WO2019072578A1 - Procédé de commande des propriétés hydrophobes de polyuréthanes - Google Patents

Procédé de commande des propriétés hydrophobes de polyuréthanes Download PDF

Info

Publication number
WO2019072578A1
WO2019072578A1 PCT/EP2018/076291 EP2018076291W WO2019072578A1 WO 2019072578 A1 WO2019072578 A1 WO 2019072578A1 EP 2018076291 W EP2018076291 W EP 2018076291W WO 2019072578 A1 WO2019072578 A1 WO 2019072578A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
component
polyol
components
polyester
Prior art date
Application number
PCT/EP2018/076291
Other languages
German (de)
English (en)
Inventor
Robert Magunia
Patrick Schmidt-Winkel
Original Assignee
Lisa Dräxlmaier GmbH
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 Lisa Dräxlmaier GmbH filed Critical Lisa Dräxlmaier GmbH
Publication of WO2019072578A1 publication Critical patent/WO2019072578A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to a method for controlling the hydrophobic properties of polyurethanes, in particular for controlling the hydrolysis resistance of polyurethanes in adhesives.
  • Polyurethanes are known in the art and have excellent physical properties in many respects. They are therefore used in numerous fields of application.
  • polyurethanes are their limited resistance to hydrolysis, e.g. in environments with high humidity in combination with elevated temperatures.
  • polyester polyurethanes are susceptible to hydrolysis, so that such polyurethane derivatives escape a whole number of potential fields of application.
  • One of the essential building blocks in polyurethane materials is the polyol component (first component), which reacts with its hydroxyl functional groups, the reaction with the isocyanate groups of Isoycyanat component (second component) to urethane groups. In the further course of these reactions, the final result is polyurethanes.
  • polyester-based polyurethanes usually have very good mechanical properties, while polyether-based polyurethanes typically have a significantly better hydrolysis resistance.
  • Polyurethane adhesives based on a polyol component (first component) and an isocyanate component (second component) - so-called two-component (2K) polyurethane adhesives - are known from the prior art.
  • German Offenlegungsschrift DE 10 2007 062529 discloses a two-component polyurethane adhesive comprising essentially a polyol component comprising at least one polyesterdiol having a molecular weight of more than 1000 g / mol and at least one functional polyol, as well as hydrophobic polyols and further additives or Adjuvants, as well as a crosslinker component, which is represented by polyisocyanates.
  • International Patent Application WO 2014/206779 discloses a polyurethane-based adhesive comprising an isocyanate component A and a polyol component B, wherein the isocyanate component A comprises at least one diisocyanate or at least one polyisocyanate and the polyol component B the Alkylation product of a mixture of castor oil or ricinoleic acid, an aromatic di- or polyol and an OH-functional compound having aliphatically bonded OH groups and an OH functionality of 1 to 8 and optionally certain cyclic anhydrides of dicarboxylic acids optionally in addition to other ingredients, such as cyclic mono- or diesters.
  • the adhesive is prepared by blending a suitable polyether polyol with a polyester polyol and subsequently reacting with an isocyanate, the polyester polyol embodying a low molecular weight side chain polyester polyol having hydroxyl groups at the terminal positions.
  • Polyurethane-based adhesives are used in a variety of applications, i.a. in vehicle construction - such as in the automotive industry when joining, gluing and foam-foiling interior components.
  • Premium variants of interior components - such as instrument panels, door panels or center armrests - are often produced in such a way that a suitable substructure containing a dimensionally stable support and possibly an additional suitable intermediate layer with high-quality surface materials such as real leather, artificial leather or spray skins
  • adhesives for example hotmelt or dispersion adhesives, based on polyurethanes, are typically used.
  • catalysts or their degradation products can, especially in the presence of moisture in conjunction with higher Temperatures in the multi-layer structure of the components - in particular of the mentioned interior components - tend to migrate, become mobile and thereby come into contact with the laminating adhesive layer or disadvantageously diffuse into it
  • a further aspect of the present invention relates to polyurethane adhesive formulations which have, for example, olefinic or nonpolar constituents which have not been introduced by way of physical admixture for increasing interfacial compatibility, adhesion resistance and / or hydrolysis resistance, but by targeted chemical incorporation into the polyurethane structure .
  • Physical admixtures have the disadvantage that they are not incorporated into the adhesive by reactive chemical reactions (for example by the formation of covalent or stable polar bonds) and therefore become mobile in the adhesive, migrate and, if appropriate, also be able to outgas later. In the worst case, this property can lead, for example, to an undesirable phase separation or to the exudation of the polyolefins / non-polar components from the adhesive.
  • the object of the present invention is therefore to provide a polyurethane adhesive (for example a "hotmelt", a dispersion or a two-component adhesive), in particular as a laminating adhesive, in which the hydrolytic degradation of the adhesive is delayed or delayed It also suppresses or delays the migration of catalysts and / or their degradation products into the laminating adhesive layer, which is promoted or induced by moisture and increased temperature.
  • a polyurethane adhesive for example a "hotmelt", a dispersion or a two-component adhesive
  • a laminating adhesive in which the hydrolytic degradation of the adhesive is delayed or delayed It also suppresses or delays the migration of catalysts and / or their degradation products into the laminating adhesive layer, which is promoted or induced by moisture and increased temperature.
  • polyurethane adhesive formulations containing, for example, to increase compatibility, adhesion resistance and hydrolysis resistance olefinic or non-polar material components that eliminate migration or a phase separation of these admixtures or auxiliaries.
  • the solution according to the invention is provided by a method according to claim 1 or by the use according to the invention according to claim 31.
  • Advantageous embodiments are given in the dependent from the claims 1 and 32 dependent claims.
  • the polyurethane adhesive is not on Laminating adhesive, but can also be applied to many other adhesive applications or foaming with two-component polyurethanes, where an increased resistance to hydrolysis is sought.
  • the solution according to the invention allows a targeted, depending on the requirement stepwise adjustment of the hydrophobicity of the adhesive, whereby a hydrolytic degradation of the adhesive can be reduced or delayed in the respective desired extent.
  • Instrument panels, door panels or center armrests - are often fabricated in such a way that a suitable substructure comprising a dimensionally stable support and - as already mentioned - optionally a suitable intermediate layer with high-quality surface materials - such. with real leather, with artificial leather or with a sprayed skin - is laminated.
  • a suitable spacer fabric e.g. a suitable spacer fabric, a sprayed polyurethane layer (elastomer), a TPO film (thermoplastic olefin film), or a PVC layer are joined to a dimensionally stable support.
  • a particularly advantageous embodiment of the solution according to the invention consists in the combination of a suitable film or layer - preferably one of the above-mentioned films or layers - with a polyurethane spray skin.
  • the intermediate layer comprises one or more layers or layers comprising the same or different materials.
  • the layers or layers may each comprise individual layers / layers or contain composite materials.
  • the intermediate layer contains a foamed polyurethane layer, to which either directly or indirectly via further intermediate or spacing layers such.
  • foamed polyurethane layer to which either directly or indirectly via further intermediate or spacing layers such.
  • connection between carrier and polyurethane spray skin is produced, for example, by foaming the polyurethane spray skin with a polyurethane foam.
  • a suitable polyurethane foam can be such. also adjust the impression strength of the interior components.
  • the upper part and the lower part of the polyurethane spray skin in a continuous piece consisting of upper and lower part. If only the instrument panel upper part is laminated later, it is advantageous to produce the surface / decorative surface of the instrument panel base made of UV-light-stable aliphatic polyurethane and the later to be laminated instrument panel shell of inexpensive, reactive, aromatic, polyurethane manufacture.
  • the surface / decorative surface of the instrument panel base made of UV-light-stable aliphatic polyurethane and the later to be laminated instrument panel shell of inexpensive, reactive, aromatic, polyurethane manufacture.
  • significant additions of particular catalysts are necessary in preparing the aliphatic polyurethane spray skin.
  • the targeted and stepwise implementable hydrophobization of the laminating adhesive of the present invention eliminates, for example, the use of costly physical barriers to prevent aliphatic overspraying on the surface of the aromatic spray skin shell.
  • the present invention relates to a process for controlling the hydrophobicity of polyurethane adhesives in which, in the formation of the polyurethane polymer, the isocyanate group-containing component is reacted with at least one polyether polyol component having one or more hydroxyl groups and optionally with a polyester polyol component wherein the proportions of the polyether polyol component and the polyester polyol component are selected according to the desired degree of hydrophobicity and hydrolysis resistance.
  • the present invention relates to a method for limiting the mobility and migration of catalysts or catalyst degradation products in polyurethane polymers, in which the polyurethane of an isocyanate component, at least one polyether polyol component and optionally from a polyester component according to the first embodiment is constructed.
  • the present invention relates to a method according to one of the embodiments described above, in which the method product resulting from the method has the ratio determined by nuclear magnetic resonance spectroscopy between polyether polyol and polyester polyol in the polyurethane at an interval of 100: 0 to 1:99, preferably from 100: 0 to 50:50, more preferably from 100: 0 to 80:20, and most preferably at an interval of 100: 0 to 95: 5 lies.
  • the present invention relates to a process in which the isocyanate component used comprises an aromatic or an aliphatic isocyanate.
  • the present invention relates to a process in which the isocyanate component used comprises a monomeric, trimeric, oligomeric, prepolymeric or polymeric diisocyanate.
  • the present invention relates to a process in which the isocyanate component used contains a mixture of at least two components selected from the group consisting of monomeric, trimeric, oligomeric, prepolymeric or polymeric diisocyanate.
  • the present invention relates to a process in which the polyester polyol component used comprises at least one unsaturated polyester.
  • the present invention relates to a process in which the unsaturated polyester used has at least one ethylenically unsaturated partial structure per molecule.
  • the present invention relates to a process in which the polyether polyol used comprises a linear or a branched polether polyol. In a further preferred embodiment, the present invention relates to a process in which the polyether polyol used contains at least one polyoxyalkylene polyol. In a further preferred embodiment, the present invention relates to a process in which, as a further component in the formation of the polyurethane, a polyolefin polyol is present, which is capable of forming a chemical bond with the isocyanate component used.
  • the present invention relates to a process in which the polyolefin polyol used branched and / or unbranched olefin partial structures which have a diene structure having 2 to 12 carbon atoms, preferably 4 to 10 and more preferably 4 to 6 carbon atoms Carbon atoms contains.
  • the present invention relates to a process in which the polyolefin polyol has a structure of the general formula I:
  • the present invention relates to a process in which the polyolefin polyol used has at least one vinylaromatic partial structure. In a further preferred embodiment, the present invention relates to a process in which at least one adjuvant and / or additive of organic or inorganic nature is additionally present in the formation of the polyurethane. In a further preferred embodiment, the present invention relates to a process in which at least one adjuvant and / or additive is mineral in nature.
  • the present invention relates to a process in which the adjuvant and / or the mineral-type additive contains a silicate and / or a metal oxide, a sulfate or a carbonate of an alkali metal, alkaline earth metal or a metal, or a mixture thereof Auxiliaries or additives.
  • the present invention relates to a process in which the mineral auxiliary or the additive contains a silicate oxide, alumina, titanium dioxide or a metallic mixed oxide or a mixture of these compounds.
  • the present invention relates to a process in which the polyurethane additionally comprises at least one additive which is selected from the group comprising fillers, surface-active substances, pigments, dyes, hydrolysis inhibitors, antistatic agents, fungicidal and / or biocidal agents and / or water scavengers and / or antioxidant systems.
  • at least one additive which is selected from the group comprising fillers, surface-active substances, pigments, dyes, hydrolysis inhibitors, antistatic agents, fungicidal and / or biocidal agents and / or water scavengers and / or antioxidant systems.
  • the present invention relates to a process in which the formation of the polyurethane takes place in the presence of at least one catalyst.
  • the present invention relates to a process in which the catalyst system contains at least one amine compound.
  • the present invention relates to a process in which the catalyst system contains at least one tin, zinc and / or bismuth compound, with a tin (II) carboxylate being preferred among the tin compounds.
  • the present invention relates to a process in which the formation of the polyurethane is carried out in the presence of a further catalyst, ie in the presence of a co-catalyst.
  • the present invention relates to a process in which the formation of the polyurethane takes place in the presence of a chain extender.
  • the present invention relates to a process in which the chain extender contains at least one diol.
  • the present invention relates to a process in which the chain extender comprises at least one diol component from the group of monomeric, oligomeric or polymeric ethylene or propylene glycols.
  • the present invention relates to the use of a polyurethane in any of claims 1 to 30 for joining, gluing or joining two or more components.
  • the present invention relates to a use in which the introduction of the polyurethane between the components to be joined or adhered takes place in the form of a layer application.
  • the present invention relates to a use in which the joining or gluing of the components / materials by means of a so-called two-component polyurethane by introducing at least one reactive polyol-resin component (first component) and a reactive Isocyanate component (second component) takes place between the components to be joined or bonded.
  • first component reactive polyol-resin component
  • second component reactive Isocyanate component
  • the present invention relates to a use in which the joining or gluing of the components / materials by so-called back-foaming by means of a two-component polyurethane by introducing at least one reactive polyol-resin component (first component) and a reactive isocyanate component (second component) takes place between the components or materials to be joined or adhesively bonded.
  • first component reactive polyol-resin component
  • second component reactive isocyanate component
  • the polyurethane bond can be effected by the reaction of suitable polyether-based polyols with suitable isocyanate components.
  • the isocyanate component may include aromatic or aliphatic isocyanates or optionally also combinations of such isocyanates.
  • the isocyanate component of the adhesive composition contains, for example, one or more of the various suitable monomeric, trimeric, oligomeric, prepolymeric or polymeric isocyanates or diisocyanates. It is also possible to use mixtures of the isocyanate types mentioned as isocyanate component.
  • Suitable diisocyanates are - for example - by ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1, 4 and / or 1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate; Cyclobutane-1,3-diisocyanate; Cyclohexane-1, 3- and cyclohexane-1, 4-diisocyanate and mixtures of both isomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; 2,4- and 2,6-hexahydrotoluene diisocyanate and mixtures of these isomers; Hexahydro-1,3- and / or 1,4-phenylenediisocyanate; Perhydro-2,4'- and / or 4,4'-diphenylmethane diisocyanate; 1, 3 and 1, 4-phenylene diisocyanate; 2,4- and 2,
  • diphenylmethane hexamethylene diisocyanate; Dicyclohexylmethane-hexylmethandiisocyanat; isophoronediisocyanates; 1-methoxy-2,4-phenylene diisocyanate; 1-chlorophenyl-2,4-diisocyanate; p- (1-isocyanatoethyl) phenyl isocyanate; m- (3-isocyanatobutyl) phenyl isocyanate and 4- (2-isocyanato-cyclohexylmethyl) phenyl isocyanate, toluenediisocyanates and mixtures thereof.
  • polyether polyols include linear and / or branched polyether units. According to the invention, such polyether polyols contain substantially no functional groups other than hydroxyl groups.
  • preferred polyether polyols are represented by polyoxyalkylene polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like.
  • homopolymers and copolymers of the polyoxyalkylene or adducts of said polymers can be used.
  • the preferred copolymers of the polyoxyalkylene include, for example, adducts of at least one compound selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 2-ethylhexane-1, 3-diol, glycerol, 1, 2,6-hexanetriol, Trimethylolpropane, trimethylolethane, tris (hydroxyphenyl) propane, triethanolamine, triisopropanolamine, ethylenediamine and ethanolamine with at least one compound selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide.
  • polyether-based diols or mixtures of polyether-based diols and polyols.
  • the polyether-based polyols have the advantage of increased hydrolysis resistance within the polyol partial structure (so-called "soft segments") of the polyurethane adhesive.
  • polyester-based polyols or diols can also be combined with polyether-based polyols or diols.
  • polyester polyols examples include unsaturated polyester polyols having at least one ethylenically unsaturated group per molecule and having predominantly terminal hydroxyl groups.
  • polyolefin polyols can be used to increase the hydrophobicity and hydrolysis resistance of the polyurethane adhesive in the process according to the invention.
  • the polymer backbone of a polyolefin polyol typically contains the polymerized one Product of an olefin monomer or, what is possible, an olefin monomer and a vinylaromatic monomer.
  • the olefin monomer usually contains 2 to 12 carbon atoms.
  • the olefin monomer represents a diene having 4 to 10 carbon atoms, more preferably 4 to 6 carbon atoms, and most preferably is butadiene or isoprene, but more preferably 1, 3-butadiene.
  • the vinyl aromatic monomer which may also be used is preferably a monovinyl aromatic monomer, e.g. Styrene or an alkyl-substituted styrene wherein the alkyl substituent (s) preferably has 1 to 3 carbon atoms. Most preferably, the vinyl aromatic monomer embodies styrene or a monoalkyl substituted styrene.
  • the polyolefin polyol to be used in the present invention may optionally contain up to 50% by weight of polymerized vinylaromatic monomer, e.g. 0.01 to 20 wt .-%, in particular 0.1 to 5 wt .-%.
  • the polyolefin polyol does not contain a polymerized vinyl aromatic monomer.
  • the polyolefin polyol is preferably a polydiene polyol, more preferably a polydiene diol. Most preferred as the polyolefin polyol is a polydiene diol.
  • the polydiene polyol has a functionality in the range of from 1.5 to 3 hydroxyl groups per molecule, e.g. In the range of 1.8 to 2.6, more preferably in the range of 1.9 to 2.1.
  • Polyolefin polyols which can preferably be used according to the invention satisfy the general formulas I:
  • Particularly preferred polyolefin polyols are selected from the group comprising polybutadiene polyols, preferably poly-1, 3-butadiene polyols, hydrogenated polybutadiene polyols and / or polyisoprene polyols.
  • organic or inorganic (mineral) auxiliaries and / or additives may also be added to the adhesive.
  • mineral auxiliaries or additives all mineral compounds which are inert towards the educts and the cured adhesive and which are capable of entering into competitive or coordinative interactions with the catalysts used or with the hydrolysis-sensitive functional groups of the polyurethane can be used as mineral auxiliaries or additives.
  • inorganic or mineral auxiliaries are preferred, of which silicates and / or metal oxides, sulfates or carbonates of alkaline earth metals are preferably used, among which silicate oxides, alumina, titanium dioxide or metallic mixed oxides are particularly preferred.
  • the mineral adjuvants or additives can be used alone or as a mixture of different substances.
  • additives or additives suitable for the respective intended purposes known per se substances, for example, optionally in addition to fillers surface-active substances, pigments, dyes, other hydrolysis, antistatic, fungicidal or biocidal agents, antioxidants, water scavengers, etc .. are used. Further details of the starting materials, blowing agents, catalysts and auxiliaries and / or additives used for carrying out the process according to the invention can be found, for example, in the Kunststoffhandbuch, Volume 7, "Polyurethane” Carl Hanser Verlag Kunststoff, 3rd edition, 1993.
  • the described here Solution according to the invention enables a targeted, depending on the requirement stepwise possible hydrophobization of the adhesive, whereby a hydrolytic degradation of the adhesive is reduced, delayed or prevented.
  • the catalyst used in the composition may be present in about 0.001% to about 1% by weight of the adhesive, preferably at an interval of from about 0.01% to about 0.1% by weight of the adhesive.
  • the catalysts which may optionally be included in the catalyst compositions are conventional catalysts well known in the art for the reaction of hydroxyl-containing organic molecules with isocyanates to form urethane groups.
  • the polyurethane adhesive composition may be added to chain extenders according to the present invention.
  • chain extenders are low molecular weight diols and polyols such as ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, hexanediol, trimethylolpropane, glycerol, hydroxyl-terminated polyethylene oxide (polyethylene glycol), glycerol and mixtures thereof.
  • a preferred chain extender useful in the present invention is ethylene glycol.
  • Other common chain extenders that can be used in the invention include diamines and polyamines which, when mixed with the polyol component and reacted with the isocyanate component, do not separate from the compositions.
  • amine compounds examples include ethylenediamine, polyoxypropylenediamine, 1, 2- and 1, 4-diaminocyclohexane in trans or c / s configuration including mixtures thereof, dimethyldiaminodicyclohexylmethane and 1,2-propanediamine.
  • chain extenders which can be used according to the present invention include amine-containing alcohols or low molecular weight polyols. Examples are monoethanolamine, diethanolamine, triethanolamine, tetra (2-hydroxypropyl) ethylenediamine.
  • suitable chain extenders may impart several additional benefits to the compositions of the present invention, e.g. the adaptation of the material properties of the polyurethane adhesive (for example with regard to flexibility and impact resistance).
  • the reaction and curing rate can also be influenced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de commande des propriétés hydrophobes d'adhésifs à base de polyuréthane. Lors de la formation de l'adhésif à base de polyuréthane, le composant isocyanate est mis en réaction avec au moins un composant polyéther-polyol et éventuellement avec un composant polyester-polyol, les proportions du composant polyéther-polyol et du composant polyester étant choisies en fonction du degré d'hydrophobie voulu. L'incorporation chimique réactive supplémentaire de polyoléfine-polyols permet d'augmenter encore davantage l'hydrophobie ou la résistance à l'hydrolyse du polyuréthane.
PCT/EP2018/076291 2017-10-11 2018-09-27 Procédé de commande des propriétés hydrophobes de polyuréthanes WO2019072578A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017123675.9A DE102017123675A1 (de) 2017-10-11 2017-10-11 Verfahren zur Steuerung der hydrophoben Eigenschaften von Polyurethanen
DE102017123675.9 2017-10-11

Publications (1)

Publication Number Publication Date
WO2019072578A1 true WO2019072578A1 (fr) 2019-04-18

Family

ID=63720684

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/076291 WO2019072578A1 (fr) 2017-10-11 2018-09-27 Procédé de commande des propriétés hydrophobes de polyuréthanes

Country Status (2)

Country Link
DE (1) DE102017123675A1 (fr)
WO (1) WO2019072578A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110776869A (zh) * 2019-06-21 2020-02-11 南京威邦新材料有限公司 一种耐高温高强度聚氨酯结构胶及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113999385A (zh) * 2021-12-06 2022-02-01 四川朗迪新材料有限公司 一种基于动态氨酯键的可回收、可再加工的固固相变材料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10238143A1 (de) * 2002-08-15 2004-03-04 Basf Ag Verfahren zur Herstellung von Polyurethanschaumstoffen mit verbesserter Langzeitstabilität
DE102007062529A1 (de) 2007-12-20 2009-06-25 Henkel Ag & Co. Kgaa 2K-PU-Klebstoff zum Verkleben von Faserformteilen
DE102008000419A1 (de) * 2008-02-27 2009-09-03 Basf Se Mehrschichtige Verbundmaterialien, die ein textiles Flächengebilde umfassen, Verfahren zu ihrer Herstellung und ihre Verwendung
CN102181258A (zh) 2010-10-20 2011-09-14 上海汇得化工有限公司 一种耐溶剂、耐水解聚氨酯树脂粘合剂
WO2014206779A1 (fr) 2013-06-25 2014-12-31 Basf Se Adhésif polyuréthane hydrophobe
WO2015081068A1 (fr) * 2013-11-26 2015-06-04 Basf Se Composition élastomère de polyuréthanne et son procédé de préparation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10238143A1 (de) * 2002-08-15 2004-03-04 Basf Ag Verfahren zur Herstellung von Polyurethanschaumstoffen mit verbesserter Langzeitstabilität
DE102007062529A1 (de) 2007-12-20 2009-06-25 Henkel Ag & Co. Kgaa 2K-PU-Klebstoff zum Verkleben von Faserformteilen
DE102008000419A1 (de) * 2008-02-27 2009-09-03 Basf Se Mehrschichtige Verbundmaterialien, die ein textiles Flächengebilde umfassen, Verfahren zu ihrer Herstellung und ihre Verwendung
CN102181258A (zh) 2010-10-20 2011-09-14 上海汇得化工有限公司 一种耐溶剂、耐水解聚氨酯树脂粘合剂
WO2014206779A1 (fr) 2013-06-25 2014-12-31 Basf Se Adhésif polyuréthane hydrophobe
WO2015081068A1 (fr) * 2013-11-26 2015-06-04 Basf Se Composition élastomère de polyuréthanne et son procédé de préparation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Kunststoffhandbuch", vol. 7, 1993, CARL-HANSER-VERLAG MÜNCHEN, article "Polyurethane"
BROCKMANN W.: "Klebtechnik: Klebstoffe, Anwendungen und Verfahren", 2005, WILEY-VCH-VERLAG, pages: 66 ff

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110776869A (zh) * 2019-06-21 2020-02-11 南京威邦新材料有限公司 一种耐高温高强度聚氨酯结构胶及其制备方法
CN110776869B (zh) * 2019-06-21 2024-05-17 南京威邦新材料有限公司 一种耐高温高强度聚氨酯结构胶及其制备方法

Also Published As

Publication number Publication date
DE102017123675A1 (de) 2019-04-11

Similar Documents

Publication Publication Date Title
EP1432749B1 (fr) Procede de fabrication d' elastomeres de polyurethanne et utilisation
DE2637115C3 (de) Verfahren zur Herstellung von Polyurethanharnstoffen
DE69014609T2 (de) Polyurethan-ionomere in der masse.
EP1059379B1 (fr) Stratifiés avec une ou plusieurs couches de polyuréthane, procédé d'obtention et leur utilisation
EP3183282B1 (fr) Polybutadienole modifié par polyester destiné à fabriquer un élastomère de polyuréthane et polyuréthane thermoplastique
EP2262842B1 (fr) Mélanges d'isocyanates à base de 2,2'-mdi, leur production et leur utilisation
DE19908562A1 (de) Polyurethan und polyurethanhaltige Zubereitung
EP2791156A1 (fr) Composés complexes métalliques utilisés comme catalyseurs pour compositions de polyuréthane
DE69619971T2 (de) Teppiche mit polyurethanschaumstoff-teppichrückenbeschichtungen unter verwendung von katalysatoren
DE2447625B2 (de) Verfahren zur Herstellung elastischer Flächengebilde
DE102014209183A1 (de) Reaktive Zusammensetzung aus einer Uretdiongruppen haltigen Dispersion und Polyaminen
EP3109269B1 (fr) Dispersions de polyurethane sans uree
EP3186293A1 (fr) Garniture d'étanchéité en polyuréthane résistante au vieillissement
EP0095116B1 (fr) Compositions de polyol stables en monophase au stockage possédant de l'éthylène glycol en grande quantité et leur utilisation pour la préparation de polyuréthannes
DE3522978A1 (de) Verfahren zur herstellung von lichtechten, loesungsmittelbestaendigen polyurethanharnstoffelastomerbeschichtungen im reaktiv-beschichtungsverfahren
EP0747408A1 (fr) Procédé pour la préparation en continu d'élastomères de polyuréthane urée
WO2019072578A1 (fr) Procédé de commande des propriétés hydrophobes de polyuréthanes
EP1685175A1 (fr) Compositions de polyurethane a reactivite nco et silyle
DE2455679B2 (de) Verfahren und Bindemittel zum Herstellen einer elastischen Schicht aus Granulaten und einem Bindemittel
EP0407829B1 (fr) Mélanges thermodurcissables et leur utilisation pour la préparation de revêtements de substrats résistants à la chaleur
EP0675911B1 (fr) Materiau a deux composants pouvant etre transforme en mousse, a base de polyurethane
EP1127913B1 (fr) Procédé de préparation de mousses de polyuréthanne
EP2791155A1 (fr) Liaisons complexes de fer(iii) en tant que catalyseurs pour des composés de polyuréthane
DE2808668A1 (de) Herstellung von elastomeren aus heterodispersen systemen im reaktionsguss
EP1053269B1 (fr) Procede de production de corps moules en polyurethane elastiques mous, mi-durs ou durs, exempts d'hydrocarbure fluorochlore, comportant un noyau cellulaire et une zone marginale compactee

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18780087

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18780087

Country of ref document: EP

Kind code of ref document: A1