EP3841143A1 - Polyuréthane présentant une dureté améliorée - Google Patents

Polyuréthane présentant une dureté améliorée

Info

Publication number
EP3841143A1
EP3841143A1 EP19755393.6A EP19755393A EP3841143A1 EP 3841143 A1 EP3841143 A1 EP 3841143A1 EP 19755393 A EP19755393 A EP 19755393A EP 3841143 A1 EP3841143 A1 EP 3841143A1
Authority
EP
European Patent Office
Prior art keywords
groups
polyester polyol
mol
hardness
proportion
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.)
Pending
Application number
EP19755393.6A
Other languages
German (de)
English (en)
Inventor
Hans Georg Grablowitz
Hartmut Nefzger
Olaf Fleck
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.)
Covestro Deutschland AG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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 Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3841143A1 publication Critical patent/EP3841143A1/fr
Pending legal-status Critical Current

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
    • C08G18/40—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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to polyester polyols with particular purity and their use for the production of polyurethanes with improved properties, in particular with improved hardness.
  • Polyurethanes are a class of plastics well known to those skilled in the art. They are produced by the addition reaction of polyhydric alcohols with polyisocyanates. In principle, many compounds with at least two hydroxyl groups per molecule are suitable as polyhydric alcohols. These can be monomeric compounds such as Be glycerin. However, technically and economically more important are polyhydric alcohols, which are themselves polymers. In particular, polycarbonate polyols, polyester polyols, polyether polyols, polyether carbonate polyols or polyether esters are used.
  • Polycarbonate polyols are obtained by a condensation reaction of low molecular weight carbonates and low molecular weight polyhydric alcohols.
  • the molar ratio of carbonate to polyol determines the molar mass of the polycarbonate polyol.
  • a molar excess of polyol is used to obtain hydroxyl-functional end products.
  • the low-molecular alcohol used contains impurities. 1,6-hexanediol often also contains 1,4-cyclohexanediol. If these impurities are incorporated into the polyol, products are formed which, in addition to primary OH groups, also have secondary OH groups.
  • EP 2 213 696 has shown that a high proportion of by-products with secondary hydroxyl groups means that the polyurethanes produced from the corresponding polycarbonate have a lower tensile strength and a lower resistance to oleic acid. There is no noticeable influence of the proportion of secondary hydroxyl groups in the polycarbonate polyol on the hardness of the polyurethane produced therefrom.
  • Polyester polyols are produced by a condensation reaction of polyhydric carboxylic acids and polyhydric alcohols. The quantitative ratio of the two components is chosen so that there is a molar excess of hydroxyl groups in the reaction mixture and the resulting polymer therefore has free, terminal hydroxyl groups.
  • Polyester polyols commonly used for the production of polyurethanes have a number average molecular weight between 500 and 4000 g / mol and an average OH functionality between 1.8 and 3.5. But they can also have molecular weights below 500 and above 4000 Da; likewise functionalities of less than 1.80 and more than 3.5. Common polyester polyols and suitable production processes are described in M.
  • the present patent application relates to polyester polyols with a low content of secondary hydroxyl groups, and their use for the production of polyurethanes with improved hardness.
  • the present invention relates to a polyester polyol with a proportion of secondary OH groups in the total amount of terminal OH groups of at most 5%.
  • the polyester polyols have OH numbers of 18 to 300 mg KOH / g and consist of at least 95% by weight, preferably at least 98% by weight, of bifunctional structural components.
  • The% by weight missing from 100% can be more than bifunctional, for example trifunctional or tetrafunctional, but also monofunctional, with mixtures of, for example, trifunctional and tetrafunctional structural components also possible.
  • trifunctional structural components are glycerol, 1,1,1-trimethylolpropane, pentaerythritol, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, malic acid and tartaric acid.
  • polyester polyols which can be obtained from exclusively bifunctional structural components.
  • One or more of the structural components can be bio-based, i.e. be produced from renewable raw materials and / or by means of at least one fermentative process step.
  • the structural components for the polyester polyols according to the invention are a.) At least one aromatic and / or aliphatic dicarboxylic acid and / or dicarboxylic acid equivalent and
  • dicarboxylic acid equivalents can be used as structural component a).
  • all aliphatic diols having 2 to 14 carbon atoms can be used as structural component b).
  • the aliphatic diols with 2 to 14 carbon atoms are linear, but can also have one or more alkyl side chains.
  • Suitable structural components a) are: phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, tetrachlorophthalic acid, maleic acid, non-succinic acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, 3,3-diethylglutaric acid and 2,2-dimethylsuccinic acid.
  • diarboxylic acid equivalents can also be used as the acid source.
  • component a) Particularly suitable as component a) are linear, unbranched dicarboxylic acids having 4 to 10 carbon atoms, adipic acid, succinic acid, phthalic acid, isophthalic acid and terephthalic acid, and the dicarboxylic acid equivalents of the abovementioned compounds.
  • Examples include: phthalic anhydride, succinic anhydride, dimethyl terephthalate,
  • Suitable structural components b) are, for example: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-decanediol, 2-methyl-propanediol-1,3,2,2-dimethyl-propanediol-1,3,3-methylpentanediol-1,5.
  • component b) are linear, unbranched diols having 2 to 12 carbon atoms selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-decanediol and 2,2-dimethyl-propanediol-1,3.
  • Linear, unbranched hydroxycarboxylic acids with> 6 and ⁇ 10 C atoms can be considered as component c).
  • 6-Hydroxycaproic acid and e-caprolactone are particularly preferred.
  • the molar proportions of components a), b) and optionally c) determine the average degree of polymerization of the polyester polyols. In any case, the components must be composed such that the number of hydroxyl groups used exceeds the number of carboxyl groups used.
  • polyester polyols are produced in a manner known per se by polycondensation.
  • catalysts known for the production of polyesters can be used as catalysts. These are, for example, tin salts, e.g. Tin dichloride, titanates, e.g. Tetrabutyl titanate, bismuth salts, e.g. Bismuth acetate and bismuth neodecanoate or strong acids, e.g. p-toluenesulfonic acid and sulfuric acid.
  • tin salts e.g. Tin dichloride
  • titanates e.g. Tetrabutyl titanate
  • bismuth salts e.g. Bismuth acetate and bismuth neodecanoate
  • strong acids e.g. p-toluenesulfonic acid and sulfuric acid.
  • p-toluenesulfonic acid and sulfuric acid e.g. p-toluenesulfonic acid and sulfuric acid.
  • the polyesters can also be produced without the use of
  • the polyesters are made without the use of a solvent.
  • a solvent in particular a water-carrying solvent (azeotropic esterification), such as benzene, toluene or dioxane.
  • azeotropic esterification such as benzene, toluene or dioxane.
  • the discharge of the water of reaction in the solvent-free variant is normally supported by applying a negative pressure, in particular towards the end of the esterification.
  • pressures from 1 to 500 mbar are used.
  • esterification is also possible above 500 mbar.
  • the discharge of the water of reaction can also be supported by passing an inert gas, such as nitrogen or argon.
  • reaction temperature is carried out at an elevated temperature. Reaction temperatures of 100 to 250 ° C., preferably 160 to 230 ° C., are customary in the solvent-free variant. In azeotropic esterification, the reaction temperature is determined by the type and amount of entrainer and is usually in the range from 100 to 180 ° C.
  • the reaction is carried out until a conversion in which the acid number of the polyester polyols according to the invention is at most 10, preferably at most 5, particularly preferably at most 2 and very particularly preferably ⁇ 1 mg KOH / g.
  • the proportion of secondary hydroxyl groups in the total amount of the hydroxyl groups present in the polyester polyol is at most 5 mol%, preferably at most 2 mol% and even more preferably at 1 mol%.
  • the proportion is preferably determined by means of 13 C-NMR at a measuring frequency of 151.0 MHz in chloroform-dl.
  • the proportion of primary hydroxyl groups (CH -OH) is preferably determined using the following formula:
  • F is the area of the respective signal in the NMR spectrum and CH-OH stands for secondary bonded OH groups.
  • polyester polyols with the low secondary hydroxyl group content required according to the invention it is necessary to use sufficiently pure alcohols to prepare the polyester.
  • the suitability of an alcohol for the production of a polyester polyol suitable according to the invention can be checked by conventional analysis methods such as gas chromatography or high-performance liquid chromatography.
  • the proportions of all polyols with at least one secondary OH group are a maximum of half of the desired value for the finished polyester polyol.
  • the present invention relates to a polymerizable composition
  • a polymerizable composition comprising at least one polyester polyol with the one further above in this Registration defined maximum content of secondary OH groups based on the total amount of terminal OH groups present and at least one polyisocyanate.
  • polyisocyanate denotes molecules with an average isocyanate functionality of at least 2. Suitable polyisocyanates are aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates. Mixtures of such polyisocyanates can also be used.
  • Preferred polyisocyanates are selected from the group consisting of butylene diisocyanate and hexamethylene diisocyanate (HDI ), 1,5-pentamethylene diisocyanate (PDI), isophorone diisocyanate (IPDI), 2,2,4 and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or their mixtures of any isomer content , isocyanatomethyl-l, 8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4 ' - Diphenylmethane diisocyanate, triphenylmethane-4,4 ', 4 "-triis
  • the polymerizable composition is preferably characterized in that the molar ratio of isocyanate groups to hydroxyl groups of the at least one polyester polyol is between 0.7: 1.0 and 2.5 to 1.0, more preferably between 0.8: 1.0 and 2, 0 to 1.0, and more preferably 0.9: 1.0 to 1.8: 1.0.
  • the polymerizable composition according to the invention preferably additionally contains at least one catalyst which accelerates the formation of urethane groups from hydroxyl and isocyanate groups.
  • All urethanization catalysts known to the person skilled in the art can be used for this, such as organometallic compounds and tertiary amines. Tin dioctoate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2,2,2] octane and bismuth dioctoate are particularly preferred.
  • the present invention relates to the use of a polyester polyol or a polymerizable composition as defined above in this application for the production of a polyurethane plastic.
  • polyester polyol or a polymerizable composition for producing a polyurethane plastic with particularly high hardness.
  • Particularly high hardness here denotes the improvement in the hardness of the polyurethane plastic produced according to the invention compared to polyurethane plastics which were produced from polyester polyols with a higher proportion of secondary hydroxyl groups.
  • the polyurethane plastic produced has a Shore D hardness which is at least 3 mol% higher than the hardness of a polyurethane plastic which is coated with a polyester polyol containing secondary hydroxyl groups of at least 5 mol%. % of the total of the terminal hydroxyl groups
  • the Shore D hardness is preferably measured in accordance with DIN ISO 7619-1 in the version from February 2012.
  • the alcohol component of the polyester polyol consists of at least 90% by weight, more preferably at least 95% by weight, of 1,6-hexanediol.
  • the polyurethane plastic has a Shore D hardness that is at least 8% above the value that is otherwise identical when using one
  • Polyester polyol with a proportion of secondary OH groups in the total amount of terminal OH groups of at least 5 mol% is measured.
  • the alcohol component of the polyester polyol consists of at least 90% by weight, more preferably at least 95% by weight, of 1,6-hexanediol.
  • the polyurethane plastic has a König pendulum hardness that is at least 5% above the value measured when using an otherwise identical polyester polyol with a proportion of secondary OH groups in the total amount of terminal OH groups of at least 5 mol% becomes.
  • the alcohol component of the polyester polyol consists of at least 90% by weight, more preferably at least 95% by weight, of 1,4-butanediol.
  • the polyurethane plastic has a Shore D Hardness which is at least 3% above the value measured when using an otherwise identical polyester polyol with a proportion of secondary OH groups in the total amount of terminal OH groups of at least 5 mol%.
  • the alcohol component of the polyester polyol consists of at least 90% by weight, more preferably at least 95% by weight, of 1,4-butanediol.
  • the polyurethane plastic has a König pendulum hardness which is at least 4% above the value measured when using an otherwise identical polyester polyol with a proportion of secondary OH groups in the total amount of terminal OH groups of at least 5 mol% becomes.
  • the present invention relates to a process for the production of polyurethane plastics with particularly high hardness, comprising the steps of a) mixing a polyester polyol with a proportion of secondary hydroxyl groups in the total amount of terminal hydroxyl groups of at most 2% with at least one polyisocyanate; b) reaction of the mixture to form a polyurethane.
  • process step a) The mixing of polyester polyol and polyisocyanate in process step a) can be carried out using all processes known to the person skilled in the art.
  • the product of process step a) is the polymerizable composition defined earlier in this application.
  • the methods of reacting a polymerizable composition to a polyurethane are well known to those skilled in the art. All methods known from polyurethane chemistry and suitable for the specific polymerizable composition can be used.
  • the reaction of the polyester polyol with the polyisocyanate to form a polyurethane can be carried out in various ways, for example by heating the mixture in a reaction vessel to a defined conversion or placing the mixture on a substrate or a mold and the reaction on the substrate or the mold takes place. In addition, it is also possible to bring the mixture onto a substrate or into a mold by an in-situ mixing process, where the further reaction to the polyurethane then takes place.
  • the resulting polyurethane can optionally be processed further in subsequent reactions, for example by one in the case of free isocyanate groups Chain extension is carried out with polyamines or a reaction with atmospheric moisture to give polyurethaneureas.
  • Chain extension is carried out with polyamines or a reaction with atmospheric moisture to give polyurethaneureas.
  • An overview of such processes can be found in the Plastics Handbook, Vol. 7, Polyurethanes; Becker, Braun and Oertel, Hanser Verlag, (1993).
  • polyurethanes described above can be used in a wide variety of applications, in particular as moldings, elastomers, adhesives, coatings, films, sealants and fibers. These include in the volumes of the plastics handbook (see above) or in: Polyurethanes: lacquers, adhesives and sealants; Meier-Westhues, Vincentz-Verlag, (2007).
  • Acid number was determined according to DIN EN ISO 2114 (June 2002).
  • Viscosity Dynamic viscosity: Rheometer MCR 51 from Anton Paar according to DIN 53019-1 (version from September 2008) with a measuring cone CP 50-1, diameter 50 mm, angle 1 ° at shear rates of 25, 100, 200 and 500 s 1st
  • the polyols according to the invention and not according to the invention show viscosity values which are independent of the shear rate.
  • Shore hardness DIN ISO 7619-1; Version of Feb. 2012
  • Viscosity 1600 mPas at 75 ° C
  • polyester polyols A-2 (V) and A-3 (V) were analogous as for Ex. A-1.
  • Table 1 shows that only the polyester polyols A-1 and B-1 have almost exclusively primary hydroxyl end groups. Comparative examples A-2 (V), A-3 (V), B-2 (V) and B-3 (V) have surprisingly high proportions of secondary hydroxyl end groups in the light of the small amounts of diol used with secondary hydroxyl groups, such as does the following:
  • the polyesters listed in Table 1 are crosslinked with a commercially available polyisocyanate (Desmodur N3300) in the ratio (NCO / OH: 1.0).
  • a leveling agent (Byk 302; 0.1% by weight) and a catalyst which is customary for this reaction (DBTL, 10% in butyl acetate; 0.02% by weight on solids content) are used to obtain suitable test specimens.
  • the 2-component systems and test specimens based on the polyester and the polyisocyanate are manufactured according to the following detailed formulation and the steps described below:
  • the polyester is weighed into a suitable vessel and heated to 80 ° C.
  • the catalyst DBTL with 0.02% (on solids content) and Byk 302 with 0.1% (on solids content) are added immediately after the addition of the polyisocyanate and after homogenization and stirred vigorously, but as free of bubbles as possible.
  • the systems are mounted on a glass plate and a backing paper for free films with 500 pm wet film.
  • the coated lacquer films are tempered for 16 hours at 80 ° C in a convection oven. After tempering the glass plates, they are conditioned for approx. 1 hour at room temperature (approx. 23 ° C). Then the layer thickness is measured and the paint film is patterned according to further criteria.
  • test specimen is cast to determine the Shore hardness.
  • the networked system is applied bubble-free in a plastic lid with a diameter of approx. 6 cm and also tempered at 80 ° C for 16 h.
  • the resulting test specimen should have a diameter of at least 35 mm and a thickness of at least 6 mm.
  • all test specimens are conditioned for a sufficiently long time in a standard atmosphere (for plastics, 23 ° C, 50% relative humidity).
  • the tests of the shore hardness, the pendulum hardness according to König and the execution of the tensile tests are carried out according to the underlying standards known to the person skilled in the art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne des polyester polyols ayant une pureté particulière et leur utilisation pour produire des polyuréthanes présentant des propriétés améliorées, en particulier une dureté améliorée.
EP19755393.6A 2018-08-24 2019-08-21 Polyuréthane présentant une dureté améliorée Pending EP3841143A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18190762.7A EP3613787A1 (fr) 2018-08-24 2018-08-24 Polyuréthane à dureté améliorée
PCT/EP2019/072373 WO2020038998A1 (fr) 2018-08-24 2019-08-21 Polyuréthane présentant une dureté améliorée

Publications (1)

Publication Number Publication Date
EP3841143A1 true EP3841143A1 (fr) 2021-06-30

Family

ID=63405080

Family Applications (2)

Application Number Title Priority Date Filing Date
EP18190762.7A Ceased EP3613787A1 (fr) 2018-08-24 2018-08-24 Polyuréthane à dureté améliorée
EP19755393.6A Pending EP3841143A1 (fr) 2018-08-24 2019-08-21 Polyuréthane présentant une dureté améliorée

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP18190762.7A Ceased EP3613787A1 (fr) 2018-08-24 2018-08-24 Polyuréthane à dureté améliorée

Country Status (5)

Country Link
US (1) US20210189060A1 (fr)
EP (2) EP3613787A1 (fr)
JP (1) JP2021535248A (fr)
CN (1) CN112739737B (fr)
WO (1) WO2020038998A1 (fr)

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US3605848A (en) * 1968-12-23 1971-09-20 Inter Polymer Res Corp Microcellular urethane elastomers of relatively low density
GB9225030D0 (en) * 1992-11-30 1993-01-20 Baxenden Chem Solvent based enzymatic synthesis
US5512635A (en) * 1993-05-27 1996-04-30 Amoco Corporation Process for preparing linear monofunctional and telechelic difunctional polymers and compositions obtained thereby
CN101855270B (zh) 2007-11-16 2014-03-12 旭化成化学株式会社 聚碳酸酯二醇
WO2011000546A1 (fr) * 2009-07-01 2011-01-06 Bayer Materialscience Ag Procédé de préparation d'un polymère de polyuréthane comportant des polyesterpolyols portant des groupes terminaux hydroxyle secondaires
WO2011083000A1 (fr) * 2009-12-16 2011-07-14 Basf Se Procédé de préparation de polyols de polyester, polyols de polyester préparés à l'aide de ces derniers et polyuréthanes obtenus à partir de ces derniers
DE102011078768A1 (de) * 2011-07-07 2013-01-10 Bayer Materialscience Aktiengesellschaft Verfahren zum Ausfüllen von Hohl- und Zwischenräumen mit duroplastischen Polyurethanschaumstoffen
WO2013024107A1 (fr) * 2011-08-16 2013-02-21 Bayer Intellectual Property Gmbh Procédé de production d'une mousse rigide polyuréthane-polyisocyanurate
WO2013024108A1 (fr) * 2011-08-16 2013-02-21 Bayer Intellectual Property Gmbh Procédé servant à produire une mousse rigide de polyuréthane-polyisocyanurate
US9034983B2 (en) * 2012-03-01 2015-05-19 Saudi Basic Industries Corporation Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof
US8895660B2 (en) * 2012-03-01 2014-11-25 Saudi Basic Industries Corporation Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof
JP2017512863A (ja) * 2014-03-25 2017-05-25 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Ｔｐｕ空気ホース
BR112018004019A2 (pt) * 2015-09-24 2018-12-11 Basf Se ?poliuretano termoplástico, processo para a preparação de um poliuretano termoplástico, utilização de um poliuretano termoplástico e mangueira?
US10927253B2 (en) * 2016-02-22 2021-02-23 Basf Se Nucleating agent for compact thermoplastic polyurethanes
WO2018210608A1 (fr) * 2017-05-17 2018-11-22 Basf Se Mélange de polyester résistant aux chocs
ES2878295T3 (es) * 2017-06-26 2021-11-18 Basf Se Poliuretano termoplástico

Also Published As

Publication number Publication date
WO2020038998A1 (fr) 2020-02-27
EP3613787A1 (fr) 2020-02-26
CN112739737B (zh) 2023-04-11
CN112739737A (zh) 2021-04-30
US20210189060A1 (en) 2021-06-24
JP2021535248A (ja) 2021-12-16

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