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WO2025216809A1 - Mousse rigide de polyuréthane soufflée à l'eau présentant des propriétés mécaniques améliorées - Google Patents

Mousse rigide de polyuréthane soufflée à l'eau présentant des propriétés mécaniques améliorées

Info

Publication number
WO2025216809A1
WO2025216809A1 PCT/US2025/017179 US2025017179W WO2025216809A1 WO 2025216809 A1 WO2025216809 A1 WO 2025216809A1 US 2025017179 W US2025017179 W US 2025017179W WO 2025216809 A1 WO2025216809 A1 WO 2025216809A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyether polyol
components
total weight
glycerin
water
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.)
Pending
Application number
PCT/US2025/017179
Other languages
English (en)
Inventor
Thomas MOSCIATTI
Davide Micheletti
Cecilia Girotti
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.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
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Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of WO2025216809A1 publication Critical patent/WO2025216809A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—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
    • 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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having 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
    • C08G18/28—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
    • C08G18/4825—Polyethers containing two 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
    • C08G18/28—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
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • WATER-BLOWN POLYURETHANE RIGID FOAM WITH IMPROVED MECHANICAL PROPERTIES Technical Field The present disclosure relates to polyurethane compositions and in particular to full water blown polyurethane compositions.
  • Background The goal of preparing a fully water blown (WB) rigid polyurethane foam has been sought after for many years. Reasons for this pursuit include the fact that utilizing a fully water blown rigid polyurethane foam process can lead to a zero ozone deployment potential, a very low global warming potential, is a much less expensive blowing agent as compared to a hydrocarbon based blowing agent and, unlike hydrocarbon based blowing agents, water is non-flammable.
  • the water blown polyurethane composition of the present disclosure helps to overcome the issues associated with forming a rigid polyurethane foam under low molding temperatures (35 – 40 °C) commonly encountered in the cold chain industry, which is known to still use machinery having wooden or epoxy resin made mold plates.
  • the process and composition of the present disclosure has the ability to utilize high levels of water as the blowing agent to avoid or reduce the problems mentioned above.
  • Embodiments of the present disclosure also help to improve the adhesion performance of rigid polyurethane foams to a variety of substrates (e.g., a metal facing substrate) in cold chain application, where they achieve improvements in tensile bond strength values to substrates such as metal and polymers.
  • the present disclosure provides for a water blown polyurethane composition that includes (1) an isocyanate; (2) an isocyanate reactive component that includes; (a) from 40 to 60 weight percent (wt.%), based on the total weight of components (2) through (6), of at least one polyoxypropylene polyether polyol , having a hydroxyl value from 310 to 550 milligrams of potassium hydroxide per gram of the polyoxypropylene polyether polyol and a functionality greater than 4; (b) from 10 to 20 wt.%, based on the total weight of the components (2) through (6), of at least one polypropylene glycol having a hydroxyl value from 80 to 300 milligrams potassium hydroxide per gram of the polypropylene glycol, each of the at least one polypropylene glycol being different than the at least one polyoxypropylene polyether polyol
  • the isocyanate component can be selected from the group consisting of 4,4′-, 2,4′- and 2,2′-diphenylmethanediisocyanate; 2,4- and/or 2,6-toluenediisocyanate; mixtures of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanate; mixtures of toluenediisocyanates and polyphenyl polymethylene polyisocyanate; and polyphenyl polymethylene polyisocyanate.
  • the catalyst can be selected from the group consisting of dimethyl benzyl amine, N,N,N,N,N-pentamethyl diethylenetriamine (PMDETA), and combinations thereof.
  • the amount of water as a blowing agent can be from 3 to 5 wt.% based on the total weight of component (2) through (6).
  • the organo-silicone copolymer includes a silicone backbone with functional groups that include polyether moieties.
  • the composition further includes from 5 to 15 wt.%, based on the weight of components (2) through (6), of a phosphorus-based, halogen free flame retardant.
  • the present disclosure also provides for a process of preparing a rigid polyurethane foam from the water blown polyurethane composition provided herein by reacting the formulation that includes (1) through (6) as provided above and herein.
  • the present disclosure provides a composition for a fully water blown rigid polyurethane foam that has desirable properties, including improved adhesion properties when formed at low temperatures.
  • the water blown polyurethane composition of the present disclosure helps to overcome the issues associated with forming a rigid polyurethane foam under low molding temperatures (35 – 40 °C) commonly encountered in the cold chain industry, which is known to still use machinery having wooden or epoxy resin made mold plates.
  • the process and composition of the present disclosure has the ability to utilize high levels of water as the blowing agent to avoid or reduce the problems mentioned herein.
  • Embodiments of the present disclosure also help to improve the adhesion performance of rigid polyurethane foams to a variety of substrates (e.g., a metal facing substrate) in cold chain application, where they achieve improvements in tensile bond strength values to substrates such as metal and polymers. Such improvements can be highly useful to customers producing cold chain appliances or sandwich panels by means of, for example, a discontinuous process.
  • the present disclosure provides for a water blown (WB) polyurethane composition that includes (1) an isocyanate; (2) an isocyanate reactive component that includes; (a) from 40 to 60 weight percent (wt.%), based on the total weight of components (2) through (6), of at least one polyoxypropylene polyether polyol , having a hydroxyl value from 310 to 550 milligrams of potassium hydroxide per gram of the polyoxypropylene polyether polyol and a functionality greater than 4; (b) from 10 to 20 wt.%, based on the total weight of the components (2) through (6), of at least one polypropylene glycol having a hydroxyl value from 80 to 300 milligrams potassium hydroxide per gram of the polypropylene glycol, each of the at least one polypropylene glycol being different than the at least one polyoxypropylene polyether polyol; and (c) from 15 to 20 wt.%, based on the total weight of components (2)
  • the wt.% of (2) through (6) for the WB polyurethane composition of the present disclosure can total 100 wt.%.
  • the WB polyurethane composition of the present disclosure can, however, further include (7) optional additives as provided herein below.
  • the Isocyanate The WB polyurethane composition of the present disclosure includes an isocyanate.
  • the isocyanate can include a polyisocyanate. As used herein, the polyisocyanate is referred to in the United States as the “A-component” (in Europe, as the “B- component”).
  • the part of the formulation not including the isocyanate is referred to herein as the B-component (e.g., at least (2) through (6) as provided herein).
  • Selection of the isocyanate may be made from a wide variety of polyisocyanates, including but not limited to those that are well known to those skilled in the art.
  • organic polyisocyanates, modified polyisocyanates, isocyanate-based prepolymers, and mixtures thereof may be employed. These can further include aliphatic and cycloaliphatic isocyanates, and in particular aromatic and, more particularly, multifunctional aromatic isocyanates.
  • PMDI polyphenyl polymethylene polyisocyanates
  • polyisocyanates useful in the present disclosure for the isocyanate also include 2,4- and 2,6-toluenediisocyanate and the corresponding isomeric mixtures; 4,4′-, 2,4′- and 2,2′-diphenyl- methanediisocyanate and the corresponding isomeric mixtures; mixtures of 4,4′-, 2,4′- and 2,2′- diphenyl-methanediisocyanates and polyphenyl polymethylene polyisocyanates (PMDI); and mixtures of PMDI and toluene diisocyanates.
  • 2,4- and 2,6-toluenediisocyanate and the corresponding isomeric mixtures
  • aliphatic and cycloaliphatic isocyanate compounds such as 1,6-hexamethylene-diisocyanate; 1-isocyanato-3,5,5-trimethyl-1,3-isocyaantomethyl-cyclohexane; 2,4- and 2,6-hexahydro-toluene-diisocyanate, as well as the corresponding isomeric mixtures; 4,4′-, 2,2′- and 2,4′-dicyclohexyl-methanediisocyanate, as well as the corresponding isomeric mixtures.
  • 1,3-tetramethylene xylene diisocyanate may also be used with the present disclosure.
  • isocyanate for the WB polyurethane composition are the so-called modified multifunctional isocyanates, that is, products that are obtained through chemical reactions of the above diisocyanates and/or polyisocyanates.
  • modified multifunctional isocyanates that is, products that are obtained through chemical reactions of the above diisocyanates and/or polyisocyanates.
  • exemplary are polyisocyanates containing esters, ureas, biurets, allophanates and preferably carbodiimides and/or uretoneimines; isocyanurate and/or urethane group containing diisocyanates or polyisocyanates.
  • Liquid polyisocyanates containing carbodiimide groups, uretoneimines groups and/or isocyanurate rings, having isocyanate groups (NCO) contents of from 120 to 40 weight percent, more preferably from 20 to 35 weight percent, can also be used.
  • NCO isocyanate groups
  • These include, for example, polyisocyanates based on 4,4′- 2,4′- and/or 2,2′-diphenylmethane diisocyanate and the corresponding isomeric mixtures, 2,4- and/or 2,6-toluenediisocyanate and the corresponding isomeric mixtures.
  • the isocyanate component can preferably be selected from the group consisting of 4,4′-, 2,4′- and 2,2′-diphenylmethanediisocyanate; 2,4- and/or 2,6-toluenediisocyanate; mixtures of diphenylmethane diisocyanates and PMDI; mixtures of toluenediisocyanates and PMDI; and/or polyphenyl polymethylene polyisocyanate.
  • Suitable prepolymers for use as the isocyanate for the WB polyurethane composition of the present disclosure are prepolymers having NCO group contents of from 2 to 40 weight percent, more preferably from 4 to 30 weight percent.
  • prepolymers are prepared by reaction of the di- and/or poly-isocyanates with materials including lower molecular weight diols and triols, but also can be prepared with multivalent active hydrogen compounds such as di- and tri-amines and di- and tri-thiols.
  • materials including lower molecular weight diols and triols, but also can be prepared with multivalent active hydrogen compounds such as di- and tri-amines and di- and tri-thiols.
  • Individual examples are aromatic polyisocyanates containing urethane groups, preferably having NCO contents of from 5 to 40 weight percent, more preferably 20 to 35 weight percent, obtained by reaction of diisocyanates and/or polyisocyanates with, for example, lower molecular weight diols, triols, oxyalkylene glycols, dioxyalkylene glycols, or polyoxyalkylene glycols having molecular weights up to about 800.
  • polyols can be employed individually or in mixtures as di- and/or polyoxyalkylene glycols.
  • diethylene glycols, dipropylene glycols, polyoxyethylene glycols, ethylene glycols, propylene glycols, butylene glycols, polyoxypropylene glycols and polyoxypropylene-polyoxyethylene glycols can be used.
  • Polyester polyols can also be used, as well as alkyl diols such as butane diol.
  • Other diols also useful include bishydroxyethyl- or bishydroxypropyl-bisphenol A, cyclohexane dimethanol, and bishydroxyethyl hydroquinone.
  • isocyanate of the prepolymer formulations that may be used in the present disclosure are: (i) polyisocyanates having an NCO content of from 8 to 40 weight percent containing carbodiimide groups and/or urethane groups, from 4,4′-diphenylmethane diisocyanate or a mixture of 4,4′- and 2,4′-diphenylmethane diisocyanates; (ii) prepolymers containing NCO groups, having an NCO content of from 2 to 35 weight percent, based on the weight of the prepolymer, prepared by the reaction of polyols, having a functionality of preferably from 1.75 to 4 and a molecular weight of from 800 to 15,000, with 4,4′-diphenylmethane diisocyanate or with a mixture of 4,4′- and 2,4′-diphenylmethane diisocyanate and mixtures of (i) and (ii); and (iii) 2,4′ and 2,6-toluen
  • PMDI in any of its forms is the most preferred isocyanate for use with the present disclosure.
  • it preferably has an equivalent weight from 125 to 300, more preferably from 130 to 175, and an average functionality of greater than about 1.5. More preferred is an average functionality of from 1.75 to 3.5.
  • the dynamic viscosity of the isocyanate is preferably from 25 to 5,000 centipoises (cPs) (0.025 to about 5 Pascal*seconds (Pa*s)), but values from 100 to 1,000 cPs at 25° C. (0.1 to 1 Pa*s) are preferred for ease of processing. Similar dynamic viscosities are preferred where alternative polyisocyanates are selected.
  • the isocyanate of the WB polyurethane composition of the present disclosure is preferably selected from the group consisting of MDI, PMDI, an MDI prepolymer, a PMDI prepolymer, a modified MDI, and mixtures thereof.
  • the total amount of this isocyanate is preferably sufficient such that, relative to the isocyanate-reactive component in the formulation, it provides an isocyanate reaction index of from 100 to 300; more preferably the index is from 100 to 200; and still more preferably from 100 to 160.
  • the isocyanate index is the stoichiometric equivalents of isocyanate per equivalent of isocyanate reactive groups times 100.
  • the WB polyurethane composition of the present disclosure further includes (2) an isocyanate reactive component.
  • isocyanate-reactive is meant that this component has at least one functional group that reacts with an —N ⁇ C ⁇ O— group.
  • the functional group is a hydroxyl (—OH—) linkage.
  • the functional group is an amine (—NH) group
  • the result is a urea.
  • the reactant is water (H 2 O)
  • this isocyanate- reactive component comprises at least three constituents, as described hereinbelow.
  • the isocyanate-reactive component can also comprise additional constituents, as also described hereinbelow.
  • the isocyanate reactive component includes; (a) from 40 to 60 wt.%, based on the total weight of components (2) through (6), of at least one polyoxypropylene polyether polyol, having a hydroxyl value from 310 to 550 milligrams of potassium hydroxide per gram of the polyoxypropylene polyether polyol and a functionality greater than 4; (b) from 10 to 20 wt.%, based on the total weight of the components (2) through (6), of at least one polypropylene glycol having a hydroxyl value from 80 to 300 milligrams potassium hydroxide per gram of the polypropylene glycol, each of the at least one polypropylene glycol being different than the at least one polyoxypropylene polyether polyol; and (c) from 15 to 20 wt.%, based on the total weight of components (2) through (6)
  • the (2) isocyanate reactive component of the WB polyurethane composition of the present disclosure includes (a) from 40 to 60 wt.%, based on the total weight of components (2) through (6), of at least one polyoxypropylene polyether polyol, having a hydroxyl value from 310 to 550 milligrams of potassium hydroxide per gram of the polyoxypropylene polyether polyol (mg KOH/g) and a functionality greater than 4.
  • the WB polyurethane composition of the present disclosure includes (a) from 45 to 55 wt.%, based on the total weight of components (2) through (6), of at least one polyoxypropylene polyether polyol.
  • a polyoxypropylene polyether polyol can be produced, as is known in the art, through a process known as propoxylation, which involves the addition of propylene oxide (PO) to an initiator molecule in the presences of a catalyst.
  • Suitable initiators can include polyfunctional alcohols such as glycerol, trimethylolpropane (TMP), ethylene glycol, sucrose and/or sorbitol.
  • Initiator molecules particularly suitable for the polyoxypropylene polyether polyol are sucrose and/or sorbitol.
  • Sucrose may be obtained from sugar cane or sugar beets, honey, sorghum, sugar maple, fruit, and the like.
  • sucrose component Means of extraction, separation, and preparation of the sucrose component vary depending upon the source, but are widely known and practiced on a commercial scale by those skilled in the art. Sorbitol can also be obtained via the hydrogenation of D-glucose over a suitable hydrogenation catalysts as are known in the art. Nickel-aluminum and ruthenium-carbon catalysts are just two of the many possible catalysts for this reaction. Alternatively, preparation of sorbitol may begin with a starch hydrolysate which has been hydrogenated.
  • the polyoxypropylene polyether polyol of the present disclosure can have a hydroxyl value (or number) of 310 to 550 mg KOH/g and a functionality greater than 4.
  • the polyoxypropylene polyether polyol of the present disclosure can have a hydroxyl value (or number) of 350 to 490 mg KOH/g and a functionality of 4 to 7.
  • the polyoxypropylene polyether polyol of the present disclosure can also have a hydroxyl equivalent weight of 100 to 180 g/equivalent.
  • the (a) at least one polyoxypropylene polyether polyol can include two polyoxypropylene polyether polyols, as provided herein.
  • Nonlimiting examples of suitable polyoxypropylene polyether polyols can include those sold under the trade designators VORANOL TM (DOW®), Pluracol® (BASF®); NiaxTM (Momentive Performance Materials); Poly-G® (Huntsman Corp.) and Desmophen® (Covestro).
  • VORANOL TM DOW®
  • Pluracol® BASF®
  • NiaxTM Momentive Performance Materials
  • Poly-G® Hauntsman Corp.
  • Desmophen® Covestro
  • suitable polyoxypropylene polyether polyols include VORANOL TM RN 482, a sorbitol-initiated polyoxypropylene polyether polyol having an hydroxyl number of 478, a nominal functionality of 6, and an equivalent weight of 117 g/equiv; and VORANOL TM RH 360, a sucrose- glycerine-initiated polyoxypropylene polyether polyol having an OH number of about 360, a functionality of about 4.6 and an equivalent weight of 156 g/equiv., each available from The Dow Chemical Company.
  • the (2) isocyanate reactive component of the WB polyurethane composition of the present disclosure further includes (b) from 10 to 20 wt.%, based on the total weight of the components (2) through (6), of at least one polypropylene glycol having a hydroxyl value from 80 to 300 milligrams potassium hydroxide per gram of the polypropylene glycol, each of the at least one polypropylene glycol being different than the at least one polyoxypropylene polyether polyol.
  • the WB polyurethane composition of the present disclosure includes (b) from 10 to 15 wt.%, based on the total weight of components (2) through (6), of at least one polypropylene glycol as provided herein.
  • a polyoxypropylene polyether polyol can be produced, as is known in the art, through a process known as propoxylation, which involves the addition of propylene oxide (PO) and/or propylene glycol oligomers with water and an initiator molecule in the presences of an acidic or basic catalyst.
  • Suitable initiators can include monohydric alcohols such as ethylene glycol or diols such as dipropylene glycol.
  • the polymerization reaction is typically catalyzed by alkaline catalysts such as potassium hydroxide (KOH) or double metal cyanide (DMC) complexes, as are known in the art.
  • the polypropylene glycol of the present disclosure can have a hydroxyl value (or number) of 80 to 300 milligrams potassium hydroxide per gram of the polypropylene glycol (mg KOH/g).
  • the polypropylene glycol of the present disclosure can have a hydroxyl value (or number) of 100 to 270 mg KOH/g of the polypropylene glycol.
  • the polypropylene glycol of the present disclosure can have a functionality of 2.
  • the polypropylene glycol of the present disclosure can have a weight average molecular weight of about 300 to 1200 g/mol.
  • the polypropylene glycol of the present disclosure can have a weight average molecular weight of about 350 to 1100 g/mol.
  • the polypropylene glycol of the present disclosure can also have a hydroxyl equivalent weight of 200 to 500 g/equivalent.
  • the (b) at least one polypropylene glycol of the present disclosure can include two polypropylene glycols, as provided herein.
  • suitable polypropylene glycols can include those sold under the trade designators VORANOL TM , CARBOWAXTM and CARBOWAX SENTRYTM products offered by The Dow Chemical Company.
  • suitable polypropylene glycols of the present disclosure include VORANOL TM 1010 L, a polypropylene glycol, having a functionality of 2, a weight average molecular weight of about 1000 g/mol, an OH number of 110 and an equivalent weight of 510 g/equiv.; and VORANOL TM P 400, a polypropylene glycol, having a functionality of 2, a weight average molecular weight of about 400 g/mol., an OH number of 260 and an equivalent weight of 216 g/equiv., each available from The Dow Chemical Company.
  • the (2) isocyanate reactive component of the WB polyurethane composition of the present disclosure further includes (c) from 15 to 20 wt.%, based on the total weight of components (2) through (6), of at least one glycerin-initiated polyether polyol, having a hydroxyl value from 100 to 200 milligrams potassium hydroxide per gram of the glycerin-initiated polyether polyol, each of the at least one glycerin-initiated polyether polyol being different than the (a) at least one polyoxypropylene polyether polyol and the (b) at least one polyether polyol.
  • the glycerin-initiated polyether polyol of the present disclosure can be produced, as is known in the art, through a polymerization process involving the reaction of glycerin (triol) with polyethylene oxide in the presence of an alkaline catalyst such as potassium hydroxide (KOH) or double metal cyanide (DMC) complexes, as are known in the art.
  • an alkaline catalyst such as potassium hydroxide (KOH) or double metal cyanide (DMC) complexes, as are known in the art.
  • the glycerin-initiated polyether polyol of the present disclosure can have a hydroxyl value (or number) of 100 to 2300 milligrams potassium hydroxide per gram of the glycerin-initiated polyether polyol (mg KOH/g).
  • the glycerin-initiated polyether polyol of the present disclosure can have a hydroxyl value (or number) of 140 to 170 mg KOH/g of the glycerin-initiated polyether polyol.
  • the glycerin- initiated polyether polyol of the present disclosure can have a functionality from 2 to 4.
  • the glycerin-initiated polyether polyol of the present disclosure can have a functionality of about 3.
  • the glycerin-initiated polyether polyol of the present disclosure can have a weight average molecular weight of about 800 to 1200 g/mol.
  • the glycerin-initiated polyether polyol of the present disclosure can have a weight average molecular weight of about 900 to 1100 g/mol.
  • the glycerin-initiated polyether polyol of the present disclosure can also have a hydroxyl equivalent weight of 200 to 500 g/equivalent.
  • the glycerin-initiated polyether polyol of the present disclosure can also have a hydroxyl equivalent weight of 300 to 400 g/equivalent.
  • suitable glycerin-initiated polyether polyols of the present disclosure can include those sold under the trade designators VORANOL TM offered by The Dow Chemical Company.
  • a suitable glycerin-initiated polyether polyols of the present disclosure include VORANOL TM 220-110, VORATECTM SD301, VORANOLTM CP 260, VORANOLTM CP 450, VORANOLTM CP 755, VORANOLTM CP 1000, VORANOLTM CP 1050 and VORANOLTM CP 1055, available from The Dow Chemical Company.
  • the glycerin-initiated polyether polyol of the present disclosure is VORANOLTM CP 1055, which is a glycerin initiated polyoxypropylene polyol with a weight average molecular weight of about 1000 g/mol, an OH number of about 156, a functionality of 3 and an equivalent weight of 360 g/equiv.
  • a Catalyst The WB polyurethane composition of the present disclosure further include (3) a catalyst. Specifically, the WB polyurethane composition of the present disclosure further include from 0.05 to 3 wt.%, based on the total weight of components (2) through (6), of (3) the catalyst.
  • the catalyst can be selected from the group consisting of dimethyl benzyl amine, N,N,N,N,N-pentamethyl diethylenetriamine (PMDETA), and combinations thereof.
  • the catalyst includes a combination of benzyl dimethyl amine and PMDETA.
  • PMDETA may be obtained from, for example, EVONIK under the trade designator POLYCAT® 5, and benzyl dimethyl amine is sold under the trade designation Dabco® BDMA by EVONIK.
  • the total amount of the combination of benzyl dimethyl amine and PMDETA can range from 0.0 to 3 wt.%, based on the total weight of components (2) through (6).
  • a combination of dimethyl benzyl amine and PMDETA are used as (3) the catalyst.
  • the relative amount of each of the dimethyl benzyl amine and the PMDETA can vary depending on the desired properties of the rigid polyurethane foam formed from the WB polyurethane composition.
  • the (3) catalyst includes 0.04 to 2.5 wt.% of dimethyl benzyl amine and 0.01 to 0.5 wt.% of PMDETA in arriving at the 0.05 to 3 wt.% of the (3) catalyst based on the total weight of components (2) through (6).
  • the (3) catalyst includes 1 to 2.5 wt.% of dimethyl benzyl amine and 0.05 to 0.2 wt.% of PMDETA based on the total weight of the WB polyurethane composition. In one embodiment, the (3) catalyst includes 2 wt.% of dimethyl benzyl amine and 0.1 wt.% of PMDETA based on the total weight of the WB polyurethane composition.
  • Catalysts for the WB polyurethane composition of the present disclosure do not include trimerization catalysts such as a glycine salt, tri(dimethyl aminomethyl)phenol) as are known in the art.
  • (4) Water The WB polyurethane composition of the present disclosure further include (4) water as a blowing agent.
  • the WB polyurethane composition of the present disclosure further include from 2 to 6 wt.%, based on the total weight of components (2) through (6), of water as a blowing agent.
  • the WB polyurethane composition of the present disclosure can include (4) from 3 to 6 wt.%, based on the total weight of components (2) through (6), of water as a blowing agent.
  • the WB polyurethane composition of the present disclosure can include (4) from 3 to 5 wt.%, based on the total weight of components (2) through (6), of water as a blowing agent.
  • water is used as the sole blowing agent.
  • one or more additional chemical blowing agents may be included in the formulation with the water.
  • the WB polyurethane composition of the present disclosure further include (5) 3- octylheptamethyltrisiloxane (CAS #17955-88-3): For the various can be present in the WB polyurethane composition from 1 to 5 wt.% based on the total weight of components (2) through (6) as provided herein.
  • the 3-octylheptamethyltrisiloxane is present as a surfactant additive for the WB polyurethane composition. It has been found that 3- octylheptamethyltrisiloxane is miscible with (2) the isocyanate reactive component as provided herein, and its use surprisingly improves tensile bond strength performance of a rigid polyurethane foamed formed therewith by about 20-40%, as illustrated in the Examples section herein.
  • the 3-octylheptamethyltrisiloxane can be present in the WB polyurethane composition from 3 to 5 wt.% based on the total weight of components (2) through (6) as provided herein.
  • the WB polyurethane composition of the present disclosure further include (6) an organo- silicone copolymer.
  • the WB polyurethane composition of the present disclosure can include from 1 to 5 wt.% based on the total weight of components (2) through (6) of the organo- silicone copolymer.
  • the organo-silicone copolymer can be present in the WB polyurethane composition from 3 to 5 wt.% based on the total weight of components (2) through (6) as provided herein.
  • the organo-silicone copolymer can include a silicone backbone with functional groups that include polyether moieties.
  • the organo-silicone copolymer may be selected from the group consisting of polydimethylsiloxane, polycyclomethylsiloxane, polysiloxane-oxyalkylene copolymer, and cationic types thereof.
  • the organo-silicone copolymer useful in the WB polyurethane composition of the present disclosure may be selected from commercially available products such as NiaxTM L-6861, L-6863, L-6866, L-6884, L-6889, L-6915LV, L-6988, L-6900, L-6887, L-6900, L-6920, among others, from Momentive; Matestab® AK8805, AK8806 AK8810, AK8811, AK8818, AK8863, among others, of Maysta Chemical.
  • the WB polyurethane composition may also include, accordingly and in non-limiting embodiments, (7) optional additives such as chain extenders, fillers, pigments, property modifiers such as fire retardants, and other additives such as will be generally familiar to those skilled in the art.
  • optional additives such as chain extenders, fillers, pigments, property modifiers such as fire retardants, and other additives such as will be generally familiar to those skilled in the art.
  • very minor amounts (less than 1.5 wt.% total, based on weight of (2) through (6), of other catalysts may be included in the WB polyurethane compositions and may be directed toward blowing and/or curing and/or trimerization.
  • Such may include, but are not limited to, amine-based catalysts other than those provided herein.
  • short chain tertiary amines or tertiary amines containing at least an oxygen may tend to promote blowing in particular and may include bis-(2-dimethylaminoethyl)ether; triethylamine, tributyl amine, N,N- dimethylaminopropylamine, dimethylethanolamine, N,N,N′,N′-tetra-methylethylenediamine, urea, and combinations thereof. Combinations of any of the above may also be selected.
  • Optional additional curing catalysts may include, generally, amidines, longer chain tertiary amines, organo-metallic compounds, and combinations thereof.
  • amidines such as 1,8-diazabicyclo[5.4.0]undec-7-ene and 2,3-dimethyl-3,4,5,6- tetrahydro-pyrimidine, salts thereof, and combinations thereof.
  • the organometallic compounds may include organotin compounds, such as tin(II) salts of organic carboxylic acids, e.g., tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate.
  • organotin compounds such as tin(II) salts of organic carboxylic acids, e.g., tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate
  • Bismuth salts of organic carboxylic acids may also be selected, e.g., bismuth octanoate.
  • the organometallic compounds may be selected for use alone or in combinations, or, in some embodiments, in combination with one or more of the highly basic amines listed hereinabove.
  • additional catalysts allowable within the maximum limitation of the catalyst amounts mentioned hereinabove, generally capable of promoting both blowing and curing reactions, are cyclic tertiary amines and long chain amines containing several nitrogen atoms, such as triethylamine, tributylamine, N-methyl-, N-ethyl-, and N-cyclohexyl-morpholine, N,N,N′,N′- tetramethyl-ethylenediamine, N,N,N′,N′-tetramethyl-butanediamine and -hexanediamine, tetramethyl-diaminoethyl ether, bis(dimethylaminopropyl)urea, dimethyl-piperazine, dimethyl- cyclohexylamine, 1,2-dimethyl-imidazole, 1-aza-bicyclo[3.3.0]octane, triethylene-diamine (TEDA), and combinations thereof.
  • triethylamine tribu
  • alkanolamine compounds may be employed. Such may include triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine, dimethylethanolamine, and combinations thereof.
  • blowing, curing or blowing/curing catalysts include NIAX A-4, NIAX A6, POLYCAT® 6, POLYCAT® 8, NIAX A1; POLYCAT® 58, DABCO® T, DABCO® NE 300, TOYOCAT® RX 20, DABCO® DMDEE, JEFFCAT® ZR 70, DABCO® 33 LV, NIAX® A-33, DABCO® R-8020, NIAX® TMBDA, POLYCAT® 77, POLYCAT® 6, POLYCAT® 9, POLYCAT® 15, JEFFCAT® ZR 50, TOYOCAT® NP, TOYOCAT® F94, DABCO® NEM, and the like.
  • POLYCAT® and DABCO® are available from Air Products; TOYOCAT® catalysts are available from Tosho Corporation; NIAX® Catalysts are available from Momentive Performance Material; and JEFFCAT® catalysts are available from Huntsman.
  • additional trimerization catalysts include tris(dialkylaminoalkyl)-s-hexahydrotriazines, such as 1,3,5-tris(N,N-dimethylaminopropyl)-s- hexahydrotriazine; DABCO® TMR 30; DABCO® K 2097 (potassium acetate), DABCO® K15 (potassium octoate); POLYCAT® 41, POLYCAT® 43, POLYCAT® 46, DABCO® TMR, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; alkali metal
  • Some of these catalysts are solids or crystals and can be dissolved in a suitable solvent.
  • solvents are one or more of the polyols, water, dipropylene glycol or any other carrier useful in the polyurethane foaming composition.
  • Further additives or modifiers such as are well-known in the art may also be included in the WB polyurethane composition as a whole.
  • surfactants, flame retardants, crosslinkers and/or fillers may be employed.
  • Flame retardants may include one or more brominated or non- brominated compounds, such as diammonium phosphate, various halogenated aromatic compounds, antimony oxide, alumina trihydrate, polyvinyl chloride, and combinations thereof.
  • Halogen free flame retardants particularly phosphorus-based halogen free flame retardants, may be particularly useful.
  • the flame retardant can be present in an amount of 5 to 15 wt.% based on the weight of components (2) through (6).
  • the WB polyurethane composition of the present disclosure can include from 5 to 15 wt.%, based on the weight of components (2) through (6), of the phosphorus-based, halogen free flame retardant.
  • Dispersing agents, cell stabilizers, and surfactants may also be incorporated into the formulations. Surfactants, including organic surfactants and additional silicone based surfactants, may also be added to serve as additional cell stabilizers.
  • surfactants that may be useful herein are polyethylene glycol ethers of long-chain alcohols, tertiary amine or alkanolamine salts of long-chain allyl acid sulfate esters, alkylsulfonic esters, alkyl arylsulfonic acids, and combinations thereof. Such surfactants are employed in amounts sufficient to stabilize the foaming reaction against collapse and the formation of large uneven cells. Typically, a surfactant total amount from about 0.2 to about 3 wt.%, based on the formulation as a whole, is sufficient for this purpose.
  • a surfactant may be included in the inventive formulations in any amount ranging from 0 to 6 wt.%, based on the weight of components (2) through (6).
  • other additives such as fillers and pigments may be included in the inventive rigid polyurethane foam formulations.
  • Such may include, in non-limiting embodiments, barium sulfate, calcium carbonate, graphite, carbon black, titanium dioxide, iron oxide, microspheres, alumina trihydrate, wollastonite, prepared glass fibers (dropped or continuous), polyester fibers, other polymeric fibers, combinations thereof, and the like.
  • additives that may be useful in the present disclosure include those wherein nucleating agents, such as liquid perfluoroalkanes and hydrofluoroethers, and inorganic solids, such as unmodified, partially modified and modified clays, including, for example, spherical silicates and aluminates, flat laponites, montmorillonites and vermiculites, and particles comprising edge surfaces, such as sepiolites and kaolinite-silicas.
  • nucleating agents such as liquid perfluoroalkanes and hydrofluoroethers
  • inorganic solids such as unmodified, partially modified and modified clays, including, for example, spherical silicates and aluminates, flat laponites, montmorillonites and vermiculites, and particles comprising edge surfaces, such as sepiolites and kaolinite-silicas.
  • organic and inorganic pigments and compatibilizers such as titanates and siliconates, may also be included in useful polyol dispersions as or as part of
  • the low density, primarily or fully WB polyurethane foam prepared according to the process of this disclosure is a rigid, foamed, closed-cell polymer.
  • a polymer is typically prepared by intimately mixing all of the reaction components, though mixing protocol may be tailored according to preference and/or equipment capabilities.
  • (2) the isocyanate-reactive component, (3) catalyst, (5) 3-octylheptamethyltrisiloxane, (6) the organo- silicone copolymer and any (7) additional components, as allowed and desired, may be combined in one stream; the (4) water as a primary or sole blowing agent may represent a second stream; and the (1) isocyanate may be a third stream.
  • the reacting mixture is then poured or otherwise deposited onto a flat substrate, such as a rigid or flexible facing sheet made of foil or another material which is being conveyed along a production line, or into a cavity or container wherein the inner surface or surfaces for a substrate for the rigid polyurethane foam.
  • a flat substrate such as a rigid or flexible facing sheet made of foil or another material which is being conveyed along a production line, or into a cavity or container wherein the inner surface or surfaces for a substrate for the rigid polyurethane foam.
  • the reacting mixture may be deposited into an open mold or distributed via laydown equipment into an open mold or simply deposited at or, as noted hereinabove, into any location for which it is destined, i.e., a pour-in-place application, such as between the interior and exterior walls of a structure such as a refrigeration appliance.
  • a second sheet may be applied on top of the deposited mixture.
  • the mixture may be injected into a closed mold, with or without vacuum assistance for cavity-filling. If a mold is employed, it is most typically heated prior to deposition of the reacting mixture. In general, such applications may be accomplished using the well-known one-shot technique together with conventional mixing methods.
  • the mixture on reacting, takes the shape of the mold or adheres to the substrate to produce a three-dimensional rigid polyurethane polymer of a relatively predefined shape and internal structure, which is then allowed to cure in place or in the mold, either partially or fully.
  • Suitable conditions for promoting the curing of the polymer include a temperature of typically from 20 °C to 60 °C, preferably from 35 °C to 55 °C, and more preferably from 40 °C to 50 °C. Such temperatures will usually permit the sufficiently cured polymer to be removed from the mold, typically within from 1 to 60 minutes and more typically within from 5 to 40 minutes after mixing of the reactants. Optimum demold time will generally depend, to a significant extent, upon the thickness of the produced foam. Furthermore, optimum cure conditions will depend upon the particular components selected for the formulation, including in particular the catalysts and quantities used in preparing the polymer and also the size and shape of the article manufactured.
  • the result may be a rigid foam in the form of slabstock, a molding, a filled cavity, including but not limited to a pipe or filled and/or insulated wall or hull structure, a sprayed foam, a frothed foam, or a continuously- or discontinuously-manufactured laminated product, including but not limited to a laminated product formed with other materials, such as hardboard, plasterboard, plastics, paper or metal.
  • the inventive rigid foams may be useful in commercial appliances, professional displays, and some types of machinery applications.
  • the WB polyurethane composition of the present disclosure and produced rigid polyurethan foams may exhibit desirable foam processability and mechanical properties, including adhesion to a substrate and dimensional stability, at surprisingly low temperatures and applied density, in comparison with traditional WB foams that have been prepared using blowing agents other than, or in addition to, water.
  • the description hereinabove is intended to be general and is not intended to be inclusive of all possible embodiments of the disclosure.
  • the examples hereinbelow are provided to be illustrative only and are not intended to define or limit the disclosure in any way. Those skilled in the art will be fully aware that other embodiments, within the scope of the claims, will be apparent from consideration of the specification and/or practice of the disclosure as disclosed herein.
  • Such other embodiments may include selections of specific components and constituents and proportions thereof; mixing and reaction conditions, vessels, deployment apparatuses, and protocols; performance and selectivity; identification of products and by-products; subsequent processing and use thereof; and the like; and that those skilled in the art will recognize that such may be varied within the scope of the claims appended hereto.
  • EXAMPLES The materials used in the Examples and Comparative Examples are listed and described in Table 1. Unless specified otherwise, the amount of materials are parts by weight.
  • a free rise foam is poured into a polyethylene bag of dimensions 50 ⁇ 40 centimeters (cm) placed into a wooden box of 20 ⁇ 20 ⁇ 20 cm and the reaction parameters (cream, gel and tack free time) are then determined.
  • the free rise density is determined after 30 minutes by cutting the specimen into a regular shape that is as large as possible.
  • Mechanical properties Compressive strength is measured according to EN 826 standard. The test is performed on the 10 ⁇ 10 ⁇ 5 cm specimens, cut from Brett panels, in the direction perpendicular to rise (foam thickness). The compressive strength is reported as the average value of five (5) specimens taken in different positions covering the whole panel length. Dimensional stability.
  • the test is performed according to EN 1604 standard, conditioning the specimens, which are 8 ⁇ 8 ⁇ 4 cm, at both high (80 °C) and low ( ⁇ 25 °C) temperature for 20 hours.
  • Tensile bond strength (TBS, an adhesion test). This test is performed according to EN 14509 (European product standard for sandwich panels), which refers to EN 1607. The foam sample's adhesion to the two facings (top and bottom) is measured simultaneously through a tensile test, perpendicular to the faces of the specimens.
  • EX and CE Discussion 3-Octylheptamethyltrisiloxane was selected and tested as lambda performance improvement enabler. Unexpectedly a consistent improvement of tensile bond strength was observed for tested WB PUR systems.

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Abstract

La présente divulgation concerne une composition de polyuréthane soufflée à l'eau qui comprend (1) un isocyanate ; (2) un composant réactif à l'isocyanate qui comprend au moins un polyéther polyol polyoxypropylène ; au moins un polypropylène glycol ; et au moins un polyéther polyol initié par la glycérine ; (3) un catalyseur ; (4) de l'eau en tant qu'agent gonflant ; (5) du 3-octylheptaméthyltrisiloxane ; et (6) un copolymère organo-silicone. Pour les divers modes de réalisation, le copolymère organo-silicone comprend un squelette de silicone avec des groupes fonctionnels qui comprennent des fractions polyéther. La divulgation concerne en outre un procédé de préparation d'une mousse rigide de polyuréthane comprenant la réaction d'une formulation qui comprend les étapes (1) à (6).
PCT/US2025/017179 2024-04-09 2025-02-25 Mousse rigide de polyuréthane soufflée à l'eau présentant des propriétés mécaniques améliorées Pending WO2025216809A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5334105B2 (ja) * 2009-02-09 2013-11-06 株式会社イノアックコーポレーション ポリウレタン発泡体
CN104169318A (zh) * 2012-03-15 2014-11-26 陶氏环球技术有限责任公司 低密度全水发泡聚氨酯硬质泡沫体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5334105B2 (ja) * 2009-02-09 2013-11-06 株式会社イノアックコーポレーション ポリウレタン発泡体
CN104169318A (zh) * 2012-03-15 2014-11-26 陶氏环球技术有限责任公司 低密度全水发泡聚氨酯硬质泡沫体

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