WO2010022895A1 - Mousses rigides de polyuréthane et de polyisocyanurate viscoélastiques - Google Patents

Mousses rigides de polyuréthane et de polyisocyanurate viscoélastiques Download PDF

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Publication number
WO2010022895A1
WO2010022895A1 PCT/EP2009/006061 EP2009006061W WO2010022895A1 WO 2010022895 A1 WO2010022895 A1 WO 2010022895A1 EP 2009006061 W EP2009006061 W EP 2009006061W WO 2010022895 A1 WO2010022895 A1 WO 2010022895A1
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WO
WIPO (PCT)
Prior art keywords
hollow microspheres
foam
polyisocyanuratschäume
hard polyurethane
range
Prior art date
Application number
PCT/EP2009/006061
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German (de)
English (en)
Inventor
Stephanie Vogel
Klaus Gerke
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Bayer Materialscience Ag
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Publication date
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Publication of WO2010022895A1 publication Critical patent/WO2010022895A1/fr

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Classifications

    • 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
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0076—Microcapsules
    • 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
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/048—Bimodal pore distribution, e.g. micropores and nanopores coexisting in the same foam
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to rigid polyurethane and polyisocyanurate foams comprising from 5.0 to 20.0% by weight of hollow microspheres based on the total weight of the foam, to processes for their preparation, and to their use for producing elements of wind turbines, automobiles and sports equipment, for the insulation of equipment, in particular household appliances, for the production of insulation boards and for use as a model building foam.
  • Rigid foams are known in the art and find their application in heat insulation materials, as sound insulation and insulation.
  • the steady and not inconsiderable increase in the cost of starting materials for the production of rigid foams has contributed to the development and use of filling materials, which serve to reduce the deficiencies of the raw materials used.
  • proposed filler materials are, for example, hollow microspheres.
  • Polyurethane and Polyisocyanuratschaumstoffe have a relatively high brittleness. Therefore, their use in the field of wind turbines is critical, since very good dynamic mechanical properties such as shear, tensile, bending and compressive strength and thus a certain toughness and viscoelasticity is imperative for these purposes.
  • Another object of the present invention is to provide rigid polyurethane and polyisocyanurate foams having good heat insulating properties.
  • these foams exhibit a k-factor in the range 20 to 25 mWm 'K' ".
  • Another object of the present invention is to provide rigid polyurethane and polyisocyanurate foams whose heat-insulating properties remain unchanged over an extended period of time.
  • the foregoing objects have been achieved by providing a rigid polyurethane and polyisocyanurate foam having a bimodal cell size distribution comprising 5.0 to 20.0 weight percent microballoons based on the total weight of the foam.
  • the polyurethane and polyisocyanurate foams according to the invention show improved heat-insulating properties and a considerably increased dimensional stability.
  • the foams according to the invention have viscoelastic properties.
  • the foams preferably have a modulus of elasticity of 1.5 to 3.5 MPa in the foaming direction and a modulus of elasticity of 7.0 to 10.0 MPa perpendicular to the foaming direction.
  • the foams in the foaming direction according to DEST 53423 particularly preferably have a modulus of elasticity of from 2.0 to 3.0 MPa.
  • the foams perpendicular to the foaming direction according to DIN 53423 have a modulus of elasticity of 8.0 to 9.0 MPa.
  • the foam according to the invention preferably comprises 6.0 to 10.0% by weight of hollow microspheres, based on the total weight of the foam.
  • the proportion of hollow microspheres used depends on the desired properties such as heat-insulating properties, viscoelastic properties and compressive strength.
  • the hollow microspheres can be added directly to a foam formulation as a solid additive.
  • the hard polyurethane and polyisocyanurate foams according to the invention exhibit a bimodal cell size distribution in which the mean diameter of the hollow microspheres present in the finished foam differs by at least one to two orders of magnitude from that of the foamed matrix.
  • the hollow microspheres have an average diameter in the range of 6 to 45 microns, more preferably in the range of 8 to 20 microns.
  • the cells of the foam have an average diameter in the range of 80 to 350 microns, preferably in the range of 110 to 250 microns.
  • the hollow microspheres are preferably selected from the group consisting of hollow thermoplastic microspheres, hollow glass microspheres and glass ceramic microspheres.
  • glass or glass-ceramic microspheres are the commercially available Z-Lite W-1000 hollow microspheres from Zeelan Industries and Scotchlite from 3M and CEL 300 and 650 from PQ Corporation.
  • thermoplastic hollow microspheres Preference is given to the use of thermoplastic hollow microspheres.
  • the thermoplastic hollow microspheres used herein are known to those skilled in the art and commercially available under the product name Expancel (Akzo Nobel) from Schönox GmbH (Essen Germany). These are hollow microspheres whose shell is based on a copolymer consists of acrylonitrile and the cavity is filled with a propellant gas.
  • the unexpanded hollow microspheres have a diameter of 6 to 45 ⁇ m and a density of 1000 to 1300 kg / m 3 .
  • the propellants are typically volatile hydrocarbons such as butane, pentane, hexane, heptane, isobutene, isopentane, neopentane, cyclobutane, cyclobutane and cyclopropane. If necessary, these hollow spheres can be made and filled with any other low-boiling solvents. If the hollow microspheres are heated, the gas increases the internal pressure, the polymer layer softens and the expansion process begins. Upon complete expansion, the hollow microsphere has increased its diameter three to four times its original diameter and increased its volume by more than forty times its original volume. The density is ⁇ 30 kg / m 3 after the expansion process. The expansion temperatures are generally in the range between 80 and 190 ° C. After cooling, the thermoplastic material solidifies again, so that the expanded volume is retained.
  • volatile hydrocarbons such as butane, pentane, hexane, heptane, isobutene, isopentane
  • the polyurethane and polyisocyanurate foam according to the invention is advantageously closed-cell. Particularly preferred is a proportion of ⁇ 10% open cells, since this can improve the heat insulating properties.
  • the proportion of open and closed cells is determined using a pycnometer (AccuPyc 1330, Micromeritics GmbH, Mönchengladbach, Germany) according to the principle of gas phase displacement.
  • a foam according to the present invention directly after its production a by 0.3 to 1.0 mWm '' K '' has reduced, more preferably is reduced by 0.4 to 0.8 mWm 'K "1 thermal conductivity.
  • a foam according to the present invention directly after its production a by 0.3 to 1.0 mWm '' K '' has reduced, more preferably is reduced by 0.4 to 0.8 mWm 'K "1 thermal conductivity.
  • After 30 days, has an inventive foam relative to a foam without hollow microspheres preferably by 0.8 to 2.0 HiWm reduced -1 K "1, more preferably reduced to 1.0 to 1.4 mWm 'K' 1 thermal conductivity.
  • the cells of the foam preferably have an average diameter in the range from 80 to 350 ⁇ m, particularly preferably in the range from 110 to 250 ⁇ m. This was determined by means of digital image analysis of five light microscopic images on thin sections of the various rigid foam samples. Only those cells were counted manually, which were clearly defined as such. For each sample at least 500 cells were evaluated according to their diameter.
  • the foam of the present invention exhibits a bimodal cell size distribution in that the average diameter of the hollow microspheres embedded as a filler is smaller by 1 to 2 orders of magnitude than that of the foam matrix ( Figure 1).
  • Fig. 2 shows the cell size distribution of a classic rigid polyurethane foam in a light micrograph.
  • the production of rigid foams of the present invention is known and has been described, for example, in German Offenlegungsschriften DE 1,694,142, DE 1,694,215 and DE 1,720,768 as well as in Kunststoff-Handbuch, Volume VII, Polyurethane, Vieweg and Hochtlen (ed.), Carl Hanser Verlag, Kunststoff (1966) and in the more recent edition of this volume, edited by G. Oertel, Carl Hanser Verlag, Kunststoff, Vienna (1983).
  • foams are mainly those which contain urethane and / or isocyanurate and / or allophanate and / or uretdione and / or urea and / or carbodiimide groups.
  • the following may be used to prepare the isocyanate-based bimodal foams using the hollow microspheres of the present invention:
  • aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as those described by W. Siefken in Justus Liebigs Annalen der Chemie 562, pp. 75-136, e.g. those of the formula
  • polyisocyanates which are technically readily available, such as 2,4- and 2,6-toluene diisocyanate (TDI) and mixtures of these isomers.
  • TDI 2,4- and 2,6-toluene diisocyanate
  • Polyphenyl polymethylene polyisocyanates such as e.g.
  • polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups modified polyisocyanates
  • modified polyisocyanates in particular those modified polyisocyanates derived from 2,4- and / or 2,6-toluene diisocyanate and from 4,4'- and / or 2,4'-diphenylmethane diisocyanate.
  • the starting components may also be compounds having a molecular weight of usually 400 to 10,000, which contain at least two hydrogen atoms and are reactive towards isocyanates.
  • this preferably comprises compounds having hydroxyl groups, especially those containing one Molecular weight of 1000 to 6000 g / mol, preferably 2000 to 6000 g / mol such as polyether and polyester and polycarbonates and polyester amides having at least 2, usually 2 to 8, preferably 2 to 6 hydroxyl groups.
  • the use of these compounds for the preparation of homogeneous and cellular polyurethanes is known per se and disclosed for example in DE-OS 2,832,253, pp. 11-18.
  • compounds having at least two isocyanate-reactive hydrogen atoms and having a molecular weight of from 32 to 399 can also be used as further starting components.
  • compounds having hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl groups, preferably compounds having hydroxyl groups and / or amino groups are understood to mean those which are used as chain extenders or crosslinkers.
  • These compounds usually have 2 to 8, preferably 2 to 4, hydrogen atoms which are reactive toward isocyanates. Suitable examples are disclosed in DEG-OS 2,832,253, pages 19-20.
  • the blowing agents used in connection with the present invention may include both chemical blowing agents such as water and / or physical blowing agents in the form of volatile organic or inorganic substances and other volatile blowing agents typically used to foam PUR / PIR. Foams are used.
  • Organic leavening agents include acetone, ethyl acetate, halo-substituted alkanes such as methylene chloride, chloroform, ethylene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, dichlorodifluoroethane, dichlorotrifluoroethane; also butane, pentane, hexane, heptane or diethyl ether.
  • blowing agents include: 1,1,1,4,4,4-hexafluorobutane (HFC-356); Tetrafluoroethanes such as 1,1,1,2-tetrafluoroethane (HFC-134a); 1,1,2,3,3-pentafluoropropane (HFC-245ea); 1,1,1,2,3-pentafluoropropane (HFC-245ca) and 1,1,2,2,3,3-hexafluoropropane (HFC-236ca); Nexafluoropropanes such as 1,1,2,2,3,3-hexafluoropropane (HFC-236ca); 1,1,1,2,2,3-hexafluoropropane (HFC-236cb); 1,1,1,2,3,3-hexafluoropropane (HFC-236ea); 1,1,1,3,3,3-hexafluoropropane (HFC-236fa); Pentafluorobutanes such as 1,1,1,3,3-pent
  • blowing agents examples include air, CO 2 and N 2 O.
  • a blowing effect can also be achieved by adding compounds which decompose at temperatures above room temperature and release gases such as azodicarbonamide or azoisobutyronitrile.
  • Further examples of blowing agents can be found in the Plastics Handbook, Volume VE, Polyurethane, Vieweg and Hochtlen (ed.), Carl Hanser Verlag, Kunststoff (1966) on pages 108-109, 453-455 and 507-510.
  • auxiliaries and additives may also be used simultaneously, for example well-known catalysts in amounts of up to 10% by weight, surface-active additives such as emulsifiers and foam stabilizers and reaction retardants such as acidic substances such as hydrochloric acid or halides of organic acids, as well as well-known Cell regulators such as paraffins, fatty alcohols or dimethylpolysiloxanes and pigments or dyes and / or other well-known flame retardants such as Trikre- sylphosphat, stabilizers against aging and weathering, plasticizers, fungicides, bactericides and fillers such as barium sulfate, diatomaceous earth, carbon black or whiting.
  • surface-active additives such as emulsifiers and foam stabilizers and reaction retardants such as acidic substances such as hydrochloric acid or halides of organic acids
  • Cell regulators such as paraffins, fatty alcohols or dimethylpolysiloxanes and pigments or dyes
  • the proportion of the blowing agent in relation to the weight of the entire foam formulation is preferably in the range from 0.1 to 5.0% by weight, more preferably in the range from 1.0 to 5.0% by weight, most preferably in the range from 2.0 to 4.0% by weight.
  • the density of the hard polyurethane / polyisocyanurate foams according to the invention is preferably in the range between 20 and 80 kg / m 3 , particularly preferably in the range between 25 and 65 kg / m 3 , very particularly preferably in the range between 28 and 35 kg / m 3 .
  • the foams according to the invention can be prepared by methods known to the person skilled in the art.
  • the reactants are reacted by a well-known one step process, the prepolymer or semi-prepolymer process, often using engineering equipment disclosed in US Patent 2,764,565. Details relating to the processing plant, which are also relevant with respect to the invention, can be found on pages 121-205 of the Plastics Handbook, Volume VE, Polyurethane, Vieweg and Hochtlen / hrsg), Carl Hanser Verlag, Kunststoff 1966) ,
  • the hollow microspheres are hereby fed to the polyol formulation immediately prior to the addition of the isocyanate component as a solid filler.
  • This processing method offers the advantage that the processability of the microballoon-containing formulations is easier compared to the prior art due to the low filler content required and the fact that only unexpanded material is used, and in contrast, no adaptation or modification of generally conventional formulations. Chen plants for the production of hard polyurethane and PolyisocyanuratCumen is required.
  • the hollow microspheres used for the purposes of the invention are used as a free-flowing solid in completely unexpanded form (DE quality of the manufacturer, DE being “dry unexpanded”)
  • completely unexpanded means that the hollow microspheres are used without further work-up step without having previously been dispersed in a polyurethane raw material and / or expanded.
  • Thermoplastic hollow microspheres consist of a shell of a thermoplastic polymer which includes a blowing agent. It has now surprisingly been found that the exothermic nature of a polyurethane or a combined polyurethane and polyisocyanurate reaction is sufficient to cause expansion of the hollow thermoplastic microspheres in situ during the foaming process. Neither does the expansion of the hollow microspheres due to the rapid setting of the PUR-ZPIR matrix nor the PUR / PIR reactions adversely affect the expansion of the blowing agent-containing thermoplastic hollow microspheres.
  • the polyurethane-PolyisocyanuratWarume invention are suitable for the production of elements of wind turbines, automobiles and sports equipment, for the isolation of equipment, in particular household appliances, for the production of insulation boards and for use as a model foam.
  • Fig. 1 REM-Avemhahmen a rigid polyurethane foam, embedded in the matrix thermoplastic microspheres.
  • Fig. 2 light micrographs of a standard rigid polyurethane foam.
  • a hard polyurethane product having a bulk density of 32 kg / m 3 and serving as a comparison was obtained by mixing the following substances: a) 100 parts by weight. Polyol / b) 2.4 parts by weight. Stabilizer, 2 c) 1.4 parts by weight. Water, d) 18 parts by weight. Tris (2-chloroisopropyl) phosphate, e) 2.5 parts by weight. Cyclohexyldimethylamine, f) 16 parts by weight. n-pentane g) 195 parts by weight. polymeric MDI /
  • thermoplastic hollow microspheres 7 A hard polyurethane product according to the present invention having a bulk density of 32 kg / m 3 and containing 8.2% by weight thermoplastic hollow microspheres was obtained by mixing the following substances: a) 30 parts by weight. thermoplastic hollow microspheres 7 , b) 100 parts by weight. Polyol, 2 c) 2.4 parts by weight. Stabilizer, 5 d) 1.5 parts by weight. Water, e) 18 parts by weight. Tris- (2-chloroisopropyl) phosphate, f) 2.7 parts by weight. Cyclohexyldimethylamine, g) 12 parts by weight. n-pentane h) 198 parts by weight. polymeric MDI /
  • E-module DIN 53 423 from three-point bending test.
  • E-module DIN EN 826 from compression test.
  • E-modulus DIN 53 430 from tensile test.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des mousses rigides de polyuréthane et de polyisocyanurate comprenant 5 à 20 % en poids de microsphères creuses par rapport au poids total de la mousse. L'invention concerne en outre des procédés de fabrication de ces mousses, ainsi que l'utilisation des mousses selon l'invention pour fabriquer des éléments de rotors d'éoliennes, d'automobiles et d'équipements sportifs, pour isoler des appareils, en particulier des appareils électroménagers, pour fabriquer des panneaux isolants et pour fabriquer des maquettes.
PCT/EP2009/006061 2008-08-27 2009-08-17 Mousses rigides de polyuréthane et de polyisocyanurate viscoélastiques WO2010022895A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008039944 2008-08-27
DE102008039944.2 2008-08-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109537093A (zh) * 2018-12-05 2019-03-29 浙江华峰氨纶股份有限公司 一种微孔中空聚氨酯弹性纤维的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260343A (en) * 1993-01-04 1993-11-09 Basf Corporation Low density flexible integral skin polyurethane systems using thermoplastic hydrocarbon microspheres and water as co-blowing agents
EP1057841A2 (fr) * 1999-06-04 2000-12-06 Fuji Spinning Co., Ltd. Pièces de polyuréthane moulées pour tampon à polir et procédé pour sa préparation
US6166109A (en) * 1997-08-11 2000-12-26 Bayer Corporation Syntactic rigid PUR/PIR foam boardstock
WO2002102887A1 (fr) * 2001-06-19 2002-12-27 Basf Aktiengesellschaft Procede de production de polyurethane syntactique
EP1447208A2 (fr) * 2003-02-13 2004-08-18 General Electric Company Mousses à haut module d'élasticité et résistantes aux chocs, pour éléments de structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260343A (en) * 1993-01-04 1993-11-09 Basf Corporation Low density flexible integral skin polyurethane systems using thermoplastic hydrocarbon microspheres and water as co-blowing agents
US6166109A (en) * 1997-08-11 2000-12-26 Bayer Corporation Syntactic rigid PUR/PIR foam boardstock
EP1057841A2 (fr) * 1999-06-04 2000-12-06 Fuji Spinning Co., Ltd. Pièces de polyuréthane moulées pour tampon à polir et procédé pour sa préparation
WO2002102887A1 (fr) * 2001-06-19 2002-12-27 Basf Aktiengesellschaft Procede de production de polyurethane syntactique
EP1447208A2 (fr) * 2003-02-13 2004-08-18 General Electric Company Mousses à haut module d'élasticité et résistantes aux chocs, pour éléments de structure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109537093A (zh) * 2018-12-05 2019-03-29 浙江华峰氨纶股份有限公司 一种微孔中空聚氨酯弹性纤维的制备方法
CN109537093B (zh) * 2018-12-05 2021-02-26 华峰化学股份有限公司 一种微孔中空聚氨酯弹性纤维的制备方法

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