EP2516496A2 - Procédé en une seule phase pour la production de polyuréthane thermoplastique modifié par des copolymères styréniques séquencés - Google Patents

Procédé en une seule phase pour la production de polyuréthane thermoplastique modifié par des copolymères styréniques séquencés

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Publication number
EP2516496A2
EP2516496A2 EP10814693A EP10814693A EP2516496A2 EP 2516496 A2 EP2516496 A2 EP 2516496A2 EP 10814693 A EP10814693 A EP 10814693A EP 10814693 A EP10814693 A EP 10814693A EP 2516496 A2 EP2516496 A2 EP 2516496A2
Authority
EP
European Patent Office
Prior art keywords
polyester
styrenic block
extruder
tpu
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10814693A
Other languages
German (de)
English (en)
Inventor
Andrea Martignoni
Andrea Correnti
Davide Brambillasca
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Epaflex Polyurethanes Srl
Original Assignee
Epaflex Polyurethanes Srl
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Epaflex Polyurethanes Srl filed Critical Epaflex Polyurethanes Srl
Publication of EP2516496A2 publication Critical patent/EP2516496A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a one-shot process for the production of a thermoplastic elastomer based on polyurethane and styrenic block copolymers, and to the elastomer thus obtained. More in detail, the present invention relates to a process and a product obtained by reacting together the compounds forming a polyurethane "system” and styrenic block copolymers under kneading and heating.
  • the material object of this invention is flexible, resistant to hydrolysis, with a Shore hardness from 55 A to 98 A and can be processed in machines that are commonly used to process thermoplastic rubbers based on styrene block copolymers, without substantially modifying them.
  • thermoplastic polyurethane is a versatile elastomer that is used in footwear products, automotive, electronics, and for industrial machinery.
  • thermoplastic polyurethanes show a good performance regarding resistance to chemicals and hydrolysis, tear and abrasion resistance, low temperature flexibility and tensile strength.
  • TPU is a block copolymer that owes its elastic properties to the phase separation of so-called “hard blocks” and “soft blocks”.
  • Hard blocks are rigid structures that are physically cross-linked (i.e. by electrostatic forces, without chemical bonds) and give the polymer its firmness; soft blocks are stretchable chains that give the polymer its elasticity.
  • Thermoplastic polyurethane can be produced in several ways.
  • reactive processing also known as reactive extrusion, i.e. a process in which the first component of the "system” (polyol containing poly-hydroxyl compounds, chain extenders and additives) and the second one (isocyanate) are fed to the extruder in a precise ratio by a metering system.
  • the chain extender is fed through a third line separated from the other polyol components.
  • reaction and transport take place simultaneously and the reacting materials are transported from the feed zone to the outlet die.
  • the polymer formed is cooled in water and granulated.
  • twin-screw extruder For reactive processing, a closely intermeshing co-rotating twin-screw extruder is often the preferred choice.
  • the second screw wipes the first one, which prevents slippage and guarantees forward conveying. Due to the self-wiping action, the transport of material is largely independent of the viscosity of the material: this is an advantage for a reactive system, since the viscosity rises exponentially along the screw.
  • Another process provides for feeding the two components into a flat and large container where they are reacted, curing the reacted product and subsequently chop it to pieces and extrude the pieces into granules.
  • TPU properties can be modified to try to achieve the properties needed in the final application; however this method is not flexible enough to obtain all the desirable properties.
  • US 6291587 discloses the melt blending of rigid TPUs with rubber-like materials such as SBR, EPDM, NBR, EPR, SBS, SIS, SEBS, EVA and blends of plastics and rubbers in general.
  • the main disadvantage of this method is that the compounding process, since it is done a relatively high temperatures, has a detrimental effect on the physical properties of the modified TPU produced that way, since it will undergo a thermal degradation and a partial de-polymerisation; another disadvantage is that the production is long and costly.
  • a further disadvantage is that a compatibilizing agent is required to prevent separation of the styrenic block copolymer from the polyurethane during the processing of the materials.
  • US 2005/0261427 relates to a TPU composition containing styrene-based block copolymers containing hydroxyl groups.
  • the process to manufacture this composition provides for reacting the polyol and the isocyanate compounds in the feed zone of an extruder and in adding the functionalized styrene copolymer in the compression zone of the said extruder.
  • the reaction process of polyurethane formation has already progressed and the obtained polyurethane is hard enough to be compressed.
  • hydroxyl functional groups on the styrene block copolymer are required in order to react with the polyurethane product and favour mutual compatibilization of the TPU and block copolymers.
  • US 2004/0176525 carries out a process similar to the one previously disclosed with reference to US 2005/0261427, i.e. the styrene block copolymers are provided with an hydroxyl functional group.
  • EP 0611806 discloses a composition resulting from TPU and a styrene block copolymer that have been blended together at 200°C.
  • the TPU is obtained from a poly(3-methyl-1 ,5-pentane adipate)diol, that is said to be critical to obtain the final result i.e. a compatibilization of the TPU and styrene copolymer.
  • thermoplastic elastomers based on TPU and styrenic block copolymers as SBS, SEBS, SIS or mixtures thereof and that are suitable to be used in production of shoe soles or other items like wheels (e.g. for industrial carriages), profiles, household items or similar products.
  • the above aim is reached by means of the present invention, that provides a process to obtain this elastomer using a one-shot process by polymerizing components usually used for TPU production (a diisocyanate, a polyol containing relatively high molecular weight polyol, chain-extender, antioxidants and catalyst) in the presence of styrenic block copolymers used in quantities from 10 to 45 weight percent of the total mixture of isocyanate, high molecular weight polyol, additives and chain extender.
  • components usually used for TPU production a diisocyanate, a polyol containing relatively high molecular weight polyol, chain-extender, antioxidants and catalyst
  • the polymerization reaction of the starting compounds for producing the TPU is carried out in the presence of the styrenic block copolymers.
  • the above mentioned starting compounds for the TPU forming reaction and the styrenic block copolymers are all fed together to the feeding zone (or feeding area) of an extruder so that also the styrenic polymers are mixed together with the liquid reaction components for the TPU substantially from the very first steps of the TPU polymerization reaction, i.e. the polymerization reaction is started and occurs in the presence of the styrenic block copolymers.
  • a further object of the invention is a composition according to claim 9.
  • Another object of the invention is an extruder according to claim 11.
  • the diisocyanate is 4,4'diisocyanatediphenylmethane or a mixture of 4,4'diisocyanatediphenylmethane and 2,4-diisocyanatodiphenylmethane wherein the amount of 2,4 is up to 5% by weight of the total amount of diisocyanate, i.e. the amount of the 2,4 isomer is within the range of 0 to 5 % in weight.
  • Polyols suitable for the present invention have an average molecular weight from 1000 to 4000 g/mol, preferably from 1750 to 3250 g/mol.
  • Poyois that can be used are polyester polyols, most preferably polyester polyols based on adipic acid or on caprolactone derivatives or mixtures thereof.
  • Poly(3- methyl-1 ,5-pentane adipate) diol is excluded from the scope of the products of the present invention.
  • Styrenic block copolymers (SBC) suitable for the present invention are SBS (styrene-butadiene-styrene), SEBS (styrene-ethylene-butadiene-styrene) and
  • SIS styrene-isoprene-styrene copolymers, linear or branched or grafted.
  • the rubber (SBC) is selected from
  • SEBS and SBS copolymers and mixtures thereof the total amount of rubber being within the range of 10 to 45% (w/w) of the total weight of isocyanates, polyols additives and chain extenders.
  • SBS copolymer is used, in this case, the polymer is grafted with maleic anhydride or with methyl-acrylate or a mixture thereof.
  • the styrenic copolymers contain fillers and/or are oil extended, i.e. they contain paraffinic or naphtenic oils.
  • the amount of oil can reach 35-40% (w/w) and the amount of fillers (generally inorganic fillers) can reach 50-60% (w/w).
  • Chain extenders suitable for the invention can be selected from the following ones: 1 ,4 butanediol, 1 ,6 hexanediol, monoethylene glycol, diethylene glyocol, hydroquinone di-p-hydroxyethyl ether and mixtures thereof.
  • the common additives and ancillary materials known to those skilled in the art of production of thermoplastic polyurethane via reactive extrusion can be used, including, for example, antioxidants, catalysts, fillers, pigments, anti- hydrolysis agents, lubricants, UV-protectors, plasticizers and flame retardants.
  • the process subject of the present invention provides several advantages over the prior art. First of all, it was surprisingly found that the process provides such a high degree of compatibility between the styrenic polymers and the TPU that it is possible to obtain transparent products.
  • transparency, or total luminous transmission is measured according to ASTM D-1008, method B. The measures were taken with a BYK Gardner Spectrophotomer. The higher the transparency value, the more transparent the final product is. Transparency is also an indicator of the degree of compatibilization between the polyurethane portion and the rubber portion as obtained by the reaction.
  • the products of the invention have a transparency (measured as above disclosed) of at least 40, preferably of at least 70, more preferably of at least 80, and can reach very high values, e.g. 99 as disclosed in example 3
  • the modified TPU obtained with the current process thus has better mechanical properties than the modified TPU obtained with the conventional two-step process.
  • the process is less energy intensive, since it is a single step process and it is possible to carry out at the same time the PU reaction (extrusion-reaction) and the blending/mixing with the rubber from the very beginning of the extruder, if an extruder is used.
  • a further advantage is that by changing the amount of rubber, without exiting the claimed range 10-65% (w/w), and/or by modifying the ratio of the claimed diisocyanates and polyester polyols, the product properties can be effectively controlled in a simple and reliable way, as disclosed by the following examples 1-4. Moreover, the process is carried out without using compatibilizing agents, i.e. the composition is free from compatibilizing agents.
  • - Fig. 1 is a scheme of a twin screw extruder suitable for the invention process.
  • TPU that are flexible and have a Shore-A hardness (as measured by ISO 868) within the range of 55 to 98 shore A, are obtained by reacting 4,4'diisocyanatodiphenylmethane or a mixture of 4,4'diisocyanatodiphenylmethane and 2,4- diisocianatodiphenylmethane wherein the amount of the 2,4 isomer is within the range of 0 to 5% in weight of the total diisocyanate fraction, with polyols having an average molecular weight from 1000 to 4000 in the presence of chain extenders, additives, a styrenic block copolymer selected from SBS, SEBS, SIS and mixtures thereof.
  • the amount of the rubber fraction is within the range of 5 to 65% (w/w) of the total weight of the final composition, preferably 10 to 55% (w/w), most preferably 20 to 45% (w/w) on the total weight of the composition.
  • the reaction of the starting compounds for producing the TPU is carried out in the presence of the styrenic block copolymers or, to put it into different words, a solid styrenic block copolymer is added to liquid polyols and isocyanates.
  • the above mentioned starting compounds for the TPU forming reaction and the styrenic block copolymers are fed to the feeding zone (or feeding area) of an extruder so as to start and carry out at least part of the polymerization reaction in the feeding area together with, i.e. in the presence of, the styrenic block copolymers.
  • the feeding area of an extruder used in a reaction extrusion process is the first area of the extruder, where the polymerization reaction occurs, while the compression zone is the area or part of the extruder where the formed TPU is solid enough to be compressed and plasticized.
  • Fig. 1 shows a scheme of a twin screw extruder 1 and the localization of the feeding zone 2, where the TPU polymerization reaction is carried out, and a compression zone 7; the starting material, i.e. isocyanates, polyols and additives and the SBC rubbers are fed to the same feeding means 6 provided at the extruder's feeding zone 2, from respective containers 3, 4 and 5.
  • the starting material i.e. isocyanates, polyols and additives and the SBC rubbers
  • a further advantage of the invention is that the SBC rubber is fed in an area of the extruder where feeding the rubber into the extruder is much easier than feeding the same rubber to an area of the extruder where the pressure is high, as is the case in the compression area.
  • the reaction is preferably carried out in a double screw co-rotating extruder having a L/D from 25 to 60 of a type well known to those skilled in the art.
  • the temperatures used in the barrels of such extruder are within the range from 170 to 220 °C.
  • the diisocyanate employed in the process is 4,4'diisocyanatodiphenylmethane 4,4'diisocyanatodiphenylmethane or a mixture of 4,4'diisocyanatodiphenylmethane and 2,4- diisocianatodiphenylmethane, the amount of 2,4 diisocianatodiphenylmethane being up to 5% by weight, preferably from 0 to 2,5% in weight.
  • the stoichiometric ratio diisocyanate/polyol is greater than 1.0, i.e. there is fed to the extruder a greater amount (moles) of diisocyanate than of polyols. This ratio will provide a very good transparency of the final product.
  • the preferred range is 1.0 to 1.2.
  • Suitable relatively high molecular weight polyols are those based on adipic acid/(1 ,4 butanediol) polyesters, or adipic acid/(1 ,6 hexanediol) polyesters, or adipic acid /(1 ,4-butanediol and 1 ,2-ethanediol) polyesters.
  • the ratio (1 ,4-butanediol / 1 ,2-ethanediol) can vary from 1 ,5 to 0,5.
  • Also suitable are relatively high molecular weight polyesters based on polycaprolactones.
  • the polyester polyol is at least 90% (w/w) of the polyol fraction of the TPU.
  • Suitable polyesters can be used alone or in mixtures. Suitable polyesters contain terminal hydroxyl groups and a number average molecular weight from 1000 g/mol to 4000 g/mol, preferably from 1750 g/mol to 3250 g/mol. From the scope of the products of the present invention poly(3-methyl-1 ,5-pentane adipate) diol is excluded.
  • Chain extenders employed in the process can be 1 ,4 butanediol, 1 ,2 ethanediol, diethylene glycol, hexanediol and hydroquinone di-3-hydroxyethyl ether or mixtures thereof.
  • Suitable antioxidants are those based on sterically hindered phenols, such as, for example octadecyl 3,5-di-tert-butyl-4- hydroxycinnamate or based on mixtures of sterically hindered phenols and alkyl phosphates, such as, for example, di-isodecyl phenyl phosphate.
  • Antioxydants are used in quantities from 0,05 to 2,5 weight %.
  • Suitable catalysts are those based on metal-organic compounds, particularly organic tin derivatives, organic titanium derivatives, organic bismuth derivatives and organic zirconium derivatives, preferably stannous octoate, alkyl titanates, titanium acetilacetonate, bismuth tris neo-decanoate and zirconium chelates.
  • additives routinely used in the production of thermoplastic polyurethane via reactive extrusion can be used also in the present invention.
  • additives include anti-hydrolysis agents (based on carbodiimide chemistry), anti-UV agents (based on the so-called HALS chemistry or on similar chemistries), inorganic fillers or pigments, organic pigments or reactive dyes, lubricants based on polyethylene waxes or montanic acid waxes, plasticizers based on phthalate esters or benzoate esters or adipate esters or citrate esters or mixtures thereof.
  • anti-hydrolysis agents based on carbodiimide chemistry
  • anti-UV agents based on the so-called HALS chemistry or on similar chemistries
  • inorganic fillers or pigments organic pigments or reactive dyes
  • lubricants based on polyethylene waxes or montanic acid waxes
  • plasticizers based on phthalate esters or benzoate esters or adipate esters or
  • thermoplastic rubbers that can be used in the present invention are styrenic block copolymers like SBS, SEBS, SIS.
  • Suitable polymers include linear, branched or grafted copolymers based on styrene and butadiene, or based on styrene -ethylene-butadiene, or based on styrene and isoprene, or based on a mixture thereof.
  • Suitable polymers have a polystyrene content ranging from 10 to 30 % in weight, based on the total polymer weight.
  • grafted polymers where grafting is obtained with a reaction of maleic anhydride or methyl acrylate or a mixture of them onto the rubber mid-block
  • styrenic copolymers carrying an hydroxyl group are excluded from the scope of present invention and do not fall within the definition of SBS, SEBS, SIS (either grafted and non grafted) previously given.
  • thermoplastic rubbers are generally used in amounts within the range of 5 to 65% (w/w) of the total weight of the composition, preferably 10 to 55% (w/w), most preferably 20 to 45% (w/w) on the total weight of the composition.
  • thermoplastic elastomer polyurethane-based was produced introducing in the feed zone of a twin-screw extruder the following starting materials:
  • n. 2 linear tri-block copolymer based on styrene and ethylene/butylenes with a polystyrene content of 30% and with maleic anhydride (MA) grafted onto the rubber mid block;
  • Components 1.A and 1.B were introduced in the feed zone: the first one from a storage vessel kept at 100 °C, the second one from the storage vessel kept at 55 °C.
  • the temperature of the feed zone of the extruder is generally of about 195-200°C.
  • the extruder is comprising a total of 11 sections as per the following tables.
  • the elastomer polyurethane-based was processed in conventional injection-moulding machine and the specimens after post-curing for 12 h at 70 °C were tested to verify:
  • component 1 80 parts of component 1 and 20 parts of component 2 are used, i.e. the rubber portion is 20% (w/w) of the composition, and the barrel temperatures were as follows:
  • the values reflect the results obtained by modifying the ratio (w/w) of components 1a and 1 b from a ratio that is below the stechiometric ratio and a ratio that is above the stoichiometric.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention a pour objet des polyuréthanes thermoplastiques modifiés souples ayant une dureté Shore A comprise dans la gamme allant de 55 à 98 Shore A, qui sont préparés par le mélange et la réaction conjointe : a) de 4,4'-diisocyanatodiphénylméthane ou d'un mélange de celui-ci et de 2,4-diisocianatodiphénylméthane, b) de polyols de polyester ayant un poids moléculaire moyen allant de 1 000 à 4 000, c) d'extenseurs de chaîne, d) d'additifs, e) d'un copolymère styrénique séquencé choisi parmi le SBS, le SEBS, le SIS ou leurs mélanges, la quantité d'un tel copolymère étant comprise dans la gamme allant de 5 à 65 % (en poids / poids) du poids total de la composition, et par le chauffage et le malaxage du mélange réactionnel, de préférence dans une extrudeuse, de sorte à mettre en œuvre un procédé en une seule phase.
EP10814693A 2009-12-23 2010-12-21 Procédé en une seule phase pour la production de polyuréthane thermoplastique modifié par des copolymères styréniques séquencés Withdrawn EP2516496A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IB2009007892 2009-12-23
PCT/IB2010/003331 WO2011077234A2 (fr) 2009-12-23 2010-12-21 Procédé en une seule phase pour la production de polyuréthane thermoplastique modifié par des copolymères styréniques séquencés

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EP2516496A2 true EP2516496A2 (fr) 2012-10-31

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EP (1) EP2516496A2 (fr)
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WO (1) WO2011077234A2 (fr)

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ES2645887T3 (es) 2015-02-12 2017-12-11 Dynasol Elastómeros S.A. Composición de copolímero segmentado con propiedades mejoradas
CN112679742B (zh) * 2020-12-25 2021-12-31 广东炫丽新材料科技有限公司 一种sebs接枝共聚物的制备方法
CN114605808A (zh) * 2022-03-10 2022-06-10 上海升广科技有限公司 以热塑性聚氨酯弹性体为基础的塑料及其制备方法
CN118165218A (zh) * 2024-04-24 2024-06-11 青岛伊科思技术工程有限公司 一种sebs橡胶组合物及其制备方法

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DE10100225A1 (de) 2001-01-04 2002-07-11 Basf Ag Weiche thermoplastische Polyurethan-Blends
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BR112012015378A2 (pt) 2017-09-12
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