol mixture and where - the first polyether polyol is having a molecular weight in the range 1000 to 2000 and is selected from polytetrahydrofuran - the second polyether polyol is having a molecular weight in the range of 4000 to 6000, preferably around 5000 and an ethylene oxide content of 10 to 20% by weight and in which ethylene oxide groups are present at the end of the polyether (tip) polyol , and - the molecular weight of the mixture is preferably in the range of 2000 to 4000 and where the ratio of the first polyether polyol to the second polyether polyol is preferably in the range 80/20 to 40/60.
    [0030] According to the modalities of the invention, the blowing agents used in the reaction system according to the invention are selected from fluorine-based hydrocarbon compounds (hydrofluorocarbon compounds) and / or acetal-based compounds and / or water.
    [0031] According to modalities of the invention, the blowing agents used in the reaction system according to the invention are an acetal-based compound such as methylal and are preferably used in the absence of other blowing agents in the range of 4 to 8% by weight calculated on the total weight of the reaction system.
    [0032] In accordance with embodiments of the invention, the blowing agents used in the reaction system according to the invention are water, preferably in the absence of other blowing agents, and are used in the range of at least 0.3 parts by weight , preferably from 0.3 to 1.3 parts by weight, per 100 parts of the reaction system.
    [0033] In accordance with embodiments of the invention, the reaction system according to the invention may additionally comprise additives such as catalysts, surfactants, colorants, stabilizers, fillers and mold release agents.
    [0034] According to the modalities of the invention, the chain extenders and / or crosslinkers used in the reaction system according to the invention are selected from polyols having a hydroxyl functionality of 2 to 6 and preferably 2 to 4 and a molecular weight of 62 to 499 such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylolpropane, hexanediol, pentaerythritol and polyethylene glycols of 499 MW and less and in which the amount of chain extenders and crosslinker is a maximum of 15 parts by weight per 100 parts by weight of the polyol used to react with the polyisocyanate composition, more preferably the amount of chain extenders and crosslinker is in the range of 5 to 15 parts by weight per 100 parts by weight of the polyol used to react with the polyisocyanate composition.
    [0035] According to the modalities of the invention, the chain extenders and / or crosslinkers used in the reaction system according to the invention are selected from mono ethylene glycol (MEG), butanediol and / or hexanediol.
    [0036] According to a third aspect, a process for making the polyurethane elastomer according to the invention is described, said process comprising reacting in an isocyanate index in the range of 90 to 110, preferably in the range of 100 to 105 the reactive system according to the second aspect of the invention.
    [0037] According to embodiments of the invention, the process for making the polyurethane elastomer according to the invention is such that the polymer polyether polyol is pre-mixed with the chain extenders, catalysts, blowing agents, and others additives and then reacted with the polyisocyanate composition.
    [0038] According to embodiments of the invention, the process for making the polyurethane elastomer according to the invention comprises at least the steps of: i. pre-mixing the polymer polyether polyol with the chain extenders, catalysts, blowing agents, and other additives, and then ii. mixing the polyisocyanate composition with the pre-mixed polymer polyether polyol obtained in step i) and then iii. molding the mixed polyisocyanate composition obtained in step ii) into a mold to obtain a reacted polyisocyanate composition, and then iv. curing the reacted polyisocyanate composition obtained in step iii) at an elevated temperature, and then v. demould the obtained tire made of polyurethane cell elastomer.
    [0039] According to embodiments of the invention, the process for making the polyurethane elastomer according to the invention is such that the step of mixing the polyisocyanate composition with the premixed polymer polyether polyol obtained in step i ) is performed using a 2-component high-pressure mixing system or a 2-component dynamic mixing system.
    [0040] According to embodiments of the invention, the process for making the polyurethane elastomer according to the invention is such that the step of molding the mixed polyisocyanate composition obtained in step ii) is carried out using an open mold, preferably an open rotatable mold preferably at a speed of rotation in the range of 150 to 250 rpm and in which the step of curing the reacted polyisocyanate composition obtained in step iii) is carried out at elevated temperatures in the range of 50 to 60 ° C.
    [0041] Independent and dependent claims define particular and preferred features of the invention. Features from the dependent claims can be combined with features from the independent claims or other dependent claims as appropriate.
    [0042] The above characteristics and other characteristics, functionalities and advantages of the present invention will be apparent from the following detailed description, taken in conjunction with the attached examples that illustrate, by way of example, the principles of the invention. DEFINITIONS AND TERMS
    [0043] In the context of the present invention the following terms have the following meaning: 1) The isocyanate index or NCO index or index is the ratio of NCO groups on isocyanate-reactive hydrogen atoms present in a formulation, given as a percentage : [NCO] x 100 / [active hydrogen] (%)
    [0044] In other words the NCO index expresses the percentage of isocyanate actually used in a formulation with respect to the amount of isocyanate theoretically needed to react with the amount of isocyanate - reactive hydrogen used in a formulation.
    [0045] It should be noted that the isocyanate index as used here is not considered only from the point of view of the actual polymerization process by preparing the material involving the isocyanate ingredients and the isocyanate reactive ingredients. Any isocyanate group consumed in a preliminary step to produce modified polyisocyanates (including such isocyanate derivatives referred to in the art as prepolymers) or any active hydrogen consumed in a preliminary step (for example, reacted with isocyanate to produce polyols or polyamines modified) are also taken into account when calculating the isocyanate index. 2) The term "isocyanate-reactive hydrogen atoms" as used here for the purpose of calculating the isocyanate index refers to the total of active hydrogen atoms in hydroxyl and amine groups present in the reactive compositions; this means that for the purpose of calculating the isocyanate index in the current polymerization process a hydroxyl group is considered to comprise a reactive hydrogen, a primary amine group is considered to comprise a reactive hydrogen and a water molecule is considered to comprise two active hydrogens. 3) The term “average nominal hydroxyl functionality” (or in short “functionality”) is used here to indicate the average numerical functionality (number of hydroxyl groups per molecule) of the polyol or polyol composition in the event that the average numerical functionality (number of active hydrogen atoms per molecule) of the primers used in its preparation, although in practice it is generally somewhat less because of some terminal unsaturation. 4) The word “average” refers to the numerical average unless otherwise indicated. 5) "Liquid" means having a viscosity of less than 10 Pa.s measured according to ASTM D445-11a at 20 ° C. 6) “pbw” means part by weight. 7) The term "reaction system" refers to a combination of ingredients in which the polyisocyanate composition is kept in a container separate from the isocyanate-reactive ingredients. 8) The term “inflated tires” as used here refers to tires that do not contain hollow inserts containing compressed air or gas. These tires are preferably completely made of polymeric materials, such as foamed polyurethane. DETAILED DESCRIPTION
    [0046] According to a first aspect of the invention, a tire made of a cellular polyurethane elastomeric material is described, in particular low-speed vehicle tires such as bicycle tires. Said elastomeric cellular polyurethane material is having the following properties: - Shore A hardness (according to ASTM D2240) of at least 45 and less than 85, preferably in the range of 45 to 80; - Compression set at room temperature less than 10% (according to ASTM D395) and at 70 ° C less than 40%; - Ball rebound (according to ASTM D3574) of at least 40%, preferably from 40 to 70%.
    [0047] According to modalities, the cellular polyurethane elastomeric material according to the invention is having a molded density in the range of 400 to 700 kg / m3, preferably from 500 to 600 kg / m3.
    [0048] According to modalities, the cellular polyurethane elastomeric material according to the invention is having a free lifting density in the range of 250 to 350 kg / m3 preferably in the range of 300 to 320 kg / m3measured according to ISO 845 .
    [0049] According to modalities, the cellular polyurethane elastomeric material according to the invention is having the compression set at room temperature (according to ASTM D395) less than 10%, such as compression set values of 3 , 4%, 4.3%, 5% and 6%.
    [0050] According to modalities, the Shore A hardness of the cellular polyurethane elastomeric material according to the invention is at least 50 and less than 85, preferably in the range of 50 to 80.
    [0051] According to modalities, the Shore A hardness of the cellular polyurethane elastomeric material according to the invention may be different depending on the application. For use as tires on children's bikes, the hardness is preferably in the range of 45 to 55, more preferably it is in the range of 50 to 55 while for the use as tires on adult bikes, the hardness is preferably in the range of 70 to 80.
    [0052] According to modalities, the tire is made entirely of the cellular polyurethane elastomeric material according to the invention.
    [0053] According to modalities, the tire is completely made of the cellular polyurethane elastomeric material according to the invention and can optionally be coated with an additional layer, such as a protective wear layer.
    [0054] According to a second aspect of the invention a reaction system for making the cellular polyurethane elastomer according to the first aspect of the invention is described. Said reaction system comprising at least: a) a polyisocyanate composition having a free NCO value of 15 to 25% by weight comprising an isocyanate-terminated prepolymer which is the reaction product of an excess of a poly -organic isocyanate and a polyether polyol having an average nominal hydroxyl functionality of 2 to 4, a numerical average molecular weight of 2000 to 6000 and an ethylene oxide content of 20 to 35% by weight, where at least 50% of the ethylene oxide groups are present at the end of the polyether polyol, and b) at least one polymer polyether polyol having a molecular weight in the range of 2000 to 7000 and having solid particles in the range of 15 to 35% by weight calculated in the total polyol weight; and c) chain extenders, and d) catalysts, and e) blowing agents.
    [0055] Organic polyisocyanates that can be used in the preparation of the polyisocyanate compositions of the invention include aliphatic, cycloaliphatic and araliphatic polyisocyanates, for example, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1 , 4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate and p-xylylene diisocyanate.
    Preferred polyisocyanates, however, are aromatic polyisocyanates, for example, phenylene diisocyanates, tolylene diisocyanates, 1,5-naphthylene diisocyanate and especially polyisocyanates based on diphenylmethane di -isocyanate (MDI) available as isomers of MDI, which means 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and mixtures thereof.
    [0057] More preferably the amount of 4,4'-diphenylmethane diisocyanate used as organic polyisocyanate is more than 95% by weight calculated on the total weight of the organic polyisocyanate, even more preferably the amount of 4, 4'-diphenylmethane diisocyanate used as an organic polyisocyanate is more than 97% by weight calculated on the total weight of the organic polyisocyanate.
    [0058] While diisocyanates are the preferred polyisocyanates for use in the preparation of polyisocyanate compositions, mixtures of diisocyanates with lower proportions of polyisocyanates of greater functionality can be used if desired. Other variants of MDI are well known in the art and include liquid products obtained by introducing residues of urethane, allophanate, urea, biuret, carbodiimide, uretonimine and / or isocyanurate.
    [0059] According to modalities, the polyether polyols used to prepare the prepolymer contain from 20 to 35% by weight of ethylene oxide groups in which at least 50%, preferably at least 75% and more preferably all ( 100%) of these ethylene oxide groups are present at the end of the polyether (tip) polyol. These polyether polyols have an average nominal functionality of 2 to 6, preferably 2 to 4. They have a numerical average molecular weight of 2000 to 6000 and preferably 2000 to 5000 and even more preferably 3000 to 5000.
    [0060] Polyether polyols that can be used to prepare the isocyanate-terminated prepolymer include products obtained by polymerizing ethylene oxide with another cyclic oxide, for example, propylene oxide or tetrahydrofuran in the presence of polyfunctional initiators. Suitable initiator compounds contain a plurality of active hydrogen atoms and include water and polyols, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2 , 6-hexanotriol or pentaerythritol. Mixtures of initiators and / or cyclic oxides can be used.
    [0061] Especially useful polyether polyols include poly (oxyethylene - oxypropylene) diols and triols obtained by the sequential addition of propylene and ethylene oxides to difunctional or trifunctional initiators as fully described in the prior art. Mixtures of said diols and triols can also be useful.
    [0062] The isocyanate-terminated prepolymer is prepared by reacting an excessive amount of the polyisocyanate with the polyether polyol in order to obtain a prepolymer having the indicated NCO value. Methods for preparing prepolymers have been described in the art. The relative amounts of polyisocyanate and polyether polyol depend on their equivalent weights and the desired NCO value and can be determined easily by those skilled in the art. If desired, the reaction can be conducted in the presence of catalysts that enhance the formation of urethane groups, such as tin compounds and tertiary amines. In general the reaction time is between 30 minutes and 4 hours and the temperature between 50 and 90 ° C.
    [0063] At least 90% of the groups obtained by reacting the polyisocyanate with the polyether polyol to prepare the prepolymer are polyurethane groups. To the prepolymers prepared in this way a polyisocyanate can be added provided that the NCO value remains in the indicated range. The amount added is generally less than 25% by weight based on the total polyisocyanate composition. The added polyisocyanate can be selected from those mentioned above. Aromatic polyisocyanates and in particular MDI-based polyisocyanates are preferred.
    [0064] According to modalities, at least one polymer polyether polyol is selected from a filled polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol and is having a content ethylene oxide medium of a maximum of 20% by weight, preferably 10 to 20% by weight, and wherein the ethylene oxide groups are present at the end of the polyether (tip) polyol.
    [0065] According to modalities, the at least one polyol polymer is selected from a filled polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol and wherein said polymer polyol it is a dispersion of solid polymer particles such as styrene-based polymer particles in the polyol. Examples of styrene polymer particles include so-called styrene acrylonitrile "SAN" particles.
    [0066] According to a preferred embodiment, the at least one polymer polyether polyol is a mixture of polyols comprising a first polyether polyol and a second polyether polyol provided that the mixture is having solid particles in the range of 15 to 35 % by weight calculated on the total weight of the polyol mixture. The molecular weight of the mixture is preferably in the range of 4000 to 7000. The first polyether polyol is preferably having a molecular weight in the range of 5000 to 7000 and an ethylene oxide content of 10 to 20% by weight and in which the groups of ethylene oxide are present at the end of the polyether (tip) polyol. The second polyether polyol is preferably having a molecular weight in the range of 4000 to 6000, preferably around 5000 and an ethylene oxide content of 10 to 20% by weight and in which the ethylene oxide groups are present at the end of the polyether polyol (cutting edge). The ratio of the first polyether polyol to the second polyether polyol preferably ranges from 20/80 to 40/60. Suitable examples of the first polyether polyol in the polymer polyol include, but are not limited to Hyperlite® 1650 (obtained from Bayer), KE® 885 (obtained from Konix), SPEC FLEX NC 700 (obtained from DOW ).
    [0067] According to another preferred embodiment, the at least one polymer polyether polyol is a mixture of polyols comprising a first polyether polyol and a second polyether polyol provided that the mixture is having solid particles in the range of 15 to 35 % by weight calculated on the total weight of the polyol mixture. The molecular weight of the mixture is preferably in the range of 2000 to 4000. The first polyether polyol is preferably having a molecular weight in the range of 1000 to 2000 and is preferably selected from polytetrahydrofuran (also called polytetramethylene ether glycol). The second polyether polyol is preferably having a molecular weight in the range of 4000 to 6000, preferably around 5000 and having an ethylene oxide content of 10 to 20% by weight and in which ethylene oxide groups are present in the end of the polyether (tip) polyol. The ratio of the first polyether polyol to the second polyether polyol preferably ranges from 80/20 to 40/60. Suitable examples of the first polyether polyol in the polymer polyol include, but are not limited to Terathane® from Invista and PolyTHF® from BASF.
    [0068] According to modalities, blowing agents can be selected from fluorine-based hydrocarbon compounds (hydrofluorocarbon compounds) and / or alternatively from compounds based on acetal and / or water. The blowing agents used can be a combination of compounds mentioned above.
    [0069] According to modalities, the blowing agent can be a fluorine-based hydrocarbon compound. A suitable fluorine-based hydrocarbon compound is Forane ® 365 (available from Arkema). The amount of fluorine-based hydrocarbon compound (if used alone) is in the range of 3 to 6% by weight calculated on the total weight of the reaction system.
    [0070] According to modalities, the blowing agent can be an acetal based compound. A suitable acetal-based compound is methylal. The amount of acetal-based compound as a blowing agent (if used alone) is in the range of 4 to 8% by weight calculated on the total weight of the reaction system.
    [0071] The amount of water used as a foaming agent, preferably in the absence of other blowing agents, can be varied in a known manner in order to achieve the desired density. Suitable amounts of water in general are at least 0.3 parts by weight, preferably 0.3 to 1.3 parts by weight, per 100 parts of the reaction system. Preferably water is the only blowing agent.
    [0072] The reaction system may additionally comprise conventional additives such as catalysts, surfactants, colorants, stabilizers, fillers and mold release agents.
    [0073] Preferably the chain extenders and crosslinkers are polyols having a hydroxyl functionality of 2 to 6 and preferably 2 to 4 and a molecular weight of 62 to 499, such as ethylene glycol, (mono) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylolpropane, hexanediol, pentaerythritol and polyethylene glycols of 499 MW and less. The amount of chain extenders and crosslinker is a maximum of 15 parts by weight per 100 parts by weight of the polyol used to react with the polyisocyanate composition. Most preferably the amount of chain extenders and crosslinker is preferably in the range of 5 to 15 parts by weight per 100 parts by weight of the polyol used to react with the polyisocyanate composition
    [0074] According to preferred embodiments, the chain extender is mono-ethylene glycol (MEG), butanediol and / or hexanediol especially if rotary molding is applied.
    [0075] According to a third aspect of the invention a process for making the polyurethane elastomer according to the first aspect of the invention is described. Said process comprises reacting in an isocyanate index in the range of 90 to 110, preferably in the range of 100 to 105, the reactive system according to the second aspect of the invention.
    [0076] Conventionally the polymer polyether polyol is pre-mixed with chain extenders, catalysts, blowing agents, and other additives and then reacted with the polyisocyanate composition.
    [0077] The method for making the polyurethane elastomer according to the first aspect of the invention comprises reacting the reaction system ingredients in a mold.
    [0078] According to modalities, the process for making tires made of the cellular polyurethane elastomer according to the first aspect of the invention comprises at least the steps of: i. pre-mixing the polymer polyether polyol with chain extenders, catalysts, blowing agents, and other additives, and ii. mixing the polyisocyanate composition with the pre-mixed polymer polyether polyol obtained in step i), and iii. molding the mixed polyisocyanate composition obtained in step ii) into a mold to obtain a reacted polyisocyanate composition, and then iv. curing the reacted polyisocyanate composition obtained in step iii) at an elevated temperature, and then v. demould the obtained tire made of polyurethane cell elastomer.
    [0079] According to modalities, the step of mixing the polyisocyanate composition with the pre-mixed polymer polyether polyol obtained in step i) is carried out using a 2-component high pressure mixing system.
    [0080] According to modalities, the step of mixing the polyisocyanate composition with the pre-mixed polymer polyether polyol obtained in step i) is carried out using a dynamic 2-component mixing system.
    [0081] According to modalities, the step of molding the mixed polyisocyanate composition obtained in step ii) is carried out using an open mold, preferably an open rotary mold. The rotation speed can be in the range of 150 to 350 rpm, a suitable rotation speed is 200 rpm.
    [0082] According to modalities, the step of curing the reacted polyisocyanate composition obtained in step iii) is carried out at elevated temperatures in the range of 50 to 60 ° C. Preferably, curing is carried out in an oven.
    [0083] According to modalities, the molding process is a rotational molding process and the chain extender used is selected from mono-ethylene glycol (MEG), butanediol and / or hexanediol.
    [0084] The invention is illustrated with the following examples. EXAMPLES
    [0085] Chemicals used: Water Forane 365 = blowing agent (Arkema) Oil = abrasion enhancer (Dow Corning) Catalyst A = metal-healing skin catalyst Catalyst B = amine gelation catalyst Catalyst C = catalyst surfactant Catalyst D = amine curing catalyst Catalyst E = amine gelation catalyst Butanediol 1.4 = MonoEthylene Glycol chain extender (MEG) = Polyether A polyol (triol) chain extender loaded with SAN particles, MW = 5000, 17% by weight of EO Polyether B (triol) MW = 6000, 17% by weight of EO Polyol C (Polytetrahydrofuran) MW = 2000 Polyether D (triol) MW = 4800, 15% by weight IT'S THE
    [0086] Suprasec® 2733 isocyanate prepolymer (Huntsman) having NCO = 19.5 and which is a reaction product of a polyisocyanate based on 4.4 MDI and a polyether polyol with 20 to 35% by weight EO ( all cutting edge) and having an average numerical MW in the range of 3000 to 4000.
    [0087] Suprasec® 2021 isocyanate prepolymer (Huntsman) having NCO = 23.2 and which is a reaction product of a polyisocyanate based on 4.4 MDI and a polyether polyether free of ethylene oxide (EO) having a numerical average MW below 500. Examples 1-2: preparation of cell composition of polyurethane elastomer to make bicycle tires
    [0088] The reactive polyisocyanate composition was prepared by mixing the polymer polyol composition with the isocyanate prepolymer composition (index 104). Subsequently, the reactive polyisocyanate composition was poured into an open rotation mold (200 rpm) resulting in a bicycle tire. After 5 minutes of curing from 50 to 60 ° C in an oven the solid molding was demoulded from the mold.
    [0089] Examples 1 and 2 are according to the invention, the comparative example is using a reactive composition according to the state of the art. Table 1 below shows the composition of the reactive systems, more in particular the polymer polyol composition and the isocyanate prepolymer composition used in pbw.
    [0090] All examples are the result of cellular polyurethane elastomeric material (here a bicycle tire) having a density (molded) around 500 kg / m3. Table 1

    [0091] Table 2 below shows the characteristics of the elastomer obtained through the reaction of the reactive composition according to Table 1 at an isocyanate index of 104. Table 2
    Example 3: preparation of cell composition of polyurethane elastomer using polyols based on polymer and Polytetrahydrofuran
    [0092] The reactive polyisocyanate composition was prepared by mixing the polymer polyol composition with the isocyanate prepolymer composition (index 104) using low pressure mixing. Subsequently, the reactive polyisocyanate composition was poured into an open mold. After 5 minutes of curing from 50 to 60 ° C in an oven the solid wrapper was demoulded from the mold.
    [0093] Example 3 is according to the invention, the comparative example is using a reactive composition according to the state of the art. Table 3 below shows the composition of the reactive systems, more in particular the polymer polyol composition and the isocyanate prepolymer composition used in pbw. Table 3

    [0094] Table 4 below shows the characteristics of the elastomer obtained by reacting the reactive composition according to Table 1 at an isocyanate index of 104. Table 4
    Performance of bicycle tires made of cellular polyurethane elastomer according to the invention
    [0095] The performance of tires made from cellular polyurethane elastomers according to the invention is compared with tires made from cellular polyurethane elastomers according to the state of the art.
    [0096] Cellular polyurethane elastomer tire 1 is a cellular polyurethane elastomer according to the present invention in which the tire has Shore A Hardness of 70 to 75 (using the reactive formulation for sample 2 in Table 1).
    [0097] Cellular polyurethane elastomer tire 2 is a cellular polyurethane elastomer according to the present invention in which the tire has Shore A Hardness of 60 to 65 (using the reactive formulation for sample 2 in Table 1 with the exception that the amount of butanediol is 7 bpw).
    [0098] The cell polyurethane elastomer tire 3 is a cell polyurethane elastomer according to the present invention in which the tire has Shore A Hardness of 50 (using the reactive formulation for sample 2 in Table 1 with the exception of that the amount of butanediol is 5.5 bpw).
    [0099] The prior art cellular polyurethane elastomer tire 1 is a cellular polyurethane elastomer in which the tire has a Shore A hardness of 75 (using the reactive formulation, for example, comparative in Table 1).
    [00100] Table 5 illustrates the power performance for tires loaded with a total weight of 25, 50 and 100 kg and the power required to reach a speed of 20 km / h.
    [00101] It can be concluded that the lower the power, the better (lower) the rolling resistance and thus the tire performance. An improvement of more than 20% is achieved when using the cellular polyurethane composition of the invention. Table 5
    权利要求:
    Claims (20)
    [0001]
    1. Reaction system for making inflated tires made of a polyurethane-urea elastomer material or cellular polyurethane, said reaction system characterized by the fact that it comprises at least: - a polyisocyanate composition having a NCO value free of 15 to 25% by weight comprising an isocyanate-terminated prepolymer which is the reaction product of an excess of an organic polyisocyanate and a polyether polyol having an average nominal hydroxyl functionality of 2 to 6, an average molecular weight numerical from 2000 to 6000 and an ethylene oxide content of 20 to 35% by weight, in which at least 50% of the ethylene oxide groups are present at the end of the polyether polyol, and - a polyol composition comprising at least a polymer polyether polyol having a molecular weight in the range of 2000 to 7000 and having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol; and - chain extenders, and / or crosslinkers, and - catalysts, and - blowing agents.
    [0002]
    2. Reaction system according to claim 1, characterized by the fact that the organic polyisocyanate used in the preparation of the polyisocyanate composition is selected from aliphatic, cycloaliphatic and / or araliphatic polyisocyanates, preferably selected from of aromatic polyisocyanates, more preferably from polyisocyanates based on diphenylmethane diisocyanate (MDI), even more preferably polyisocyanates based on diphenylmethane diisocyanate (MDI) having> 95% by weight of 4, 4'-MDI calculated on the total weight of the organic polyisocyanate mixture.
    [0003]
    Reaction system according to claim 1 or 2, characterized in that the polyether polyols used to prepare the prepolymer contain from 20 to 35% by weight of ethylene oxide groups in which at least 50% , preferably at least 75% and most preferably all (100%) of these ethylene oxide groups are present at the end of the polyether (tip) polyol and wherein said polyether polyols have an average nominal functionality of 2 to 6, preferably from 2 to 4, a numerical average molecular weight from 2000 to 6000 and preferably from 2000 to 5000 and even more preferably from 3000 to 5000.
    [0004]
    Reaction system according to any one of claims 1 to 3, characterized in that the polyether polyols used to prepare the prepolymer are selected from poly (oxyethylene-oxypropylene) diols and triols.
    [0005]
    Reaction system according to any one of claims 1 to 4, characterized in that the at least one polymer polyether polyol is selected from a filled polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol and is having an ethylene oxide content of a maximum of 20% by weight, preferably in the range of 10 to 20% by weight and where ethylene oxide groups are present at the end of the polyol polyester (cutting edge).
    [0006]
    Reaction system according to any one of claims 1 to 5, characterized in that the at least one polymer polyether polyol is selected from a filled polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol and wherein said polymer polyether polyol is a dispersion of solid polymer particles such as styrene-based polymer particles, preferably styrene-acrylonitrile particles.
    [0007]
    Reaction system according to any one of claims 1 to 6, characterized in that the polyol composition comprising at least one polymer polyether polyol is a mixture of a first polyether polyol and a second polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol mixture and where - the first polyether polyol is having a molecular weight in the range of 5000 to 7000 and an ethylene oxide content of 10 to 20 % by weight and the ethylene oxide groups are present at the end of the polyether (tip) polyol, and - the second polyether polyol is having a molecular weight in the range of 4000 to 6000, preferably around 5000 and a content of ethylene oxide of 10 to 20% by weight and in which groups of ethylene oxide are present at the end of the polyether (tip) polyol, and - the molecular weight of the mixture is preferably in the range of 4000 to 7000 and in that the reason for the first polio l of polyether for the second polyether polyol preferably is in the range of 20/80 to 40/60.
    [0008]
    Reaction system according to any one of claims 1 to 7, characterized in that the polyol composition comprises at least one polymer polyether polyol is a mixture of a first polyether polyol and a second polyether polyol having solid particles in the range of 15 to 35% by weight calculated on the total weight of the polyol mixture and where - the first polyether polyol is having a molecular weight in the range of 1000 to 2000 and is selected from polytetrahydrofuran, and - the second polyether polyol is having a molecular weight in the range of 4000 to 6000, preferably around 5000 and an ethylene oxide content of 10 to 20% by weight and in which the ethylene oxide groups are present at the end of the (tip) polyether polyol, and - the molecular weight of the mixture is preferably in the range of 2000 to 4000 and the ratio of the first polyether polyol to the second polyether polyol is preferably in the range of 80/20 to 40 / 60.
    [0009]
    Reaction system according to any one of claims 1 to 8, characterized in that the blowing agents are selected from fluorine-based hydrocarbon compounds (hydrofluorocarbon compounds) and / or acetal-based compounds and / or water.
    [0010]
    Reaction system according to any one of claims 1 to 9, characterized in that the blowing agent is an acetal-based compound such as methylal and is preferably used in the absence of other blowing agents in the range of 4 to 8% by weight calculated on the total weight of the reaction system.
    [0011]
    Reaction system according to any one of claims 1 to 10, characterized in that the blowing agent is water, preferably in the absence of other blowing agents, and is used in the range of at least 0.3 parts in weight, preferably 0.3 to 1.3 parts by weight, per 100 parts of the reaction system.
    [0012]
    Reaction system according to any one of claims 1 to 11, characterized in that the chain extenders and crosslinkers are polyols having a hydroxyl functionality of 2 to 6 and preferably 2 to 4 and a molecular weight of 62 to 499 such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylolpropane, hexanediol, pentaerythritol and polyethylene glycols and where the amount of chain extenders and crosslinker is a maximum of 15 parts by weight per 100 parts by weight of polyol used to react with the polyisocyanate composition, more preferably the amount of chain extenders and crosslinker is in the range of 5 to 15 parts by weight per 100 parts by weight of polyol used to react with the composition of polyisocyanate.
    [0013]
    Reaction system according to any one of claims 1 to 12, characterized in that the chain extender is mono ethylene glycol, butanediol and / or hexanediol.
    [0014]
    14. Inflated tire, characterized by the fact that it is made of an elastomeric material of polyurethane-urea or cellular polyurethane obtained using the reactive mixture as defined in any of claims 1 to 13, said elastomeric material having the following properties: - Hardness Shore A according to ASTM D2240 of at least 45 and less than 85, preferably in the range of 45 to 80; - Compression set at room temperature less than 10% and at 70 ° C less than 40% according to ASTM D395; - Ball rebound according to ASTM D3574 of at least 40%, preferably from 40 to 70%.
    [0015]
    15. Tire according to claim 14, characterized in that the tire is a low speed vehicle tire such as a bicycle tire.
    [0016]
    16. Tire according to claim 14 or 15, characterized by the fact that the cellular polyurethane elastomeric material is having a molded density in the range of 400 to 700 kg / m3, preferably in the range of 500 to 600kg / m3 and a density free lift in the range 250 to 350 kg / m3 preferably in the range 300 to 320 kg / m3 according to ISO 845.
    [0017]
    17. Process for making a polyurethane elastomer as defined in any of claims 14 to 16, said process characterized by the fact that it comprises reacting in an isocyanate index in the range of 90 to 110, preferably in the range of 100 to 105 o reactive system as defined in any one of claims 1 to 13 in a mold.
    [0018]
    18. Process according to claim 17, characterized in that the polymer polyether polyol is pre-mixed with the chain extenders, catalysts, blowing agents, and other additives and then reacted with the polyisocyanate composition .
    [0019]
    19. Process according to claim 17 or 18, characterized by the fact that the process comprises at least the steps of: i. pre-mixing the polymer polyether polyol with the chain extenders, catalysts, blowing agents, and other additives, and then ii. mixing the polyisocyanate composition with the pre-mixed polymer polyether polyol obtained in step i) and then iii. molding the mixed polyisocyanate composition obtained in step ii) into a mold to obtain a reacted polyisocyanate composition, and then iv. curing the reacted polyisocyanate composition obtained in step iii) at an elevated temperature, and then v. demould the obtained tire made of polyurethane cell elastomer.
    [0020]
    Process according to any one of claims 17 to 19, characterized in that the step of mixing the polyisocyanate composition with the pre-mixed polymer polyether polyol obtained in step i) is carried out using a mixing system high-pressure 2-component or a dynamic 2-component mixing system and where the step of molding the mixed polyisocyanate composition obtained in step ii) is carried out using an open mold, an open rotating mold at a rotational speed in the range of 150 to 250 rpm and in which the step of curing the reacted polyisocyanate composition obtained in step iii) is carried out at elevated temperatures in the range of 50 to 60 ° C.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3605848A|1968-12-23|1971-09-20|Inter Polymer Res Corp|Microcellular urethane elastomers of relatively low density|
    US4206170A|1975-05-06|1980-06-03|The Goodyear Tire & Rubber Company|Method of molding a torus shaped article|
    US4125691A|1977-04-01|1978-11-14|The Goodyear Tire & Rubber Company|Zero pressure device such as tires or run-flat rings|
    US5821316A|1997-01-24|1998-10-13|Air Products And Chemicals, Inc.|Polyurethane prepolymers for making elastomers having improved dynamic properties|
    US6031010A|1997-08-11|2000-02-29|Imperial Chemical Industries Plc|Polyurethane foam composition having improved flex fatigue|
    US6303060B1|1997-10-20|2001-10-16|Pacific Circle Technologies, Inc.|Method of making non-deflatable tire and wheel assembly|
    US6100310A|1998-09-25|2000-08-08|Bayer Antwerp N.V.|Process for making microcellular polyurethane elastomers|
    WO2001018086A1|1999-09-04|2001-03-15|Basf Aktiengesellschaft|Cellular polyisocyanate polyaddition products|
    US6431235B1|2000-05-11|2002-08-13|Richard A. Steinke|Non-pneumatic tire and rim combination|
    DE10142296C1|2001-08-29|2003-02-13|Bayer Ag|Polyurethane elastomers, used for making moldings, e.g. shoe soles, are produced using an amine catalyst and a catalyst mixture of organic titanium and/or zirconium and lithium compounds in reaction of isocyanate and polyether polyol|
    DE102006030531A1|2006-07-01|2008-01-03|Goldschmidt Gmbh|Silicone stabilizers for flame-retardant rigid polyurethane or polyisocyanurate foams|
    KR101401757B1|2006-11-01|2014-06-19|다우 글로벌 테크놀로지스 엘엘씨|Polyurethane compositions and articles prepared therefrom, and methods for making the same|
    CN101565495A|2008-04-23|2009-10-28|拜耳材料科技贸易有限公司|Polyurethane elastomer as well as preparation method and usage thereof|
    US20110253277A1|2009-01-08|2011-10-20|Gerhard Mueller|Polyurethane or polyurethane-urea tire fillings plasticized with fatty acid esters|
    ITMI20110062A1|2011-01-24|2012-07-25|Dow Chemical Co|POLYURETHANE POLYETERIES WITH BETTER SLIP RESISTANCE IN HUMID CONDITIONS|
    TWM409188U|2011-03-01|2011-08-11|Unique Product & Design Co Ltd|Filled tire for lightweight vehicle|
    WO2017078990A1|2015-11-03|2017-05-11|Dow Global Technologies Llc|Polyurethane foam for noise and vibration absorption|US10675527B2|2017-01-25|2020-06-09|Trugrit Traction, Inc.|Pipe transporter traction wheel|
    US10634274B2|2017-01-25|2020-04-28|Trugrit Traction, Inc.|Pipe transporter traction wheel|
    CN106832190A|2017-02-08|2017-06-13|滁州市玉林聚氨酯有限公司|A kind of seamless polyurethane solid tyre|
    CN110520457B|2017-03-03|2022-01-18|陶氏环球技术有限责任公司|Low density polyurethane elastomer foam with high ball rebound|
    CN107199832A|2017-05-23|2017-09-26|宁波格林美孚新材料科技有限公司|A kind of inflation-free solid tyre|
    CN107444017A|2017-07-07|2017-12-08|庄树强|Tire|
    CN111615527A|2018-01-05|2020-09-01|科思创德国股份有限公司|Non-pneumatic tire, method for producing same and use thereof|
    CN110317446A|2018-03-30|2019-10-11|巴斯夫欧洲公司|Non-inflatable tyre containing polyurethane matrix and foamed thermoplastic elastomers particle|
    EP3556788A1|2018-04-18|2019-10-23|Covestro Deutschland AG|Non-pneumatic tire and method for preparing the same and use thereof|
    CN108973534A|2018-07-20|2018-12-11|滁州市玉林聚氨酯有限公司|A kind of suction ground antiskid polyurethane tire and preparation method thereof|
    WO2020114786A1|2018-12-07|2020-06-11|Covestro Deutschland Ag|Polyurethane microcellular elastomer, non-pneumatic tire and preparation process thereof|
    WO2020152012A1|2019-01-21|2020-07-30|Covestro Intellectual Property Gmbh & Co. Kg|Non-pneumatic tire and preparation process and use thereof|
    EP3722345A1|2019-04-09|2020-10-14|Covestro Deutschland AG|Non-pneumatic tire and preparation process and use thereof|
    CN111848903A|2019-10-16|2020-10-30|宁波途锐达休闲用品有限公司|Microporous polyurethane foam material and its production process|
    CN111533868B|2020-05-28|2021-10-26|浙江华峰新材料有限公司|Polyurethane for low-speed solid tire|
    CN112109263B|2020-08-27|2021-12-31|同济大学|Solid tyre filling device|
    法律状态:
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/09/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13198741.4|2013-12-20|
    IN3729DE2013|2013-12-20|
    EP13198741.4A|EP2886369A1|2013-12-20|2013-12-20|Polyurethane filled tires|
    IN3729/DEL/2013|2013-12-20|
    PCT/EP2014/069609|WO2015090653A1|2013-12-20|2014-09-15|Polyurethane filled tires|
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