EP4107214A1 - Polyurethane insulating foams and production thereof - Google Patents

Polyurethane insulating foams and production thereof

Info

Publication number
EP4107214A1
EP4107214A1 EP21705914.6A EP21705914A EP4107214A1 EP 4107214 A1 EP4107214 A1 EP 4107214A1 EP 21705914 A EP21705914 A EP 21705914A EP 4107214 A1 EP4107214 A1 EP 4107214A1
Authority
EP
European Patent Office
Prior art keywords
polymer particles
foam
foams
parts
polyurethane
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.)
Withdrawn
Application number
EP21705914.6A
Other languages
German (de)
French (fr)
Inventor
Michael SUCHAN
Martin Glos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Operations 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 Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP4107214A1 publication Critical patent/EP4107214A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate 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
    • C08G18/08—Processes
    • C08G18/14—Manufacture of cellular products
    • 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
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • 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
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08L75/06—Polyurethanes from polyesters
    • 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
    • C08L75/08—Polyurethanes from 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the present invention is in the field of rigid polyurethane foams.
  • it relates to the production of rigid polyurethane foams using special polymer particles, and also to the use of the foams that were produced therewith.
  • thermosetting insulating foams For the production of thermosetting insulating foams, it may be desirable, for example, to produce hard foams with a preferably relatively low density of ⁇ 60 kg / m 3 and preferably as many small closed cells as possible (high cell density).
  • the cells should preferably be evenly distributed over the entire molded part, ie should not have a gradient.
  • a propellant gas is required so that a foam can form.
  • This can be e.g. CO2, which is formed from the reaction of isocyanate with water or is additionally added, and / or an added low-boiling organic liquid.
  • WO 2002/034823 describes, for example, an extrusion process on thermoplastics that leads to the formation of multimodal thermoplastic polymer foams.
  • the systems of non-thermoplastic, but rather thermoset polyurethane foams considered here as preferred, on the other hand, are preferably distinguished by a generally uniform, monomodal cell size distribution and cannot be obtained by extrusion processes either.
  • cell-stabilizing additives are usually used, which are intended to ensure a fine-grained, uniform and low-disruption foam structure and thus have a positive effect on the properties of use, especially the thermal insulation capacity of the rigid foam.
  • Surfactants based on polyether-modified siloxanes which are therefore the preferred type of foam stabilizer, are particularly effective.
  • EP1544235 describes typical polyether-modified siloxanes for PU rigid foam applications.
  • siloxanes with 60 to 130 Si atoms and different polyether substituents R whose mixed molar weight is 450 to 1000 g / mol and whose ethylene oxide content is 70 to 100 mol%, are used.
  • WO2009092505A1 describes a process for the production of polyurethane or polyisocyanurate insulating foams on the basis of foamable reaction mixtures containing polyisocyanates, compounds with reactive hydrogen atoms, blowing agents, stabilizers, nucleating agents and optionally other additives, with porous solids as nucleating agents, in particular silicates with a zeolite structure, be used.
  • PU foams in particular rigid PU foams, based on foamable reaction mixtures containing polyisocyanates, compounds with reactive hydrogen atoms, blowing agents, foam stabilizers, and optionally other additives, with polymer particles additionally being used, the mean particle size of the polymer particles ⁇ 100 ⁇ m, preferably ⁇ 70 ⁇ m, in particular 5 to 50 ⁇ m, solves the problem.
  • This method is the subject of the invention.
  • polyurethane is understood to mean, in particular, a product obtainable by reacting polyisocyanates and polyols or compounds with isocyanate-reactive groups.
  • other functional groups can also be formed, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and / or uretimines.
  • PU therefore means both polyurethane and polyisocyanurate, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretimine groups.
  • polyurethane foam is understood to mean, in particular, foam which is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups.
  • other functional groups can also be formed, such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines.
  • PU foams in the context of this invention also includes what are known as polyurethane foam moldings, in particular hard polyurethane foam moldings.
  • the polymer particles to be used according to the invention are distinguished by the fact that the mean grain size of the polymer particles is ⁇ 100 ⁇ m, preferably ⁇ 70 ⁇ m, in particular 5 to 50 ⁇ m.
  • the mean grain size (volume mean) of the polymer particles is determined based on ISO 13320-1 by means of laser diffraction spectroscopy.
  • the polymer particles to be used according to the invention and their production processes are known per se.
  • the polymerization of ethylenically unsaturated compounds is well known.
  • Corresponding polymer particles are also commercially available, e.g. corresponding polymethyl methacrylate particles, e.g. available from Evonik Industries AG as DEGACRYL®.
  • Mw molecular weights for the polymethyl methacrylate are in the range from 200,000 to 1,500,000, preferably 300,000 to 1,000,000, in particular 350,000 to 700,000, Mw determinable in accordance with DIN 55672-1.
  • the polymer particles are made of polymer including polyethylene (PE), polypropylene (PP), polyamide (in particular including PA6, PA6.6, PA10, PA11 and / or PA12), polyester (in particular including PET, PBT and / or PCL), polystyrene, polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymers, polyether, polylactic acid, polyurethane, polysulfones, polyether sulfone, polyetherimide, polyimide or mixtures thereof, in particular comprising polystyrene and / or polymethyl methacrylate, are formed.
  • PE polyethylene
  • PP polypropylene
  • polyamide in particular including PA6, PA6.6, PA10, PA11 and / or PA12
  • polyester in particular including PET, PBT and / or PCL
  • polystyrene polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymers
  • the rigid polyurethane foam has a density of 5 to 900 kg / m 3 , preferably 8 to 800, particularly preferably 10 to 600 kg / m 3 , in particular 20 to 150 kg / m 3 .
  • the effectiveness of the polymer particles used according to the invention is advantageously independent of the basic polyurethane or polyisocyanurate formulation, i.e. the polymer particles can be used in a large number of polyurethane or polyisocyanurate formulations to improve the thermal insulation properties.
  • a reduction in thermal conductivity due to admixture of the polymer particles can be observed both in the case of formulations which have already been optimized with regard to low thermal conductivity using the methods known to the person skilled in the art and which correspond to the current state of the art for use as an insulating foam, and in the case of formulations which, with regard to other foam properties have been optimized and do not yet show the best thermal conductivity achievable according to the prior art.
  • the foams according to the invention have a thermal conductivity of preferably less than or equal to 25 mW / m * K, which can optionally be further reduced by the optional addition of further auxiliaries and additives known to the person skilled in the art.
  • a thermal conductivity of less than 20 mW / m * K is particularly preferred.
  • thermal conductivity values of the foams according to the invention are significantly below the thermal conductivity values of those foams which were otherwise produced in the same way without the addition of polymer particles to be used according to the invention, usually the thermal conductivity values are at least 0.5 to 1.5 mW / m * K lower. This is demonstrated in the examples.
  • the polymer particles to be used according to the invention can also be exposed to a wide variety of substances.
  • a pretreatment of the polymer particles for the targeted application of the particles can even further improve the cell-refining effect of the particles when they are used for the production of PU foams, in particular rigid PU foams.
  • the polymer particles have been exposed to hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, perfluorinated compounds such as perfluoropentane and perfluorohexane, fluorochlorohydrocarbons , preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1224yd, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane as Proven very advantageous within the meaning of the invention. This corresponds to a preferred embodiment of the invention.
  • fluorocarbons preferably HFC 245fa, H
  • the invention therefore also relates to the use of appropriately pretreated polymer particles, as described above, for the production of PU foams, in particular PU foams Rigid foams and the PU foams produced in this way, in particular rigid PU foams.
  • the polymer particles to be used according to the invention are pretreated for exposure. It is preferred that the aforementioned compounds, such as, in particular, fluorine-containing organic compounds and / or linear, branched and / or cyclic hydrocarbons (in particular comprising propane, butane and / or pentane) are applied to the polymer particles.
  • the aforementioned compounds such as, in particular, fluorine-containing organic compounds and / or linear, branched and / or cyclic hydrocarbons (in particular comprising propane, butane and / or pentane) are applied to the polymer particles.
  • the polymer particles can be added directly to the reactive mixture for producing the PU foam or premixed in one of the components, preferably the polyol component, optionally with other auxiliaries and additives. This corresponds to a preferred embodiment of the invention.
  • the polymer particles are preferably used in amounts of 0.01 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, in particular 0.1 to 5 parts by weight, per 100 parts by weight of the polyol component. This corresponds to a particularly preferred embodiment of the invention.
  • the polymer particles used according to the invention can be used in the customary foamable formulations for PU foams, in particular rigid PU foams made from compounds with reactive hydrogen atoms (A), the polyisocyanate component (B) and customary auxiliaries and additives (C).
  • Polyols suitable as polyol components (A) for the purposes of the present invention are all organic substances with one or more groups that are reactive toward isocyanates, preferably OH groups, and their preparations.
  • Preferred polyols are all polyether polyols and / or polyester polyols and / or hydroxyl-containing aliphatic polycarbonates, in particular polyether polycarbonate polyols and / or polyols of natural origin, so-called " natural oil based polyols "(NOPs).
  • the polyols usually have a functionality of 1.8 to 8 and preferably number-average molecular weights in the range from 500 to 15,000.
  • the polyols with OH numbers in the range from 10 to 1200 mg KOH / g are usually used.
  • Isocyanates suitable as isocyanate components (B) for the purposes of this invention are all isocyanates which contain at least two isocyanate groups.
  • all aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates known per se can be used.
  • alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical such as 1, 12-dodecane diisocyanate, 2-ethyltetramethylene diisocyanate-1, 4, 2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate-1,4, and preferably hexamethylene diisocyanate-1,6 (HMDI), cycloaliphatic diisocyanates such as cyclohexane-1,3 and 1-4-diisocyanate and any mixtures of these isomers, 1 -Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), 2,4- and 2,6- hexahydrotolylene diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates, such as 2,4- and 2,6-
  • the organic di- and polyisocyanates can be used individually or in the form of their mixtures.
  • Corresponding “oligomers” of the diisocyanates can also be used (IPDI trimer based on isocyanurate, biurete urethdiones.)
  • prepolymers based on the above-mentioned isocyanates can be used.
  • isocyanate component and polyisocyanate are used synonymously in the context of the invention.
  • modified isocyanates which have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups.
  • Particularly suitable organic polyisocyanates and therefore particularly preferably used are various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomer mixtures of different compositions), 4,4'-diphenylmethane diisocyanate (MDI), the so-called “crude MDI” or “polymeric MDI” (contains the 4,4'- and 2,4'- and 2,2'-isomers of MDI and higher-core products) as well as the two-core product called “pure MDI” from predominantly 2,4'- and 4,4'-isomer mixtures or their prepolymers.
  • TDI toluene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • the so-called “crude MDI” or “polymeric MDI” contains the 4,4'- and 2,4'- and 2,2'-isomers of MDI
  • a preferred ratio of isocyanate and polyol, expressed as the index of the formulation, ie as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (eg OH groups, NH groups) multiplied by 100, is in the range from 10 to 1000, preferably 80 to 500.
  • An index of 100 stands for a molar ratio of the reactive groups of 1 to 1.
  • auxiliaries and additives (C) it is possible in particular to use the compounds customary for the formulation of PU foams, in particular rigid PU foams, including catalysts, foam stabilizers, blowing agents, flame retardants, fillers, dyes and light stabilizers.
  • Suitable catalysts for the purposes of this invention are substances which catalyze the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) or the dimerization or trimerization of the isocyanate.
  • catalysts known from the prior art can be used here, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and metal salts, preferably those of tin, iron , Bismuth, potassium and zinc.
  • amines cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups
  • ammonium compounds preferably those of tin, iron , Bismuth, potassium and zinc.
  • mixtures of several components can be used as catalysts. Suitable amounts used depend on the type of catalyst and are in particular in the range from 0.05 to 5 parts by weight, or 0.1 to 10 parts by weight for potassium salts, based on 100 parts by weight of polyol.
  • Suitable foam stabilizers are surface-active substances such as, for example, organic surfactants or, preferably, polyether-modified siloxanes (PES). In the context of this invention, all those can be used that support foam production (stabilization, cell regulation, cell opening, etc.). These compounds are well known from the prior art.
  • Typical amounts of polyether siloxane foam stabilizers used are preferably 0.5 to 5 parts by weight per 100 parts by weight of polyol, preferably 1 to 3 parts by weight per 100 parts by weight of polyol.
  • Water is preferably added to the foamable formulation as a chemical blowing agent, since it reacts with isocyanates with the evolution of carbon dioxide gas.
  • Suitable water contents for the purposes of this invention depend on whether physical blowing agents are used in addition to water or not. In the case of purely water-blown foams, the values are preferably 1 to 20 parts by weight per 100 parts by weight of polyol; if other blowing agents are also used, the amount used is preferably reduced to 0.1 to 5 parts by weight per 100 parts by weight of polyol.
  • Corresponding compounds with suitable boiling points can be used as physical blowing agents. It is also possible to use chemical blowing agents which react with NCO groups and release gases, such as, for example, water or formic acid already mentioned.
  • propellants are liquefied CO2, nitrogen, air, volatile liquids, for example hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons , preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1224yd, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
  • polyurethane foams in particular polyurethane foams, such as crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, can be used as additives , Cell openers, solid fillers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, etc.
  • Flame retardants that can be used for this purpose are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. triethyl phosphate (TEP), halogenated phosphates, e.g. tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. dimethyl methane phosphonate (DMMP), dimethyl propane phosphonate (DMPP) or solids such as ammonium polyphosphate (APP) and red phosphorus.
  • halogenated compounds for example halogenated polyols, and solids such as expandable graphite and melamine are suitable as flame retardants.
  • composition suitable for the production of rigid polyurethane or polyisocyanurate foams containing at least one isocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane and / or isocyanurate catalyst, water and / or blowing agent, and optionally at least a flame retardant and / or further additives, which is characterized in that polymer particles are additionally used, the mean grain size of the polymer particles being ⁇ 100 ⁇ m, preferably ⁇ 70 ⁇ m, in particular 5 to 50 ⁇ m,
  • the present invention also relates to the use of polyurethane foams according to the invention as insulation boards and insulation means and a cooling apparatus which has a polyurethane foam according to the invention as the insulating material.
  • Yet another object of the invention is the use of the polymer particles, as previously characterized in the description, to reduce the thickness of a PU rigid foam insulation layer while maintaining the thermal insulation performance, in particular in insulation boards and insulation means.
  • the invention still further provides a dispersion for use in compositions according to the invention for polyurethane foam, comprising polymer particles, as characterized above in the description, and at least one polyol and / or solvent, optionally blowing agent and / or optionally dispersing additives.
  • Polyol and optional blowing agent are characterized in particular according to the criteria as set out above in the description.
  • Suitable solvents include mono-, di- and polyfunctional alcohols such as monoethylene glycol (MEG) diethylene glycol (DEG), dipropylene glycol (DPG), alkoxylates or organic solvents such as DMSO or propylene carbonate.
  • MEG monoethylene glycol
  • DEG diethylene glycol
  • DPG dipropylene glycol
  • alkoxylates alkoxylates
  • organic solvents such as DMSO or propylene carbonate.
  • the polymer particles can also be preloaded or charged with the abovementioned compounds in the dispersion, in particular with hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, perfluorinated compounds such as perfluoropentane and perfluorohexane, chlorofluorocarbons, preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1224yd, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
  • hydrocarbons with 3, 4 or 5 carbon atoms preferably cyclo-, iso- and n-pentane
  • Suitable dispersing additives are known to the person skilled in the art. As is known, they are additives which improve the dispersion, that is to say the optimal mixing of at least two, actually immiscible phases or substances. Dispersing additives that can be used with preference are described, for example, in DE 199 40 797 A1 and DE 100 29 648 C1.
  • a dispersion comprising polymer particles, as characterized above in the description, and at least one foam stabilizer (in particular polyether siloxane), optionally polyol and / or solvent and / or optionally dispersing additives corresponds to a preferred embodiment of the invention.
  • foam stabilizer in particular polyether siloxane
  • optionally polyol and / or solvent and / or optionally dispersing additives corresponds to a preferred embodiment of the invention.
  • a preferred PU foam formulation for the purposes of this invention comprises the polymer particles according to the invention and gives a density of 10 to 900 kg / m 3 and has the following composition, according to a preferred embodiment of the invention:
  • the processing of the formulations according to the invention to give the desired PU foams can be carried out by any of the methods familiar to the person skilled in the art.
  • Polyurethane rigid foam or PU rigid foam is a fixed technical term.
  • the well-known and fundamental difference between flexible foam and rigid foam is that flexible foam shows elastic behavior and the deformation is therefore reversible.
  • the rigid foam is permanently deformed.
  • rigid polyurethane foam is understood to mean, in particular, a foam in accordance with DIN 7726 which has a compressive strength in accordance with DIN 53 421 / DIN EN ISO 604: 2003-12 of advantageously> 20 kPa, preferably> 80 kPa, preferably> 100 kPa, more preferably> 150 kPa, particularly preferably> 180 kPa.
  • the rigid polyurethane foam according to DIN EN ISO 4590: 2016-12 advantageously has a closed-cell content of greater than 50%, preferably greater than 80% and particularly preferably greater than 90%.
  • the rigid PU foams according to the invention can be used as or for the production of insulating materials, preferably insulating boards, refrigerators, insulating foams, headliners, packaging foams or spray foams.
  • the PU foams according to the invention can be used with advantage.
  • Another object of the invention is the use of rigid PU foam as an insulation material in refrigeration technology, in refrigeration units, in the construction, automotive, shipbuilding and / or electronics sectors, as insulation boards, as spray foam, as one-component foam.
  • the comparison foaming was carried out using the hand-mixing method.
  • polyol, catalysts, water, foam stabilizer, particles and blowing agent were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) for 30 s at 1,000 rpm.
  • the amount of propellant evaporated during the mixing process was determined by reweighing and replenished.
  • the MDI was added, the reaction mixture was stirred with the stirrer described for 7 s at 2,500 rpm and immediately transferred to an aluminum mold of 145 cm x 14 cm x 3.5 cm in size thermostated to 45 ° C, which was set at an angle of 10 ° (along the 145 cm measuring side) was inclined and lined with polyethylene film.
  • the foam formulation was entered on the lower-lying side so that the expanding foam fills the mold in the pouring area and rises in the direction of the higher-lying side.
  • the amount of foam formulation used was calculated in such a way that it was 10% above the amount necessary for the minimum filling of the mold.
  • the foams were removed from the mold after 10 minutes.
  • the foams were analyzed one day after foaming. Surface and internal defects were assessed subjectively on a scale from 1 to 10, with 10 representing an (idealized) undisturbed foam and 1 an extremely badly disturbed foam.
  • the coefficient of thermal conductivity was measured on 2.5 cm thick panes using a Hesto l Control device at temperatures on the underside and top of the sample of 10 ° C and 36 ° C. To determine an aging value of the thermal conductivity, the Test specimen stored for 7 days at 70 ° C and then measured again. The open-cell content was measured with an AccuPyc II 1340 gas pycnometer from Micromeritics.
  • the comparison foaming was carried out using the hand-mixing method.
  • polyol, catalysts, water, foam stabilizer, flame retardant, particles and propellant were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) for 30 s at 1,000 rpm.
  • the amount of propellant evaporated during the mixing process was determined by reweighing and replenished.
  • the MDI was now added, the reaction mixture was stirred with the stirrer described for 5 s at 3,000 rpm and immediately transferred to an aluminum mold of 25 cm ⁇ 50 cm ⁇ 7 cm in size, thermostated to 60 ° C., which was lined with polyethylene film.
  • the foams were removed from the mold after 10 minutes.
  • the foams were analyzed one day after foaming. Surface and internal defects were assessed subjectively using a scale from 1 to 10, with 10 representing an (idealized) undisturbed foam and 1 an extremely badly disturbed foam.
  • the coefficient of thermal conductivity was measured on 2.5 cm thick panes using a Hesto 1 Control device at temperatures on the underside and top of the sample of 10 ° C and 36 ° C. To determine an aging value of the thermal conductivity, the test specimens were stored at 70 ° C. for 7 days and then measured again. The open-cell content was measured with an AccuPyc II 1340 gas pycnometer from Micromeritics.

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Abstract

The invention relates to a method for producing PU foams, in particular PU rigid foams, on the basis of foamable reaction mixtures containing polyisocyanates, compounds with reactive hydrogen atoms, blowing agents, foam stabilisers, and optionally further additives. According to the invention, additional polymer particles are used, the average particle size of the polymer particles being < 100 µm, preferably < 70 µm, in particular 5 to 50µm.

Description

Polvurethan-Isolierschaumstoffe und ihre Herstellung Polyurethane insulation foams and their manufacture
Die vorliegende Erfindung liegt auf dem Gebiet der Polyurethanhartschäume. Insbesondere betrifft sie die Herstellung von Polyurethanhartschäumen unter Verwendung spezieller Polymerpartikel, sowie weiterhin die Verwendung der Schäume, die damit hergestellt wurden. The present invention is in the field of rigid polyurethane foams. In particular, it relates to the production of rigid polyurethane foams using special polymer particles, and also to the use of the foams that were produced therewith.
Die Herstellung von Polyurethanschaumstoffen durch Verschäumung schaumfähiger Reaktionsmischungen auf der Basis von Isocyanaten, Verbindungen mit reaktionsfähigen Wasserstoffatomen, Treibmitteln, Stabilisatoren und gegebenenfalls weiteren Zusatzstoffen wird heute im großtechnischen Maßstab betrieben. Dazu werden in der Regel alle Komponenten mit Ausnahme des Isocyanates zu einer verarbeitungsfähigen Mischung vorformuliert und diese in einer Verschäumungsanlage mit dem Isocyanat gemischt. In der zunächst flüssigen Reaktionsmischung erfolgen Schaumbildung und Polyadditionsreaktion gleichzeitig, bis die Masse zu dem gewünschten Schaumstoff ausgehärtet ist. The production of polyurethane foams by foaming foamable reaction mixtures based on isocyanates, compounds with reactive hydrogen atoms, blowing agents, stabilizers and, if appropriate, other additives is now carried out on an industrial scale. For this purpose, all components, with the exception of the isocyanate, are usually pre-formulated into a processable mixture and this is mixed with the isocyanate in a foaming system. In the initially liquid reaction mixture, foam formation and polyaddition reaction take place simultaneously until the mass has cured to form the desired foam.
Zur Herstellung von duroplastischen Isolierschaumstoffen kann es z.B. gewünscht sein, harte Schäume mit vorzugsweise relativ niedrigem Raumgewicht von < 60 kg/m3 und vorzugsweise möglichst vielen kleinen geschlossenen Zellen (hohe Zelldichte) zu erzeugen. Die Zellen sollen dabei vorzugsweise gleichmäßig über das gesamte Formteil verteilt sein, d.h. keinen Gradienten aufweisen. For the production of thermosetting insulating foams, it may be desirable, for example, to produce hard foams with a preferably relatively low density of <60 kg / m 3 and preferably as many small closed cells as possible (high cell density). The cells should preferably be evenly distributed over the entire molded part, ie should not have a gradient.
Damit sich ein Schaum bilden kann, ist ein Treibgas erforderlich. Dies kann z.B. CO2, das sich aus der Reaktion von Isocyanat mit Wasser bildet oder zusätzlich hinzugefügt wird, und/oder eine hinzugefügte leichtsiedende organische Flüssigkeit, sein. A propellant gas is required so that a foam can form. This can be e.g. CO2, which is formed from the reaction of isocyanate with water or is additionally added, and / or an added low-boiling organic liquid.
Der Vollständigkeit halber sei erwähnt, dass neben der Schaumbildung während der Polymerisationsreaktion, wie hier bei der Polyurethanbildung beschrieben, auch die Schaumbildung bei Extrusionsverfahren erfolgen kann. Diese Extrusionsverfahren sind jedoch grundsätzlich zu unterscheiden von den hier beschriebenen Polyurethanschaumverfahren. Die WO 2002/034823 beschreibt so beispielsweise ein Extrusionsverfahren an Thermoplasten, dass zur Bildung von multimodalen thermoplastischen Polymerschäumen führt. Die vorliegend bevorzugt betrachteten Systeme der nicht-thermoplastischen, sondern duroplastischen Polyurethanschäume hingegen zeichnen sich vorzugsweise durch eine im Allgemeinen einheitliche, monomodale Zellgrößenverteilung aus, und sind auch nicht durch Extrusionsverfahren zu erhalten. For the sake of completeness, it should be mentioned that in addition to foam formation during the polymerization reaction, as described here for polyurethane formation, foam formation can also take place in extrusion processes. However, these extrusion processes are fundamentally different from the polyurethane foam processes described here. WO 2002/034823 describes, for example, an extrusion process on thermoplastics that leads to the formation of multimodal thermoplastic polymer foams. The systems of non-thermoplastic, but rather thermoset polyurethane foams considered here as preferred, on the other hand, are preferably distinguished by a generally uniform, monomodal cell size distribution and cannot be obtained by extrusion processes either.
Bei der Herstellung von Polyurethan- und Polyisocyanurat-Hartschaumstoffen werden gewöhnlich zellstabilisierende Additive eingesetzt, welche für eine feinzeilige, gleichmäßige und störungsarme Schaumstruktur sorgen sollen und damit die Gebrauchseigenschaften, besonders das thermische Isolationsvermögen des Hartschaumstoffes im wesentlichen Maße positiv beeinflussen. Besonders effektiv sind Tenside auf der Basis von Polyether-modifizierten Siloxanen, welche daher den bevorzugten Typ der Schaumstabilisatoren darstellen. EP1544235 beschreibt typische Polyether-modifizierte Siloxane für PU-Hartschaumanwendungen. Hier werden Siloxane mit 60 bis 130 Si-Atomen und unterschiedlichen Polyethersubstituenten R, deren Mischungsmolgewicht 450 bis 1000 g/mol beträgt und deren Ethylenoxidanteil bei 70 bis 100 mol % liegt, verwendet. In the production of rigid polyurethane and polyisocyanurate foams, cell-stabilizing additives are usually used, which are intended to ensure a fine-grained, uniform and low-disruption foam structure and thus have a positive effect on the properties of use, especially the thermal insulation capacity of the rigid foam. Surfactants based on polyether-modified siloxanes, which are therefore the preferred type of foam stabilizer, are particularly effective. EP1544235 describes typical polyether-modified siloxanes for PU rigid foam applications. Here, siloxanes with 60 to 130 Si atoms and different polyether substituents R, whose mixed molar weight is 450 to 1000 g / mol and whose ethylene oxide content is 70 to 100 mol%, are used.
Obwohl diese Verbindungen in gewissem Maße die Feinheit und Regelmäßigkeit der Zellstruktur beeinflussen, gibt es eine Grenze in der Feinzelligkeit, über die hinaus eine Zellverfeinerung und damit einhergehend eine Verbesserung der thermischen Isolationswirkung durch weitere Erhöhung der Stabilisatorkonzentration nicht möglich ist. Although these compounds influence the fineness and regularity of the cell structure to a certain extent, there is a limit to the fine cell structure beyond which cell refinement and the associated improvement of the thermal insulation effect by further increasing the stabilizer concentration is not possible.
Um die Herstellung von Polyurethanschaumstoffen mit verbesserter thermischer Isolierwirkung zu ermöglichen, wurde im Stand der Technik als eine technische Lösung die heterogene Keimbildung an Feststoffen vorgeschlagen, wobei insbesondere Zeolithe Verwendung fanden. So beschreibt die W02009092505A1 ein Verfahren zur Herstellung von Polyurethan- bzw. Polyisocyanurat- Isolierschaumstoffen auf der Basis schaumfähiger Reaktionsmischungen enthaltend Polyisocyanate, Verbindungen mit reaktionsfähigen Wasserstoffatomen, Treibmittel, Stabilisatoren, Nukleierungsmitteln und gegebenenfalls weiteren Zusatzstoffen, wobei als Nukleierungsmittel poröse Feststoffe, insbesondere Silikate mit Zeolithstruktur, verwendet werden. In order to enable the production of polyurethane foams with improved thermal insulation properties, the prior art proposed heterogeneous nucleation on solids as a technical solution, with zeolites in particular being used. Thus, WO2009092505A1 describes a process for the production of polyurethane or polyisocyanurate insulating foams on the basis of foamable reaction mixtures containing polyisocyanates, compounds with reactive hydrogen atoms, blowing agents, stabilizers, nucleating agents and optionally other additives, with porous solids as nucleating agents, in particular silicates with a zeolite structure, be used.
Es besteht allerdings weiterhin ein Bedarf, die Bereitstellung von Polyurethanschaumstoffen mit verbesserter thermischer Isolierwirkung zu ermöglichen. Dies entspricht der Aufgabe der Erfindung. However, there is still a need to make it possible to provide polyurethane foams with an improved thermal insulating effect. This corresponds to the object of the invention.
Überraschenderweise wurde nun gefunden, dass ein Verfahren zur Herstellung von PU- Schaumstoffen, insbesondere PU-Hartschaumstoffen, auf der Basis schaumfähiger Reaktionsmischungen enthaltend Polyisocyanate, Verbindungen mit reaktionsfähigen Wasserstoffatomen, Treibmitteln, Schaumstabilisatoren, und gegebenenfalls weiteren Zusatzstoffen, wobei zusätzlich Polymerpartikel eingesetzt werden, wobei die mittlere Korngröße der Polymerpartikel < 100 pm, vorzugsweise < 70 gm, insbesondere 5 bis 50 pm beträgt, die gestellte Aufgabe löst. Dieses Verfahren ist der Gegenstand der Erfindung. Surprisingly, it has now been found that a process for the production of PU foams, in particular rigid PU foams, based on foamable reaction mixtures containing polyisocyanates, compounds with reactive hydrogen atoms, blowing agents, foam stabilizers, and optionally other additives, with polymer particles additionally being used, the mean particle size of the polymer particles <100 μm, preferably <70 μm, in particular 5 to 50 μm, solves the problem. This method is the subject of the invention.
Mit der Erfindung gehen mehrere Vorteile einher. Es tritt eine Verbesserung der thermischen Isolierwirkung der resultierenden PU-Schäume auf, verglichen mit entsprechenden Schäumen ohne Beigabe der Polymerpartikel. Dieser Effekt bleibt auch dann erhalten, wenn zwischen der Dispergierung der Partikel in den PU-Schaumrohstoffen bzw. -Systemen und deren Verarbeitung zum PU-Schaumstoff praxisübliche Lagerzeiten auftreten. Die verbesserte thermische Isolierwirkung der resultierenden PU-Schäume konnte sowohl im Initialstatus als auch im gealterten Zustand der Schäume beobachtet werden. Alle anderen für den Gebrauch relevanten Schaumeigenschaften werden durch die erfindungsgemäßen Polymerpartikel nicht oder nur unwesentlich beeinflusst. Auch bei der recht sensibel reagierenden Oberflächenqualität der Schaum-Probekörper findet man keine oder allenfalls nur eine marginale Veränderung. Ein weiterer ganz besonderer Vorteil konnte darin erkannt werden, dass der Einsatz der erfindungsgemäßen Polymerpartikel insbesondere im direkten Vergleich zu Zeolithen außergewöhnlich werkzeugschonend ist, was insbesondere das Einspritzwerkzeug bzw. den Mischkopf betrifft. Es tritt kein oder kaum Abrieb in der PU- Verschäumungsanlage auf. Several advantages are associated with the invention. There is an improvement in the thermal insulation effect of the resulting PU foams compared with corresponding foams without the addition of the polymer particles. This effect is retained even if storage times customary in practice occur between the dispersion of the particles in the PU foam raw materials or systems and their processing into PU foam. The improved thermal insulation effect of the resulting PU foams could be observed both in the initial status and in the aged condition of the foams. All other foam properties relevant for use are not or only insignificantly influenced by the polymer particles according to the invention. Even with the surface quality of the foam test specimens, which reacts quite sensitively, there is no change, or at most only a marginal change. Another very special advantage could be recognized in the fact that the use of the polymer particles according to the invention is exceptionally gentle on tools, especially in direct comparison to zeolites, which is particularly the case Injection tool or the mixing head concerns. There is little or no abrasion in the PU foaming system.
Unter Polyurethan (PU) wird im Rahmen der vorliegenden Erfindung insbesondere ein Produkt erhältlich durch Reaktion von Polyisocyanaten und Polyolen bzw. Verbindungen mit Isocyanat- reaktiven Gruppen verstanden. Es können hierbei neben dem Polyurethan auch weitere funktionelle Gruppen gebildet werden, wie z.B. Uretdione, Carbodiimide, Isocyanurate, Allophanate, Biurete, Harnstoffe und/oder Uretimine. Daher werden unter PU im Sinne der vorliegenden Erfindung sowohl Polyurethan als auch Polyisocyanurat, Polyharnstoffe und Uretdion-, Carbodiimid-, Allophanat-, Biuret- und Uretimin-Gruppen enthaltende Polyisocyanat-Reaktionsprodukte verstanden. Unter Polyurethanschaum (PU-Schaum) wird im Rahmen der vorliegenden Erfindung insbesondere Schaum verstanden, der als Reaktionsprodukt basierend auf Polyisocyanaten und Polyolen bzw. Verbindungen mit Isocyanat-reaktiven Gruppen erhalten wird. Es können hierbei neben dem Namen gebenden Polyurethan auch weitere funktionelle Gruppen gebildet werden, wie z.B. Allophanate, Biurete, Harnstoffe, Carbodiimide, Uretdione, Isocyanurate oder Uretimine. Der Begriff der PU- Schaumstoffe im Sinne dieser Erfindung umfasst auch die sogenannten Polyurethanschaumstoff- Formteile, insbesondere harten Polyurethanschaumstoff-Formteile. In the context of the present invention, polyurethane (PU) is understood to mean, in particular, a product obtainable by reacting polyisocyanates and polyols or compounds with isocyanate-reactive groups. In addition to the polyurethane, other functional groups can also be formed, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and / or uretimines. For the purposes of the present invention, PU therefore means both polyurethane and polyisocyanurate, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretimine groups. In the context of the present invention, polyurethane foam (PU foam) is understood to mean, in particular, foam which is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups. In addition to the polyurethane that gives it its name, other functional groups can also be formed, such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines. The term PU foams in the context of this invention also includes what are known as polyurethane foam moldings, in particular hard polyurethane foam moldings.
Die erfindungsgemäß einzusetzenden Polymerpartikel zeichnen sich dadurch aus, dass die mittlere Korngröße der Polymerpartikel < 100 pm, vorzugsweise < 70 pm, insbesondere 5 bis 50 pm beträgt. Die mittlere Korngröße (Volumenmittel) der Polymerpartikel wird in Anlehnung an ISO 13320-1 mittels Laserbeugungsspektroskopie bestimmt. The polymer particles to be used according to the invention are distinguished by the fact that the mean grain size of the polymer particles is <100 μm, preferably <70 μm, in particular 5 to 50 μm. The mean grain size (volume mean) of the polymer particles is determined based on ISO 13320-1 by means of laser diffraction spectroscopy.
Die erfindungsgemäß einzusetzenden Polymerpartikel und ihre Herstellungsverfahren sind an sich bekannt. Insbesondere die Polymerisation ethylenisch ungesättigter Verbindungen ist wohlbekannt. The polymer particles to be used according to the invention and their production processes are known per se. In particular, the polymerization of ethylenically unsaturated compounds is well known.
Entsprechende Polymerpartikel sind auch kommerziell erhältlich, wie z.B. entsprechende Polymethylmethacrylat-Partikel, z.B. erhältlich von der Evonik Industries AG als DEGACRYL®. Corresponding polymer particles are also commercially available, e.g. corresponding polymethyl methacrylate particles, e.g. available from Evonik Industries AG as DEGACRYL®.
Besonders bevorzugte Molekulargewichte (Mw) für das Polymethylmethacrylat liegen im Bereich von 200 000 bis 1 500 000, vorzugsweise 300 000 bis 1 000 000, insbesondere 350 000 bis 700 000, Mw bestimmbar nach DIN 55672-1 . Particularly preferred molecular weights (Mw) for the polymethyl methacrylate are in the range from 200,000 to 1,500,000, preferably 300,000 to 1,000,000, in particular 350,000 to 700,000, Mw determinable in accordance with DIN 55672-1.
Es entspricht einer bevorzugten Ausführungsform der Erfindung, wenn die Polymerpartikel aus Polymer, umfassend Polyethylen (PE), Polypropylen (PP), Polyamid (insbesondere umfassend PA6, PA6.6, PA10, PA11 und/oder PA12), Polyester (insbesondere umfassend PET, PBT und/oder PCL), Polystyrol, Polyacrylat, Polymethylmethacrylat, Polycarbonat, Styrol-Acrylnitril-Copolymere, Polyether, Polymilchsäure, Polyurethan, Polysulfone, Polyethersulfon, Polyetherimid, Polyimid oder Mischungen davon, insbesondere umfassend Polystyrol und/oder Polymethylmethacrylat, gebildet sind. Gemäß einer bevorzugten Ausführungsform der Erfindung weist der Polyurethanhartschaum ein Raumgewicht von 5 bis 900 kg/m3, bevorzugt 8 bis 800, besonders bevorzugt 10 bis 600 kg/m3, insbesondere 20 bis 150 kg/m3 auf. It corresponds to a preferred embodiment of the invention if the polymer particles are made of polymer including polyethylene (PE), polypropylene (PP), polyamide (in particular including PA6, PA6.6, PA10, PA11 and / or PA12), polyester (in particular including PET, PBT and / or PCL), polystyrene, polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymers, polyether, polylactic acid, polyurethane, polysulfones, polyether sulfone, polyetherimide, polyimide or mixtures thereof, in particular comprising polystyrene and / or polymethyl methacrylate, are formed. According to a preferred embodiment of the invention, the rigid polyurethane foam has a density of 5 to 900 kg / m 3 , preferably 8 to 800, particularly preferably 10 to 600 kg / m 3 , in particular 20 to 150 kg / m 3 .
Die Wirksamkeit der erfindungsgemäß verwendeten Polymerpartikel ist vorteilhafterweise von der Polyurethan- bzw. Polyisocyanurat-Basisrezeptur unabhängig, d.h. die Polymerpartikel lassen sich zur Verbesserung der thermischen Isoliereigenschaften in einer großen Vielzahl an Polyurethan- bzw. Polyisocyanurat-Formulierungen einsetzen. Eine Verringerung der Wärmeleitfähigkeit durch Beimischung der Polymerpartikel kann sowohl bei Formulierungen beobachtet werden, die bereits unter Ausschöpfung der dem Fachmann bekannten Methoden hinsichtlich niedriger Wärmeleitfähigkeit optimiert wurden und dem aktuellen Stand der Technik für die Anwendung als Isolierschaum entsprechen als auch bei Formulierungen, die im Hinblick auf andere Schaumeigenschaften optimiert wurden und noch nicht die beste nach dem Stand der Technik erreichbare Wärmeleitfähigkeit zeigen. The effectiveness of the polymer particles used according to the invention is advantageously independent of the basic polyurethane or polyisocyanurate formulation, i.e. the polymer particles can be used in a large number of polyurethane or polyisocyanurate formulations to improve the thermal insulation properties. A reduction in thermal conductivity due to admixture of the polymer particles can be observed both in the case of formulations which have already been optimized with regard to low thermal conductivity using the methods known to the person skilled in the art and which correspond to the current state of the art for use as an insulating foam, and in the case of formulations which, with regard to other foam properties have been optimized and do not yet show the best thermal conductivity achievable according to the prior art.
Die erfindungsgemäßen Schäume weisen eine Wärmeleitfähigkeit von vorzugsweise kleiner gleich 25 mW/m*K auf, die sich durch optionalen Zusatz von dem Fachmann bekannter weiteren Hilfs- und Zuschlagstoffe ggf. noch deutlich absenken lässt. Besonders bevorzugt ist eine Wärmeleitfähigkeit von weniger als 20 mW/m*K. The foams according to the invention have a thermal conductivity of preferably less than or equal to 25 mW / m * K, which can optionally be further reduced by the optional addition of further auxiliaries and additives known to the person skilled in the art. A thermal conductivity of less than 20 mW / m * K is particularly preferred.
Die Wärmeleitfähigkeitswerte der erfindungsgemäßen Schäume liegen sowohl im frischen als auch im gealterten Zustand der Schäume signifikant unter den Wärmeleitfähigkeitswerten solcher Schäume, die ohne den Zusatz von erfindungsgemäß einzusetzenden Polymerpartikeln aber ansonsten in gleicher Weise hergestellt wurden, in der Regel liegen die Wärmeleitfähigkeitswerte zumindest 0,5 bis 1 ,5 mW/m*K niedriger. Dies wird in den Beispielen belegt. The thermal conductivity values of the foams according to the invention, both in the fresh and in the aged state of the foams, are significantly below the thermal conductivity values of those foams which were otherwise produced in the same way without the addition of polymer particles to be used according to the invention, usually the thermal conductivity values are at least 0.5 to 1.5 mW / m * K lower. This is demonstrated in the examples.
Die erfindungsgemäß einzusetzenden Polymerpartikel können außerdem mit verschiedensten Substanzen beaufschlagt werden. Eine Vorbehandlung der Polymerpartikel zur gezielten Beaufschlagung der Partikel kann die Zell-verfeinernde Wirkung der Partikel bei deren Einsatz zur Herstellung von PU-Schaumstoffen, insbesondere PU- Hartschaumstoffen sogar noch weiter verbessern. Beispielsweise hat sich eine Beaufschlagung der Polymerpartikel mit Kohlenwasserstoffen mit 3, 4 oder 5 Kohlenstoff-Atomen, bevorzugt cyclo-, iso- und n-Pentan, Fluorkohlenwasserstoffen, bevorzugt HFC 245fa, HFC 134a und HFC 365mfc, perfluorierten Verbindungen wie Perfluorpentan und Perfluorhexan, Fluorchlorkohlenwasserstoffe, bevorzugt HCFC 141 b, Hydrofluoroolefinen (HFO) oder Hydrohaloolefinen wie z.B. 1234ze, 1234yf, 1224yd, 1233zd(E) oder 1336mzz, Sauerstoff-haltigen Verbindungen wie Methylformiat, Aceton und Dimethoxymethan, oder Chlorkohlenwasserstoffen, bevorzugt Dichlormethan und 1 ,2-Dichlorethan als sehr vorteilhaft im Sinne der Erfindung erwiesen. Dies entspricht einer bevorzugten Ausführungsform der Erfindung. The polymer particles to be used according to the invention can also be exposed to a wide variety of substances. A pretreatment of the polymer particles for the targeted application of the particles can even further improve the cell-refining effect of the particles when they are used for the production of PU foams, in particular rigid PU foams. For example, the polymer particles have been exposed to hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, perfluorinated compounds such as perfluoropentane and perfluorohexane, fluorochlorohydrocarbons , preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1224yd, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane as Proven very advantageous within the meaning of the invention. This corresponds to a preferred embodiment of the invention.
Gegenstand der Erfindung ist daher auch die Verwendung von entsprechend vorbehandelten Polymerpartikeln, wie zuvor beschrieben, zur Herstellung von PU-Schaumstoffen, insbesondere PU- Hartschaumstoffen sowie die derart hergestellten PU-Schaumstoffe, insbesondere PU- Hartschaumstoffe. The invention therefore also relates to the use of appropriately pretreated polymer particles, as described above, for the production of PU foams, in particular PU foams Rigid foams and the PU foams produced in this way, in particular rigid PU foams.
Es entspricht daher einer bevorzugten Ausführungsform der Erfindung, wenn die erfindungsgemäß einzusetzenden Polymerpartikel zur Beaufschlagung vorbehandelt werden. Dabei ist es bevorzugt, dass die Polymerpartikel mit den zuvor genannten Verbindungen, wie insbesondere mit Fluorhaltigen organischen Verbindungen und/oder linearen, verzweigten und/oder zyklischen Kohlenwasserstoffen (insbesondere umfassend Propan, Butan und/oder Pentan) beaufschlagt werden. It therefore corresponds to a preferred embodiment of the invention if the polymer particles to be used according to the invention are pretreated for exposure. It is preferred that the aforementioned compounds, such as, in particular, fluorine-containing organic compounds and / or linear, branched and / or cyclic hydrocarbons (in particular comprising propane, butane and / or pentane) are applied to the polymer particles.
Die Polymerpartikel können der reaktiven Mischung zur Herstellung des PU-Schaums direkt zugegeben oder in einer der Komponenten, vorzugsweise der Polyolkomponente, gegebenenfalls mit weiteren Hilfs- und Zusatzstoffen, vorgemischt werden. Dies entspricht einer bevorzugten Ausführungsform der Erfindung. The polymer particles can be added directly to the reactive mixture for producing the PU foam or premixed in one of the components, preferably the polyol component, optionally with other auxiliaries and additives. This corresponds to a preferred embodiment of the invention.
Die Polymerpartikel werden vorzugsweise in Mengen von 0,01 bis 20 Gew. -Teile, weiter bevorzugt 0,05 bis 5 Gew. -Teile, insbesondere 0,1 bis 5 Gew. -Teile pro 100 Gew. -Teilen der Polyolkomponete verwendet. Dies entspricht einer besonders bevorzugten Ausführungsform der Erfindung. The polymer particles are preferably used in amounts of 0.01 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, in particular 0.1 to 5 parts by weight, per 100 parts by weight of the polyol component. This corresponds to a particularly preferred embodiment of the invention.
Die erfindungsgemäß verwendeten Polymerpartikel sind in den üblichen schäumbaren Formulierungen für PU-Schaumstoffen, insbesondere PU- Hartschaumstoffe aus Verbindungen mit reaktionsfähigen Wasserstoffatomen (A), der Polyisocyanatkomponente (B) und üblichen Hilfs- und Zusatzstoffen (C) verwendbar. The polymer particles used according to the invention can be used in the customary foamable formulations for PU foams, in particular rigid PU foams made from compounds with reactive hydrogen atoms (A), the polyisocyanate component (B) and customary auxiliaries and additives (C).
Als Polyolkomponenten (A) geeignete Polyole im Sinne der vorliegenden Erfindung sind alle organischen Substanzen mit einer oder mehreren gegenüber Isocyanaten reaktiven Gruppen, vorzugsweise OH-Gruppen, sowie deren Zubereitungen. Polyols suitable as polyol components (A) for the purposes of the present invention are all organic substances with one or more groups that are reactive toward isocyanates, preferably OH groups, and their preparations.
Bevorzugte Polyole sind alle zur Herstellung von Polyurethan-Systemen, wie vorzugsweise Polyurethan-Beschichtungen, Polyurethan-Elastomeren und insbesondere Schaumstoffen üblicherweise verwendeten Polyetherpolyole und/oder Polyesterpolyole und/oder hydroxylgruppen-haltigen aliphatischen Polycarbonate, insbesondere Polyetherpolycarbonatpolyole und/oder Polyole natürlicher Herkunft, sogenannte „natural oil based polyols“ (NOPs). Üblicherweise besitzen die Polyole eine Funktionalität von 1 ,8 bis 8 und vorzugsweise zahlengemittelte Molekulargewichte im Bereich von 500 bis 15000. Üblicherweise kommen die Polyole mit OH-Zahlen im Bereich von 10 bis 1200 mg KOH/g zum Einsatz. Preferred polyols are all polyether polyols and / or polyester polyols and / or hydroxyl-containing aliphatic polycarbonates, in particular polyether polycarbonate polyols and / or polyols of natural origin, so-called " natural oil based polyols "(NOPs). The polyols usually have a functionality of 1.8 to 8 and preferably number-average molecular weights in the range from 500 to 15,000. The polyols with OH numbers in the range from 10 to 1200 mg KOH / g are usually used.
Als Isocyanatkomponenten (B) geeignete Isocyanate im Sinne dieser Erfindung sind alle Isocyanate, die mindestens zwei Isocyanat-Gruppen enthalten. Generell können alle an sich bekannten aliphatischen, cycloaliphatischen, arylaliphatischen und vorzugsweise aromatischen mehrfunktionalen Isocyanate verwendet werden. Isocyanates suitable as isocyanate components (B) for the purposes of this invention are all isocyanates which contain at least two isocyanate groups. In general, all aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates known per se can be used.
Beispielhaft genannt werden können hier Alkylendiisocyanate mit 4 bis 12 Kohlenstoffatomen im Alkylenrest, wie 1 ,12-Dodecandiisocyanat, 2-Ethyltetramethylendiisocyanat-1 ,4, 2-Methylpentamethylen-diisocyanat-1 ,5, Tetramethylendiisocyanat-1 ,4, und vorzugsweise Hexamethylendiisocyanat-1 ,6 (HMDI), cycloaliphatische Diisocyanate, wie Cyclohexan-1 ,3- und 1- 4-diisocyanat sowie beliebige Gemische dieser Isomeren, 1-lsocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexan (Isophorondiisocyanat oder kurz IPDI), 2,4- und 2,6- Hexahydrotoluylendiisocyanat sowie die entsprechenden Isomerengemische, und vorzugsweise aromatische Di- und Polyisocyanate, wie beispielsweise 2,4- und 2,6-Toluoldiisocyanat (TDI) und die entsprechenden Isomerengemische, Naphthalindiisocyanat, Diethyltoluoldiisocyanat, Mischungen aus 2,4‘- und 2,2‘-Diphenylmethandiisocyanaten (MDI) und Polyphenylpolymethylenpolyisocyanate (Roh-MDI) und Mischungen aus Roh-MDI und Toluoldiisocyanaten (TDI). Die organischen Di- und Polyisocyanate können einzeln oder in Form ihrer Mischungen eingesetzt werden. Ebenso können entsprechende „Oligomere“ der Diisocyanate eingesetzt werden (IPDI-Trimer auf basis Isocyanurat, Biurete- Urethdione.) Des Weiteren ist der Einsatz von Präpolymeren auf Basis der oben genannten Isocyanate möglich. Examples which may be mentioned here are alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1, 12-dodecane diisocyanate, 2-ethyltetramethylene diisocyanate-1, 4, 2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate-1,4, and preferably hexamethylene diisocyanate-1,6 (HMDI), cycloaliphatic diisocyanates such as cyclohexane-1,3 and 1-4-diisocyanate and any mixtures of these isomers, 1 -Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), 2,4- and 2,6- hexahydrotolylene diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate (TDI) and the corresponding isomer mixtures, naphthalene diisocyanate, diethyltoluene diisocyanate, mixtures of 2,4'- and 2,2'-diphenylmethane diisocyanates (MDI) and polyphenylpolymethylene polyisocyanates (crude MDI) and mixtures of crude MDI and toluene diisocyanates (TDI). The organic di- and polyisocyanates can be used individually or in the form of their mixtures. Corresponding “oligomers” of the diisocyanates can also be used (IPDI trimer based on isocyanurate, biurete urethdiones.) In addition, prepolymers based on the above-mentioned isocyanates can be used.
Die Begriffe Isocyanatkomponente und Polyisocyanate werden im Rahmen der Erfindung synonym verwendet. The terms isocyanate component and polyisocyanate are used synonymously in the context of the invention.
Es ist auch möglich, Isocyanate einzusetzen, die durch den Einbau von Urethan-, Uretdion-, Isocyanurat , Allophanat- und anderen Gruppen modifiziert wurden, sogenannte modifizierte Isocyanate. It is also possible to use isocyanates which have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, so-called modified isocyanates.
Besonders geeignete organische Polyisocyanate und daher besonders bevorzugt angewendet werden verschiedene Isomere des Toluoldiisocyanat (2,4- und 2,6-Toluoldiisocyanat (TDI), in reiner Form oder als Isomerengemische unterschiedlicher Zusammensetzung), 4,4‘- Diphenylmethandiisocyanat (MDI), das so genannte „crude MDI“ oder „polymere MDI“ (enthält neben dem 4,4‘- auch die 2,4‘- und 2,2‘-lsomeren des MDI und höherkernige Produkte) sowie das als „pure MDI“ bezeichnete zweikernige Produkt aus überwiegend 2,4‘- und 4,4‘-lsomerengemischen bzw. deren Prepolymeren. Beispiele für besonders geeignete Isocyanate sind beispielsweise in EP 1712578, EP 1161474, WO 00/58383, US 2007/0072951 , EP 1678232 und der WO 2005/085310 aufgeführt, auf die hier in vollem Umfang Bezug genommen wird. Particularly suitable organic polyisocyanates and therefore particularly preferably used are various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomer mixtures of different compositions), 4,4'-diphenylmethane diisocyanate (MDI), the so-called “crude MDI” or “polymeric MDI” (contains the 4,4'- and 2,4'- and 2,2'-isomers of MDI and higher-core products) as well as the two-core product called “pure MDI” from predominantly 2,4'- and 4,4'-isomer mixtures or their prepolymers. Examples of particularly suitable isocyanates are listed, for example, in EP 1712578, EP 1161474, WO 00/58383, US 2007/0072951, EP 1678232 and WO 2005/085310, all of which are hereby incorporated by reference.
Ein bevorzugtes Verhältnis von Isocyanat und Polyol, ausgedrückt als Index der Formulierung, d.h. als stöchiometrisches Verhältnis von Isocyanat-Gruppen zu gegenüber Isocyanat reaktiven Gruppen (z.B. OH-Gruppen, NH-Gruppen) multipliziert mit 100, liegt im Bereich von 10 bis 1000, bevorzugt 80 bis 500. Ein Index von 100 steht für ein molares Verhältnis der reaktiven Gruppen von 1 zu 1 . A preferred ratio of isocyanate and polyol, expressed as the index of the formulation, ie as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (eg OH groups, NH groups) multiplied by 100, is in the range from 10 to 1000, preferably 80 to 500. An index of 100 stands for a molar ratio of the reactive groups of 1 to 1.
Als Hilfs- und Zusatzstoffe (C) können insbesondere die für die Formulierung von PU- Schaumstoffen, insbesondere PU-Hartschaumstoffen üblichen Verbindungen verwendet werden, darunter Katalysatoren, Schaumstabilisatoren, Treibmittel, Flammschutzmittel, Füllstoffe, Farbstoffe und Lichtschutzmittel. Geeignete Katalysatoren im Sinne dieser Erfindung sind Substanzen die die Gelreaktion (Isocyanat- Polyol), die Treibreaktion (Isocyanat-Wasser) oder die Di- bzw. Trimerisierung des Isocyanats katalysieren. Hierbei kann auf die üblichen aus dem Stand der Technik bekannten Katalysatoren zurückgegriffen werden, umfassend z.B. Amine (cyclische, acyclische; Monoamine, Diamine, Oligomere mit einer oder mehreren Aminogruppen), Ammonium-Verbindungen, metallorganische Verbindungen und Metallsalze, vorzugsweise die des Zinn, Eisen, Bismut, Kalium und Zink. Insbesondere können als Katalysatoren Gemische mehrerer Komponenten eingesetzt werden. Geeignete Einsatzmengen richten sich nach dem Typ des Katalysators und liegen insbesondere im Bereich von 0,05 bis 5 Gewichtsteilen, bzw. 0,1 bis 10 Gewichtsteilen für Kaliumsalze, bezogen auf 100 Gewichtsteile Polyol. As auxiliaries and additives (C) it is possible in particular to use the compounds customary for the formulation of PU foams, in particular rigid PU foams, including catalysts, foam stabilizers, blowing agents, flame retardants, fillers, dyes and light stabilizers. Suitable catalysts for the purposes of this invention are substances which catalyze the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) or the dimerization or trimerization of the isocyanate. The usual catalysts known from the prior art can be used here, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and metal salts, preferably those of tin, iron , Bismuth, potassium and zinc. In particular, mixtures of several components can be used as catalysts. Suitable amounts used depend on the type of catalyst and are in particular in the range from 0.05 to 5 parts by weight, or 0.1 to 10 parts by weight for potassium salts, based on 100 parts by weight of polyol.
Geeignete Schaumstabilisatoren sind oberflächenaktive Substanzen wie beispielsweise organische Tenside oder bevorzugt Polyether-modifizierte Siloxane (PES). Hierbei können im Rahmen dieser Erfindung alle solchen eingesetzt werden, die die Schaumherstellung unterstützen (Stabilisierung, Zellregulierung, Zellöffnung, etc.). Diese Verbindungen sind aus dem Stand der Technik hinreichend bekannt. Typische Einsatzmengen an Polyethersiloxan-Schaumstabilisatoren liegen vorzugsweise bei 0,5 bis 5 Gewichtsteile pro 100 Gewichtsteile Polyol, bevorzugt bei 1 bis 3 Gewichtsteile pro 100 Gewichtsteile Polyol. Suitable foam stabilizers are surface-active substances such as, for example, organic surfactants or, preferably, polyether-modified siloxanes (PES). In the context of this invention, all those can be used that support foam production (stabilization, cell regulation, cell opening, etc.). These compounds are well known from the prior art. Typical amounts of polyether siloxane foam stabilizers used are preferably 0.5 to 5 parts by weight per 100 parts by weight of polyol, preferably 1 to 3 parts by weight per 100 parts by weight of polyol.
Entsprechende, im Sinne dieser Erfindung einsetzbare PES werden z.B. in den folgenden Patentschriften beschrieben: CN 103665385, CN 103657518, CN 103055759, CN 103044687, US 2008/ 0125503, US 2015/0057384, EP 1520870 A1 , EP 1211279, EP 0867464, EP 0867465, EP 0275563. Corresponding PESs that can be used for the purposes of this invention are described, for example, in the following patents: CN 103665385, CN 103657518, CN 103055759, CN 103044687, US 2008/0125503, US 2015/0057384, EP 1520870 A1, EP 1211279, EP 0867464, EP 0867465 , EP 0275563.
Vorzugsweise wird der schäumbaren Formulierung Wasser als chemisches Treibmittel zugesetzt, da es mit Isocyanaten unter Entwicklung von Kohlendioxid-Gas reagiert. Geeignete Wasser-Gehalte im Sinne dieser Erfindung hängen davon ab, ob zusätzlich zum Wasser noch physikalische Treibmittel eingesetzt werden oder nicht. Bei rein Wasser-getriebenen Schäumen liegen die Werte vorzugsweise bei 1 bis 20 Gewichtsteile pro 100 Gewichtsteile Polyol, werden zusätzlich andere Treibmittel eingesetzt, verringert sich die Einsatzmenge vorzugsweise auf 0,1 bis 5 Gewichtsteile pro 100 Gewichtsteile Polyol. Water is preferably added to the foamable formulation as a chemical blowing agent, since it reacts with isocyanates with the evolution of carbon dioxide gas. Suitable water contents for the purposes of this invention depend on whether physical blowing agents are used in addition to water or not. In the case of purely water-blown foams, the values are preferably 1 to 20 parts by weight per 100 parts by weight of polyol; if other blowing agents are also used, the amount used is preferably reduced to 0.1 to 5 parts by weight per 100 parts by weight of polyol.
Als physikalische Treibmittel können entsprechende Verbindungen mit passenden Siedepunkten eingesetzt werden. Ebenso können, chemische Treibmittel eingesetzt werden, die mit NCO-Gruppen und Freisetzung von Gasen reagieren, wie beispielsweise bereits genannt Wasser oder Ameisensäure. Beispiele für Treibmittel sind verflüssigtes C02, Stickstoff, Luft, leichtflüchtige Flüssigkeiten, beispielsweise Kohlenwasserstoffe mit 3, 4 oder 5 Kohlenstoff-Atomen, bevorzugt cyclo-, iso- und n-Pentan, Fluorkohlenwasserstoffe, bevorzugt HFC 245fa, HFC 134a und HFC 365mfc, Fluorchlorkohlenwasserstoffe, bevorzugt HCFC 141 b, Hydrofluoroolefine (HFO) oder Hydrohaloolefine wie z.B. 1234ze, 1234yf, 1224yd, 1233zd(E) oder 1336mzz, Sauerstoff-haltige Verbindungen wie Methylformiat, Aceton und Dimethoxymethan, oder Chlorkohlenwasserstoffe, bevorzugt Dichlormethan und 1 ,2-Dichlorethan. Als Zusatzstoffe können alle nach dem Stand der Technik bekannten Substanzen verwendet werden, die bei der Herstellung von Polyurethanen, insbesondere von Polyurethanschaumstoffen, Verwendung finden, wie zum Beispiel Vernetzer und Kettenverlängerer, Stabilisatoren gegen oxidativen Abbau (so genannte Antioxidantien), Flammschutzmittel, Tenside, Biozide, Zellöffner, feste Füllstoffe, Antistatik-Additive, Verdicker, Farbstoffe, Pigmente, Farbpasten, Duftstoffe, Emulgatoren, usw. Corresponding compounds with suitable boiling points can be used as physical blowing agents. It is also possible to use chemical blowing agents which react with NCO groups and release gases, such as, for example, water or formic acid already mentioned. Examples of propellants are liquefied CO2, nitrogen, air, volatile liquids, for example hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons , preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1224yd, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane. All substances known from the prior art that are used in the production of polyurethanes, in particular polyurethane foams, such as crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, can be used as additives , Cell openers, solid fillers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, etc.
Isolationsschaumstoffe für die Wärmedämmung von Gebäuden unterliegen Brandschutzanforderungen. Einsetzbare Flammschutzmittel zu diesem Zweck sind bevorzugt flüssige organische Phosphor-Verbindungen, wie halogenfreie organische Phosphate, z.B. Triethylphosphat (TEP), halogenierte Phosphate, z.B. Tris(1-chlor-2-propyl)phosphat (TCPP) und Tris(2-chlorethyl)phosphat (TCEP) und organische Phosphonate, z.B. Dimethylmethanphosphonat (DMMP), Dimethylpropanphosphonat (DMPP) oder Feststoffe wie Ammoniumpolyphosphat (APP) und roter Phosphor. Des Weiteren sind als Flammschutzmittel halogenierte Verbindungen, beispielsweise halogenierte Polyole, sowie Feststoffe wie Blähgraphit und Melamin geeignet. Insulation foams for the thermal insulation of buildings are subject to fire protection requirements. Flame retardants that can be used for this purpose are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. triethyl phosphate (TEP), halogenated phosphates, e.g. tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. dimethyl methane phosphonate (DMMP), dimethyl propane phosphonate (DMPP) or solids such as ammonium polyphosphate (APP) and red phosphorus. Furthermore, halogenated compounds, for example halogenated polyols, and solids such as expandable graphite and melamine are suitable as flame retardants.
Weitere Gegenstände der vorliegenden Erfindung sind: Further objects of the present invention are:
(i) eine Zusammensetzung, geeignet zur Herstellung von Polyurethan- oder Polyisocyanurat- Hartschaumstoffen, enthaltend zumindest eine Isocyanatkomponente, zumindest eine Polyolkomponente, zumindest einen Schaumstabilisator, zumindest einen Urethan- und/oder Isocyanurat-Katalysatoren, Wasser und/oder Treibmittel, und optional zumindest ein Flammschutzmittel und/oder weitere Additive, welche dadurch gekennzeichnet ist, dass zusätzlich Polymerpartikel eingesetzt werden, wobei die mittlere Korngröße der Polymerpartikel < 100 pm, vorzugsweise < 70 gm, insbesondere 5 bis 50pm beträgt,(i) a composition suitable for the production of rigid polyurethane or polyisocyanurate foams, containing at least one isocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane and / or isocyanurate catalyst, water and / or blowing agent, and optionally at least a flame retardant and / or further additives, which is characterized in that polymer particles are additionally used, the mean grain size of the polymer particles being <100 μm, preferably <70 μm, in particular 5 to 50 μm,
(II) ein Verfahren zur Herstellung von Polyurethan- oder Polyisocyanurat-Hartschaumstoffen, durch Umsetzung dieser Zusammensetzung sowie (II) a process for the production of rigid polyurethane or polyisocyanurate foams, by reacting this composition as well
(III) die dadurch erhältlichen Polyurethan- oder Polyisocyanurat-Hartschaumstoffe. Um Wiederholungen zu vermeiden sei bezüglich der vorgenannten Gegenstände, insbesondere der erfindungsgemäßen Zusammensetzung ausdrücklich auch auf die bisherigen Ausführungen zum erfindungsgemäßen Verfahren verwiesen, die entsprechend Gültigkeit haben für die vorgenannten Gegenstände. Das gilt insbesondere für die bisher genannten bevorzugten Ausführungsformen. (III) the resulting rigid polyurethane or polyisocyanurate foams. In order to avoid repetition, with regard to the aforementioned subjects, in particular the composition according to the invention, express reference is also made to the previous statements on the method according to the invention, which are correspondingly valid for the aforementioned subjects. This applies in particular to the preferred embodiments mentioned so far.
Außerdem ist Gegenstand der vorliegenden Erfindung die Verwendung von erfindungsgemäßen Polyurethanschaumstoffen als Dämmplatten und Isolationsmittel sowie eine Kühlapparatur, die als Isoliermaterial einen erfindungsgemäßen Polyurethanschaumstoff aufweist. The present invention also relates to the use of polyurethane foams according to the invention as insulation boards and insulation means and a cooling apparatus which has a polyurethane foam according to the invention as the insulating material.
Wiederum ein weiterer Gegenstand der Erfindung liegt in der Verwendung der Polymerpartikel, wie zuvor in der Beschreibung charakterisiert, zur Reduktion der Dicke einer PU-Hartschaum- Isolationsschicht bei Erhalt der thermischen Isolationsleistung, insbesondere in Dämmplatten und Isolationsmitteln. Ein noch weiterer Gegenstand der Erfindung ist eine Dispersion zum Einsatz in erfindungsgemäßen Zusammensetzungen für Polyurethanschaum, umfassend Polymerpartikel, wie zuvor in der Beschreibung charakterisiert, sowie zumindest ein Polyol und/oder Lösungsmittel, optional Treibmittel und/oder optional Dispergieradditive. Polyol sowie optionales Treibmittel sind insbesondere nach den Maßgaben, wie zuvor in der Beschreibung dargelegt, charakterisiert. Geeignete Lösungsmittel umfassen mono-, di- und polyfunktionelle Alkohole wie z.B. Monoethylenglykol (MEG) Diethylenglykol (DEG), Dipropylenglykol (DPG), Alkoxylate oder organische Lösungsmittel wie beispielsweise DMSO oder Propylencarbonat. Die Polymerpartikel können auch in der Dispersion mit den oben genannten Verbindungen vorbeladen bzw. beaufschlagt sein, insbesondere mit Kohlenwasserstoffen mit 3, 4 oder 5 Kohlenstoff-Atomen, bevorzugt cyclo-, iso- und n-Pentan, Fluorkohlenwasserstoffen, bevorzugt HFC 245fa, HFC 134a und HFC 365mfc, perfluorierten Verbindungen wie Perfluorpentan und Perfluorhexan, Fluorchlorkohlenwasserstoffe, bevorzugt HCFC 141 b, Hydrofluoroolefinen (HFO) oder Hydrohaloolefinen wie z.B. 1234ze, 1234yf, 1224yd, 1233zd(E) oder 1336mzz, Sauerstoff-haltigen Verbindungen wie Methylformiat, Aceton und Dimethoxymethan, oder Chlorkohlenwasserstoffen, bevorzugt Dichlormethan und 1 ,2-Dichlorethan. Yet another object of the invention is the use of the polymer particles, as previously characterized in the description, to reduce the thickness of a PU rigid foam insulation layer while maintaining the thermal insulation performance, in particular in insulation boards and insulation means. The invention still further provides a dispersion for use in compositions according to the invention for polyurethane foam, comprising polymer particles, as characterized above in the description, and at least one polyol and / or solvent, optionally blowing agent and / or optionally dispersing additives. Polyol and optional blowing agent are characterized in particular according to the criteria as set out above in the description. Suitable solvents include mono-, di- and polyfunctional alcohols such as monoethylene glycol (MEG) diethylene glycol (DEG), dipropylene glycol (DPG), alkoxylates or organic solvents such as DMSO or propylene carbonate. The polymer particles can also be preloaded or charged with the abovementioned compounds in the dispersion, in particular with hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, perfluorinated compounds such as perfluoropentane and perfluorohexane, chlorofluorocarbons, preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1224yd, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
Geeignete Dispergieradditive sind dem Fachmann bekannt. Es sind bekanntermaßen Additive, die das Dispergieren, also die optimale Durchmischung von mindestens zwei, eigentlich nicht mischbaren Phasen bzw. Substanzen verbessern. Bevorzugt einsetzbare Dispergieradditive werden beispielsweise in der DE 199 40 797 A1 und DE 100 29 648 C1 beschrieben. Suitable dispersing additives are known to the person skilled in the art. As is known, they are additives which improve the dispersion, that is to say the optimal mixing of at least two, actually immiscible phases or substances. Dispersing additives that can be used with preference are described, for example, in DE 199 40 797 A1 and DE 100 29 648 C1.
Eine Dispersion, umfassend Polymerpartikel, wie zuvor in der Beschreibung charakterisiert, sowie zumindest einen Schaumstabilisator (insbesondere Polyethersiloxan), optional Polyol und/oder Lösungsmittel und/oder optional Dispergieradditive entspricht einer bevorzugten Ausführungsform der Erfindung. A dispersion comprising polymer particles, as characterized above in the description, and at least one foam stabilizer (in particular polyether siloxane), optionally polyol and / or solvent and / or optionally dispersing additives corresponds to a preferred embodiment of the invention.
Eine bevorzugte PU-Schaumformulierung im Sinne dieser Erfindung umfasst die erfindungsgemäßen Polymerpartikel und ergibt ein Raumgewicht von 10 bis 900 kg/m3 und weist die folgende Zusammensetzung auf, entsprechend einer bevorzugten Ausführungsform der Erfindung: Die Verarbeitung der erfindungsgemäßen Formulierungen zu den gewünschten PU-Schaumstoffen kann nach allen dem Fachmann geläufigen Verfahren erfolgen. A preferred PU foam formulation for the purposes of this invention comprises the polymer particles according to the invention and gives a density of 10 to 900 kg / m 3 and has the following composition, according to a preferred embodiment of the invention: The processing of the formulations according to the invention to give the desired PU foams can be carried out by any of the methods familiar to the person skilled in the art.
Polyurethan-Hartschaum bzw. PU-Hartschaum ist ein feststehender technischer Begriff. Der bekannte und prinzipielle Unterschied zwischen Weichschaum und Hartschaum ist, dass ein Weichschaum ein elastisches Verhalten zeigt und damit die Verformung reversibel ist. Der Hartschaum wird demgegenüber dauerhaft verformt. Im Rahmen der vorliegenden Erfindung wird unter Polyurethan-Hartschaumstoff insbesondere ein Schaumstoff gemäß DIN 7726 verstanden, der eine Druckfestigkeit nach DIN 53 421 / DIN EN ISO 604:2003-12 von vorteilhafterweise > 20 kPa, vorzugsweise > 80 kPa, bevorzugt > 100 kPa, weiter bevorzugt > 150 kPa, besonders bevorzugt > 180 kPa aufweist. Weiterhin verfügt der Polyurethan-Hartschaumstoff nach DIN EN ISO 4590:2016- 12 vorteilhafterweise über eine Geschlossenzelligkeit von größer 50%, vorzugsweise größer 80% und besonders bevorzugt größer 90%. Polyurethane rigid foam or PU rigid foam is a fixed technical term. The well-known and fundamental difference between flexible foam and rigid foam is that flexible foam shows elastic behavior and the deformation is therefore reversible. In contrast, the rigid foam is permanently deformed. In the context of the present invention, rigid polyurethane foam is understood to mean, in particular, a foam in accordance with DIN 7726 which has a compressive strength in accordance with DIN 53 421 / DIN EN ISO 604: 2003-12 of advantageously> 20 kPa, preferably> 80 kPa, preferably> 100 kPa, more preferably> 150 kPa, particularly preferably> 180 kPa. Furthermore, the rigid polyurethane foam according to DIN EN ISO 4590: 2016-12 advantageously has a closed-cell content of greater than 50%, preferably greater than 80% and particularly preferably greater than 90%.
Die erfindungsgemäßen PU-Hartschäume können als oder zur Herstellung von Isoliermaterialien, vorzugsweise Dämmplatten, Kühlschränken, Isolierschäumen, Dachhimmeln, Verpackungsschäumen oder Sprühschäumen verwendet werden. The rigid PU foams according to the invention can be used as or for the production of insulating materials, preferably insulating boards, refrigerators, insulating foams, headliners, packaging foams or spray foams.
Insbesondere in der Kühlhaus-, Kühlgeräte- und Hausgeräteindustrie; z. B. zur Herstellung von Dämmplatten für Dächer und Wände, als Isoliermaterial in Containern und Lagerhäusern für tiefgekühlte Ware sowie für Kühl- und Gefriergeräte, können die erfindungsgemäßen PU-Schäume mit Vorteil eingesetzt werden. In particular in the cold store, refrigeration appliance and household appliance industries; z. B. for the production of insulation panels for roofs and walls, as insulating material in containers and warehouses for frozen goods and for refrigerators and freezers, the PU foams according to the invention can be used with advantage.
Weitere bevorzugte Anwendungsfelder liegen im Fahrzeugbau, insbesondere zur Herstellung von Fahrzeughimmel, Karosserieteilen, Innenverkleidungen, Kühlfahrzeugen, Großcontainern, Transportpaletten, Verpackungslaminaten, in der Möbelindustrie, z.B. für Möbelteile, Türen, Verkleidungen, in Elektronikanwendungen. Other preferred fields of application are in vehicle construction, in particular for the production of headliners, body parts, interior cladding, refrigerated vehicles, large containers, transport pallets, packaging laminates, in the furniture industry, e.g. for furniture parts, doors, cladding, in electronics applications.
Ein weiterer Gegenstand der Erfindung liegt in der Verwendung des PU-Hartschaums als Isolationsmaterial in der Kältetechnik, in Kühlmöbeln, im Bau-, Automobil-, Schiffbau- und/oder Elektronikbereich, als Dämmplatten, als Sprühschaum, als Einkomponentenschaum. Another object of the invention is the use of rigid PU foam as an insulation material in refrigeration technology, in refrigeration units, in the construction, automotive, shipbuilding and / or electronics sectors, as insulation boards, as spray foam, as one-component foam.
In den nachfolgend aufgeführten Beispielen wird die vorliegende Erfindung beispielhaft beschrieben, ohne dass die Erfindung, deren Anwendungsbreite sich aus der gesamten Beschreibung und den Ansprüchen ergibt, auf die in den Beispielen genannten Ausführungsformen beschränkt sein soll. BEISPIELE: In the examples listed below, the present invention is described by way of example without the invention, the scope of which is evident from the entire description and the claims, being restricted to the embodiments mentioned in the examples. EXAMPLES:
Beispiel 1 : PUR Hartschaum Example 1: PUR rigid foam
Für den anwendungstechnischen Vergleich wurde folgende Schaumformulierung verwendet: The following foam formulation was used for the performance comparison:
* Daltolac® R 471 der Firma Huntsman, OH-Zahl 470 mgKOH/g * Daltolac® R 471 from Huntsman, OH number 470 mgKOH / g
** POLYCAT® 8 der Firma Evonik Industries AG ** POLYCAT® 8 from Evonik Industries AG
*** TEGOSTAB® B 84510 der Firma Evonik Industries AG *** TEGOSTAB® B 84510 from Evonik Industries AG
**** DEGACRYL® M 527, Polymethylmethacrylat-Pulver, Mittlere Korngröße 33 - 41 pm nach ISO**** DEGACRYL® M 527, polymethyl methacrylate powder, mean grain size 33 - 41 pm according to ISO
13320-1 , der Firma Evonik Industries AG 13320-1, from Evonik Industries AG
***** Polymeres MDI, 200 mPa*s, 31 ,5% NCO, Funktionalität 2,7. ***** Polymeric MDI, 200 mPa * s, 31.5% NCO, functionality 2.7.
Die Durchführung der Vergleichsverschäumungen erfolgte im Handmischverfahren. Dazu wurden Polyol, Katalysatoren, Wasser, Schaumstabilisator, Partikel und Treibmittel in einen Becher eingewogen und mit einem Tellerrührer (6 cm Durchmesser) 30 s bei 1.000 Upm vermischt. Durch erneutes Abwiegen wurde die beim Mischvorgang verdunstete Treibmittelmenge bestimmt und wieder ergänzt. Jetzt wurde das MDI zugegeben, die Reaktionsmischung mit dem beschriebenen Rührer 7 s bei 2.500 Upm verrührt und sofort in eine auf 45 °C thermostatisierte Aluminiumform von 145 cm x 14 cm x 3,5 cm Größe überführt, welche im Winkel von 10° (entlang der 145 cm messenden Seite) geneigt und mit Polyethylenfolie ausgekleidet war. Die Schaumformulierung wurde dabei an der tiefer liegenden Seite eingetragen, so dass der expandierende Schaum die Form im Eingussbereich ausfüllt und in Richtung der höher liegenden Seite aufsteigt. Die Einsatzmenge an Schaumformulierung war dabei so bemessen, dass sie um 10 % über der zur Mindestbefüllung der Form notwendigen Menge lag. The comparison foaming was carried out using the hand-mixing method. For this purpose, polyol, catalysts, water, foam stabilizer, particles and blowing agent were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) for 30 s at 1,000 rpm. The amount of propellant evaporated during the mixing process was determined by reweighing and replenished. Now the MDI was added, the reaction mixture was stirred with the stirrer described for 7 s at 2,500 rpm and immediately transferred to an aluminum mold of 145 cm x 14 cm x 3.5 cm in size thermostated to 45 ° C, which was set at an angle of 10 ° (along the 145 cm measuring side) was inclined and lined with polyethylene film. The foam formulation was entered on the lower-lying side so that the expanding foam fills the mold in the pouring area and rises in the direction of the higher-lying side. The amount of foam formulation used was calculated in such a way that it was 10% above the amount necessary for the minimum filling of the mold.
Nach 10 min wurden die Schaumstoffe entformt. Einen Tag nach der Verschäumung wurden die Schaumstoffe analysiert. Oberfläche und Innenstörungen wurden subjektiv anhand einer Skala von 1 bis 10 beurteilt, wobei 10 einem (idealisierten) ungestörten Schaum und 1 einen extrem stark gestörten Schaum repräsentiert. Die Wärmeleitzahl wurde an 2,5 cm dicken Scheiben mit einem Gerät vom Typ Hesto l Control bei Temperaturen an Probenunter- und -Oberseite von 10 °C und 36 °C gemessen. Zur Bestimmung eines Alterungswertes der Wärmeleitfähigkeit wurden die Probekörper über 7 Tage bei 70 °C gelagert und danach erneut vermessen. Die Offenzelligkeit wurde mit einem Gaspyknometer AccuPyc II 1340 der Firma Micromeritics gemessen. The foams were removed from the mold after 10 minutes. The foams were analyzed one day after foaming. Surface and internal defects were assessed subjectively on a scale from 1 to 10, with 10 representing an (idealized) undisturbed foam and 1 an extremely badly disturbed foam. The coefficient of thermal conductivity was measured on 2.5 cm thick panes using a Hesto l Control device at temperatures on the underside and top of the sample of 10 ° C and 36 ° C. To determine an aging value of the thermal conductivity, the Test specimen stored for 7 days at 70 ° C and then measured again. The open-cell content was measured with an AccuPyc II 1340 gas pycnometer from Micromeritics.
Die Ergebnisse sind in der folgenden Tabelle zusammengestellt: The results are compiled in the following table:
Die Ergebnisse zeigen, dass mit den erfindungsgemäßen Partikeln eine signifikante Verbesserung der Wärmeleitfähigkeit erzielt werden kann. Die Werte liegen sowohl im frischen als auch im gealterten Zustand sehr deutlich unter dem Referenzwert des Schaums ohne Zusatz von Polymerpartikel. Alle anderen für den Gebrauch relevanten Schaumeigenschaften werden durch die erfindungsgemäßen Partikel nicht oder nur unwesentlich beeinflusst. Auch bei der recht sensibel reagierenden Oberflächenqualität der Schaum-Probekörper findet man keine oder nur eine marginale Verschlechterung. Beispiel 2: PIR Hartschaum The results show that a significant improvement in thermal conductivity can be achieved with the particles according to the invention. Both in the fresh and in the aged state, the values are very clearly below the reference value of the foam without the addition of polymer particles. All other foam properties relevant for use are not or only insignificantly influenced by the particles according to the invention. Even with the surface quality of the foam test specimens, which reacts very sensitively, there is no or only a marginal deterioration. Example 2: PIR rigid foam
Für den anwendungstechnischen Vergleich wurde folgende Schaumformulierung verwendet : * Stepanpol® PS 2352 der Firma Stepan, OH-Zahl 250 mgKOH/g ** POLYCAT® 5 der Firma Evonik Industries AG *** KOSMOS® 75 der Firma Evonik Industries AG **** TEGOSTAB® B 84510 der Firma Evonik Industries AG The following foam formulation was used for the performance comparison: * Stepanpol® PS 2352 from Stepan, OH number 250 mgKOH / g ** POLYCAT® 5 from Evonik Industries AG *** KOSMOS® 75 from Evonik Industries AG **** TEGOSTAB® B 84510 from Evonik Industries AG
***** DEGACRYL® M 527, Polymethylmethacrylat-Pulver, Mittlere Korngröße 33 - 41 pm nach ISO 13320-1 der Firma Evonik Industries AG ***** DEGACRYL® M 527, polymethyl methacrylate powder, mean grain size 33 - 41 μm according to ISO 13320-1 from Evonik Industries AG
****** p0|ymeres MDI, 200 mPa*s, 31 ,5% NCO, Funktionalität 2,7. ****** p 0 | y m older MDI, 200 mPa * s, 31, 5% NCO, functionality 2.7.
Die Durchführung der Vergleichsverschäumungen erfolgte im Handmischverfahren. Dazu wurden Polyol, Katalysatoren, Wasser, Schaumstabilisator, Flammschutzmittel, Partikel und Treibmittel in einen Becher eingewogen und mit einem Tellerrührer (6 cm Durchmesser) 30 s bei 1.000 Upm vermischt. Durch erneutes Abwiegen wurde die beim Mischvorgang verdunstete Treibmittelmenge bestimmt und wieder ergänzt. Jetzt wurde das MDI zugegeben, die Reaktionsmischung mit dem beschriebenen Rührer 5 s bei 3.000 Upm verrührt und sofort in eine auf 60 °C thermostatisierte Aluminiumform von 25 cm x 50 cm x 7 cm Größe überführt, welche mit Polyethylenfolie ausgekleidet war. The comparison foaming was carried out using the hand-mixing method. For this purpose, polyol, catalysts, water, foam stabilizer, flame retardant, particles and propellant were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) for 30 s at 1,000 rpm. The amount of propellant evaporated during the mixing process was determined by reweighing and replenished. The MDI was now added, the reaction mixture was stirred with the stirrer described for 5 s at 3,000 rpm and immediately transferred to an aluminum mold of 25 cm × 50 cm × 7 cm in size, thermostated to 60 ° C., which was lined with polyethylene film.
Nach 10 min wurden die Schaumstoffe entformt. Einen Tag nach der Verschäumung wurden die Schaumstoffe analysiert. Oberfläche und Innenstörungen wurden subjektiv anhand einer Skala von 1 bis 10 beurteilt, wobei 10 einem (idealisierten) ungestörten Schaum und 1 einen extrem stark gestörten Schaum repräsentiert. Die Wärmeleitzahl wurde an 2,5 cm dicken Scheiben mit einem Gerät vom Typ Hesto l Control bei Temperaturen an Probenunter- und -Oberseite von 10 °C und 36 °C gemessen. Zur Bestimmung eines Alterungswertes der Wärmeleitfähigkeit wurden die Probekörper über 7 Tage bei 70 °C gelagert und danach erneut vermessen. Die Offenzelligkeit wurde mit einem Gaspyknometer AccuPyc II 1340 der Firma Micromeritics gemessen. The foams were removed from the mold after 10 minutes. The foams were analyzed one day after foaming. Surface and internal defects were assessed subjectively using a scale from 1 to 10, with 10 representing an (idealized) undisturbed foam and 1 an extremely badly disturbed foam. The coefficient of thermal conductivity was measured on 2.5 cm thick panes using a Hesto 1 Control device at temperatures on the underside and top of the sample of 10 ° C and 36 ° C. To determine an aging value of the thermal conductivity, the test specimens were stored at 70 ° C. for 7 days and then measured again. The open-cell content was measured with an AccuPyc II 1340 gas pycnometer from Micromeritics.
Die Ergebnisse sind in der folgenden Tabelle zusammengestellt: The results are compiled in the following table:
Die Ergebnisse zeigen wiederum, dass mit den erfindungsgemäßen Polymerpartikeln eine signifikante Verbesserung der Wärmeleitfähigkeit erzielt werden kann, wobei die Werte auch hier sowohl im frischen als auch im gealterten Zustand deutlich unter dem Referenzwert des Schaums ohne Zusatz von Polymerpartikeln liegen. Hierbei ist besonders hervorzuheben, dass bereits eine sehr geringe Zugabe an erfindungsgemäßen Partikeln zu messbaren Verbesserungen führt. The results again show that a significant improvement in thermal conductivity can be achieved with the polymer particles according to the invention, the values here as well, both in the fresh and in the aged state, being well below the reference value of the foam without the addition of polymer particles. It should be particularly emphasized here that even a very small addition of particles according to the invention leads to measurable improvements.
Alle anderen für den Gebrauch relevanten Schaumeigenschaften werden durch die erfindungsgemäßen Partikel nicht oder nur unwesentlich beeinflusst. Auch bei der recht sensibel reagierenden Oberflächenqualität der Schaum-Probekörper findet man keine oder nur eine marginale Verschlechterung. All other foam properties relevant for use are not or only insignificantly influenced by the particles according to the invention. Even with the surface quality of the foam test specimens, which reacts very sensitively, there is no or only a marginal deterioration.

Claims

Patentansprüche: Patent claims:
1. Zusammensetzung zur Herstellung von Polyurethanhartschaum, umfassend zumindest eine Isocyanat-Komponente, eine Polyolkomponente, optional einen Katalysator, der die Ausbildung einer Urethan- oder Isocyanurat-Bindung katalysiert, optional Treibmittel, optional Schaumstabilisator, dadurch gekennzeichnet, dass die Zusammensetzung zusätzlich Polymerpartikel umfasst, wobei die mittlere Korngröße der Polymerpartikel < 100 pm, vorzugsweise < 70 pm, insbesondere 5 bis 50 pm beträgt. 1. Composition for the production of rigid polyurethane foam, comprising at least one isocyanate component, a polyol component, optionally a catalyst which catalyzes the formation of a urethane or isocyanurate bond, optionally blowing agent, optionally foam stabilizer, characterized in that the composition additionally comprises polymer particles, the mean grain size of the polymer particles being <100 μm, preferably <70 μm, in particular 5 to 50 μm.
2. Zusammensetzung gemäß Anspruch 1 , dadurch gekennzeichnet, dass die Polymerpartikel aus Polymer, umfassend Polyethylen, Polypropylen, Polyamid (insbesondere umfassend PA6, PA6.6, PA10, PA11 und/oder PA12), Polyester (insbesondere umfassend Polyethylenterephthalat, Polybutylenterephthalat und/oder Poly-s-Caprolacton), Polystyrol, Polyacrylat, Polymethylmethacrylat, Polycarbonat, Styrol-Acrylnitril-Copolymere, Polyether, Polymilchsäure, Polyurethan, Polysulfone, Polyethersulfon, Polyetherimid, Polyimid oder Mischungen davon, insbesondere umfassend Polystyrol und/oder Polymethylmethacrylat, gebildet sind. 2. Composition according to claim 1, characterized in that the polymer particles made of polymer, comprising polyethylene, polypropylene, polyamide (in particular comprising PA6, PA6.6, PA10, PA11 and / or PA12), polyester (in particular comprising polyethylene terephthalate, polybutylene terephthalate and / or Poly-s-caprolactone), polystyrene, polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymers, polyethers, polylactic acid, polyurethane, polysulfones, polyethersulfone, polyetherimide, polyimide or mixtures thereof, in particular comprising polystyrene and / or polymethyl methacrylate.
3. Zusammensetzung gemäß mindestens einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die Polymerpartikel in einer Gesamtmenge von 0,01 bis 20 Teile, vorzugsweise 0,05 bis 5 Teile, besonders bevorzugt 0,1 bis 5 Teile, bezogen auf 100 Teile Polyole eingesetzt werden. 3. Composition according to at least one of claims 1 or 2, characterized in that the polymer particles in a total amount of 0.01 to 20 parts, preferably 0.05 to 5 parts, particularly preferably 0.1 to 5 parts, based on 100 parts Polyols are used.
4. Zusammensetzung gemäß mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Polymerpartikel mit Kohlenwasserstoffen mit 3, 4 oder 5 Kohlenstoff-Atomen, bevorzugt cyclo-, iso- und n-Pentan, Fluorkohlenwasserstoffen, bevorzugt HFC 245fa, HFC 134a und HFC 365mfc, perfluorierten Verbindungen wie Perfluorpentan und Perfluorhexan, Fluorchlorkohlenwasserstoffe, bevorzugt HCFC 141 b, Hydrofluoroolefinen (HFO) oder Hydrohaloolefinen wie z.B. 1234ze, 1234yf, 1224yd, 1233zd(E) oder 1336mzz, Sauerstoff-haltigen Verbindungen wie Methylformiat, Aceton und Dimethoxymethan, oder Chlorkohlenwasserstoffen, bevorzugt Dichlormethan und 1 ,2- Dichlorethan beaufschlagt sind. 4. Composition according to at least one of claims 1 to 3, characterized in that the polymer particles with hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, perfluorinated compounds such as perfluoropentane and perfluorohexane, chlorofluorocarbons, preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1224yd, 1233zymd (E) or 1336mzz, oxygen-containing compounds such as methyl formate., Chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane are acted upon.
5. Verfahren zur Herstellung von PU-Schaumstoffen, insbesondere PU-Hartschaumstoffen, auf der Basis schaumfähiger Reaktionsmischungen enthaltend Polyisocyanate, Verbindungen mit reaktionsfähigen Wasserstoffatomen, Treibmitteln, Schaumstabilisatoren, und gegebenenfalls weiteren Zusatzstoffen, dadurch gekennzeichnet, dass zusätzlich Polymerpartikel eingesetzt werden, wobei die mittlere Korngröße der Polymerpartikel < 100 pm, vorzugsweise < 70 pm, insbesondere 5 bis 50pm beträgt. 5. A process for the production of PU foams, in particular rigid PU foams, based on foamable reaction mixtures containing polyisocyanates, compounds with reactive hydrogen atoms, blowing agents, foam stabilizers, and optionally other additives, characterized in that polymer particles are additionally used, the mean grain size being the polymer particle is <100 pm, preferably <70 pm, in particular 5 to 50 pm.
6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, dass die Polymerpartikel aus Polymer, umfassend Polyethylen, Polypropylen, Polyamid (insbesondere umfassend PA6, PA6.6, PA10, PA11 und/oder PA12), Polyester (insbesondere umfassend6. The method according to claim 5, characterized in that the polymer particles made of polymer comprising polyethylene, polypropylene, polyamide (in particular comprising PA6, PA6.6, PA10, PA11 and / or PA12), polyester (in particular comprising
Polyethylenterephthalat, Polybutylenterephthalat und/oder Poly-s-Caprolacton), Polystyrol, Polyacrylat, Polymethylmethacrylat, Polycarbonat, Styrol-Acrylnitril-Copolymere, Polyether, Polymilchsäure, Polyurethan, Polysulfone, Polyethersulfon, Polyetherimid, Polyimid oder Mischungen davon, insbesondere umfassend Polystyrol und/oder Polymethylmethacrylat, gebildet sind. Polyethylene terephthalate, polybutylene terephthalate and / or poly-s-caprolactone), polystyrene, polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymers, polyethers, polylactic acid, polyurethane, polysulfones, polyethersulfone, polyetherimide, polyimide or mixtures thereof, in particular or comprising Polymethyl methacrylate.
7. Verfahren gemäß mindestens einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, dass die Polymerpartikel in einer Gesamtmenge von 0,01 bis 20 Teile, vorzugsweise 0,05 bis 5 Teile, besonders bevorzugt 0,1 bis 5 Teile, bezogen auf 100 Teile Polyole eingesetzt werden. 7. The method according to at least one of claims 5 or 6, characterized in that the polymer particles in a total amount of 0.01 to 20 parts, preferably 0.05 to 5 parts, particularly preferably 0.1 to 5 parts, based on 100 parts Polyols are used.
8. Verfahren gemäß mindestens einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, dass die Polymerpartikel mit Kohlenwasserstoffen mit 3, 4 oder 5 Kohlenstoff-Atomen, bevorzugt cyclo-, iso- und n-Pentan, Fluorkohlenwasserstoffen, bevorzugt HFC 245fa, HFC 134a und HFC 365mfc, perfluorierten Verbindungen wie Perfluorpentan und Perfluorhexan, Fluorchlorkohlenwasserstoffe, bevorzugt HCFC 141 b, Hydrofluoroolefinen (HFO) oder Hydrohaloolefinen wie z.B. 1234ze, 1234yf, 1233zd(E) oder 1336mzz, Sauerstoff-haltigen Verbindungen wie Methylformiat, Aceton und Dimethoxymethan, oder Chlorkohlenwasserstoffen, bevorzugt Dichlormethan und 1 ,2-Dichlorethan beaufschlagt sind. 8. The method according to at least one of claims 5 to 7, characterized in that the polymer particles with hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, perfluorinated compounds such as perfluoropentane and perfluorohexane, chlorofluorocarbons, preferably HCFC 141b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, preferably dichloromethane and 1,2-dichloroethane are applied.
9. PU-Schaumstoff, insbesondere PU-Hartschaumstoff, hergestellt gemäß zumindest einem der Verfahren gemäß den Ansprüchen 5 bis 8. 9. PU foam, in particular PU rigid foam, produced according to at least one of the processes according to claims 5 to 8.
10. Verwendung von PU-Schaumstoff gemäß Anspruch 9 zur Reduktion des Energieverbrauches von Kühlgeräten, insbesondere Gefrierschrank bzw. -frühe, Kühlregal sowie Kühlschrank. 10. Use of PU foam according to claim 9 for reducing the energy consumption of refrigerators, in particular freezers or freezers, refrigerated shelves and refrigerators.
11 . Verwendung der Polymerpartikel, wie in den Ansprüchen 5 bis 8 charakterisiert, zur 11. Use of the polymer particles as characterized in claims 5 to 8 for
(a) Herstellung von Polyurethanhartschaumstoffen, insbesondere unter Einsatz einer Zusammensetzung gemäß einem der Ansprüche 1 bis 4, (a) Production of rigid polyurethane foams, in particular using a composition according to one of Claims 1 to 4,
(b) Verbesserung der thermischen Isolationseigenschaften von Polyurethanschaum, vorzugsweise PU-Hartschaum, insbesondere in Bauanwendungen oder im Kühlbereich, und/oder (b) Improvement of the thermal insulation properties of polyurethane foam, preferably PU rigid foam, in particular in construction applications or in the cooling area, and / or
(c) Reduktion der Dicke einer PU-Hartschaum-lsolationsschicht bei Erhalt der thermischen Isolationsleistung, insbesondere in Bauanwendungen oder im Kühlbereich. (c) Reduction of the thickness of a PU rigid foam insulation layer while maintaining the thermal insulation performance, especially in construction applications or in the cooling area.
12. Dispersion, umfassend Polymerpartikel, wie in den Ansprüchen 5 bis 8 charakterisiert, sowie zumindest ein Poyol und/oder Lösungsmittel, optional Treibmittel und/oder optional Dispergieradditive, wobei die Polymerpartikel vorzugsweise mit Fluor-haltigen organischen Verbindungen und/oder linearen, verzweigten und/oder zyklischen Kohlenwasserstoffen (insbesondere umfassend Propan, Butan und/oder Pentan) beaufschlagt sind, wobei die Dispersion vorzugsweise Polyethersiloxan umfasst. 12. Dispersion comprising polymer particles, as characterized in claims 5 to 8, and at least one polyol and / or solvent, optionally blowing agent and / or optionally dispersing additives, the polymer particles preferably with fluorine-containing organic compounds and / or linear, branched and / or cyclic hydrocarbons (in particular comprising propane, butane and / or pentane) are acted upon, the dispersion preferably comprising polyether siloxane.
EP21705914.6A 2020-02-19 2021-02-12 Polyurethane insulating foams and production thereof Withdrawn EP4107214A1 (en)

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