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WO2005019293A1 - Polyurethane thermoplastique contenant des groupes silane - Google Patents

Polyurethane thermoplastique contenant des groupes silane Download PDF

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Publication number
WO2005019293A1
WO2005019293A1 PCT/EP2004/007259 EP2004007259W WO2005019293A1 WO 2005019293 A1 WO2005019293 A1 WO 2005019293A1 EP 2004007259 W EP2004007259 W EP 2004007259W WO 2005019293 A1 WO2005019293 A1 WO 2005019293A1
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WO
WIPO (PCT)
Prior art keywords
groups
thermoplastic polyurethane
silane
organic
compounds
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.)
Ceased
Application number
PCT/EP2004/007259
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German (de)
English (en)
Inventor
Oliver Steffen Henze
Sabine Peters
Johann Diedrich Brand
Christa Hackl
Markus Krämer
Klaus Hilmer
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BASF SE
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BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DE112004001118T priority Critical patent/DE112004001118A5/de
Publication of WO2005019293A1 publication Critical patent/WO2005019293A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G18/28—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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon

Definitions

  • the invention relates to thermoplastic polyurethane, in particular fibers, cable sheathing and hoses, in particular compressed air hoses based on thermoplastic polyurethane, containing silicon-organic groups. Furthermore, the invention relates to processes for the production of modified with organic silicon compounds, i.e. Thermoplastic polyurethane containing silicon-organic groups and crosslinkable TPU, in particular fibers, cable sheaths and hoses, in particular compressed air hoses, and the corresponding products crosslinked via the silicon-organic groups, in particular siloxane groups.
  • Thermoplastic plastics are plastics that, when repeatedly heated and cooled in the temperature range typical for the material for processing and application, remain thermoplastic.
  • Thermoplastic is understood to mean the property of a plastic to repeatedly soften in the heat in a temperature range typical for it and to harden on cooling and in the softened state to be capable of being repeatedly formed by molding, extrudate or molded part into semi-finished products or objects.
  • Thermoplastic materials are widely used in technology and can be found in the form of fibers, sheets, foils, moldings, bottles, jackets, packaging, etc.
  • Thermoplastic polyurethane (hereinafter referred to as TPU) is an elastomer that is used in many applications , e.g.
  • the object of the present invention was to develop thermoplastic polyurethane, in particular fibers based on thermoplastic polyurethane, containing silicon-organic groups, which are accessible via a simple, fast and inexpensive production process, have excellent crosslinking properties and, in particular, are used as fibers have a very good level of properties when networked.
  • silane used in this document is to be understood as meaning organic silane compounds. Accordingly, the term “modified with silane” is understood to mean that the corresponding substance is modified with an organic silicon compound.
  • silicon-organic groups are connected to the thermoplastic polyurethane via two urea groups and that no allophanate groups or urethane groups are present between the urea group or the silane groups.
  • connection with which the silane is introduced into the TPU is built directly into the polyurethane.
  • it is not connected to the TPU indirectly, via a cross-linker, but is present in the TPU structure itself.
  • Another object was to provide an improved, simpler, faster and more economical process for producing crosslinkable TPU, especially processes for producing silane-modified, i.e. To develop thermoplastic polyurethane having organic silicon groups.
  • thermoplastic polyurethane uses organic silicon compounds which have one or two, preferably two amino groups, particularly preferably one or two secondary amino groups.
  • the method according to the invention is characterized in that the silane group can be introduced directly during the manufacturing process of the TPU. Complicated additional steps, such as the reaction of a finished TPU with isocyanates and the subsequent reaction of the isocyanate-modified TPU with silanes, as taught, for example, in US 2002/0169255, are not necessary. It was surprisingly found that the silane groups, which are integrated into the TPU during the manufacturing process, do not lead to cross-links in the further processing of the TPU before the actual shaping. This is surprising since the processing of the TPU, for example granulation under water, is optionally carried out in the presence of moisture, which can be followed by drying at elevated temperatures. These moist and warm conditions usually support the crosslinking reaction of the silanes, but this is only desired after the actual shaping, ie after extrusion, injection molding or spinning.
  • the crosslinkable thermoplastic polyurethane can preferably be prepared by reacting (a) isocyanates with (b) compounds which are reactive toward isocyanates and have a molecular weight between 500 and 10,000 and (c) chain extenders with a molecular weight of 50 to 499 and silane which preferably has two amino groups may have two secondary amino groups in the presence of (d) catalysts and / or (e) customary additives, the ratio of the sum of the isocyanate groups of component (a) to the sum of the isocyanate-reactive functions of components (b), (c ) and the amino groups of the silanes and optionally (d) and (e) is between 0.7: 1 and 1.3: 1.
  • This preferred ratio thus describes the molar ratio of all isocyanate groups to the sum of all functions reactive towards isocants, i.e. reactive hydrogen atoms.
  • This ratio is usually also referred to as a key figure, a ratio of 1: 1 corresponding to a key figure of 100. If the index is 100, an isocyanate group of component (a) has an active hydrogen atom, i.e. a function reactive towards isocyanates. With key figures above 100, there are more isocyanate groups than, for example, OH groups.
  • the silanes can thus already be incorporated during the TPU production process.
  • organosilicon compounds or “silanes” or “organosilicon groups” or “silane groups” refers to compounds, in particular generally known alkoxysilanes, for example di- or tri-methoxy and / or ethoxysilanes , understood, which preferably contain the following general structural unit: -Si (R) 3-x (OR) x
  • R alkyl radical or aryl radical, which can optionally be heteroatom-substituted, preferably alkyl radical with 1 to 10, preferably 1 to 6 carbon atoms, preferably methyl and / or ethyl, x: 1, 2 or 3, preferably 2 or 3, particularly preferably 3,
  • the molar ratio of the polyols and chain extenders (b) and (c) to the silanes is preferably between 1: 0.01 and 1: 0.5.
  • Thermoplastic polyurethane means that it is preferably a thermoplastic elastomer based on polyurethane.
  • a thermoplastic elastomer is an elastomer that, when repeatedly heated and cooled in the temperature range typical of the material for processing and application, remains thermoplastic.
  • Thermoplastic is understood to mean the property of a plastic to repeatedly soften in the heat in a temperature range typical for it and to harden on cooling and in the softened state to be capable of being repeatedly formed by molding, extrudate or molded part into semi-finished products or objects.
  • thermoplastic polyurethane are TPUs that have a Shore hardness of 50 A to 80 D. Also preferred are TPUs which have one, more or preferably all of the following properties:
  • ⁇ a modulus of elasticity from 10 MPa to 10,000 MPa measured according to DIN EN ISO 527-2 on a sample body of type A according to DIN EN ISO 3167 at a test speed of 1 mm / min.
  • the modulus of elasticity is calculated from the initial slope of the stress-strain curve as a ratio of stress and strain.
  • ⁇ a glass transition temperature T g measured by DSC (at 10K / min) less than minus 10 ° C for types up to a maximum of 64 Shore D types up to less than minus 40 ° C for types minimum 85 Shore A types.
  • the TPU exhibits these preferred properties in the uncrosslinked state, i.e. without cross-linking via the silane groups.
  • TPUs Processes for the production of thermoplastic polyurethanes, also referred to in this document as TPU, are generally known.
  • TPUs are reacted by reacting (a) isocyanates with (b) isocyanate-reactive compounds, usually with a molecular weight (M w ) of 500 to 10,000, preferably 500 to 5000, particularly preferably 800 to 3000 and (c) chain extenders with a molecular weight of 50 to 499 optionally in the presence of (d) catalysts and / or (e) customary additives.
  • M w molecular weight
  • the silanes are preferably additionally used according to the invention.
  • organic isocyanates for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2- Methyl-pentamethylene-diisocyanate-1, 5, 2-ethyl-butylene-diisocyanate-1,4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-isocyanato-3,3,5-trimethyl- 5-isocyanato-methyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1-methyl-2,4 - and / or -2,
  • the compounds (b) which are reactive toward isocyanates can be the generally known compounds which are reactive toward isocyanates, for example polyesterols, polyetherols and / or polycarbonate diols, which are usually also summarized under the term "polyols", with molecular weights between 500 and 8000 , preferably 600 to 6000, in particular 800 to less than 3000, and preferably an average functionality over isocyanates of 1.8 to 2.3, preferably 1.9 to 2.2, in particular 2.
  • Polyether polyols are preferably used, for example those the basis of generally known starter substances and customary alkylene oxides, for example ethylene oxide, propylene oxide and / or butylene oxide, preferably polyetherols based on propylene oxide-1, 2 and ethylene oxide and in particular polyoxytetramethylene glycols.
  • the polyetherols have the advantage that they have a higher hydrolysis stability than polyesterols.
  • So-called low-unsaturated polyetherols can also be used as polyetherols.
  • low-unsaturated polyols are understood in particular to mean polyether alcohols with an unsaturated compound content of less than 0.02 meg / g, preferably less than 0.01 meg / g.
  • Such polyether alcohols are usually produced by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, onto the diols or triols described above in the presence of highly active catalysts.
  • highly active catalysts are, for example, cesium hydroxide and multimetal cyanide catalysts, also referred to as DMC catalysts.
  • DMC catalysts A frequently used DMC catalyst is zinc hexacyanocobaltate. After the reaction, the DMC catalyst can be left in the polyether alcohol; it is usually removed, for example by sedimentation or filtration.
  • polybutadiene diols with a molar mass of 500-10000 g / mol, preferably 000-5000 g / mol, in particular 2000-3000 g / mol can be used.
  • TPUs which have been produced using these polyols can be crosslinked by radiation after thermoplastic processing. This leads e.g. for better burning behavior.
  • the chain extenders (c) used are generally known aliphatic, aromatic lipatic, aromatic and / or cycloaliphatic compounds with a molecular weight of 50 to 499, preferably 2-functional compounds, for example diamines and / or alkanediols with 2 to 10 C atoms in the alkylene radical, in particular 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and / or Di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols with 3 to 8 carbon atoms, preferably corresponding oligo- and / or polypropylene glycols, whereby also mixtures of Chain extenders can be used.
  • Components a) to c) are particularly preferably difunctional
  • connections i.e. Diisocyanates (a), difunctional polyols, preferably polyetherols (b) and difunctional chain extenders, preferably diols.
  • Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the structural components (b) and (c) are the tertiary amines known and customary in the prior art, such as e.g. Triethylamine, dimethylcyclohexylamine, N-methylimorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds such as e.g. Iron (III) acetylacetonate, tin compounds e.g.
  • Triethylamine dimethylcyclohexylamine, N-methylimorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like
  • the catalysts are usually used in amounts of 0.0001 to 0.1 part by weight per 100 parts by weight of polyhydroxy compound (b).
  • auxiliaries and / or additives (e) can also be added to the structural components (a) to (c).
  • examples include blowing agents, surface-active substances, fillers, nucleating agents, lubricants and mold release agents, dyes and pigments, antioxidants, for example against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, flame retardants, reinforcing agents and plasticizers, metal deactivators.
  • component (e) also includes hydrolysis stabilizers such as, for example, polymeric and low-molecular carbodiimides.
  • the thermoplastic polyurethane particularly preferably contains melamine cyanurate in the materials according to the invention, which acts as a flame retardant.
  • Melamine cyanurate is preferably used in an amount between 0.1 and 60% by weight, particularly preferably between 5 and 40% by weight, in particular between 15 and 25% by weight, in each case based on the total weight of the TPU.
  • the thermoplastic polyurethane preferably contains triazole and / or triazole derivative and antioxidants in an amount of 0.1 to 5% by weight, based on the total weight of the thermoplastic polyurethane.
  • Substances which inhibit or prevent undesired oxidative processes in the plastic to be protected are generally suitable as antioxidants. In general, antioxidants are commercially available.
  • antioxidants tien are hindered phenols, aromatic amines, thiosynergists, organophosphorus compounds of trivalent phosphorus, and hindered amine light stabilizers.
  • examples of sterically hindered phenols can be found in Plastics Additive Handbook, 5th edition, H. Doubt, ed, Hanser Publishers, Kunststoff, 2001 ([1]), _ p. 98-107 and pp. 116 - p. 121.
  • aromatic amines can be found in [1] pp. 107-108.
  • thiosynergists are given in [1], pp.104-105 and pp.112-113.
  • Phenolic antioxidants are preferably suitable for use in the antioxidant mixture according to the invention.
  • the antioxidants in particular the phenolic antioxidants, have a molar mass of greater than 350 g / mol, particularly preferably of greater than 700 g / mol and a maximum molar mass of ⁇ 10,000 g / mol, preferably ⁇ 3000 g / mol.
  • they preferably have a melting point of less than 180DC.
  • Antioxidants which are amorphous or liquid are also preferably used. Mixtures of two or more antioxidants can also be used as component (i).
  • chain regulators In addition to components a), b) and c) and, if appropriate, d) and e), chain regulators, usually with a molecular weight of 31 to 3000, can also be used.
  • Such chain regulators are compounds that have only one isocyanate-reactive functional group, such as. B. monofunctional alcohols, monofunctional amines and / or monofunctional polyols.
  • a flow behavior in particular with TPUs, can be specifically set.
  • Chain regulators can generally be used in an amount of 0 to 5, preferably 0.1 to 1 part by weight, based on 100 parts by weight of component b), and by definition fall under component (c).
  • the build-up components (b) and (c) can be varied in relatively wide molar ratios.
  • the TPU can be produced continuously using the known processes, for example using reaction extruders or the belt process using one-shot or the prepolymer process, or batchwise using the known prepolymer process.
  • the components (a), (b), (c) and optionally (d) and / or (e) are mixed in succession or simultaneously with one another, the reaction commencing immediately.
  • the build-up components (a), (b), (c) and optionally (d) and / or (e) are introduced into the extruder individually or as a mixture, for example at temperatures from 100 to 280 ° C., preferably 140 to 250 ° C, and reacted.
  • the TPU obtained is usually extruded, cooled and granulated.
  • the TPU can optionally be modified by assembly on an extruder. With this assembly, the TPU can be modified, for example, in terms of its melt index or its granulate shape in accordance with the requirements.
  • TPUs produced according to the invention which are usually in the form of granules or in powder form, into injection molding and extrusion articles, e.g.
  • the desired foils, molded parts, rolls, fibers, cladding in automobiles, hoses, cable plugs, bellows, trailing cables, cable sheathing, seals, belts or damping elements are made using standard methods, such as Injection molding or extrusion.
  • Such injection molding and extrusion articles can also be made from compounds containing the TPU according to the invention and at least one further thermoplastic, in particular a polyethylene, polypropylene, polyester, polyether, polystyrene, PVC, ABS, ASA, SAN, polyacrylonitrile, EVA, PBT, PET, polyoxy- methylene.
  • the TPU produced according to the invention can be used to produce the articles shown at the beginning.
  • the silane-modified thermoplastic polyurethane will be spun into fibers according to generally known processes and then the thermoplastic polyurethane will be crosslinked via the silane groups by means of moisture, optionally using a catalyst which accelerates the crosslinking.
  • the crosslinking reactions above and through the silane groups are familiar to the person skilled in the art and are generally known.
  • This crosslinking is usually carried out by moisture and can be carried out by heat or catalysts known for this purpose, e.g. Lewis acids, Lewis bases, Bronsted bases, Bronsted acids are accelerated.
  • Tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or the like.
  • the product crosslinked via the silane groups preferably has the following properties: Vicat temperature (Vicat softening temperature, VST) according to DIN EN ISO 306 (10N / 120 K / h) greater than 145 ° C.
  • a fiber without silane crosslinking according to the invention shows an HDT (heat distortion temperature, measurement under a pretension of 0.04 mN / dtex; heating rate 10K / min; measuring range from -100 ° C. to 250 ° C.) of 120 ° C.
  • the crosslinking by the silane groups increased the HDT to 173 ° C.
  • melt-spun elastomer fibers according to the invention Another advantage of the crosslinking of melt-spun elastomer fibers according to the invention is the improved resistance to conventional spinning preparations. While melt-spun fibers without crosslinking according to the invention in contact with spin finishes are attacked even at low temperatures ( ⁇ 120 ° C.) and in some cases completely destroyed, crosslinked fibers according to the invention show almost no damage even at temperatures above 190 ° C.
  • thermoplastically processable polyurethane elastomers according to the invention can be used for extrusion, injection molding, calendar articles and for powder slush processes.
  • the solidified elastomer material was then crushed after an intermediate storage period of 12 hours at 80 ° C and processed into test specimens by means of injection molding. These test specimens were stored at 80 ° C. in water with the addition of catalytic amounts of acetic acid and were then insoluble in dimethyiformamide.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un polyuréthane thermoplastique contenant des groupes silicium organique, les groupes silicium organique étant reliés au polyuréthane thermoplastique par deux groupes urée, et aucun groupe allophanate ou uréthane ne se trouvant entre le(s) groupe(s) urée et les groupes silane.
PCT/EP2004/007259 2003-07-25 2004-07-03 Polyurethane thermoplastique contenant des groupes silane Ceased WO2005019293A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112004001118T DE112004001118A5 (de) 2003-07-25 2004-07-03 Thermoplastisches Polyurethan enthaltend Silangruppen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10334264.8 2003-07-25
DE2003134264 DE10334264A1 (de) 2003-07-25 2003-07-25 Thermoplastisches Polyurethan enthaltend Silangruppen

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WO2005019293A1 true WO2005019293A1 (fr) 2005-03-03

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886226A (en) * 1972-02-17 1975-05-27 Mitsui Toatsu Chemicals Polyurethane composition
US20020169255A1 (en) * 1999-06-08 2002-11-14 Gemoplast(Societe Anonyme) Method for producing a thermosetting polyurethane from a thermoplastic polyurethane and thermoset polyurethane obtainable using said method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886226A (en) * 1972-02-17 1975-05-27 Mitsui Toatsu Chemicals Polyurethane composition
US20020169255A1 (en) * 1999-06-08 2002-11-14 Gemoplast(Societe Anonyme) Method for producing a thermosetting polyurethane from a thermoplastic polyurethane and thermoset polyurethane obtainable using said method

Also Published As

Publication number Publication date
DE10334264A1 (de) 2005-02-24

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