WO2006029853A1 - Polyurethanes thermoplastiques contenant des polytetrahydrofuranes presentant differents poids moleculaires - Google Patents

Polyurethanes thermoplastiques contenant des polytetrahydrofuranes presentant differents poids moleculaires Download PDF

Info

Publication number
WO2006029853A1
WO2006029853A1 PCT/EP2005/009910 EP2005009910W WO2006029853A1 WO 2006029853 A1 WO2006029853 A1 WO 2006029853A1 EP 2005009910 W EP2005009910 W EP 2005009910W WO 2006029853 A1 WO2006029853 A1 WO 2006029853A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
mixture
polytetrahydrofurans
weight
molecular weight
Prior art date
Application number
PCT/EP2005/009910
Other languages
German (de)
English (en)
Inventor
Hauke Malz
Thomas Flug
Martin Vallo
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2006029853A1 publication Critical patent/WO2006029853A1/fr

Links

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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group

Definitions

  • the invention relates to thermoplastic polyurethanes based on polytetrahydrofuran, preferably obtainable by reacting (a) isocyanate with (b) isocyanate-reactive compounds having a molecular weight of 500 g / mol to 10000 g / mol and optionally (c) Chain extenders having a molecular weight of from 50 g / mol to 499 g / mol, if appropriate in the presence of (d) catalysts and / or (e) customary auxiliaries, the polytetrahydrofuran according to the invention being used as (b).
  • the invention relates to processes for the preparation of these preferably transparent, soft thermoplastic polyurethanes.
  • Thermoplastic polyurethanes are synthetic materials with a diverse field of application.
  • TPUs are found in the automotive industry, e.g. in dashboard skins, in films, in cable sheathing, in the leisure industry, as heel stains, as a functional and design element in sports shoes, as a soft component in hard-soft combinations and in many other applications.
  • TPU have a hardness of 80 Shore A to 74 Shore D.
  • plasticizers are benzoates, phthalates and phosphoric acid esters.
  • the plasticizer it is preferable to ensure that the product is compatible with the TPU.
  • Compatible in this context means that the plasticizer must be admixed with the TPU during the usual procedure for TPU production and that the plasticizer then remains as far as possible in the product during the entire time and is not lost by exudation or evaporation.
  • the mechanical properties of the TPU e.g. the abrasion and the elastomeric properties are not getting worse.
  • plasticized TPUs are used in applications which are also exposed to sunlight, e.g. Design elements of the shoe industry. Here it is disadvantageous if the plasticizer contributes to a yellowing of the product by UV degradation.
  • plasticized TPUs are exposed in their application to environmental influences that lead to hydrolytic molar mass degradation. Accordingly, it is problematic if the plasticizer also enhances the hydrolysis, either catalytically or by decomposition products of the plasticizer, for example by hydrolysis of the plasticizer Plasticizers are, for example, carboxylic acids from the hydrolysis of an ester-containing plasticizer.
  • plasticized TPU seals for fuel tanks e.g. come to the migration of the plasticizer in the fuel. This leads to embrittlement of the seal.
  • plasticizer may migrate into the food. Plasticized TPU's are therefore generally not suitable for food applications.
  • Polytetrahydrofurans are polyols which are prepared by cationic polymerization from tetrahydrofuran. Due to the production mechanism, the PTHF generally have a low molar mass distribution. For a PTHF 1000, the polydispersity, which is a measure of the molecular weight distribution, is usually 1.5. The distribution is monomodal, i. the molecular weight distribution has a maximum.
  • EP 1342740 A1 describes a TPU consisting of a low molecular weight polyol and a "low monool polypropyleneglykol polyol" having a molecular weight of 2000-12000 with at least 60% proportion of Bacpolylol.
  • the object of the present invention was thus to develop a soft thermoplastic polyurethane, which has a Shore hardness of less than or equal to 80 A, more preferably between 40 A and 70 A.
  • the soft TPU should have no migration of a plasticizer from the TPU and if possible have a very good stability to weathering.
  • the TPU should preferably be transparent.
  • thermoplastic polyurethanes based on polytetrahydrofuran wherein the polytetrahydrofuran a mixture dar ⁇ (represents) with a number average molecular weight between 1200 g / mol and 1500 g / mol and wherein in the mixture of the weight fraction of polytetrahydrofurans having a degree of polymerization of less than or equal to 14 greater than 21% by weight, preferably greater than 26% by weight, particularly preferably greater than 26% by weight and less than 40% by weight, in particular greater than 26% by weight.
  • % and less than 34% by weight in each case based on the relative weight of the polytetrahydrofurans contained in the mixture, and in the mixture the proportion by weight of the polytetrahydrofurans having a degree of polymerization greater than 40 less than 40% by weight less than 32% by weight, more preferably less than 32% by weight and more than 10% by weight, in particular less than 32% by weight and greater than 25% by weight, based in each case on the total weight of the polytetrahydrofurans contained in the mixture.
  • degree of polymerization is meant how many tetrahydrofurans are present in the polytetrahydrofuran.
  • degree of polymerization P molecular weight of the polymer chain / molecular weight of the individual basic unit.
  • the degree of polymerization is used for the single macromolecule.
  • the reaction product of the isocyanates (a) with the chain extenders (c) forms the so-called hard segment in a thermoplastic polyurethane
  • the reaction product of the isocyanate (a) with the higher molecular weight diols (b) represents the so-called soft segment of the thermoplastic polyurethane.
  • the structural components (b) and (c) can be varied in relatively broad molar ratios. For example, the molar ratio of (b) and (c) between a molar ratio of 1: 1, corresponding to a soft TPU Shore hardness 80 A and 1: 5.6, corresponding to a hard TPU Shore hardness 75 D, vary.
  • the hardness of the TPU is also further reduced. If, however, a ratio of (b) to (c) is chosen to be significantly greater than 1, the crystallization of the hard segments is hindered. The crystallization of the TPU takes place so slowly that the cycle times for the processing of the thermoplastic polyurethane become uneconomically long. At the same time, the TPU loses its desired thermal and mechanical properties.
  • the amount of (c) can be lowered further without significantly changing the minimum ratio of (b) to (c) of about 1: 1, which is recognized as good.
  • a molecular weight of polytetrahydrofuran also referred to in this document as PTHF, of about 1500 g / mol, however, there is an effect that is commonly known as the mother of pearl effect.
  • Hard segments of the TPU then crystallize due to their incompatibility with the soft phase, and the TPU retains a pearlescent, non-transparent appearance, which in many cases is undesirable.
  • an increase in the molecular weight of the soft phase polyol often leads to a crystallization of the soft phase at temperatures around the freezing point.
  • the TPU By using the PTHF with the molecular weight distribution according to the invention, the TPU remained transparent despite increasing the number average molecular weight of the polyol. It did not come to the above-described nacreous effect. Surprisingly, the TPUs containing the PTHF with different molar mass also showed no hard phase crystallization. This ensures good low-temperature properties.
  • thermoplastic polyurethanes according to the invention preferably have a Shore hardness between 40 A and 75 A.
  • the thermoplastic polyurethanes according to the invention are preferably transparent.
  • Polytetrahydrofuran is well known and commercially available in various molecular weights from BASF Aktiengesellschaft. Essential to the invention is the use of polytetrahydrofurans having the molecular weight distribution according to the invention. It is preferred if the polytetrahydrofuran mixture (i) is based on the mixture of at least two, preferably separately prepared, polytetrahydrofuran batches.
  • the term "at least two polytatrahydrofuran charges" is understood to mean that two different polytetrahydrofurans are used, which have different mean molecular weight information, and it is particularly preferred if at least two of the separately prepared polytetrahydrofuran charges are at least 500 g / mol. preferably have at least 800 g / mol of strigie ⁇ denes number-average molecular weight.
  • a Polytetrahydrofurancharge a number average molecular weight between 900 g / mol and 1100 g / mol and another polytetrahydrofuran has a number average molecular weight between 1900 g / mol and 2100 g / mol.
  • the synthesis components (b) and (c) may preferably be used in molar ratios of component (b) to total chain extenders (c) to be used between 1: 0.35 and 1: 2.0 between 1: 0.50 and 1: 1, 5, in particular between 1: 0.7 and 1: 1, 1 are used.
  • thermoplastic polyurethanes can be prepared by reacting (a) isocyanates with (b) isocyanate-reactive compounds having a molecular weight of 500 to 10,000 and optionally (c) chain extenders having a molecular weight of 50 to 499, optionally in the presence of (d) catalysts and / or (e) customary auxiliaries.
  • thermoplastic polyurethanes thus takes place by reacting (a) isocyanates with (b) isocyanate-reactive compounds having a molecular weight of 500 g / mol to 10000 g / mol, preferably 500 g / mol to 4000 g / mol and optionally ( c) chain extenders having a molecular weight of from 50 g / mol to 499 g / mol, if appropriate in the presence of (d) catalysts and / or customary auxiliaries, where a polytetrahydrofuran mixture is used as the isocyanate-reactive compound (b) number average molecular weight between 1200 g / mol and 1500 g / mol and wherein in the mixture, the proportion by weight of polytetrahydrofurans having a degree of polymerization of less than or equal to 14 greater than 21Gew .-%, preferably greater than 26 wt .-%, particularly preferably greater 26
  • thermoplastic polyurethane can be processed thermoplastically, without losing the effect of the plasticizer according to the invention.
  • the starting components and processes for the preparation of the preferred TPU are shown.
  • the components (a), (b), (c) and optionally (d) and / or (e) which are usually used in the preparation of the TPU are described below by way of example:
  • organic isocyanates it is possible to use generally known aromatic, aliphatic, cycloaliphatic and / or araliphatic isocyanates, preferably diisocyanates, for example 2,2 ', 2,4' and / or 4,4 ' Diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2 Diphenylethane diisocyanate and / or phenylene diisocyanate, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene diisocyanate 1, 5, 2-ethyl-1-butylene
  • HXDI Bis (isocyanatomethyl) cyclohexane
  • 1,4-cyclohexane diisocyanate 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or 2,6-cyclohexane diisocyanate and / or 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate, preferably 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), hexamethylene diisocyanate and / or IPDI, in particular 4,4'-MDI and / or hexamethylene diisocyanate.
  • MDI 2,2'-, 2,4'- and / or 4,4'-diphenylmethane di
  • isocyanate-reactive compounds the dar ⁇ put polytetrahydrofuran are used.
  • isocyanate-reactive compounds may also be used, for example polyesterols, polyetherols and / or polycarbonate diols, which are usually also grouped under the term "polyols", with molecular weights of 500 to 12,000 g / mol, preferably 600 to 6,000 , in particular 800 to 4000, and preferably an average functionality of 1, 8 to 2.3, preferably 1, 9 to 2.2, in particular 2.
  • chain extenders (c) it is possible to use generally known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499, preferably 2-functional compounds, for example diamines and / or alkanediols having 2 to 10C -Atomen in the alkylene radical, especially butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or Dekaalkylenglykole with 3 to 8 carbon atoms, preferably corresponding oligo- and / or polypropylene glycols, wherein mixtures of the chain extenders can be used.
  • 2-functional compounds for example diamines and / or alkanediols having 2 to 10C -Atomen in the alkylene radical, especially butaned
  • Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the constituent components (b) and (c) are the tertiary amines known and customary in the prior art, such as Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo- (2,2,2) -octane and the like, and in particular organi ⁇ metallic compounds such as titanic acid esters, iron compounds such. Iron (III) acetylacetonate, tin compounds, e.g.
  • the catalysts are usually used in amounts of from 0.00001 to 0.1 parts by weight per 100 parts by weight of poly (hydroxyl) compound (b).
  • auxiliaries e)
  • synthesis components (a) to (c) e)
  • auxiliaries e)
  • surface-active substances fillers, flame retardants, nucleating agents, oxides. dationsstabilisatoren, lubricants and mold release agents, dyes and pigments, optionally in addition to the stabilizers according to the invention further stabilizers, for example against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers.
  • Hydroxyl-protecting agents used are preferably oligomeric and / or polymeric aliphatic or aromatic carbodiimides.
  • stabilizers are preferably added to the TPU.
  • Stabilizers in the context of the present invention are additives which protect a plastic or a plastic mixture against harmful environmental influences. Examples are primary and secondary antioxidants, hindered amines
  • Light stabilizer, UV absorber, hydrolysis protection agent, quencher and flame retardant examples of commercial stabilizers are given in Plastics Additive Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001 ([1]), p. 98-S. 136.
  • antioxidants may be added.
  • phenolic antioxidants are used. Examples of phenolic antioxidants are given in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Kunststoff, 2001, pp. 98-107 and pp. 116- p. 121.
  • An example of a preferably used phe ⁇ nolisches antioxidant is pentaerythrityl-tetrakis (3- (3,5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl) propionate) (Irganox ® 1010).
  • the phenolic antioxidants are generally used in concentrations between 0.1 and 5% by weight, preferably between 0.1 and 2% by weight, in particular between 0.5 and 1.5% by weight, in each case based on on the total weight of the TPU.
  • TPUs according to the invention are significantly more stable to ultraviolet radiation than, for example, TPUs softened with phthalates or benzoates, stabilization containing only phenolic stabilizers is often insufficient. For this reason, the TPUs according to the invention, which are exposed to UV light, preferably additionally with a
  • UV absorber stabilized UV absorbers are molecules that absorb high-energy UV light and dissipate the energy. Common UV absorbers which are used in the art include e.g. to the group of cinnamic acid esters, diphenylcyanoacrylates, formamidines, benzylidenemalonates, dia- rylbutadienes, triazines and benzotriazoles. Examples of commercial UV-
  • UV absorbers can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Kunststoff, 2001, pages 116-122.
  • the UV absorbers have a number-average molecular weight of greater than 300 g / mol, in particular greater than 390 g / mol. Further, the preferred UV absorbers should have a molecular weight of not greater than
  • UV absorber is the group of benzotriazoles.
  • benzotriazoles are Tinuvin ® 213, Tinuvin ® 328, Tinuvin ® 571 and Tinuvin ® 384 and the Eversorb ® 82.
  • the UV absorber in amounts between 0.01 and 5 wt .-%, based on the Ge ⁇ total mass TPU metered, more preferably between 0.1 and 2.0 wt .-%, in particular between 0.2 and 0.5 wt .-%, each based on the Intel ⁇ weight of the TPU.
  • HALS Hinderred Amine Light Stabilizer
  • Hindered Amine Light Stabilizers are preferably Hindered Amine Light Stabilizers in which the number average molecular weight is greater than 500 g / mol. Furthermore, the molecular weight of the preferred HALS compounds should preferably not be greater than 10,000 g / mol, more preferably not greater than 5,000 g / mol.
  • hindered amine light stabilizers are bis (1, 2 I 2,6,6-pentamethylpiperidyl) sebacate (Tinuvin ® 765, Ciba Specialty Chemicals Inc.), and the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl 4-hydroxypiperidines and succinic acid
  • Tinuvin ® 622 Particularly preferred is the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidines and succinic acid (Tinuvin ® 622) when the titanium content of the product ppm ⁇ 150, preferably ⁇ 50 ppm more preferably ⁇ 10 ppm is.
  • HALS compounds are preferably used in a concentration between 0.01 and 5 wt .-%, be ⁇ particularly preferably between 0.1 and 1 wt .-%, in particular between 0.15 and 0.3 wt .-%, in each case based on the total weight of the TPU.
  • a particularly preferred UV stabilization comprises a mixture of a phenolic stabilizer, a benzotriazole and a HALS compound in the preferred amounts described above.
  • the reaction can be carried out under customary code numbers, preferably at a code number between 950 and 1050, particularly preferably at a code number between 970 and 1010, in particular between 980 and 995.
  • the index is defined by the ratio of the total isocyanate groups used in the reaction Component (a) to the isocyanate-reactive groups, ie the active hydrogens, of components (b) and (c).
  • an isocyanate group of component (a) has an active hydrogen atom, ie a function which is reactive toward isocyanates, of components (b) and (c).
  • active hydrogen atom ie a function which is reactive toward isocyanates, of components (b) and (c).
  • more isocyanate groups exist than OH groups.
  • the preparation of the TPU can be carried out continuously by the known processes, for example with reaction extruders or the strip process according to one-shot or the prepolymer process, or batchwise by the known prepolymer process. In these processes, the components (a), (b) and, if appropriate, (c), (d) and / or (e) can be mixed successively or simultaneously with one another, the reaction beginning immediately.
  • the constituent components (a), (b) and optionally (c), (d) and / or (e) are introduced into the extruder individually or as a mixture, for example at temperatures of from 100 to 28O 0 C, Preferably 140 to 25O 0 C reacted, the resulting TPU is extruded, cooled Tool and granulated.
  • thermoplastic polyurethanes obtainable by the process according to the invention, preferably the films, moldings, shoe soles, rolls, fibers, linings in automobiles, wiper blades, hoses, cable connectors, folded bellows, trailing cables, cable sheathings, seals, belts or damping elements have the initially described Advantages.
  • tinplate bucket 1000g of a polyol mixture were composed of PTHF 1000 (BASF Aktiengesellschaft) and PTHF 2000 (BASF Aktiengesellschaft) in the weight ratio 1: 1 and 65.86 g of 1, 4-butanediol weighed and completed ⁇ to 90 0 C heated. 1098 and 0.5 wt .-% Irganox ® 1010 and 2.5 ppm was then heated with stirring 0.5 wt .-% Irganox® tin dioctoate were added.
  • tinplate bucket 1000 were g of a polyol mixture consisting of 150 g of PTHF 1000 (BASF Aktiengesellschaft) and 850g Lupranol ® 1000 (BASF Aktien ⁇ Company) and 66.37 g of 1, weighed 4-butanediol and heated to 90 0 C. On closing octoate was tin-di-added under stirring 0.5 wt .-% Irganox ® 1098 and 0.5 wt .-% Irganox ® 1010 and 5.0 ppm.
  • the L value was determined using an UltraScan colorimeter from HunterLab.
  • the TPU plate was measured once against a white tile and against a light trap in reflection under exclusion of gloss.
  • the measured brightness values (L values according to DIN 6174) were then compared and expressed as opacity in%.

Abstract

L'invention concerne des polyuréthanes thermoplastiques à base de polytétrahydrofurane, lequel est un mélange (i) de poids moléculaire moyen oscillant entre 1200 g/mol et 1500 g/mol. Dans ce mélange, la part en poids des polytétrahydrofuranes ayant un degré de polymérisation inférieur ou égal à 14 est supérieure à 21 %, relativement au poids total des polytétrahydrofuranes contenus dans le mélange, et la part en poids des polytétrahydrofuranes ayant un degré de polymérisation supérieur à 40 est inférieure à 40 %, relativement au poids total des polytétrahydrofuranes contenus dans le mélange.
PCT/EP2005/009910 2004-09-17 2005-09-15 Polyurethanes thermoplastiques contenant des polytetrahydrofuranes presentant differents poids moleculaires WO2006029853A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004045619.4 2004-09-17
DE200410045619 DE102004045619A1 (de) 2004-09-17 2004-09-17 Thermoplastische Polyurethane enthaltend Polytetrahydrofuran

Publications (1)

Publication Number Publication Date
WO2006029853A1 true WO2006029853A1 (fr) 2006-03-23

Family

ID=35385574

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/009910 WO2006029853A1 (fr) 2004-09-17 2005-09-15 Polyurethanes thermoplastiques contenant des polytetrahydrofuranes presentant differents poids moleculaires

Country Status (2)

Country Link
DE (1) DE102004045619A1 (fr)
WO (1) WO2006029853A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8277157B2 (en) 2009-02-12 2012-10-02 Ford Motor Company of Australia Ltd. Tie-down device
US20170233520A1 (en) * 2014-03-25 2017-08-17 Basf Se Tpu pneumatic hose
WO2019234117A1 (fr) * 2018-06-06 2019-12-12 Basf Se Chaussures de ski comprenant un module électronique indépendant de la température

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5590779B2 (ja) * 2008-06-20 2014-09-17 ダンロップスポーツ株式会社 ゴルフボール

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1149851A1 (fr) * 2000-04-25 2001-10-31 Bayer Ag Polyuréthane thermoplastique aliphatique et son utilisation
EP1338614A1 (fr) * 2002-02-23 2003-08-27 Bayer Ag Procédé de production des elastomères de polyuréthane thermoplastiques, mous, facilement démoulables et à retrait minime
EP1367072A1 (fr) * 2002-05-30 2003-12-03 Bayer Corporation Polyuréthanes/urées, utiles à la synthèse de Spandex et leur procédé de préparation
WO2005005509A1 (fr) * 2003-06-30 2005-01-20 Noveon Ip Holdings Corp. Fibres tpur-polyether filees par fusion presentant des polyols melanges et procede de fabrication associe

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1149851A1 (fr) * 2000-04-25 2001-10-31 Bayer Ag Polyuréthane thermoplastique aliphatique et son utilisation
EP1338614A1 (fr) * 2002-02-23 2003-08-27 Bayer Ag Procédé de production des elastomères de polyuréthane thermoplastiques, mous, facilement démoulables et à retrait minime
EP1367072A1 (fr) * 2002-05-30 2003-12-03 Bayer Corporation Polyuréthanes/urées, utiles à la synthèse de Spandex et leur procédé de préparation
WO2005005509A1 (fr) * 2003-06-30 2005-01-20 Noveon Ip Holdings Corp. Fibres tpur-polyether filees par fusion presentant des polyols melanges et procede de fabrication associe

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8277157B2 (en) 2009-02-12 2012-10-02 Ford Motor Company of Australia Ltd. Tie-down device
US20170233520A1 (en) * 2014-03-25 2017-08-17 Basf Se Tpu pneumatic hose
WO2019234117A1 (fr) * 2018-06-06 2019-12-12 Basf Se Chaussures de ski comprenant un module électronique indépendant de la température
US11970568B2 (en) 2018-06-06 2024-04-30 Basf Se Ski boots with temperature-independent modulus of elasticity

Also Published As

Publication number Publication date
DE102004045619A1 (de) 2006-04-06

Similar Documents

Publication Publication Date Title
EP2445968B1 (fr) Polyuréthane à base de polyuréthane thermoplastique souple
EP3122795B1 (fr) Tuyau flexible pneumatique en tpu
EP2331598B1 (fr) Polyuréthanes à base de polyesterdiols présentant des caractéristiques de cristallisation améliorées
WO2007118826A1 (fr) Matières plastiques thermoplastiques, en particulier, polyuréthane, contenant des polytétrahydrofurane-esters comme plastifiants
EP1204688B1 (fr) Polyurethannes thermoplastiques
EP3394138B1 (fr) Materiau retractable en tpu
EP3016989B1 (fr) Polyuréthane à base de matières premières renouvelables
EP3420009B1 (fr) Procede de fabrication d'un copolymere dibloc
DE112005001101B4 (de) Thermoplastische Polyurethane enthaltend Weichmacher sowie Verfahren zur Herstellung thermoplastischer Polyurethane
WO2011120895A1 (fr) Encollage à la colle fusible au moyen de polyuréthane thermoplastique
EP3645597B1 (fr) Polyuréthane thermoplastique
EP1877460B1 (fr) Polyurethane thermoplastique
EP3559072B1 (fr) Polyuréthane thermoplastique présentant une résistance à la déchirure élevée
EP2569359B1 (fr) Polyuréthanne thermoplastique contenant un ester de glycérine ayant au moins un motif d'acide carboxylique aliphatique
WO2017050738A1 (fr) Polyuréthane thermoplastique
WO2006029853A1 (fr) Polyurethanes thermoplastiques contenant des polytetrahydrofuranes presentant differents poids moleculaires
WO2006010542A1 (fr) Polyurethanes thermoplastiques contenant un plastifiant
EP3810672A1 (fr) Polyuréthanes thermoplastiques durs transparents
EP3580251B1 (fr) Polyuréthane thermoplastique
WO2013124249A1 (fr) Procédé de production de mélanges de polyhydroxyalcanoates (pha) et de polyuréthanes thermoplastiques (tpu)

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase