EP3601396A1 - Procédé de préparation de polyuréthanes présentant de faibles effets d'exsudation et une bonne souplesse à froid, à base de composés hydroxylés polymères contenant un uréthane - Google Patents

Procédé de préparation de polyuréthanes présentant de faibles effets d'exsudation et une bonne souplesse à froid, à base de composés hydroxylés polymères contenant un uréthane

Info

Publication number
EP3601396A1
EP3601396A1 EP18711128.1A EP18711128A EP3601396A1 EP 3601396 A1 EP3601396 A1 EP 3601396A1 EP 18711128 A EP18711128 A EP 18711128A EP 3601396 A1 EP3601396 A1 EP 3601396A1
Authority
EP
European Patent Office
Prior art keywords
polyisocyanate
polyurethane
polyol
composition
piz
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
EP18711128.1A
Other languages
German (de)
English (en)
Inventor
Sebastian Richter
Frank Schaefer
Johannes Poppenberg
Hendrik Wagner
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.)
BASF SE
Original Assignee
BASF SE
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 SE filed Critical BASF SE
Publication of EP3601396A1 publication Critical patent/EP3601396A1/fr
Pending 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
    • C08G18/10—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
    • 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
    • C08G18/28—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
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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

Definitions

  • the present invention relates to a process for preparing a polyurethane comprising reacting a polyol composition (PZ) comprising a polyol (P1) with a polyisocyanate composition (PIZ-1) comprising a polyisocyanate (11) to obtain a hydroxy-terminated prepolymer (PP1) and the reaction of the resulting prepolymer (PP1) with a polyisocyanate composition (PIZ-2) containing a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU1), wherein in the reaction according to step (i) the molar ratio the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) in the range of 1, 3: 1 to 10: 1. Furthermore, the present invention relates to polyurethanes obtainable or obtained by such a process and the use of the polyurethanes for the production of moldings, adhesives,
  • WO15 / 000722 A1 discloses polyurethanes based on at least one polyisocyanate and at least one polyester polyol, wherein the polyester polyol is based on at least one polyhydric alcohol and a mixture of at least two dicarboxylic acids, wherein at least one of the at least two dicarboxylic acids is at least partially obtained from renewable raw materials , as well as processes for the preparation of such polyurethanes and moldings containing such polyurethanes.
  • the polyurethanes of the invention show a low tendency to bloom.
  • EP 0687695 A1 relates to the targeted reduction of the efflorescence effect by addition of a monohydric alcohol for thermoplastic polyurethanes based on polyester polyols.
  • US8790763 discloses the reduction of blooming by the use of a polyester polyol with 1,3-propylene glycol as the repeat unit.
  • thermoplastic polyurethanes with reduced blooming is described by the use of polyester polyols with bio-based glycols.
  • US 2003/0036621 relates to the reduction of efflorescence in thermoplastic polyurethanes by chain terminating additives, such as monofunctional alcohols (with chain length> C14, monoisocyanates or monoamines).
  • chain terminating additives such as monofunctional alcohols (with chain length> C14, monoisocyanates or monoamines).
  • WO 2009/103767 A1 discloses the production of thermoplastic polyurethanes with reduced deposit formation by the use of various mixtures of alkanediols as chain extenders.
  • WO 2008/1 16801 A1 discloses the preparation of thermoplastic polyurethanes in a two-stage prepolymer procedure.
  • the PU prepolymers are NCO-terminated.
  • this object is achieved by a process for the preparation of a polyurethane comprising the steps (i) and (ii)
  • step (ii) reacting the prepolymer (PP1) obtained according to step (i) with a polyisocyanate composition (PIZ-2) comprising a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU 1), wherein in the reaction according to Step (i) the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) in the range of 1, 3: 1 to 10: 1.
  • the process according to the invention comprises at least steps (i) and (ii) and may comprise further steps.
  • a polyol composition (PZ) comprising a polyol (P1) with a polyisocyanate composition (PIZ-1) comprising a polyisocyanate (11) to give a hydroxy-terminated prepolymer (PP1).
  • the prepolymer (PP1) obtained according to step (i) is reacted according to step (ii) with a polyisocyanate composition (PIZ-2) comprising a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU1).
  • the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) is in the range from 1.3: 1 to 10: 1 ,
  • the process is carried out such that initially in the reaction according to step (i) polyisocyanate composition (PIZ-1) is used and the isocyanate is substantially completely reacted to obtain the prepolymer (PP1).
  • substantially completely reacted means that more than 99% of the isocyanate groups contained in the polyisocyanate composition (PIZ-1) have reacted, preferably more than 99.5%, more preferably more than 99.9 %, more preferably more than 99.99% of the isocyanate groups present in the polyisocyanate composition (PIZ-1)
  • step (ii) it is possible that further steps take place between steps (i) and (ii) of the process according to the invention, for example separating or However, it is also possible within the scope of the present invention for step (ii) to be carried out directly after step (i) of the process according to the invention.
  • the polyol composition (PZ) comprising a polyol (P1) is reacted with the polyisocyanate composition (PIZ-1) comprising a polyisocyanate (11).
  • the polyol composition (PZ) contains at least one polyol (P1) and may contain further polyols or further components, for example solvents.
  • the polyisocyanate composition (PIZ-1) contains at least one polyisocyanate (11) and may contain further polyisocyanates or further components, for example solvents.
  • the polyisocyanate composition (PIZ-2) according to the invention contains at least one polyisocyanate (12) and may contain further polyisocyanates or further components, for example solvents.
  • a polyurethane is obtained.
  • the polyurethane obtained according to the invention is, for example, a thermoplastic polyurethane or a cast elastomer.
  • the present invention therefore also relates to a process for the preparation of a polyurethane as described above, wherein the polyurethane is thermoplastic.
  • a hydroxy-terminated prepolymer in the reaction according to step (i), a hydroxy-terminated prepolymer (PP1) is obtained.
  • a hydroxy-terminated prepolymer means that the predominant proportion, for example more than 80%, preferably more than 90%, particularly preferably more than 99%, of the end groups present are hydroxy end groups.
  • the optional remaining end groups are isocyanate end groups.
  • the prepolymer (PP1) it is possible for the prepolymer (PP1) to be isolated after step (ii). However, it is also possible that the prepolymer (PP1) is not isolated, but is further reacted directly.
  • step (ii) the prepolymer (PP1) obtained according to step (i) is reacted with a polyisocyanate composition (PIZ-2) comprising a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU 1).
  • PIZ-2 polyisocyanate composition
  • K1 chain extender
  • a polyol composition (PZ) is used containing at least one polyol (P1).
  • PZ polyol
  • Suitable polyols are known per se to the person skilled in the art. Suitable polyols are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Particular preference is given to using polyesterols or polyetherols as polyols. Likewise, polycarbonates can be used. Copolymers can also be used in the context of the present invention.
  • the number-average molecular weight of the polyols used according to the invention is preferably between 0.5 ⁇ 10 3 g / mol and 8 ⁇ 10 3 g / mol, preferably between 0.6 ⁇ 10 3 g / mol and 5 ⁇ 10 3 g / mol, in particular between 0.8 ⁇ 10 3 g / mol and 3 x 10 3 g / mol.
  • polyetherols are suitable, but also polyesterols, block copolymers and hybrid polyols, e.g. Poly (ester / amide) or poly (ester / ether).
  • Preferred polyols according to the invention are polytetramethylene ether glycol, polyethylene glycols, polypropylene glycols, polyadipates, polycarbonate (diol) s and polycaprolactone.
  • Particularly preferred polyols according to the invention are polyadipates.
  • Very particularly preferred polyols according to the invention are homopolyadipates.
  • the present invention also relates to a composition as described above, wherein the polyol composition contains a polyol selected from the group consisting of polyethers, polyesters, polycaprolactones and polycarbonates.
  • the polyol (P1) is preferably selected from the group consisting of polyester polyols and polyether polyols, more preferably polyester polyols, very particularly preferably selected from linear polyester polyols.
  • Suitable polyols are, for example, polyetherols such as polydimethylene oxides, polytrimethylene oxides or polytetramethylene oxides.
  • Suitable block copolymers are, for example, those which have ethers and ester blocks, for example polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or polyethers with polycaprolactone end blocks.
  • Preferred polyetherols according to the invention are polyethyleneglycols, polypropylene glycols. Further preferred is polycaprolactone.
  • Suitable polyesterpolyols in particular polyesterdiols, can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and polyhydric alcohols.
  • dicarboxylic acids are, for example, in Consider: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, or aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used individually or as mixtures, for example in the form of an amber, sebacic and adipic acid mixture.
  • the corresponding dicarboxylic acid derivatives such as carbonic diesters having 1 to 4 carbon atoms in the alcohol radical, for example dimethyl terephthalate or dimethyl adipate, carboxylic anhydrides, for example succinic anhydride, glutaric anhydride or phthalic anhydride, or carboxylic acid chlorides.
  • polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6 carbon atoms, for example ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, 2, 2-Dimethyl-1,3-propanediol, 1, 3-propanediol, 2-methylpropanediol-1,3,3-methylpentanediol-1,5 or dipropylene glycol.
  • the polyhydric alcohols can be used individually or as mixtures, for example in the form of a 1,4-butanediol and / or 1,3-propanediol mixture.
  • small amounts of up to 3% by weight of the total reaction mixture of higher functional, low molecular weight polyols such as 1,1,1-trimethylolpropane or pentaerythritol can also be used.
  • dimethyl esters of dicarboxylic acids are used in the preparation of the preferred polyester polyols due to incomplete transesterification, for example, small amounts of unreacted methyl ester end groups may impair the functionality of the polyesters to less than 2.0, for example to 1, 95 or even to 1 Reduce 90.
  • the polycondensation for the preparation of the polyester polyols preferably used according to the invention, particularly preferably polyester diols, is carried out by methods known to those skilled in the art, for example, by first expelling the reaction water at temperatures of 150 to 270 ° C. under atmospheric pressure or slightly reduced pressure and subsequently the pressure slowly lowers, for example to 5 to 20 mbar.
  • a catalyst is basically not required, but is preferably added.
  • tin (II) salts, titanium (IV) compounds, bismuth (III) salts and others are contemplated.
  • the molecular weight of the polyol composition (PZ) used or of the polyol used (P1) can vary within wide limits.
  • suitable are polyol compositions (PZ) which have an average molecular weight in the range from 500 to 1500 g / mol, more preferably in the range from 600 to 1200 g / mol.
  • the present invention therefore also relates to a process for producing a polyurethane as described above, wherein the sum of the components of the polyol composition (PZ) has an average molecular weight in the range of 500 to 1500 g / mol.
  • the values given in the present application are numbers of average molecular weights.
  • the polyol used (P1) has a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol, preferably in the range of 600 g / mol to 1200 g / mol. According to the invention, it is also possible to use mixtures of different polyols.
  • the polyols or the polyol composition used preferably have an average functionality in the range of 1, 7 and 2.3, preferably in the range of 1, 9 and 2.1, in particular 2.
  • the polyols used according to the invention preferably have only primary hydroxyl groups.
  • the present invention therefore also relates to a process for producing a polyurethane as described above, wherein the sum of the components of the polyol composition (PZ) has an average functionality in the range of 1.7 to 2.3.
  • the polyol used (P1) has an average functionality in the range of 1, 7 and 2.3, preferably in the range of 1, 9 and 2.1, in particular 2.
  • the polyol composition may also contain a solvent. Suitable solvents are known per se to the person skilled in the art.
  • a polyisocyanate composition (PIZ-1) comprising a polyisocyanate (11) is used in step (i).
  • a polyisocyanate composition (PIZ-2) containing a polyisocyanate (12) is used.
  • Preferred polyisocyanates in the context of the present invention are diisocyanates, in particular aliphatic or aromatic diisocyanates.
  • pre-reacted products can be used as isocyanate components in which a polyol is reacted with an isocyanate in an upstream reaction step.
  • the products obtained essentially have isocyanate end groups and can be used according to the invention as a component of the polyisocyanate composition.
  • the aliphatic diisocyanates used are conventional aliphatic and / or cycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethyltetramethylene-1 , 4-diisocyanate, hexamethylene-1,6-diisocyanate (HDI), pentamethylene-1, 5-diisocyanate, butylene-1,4-diisocyanate, trimethylhexamethylene-1,6-diisocyanate, 1-isocyanato-3, 3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohe
  • Preferred aliphatic polyisocyanates are hexamethylene-1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4'-, 2,4'- and / or 2,2 '- Methylenedicyclohexyl diisocyanate (H12MDI).
  • HDI hexamethylene-1,6-diisocyanate
  • H12MDI 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
  • H12MDI 2,2 '- Methylenedicyclohexyl diisocyanate
  • Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-diisocyanato-diphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane-4,4'-diisoyanate (EDI), diphenylmethane diisocyanate, 3,3 ' Dimethyldiphenyl diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate.
  • NDI 1,5-naphthylene diisocyanate
  • TDI 2,4- and / or 2,6-toluene diisocyanate
  • higher-functionality isocyanates are used, for example triisocyanates, for.
  • examples also include the cyanurates of the abovementioned diisocyanates, and the oligomers obtainable by partial reaction of diisocyanates with water, for example the biurets of the abovementioned diisocyanates, and also oligomers which are characterized by, for example, triphenylmethane-4,4 ', 4 "-triisocyant targeted implementation of semi-blocked diisocyanates with polyols having on average more than two and preferably three or more hydroxy groups are available.
  • the present invention relates, in a preferred embodiment, to a process wherein the at least one first and the at least one second polyisocyanate are different.
  • the polyisocyanate (11) may be selected from the group consisting of 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,4- and 2,6-toluene diisocyanate (TDI), Hexamethylene diisocyanate (HDI), 1-isocyanato-4 - [(4-isocyanatocyclohexyl) methyl] cyclohexane (H12MDI) or 1,5-naphthalene diisocyanate (NDI).
  • MDI 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate
  • TDI 2,4- and 2,6-toluene diisocyanate
  • HDI Hexamethylene diisocyanate
  • H12MDI 1-isocyanato-4 - [(4-isocyanatocyclohexyl) methyl] cyclohexane
  • NDI 1,5-na
  • the present invention therefore also relates to a process for the preparation of a polyurethane as described above, wherein the polyisocyanate (11) is selected from the group consisting of 2,2'-, 2,4'- and 4,4 'Diphenylmethane diisocyanate (MDI), 2,4- and 2,6-toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), 1-isocyanato-4- [(4-isocyanatocyclohexyl) methyl] cyclohexane (H12MDI) or 1, 5-naphthalenes Diisocyanates (NDI)
  • the polyisocyanate (12) is preferably selected from the group consisting of 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,4- and 2,6-toluene diisocyanate ( TDI), hexamethylene diisocyanate (
  • the present invention therefore also relates to a process for the preparation of a polyurethane as described above, wherein the polyisocyanate (12) is selected from the group consisting of 2,2'-, 2,4'- and 4,4 'Diphenylmethane diisocyanate (MDI), 2,4- and 2,6-toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), 1-isocyanato-4- [(4-isocyanatocyclohexyl) methyl] cyclohexane (H12MDI), and 1, 5-naphthalenes diisocyanates (NDI).
  • MDI 2,2'-, 2,4'- and 4,4 'Diphenylmethane diisocyanate
  • TDI 2,4- and 2,6-toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • H12MDI 1-isocyanato-4- [(4-iso
  • aliphatic polyisocyanates are preferably used as polyisocyanate (11).
  • the polyisocyanate (12) used are preferably aromatic polyisocyanates.
  • the present invention therefore also relates to a process for producing a polyurethane as described above, wherein the polyisocyanate (11) is selected from aliphatic polyisocyanates and the polyisocyanate (12) is selected from aromatic polyisocyanates.
  • the polyisocyanate composition (PIZ-1) and / or (PIZ-2) may also contain one or more solvents.
  • Suitable solvents are known to the person skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons.
  • the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) is in the range from 1.3: 1 to 10: 1.
  • the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) is preferably in the range from 1.4: 1 to 6.0: 1.
  • the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) is in the range from 1, 5: 1 to 3.0: 1.
  • the process is preferably carried out such that the prepolymer (PP1) obtained in step (i) has an average molecular weight in the range from 800 to 5000 g / mol, more preferably in the range from 1200 to 3000 g / mol.
  • the reaction according to step (i) is conducted at a temperature of about 80 ° C for a period of 1 to 3 hours, for example 2 hours.
  • the present invention therefore also relates to a process for producing a polyurethane as described above, wherein the prepolymer (PP1) has an average molecular weight in the range of 800 to 5000 g / mol.
  • a chain extender (KV1) is used in step (ii).
  • Suitable chain extenders are known per se to the person skilled in the art.
  • Chain extenders used are compounds having at least two isocyanate-reactive groups. Groups which are reactive toward isocyanates may in particular be NH, OH or else SH groups. Suitable examples are diamines or diols or water. At least one chain extender is preferably used, selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of ⁇ 500 g / mol. According to a further embodiment, the present invention therefore also relates to a process for the preparation of a polyurethane as described above, wherein the chain extender (K1) is selected from the group consisting of diols, diamines and or or water.
  • chain extenders for example, it is possible to use generally known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499 g / mol, preferably bifunctional compounds, for example alkanediols having 2 to 10 C atoms in the alkylene radical, for example diols is selected from the group consisting of C 2 - to C 6 -diols, preferably butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, Nona and / or Dekaalkylenglykole having 3 to 8 carbon atoms, preferably unbranched alkanediols, in particular 1, 3-propanediol, butane-1, 4-diol and 1, 6-hexanediol.
  • alkanediols having 2 to 12 C atoms in the alkylene radical, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols, are preferred.
  • alkanediols having 2 to 12 C atoms in the alkylene radical, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols, are preferred.
  • alkylene radical in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols, are preferred.
  • branched compounds such as 1,4-cyclohexyldimethanol, 2-butyl-2-ethylpopanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, pinacol, 2-ethyl-1,3-hexanediol, 1, 4-Cyclohexanediol, or N-phenyldiethanolamine are suitable as chain extenders in the context of the present invention. Also suitable are compounds with OH and NH groups such as 4-aminobutanol.
  • the amount of chain extender and polyol composition used can vary within wide limits.
  • the chain extender (KV) can be used in an amount in the range from 1:40 to 10: 1, based on the prepolymer used.
  • the molecular weight of the polyurethane according to the invention obtained in step (ii) (PU1) can vary within wide limits.
  • the polyurethane (PU1) particularly advantageously has a molecular weight in the range from 20,000 to 500,000 g / mol, determined by means of GPC, more preferably in the range from 50,000 to 200,000 g / mol.
  • the present invention also relates to a composition as described above, wherein the polyurethane has a molecular weight in the range from 20,000 to 500,000 g / mol, determined by means of GPC.
  • additives can be added in the reaction according to steps (i) and (ii), for example catalysts or auxiliaries and additives.
  • Additives and Auxiliaries are known per se to the person skilled in the art. Combinations of several additives can also be used according to the invention.
  • additive is understood in particular as meaning catalysts, auxiliaries and additives, in particular stabilizers, nucleating agents, release agents, mold release agents, fillers, flame retardants or crosslinkers.
  • Suitable additives are, for example, stabilizers, nucleating agents, fillers such as e.g. Silicates or crosslinkers such as e.g. multifunctional aluminosilicates.
  • auxiliaries and additives may be mentioned, for example, surface-active substances, flame retardants, nucleating agents, oxidation stabilizers, antioxidants, lubricants and mold release agents, dyes and pigments, stabilizers, for.
  • Suitable auxiliaries and additives may be, for example, the plastic handbook,
  • Suitable catalysts are also known in principle from the prior art and relate in particular to the reaction of nucleophiles with isocyanates.
  • Suitable catalysts are, for example, organic metal compounds selected from the group consisting of tin, titanium, zirconium, hafnium, bismuth, zinc, aluminum and iron organyls, such as tin organyl compounds, preferably tin dialkyls such as dimethyltin or diethyl tin, or tin organyl compounds aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds such as bismuth alkyl compounds or the like, or iron compounds, preferably iron (MI) acetylacetonate or the metal salts of the carboxylic acids such as Tin isooctoate, tin dioctoate, titanic acid ester or bismuth (II) n
  • the catalysts are selected from tin compounds and bismuth compounds, more preferably tin alkyl compounds or bismuth-halo compounds. Particularly suitable are the tin isooctoate and bismuth neodecanoate.
  • the catalysts are usually used in amounts of 0 to 2000 ppm, preferably 1 ppm to 1000 ppm, more preferably 2 ppm to 500 ppm, and most preferably from 5 ppm to 300 ppm.
  • Step (i) of the process according to the invention can be carried out in devices known per se for the production of prepolymers, for example heatable / coolable stirred vessels or reaction extruders.
  • Step (i) of the process according to the invention is carried out at temperatures known to those skilled in the art, for example at a temperature in the range from 20 to 250 ° C., preferably in the range from 40 to 130 ° C., more preferably at a temperature in the range from 70 to 90 ° C.
  • the present invention therefore also relates to a process for producing a polyurethane as described above, wherein the reaction according to step (i) is carried out at a temperature in the range from 40 to 130 ° C.
  • Step (i) of the process according to the invention can be carried out in the presence of at least one solvent, for example selected from the group of inert solvents, ie. H. Solvents which have no reactive hydrogen atoms, preferably selected from the group consisting of toluene, dimethylformamide, tetrahydrofuran, etc., and mixtures thereof, or be carried out in the absence of a solvent.
  • at least one solvent for example selected from the group of inert solvents, ie. H. Solvents which have no reactive hydrogen atoms, preferably selected from the group consisting of toluene, dimethylformamide, tetrahydrofuran, etc., and mixtures thereof, or be carried out in the absence of a solvent.
  • Step (ii) of the process according to the invention can generally be carried out at any temperature known to the person skilled in the art, for example at a temperature in the range from 20 to 250 ° C, preferably in the range from 40 to 230 ° C. Therefore, the present invention also relates to a process as described above, wherein step (ii) takes place at a temperature in the range of 40 to 230 ° C.
  • the prepolymer (PP1) after step (i) is not isolated and used directly in step (ii).
  • the steps (i) and (ii) can be carried out in one device, ie. H. First, the reaction according to step (i), and then the reaction according to step (ii).
  • the method comprises further steps, for example a pretreatment of the components or an aftertreatment of the resulting thermoplastic polyurethane, for example a tempering.
  • the present invention also relates to a process for producing a thermoplastic polyurethane as described above, wherein after the reaction, the resulting thermoplastic polyurethane is tempered.
  • the present invention therefore also relates to a polyurethane obtainable or obtained by the process according to the invention.
  • the present invention therefore also relates, in a further aspect, to a polyurethane obtainable or obtained by processes comprising the steps (i) and (ii):
  • Polyisocyanate composition (PIZ-1) containing a polyisocyanate (11) to give a hydroxy-terminated prepolymer (PP1)
  • step (ii) reacting the prepolymer (PP1) obtained according to step (i) with a polyisocyanate composition (PIZ-2) comprising a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU1), wherein in the reaction according to step (i) the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) in the range of 1, 3: 1 to 10: 1 ,
  • the present invention also relates to a polyurethane as described above, wherein the polyurethane is thermoplastic. According to another embodiment, therefore, the present invention also relates to a polyurethane as described above, wherein the prepolymer (PP1) has an average molecular weight in the range of 800 to 5000 g / mol.
  • the present invention of one embodiment also relates to a polyurethane as described above, wherein the polyisocyanate (11) is selected from aliphatic polyisocyanates and the polyisocyanate (12) is selected from aromatic polyisocyanates.
  • the polyurethane according to the invention or the polyurethane obtained or obtainable by a process according to the invention can be prepared by known methods to the desired films, moldings, rolls, fibers, linings in automobiles, hoses, cable connectors, bellows, trailing cables, cable sheathing, seals, belts or damping elements are further processed, such. As injection molding, calendering or extrusion.
  • the polyurethane produced according to the invention can advantageously be used in particular in all applications specific to thermoplastic polyurethanes.
  • the present invention therefore also relates to the use of a polyurethane obtainable or obtained by a process as described above or a polyurethane as described above for the production of moldings, adhesives, coatings, hoses, films, nonwoven articles or fibers.
  • a process for producing a polyurethane comprising the steps (i) and (ii)
  • step (ii) reacting the prepolymer (PP1) obtained according to step (i) with a polyisocyanate composition (PIZ-2) containing a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU1), wherein in the reaction according to step (I) the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) in the range of 1, 3: 1 to 10: 1. 2.
  • the sum of the components of the polyol composition (PZ) has an average molecular weight in the range of 500 to 1500 g / mol.
  • MDI Diphenylmethane diisocyanate
  • TDI 2,4- and 2,6-toluene diisocyanate
  • HDI hexamethylene endiisocyanate
  • H12MDI 1-isocyanato-4 - [(4-isocyanatocyclohexyl) methyl] cyclohexane
  • NDI 5-naphthalenes diisocyanates
  • polyisocyanate (12) is selected from the group consisting of 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,4 and 2,6-toluene diisocyanate (TDI), hexamethyl end isocyanate (HDI), 1-isocyanato-4 - [(4-isocyanatocyclohexyl) methyl] cyclohexane (H12MDI) and 1, 5-naphthalenes diisocyanate (NDI).
  • MDI 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate
  • TDI 2,4 and 2,6-toluene diisocyanate
  • HDI hexamethyl end isocyanate
  • H12MDI 1-isocyanato-4 - [(4-isocyanatocyclohexyl) methyl] cyclohexane
  • NDI 1, 5-naphthal
  • polyisocyanate (11) is selected from aliphatic polyisocyanates and the polyisocyanate (12) is selected from aromatic polyisocyanates.
  • chain extender (K1) is selected from the group consisting of diols, diamines and / or water.
  • a process for producing a polyurethane comprising the steps (i) and (ii)
  • step (ii) reaction of the prepolymer (PP1) obtained according to step (i) with a polyisocyanate composition (PIZ-2) comprising a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU 1), wherein in the reaction according to step (i) the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) in the range of 1, 3: 1 to 10: 1 and wherein the reaction according to step (i) is carried out at a temperature in the range from 40 to 130 ° C.
  • step (ii) reacting the prepolymer (PP1) obtained according to step (i) with a polyisocyanate composition (PIZ-2) containing a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU1), wherein in the reaction according to step (i) the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) is in the range from 1.3: 1 to 10: 1, and wherein the prepolymer (PP1) has an average molecular weight in the range of 800 to 5000 g / mol.
  • step (ii) reacting the prepolymer (PP1) obtained according to step (i) with a polyisocyanate composition (PIZ-2) containing a polyisocyanate (12) and at least one chain extender (K1) to obtain a polyurethane (PU1), wherein in the reaction according to step (i) the molar ratio of the OH groups of the components of the polyol composition (PZ) to the isocyanate groups of the components of the polyisocyanate composition (PIZ-1) is in the range from 1.3: 1 to 10: 1, and wherein the polyisocyanate (11) is selected from aliphatic polyisocyanates and the polyisocyanate (12) is selected from aromatic polyisocyanates.
  • Polyurethane obtainable or obtained by processes comprising steps (i) and (ii): Reaction of a polyol composition (PZ) comprising a polyol (P1) with a polyisocyanate composition (PIZ-1) containing a polyisocyanate (11) to obtain a hydroxy-terminated prepolymer (PP1)
  • polyisocyanate (11) is selected from aliphatic polyisocyanates and the polyisocyanate (12) is selected from aromatic polyisocyanates.
  • polyisocyanate (11) is selected from the group consisting of 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,4- and 2,6-toluene diisocyanate (TDI), hexamethylene endiisocyanate (HDI), 1-isocyanato-4 - [(4-isocyanatocyclohexyl) methyl] cyclohexane
  • MDI 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate
  • TDI 2,4- and 2,6-toluene diisocyanate
  • HDI hexamethylene endiisocyanate
  • H12MDI hydrogen-naphthalenes diisocyanate
  • NDI 1,5-naphthalenes diisocyanate
  • polyisocyanate (12) is selected from the group consisting of 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,4- and 2,6-toluene diisocyanate (TDI), hexamethylene endiisocyanate (HDI), 1-isocyanato-4 - [(4-isocyanatocyclohexyl) methyl] cyclohexane
  • MDI 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate
  • TDI 2,4- and 2,6-toluene diisocyanate
  • HDI hexamethylene endiisocyanate
  • H12MDI 1,5-naphthalenes diisocyanate
  • NDI 1,5-naphthalenes diisocyanate
  • Hoses, films, non-woven articles or fibers are examples of materials.
  • Fig. 2 shows results of dynamic mechanical analyzes (DMA measurements).
  • 2a shows the result of a DMA measurement of comparison 1 for the exemplary overview of the assessment of cold flexibility, wherein the storage modulus in MPa is plotted on the x axis and the storage modulus in MPa on the y axis in the range from -20 ° C to + 20 ° C.
  • Fig. 2b shows the result of a DMA measurement for Example 1, wherein the temperature in ° C is plotted on the x-axis, and the storage modulus in MPa on the y-axis There is no embrittlement in the range -20 ° C to + 20 ° C.
  • the following examples serve to illustrate the invention but are
  • Viscosity determination The viscosity of the polyols was, unless stated otherwise, at 75 ° C according to DIN EN ISO 3219 (01.10.1994 issue) with a Rheotec RC 20 rotational viscometer using the spindle CC 25 DIN (spindle diameter: 12.5 mm Measuring cylinder inner diameter: 13.56 mm) at a shear rate of 50 1 / s.
  • NCO value determination The determination of the NCO content was carried out in accordance with EN
  • ISO 1 1909 performed: primary and secondary amines react with isocyanates to substituted ureas. This reaction proceeds quantitatively in an excess of amine. After the reaction has ended, the excess amine is potentiometrically titrated back with hydrochloric acid.
  • Dynamic-mechanical analysis (DMA) was performed in
  • Isocyanate 1 is 1,6-hexamethylene diisocyanate (HDI), molecular weight 168.20 g / mol
  • Isocyanate 2 is 4,4'-diphenylmethane diisocyanate (4,4'-MDI), molecular weight 250.26 g / mol
  • Isocyanate 3 is 2,4- and 2,6-toluene diisocyanate in the ratio 80:20 (TDI 80)
  • Isocyanate 4 1-isocyanato-4 - [(4-isocyanatocyclohexyl) methyl] cyclohexane (H12MDI)
  • Polymer polyol 1 Polyester diol having an OH number of about 45 and composed of adipic acid and 1,4-butanediol (MW: about 2,500)
  • Polymer polyol 2 Polyester diol having an OH number of about 150 and composed of adipic acid
  • Polymer polyol 3 Polyester diol having OH number of about 1 12 composed of adipic acid
  • Polymer polyol 4 HDI-modified polymer polyol 2 having an OH number of about
  • Polymer polyol 5 HDI-modified polymer polyol 2 with an OH number of about 55
  • Polymer polyol 6 HDI-modified polymer polyol 2 having an OH number of about
  • Polymer polyol 7 HDI-modified polymer polyol 2 with an OH number of about 125
  • Polymer polyol 8 HDI-modified polymer polyol 3 having an OH number of about 51
  • Polymer polyol 9 HDI-modified polymer polyol 3 having an OH number of about 44
  • Polymer polyol 10 HDI-modified polymer polyol 3 having an OH number of about
  • Polymer polyol 1 1 H12MDI-modified polymer polyol 2 having an OH number of about 65
  • Polymer polyol 12 4,4-MDI-modified polymer polyol 2 with an OH number of about 60
  • Polymer polyol 13 4,4-MDI modified polymer polyol 2 having an OH number of about 124
  • Polymer polyol 14 TDI 80-modified polymer polyol 2 having an OH number of about 65
  • Polymerpolyol 16 Polytetrahydrofuran (pTHF; polytetramethylene ether glycol, PTMEG) with an OH number of about 12 (MW: about 1000)
  • Chain extender 1 is 1,4-butanediol, molar mass 90.12 g / mol
  • Hydrolysis protection 1 is a carbodiimide-based hydrolysis protection agent (Elastostab® H01)
  • Polymer polyol is provided at 50 ° C in a 4000 ml round bottom flask equipped with thermocouple PT100, nitrogen inlet, stirrer and heating hood and added isocyanate at this temperature.
  • the reaction mixture is heated to 70-80 ° C and optionally added Cat 1.
  • the reaction mixture is heated for 2 hours at 80 ° C, then allowed to come to room temperature and used without further treatment for the preparation of a polyurethane according to the general processing method 2.
  • the respective polymer polyol is reacted together with chain extender 1 and isocyanate. Hydrolysis protection 1 is optionally added to the reaction mixture.
  • the resulting reaction mixture is poured out on a heatable Teflon-coated table and reacted for 10 minutes at 120 ° C.
  • the resulting polymer plate is then annealed at 80 ° C for 15 hours and then granulated. The granules are injection molded into a test plate.
  • isocyanate-containing polyester polyols were first prepared according to the general processing method 1. Subsequently, the compact polyurethanes were prepared according to the general processing method 2.
  • Table 2a Example compounds used according to the invention.
  • Table 2b Example compounds used according to the invention.
  • Table 2c Exemplary compounds used according to the invention.
  • the T g was determined by differential scanning calorimetry.

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Abstract

La présente invention concerne un procédé de préparation d'un polyuréthane, comprenant la réaction d'une composition de polyols (PZ) contenant un polyol (P1) avec une composition de polyisocyanates (PIZ-1) contenant un polyisocyanate (I1), avec obtention d'un prépolymère (PP1) à terminaison hydroxy, et la réaction du prépolymère (PP1) obtenu avec une composition de polyisocyanates (PIZ-2) contenant un polyisocyanate (I2) et au moins un prolongateur de chaîne (K1), avec obtention d'un polyuréthane (PU1), le rapport en moles des groupes OH des constituants de la composition de polyols (PZ) aux groupes isocyanate des constituants de la composition de polyisocyanates (PIZ-1) étant, lors de la réaction selon l'étape (i), compris dans la plage de 1,3:1 à 10:1. La présente invention concerne un outre des polyuréthanes pouvant être obtenus ou obtenus par un procédé de ce type, ainsi que l'utilisation des polyuréthanes pour la fabrication d'objets moulés, d'adhésifs, de revêtements, de tuyaux flexibles, de feuilles, d'articles non-tissés ou de fibres.
EP18711128.1A 2017-03-21 2018-03-20 Procédé de préparation de polyuréthanes présentant de faibles effets d'exsudation et une bonne souplesse à froid, à base de composés hydroxylés polymères contenant un uréthane Pending EP3601396A1 (fr)

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EP3838944A1 (fr) * 2019-12-17 2021-06-23 Covestro Deutschland AG Polymère de polyuréthane aliphatique thermoplastique à faible enthalpie de cristallisation
EP3838953A1 (fr) * 2019-12-17 2021-06-23 Covestro Deutschland AG Polyuréthane thermoplastique ayant une contrainte à la flexion élevée
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KR20140040240A (ko) 2011-06-17 2014-04-02 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 바이오-기반 글리콜로부터의 감소된 블룸에 대한 경향을 갖는 열가소성 폴리우레탄
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