EP3353222A1 - Polyuréthane thermoplastique - Google Patents

Polyuréthane thermoplastique

Info

Publication number
EP3353222A1
EP3353222A1 EP16766986.0A EP16766986A EP3353222A1 EP 3353222 A1 EP3353222 A1 EP 3353222A1 EP 16766986 A EP16766986 A EP 16766986A EP 3353222 A1 EP3353222 A1 EP 3353222A1
Authority
EP
European Patent Office
Prior art keywords
thermoplastic polyurethane
polyol
chain extender
composition
range
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
EP16766986.0A
Other languages
German (de)
English (en)
Inventor
Elmar PÖSELT
Dirk Kempfert
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 EP3353222A1 publication Critical patent/EP3353222A1/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
    • C08G18/28—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
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • 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
    • C08G18/65—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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 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
    • C08G18/65—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
    • C08G18/65—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
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a thermoplastic polyurethane obtainable or obtained by reacting at least one polyisocyanate composition, 1,2-ethanediol as a chain extender and a polyol composition, wherein in addition to 1, 2-ethanediol no further chain extender is used.
  • the present invention relates to a thermoplastic polyurethane obtainable or obtained by reacting at least one polyisocyanate composition, 1,2-ethanediol as chain extender and a polyol composition, wherein the polyol composition contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition comprises at least methylenediphenyl diisocyanate ( MDI).
  • PTHF polytetrahydrofuran
  • MDI methylenediphenyl diisocyanate
  • the present invention relates to a process for the preparation of such thermoplastic polyurethanes, and the use of such polyurethanes for the production of injection molded products, extrude
  • Thermoplastic polyurethanes for various applications are known in principle from the prior art. By varying the starting materials different property profiles can be obtained.
  • WO 2006/082183 A1 discloses a process for the continuous preparation of thermoplastically processable polyurethane elastomers, in which a polyisocyanate, a compound having zerevitinoff-active hydrogen atoms having an average molecular weight of 450 g / mol to 5,000 g / mol, a chain extender and other auxiliary and Additives are implemented. Special property profiles are achieved through special processing.
  • EP 0 922 552 A1 discloses a process for the continuous production of granules of thermoplastic polyurethane elastomers, wherein first by reacting organic diisocyanates, difunctional polyhydroxyl compounds having molecular weights of 500 to 8000 and difunctional chain extenders having molecular weights of 60 to 400 in the presence of Catalysts and optionally auxiliaries and / or additives granules is produced.
  • the use for the production of extrusion, injection molding or calendering, in particular cable sheathing, hoses and / or films is also disclosed.
  • EP 0 959 104 A1 discloses blends comprising a thermoplastic polyurethane having a Shore hardness of 60 A to 50 D and ethylene-propylene (EPM) rubbers and / or modified ethylene-propylene (EPM) rubbers, which are also used for the production be used by hoses.
  • EPM ethylene-propylene
  • EPM modified ethylene-propylene
  • thermoplastic polymer obtained by reacting a polyisocyanate, a glycol as a chain extender and a polyether polyol.
  • Various isocyanates, chain extenders and polyols are disclosed.
  • the properties of the thermoplastic polyurethane can be varied by the nature of the starting materials and the proportions used. For example, for use as a hose material, in particular for pneumatic hoses, a high bursting pressure is required even at elevated temperatures.
  • the stability can be influenced. Processing, for example by tempering, can also influence the stability.
  • existing ester variants which show a bursting pressure of greater than 20 bar at 70 ° C. are opaque to translucent and thus unsuitable for many applications.
  • thermoplastic polyurethane for various applications, for example for use as a cable sheath, a high heat resistance of the thermoplastic polyurethane used is also advantageous.
  • a measure of the heat resistance for example, the determined by TMA onset temperature.
  • a high short-term heat distortion resistance is advantageous.
  • an object of the present invention was accordingly to provide improved materials which show a good bursting pressure even at elevated temperatures in the application for the manufacture of hoses.
  • Another object of the present invention was to provide materials with high heat resistance, in particular high short-term heat resistance.
  • thermoplastic polyurethane obtainable or obtained by reacting at least the components (i) to (iii):
  • the invention also relates to a thermoplastic polyurethane obtainable or obtained by reacting at least the components (i) to (iii):
  • a polyol composition wherein the polyol composition contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition contains at least methylenediphenyl diisocyanate (MDI), and wherein in addition to 1,2-ethanediol no further chain extender is used.
  • PTHF polytetrahydrofuran
  • MDI methylenediphenyl diisocyanate
  • 1,2-ethanediol as a chain extender, in particular in combination with the defined polyisocyanate composition and the polyol composition, it was possible to produce a hose which has a bursting pressure of greater than 20 bar at 70.degree.
  • the hoses show a substantially punctiform bursting behavior.
  • the resulting thermoplastic polyurethanes preferably also have good creep behavior.
  • thermoplastic polyurethane is obtained or is obtainable by reacting the components (i) to (iii).
  • a polyisocyanate composition, a polyol composition and 1, 2-ethanediol are implemented as a chain extender. According to the invention, no further chain extender is used in addition to 1,2-ethanediol.
  • a polyisocyanate composition containing at least methylene diphenyl diisocyanate (MDI) is reacted with a polyol composition containing at least polytetrahydrofuran (PTHF) and 1,2-ethanediol as a chain extender.
  • MDI methylene diphenyl diisocyanate
  • PTHF polytetrahydrofuran
  • the polyol composition used contains at least one polyol in the context of the present invention.
  • Polyols are generally known to the person skilled in the art and 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.
  • 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 ⁇ 10 3 g / mol.
  • polyethers are suitable, for example polytetrahydrofuran, but also polyesters, block copolymers and hybrid polyols, e.g. Poly (ester / amide).
  • Preferred polyetherols according to the invention are polyethylene glycols, polypropylene glycols, polyadipates, polycarbonates (diol) s and polycaprolactone.
  • the polyol composition contains at least one polytetrahydrofuran.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol composition used contains at least one polytetrahydrofuran.
  • the polyol used has a molecular weight Mn in the range of 500 g / mol to 1500 g / mol, preferably in the range of 600 g / mol to 1400 g / mol, more preferably in the range of 650 g / mol to 1000 g / mol.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein at least one polyol contained in the polyol composition has a molecular weight Mn in the range of 500 g / mol to 1500 g / mol.
  • Polyester polyols may also be used in the context of the present invention, preferably polyesters having a molecular weight Mn in the range from 500 g / mol to 2500 g / mol, more preferably in the range from 550 g / mol to 1800 g / mol, particularly preferably in the range from 600 g / mol to 1200 g / mol.
  • the polyol composition may also contain two or more polyols.
  • the polyols used or the polyol composition have an average functionality between 1, 8 and 2.3, preferably between 1, 9 and 2.2, in particular 2.
  • the polyols used in the invention have only primary hydroxyl groups.
  • At least one polyol composition containing at least polytetrahydrofuran is used as component (iii) for the preparation of the thermoplastic polyurethane.
  • the polyol composition in addition to polytetrahydrofuran also contain other polyols.
  • polyethers are suitable, but also polyesters, block copolymers and hybrid polyols, such as e.g. Poly (ester / amide).
  • Preferred polyetherols according to the invention are polyethyleneglycols, polypropylene glycols and polycaprolactone.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol used contains at least one polytetrahydrofuran and at least one polyol selected from the group consisting of polyethylene glycol, polypropylene glycol, polyadipates, polycarbonate (diols) and polycaprolactones.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol composition contains at least one polytetrahydrofuran and at least one further polyol selected from the group consisting of polyethylene glycol, polypropylene glycol and polycaprolactone.
  • composition of the polyol composition can vary widely within the scope of the present invention.
  • content of polytetrahydrofuran in Range from 15% to 85%, preferably in the range of 20% to 80%, more preferably in the range of 25% to 75%.
  • the polyol composition may also contain a solvent. Suitable solvents are known per se to the person skilled in the art.
  • the molecular weight Mn of the polytetrahydrofuran is preferably in the range from 650 to 1400 g / mol. More preferably, the molecular weight Mn of the polytetrahydrofuran is in the range of 750 to 1400 g / mol.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polytetrahydrofuran has a molecular weight Mn in the range of 650 g / mol to 1400 g / mol.
  • Mn molecular weight of 650 g / mol to 1400 g / mol.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol composition used is free of polytetrahydrofuran (PTHF) and in the implementation no polytetrahydrofuran (PTHF) is used as a further component.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein in addition to 1, 2-ethanediol no further chain extender is used, the polyol composition is free of polytetrahydrofuran (PTHF) and in the implementation no polytetrahydrofuran (PTHF) used as a further component becomes.
  • 1,2-ethanediol is used as a chain extender and no further chain extender is used.
  • a chain extender is understood as meaning a compound which has at least two isocyanate-reactive functional groups, for example hydroxyl groups, amino groups or thiol groups, and has a molecular weight Mw of less than 300 g / mol ,
  • the polyol composition is also free of such compounds.
  • component (iii) and component (ii) are used in a molar ratio of (iii) to (ii) of 1 to 0.7, 1 to 2.7, and 1 to 7.3.
  • a polyisocyanate cyanate composition is used to prepare the thermoplastic polyurethane.
  • the polyisocyanate composition contains at least one polyisocyanate.
  • the polyisocyanate composition can also contain two or more polyisocyanates.
  • a polyisocyanate composition is used which contains at least methylene diphenyl diisocyanate (MDI).
  • MDI methylene diphenyl diisocyanate
  • methylene diphenyl diisocyanate means 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate or a mixture of two or three isomers.
  • 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate can be used according to the invention or a mixture of two or three isomers.
  • the polyisocyanate composition may also contain further polyisocyanates.
  • the isocyanate composition it is thus also possible for the isocyanate composition to contain methylene diphenyl diisocyanate and at least one further polyisocyanate.
  • the isocyanate composition contains only methylene diphenyl diisocyanate.
  • a polyisocyanate cyanate composition which does not contain any methylenediphenyl diisocyanate (MDI) can also be used for the preparation of the thermoplastic polyurethane.
  • MDI methylenediphenyl diisocyanate
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyisocyanate composition used is free of methylenediphenyl diisocyanate (MDI).
  • the polyisocyanate composition used is free from methylene diphenyl diisocyanate (MDI)
  • MDI methylenediphenyl diisocyanate
  • Preferred polyisocyanates in the context of the present invention are diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.
  • pre-reacted prepolymers can be used as isocyanate components in which some of the OH components are reacted with an isocyanate in an upstream reaction step. These prepolymers are reacted in a subsequent step, the actual polymer reaction, with the remaining OH components and then form the thermoplastic polyurethane.
  • the use of prepolymers offers the possibility to also use OH components with secondary alcohol groups.
  • 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
  • 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 '- methylene dicyclohexyl diisocyanate (H 12MDI); 4,4'-, 2,4'- and / or 2,2'-methylenedicyclohexyl diisocyanate (H 12MDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane or mixtures thereof are particularly preferred.
  • HDI hexamethylene-1,6-diisocyanate
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyisocyanate composition used comprises at least one polyisocyanate selected from the group consisting of methylene diphenyl diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI) and 4,4 '. , 2,4'- and 2,2'-methylenedicyclohexyl diisocyanate (H12MDI).
  • the polyisocyanate composition used as polyisocyanate particularly preferably contains methylene diphenyl diisocyanate (MDI).
  • Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanato-diphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane-4,4'-diisoyanate (EDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane-diisocyanate and / or phenylene-diisocyanate.
  • NDI 1,5-naphthylene diisocyanate
  • TDI 2,4- and / or 2,6-toluene diisocyanate
  • TODI 3,3'-dimethyl-4,4'-diisocyanato-
  • Preferred examples of higher functional isocyanates are triisocyanates, e.g. B. triphenylmethane-4,4 ', 4 "-triisocyant, furthermore the cyanurates of the abovementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, for example the bisurethe of the abovementioned diisocyanates, furthermore oligomers, which can be obtained by targeted reaction of semi-blocked diisocyanates with polyols which have on average more than two and preferably three or more hydroxyl groups.
  • the polyisocyanate composition 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.
  • crosslinkers for example the above-mentioned higher-functional polyisocyanates or polyols or also other higher-functional molecules having a plurality of isocyanate-reactive functional groups, can also be used in the context of the present invention.
  • the components (i) to (iii) are used in a ratio such that the molar ratio of the sum of the functionalities of the polyol composition used and chain extenders to the sum of the functionalities of the isocyanate composition used ranges from 1 to 0, 8 to 1 to 1, 3 is located.
  • the ratio is preferably in the range from 1 to 0.9 to 1 to 1.2, more preferably in the range from 1 to 0.965 to 1 to 1:05, particularly preferably in the range from 1 to 0.98 to 1 to 1, 03 ,
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the molar ratio of the sum of the functionalities of the polyol composition used and chain extenders to the sum of the functionalities of the isocyanate composition used in the range of 1 to 0.8 to 1 to 1, 3 is located.
  • the index is defined by the ratio of the total isocyanate groups used in the reaction of component (i) to the isocyanate-reactive groups, ie in particular the groups of components (ii) and (iii).
  • an isocyanate group of component (i) has an active hydrogen atom.
  • more isocyanate groups exist than isocyanate-reactive groups.
  • the ratio in the reaction of components (i) to (iii) is preferably in the range from 965 to 1100, for example in the range from 970 to 110, more preferably in the range from 970 to 1050, particularly preferably in the range from 980 to 1030 ,
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the ratio in the reaction in the range of 965 to 1 100 is.
  • additives can be added in the reaction of components (i) to (iii), 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, fillers or crosslinkers.
  • Suitable additives or additives are for example stabilizers, nucleating agents, fillers such as silicates or crosslinkers such as polyfunctional aluminosilicates.
  • the present invention accordingly relates to a thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane contains at least one additive.
  • auxiliaries and additives may be mentioned, for example, surface-active substances, flame retardants, nucleating agents, oxidation stabilizers, antioxidants, lubricants and mold release aids, dyes and pigments, stabilizers, eg. For example, against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers.
  • Suitable auxiliaries and additives can be found, for example, in Kunststoffhandbuch, Volume VII, edited by Vieweg and Hochtlen, Carl Hanser Verlag, Kunststoff 1966 (S103 - 1 13) are removed.
  • Suitable catalysts are also known in principle from the prior art.
  • 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 Diethyltin, or tin organyl compounds of 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 (III) neodecanoate.
  • organyls such as tin
  • 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.
  • thermoplastic polyurethanes according to the invention can vary within wide ranges, depending on the application.
  • the thermoplastic polyurethanes according to the invention have for example a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505, preferably in the range of 80 A to 74 D, determined according to DIN 53505, more preferably in the range of 85A to 60 D, determined according to DIN 53505, particularly preferably in the range of 95 A to 58 D, determined according to DIN 53505.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane has a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505.
  • the present invention also relates to a process for the preparation of a thermoplastic polyurethane, comprising the reaction of components (i) to (iii):
  • thermoplastic polyurethane also relates to a process for the preparation of a thermoplastic polyurethane comprising the reaction of components (i) to (iii):
  • polystyrene resin contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition contains at least methylenediphenyl diisocyanate (MDI) and wherein in addition to 1,2-ethanediol no further chain extender is used.
  • PTHF polytetrahydrofuran
  • MDI methylenediphenyl diisocyanate
  • reaction of components (i) to (iii) can in principle be carried out under known reaction conditions.
  • the reaction can be carried out batchwise or else continuously, for example in a belt process or a reaction extrusion process.
  • Suitable methods are described, for example, in EP 0 922 552 A1 or WO 2006/082183 A1.
  • reaction of components (i) to (iii) is carried out at elevated temperatures as room temperature.
  • the heating can take place in any suitable manner known to the person skilled in the art.
  • the reaction is conducted such that the zone temperature is in the range of 170 ° C to 245 ° C, preferably in the range of 180 ° C to 235 ° C, more preferably in the range of 190 ° C to 230 ° C.
  • the present invention also relates to a process for producing a thermoplastic polyurethane as described above, wherein the reaction is carried out by a reaction extrusion method and the zone temperature is in the range of 170 ° C to 245 ° C.
  • the method comprises further steps, for example a pretreatment of the components or an aftertreatment of the resulting thermoplastic polyurethane.
  • the present invention relates to a further ren embodiment also a method for producing a thermoplastic polyurethane as described above, wherein after the reaction, the resulting thermoplastic polyurethane is annealed.
  • the thermoplastic polyurethane according to the invention or a thermoplastic polyurethane obtained or obtainable by a process according to the invention can be used in many ways.
  • the thermoplastic polyurethanes according to the invention are suitable for the production of molded parts and films, more preferably for the production of hoses.
  • the present invention therefore also relates to the use of a thermoplastic polyurethane as described above or of a thermoplastic polyurethane obtainable or obtained by a process according to the invention for the production of injection-molded products, extruded products, films, and moldings.
  • the present invention relates to the use as described above, wherein the shaped body is a hose.
  • the high bursting pressure of the thermoplastic polyurethanes according to the invention is advantageous.
  • the present invention also relates to the injection molding products, extruded products, films or moldings obtained by a process according to the invention, for example hoses, cable sheathing or conveyor belts.
  • the present invention relates to a hose comprising a thermoplastic polyurethane as described above or a thermoplastic polyurethane obtainable or obtained by a method as described above.
  • the hose can have further components.
  • the tube may be multi-layered and reinforced by conventional means. Suitable for reinforcement are, for example, fibers or fabrics, for example those made of glass, textiles or metals.
  • the present invention accordingly relates to a hose as described above, wherein the hose is constructed in multiple layers.
  • the present invention accordingly relates to a hose as described above, wherein the hose is reinforced by fibers or fabrics.
  • a shaped article according to the invention in particular a film or a tube, color pigments or liquid organic dyes are added.
  • the shaped body for example the film or the tube, to undergo an after-treatment, for example crosslinking.
  • the present invention accordingly relates to a film or a tube as described above, wherein the film or the tube has been subjected to a post-treatment.
  • thermoplastic polyurethane of the invention a hose that can be used for pneumatic applications and after annealing at the dimensions 5.8 * 8.2 mm at a Shore hardness of 98A a bursting pressure at 70 ° C of greater than 20 bar.
  • thermoplastic polyurethanes according to the invention is advantageous for use as a cable sheath.
  • the heat resistance is determined by means of the TMA onset temperature.
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) to (iii): a polyisocyanate composition;
  • polystyrene resin a polystyrene resin
  • 2-ethanediol no further chain extender is used.
  • PTHF polytetrahydrofuran
  • polyethylene glycol polypropylene glycol
  • polyadipates polycarbonate (diols)
  • diols polycaprolactones
  • MDI methylenediphenyl diisocyanate
  • HDI hexamethylene-1,6-diisocyanate
  • H12MDI 4,4'-, 2,4'- and 2,2'-methylenedicyclohexyl diisocyanate
  • thermoplastic polyurethane according to any one of embodiments 1 to 5, wherein the ratio in the reaction is in the range of 965 to 1100.
  • thermoplastic polyurethane according to one of embodiments 1 to 7, wherein the thermoplastic polyurethane has a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505.
  • thermoplastic polyurethane comprising the reaction of components (i) to (iii):
  • thermoplastic polyurethane according to any one of embodiments 1 to 8 or a thermoplastic polyurethane obtainable or obtained according to one Process according to embodiment 9 for the production of injection molded products, extrusion products, films and moldings.
  • thermoplastic polyurethane according to any of embodiments 1 to 8 or a thermoplastic polyurethane obtainable or obtained by a process according to embodiment 9. 13. Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) to (iii):
  • polystyrene resin (iii) a polyol composition wherein in addition to 1,2-ethanediol no further chain extender is used, the polyol composition containing at least polytetrahydrofuran (PTHF) and the polyisocyanate composition containing at least methylene diphenyl diisocyanate (MDI).
  • PTHF polytetrahydrofuran
  • MDI polyisocyanate
  • thermoplastic polyurethane according to any one of Embodiments 13 to 15, wherein the ratio in the reaction is in the range of 965 to 1100.
  • thermoplastic polyurethane according to one of embodiments 13 to 16, wherein the thermoplastic polyurethane has a Shore hardness in the range of 60 A to 80 D, determined according to DIN 53505.
  • thermoplastic polyurethane comprising the reaction of components (i) to (iii):
  • polystyrene resin (iii) a polyol composition, wherein in addition to 1, 2-ethanediol no further chain extender is used, wherein the polyol composition contains at least polytetrahydrofuran (PTHF) and the polyisocyanate composition contains at least methylene diphenyl diisocyanate (MDI).
  • PTHF polytetrahydrofuran
  • MDI methylene diphenyl diisocyanate
  • thermoplastic polyurethane according to any of embodiments 13 to 17 or a thermoplastic polyurethane obtainable or obtained according to one
  • a tube comprising a thermoplastic polyurethane according to any of embodiments 13 to 17 or a thermoplastic polyurethane obtainable or obtained by a method according to embodiment 18.
  • Polyol 1 Polyether polyol having an OH number of 174.7 and excluding primary OH groups (based on tetramethylene oxide, functionality: 2)
  • Polyol 2 Polyether polyol with an OH number of 1 12.2 and excluding primary OH groups (based on tetramethylene oxide, functionality: 2)
  • Polyol 3 Mixture of Polyol 2 53.33% and Polyol 4 46.67%
  • Polyol 4 Polyether polyol with an OH number of 55.8 and excluding primary
  • Polyol 5 Polyester polyol with an OH number of 140 and excluding primary
  • Isocyanate 1 aromatic isocyanate (4,4'-methylene diphenyl diisocyanate)
  • Catalyst 1 stannous isooctoate (10% in dioctyl adipate)
  • thermoplastic polyurethane (TPU) was synthesized from 4,4'-diphenylmethane diisocyanate, chain extender 1, 2-ethanediol and polytetrahydrofuran having a number average molecular weight of 1 kg / mol with stirring in a reaction vessel.
  • the starting temperature was 80 ° C.
  • the solution was poured out onto a heating plate heated to 125 ° C. and the resulting TPU
  • Granulated plate after annealing (15 h, 80 ° C).
  • the measured values were produced by injection molding plates or tubes, wherein the zone temperatures of the extruders used were between 190 ° C and 235 ° C.
  • thermoplastic polyurethanes obtained are summarized in Tables 1 and 2.
  • Example 1 Example 2
  • Example 3 Example 4 Shore D 59 47 47 56
  • Modulus of elasticity [MPa] 90 69 50
  • the speed of the twin screw was 230 min -1 .
  • the temperature setting values of the housings were 200 ° C downstream in the first worm third, 170 ° C in the second worm third, and 190 ° C in the third and last wrench thirds.
  • the output was 850 kg / h.
  • the tubing was extruded on a 45 gauge Arenz extruder with 3-zone screw with 9.8 mm die and a 6.9 mm mandrel.
  • the zone temperatures were between 180 and 225 ° C.
  • the hose geometry was adjusted by varying the take-off speed and pressure in a water bath with vacuum calibration.
  • thermoplastic polyurethanes prepared by continuous synthesis are summarized in Table 3 and Table 4.
  • Tube optic translucent translucent opaque i.a. the following measuring methods are used:
  • the creep behavior was determined by stretching a tempered (20 h / 100 ° C) S1 tensile bar by 5%. The force or tension that occurs for the first time at this stretch is maintained at room temperature for 12 hours. After relaxation, the difference in length is determined.

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

Abstract

La présente invention concerne un polyuréthane thermoplastique obtenu ou pouvant être obtenu par mise en réaction d'au moins une composition de polyisocyanates, de 1,2-éthanediol comme allongeur de chaîne et d'une composition de polyols, aucun autre allongeur de chaîne n'étant utilisé en plus du 1,2-éthanediol. L'invention concerne également un procédé de production d'un polyuréthane thermoplastique de ce type, ainsi que l'utilisation d'un polyuréthane de ce type pour fabriquer des produits moulés par injection, des produits extrudés, des films et des corps façonnés.
EP16766986.0A 2015-09-24 2016-09-20 Polyuréthane thermoplastique Pending EP3353222A1 (fr)

Applications Claiming Priority (2)

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EP15186636 2015-09-24
PCT/EP2016/072258 WO2017050738A1 (fr) 2015-09-24 2016-09-20 Polyuréthane thermoplastique

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EP3353222A1 true EP3353222A1 (fr) 2018-08-01

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CN (1) CN108026233A (fr)
BR (1) BR112018004019A2 (fr)
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WO2023239891A1 (fr) 2022-06-10 2023-12-14 Lubrizol Advanced Materials, Inc. Polyuréthanes thermoplastiques à stabilité à haute température et leurs utilisations

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JP2023029383A (ja) 2023-03-03
CN108026233A (zh) 2018-05-11
US20180265621A1 (en) 2018-09-20
JP2018528318A (ja) 2018-09-27
US11168175B2 (en) 2021-11-09
RU2018114974A3 (fr) 2020-01-29
BR112018004019A2 (pt) 2018-12-11
RU2018114974A (ru) 2019-10-28

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