WO2019030327A1 - Polyuréthane thermoplastique transparent à base de tdi - Google Patents

Polyuréthane thermoplastique transparent à base de tdi Download PDF

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Publication number
WO2019030327A1
WO2019030327A1 PCT/EP2018/071633 EP2018071633W WO2019030327A1 WO 2019030327 A1 WO2019030327 A1 WO 2019030327A1 EP 2018071633 W EP2018071633 W EP 2018071633W WO 2019030327 A1 WO2019030327 A1 WO 2019030327A1
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Prior art keywords
polyol
thermoplastic polyurethane
group
mol
bisphenol
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PCT/EP2018/071633
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German (de)
English (en)
Inventor
Frank Prissok
Sebastian HARTWIG
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Basf Se
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Publication of WO2019030327A1 publication Critical patent/WO2019030327A1/fr

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    • 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
    • C08G18/28—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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic 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
    • C08G18/42—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G18/28—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

Definitions

  • thermoplastic polyurethane based on TDI Transparent thermoplastic polyurethane based on TDI
  • the present invention relates to thermoplastic polyurethane obtainable or obtained by reacting a polyisocyanate composition comprising at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate with a polyol composition comprising at least one polyol (P1), at least one chain extender ( KV) and at least one polyol (P2).
  • a polyisocyanate composition comprising at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate
  • a polyol composition comprising at least one polyol (P1), at least one chain extender ( KV) and at least one polyol (P2).
  • the polyol (P2) is selected from the group consisting of bisphenol derivatives selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and bisphenol S derivatives having a molecular weight Mw> 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated, or from the group consisting of polyols (P3), wherein the polyol (P3) at least one aromatic
  • Polyester block (B1) Furthermore, the present invention relates to a process for the preparation of such thermoplastic polyurethanes and the use of a
  • thermoplastic polyurethane for the production of extrusion products, cables, hoses, films and moldings.
  • thermoplastic polyurethanes for various applications are known in principle from the prior art. By varying the starting materials different property profiles can be obtained. For example, thermoplastic polyurethanes (TPU) based on MDI show good mechanical properties
  • thermoplastic polyurethane partial crystallinity properties and can be processed well.
  • One reason is ⁇ the present in the thermoplastic polyurethane partial crystallinity.
  • they have crucial disadvantages: they are not lightfast and quickly discolour in outdoor applications, in the heat or under UV irradiation. Their transparency is insufficient for applications where thick-walled parts are produced, or for applications in the field of optical fibers.
  • Thermoplastic polyurethanes based on aliphatic isocyanates have a good light fastness, but are difficult to process due to the lack of crystallinity and have, in contrast to aromatic TPU only a low mechanical strength and hardness. In the case of aliphatic HDI (hexamethylene diisocyanate) based systems, these tend to have inferior crystallinity and processability.
  • aliphatic HDI hexamethylene diisocyanate
  • the discoloration of polyurethanes by UV light and / or oxidation is essentially due to an increase of existing conjugated ⁇ -electron systems, such as that of the MDI, by oxidation of bridge or heteroatoms.
  • Known from the literature attempts to replace in the production of thermoplastic polyurethanes MDI by TDI did not lead to processable thermoplastic polyurethanes.
  • the lack of crystallization of the hard phase, as well as too slow reaction of the sterically hindered NCO Group of TDI can lead to products with too low molecular weight and a partial decomposition in the injection molding process, as well as to poor mechanical properties.
  • thermoplastic polyurethanes The prior art describes further approaches for improving the property profiles of thermoplastic polyurethanes.
  • EP 1 674 494 describes a sinterable aliphatic thermoplastic polyurethane, also mentioning the possible use of bisphenol A bis (2-hydroxyethyl) as a chain extender in combination with a polyol having a molecular weight between 450 g / mol and 10,000 g / mol. This molecule is disadvantageously in
  • EP 1 394 189 describes flameproofed thermoplastic polyurethanes preparable from aliphatic diisocyanates, a polyol having a molecular weight between 450 g / mol and 10,000 g / mol, at least one organic phosphorus-containing compound based on a phosphonate and / or phosphine oxide and a chain extender, which is also 1, 4-di ( ⁇ -hydroxyethyl) bisphenol A.
  • the focus of this application is directed to the self-extinguishing properties of the thermoplastic polyurethane.
  • EP 0 358 406 A2 also discloses thermoplastic polyurethanes, which may also comprise bisphenol derivatives, which can show self-healing properties applied as a thin protective layer or coating over solvents.
  • JP 2006321950A describes the use of alkoxylated bisphenol A components in cast elastomer applications with a focus on HDI trimers as isocyanates. These materials are not suitable for thermoplastic processing. In addition, examples which are mentioned are exclusively alkoxylated bisphenol A components which are solid at room temperature.
  • thermoplastic polyurethanes for
  • thermoplastic polyurethanes and processes for the preparation of thermoplastic polyurethanes whose starting compounds are sufficient are well processable and have on the one hand a high transparency and light fastness and on the other hand a very good mechanical strength and hardness.
  • thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii): a polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • At least one polyol (P2) At least one polyol (P2), wherein the polyol (P2) is selected from
  • the present invention also relates to a
  • thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane is transparent.
  • thermoplastic polyurethanes of the invention have a good solidification behavior and a good
  • the materials of the invention also show a pronounced self-healing against scratches and surface damage.
  • At least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate and the polyol composition are used as described above.
  • the polyol composition contains at least one polyol (P1), at least one chain extender (KV) and at least one polyol (P2).
  • the polyol (P2) is selected from
  • (B) the group consisting of polyols (P3), wherein the polyol (P3) at least one
  • the present invention also relates to a thermoplastic polyurethane as described above, wherein the polyol (P2) is selected from the group consisting of bisphenol derivatives selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and bisphenol-S derivatives having a molecular weight Mw> 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated.
  • the polyol (P2) is selected from the group consisting of bisphenol derivatives selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and bisphenol-S derivatives having a molecular weight Mw> 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated.
  • the present invention also relates to a thermoplastic polyurethane as described above, wherein the polyol (P2) is selected from the group consisting of polyols (P3), wherein the polyol (P3) has at least one aromatic polyester block (B1) ,
  • Polyol composition containing other components for example, other polyols.
  • a chain extender (KV) is used, but it can also
  • the chain extenders used may preferably be aliphatic, araliphatic, aromatic and / or cycloaliphatic diols having a molecular weight of from 50 g / mol to 220 g / mol and / or water.
  • Alkanediols having 2 to 10 C atoms in the alkylene radical, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or are preferred
  • Decaalkylene glycols are more preferably 1, 2-ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol.
  • the chain extender is a diol having a molecular weight Mw ⁇ 220 g / mol.
  • more than one diol is used as a chain extender. It is thus also possible to use mixtures of chain extenders, where at least one diol has a molecular weight M w ⁇ 220 g / mol. If more than one chain extender is used, the second or further chain extender may also have a molecular weight> 220 g / mol.
  • the chain extender is selected from the group consisting of 1, 4-butanediol and 1, 6-hexanediol, particularly preferred according to the invention is 1, 4-butanediol as a chain extender.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the chain extender (KV) is a diol having a molecular weight Mw ⁇ 220 g / mol.
  • the chain extender in particular the diol having a molecular weight Mw ⁇ 220 g / mol, is preferably used in a molar ratio in the range from 40: 1 to 1:10 to the polyol (P2), in particular the bisphenol derivative.
  • the chain extender and the polyol (P2), in particular the bisphenol derivative are preferably used in a molar ratio in the range from 20: 1 to 1: 9, more preferably in the range from 10: 1 to 1: 8.5,
  • the present invention relates to a thermoplastic polyurethane as described above wherein the chain extender and the polyol (P2) are employed in a molar ratio of 40 to 1 to 1 to 10.
  • the polyol composition comprises at least one polyol (P2), which may be a bisphenol derivative selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and bisphenol-S derivatives having a molecular weight Mw > 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated.
  • P2 polyol
  • Polyol composition two or more bisphenol derivatives selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and
  • Bisphenol-S derivatives having a molecular weight Mw> 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated comprises.
  • the at least one bisphenol derivative only comprises primary OH groups.
  • At least one of the OH groups of the bisphenol derivative is alkoxylated.
  • both OH groups of the bisphenol derivative are alkoxylated.
  • both OH groups of the bisphenol derivative are alkoxylated.
  • the two OH groups on the bisphenol derivative are alkoxylated with the same alkoxyl group.
  • OH groups with ethoxyl (-O-C2H4), propoxyl (-O-C 3 H 6 -), butoxyl (-O-C 4 H 8 -), pentoxyl (-O-C5H10-) or hexoxyl groups (-O-C6H12-) are alkoxylated.
  • the two OH groups of the bisphenol derivative are two different radicals selected from the group consisting of ethoxyl (-O-C2H4), propoxyl (-0-C 3 H 6 -), butoxyl ( -0-C 4 H 8 - alkoxylated () Pentoxyl- -O-C5H10-) or Hexoxylrest (-O-C6H12-).
  • the alkoxyl radical may have one or more alkoxy groups.
  • a bisphenol derivative is used, at least one of the OH groups of the bisphenol derivative being alkoxylated, and the at least one alkoxyl radical having a molecular weight of> 40 g / mol, preferably> 60 g / mol, more preferably> 120 g / mol, in particular> 180 g / mol, for example> 250 g / mol or else> 300 g / mol.
  • the bisphenol derivative used, wherein both OH groups of the bisphenol derivative are alkoxylated, and the two alkoxyl radicals may be identical or different and independently of one another a molecular weight of> 40 g / mol, preferably> 60 g / mol, more preferably> 120 g / mol, in particular> 180 g / mol, for example> 250 g / mol or also have> 300 g / mol.
  • the bisphenol derivative is selected from the group consisting of
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the at least one bisphenol derivative has only primary OH groups.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the at least one bisphenol derivative has the following general formula (I):
  • Each R1 is independently a methyl group or H
  • R2 and R3 are a methyl group or
  • X represents a -C (R1) 2 -, -C (R1) 2 -C (R1) 2 - or -C (R1) 2 -C (R1) 2 -C (R1) 2 - group, p and q are independently an integer from 1 to 4, and
  • n and m are independently an integer> 0.
  • Each R1 is independently a methyl group or H
  • R2 and R3 are a methyl group
  • X represents a -C (R1) 2 -, -C (R1) 2 -C (R1) 2 - or -C (R1) 2 -C (R1) 2 -C (R1) 2 - group, p and q are independently an integer from 1 to 4, and
  • n and m are independently an integer> 0; or
  • Each R1 is independently a methyl group or H
  • X represents a -C (R1) 2 -, -C (R1) 2 -C (R1) 2 - or -C (R1) 2 -C (R1) 2 -C (R1) 2 - group, p and q are independently an integer from 1 to 4, and
  • n and m are independently an integer> 0.
  • the alkoxyl radical is in each case an ethoxyl radical, ie according to a preferred embodiment the at least one bisphenol derivative has the general formula (II):
  • Each R1 is independently a methyl group or H
  • R2 and R3 are a methyl group or
  • p and q are independently an integer from 1 to 4, and
  • n and m are independently an integer> 0.
  • R1 is hydrogen, i. the compound of the formula (I) or (Ia), (Ib) or (II) preferably has terminal primary alcohol groups.
  • the polyol (P2) may be a polyol selected from the group consisting of polyols (P3), where the polyol (P3) has at least one aromatic polyester block (B1).
  • the polyol (P3) comprises an aromatic polyester block (B1).
  • the aromatic polyester block (B1) may be a polyester of an aromatic dicarboxylic acid and an aliphatic diol or a polyester of an aliphatic dicarboxylic acid and an aromatic diol.
  • the aromatic polyester block (B1) in the present invention is a polyester of an aromatic dicarboxylic acid and an aliphatic diol. Suitable aromatic dicarboxylic acids are, for example, terephthalic acid,
  • suitable polyols (P3) in the context of the present invention are those which comprise, for example, at least one polyethylene terephthalate block or at least one polybutylene terephthalate block, wherein the number of repeating units of the aromatics is at least two in series.
  • the aromatic polyester block (B1) is prepared in a separate step prior to further conversion to polyol (P3) to provide sufficient
  • the present invention accordingly relates to a thermoplastic polyurethane as described above, wherein the aromatic polyester block (B1) is a polyester of an aromatic dicarboxylic acid and an aliphatic diol.
  • the present invention also relates to a thermoplastic polyurethane as described above, wherein the aromatic polyester block (B1) is a polyethylene terephthalate block.
  • the polyol (P3) is a polyol having at least one polyethylene terephthalate block.
  • polys (P3) based on aromatic polyesters such as polybutylene terephthalate (PBT) or are suitable in the context of the present invention
  • polyethylene terephthalate PET
  • the aromatic polyester is reacted with dicarboxylic acids and diols to give mixed aromatic / aliphatic polyester diols.
  • the aromatic polyester used here usually has a higher molecular weight than the blocks (B1) contained in the polyol (P3).
  • Polyester polyols (P3) which are suitable according to the invention typically contain from 1 to 70% by weight, preferably from 3 to 60% by weight, particularly preferably from 5 to 50% by weight, very particularly preferably from 10 to 40% by weight, of the aromatic polyester blocks (B1).
  • the polyol (P3) has a molecular weight Mn in the range of 500 to 2500, preferably in the range of 500 to 2000, more preferably in the range of 750 to 1500, most preferably in the range of 1000 to 1500 g / mol.
  • polyols (P3) are preferably diols having 2 to 10
  • Carbon atoms for example ethanediol, propanediol, butanediol, pentanediol, hexanediol or di- or triethylene glycol, in particular 1, 4-butanediol or mixtures thereof.
  • Short polyether diols such as PTHF250 or PTHF 650 or a short chain polypropylene glycol such as PPG 500 can also be used.
  • dicarboxylic acids for example, linear or branched chain diacids having four to 12 carbon atoms or mixtures thereof can be used.
  • adipic acid, succinic acid, glutaric acid or sebacic acid or a mixture of said acids is used.
  • Adipic acid is particularly preferred in the context of the present invention.
  • other polyesterdiols can also be used as starting materials in the preparation of the polyols (P1), for example butanediol adipate or ethylene adipate.
  • Polyol composition according to the invention at least one polyol (P1), wherein the
  • Polyol composition may also contain mixtures of different polyols,
  • the number-average molecular weight of the polyols used according to the invention are 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.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol (P1) is selected from polyetherols and polyesterols.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol (P1) is a polyol selected from the group consisting of polyetherols.
  • Preferred polyetherols according to the invention are polyethyleneglycols, polypropylene glycols and polytetrahydrofurans. Particularly preferred in the context of the present invention are difunctional polyether polyols, especially polytetrahydrofurans (PTHF).
  • PTHF polytetrahydrofurans
  • the polyol is a polytetrahydrofuran having a molecular weight in the Mn range from 600 g / mol to 2500 g / mol.
  • PTHF1000 and PTHF2000 may be used, preferably pure PTHF1000 pure or mixtures of PTHF1000 and PTHF2000, with mixtures comprising 10-30% PTHF2000 and 70-90% PTHF1000 being preferred.
  • polyol (P1) mixtures are used, which in addition to PTHF1000 and PTHF2000 contain no further polyols.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol (P1) is selected from the group consisting of polytetrahydrofurans having a molecular weight Mn in the range from 600 g / mol to 2500 g / mol.
  • Polyesterols can also be used according to the invention, for example
  • butanediol adipates as polyesterols, in particular those having a molecular weight Mw in the range from 800 g / mol to 2000 g / mol, preferably in the range from 900 to 1500 g / mol, more preferably in the range from 1000 to 1200 g / mol, for example with a molecular weight Mw of 1000 g / mol.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyol (P1) is a polyesterol having a molecular weight Mw in the range from 800 g / mol to 2000 g / mol.
  • the polyols used 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.
  • the polyol can be used in pure form or in the form of a composition comprising the polyol and at least one solvent.
  • Solvents are known per se to the person skilled in the art.
  • the polyol (P1) is preferably used in a molar ratio ranging from 40: 1 to 1:10 to the polyol (P2).
  • the polyol (P1) and the polyol (P2) are used in a molar ratio in the range from 30: 1 to 1: 9, more preferably in the range from 20: 1 to 1: 8.5, in particular in the range from 15: 1 to 1: 5, more preferably in the range from 10: 1 to 1: 2, or else in the range from 7: 1 to 1: 1, 6.
  • the polyol (P1) can be selected from the group consisting of
  • Polyetherols in a molar ratio in the range of 40: 1 to 1:10 to the polyol (P2) can be used.
  • the polyol (P1) and the polyol (P2) can be used in a ratio in the range of 40: 1 to 10: 1, in particular in the range of 30: 1 to 15: 1. It is also possible that the polyol (P1) and the polyol (P2) are used in a ratio ranging from 1:10 to 1: 9.
  • the polyisocyanate composition contains at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. According to the invention, it is also possible to use mixtures of 2,4-tolylene diisocyanate and tolylene 2,6-diisocyanate.
  • Polyisocyanate composition contains further polyisocyanates, wherein preferably the amount of further isocyanates based on the total polyisocyanate composition is less than 30 wt .-%, more preferably less than 20 wt .-%, particularly preferably less than 10 wt .-%.
  • isocyanates are, for example, hexamethylene-1,6-diisocyanate (HDI), 4,4'-, 2,4'- and / or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI), 1-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) or mixtures thereof.
  • HDI hexamethylene-1,6-diisocyanate
  • H12MDI 4,4'-, 2,4'- and / or 2,2'-methylenedicyclohexyl diisocyanate
  • IPDI isophorone diisocyanate
  • MDI 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate
  • the isocyanate and the polyol composition are used in a ratio which gives an index NCO: OH of about 1000, preferably an index NCO: OH in the range of 1000-1050.
  • 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or mixtures of the two isomers can be used.
  • suitable 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or mixtures of the two isomers can be used.
  • Mixtures are, for example, a mixture of 80% 2,4-tolylene diisocyanate and 20% of 2,6-tolylene diisocyanate or a mixture of 65% 2,4-tolylene diisocyanate and 35% tolylene 2,6-diisocyanate. Pure 2,4-tolylene diisocyanate can also be used according to the invention.
  • the present invention relates to a thermoplastic polyurethane as described above, wherein the polyisocyanate composition comprises a mixture of 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate.
  • pre-reacted prepolymers can be used as the isocyanate component, in which part of the OH components are reacted with one of the isocyanates suitable for the invention 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 polyisocyanate can be used in pure form or in the form of a composition comprising the polyisocyanate and at least one solvent.
  • 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.
  • further starting materials can be added during the reaction, for example catalysts or auxiliaries and additives.
  • auxiliaries and additives are known per se to the person skilled in the art. Mention may be made, for example, of surface-active substances, flame retardants, nucleating agents,
  • Oxidation stabilizers antioxidants, lubricants and mold release agents, dyes and pigments, stabilizers, e.g. As 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 the Kunststoffhandbuch, Volume VII, published by Vieweg and Hochtlen, Carl Hanser Verlag, Kunststoff 1966 (p.103-113).
  • 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 tin isooctoate, tin dioctoate, Dimethyltin or diethyltin, or tin organyl compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate,
  • the catalysts are selected from
  • Tin compounds and bismuth compounds are preferably tin alkyl compounds or bismuth-alkyl compounds. Particularly suitable are the tin isooctoate and
  • the catalysts are usually used in amounts of 3 ppm to 2000 ppm, preferably 10 ppm to 1000 ppm, more preferably 20 ppm to 500 ppm, and most preferably from 30 ppm to 300 ppm.
  • the present invention relates to a process for producing a thermoplastic polyurethane comprising the reaction of at least the
  • At least one polyol (P2) At least one polyol (P2), wherein the polyol (P2) is selected from
  • bisphenol A derivatives having a molecular weight M w> 315 g / mol and bisphenol S derivatives having a molecular weight M w> 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated, or
  • thermoplastic polyurethane as described above, wherein the at least one bisphenol derivative has the following general formula (I):
  • Each R1 is independently a methyl group or H
  • R2 and R3 are a methyl group or
  • X represents a -C (R1) 2 -, -C (R1) 2 -C (R1) 2 - or -C (R1) 2 -C (R1) 2 -C (R1) 2 - group, p and q are independently an integer from 1 to 4, and
  • n and m are independently an integer> 0.
  • the present invention according to another embodiment relates to a method for producing a thermoplastic polyurethane as described above, wherein a mixture of 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate is used as the polyisocyanate or pure 2,4-tolylene diisocyanate ,
  • the process can be carried out in principle under known reaction conditions. According to a preferred embodiment, the process is carried out at elevated temperatures as room temperature, more preferably in the range between 50 ° C and 200 ° C, more preferably in the range of 65 ° C and 150 ° C, in particular in the range of 75 ° C and 120 ° C.
  • the heating can be carried out according to the invention in any suitable manner known to the person skilled in the art. Preferably by electrical heating, heating with heated oil or water, induction fields, warm air or IR radiation.
  • polyurethanes obtained according to the invention have high transparency with good mechanical properties. Surprisingly, there is no discoloration even with a long UV irradiation and thermal stress.
  • Thermoplastic polyurethanes according to the invention or the polyurethanes obtained by a process according to the invention preferably have a transmission at 450 nm of greater than 85% with a layer thickness of 2 mm.
  • the transmission or opacity are measured once with a light trap as background and once with a white tile as background in reflection with exclusion of the gloss with a colorimeter.
  • the brightness values (L value according to DIN 6174) are given a ratio and are given as opacity in%.
  • the transmission or opacity was measured once with a light trap as background and once with a white tile as background in reflection excluding the gloss with a colorimeter.
  • the brightness values (L value according to DIN 6174) are given a ratio and are given as opacity in%.
  • a colorimeter "UltraScan” from HunterLab was used. The colorimeter is standardized upon reaching the operating temperature, generally 30 minutes, and operated under the following parameters:
  • the refractive index of the thermoplastic polyurethanes according to the invention or of the polyurethanes obtained by a process according to the invention is greater than 1.50, preferably greater than 1.52, determined in accordance with EN ISO 489: 1999.
  • thermoplastic polyurethane according to the invention or a polyurethane obtained by a process according to the invention is preferably characterized in that the storage modulus falls within 40 ° C to 5% of the initial value measured according to DIN IS01 1359.
  • Another aspect of the present invention relates to the use of a transparent thermoplastic polyurethane according to the present invention or a
  • thermoplastic polyurethane obtainable by a process according to the present invention for the production of extruded products, films and moldings.
  • the present invention relates to the use of a thermoplastic polyurethane or a thermoplastic polyurethane as described above obtainable or obtained according to a method of producing a thermoplastic polyurethane as described above for the production of extruded products, cables, hoses, films and moldings.
  • Preferred applications in accordance with the invention are, for example, in outdoor applications, transparent coatings, stone chipping films, housings or cable sheaths.
  • thermoplastic polyurethane According to a preferred embodiment, the use of a transparent thermoplastic polyurethane according to the present invention or a
  • thermoplastic polyurethane obtainable by a process according to the present invention, the production of a molded article, wherein the molded article is a protective film, housing, headlight and taillight housing, handset housing, a shoe sole, a sporting goods, a handle, a container or a compact disc.
  • thermoplastic polyurethane according to the present invention is preferred as a glass-substitute material, thermoformable material, construction material, adhesive, especially hot-melt adhesive, medical supplies, or optical data carrier.
  • thermoplastic polyurethane as a glass material, in particular light guides, photoconductive films, lenses, Fresnel lenses, optical glasses, spectacle lenses, safety glasses, headlamp lenses, light covers, especially in street lamps, reflectors, automotive interior lights, motorcycle visors, coverslips , Housing covers, especially for automotive applications, protective screens, mobile phone displays, bottles and other containers.
  • thermoplastic polyurethane as optical data carrier, in particular for CDs, DVDs and Blu-Ray compact disks, as well as for other optical applications, for example under water.
  • the present invention relates to the use of a thermoplastic polyurethane as described above, wherein the
  • Shaped body a protective film, housing, headlight and tail light housing,
  • Handset housing a shoe sole, a sporting goods, a handle, a container or a compact disc is.
  • the present invention according to another embodiment relates to the use of a thermoplastic polyurethane as described above, wherein the products are transparent lightfast molding compounds, wood coating or floor coating.
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii): a polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • At least one polyol (P2) At least one polyol (P2), wherein the polyol (P2) is selected from
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii): (i) a polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • At least one polyol (P2) is selected from the group consisting of bisphenol derivatives selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and bisphenol-S derivatives having a molecular weight Mw> 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated.
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii):
  • polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • At least one polyol (P2) wherein the polyol (P2) is selected from the group consisting of polyols (P3), wherein the polyol (P3) at least one aromatic polyester block (B1).
  • thermoplastic polyurethane according to any one of embodiments 1 to 3, wherein the thermoplastic polyurethane is transparent.
  • thermoplastic polyurethane according to any one of embodiments 1, 4 or 5, wherein the polyol (P2) is selected from the group consisting of bisphenol derivatives selected from the group consisting of bisphenol A derivatives with a
  • Each R1 is independently a methyl group or H
  • R2 and R3 are a methyl group or
  • X represents a -C (R1) 2 -, -C (R1) 2 -C (R1) 2 - or -C (R1) 2 -C (R1) 2 -C (R1) 2 - group, p and q are independently an integer from 1 to 4, and
  • n and m are independently an integer> 0.
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii):
  • polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • At least one polyol (P2) is selected from the group consisting of bisphenol derivatives selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and bisphenol-S derivatives having a molecular weight Mw> 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated, wherein the at least one bisphenol derivative has the following general formula (I):
  • Each R1 is independently a methyl group or H
  • R2 and R3 are a methyl group or
  • X represents a -C (R1) 2 -, -C (R1) 2 -C (R1) 2 - or -C (R1) 2 -C (R1) 2 -C (R1) 2 - group, p and q are independently an integer from 1 to 4, and
  • n and m are independently an integer> 0.
  • Thermoplastic polyurethane according to any of embodiments 1, 4 or 5, wherein the polyol (P2) is selected from the group consisting of polyols (P3), wherein the polyol (P3) has at least one aromatic polyester block (B1).
  • Polyester block (B1) is a polyester of an aromatic dicarboxylic acid and an aliphatic diol.
  • thermoplastic polyurethane according to any one of Embodiments 10 or 11, wherein the aromatic polyester block (B1) is a polyethylene terephthalate block.
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii): a polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • polyol (P2) wherein the polyol (P2) is selected from the group consisting of polyols (P3), where the polyol (P3) comprises at least one aromatic polyester block (B1) and wherein the aromatic polyester block (B1) is a
  • Polyethylene terephthalate block is.
  • thermoplastic polyurethane according to any one of embodiments 1 to 13, wherein the polyol (P1) is selected from polyetherols and polyesterols.
  • thermoplastic polyurethane according to any one of embodiments 1 to 14, wherein the polyol (P1) is a polyesterol having a molecular weight Mw in the range of 800 g / mol to 2000 g / mol.
  • thermoplastic polyurethane according to any one of embodiments 1 to 15, wherein the polyol (P1) is selected from the group consisting of polytetrahydrofurans having a molecular weight Mn in the range of 600 g / mol to 2500 g / mol. 17.
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii):
  • polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • At least one polyol (P2) At least one polyol (P2), wherein the polyol (P2) is selected from
  • Polytetrahydrofurans having a molecular weight Mn in the range of 600 g / mol to 2500 g / mol.
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii): a polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • At least one polyol (P2) is selected from the group consisting of bisphenol derivatives selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and bisphenol-S derivatives having a molecular weight Mw> 315 g / mol, wherein at least one of the OH groups of the bisphenol derivative is alkoxylated, and wherein the polyol (P1) is selected from the group consisting of
  • Polytetrahydrofurans having a molecular weight Mn in the range of 600 g / mol to 2500 g / mol.
  • Thermoplastic polyurethane obtainable or obtained by reacting at least components (i) and (ii):
  • polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • polyol (P2) at least one polyol (P2), wherein the polyol (P2) is selected from the group consisting of polyols (P3), wherein the polyol (P3) has at least one aromatic polyester block (B1), and wherein the polyol (P1) is selected from the group consisting of
  • Polytetrahydrofurans having a molecular weight Mn in the range of 600 g / mol to 2500 g / mol.
  • 21. A thermoplastic polyurethane according to any one of embodiments 1 to 19, wherein the polyisocyanate composition contains 2,4-tolylene diisocyanate and no further isocyanate.
  • thermoplastic polyurethane comprising
  • polyisocyanate composition containing at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate;
  • At least one polyol (P2) At least one polyol (P2), wherein the polyol (P2) is selected from
  • bisphenol derivatives selected from the group consisting of bisphenol A derivatives having a molecular weight Mw> 315 g / mol and bisphenol-S derivatives having a molecular weight Mw> 315 g / mol, wherein at least one of OH groups of the bisphenol derivative is alkoxylated.
  • Each R1 is independently a methyl group or H
  • R2 and R3 are a methyl group or
  • X represents a -C (R1) 2 -, -C (R1) 2 -C (R1) 2 - or -C (R1) 2 -C (R1) 2 -C (R1) 2 - group, p and q are independently an integer from 1 to 4, and
  • n and m are independently an integer> 0.
  • polyol (P2) is selected from the group consisting of polyols (P3), wherein the polyol (P3) comprises at least one aromatic polyester block (B1).
  • Polyester block (B1) is a polyethylene terephthalate block.
  • polyetherols is selected from polyetherols and polyesterols.
  • polyol (P1) is a polyesterol having a molecular weight Mw in the range of 800 g / mol to 2000 g / mol.
  • polyol (P1) is selected from the group consisting of polytetrahydrofurans having a
  • Polyisocyanate composition containing a mixture of 80% 2,4-tolylene diisocyanate and 20% of 2,6-toluene diisocyanate. 34. The method according to any one of embodiments 22 to 32, wherein the
  • Polyisocyanate composition contains 2,4-toluene diisocyanate and no further isocyanate.
  • thermoplastic polyurethane according to any one of embodiments 1 to 21 or a thermoplastic polyurethane obtainable or obtained by a process according to any of embodiments 22 to 34 for the preparation of
  • housing, headlight and taillight housing, handset housing, a shoe sole, a sporting goods, a handle, a container or a compact disc is.
  • Polyol 1 polyether polyol based on polytetrahydrofuran having an OH number of 1 12.3 and excluding primary OH groups,
  • Polyol 2 bisphenol A-started polyether polyol with an OH number of 239 and excluding primary OH groups
  • Polyol 3 adipic acid-ethylene glycol Polyesterpolyol with an OH number of 56 g / mol
  • Polyol 4 polyether polyol based on polytetrahydrofuran with an OH number of 56 and excluding primary OH groups,
  • Polyol 5 Polyether polyol based on polypropylene / polyethylene glycol with an OH number of 63 and a functionality of 1.99
  • Polyol 6 adipic acid-butanediol Polyesterpolyol with an OH number of 1 12 g / mol
  • Polyol 7 Adipic acid-butanediol Polyester polyol with an OH number of 45.5 g / mol
  • Polyol 8 Polyether polyol based on polypropylene glycol with an OH number of 56 and a functionality of 1, 96
  • Polyol 9 Polyether polyol based on 70% polyethylene / 25% propylene glycol with an OH number of 51 and a functionality of 1.98
  • Polyol 10 polyester polyol based on adipic acid, succinic acid, glutaric acid, PET and diethylene glycol and having an OH number of 75.6 and functionality: 2
  • Polyol 1 1 polyester polyol based on adipic acid, succinic acid, glutaric acid, PET and diethylene glycol and having an OH number of 1 10.6 and functionality: 2
  • Isocyanate 1 T80A (80% 2,4 TDI, 20% 2,6 TDI) isocyanate 2: T100A (100% 2,4 TDI) KV: 1, 4-butanediol
  • the polyols were introduced at 80 ° C in a container and mixed with the components according to Table 1 with vigorous stirring.
  • the reaction mixture heated to above 110 ° C and was then placed on a heated Teflon-coated table
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 ffe 1391/1/8 1391/1/17 1391/2/3 1328/39/1 1391/3/3 1391/3/6 1391/1 / 7
  • Comparative Examples 1 and 2 do not solidify into an injection-moldable mass, therefore, no mechanical properties could be determined.
  • Comparative Example 3 solidified only after 3 days of storage at 80 ° C and was difficult to process in injection molding to warp-free plates.
  • the examples according to the invention could easily be processed into transparent plates by injection molding.
  • the transparent injection-molded plates obtained from the examples according to the invention show good mechanical properties in terms of tensile strength, elongation at break and tear propagation resistance, as well as low intrinsic coloration.

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Abstract

La présente invention concerne un polyuréthane thermoplastique obtenu ou pouvant être obtenu en faisant réagir une composition de polyisocyanate contenant au moins un polyisocyanate choisi dans le groupe constitué du 2,4-toluènediisocyanate et du 2,6-toluènediisocyanate avec une composition de polyols contenant au moins un polyol (P1), au moins un allongeur de chaîne (KV) et au moins un polyol (P2). Selon l'invention, le polyol (P2) est choisi dans le groupe constitué de dérivés du bisphénol choisis dans le groupe constitué des dérivés du bisphénol A ayant un poids moléculaire Mw > 3 g/mol et des dérivés du bisphénol S ayant un poids moléculaire Mw > 315 g/mol, au moins l'un des groupes OH du dérivé du bisphénol étant alcoxylé, ou bien choisi dans le groupe constitué des polyols (P3), le polyol (P3) présentant au moins un bloc polyester aromatique (B1). La présente invention concerne en outre un procédé pour produire ce type de polyuréthanes thermoplastiques et l'utilisation d'un polyuréthane thermoplastique selon l'invention afin de fabriquer des produits extrudés, des câbles, des tuyaux, des feuilles et des corps moulés.
PCT/EP2018/071633 2017-08-09 2018-08-09 Polyuréthane thermoplastique transparent à base de tdi WO2019030327A1 (fr)

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"Kunststoffhandbuch, Band 7, Polyurethane", vol. 7, 1993, CARL HANSER VERLAG

Cited By (2)

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WO2021110623A1 (fr) * 2019-12-03 2021-06-10 Basf Se Tube médical comprenant du polyuréthane thermoplastique
CN114746465A (zh) * 2019-12-03 2022-07-12 巴斯夫欧洲公司 包含热塑性聚氨酯的医用管

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