[go: up one dir, main page]

WO2024081090A1 - Procédé de chimiolyse de mousses de polyisocyanurate - Google Patents

Procédé de chimiolyse de mousses de polyisocyanurate Download PDF

Info

Publication number
WO2024081090A1
WO2024081090A1 PCT/US2023/032683 US2023032683W WO2024081090A1 WO 2024081090 A1 WO2024081090 A1 WO 2024081090A1 US 2023032683 W US2023032683 W US 2023032683W WO 2024081090 A1 WO2024081090 A1 WO 2024081090A1
Authority
WO
WIPO (PCT)
Prior art keywords
glycol
foam
rigid
stream
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2023/032683
Other languages
English (en)
Inventor
Carl William LISKEY
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.)
Stepan Co
Original Assignee
Stepan Co
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 Stepan Co filed Critical Stepan Co
Priority to EP23786379.0A priority Critical patent/EP4602099A1/fr
Publication of WO2024081090A1 publication Critical patent/WO2024081090A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl 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
    • C08G18/09—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
    • C08G18/22—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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to a process for the chemolysis of recycled rigid polyurethane and polyisocyanurate foams using a chemolysis reagent, to produce a polyol which is then used to produce new rigid foam.
  • Polyurethane (PUR) and polyisocyanurate (PIR) rigid foams are frequently used in construction applications due to their excellent insulation characteristics. These are highly cross-linked materials that provide good foam strength, thermal stability and insulation values. Recently, regulations and sustainability efforts have put a heightened emphasis on the circularity of materials, including in the construction industry. However, because these materials are highly cross-linked thermosets, they are difficult to reprocess or repurpose at the end of their lifetime. Also, for true circularity, the rigid foam should be able to be converted back into a foam instead of being downcycled into less valuable materials.
  • Glycolysis of PUR/PIR linkages is well known in the industry. Typically, in glycolysis diethylene glycol, or some other low molecular weight glycol is reacted with foam in the presence of a catalyst to prepare a glycolyzed, liquid or polyol product, sometimes referred to as a recyclate.
  • the most common route for chemolysis of PUR and PIR foams utilize diethylene glycol (DEG) as the glycolysis reagent.
  • DEG diethylene glycol
  • the resulting polyols typically have high OHv values (>550 mg KOH/g), high viscosity, and cannot be utilized in PIR formulations at high concentrations (U.S. Pat No. 5,556,889, U.S. Pat. No.
  • Another example utilizes dipropylene glycol to glycolyze PIR foams (Polymer Degradation and Stability, 2018, 156, 151 ), which enables lower hydroxyl values of the recyclate polyol.
  • the resulting recyclate polyol exhibits very high viscosity >15,000 cP at 40% incorporation and still high levels of free glycol would be observed.
  • dipropylene glycol contains secondary hydroxyl functionalities, which exhibit poor reactivity in a PIR formulations. Therefore, the overall recycled content of PIR foams with these recyclate polyols are relatively low under workable viscosities.
  • Another strategy is to incorporate the recyclate polyols into a prepolymer as disclosed in U.S. Patent Application Publication No. 2020/0040153. While possible in flexible foam applications, this strategy cannot be used to prepare rigid PIR foams due to the high viscosity of the intermediates. The resulting products also lead to foams with poor compressive strength.
  • U.S. Patent Application Publication No. 20050096400 teaches creating a polyurethane suspension via dissolution in a solvent followed by addition of a non-solvent, and evaporation of the solvent. The resulting polyol mixture can be used in flexible foam applications.
  • EP0835901 teaches a process for improving the rate of recyclate chemolysis. However, since the glycolysis is conducted with low molecular weight glycols (ethylene glycol or diethylene glycol), the resulting polyol still contains very high hydroxyl values and viscosity.
  • the new foams will largely be used in thermal insulation applications to reduce energy usage.
  • the global warming potential of a polyol based on recycled foam should be reduced compared to polyols based on virgin materials derived from petrochemicals.
  • the invention relates to a process comprising:
  • a C4-C10 difunctional aliphatic acid stream with a glycol stream selected from monoethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol or mixtures thereof, thereby forming a chemolysis reagent having a hydroxyl value of 400 to 900 mg KOH/g and a viscosity of 10 to 500 cP;
  • a recycled rigid foam material selected from rigid polyurethane foam, rigid polyisocyanurate foam or mixtures thereof, thereby forming a first polyol having a recycled foam content of up to 55 wt%, a hydroxyl value of less than 550 mg KOH/g, a viscosity of less than 10,000 cP, and a free glycol level of less than 35 wt%.
  • the invention relates to a process comprising:
  • a C3-C10 hydroxyl-containing aliphatic acid stream with a glycol stream selected from monoethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol or mixtures thereof, thereby forming a chemolysis reagent having a hydroxyl value of 400 to 900 mg KOH/g and a viscosity of 10 to 500 cP;
  • a recycled rigid foam material selected from rigid polyurethane foam, rigid polyisocyanurate foam or mixtures thereof, thereby forming a first polyol having a recycled foam content of up to 55 wt%, a hydroxyl value of less than 550 mg KOH/g, a viscosity of less than 10,000 cP, and a free glycol level of less than 35 wt%.
  • the invention relates to a process for producing a rigid PUR or PIR foam comprising reacting:
  • a polyol stream comprising 0.0 to 99.0 wt% of a polyester polyol and 1 .0 to 100.0 wt% of a first polyol;
  • urethane catalyst optionally, a urethane catalyst, an isocyanurate catalyst, or both;
  • the invention relates to a process comprising:
  • Fig. 1 shows insulation properties of rPIR Foams.
  • Fig. 2 shows flammability properties of rPIR foams via hot plate tests.
  • Fig. 3 shows Thermogravimetric Analysis of Recyclate Polyols.
  • the current subject matter relates to a process comprising reacting a C4-C10 difunctional aliphatic acid stream with a glycol stream selected from monoethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol or mixtures thereof, thereby forming a chemolysis reagent having a hydroxyl value of 400 to 900 mg KOH/g and a viscosity of 10 to 500 cP.
  • the chemolysis reagent is reacted with a recycled rigid foam material selected from rigid polyurethane foam, rigid polyisocyan urate foam or mixtures thereof, thereby forming a first polyol having a recycled foam content of up to 55 wt%, a hydroxyl value of less than 550 mg KOH/g, a viscosity of less than 10,000 cP, and a free glycol level of less than 35 wt%.
  • a recycled rigid foam material selected from rigid polyurethane foam, rigid polyisocyan urate foam or mixtures thereof
  • the difunctional aliphatic acid stream is selected from C4-C10 difunctional aliphatic acids.
  • the difunctional aliphatic acid stream is selected from adipic acid, succinic acid, azelaic acid, sebacic acid or mixtures thereof. More preferably, the aliphatic acid stream is adipic acid.
  • the glycol stream is selected from monoethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol or mixtures thereof.
  • the glycol stream is selected from Diethylene glycol, triethylene glycol and tetraethylene glycol.
  • the chemolysis reagent produced from the reaction of the glycol stream and the difunctional aliphatic acid stream has a hydroxyl value of 400 to 900 mg KOH/g, measured according to ASTM E222, and a viscosity of 10 to 500 cP at 25 °C, measured by a Brookfield viscometer Model LVPV.
  • the hydroxyl value of the chemolysis agent is 400 to 800 mg KOH/g.
  • the chemolysis agent comprises 10.0 to 50.0 wt% of aliphatic acid and 50.0 to 90.0 wt% glycol.
  • the process of reacting the C4-C10 difunctional aliphatic acid stream with the glycol stream is preferably conducted at a temperature of 160 to 240°C. More preferably, the temperature is 200 to 220°C. Preferably, the reaction is conducted at a pressure of 0.1 to 1 .0 atm.
  • the reaction to form the chemolysis reagent is preferably conducted with a Sn or Ti based catalyst.
  • the catalyst is selected from titanium n-butoxide, titanium lactic acid chelate or titanium propoxide Recycled rigid foam material
  • the recycled rigid foam material is selected from recycled rigid polyurethane foam, rigid polyisocyanurate foam or mixtures thereof. Typically, both urethane and isocyanurate functionalities are found in these foams, which are principally used in insulating materials such as laminate board, metal panel board, or appliance insulation.
  • the recycled foam material has a density of 1 .0 to 3.0 lb/ft 3 . More preferably, the density is 1 .5 to 2.5 lb/ft 3 .
  • the recycled foam material has an isocyanate to hydroxyl ratio of 100 to 400. More preferably, the ratio of isocyanate to hydroxyl is 105 to 300.
  • the recycled foam material is polyisocyanurate foam.
  • the foam preferably has an isocyanate to hydroxyl ratio of 240 to 400.
  • the first polyol is produced from the reaction between a recycled rigid foam material and the chemolysis reagent.
  • the first polyol has a recycled foam content of up to 55 wt%, a hydroxyl value of less than 550 mg KOH/g, measured according to ASTM E222, a viscosity of less than 10,000 cP at 25 °C, measured by a Brookfield viscometer Model LVPV and a free glycol, level, measured according to calibrated gas chromatography or gel-permeation chromatography, of less than 35 wt%.
  • the viscosity of the first polyol is less than 7,000 cP.
  • the hydroxyl level of the first polyol is less than 450 KOH/g.
  • the free glycol level is less than 25 wt%.
  • the reaction of the chemolysis reagent with the recycled rigid foam material is conducted at a temperature of 160 to 240°C. More preferably, the temperature is 200 to 220°C.
  • the reaction of the chemolysis reagent with the recycled rigid foam material is conducted at a pressure of 0.1 to 1 .0 atm.
  • the reaction of the chemolysis reagent with the recycled rigid foam material is conducted with a catalyst selected from potassium hydroxide, potassium acetate, lithium acetate, or zinc acetate.
  • the invention in another embodiment, relates to a process comprising: - reacting a C3-C10 hydroxyl-containing aliphatic acid stream with a glycol stream selected from monoethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol or mixtures thereof, thereby forming a chemolysis reagent having a hydroxyl value of 400 to 900 mg KOH/g and a viscosity of 10 to 500 cP;
  • a recycled rigid foam material selected from rigid polyurethane foam, rigid polyisocyanurate foam or mixtures thereof, thereby forming a first polyol having a recycled foam content of up to 55 wt%, a hydroxyl value of less than 550 mg KOH/g, a viscosity of less than 10,000 cP, and a free glycol level of less than 35 wt%.
  • the aliphatic acid stream is selected from C3-C10 hydroxyl-containing aliphatic acids.
  • the C3-C10 hydroxyl-containing aliphatic acid stream is selected from hydroxycarproic acid, hydroxypropionic acid, hydroxypentanoic acid or mixtures thereof.
  • the hydroxyl-containing aliphatic stream may also preferably be selected from dehydrated hydroxy-containing aliphatic acid selected from caprolactone, valerolactone or mixtures thereof.
  • the hydroxyl-containing aliphatic stream may also preferably be selected from oligomeric mixtures of the hydroxyl-containing aliphatic stream.
  • the current invention relates to a process comprising reacting a glycol adipate chemolysis agent having a hydroxyl value of 400 to 900 mg KOH/g and a viscosity of 10 to 500 cP with a recycled rigid foam material selected from rigid polyurethane foam, rigid polyisocyanurate foam or mixtures thereof, thereby forming a first polyol having a recycled foam content of up to 55 wt%, a hydroxyl value of less than 550 mg KOH/g, a viscosity of less than 10,000 cP, and a free glycol level of less than 35 wt%.
  • Suitable glycol adipates include the polyester polyol derived from diethylene glycol and adipic acid with a hydroxyl value of less than 600 mg KOH/g.
  • the present subject matter relates to a process for producing a rigid PUR or PIR foam comprising reacting a polyisocyanate, water, a surfactant and a polyol stream.
  • Water is used in an amount within the range of 0.1 to 3 wt% based on the amount of polyester polyol in the rigid foam formulation.
  • the water is in the range of 0.2 to 1 .0 wt%. More preferably, the water is present in an amount from 0.2 to 0.6 wt%.
  • the polyol stream comprises 0.0 to 99.0 wt% of a polyester polyol and 1 .0 to 100.0 wt% of the first polyol described above.
  • the reaction includes a urethane catalyst, an isocyanurate catalyst, or both.
  • the reaction can also include a blowing agent, a surfactant, and a flame retardant.
  • Rigid foams produced from the above process can be formulated over a wide index range.
  • index means the ratio of isocyanate to hydroxyl equivalents multiplied by 100.
  • Rigid PU foams are produced at a relatively low index, e.g., 90 to 150, while rigid PIR foams are usually made at relatively high index, e.g., 180 to 350.
  • the polyester polyols are preferably selected from aromatic polyester polyols. Suitable aromatic polyester polyols are well known, and many are commercially available.
  • the polyester polyols can be produced from aromatic dicarboxylic acids or their derivatives, especially one or more phthalate-based compounds or compositions (e.g., terephthalic acid, dimethyl terephthalate, DMT bottoms, phthalic anhydride, isophthalic acid, and the like) and one or more glycols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1 ,3-propanediol, 2-methyl-1 ,3-propanediol, glycerin, trimethylolpropane, and the like), optionally with some aliphatic dicarboxylic acid (e.g., adipic acid, succinic acid) content.
  • the aromatic polyester polyol comprises recurring units from adipic
  • aromatic polyester polyols include products available from Stepan Company under the STEPANPOL® mark, particularly the STEPANPOL® PS- series of products, such as STEPANPOL® PS-1812, STEPANPOL® PS-1912,
  • STEPANPOL® PS-2352 STEPANPOL® PS-2412, STEPANPOL® PS-2520,
  • STEPANPOL® PS-2602 STEPANPOL® PS-3021 , STEPANPOL® PS-3422,
  • STEPANPOL® PS-3524, and TERATE® mark such as TERATE® HT-5503, TERATE®
  • HT-5510 TERATE® HT-2006V HT-5510 TERATE® HT-2006V and the like.
  • Suitable aromatic polyester polyols are also available from Huntsman (TEROL® polyols).
  • the aromatic polyester polyols have hydroxyl numbers, as measured by ASTM E- 222, within the range of 150 to 400 mg KOH/g, from 160 to 350 mg KOH/g, or in some aspects from 200 to 300 mg KOH/g, or from 230 to 250 mg KOH/g.
  • the polyols have, in some aspects, number-average molecular weights from 280 to 1100 g/mol, or from 300 to 700 g/mol., measured according to ASTM E222.
  • the aromatic polyester polyols preferably have acid values, measured according to ASTM E301 of less than 5 mg KOH/g, or less than 2 mg KOH/g, or less than 1 mg KOH/g.
  • the polyols have viscosities, measured at 25°C with a Brookfield viscometer Model LVPV, of less than 25,000 cP at 25°C, less than 10,000 cP at 25°C, or less than 5,000 cP at 25°C. In some aspects, the viscosities are within the range of 100 cP to 10,000 cP at 25°C or from 500 cP to 5,000 cP at 25°C.
  • polyisocyanates suitable for use are well known, and many are commercially available from Dow Chemical (under the PAPITM, ISONATE®, and VORONATETM marks), Evonik (VESTANAT®), BASF (LU P RAN ATE®), Covestro (MONDUR® and DESMODUR®), Huntsman (RUBINATE®), and other suppliers of polyurethane intermediates.
  • Polyisocyanates suitable for use have average NCO functionalities (reactive groups per molecule) within the range of 2.0 to 3.0.
  • the polyisocyanate can be aromatic or aliphatic.
  • Aromatic polyisocyanates include, e.g., toluene diisocyanates (TDI), 4,4’-diphenylmethane diisocyanates (MDI), or polymeric diisocyanates (p-MDI), or the like.
  • Aliphatic polyisocyanates include, e.g., hexamethylene diisocyanate (HDI), hydrogenated MDI, cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), trimethyl or tetramethylhexamethylene diisocyanate (TMXDI), or the like.
  • the catalyst When a catalyst is used in the process for producing a rigid PUR or PIR foam, the catalyst includes a urethane catalyst, an isocyanurate catalyst, or both.
  • Catalysts suitable for use include compounds that catalyze the reaction of isocyanates and water (“blowing catalysts”) and compounds that catalyze the formation of urethane, urea, or isocyanurate linkages (“PU catalysts,” “PIR catalysts,” or “trimerization catalysts”).
  • Amine catalysts are generally tertiary amines or alkanolamines and their mixtures with a diluent, typically a glycol such as dipropylene glycol.
  • a diluent typically a glycol such as dipropylene glycol.
  • Examples include bis(2- dimethylaminoethyl)ether, N,N-dimethylaminopropylamine, N,N-dimethylethanolamine, triethylenediamine, benzyldimethylamine, N,N-dimethylcyclohexylamine, N,N,N’,N’,N”- pentamethyldiethylenetriamine (PMDETA), diethanolamine, N-ethylmorpholine, N,N,N’N’-tetramethylbutanediamine, 1 ,4-diaza[2.2.2]bicyclooctane, and the like, and combinations thereof.
  • Examples include POLYCAT® 5 or POLYCAT® 8 (Evonik) and
  • catalysts include carboxylates (e.g., potassium acetate, potassium octoate), organotin compounds (e.g., dibutyltin dilaurate, stannous octoate), quaternary ammonium compounds (e.g., N-(2-hydroxyethyl)trimethylammonium chloride), and the like, and combinations thereof.
  • carboxylates e.g., potassium acetate, potassium octoate
  • organotin compounds e.g., dibutyltin dilaurate, stannous octoate
  • quaternary ammonium compounds e.g., N-(2-hydroxyethyl)trimethylammonium chloride
  • Suitable catalysts are available from Evonik (TEGOAMIN® amine catalysts, KOSMOS® metal catalysts, DABCO® TMR catalysts, DABCO® K-15 catalysts, and POLYCAT® catalysts), Huntsman (JEFFCAT® catalysts), King Industries (K-KAT® catalysts), Momentive (NIAX® catalysts), Galata Chemicals (FOMREZ® organotin catalysts), and others.
  • the blowing agents can include aliphatic or cycloaliphatic C4-C6 hydrocarbons, water, mono- and polycarboxylic acids and their salts, tertiary alcohols, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), halogenated hydrocarbons, hydrofluoroolefins (HFOs), and the like, and their mixtures.
  • CFCs chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • HFOs hydrofluoroolefins
  • Surfactants are used in the process for producing a rigid PUR or PIR foam to enable the production of a closed-cell rigid foam.
  • Representative examples include products available commercially from Evonik, Dow Chemical, Siltech, Momentive Performance Materials, and in particularly include TEGOSTAB® B silicone surfactants (Evonik), SILSTAB® silicone surfactants (Siltech), VORASURFTM surfactants (Dow), NIAX® surfactants (Momentive) and others.
  • TEGOSTAB® B silicone surfactants Evonik
  • SILSTAB® silicone surfactants Siltech
  • VORASURFTM surfactants Low
  • NIAX® surfactants Mimentive surfactants
  • Other suitable surfactants are polysiloxanes or other silicon-based surfactants.
  • suitable flame-retardant additives include solid or liquid compounds containing phosphorus, chlorine, bromine, boron, or combinations of these elements. Examples include brominated phthalate diols, ammonium polyphosphates, triethyl phosphate, tris(2- chloroisopropyl) phosphate, tetrakis(2-chloroethyl)ethylene diphosphate, tris(
  • brominated phthalate diols include ammonium polyphosphates, triethyl phosphate, tris(2- chloroisopropyl) phosphate, tetrakis(2-chloroethyl)ethylene diphosphate, tris(
  • Water is used as a reactant in the process for producing a rigid PUR or PIR foam.
  • the amount of water used depends on several factors, including the amount of polyisocyanate, the desired index, the nature and amount of the polyester polyol, the nature and amount of the fatty acid derivative, which catalysts, surfactants, and blowing agents are used, and other factors.
  • water is used in an amount within the range of 0.1 to 3 wt.%, 0.2 to 1 wt.%, or 0.2 to 0.6 wt.% based on the amount of polyester polyol in the rigid foam formulation.
  • the chemolysis agent is prepared by reacting adipic acid with diethylene glycol.
  • the target of the hydroxyl number was 650 mg KOH/g.
  • Adipic acid (156 g), diethylene glycol (482 g) and Tyzor®-LA (860 ppm) are charged to a 4-neck round bottomed flask equipped with overhead stirring, a thermocouple, nitrogen sparge inlet and a column attached to a reflux condenser. The reactor is heated to 220 °C under nitrogen sparge until the acid value is ⁇ 5 mg KOH/g and nearly the theoretical distillate is collected.
  • the polyisocyanurate core foam (index 290) is charged to the round bottom flask in 15 g increments followed by potassium acetate (up to 1 wt %) as a catalyst. The foam is charged continuously as it dissolves until 27% recycled content in the polyol is achieved. Additional catalyst is added if the reaction rate slows. The recyclate polyol is used without further purification.
  • Example 2 Recyclate Polyol 2
  • the chemolysis agent from Example 1 is charged to a 4-neck round bottomed flask equipped with overhead stirring, a thermocouple, nitrogen inlet and a column attached to a reflux condenser.
  • the polyisocyanurate core foam (index 290) is charged to the round bottom flask in 15 g increments followed by potassium acetate (up to 1 wt %) as a catalyst.
  • the foam is charged continuously as it dissolves until 40% recycled content in the polyol is achieved. Additional catalyst is added if the reaction rate slows. The recyclate polyol is used without further purification.
  • STEPANPOL® PS-2352 aromatic polyester polyol, hydroxyl number about 240 mg KOH/g is used as a polyol for making rigid foam.
  • Recyclate polyol properties are shown in Table 1 .
  • Rigid polyisocyanurate foams are prepared with the general formulation shown in Table 2.
  • the B-side blend (polyolester polyol, recyclate polyol, flame retardant, catalysts, surfactant, water and pentanes blowing agent) are mixed together with an overhead mixer.
  • the B-side and MONDUR® 489 polymeric MDI, product of Covestro
  • the two components are weighed into a one-quart cup and are mixed at >2500 rpm for 5 seconds, and the mixture is poured into a one-gallon cup.
  • the cream and gel times are recorded and the catalyst is adjusted to match reactivity. Due to the varying hydroxyl values of the mixture, the index is adjusted to keep a constant A/B ratio.
  • the crown is cut at 90 seconds.
  • the foam properties are shown in Table 2.
  • Table 3 shows improved compressive strength of the PIR foam compared to the control foam by up to 18%. While a polyether polyol can reduce the hydroxyl value relative to diethylene glycol, the foam has a lower compressive strength by up to 19%.
  • the foam samples are allowed to cure for at least 24 hours and cut to dimensions of 4” x 4” x 1 .25”.
  • the mass, thickness, and density are measured. Samples are placed on a preheated (1200 °C) hotplate for 15 min, during which time the temperature is gradually decreased to 1000 °C. Samples are weighed, cut in half to determine thickness, and analyzed for charring characteristics. A reduced mass loss and thickness loss indicates improved flammability properties for PIR foams. The results are shown in Figure 2.
  • Figure 2 demonstrates improved flammability properties of the inventive example compared to the DEG chemolyzed sample. Specifically, flammability properties are much worse for comparative example 4 when rPIR content approach 5% recycled content in foam (66/34 (PS-2352/Comp Ex 4)). Thermal Stability based on Thermogravimetric Analysis (TGA)
  • TGA was conducted using a Discovery TGA instrument (TA instruments). Polyol samples (30-40 mg) are tested in air at 25 ml/min flow rate. Temperature is increased from 25 °C to 700 °C at 10 °C/min. Data is plotted as mass retentation (%) versus temperature. A higher mass retention at a given temperature indicates higher thermal stability.
  • Figure 3 shows improved mass retention of the inventive sample compared to the recyclate polyol chemolyzed with diethylene glycol. This further demonstrates the improved flammability performance of the inventive recyclate polyols.

Landscapes

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

Abstract

La présente invention concerne un procédé comprenant les étapes consistant à : - faire réagir un flux d'acide aliphatique C4-C10 difonctionnel avec un flux de glycol choisi parmi le monoéthylène glycol, le diéthylène glycol, le propylène glycol, le triéthylène glycol, le tétraéthylène glycol ou des mélanges de ceux-ci, formant ainsi un réactif de chimiolyse ayant une valeur hydroxyle de 400 à 900 mg KOH/g et une viscosité de 10 à 500 cP ; - faire réagir le réactif de chimiolyse avec un matériau de mousse rigide recyclée choisi parmi une mousse de polyuréthane rigide, une mousse de polyisocyanurate rigide ou des mélanges de celles-ci, formant ainsi un premier polyol ayant une teneur en mousse recyclée allant jusqu'à 55 % en poids, une valeur hydroxyle inférieure à 550 mg KOH/g, une viscosité inférieure à 10 000 cP, et un taux de glycol libre inférieur à 35 % en poids.
PCT/US2023/032683 2022-10-11 2023-09-14 Procédé de chimiolyse de mousses de polyisocyanurate Ceased WO2024081090A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP23786379.0A EP4602099A1 (fr) 2022-10-11 2023-09-14 Procédé de chimiolyse de mousses de polyisocyanurate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202263414967P 2022-10-11 2022-10-11
US63/414,967 2022-10-11

Publications (1)

Publication Number Publication Date
WO2024081090A1 true WO2024081090A1 (fr) 2024-04-18

Family

ID=88297263

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2023/032683 Ceased WO2024081090A1 (fr) 2022-10-11 2023-09-14 Procédé de chimiolyse de mousses de polyisocyanurate

Country Status (2)

Country Link
EP (1) EP4602099A1 (fr)
WO (1) WO2024081090A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5556889A (en) 1994-12-22 1996-09-17 Basf Schwarzheide Gmbh Preparation of recyclate polyols
EP0835901A2 (fr) 1996-10-08 1998-04-15 Samsung Electronics Co., Ltd. Procédé de préparation de polyols de recyclage et procédé pour fabriquer des mousses de polyuréthane
US6087409A (en) 1997-04-29 2000-07-11 Basf Aktiengesellschaft Production of rigid polyurethane foams
US6359022B1 (en) 1997-10-10 2002-03-19 Stepan Company Pentane compatible polyester polyols
US20050096400A1 (en) 2003-10-30 2005-05-05 Mobius Technologies, Inc. Method for recycling polyurethane and a composition comprising recycled polyurethane
US20200040153A1 (en) 2018-08-03 2020-02-06 Magna Seating Inc Method to increase recycled content into polyurethane foam
DE102020126425A1 (de) * 2020-10-08 2022-04-14 H & S Anlagentechnik Gmbh Verfahren zur Herstellung einer Polyolkomposition enthaltend aus Polyurethan-Abfällen freigesetzte Polyole

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5556889A (en) 1994-12-22 1996-09-17 Basf Schwarzheide Gmbh Preparation of recyclate polyols
EP0835901A2 (fr) 1996-10-08 1998-04-15 Samsung Electronics Co., Ltd. Procédé de préparation de polyols de recyclage et procédé pour fabriquer des mousses de polyuréthane
US6087409A (en) 1997-04-29 2000-07-11 Basf Aktiengesellschaft Production of rigid polyurethane foams
US6359022B1 (en) 1997-10-10 2002-03-19 Stepan Company Pentane compatible polyester polyols
US20050096400A1 (en) 2003-10-30 2005-05-05 Mobius Technologies, Inc. Method for recycling polyurethane and a composition comprising recycled polyurethane
US20200040153A1 (en) 2018-08-03 2020-02-06 Magna Seating Inc Method to increase recycled content into polyurethane foam
DE102020126425A1 (de) * 2020-10-08 2022-04-14 H & S Anlagentechnik Gmbh Verfahren zur Herstellung einer Polyolkomposition enthaltend aus Polyurethan-Abfällen freigesetzte Polyole

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
POLYMER DEGRADATION AND STABILITY, vol. 156, 2018, pages 151
POLYMERS, vol. 12, 2020, pages 1752

Also Published As

Publication number Publication date
EP4602099A1 (fr) 2025-08-20

Similar Documents

Publication Publication Date Title
EP0935624B1 (fr) Mousses rigides de polyurethane
WO2010015642A1 (fr) Polyesters aromatiques, mélanges de polyols les comprenant et produits résultant de ceux-ci
CN107001565A (zh) 硬质聚氨酯泡沫及其制备方法
CN102449025B (zh) 由间苯二甲酸和/或对苯二甲酸及低聚环氧烷烃制备的聚酯多元醇
AU2003251923A1 (en) Aromatic polyester polyols
KR20170125938A (ko) 유리질 폴리우레탄의 제조를 위한 폴리부타디엔올
BR112014029715A2 (pt) poliesterol, método para a produção de espumas rígidas de poliuretano ou espumas rígidas de poliisocianurato, espuma rígida de poliuretano, uso das espumas rígidas de poliuretano e componente de poliol.
JP5833155B2 (ja) 軟質ポリウレタンフォーム製造用ポリオール組成物
US6710095B2 (en) Polyol containing glycol adduct for use in producing rigid foam
JP4461417B2 (ja) ポリイソシアネート組成物および硬質ポリウレタンフォームの製造方法
JP2002155125A (ja) ポリウレタン変性ポリイソシアヌレートフォームの製造方法
JP5866839B2 (ja) 硬質ポリウレタンフォーム組成物
EP3426708B1 (fr) Mousses de polyuréthane et de polyisocyanurate et procédés pour leur production
CN114651024B (zh) 含酰亚胺的聚酯多元醇和膨胀型硬质泡沫
CA2253216A1 (fr) Mousses rigides de polyurethane modifiees par de l&#39;isocyanurate
MX2011004694A (es) Procedimiento para la fabricacion de poliesterpolioles con bajas cantidades de rsiduos de dioxano.
WO2024081090A1 (fr) Procédé de chimiolyse de mousses de polyisocyanurate
JP5592518B2 (ja) 軟質ポリウレタンフォーム製造用ポリオール組成物
JP2002356533A (ja) 硬質ポリウレタンフォーム用ポリイソシアネート組成物、及びそれを用いた硬質ポリウレタンフォームの製造方法
JP2004010806A (ja) 硬質ポリウレタンフォーム用ポリイソシアネート組成物、並びに該組成物の製造方法及びそれを用いた硬質ポリウレタンフォームの製造方法
US20260035505A1 (en) Imide-containing polyester polyols and intumescent rigid foams
AU2024252240A1 (en) Low residual momomer glycol aromatic polyester polyols
EP4608889A1 (fr) Composant réactif à l&#39;isocyanate présentant une compatibilité améliorée vis-à-vis des hydrocarbures
WO2023277872A1 (fr) Polyol et mousse fabriquée à partir de celui-ci
JP2002356530A (ja) 硬質ポリウレタンフォーム用ポリイソシアネート組成物、及びそれを用いた硬質ポリウレタンフォームの製造方法

Legal Events

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

Ref document number: 23786379

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023786379

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023786379

Country of ref document: EP

Effective date: 20250512

WWP Wipo information: published in national office

Ref document number: 2023786379

Country of ref document: EP