WO2026020341A1 - Polyester polyol d'origine biologique, procédé de préparation associé et mousse de polyuréthane - Google Patents

Polyester polyol d'origine biologique, procédé de préparation associé et mousse de polyuréthane

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Publication number
WO2026020341A1
WO2026020341A1 PCT/CN2024/107157 CN2024107157W WO2026020341A1 WO 2026020341 A1 WO2026020341 A1 WO 2026020341A1 CN 2024107157 W CN2024107157 W CN 2024107157W WO 2026020341 A1 WO2026020341 A1 WO 2026020341A1
Authority
WO
WIPO (PCT)
Prior art keywords
bio
koh
polyester polyol
acid
mixture
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/CN2024/107157
Other languages
English (en)
Inventor
Yanbin FAN
Yuying YANG
Shaoguang Feng
Rongbin LAN
Shouxue GUO
Yinzhong Guo
Xiaomei Song
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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 Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to PCT/CN2024/107157 priority Critical patent/WO2026020341A1/fr
Publication of WO2026020341A1 publication Critical patent/WO2026020341A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/14—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic 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
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids

Definitions

  • the present disclosure relates to a bio-based polyester polyol, a process of preparing it and use in polyurethane foams.
  • the inventors After persistent exploration, the inventors have surprisingly developed a novel bio-based polyester polyol with a tunable functionality from 2 to 3 in a cost effective way by using a reaction product of a bio-based polyol (e.g., glycerol) with both bio-based di-acids and mono-acids.
  • a bio-based polyol e.g., glycerol
  • the amount of mono-acid is tailored to access the desired end functionality, as the mono-acid is a chain terminator, which allows for access to 100%bio-based multi-functional polyester polyols using cost competitive monomers of bio-based glycerol and bio-based monoacids (e.g., oleic acid, stearic acid, lauric acid, etc. ) , thus avoiding the use of expensive bio-based 1, 3-propane diol.
  • cost competitive monomers of bio-based glycerol and bio-based monoacids e.g.,
  • a process for preparing a bio-based polyester polyol via heating and distilling which comprises:
  • a polyurethane foam composition which comprises:
  • a fourth aspect of the present disclosure provides an article (e.g., PU foam) made by using the polyurethane foam composition.
  • Figure 1 shows SEM Images of the polyurethane foams containing different bio-contents according to the present invention.
  • Figure 2 shows solubility spheres of CP450, IE-7 and castor oil according to the present invention.
  • bio-based and/or “biomass-based” refers to those substances isolated from, derived from or manufactured from renewable raw material sources, for example, natural oils including animal and vegetable oils, preferably vegetable oils.
  • natural oils including animal and vegetable oils, preferably vegetable oils.
  • vegetable and animal oils that are optionally used include, but are not limited to, soybean oil, safflower oil, linseed oil, corn oil, sunflower oil, olive oil, canola oil, sesame oil, cottonseed oil, palm oil, rapeseed oil, tung oil, fish oil, or a blend of any of these oils.
  • any partially hydrogenated or epoxidized natural oil or genetically modified natural oil can be used to obtain the bio-based substances.
  • oils include, but are not limited to, high oleic safflower oil, high oleic soybean oil, high oleic peanut oil, high oleic sunflower oil, high oleic canola oil, and high erucic rapeseed oil.
  • ′′renewable resource′′ is used herein to designate animal and plant fats or oils as distinguished from, for instance, petroleum oils and derivatives.
  • hydroxyl number′′ indicates the concentration of hydroxyl moieties in a composition of polymers, particularly polyols.
  • a hydroxyl number represents mg KOH/g of polyol.
  • a hydroxyl number is determined by acetylation with pyridine and acetic anhydride in which the result is obtained as the difference between two titrations with KOH solution.
  • a hydroxyl number is, thus, defined as the weight of KOH in milligrams that will neutralize the acetic anhydride capable of combining by acetylation with 1 gram of a polyol.
  • a higher hydroxyl number indicates a higher concentration of hydroxyl moieties within a composition.
  • Fn′′ average hydroxyl functionality
  • the bio-based polyester polyol is prepared from 100%biomass-based raw materials, which comprises:
  • the di-functional carboxylic acids are independently selected from sebacic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, decanedicarboxylic acid, malonic acid, heptanoic acid, 2-methyl-1, 6-hexanedioic acid, dodecanedioic acid, maleic acid, fumaric acid and a combination thereof.
  • the di-functional carboxylic acid is in amount of 22-70 %by weight, 22-60 %by weight, 22-50 %by weight, 22-40 %by weight, 22-30 %by weight, 30-70 %by weight, 30-60 %by weight, 30-50 %by weight, 30-40 %by weight, 40-70 %by weight, 40-60 %by weight or 40-50 %by weight.
  • the polyols comprise average hydroxyl functionality of ⁇ 3, ⁇ 4 or ⁇ 5, which are independently selected from triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol and a combination thereof.
  • the polyol is in amount of 6-60 %by weight, 6-50 %by weight, 6-40 %by weight, 6-30 %by weight, 6-20 %by weight, 10-60 %by weight, 10-50 %by weight, 10-40 %by weight, 10-30 %by weight, 10-20 %by weight, 30-60 %by weight, 30-50 %by weight, 30-40 %by weight, 40-60 %by weight, 40-50 %by weight or 50-60 %by weight.
  • the monoacids are those organic acids having 1-30, 4-20 or 8-12 carbon atoms, which can be independently selected from oleic acid, stearic acid, lauric acid, palmitic acid, formic acid, acetic acid, propionic acid, butyric acid, capric acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid and a combination thereof.
  • the monoacid is in amount of 12-44%by weight, 12-40%by weight, 12-30%by weight, 12-20%by weight, 20-44%by weight, 20-40%by weight, 20-30%by weight, 30-44%by weight, 30-40%by weight or 40-44%by weight.
  • the bio-based polyester polyol can be prepared in a one-pot process with gradual heating process, that is, the mixture of at least one of bio-based C4-C20 di-functional carboxylic acids, at least one of bio-based polyols and at least one of bio-based monoacids can be charged and reacted in a single reaction vessel.
  • the gradual heating process can inhibit explosive boiling of water in reaction system due to the extreme hydrophobicity of the bio-based raw materials.
  • the one-pot process can comprise three heating stages.
  • a first heating stage the mixture is heated to a temperature in a range of 160-175°C, 162-173°C or 165-170°C with a heating ramp of ⁇ 30°C per hour, ⁇ 20°C per hour, or ⁇ 10°C per hour.
  • the heating ramp is greater than 0°C per hour, greater than 1°C per hour, greater than 5°C per hour or greater than 10°C per hour.
  • the first heating stage comprises heating to 170°C with stirring at 50-200 rpm and staying at a temperature in a range of 160-175°C, 162-173°C or 165-170°C for a digestion time of no less than 0.5 hours, 0.5-20 hours, 1-10 hours or 4-8 hours in an inert atmosphere, for example, with nitrogen flow ⁇ 2L/ (kg ⁇ min) .
  • the mixture is heated to a temperature in a range of 175-200°C, 180-195°C or 185-190°C with a heating ramp of ⁇ 30°C per hour, ⁇ 20°C per hour or ⁇ 10°C per hour.
  • the heating ramp is greater than 0°C per hour, greater than 1°C per hour, greater than 5°C per hour or greater than 10°C per hour.
  • the second heating stage comprises heating to -175-200°C with stirring at 50-200 rpm and staying at a temperature in a range of 175-200°C, 180-195°C or 185-190°C for a digestion time of no less than 0.5 hours, 0.5-20 hours, 1-10 hours or 4-8 hours in an inert atmosphere, for example, with nitrogen flow ⁇ 2L/ (kg ⁇ min) .
  • the mixture is heated, in presence of catalysts, to a temperature in a range of 175-200°C, 180-195°C or 185-190°C with a heating ramp of ⁇ 30°C per hour, ⁇ 20°C per hour or ⁇ 10°C per hour.
  • the heating ramp is greater than 0°C per hour, greater than 1°C per hour, greater than 5°C per hour or greater than 10°C per hour.
  • the third heating stage comprises heating to 175-250°C with stirring at 50-200 rpm and staying at a temperature in a range of 175-250°C, 185-240°C or 195-235°C for a digestion time of no less than 0.5 hours, 0.5-20 hours, 1-10 hours or 4-8 hours in an inert atmosphere, for example, with nitrogen flow ⁇ 2L/ (kg ⁇ min) .
  • the heating is conducted, optionally under stirring, in an inert atmosphere (e.g., nitrogen atmosphere) and/or under a negative pressure in a range of 5-100 mbar, 20-80 mbar or 40-60 mbar.
  • an inert atmosphere e.g., nitrogen atmosphere
  • a negative pressure in a range of 5-100 mbar, 20-80 mbar or 40-60 mbar.
  • the process comprises: cooling the bio-based polyester polyol down to a temperature in a range of 50-70°C or 55-65 °C before packaging.
  • the catalysts are not limited as long as they can promote reaction for forming polyester polyol, which can comprise titanium esters, such as tetrabutyl titanate, tetrapropyl titanate, etc; organic tin compounds, such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin cycloalkanoate, dibutyltin oxide, and reaction products of phthalates, and dialkyltin diacetate, such as bis (acetylacetonate) dibutyltin; dialkyltin oxide, such as dibutyltin oxide; organic aluminum compounds, such as aluminum triacetylacetylate, aluminum triethylpyruvate, etc.
  • titanium esters such as tetrabutyl titanate, tetrapropyl titanate, etc
  • organic tin compounds such as dibutyltin dilaurate, dibut
  • the catalyst is selected from tetrabutyl titanate, dibutyltin dilaurate, bis (acetylacetonate) dibutyltin, etc., preferably dibutyltin dilaurate or bis (acetylacetonate) dibutyltin.
  • the bio-based polyester polyol meets the following:
  • the polyurethane foam composition comprises:
  • Part I can further comprise other/additional bio-based polyols which is different from the bio-based polyester polyol of the present invention.
  • the additional bio-based polyols comprises castor oils, soybean oil, olive oil, palm oil, palm kernel oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, safflower oil, flaxseed oil and sunflower oil.
  • an isocyanate component is any organic compound or mixture having an average of more than 1, preferably an average of at least about 1.8, isocyanate groups per organic molecule
  • isocyanates which are optionally used in the present invention include aliphatic, cycloaliphatic, arylaliphatic and aromatic isocyanates.
  • suitable aromatic isocyanates can be selected from the group consisting of diphenylmethanediisocyanate (MDI) , toluene diisocyanate (TDI) , naphthalene diisocyanate (NDI) , phenylene diisocyanate, any isomers thereof and any combinations thereof.
  • the isomers of MDI comprise 4, 4'-MDI, 2, 4'-MDI, 2, 2'-MDI, etc.; the isomers of TDI comprise 2, 3-TDI, 2,4-TDI, 2, 5-TDI, 2, 6-TDI, 3, 4-TDI, 3, 5-TDI, etc.; the isomers of NDI comprise 1, 5-NDI, 1, 2-NDI, 1, 3-NDI, 1, 4-NDI, 1, 6-NDI, 1, 7-NDI, 1, 8-NDI, 2, 3-NDI, 2, 6-NDI, 2, 7-NDI, etc; the isomers of phenylene diisocyanate comprise 1, 2-phenylene diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, etc.
  • isocyanates are optionally used, such as the commercially available mixtures of 2, 4-and 2, 6-isomers of toluene diisocyanates.
  • a crude polyisocyanate (pMDI) is optionally used in the practice of this invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamine or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine.
  • TDI/MDI blends are optionally used.
  • MDI or TDI based prepolymers are optionally used, made with polyols described herein.
  • isocyanate-terminated prepolymers can be prepared by reacting an excess of polyisocyanate with at least one polyol, including aminated polyols or imines/enamines thereof.
  • aliphatic polyisocyanates examples include tetramethylene diisocyanate and hexamethylene diisocyanate (HDI) , 1, 12-dodecane diisocyanate, 2, 2, 4-trimethyl-hexamethylene diisocyanate, 2, 4, 4-trimethyl-hexamethylene diisocyanate, 2-methyl-1, 5-pentamethylene diisocyanate; alicyclic diisocyanates, as well as dimers and trimers thereof, such as, for example, isophorone diisocyanate (IPDI) and dicyclohexyl methane diisocyanate (HMDI) , 1, 4-cyclohexane diisocyanate, 1, 3-bis- (isocyanatomethyl) cyclohexane and mixtures thereof.
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • HMDI dicyclohexyl methane diisocyanate
  • the isocyanate component may comprise at least MDI, TDI, HDI, HMDI, XDI, PDI or their combinations, or their prepolymers.
  • the isocyanate prepolymer is a reaction product of isocyanate, the bio-based polyester polyol of the present invention and optionally additional bio-based polyols.
  • the blowing agent can comprise a chemical blowing agent and/or a physical blowing agent.
  • the physical blowing agent suitable for this invention include both unsaturated hydrofluoroolefins (HFO) and unsaturated hydrochlorofluoroolefin (HCFO) . They have negligible (low or zero) ozone-depletion and low global warming potential.
  • Suitable HFO and HCFO blowing agents include but not limited to cis-1, 1 , 1 , 4, 4, 4-Hexafluoro-2-butene (HF 0-1336mzz (Z) ) , trans-1, 1, 1 , 4, 4, 4-hexafluoro-2-butene (HFO-1336mzz (E) ) , l, l, l, 4, 4, 5, 5, 5-octafluoro-2-pentene (HFO-1438mzz) , 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf) , trans 1, 3, 3, 3-Tetrafluoroprop-l-ene (HFO 1234ze) , heptafluorobutene isomer (HFO1327) , heptafluoropentene isomers (HFO1447) , octafluoropentene isomers (HFO1438) , nonafluoropentene (HFO1429) dichlorotrifluoro
  • blowing agents are commercially available materials known as LB A, GBA, Opteon TM 1100, Opteon TM 1150, etc. Hydrofluoroolefin physical blowing agents that do not contain any chlorine atom are more preferred for use in this invention.
  • the polyurethane foam composition further include 1 to 5 wt. %of a chemical blowing agent comprising water, where the wt. %is based on the total weight of the polyurethane foam composition.
  • a chemical blowing agent comprising water
  • the chemical blowing agent can be from a lower limit of 1, 1.5, 2 or 2.5 wt. %to an upper limit of 5, 4 or 3.5 wt. %of the total weight of the polyurethane foam composition.
  • Additional chemical blowing agents may be used are those CO 2 generating materials that are not based on organic acids.
  • the chemical blowing agent is water.
  • the chemical blowing agent does not contain any formic acid.
  • the polyurethane foam composition further include 0.5 to 6 wt. %of at least one catalyst, where the wt. %is based on the total weight of the polyurethane foam composition. All individual values and subranges from 0.5 to 6 wt. %of the at least one catalyst are included; for example, the at least one catalyst can be from a lower limit of 0.5, 1, 2 or 3 wt. %to an upper limit of 6, 5 or 4 wt. %of the total weight of the polyurethane foam composition.
  • the at least one catalyst may be a blowing catalyst, a gelling catalyst, or combinations thereof.
  • the blowing catalysts and gelling catalysts may be differentiated by a tendency to favor either the urea (blow) reaction, in the case of the blowing catalyst, or the urethane (gel) reaction, in the case of the gelling catalyst.
  • the amount of any one individual catalyst in the at least one or more catalysts can be as low as 0.1 to 0.2 wt. %or less.
  • blowing catalysts examples include, but are not limited to, short chain tertiary amines or tertiary amines containing an oxygen.
  • blowing catalysts include bis- (2-dimethylaminoethyl) ether; pentamethyldiethylene-triamine, triethylamine, tributyl amine, N, N-dimethylaminopropylamine, dimethylethanolamine, N, N, N′, N′-tetra-methylethylenediamine, and combinations thereof, among others.
  • gelling catalysts e.g., catalyst that can tend to favor the gel reaction
  • examples of the gelling catalysts include, but are not limited to, organometallic compounds, cyclic tertiary amines and/or long chain amines, e.g., that contain several nitrogen atoms, and combinations thereof.
  • Organometallic compounds include organotin compounds, such as tin (II) salts of organic carboxylic acids, e.g., tin (II) diacetate, tin (II) dioctanoate, tin (II) di ethylhexanoate, 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) di ethylhexanoate, and tin (II) dilaurate
  • Bismuth salts of organic carboxylic acids may also be utilized as the gelling catalyst, such as, for example, bismuth octanoate.
  • Cyclic tertiary amines and/or long chain amines include dimethylbenzylamine, N,N, N′, N′-tetramethylbutanediamine, dimethylcyclohexylamine, triethylenediamine, and combinations thereof, and combinations thereof.
  • the petroleum-based polyol may comprise polyols having Ra 2 values of Hansen solubility parameters ⁇ 14.0, ⁇ 12.0, ⁇ 10.0 or ⁇ 8.0, with the bio-based polyester polyol of the present invention.
  • Hansen solubility parameter is generally used to describe solubility between polyols with the bio-based polyester polyol of the present invention, which indicates the association of the polyol molecules with the molecules of bio-based polyester polyol. The stability depends strongly on the intermolecular interactions between the molecules.
  • the polyurethane foam can further contain additives such as surfactants, pigments, crosslinkers, chain extenders, antioxidants, bio-retardant agents, preservatives, flame retardants, colorants, antioxidants, reinforcing agents, solvents, fillers or any combinations thereof.
  • additives such as surfactants, pigments, crosslinkers, chain extenders, antioxidants, bio-retardant agents, preservatives, flame retardants, colorants, antioxidants, reinforcing agents, solvents, fillers or any combinations thereof.
  • the polyurethane foam composition further includes 0.5 to 5 wt. %of at least one surfactant, where the wt. %is based on the total weight of the polyurethane foam composition. All individual values and subranges from 0.5 to 5 wt. %of the at least one surfactant are included; for example, the at least one surfactant can be from a lower limit of 0.5, 1, 2 or 2.5 wt. %to an upper limit of 5, 4 or 3.5 wt. %of the total weight of the polyurethane foam composition.
  • examples of the surfactant include silicon-based compounds organosilicone-polyether copolymers, such as polydimethyl siloxane and polydimethylsiloxane-polyoxyalkylene block copolymers, e.g., polyether modified polydimethyl siloxane, and combinations thereof.
  • examples of surfactants also include nonsilicone based organic surfactants such as nonylphenol ethoxylates, VORASURF TM 504, available from The Dow Chemical Company.
  • Silicone surfactants are available commercially and include those available under trade names such as NIAX TM , such as NIAX TM L 6900 and NIAX TM L 6988; DABCO TM ; and TEGOSTAB TM such as TEGOSTAB TM B 8427 and TEGOSTAB TM B 8491, among others.
  • NIAX TM such as NIAX TM L 6900 and NIAX TM L 6988
  • DABCO TM DABCO TM
  • TEGOSTAB TM such as TEGOSTAB TM B 8427 and TEGOSTAB TM B 8491, among others.
  • the present disclosure provides an article, e.g., a rigid PU foam, made by using the polyurethane foam composition.
  • Process-1 1-pot, Two-stage process
  • Polyester polyols in CE-1 to CE-3 were also synthesized according to Process-1 using the recipes listed in Table 3.
  • Polyester polyols in CE-4 were synthesized according to Process-2 using the recipes listed in Table 3.
  • Process-2 Single stage process -no digestion below 175 °C
  • CE-4 was synthesized similarly according to Process-1, except the digestion at 170- 175 °C was skipped. 202.79 g Oleic Acid (52.9 wt%) , 66.11 g Glycerol (17.3 wt%) and 114.42 g Sebacic Acid (29.8 wt%) were carefully weighed and charged into 500 ml glass reactor and mixed completely. The mixture was then directly heated to 190-196 °C with nitrogen flow ⁇ 2L/(kg ⁇ min) . Serious bumping of the reactants occurred and significant liquid reactants went to the water collector. Process-2 failed.
  • Polyester polyols in CE-5 were synthesized according to Process-3 using the recipes listed in Table 3.
  • Process-3 Single stage process -no digestion below 175 °C
  • CE-5 was synthesized similarly according to Process-1, except the digestion at 190-196 °C was skipped. 202.79 g Oleic Acid (52.9 wt%) , 66.11 g Glycerol (17.3 wt%) and 114.42 g Sebacic Acid (29.8 wt%) were carefully weighed and charged into 500 ml glass reactor and mixed completely. The mixture was then heated to 170-175 °C with nitrogen flow ⁇ 2L/(kg ⁇ min) . When the raw materials were turn to liquid, then started agitation. When the temperature of the mixture reached 170-175 °C, water was distilled out significantly and the whole mixture was digested at 170-175 °C for 3 hours. After that, the mixture was directly heated to 220-245 °C. Serious bumping of the reactants occurred at 205-210 °C. Process-3 failed.
  • CE-1 was a traditional formulation of 100%bio-mass polyester polyol, which suffered from the following problems: long reaction time due to low reactivity of dimeric acid and high cost due to 1, 3-propane diol.
  • IE-1 to IE-5 were inventive examples utilizing novel monomer combinations for synthesizing 100%bio-mass polyester polyols.
  • IE-1 and IE-2 were structurally similar to CE-1 because the long side chain of alkyl chains located in dimeric acid (used in CE-1) are moved to short polyol sides in IE-1 and IE-2. However, IE-1 and IE-2 showed much higher reactivity (shorter production cycle time) and better supply availability (lower cost) .
  • IE-3 and IE-4 were alternative monomer combinations to IE-1 or IE-2 where the monoacids were bearing shorter and shorter carbon atoms but still belonged to Inventive Examples.
  • IE-5 was also alternative inventive example to IE-1 to IE-4, using higher functionality short alcohols instead of glycerin used in IE-1 to IE-4.
  • CE-2 defined a boundary that, if Fn > 2.5 and OH value was in a proper range (i.e., 50.96 ⁇ hv ⁇ 73.17 mg KOH/g) , the acid value cannot go ⁇ 4.04 mgKOH/g otherwise the reaction system would gel.
  • CE-3 defined a boundary that, if Fn > 2.5, OH value cannot be too low (e.g., ⁇ 50.96 mg KOH/g) , otherwise the acid value cannot go ⁇ 8.16 mgKOH/g due to gelation.
  • CE-4 and CE-5 showed that digestions below 175 °C or at 176-200 °C were indispensable, otherwise the reactants would undergo explosively boiling which causeed safety and/or quality issues.
  • PU foams were made using different contents of the bio-based polyester polyols synthesized in IE-7.
  • IE-11 to IE-14 different ratios of IE7 with CP450 were blended to get hybrid polyol components for subsequent PU foam fabrication.
  • Polyurethane foams were prepared according to Table 4. Firstly, the polyols were premixed in specific weight percentage. The polyol blends, catalysts (Polycat 5 and Polycat 8) , surfactant (AK8850) , physical blowing agent (cyclopentane) , pore opener (PEG-400) and blowing agent (distilled water) were mixed in a plastic cup for 30 s using a high-speed mixer. The pMDI was added quickly into the mixture using a syringe and the mixture was mixed for another 5 s, then recording the string time and tack-free time. Subsequently, the mixture was settled for 24 h prior to analysis.
  • catalysts Polycat 5 and Polycat 8
  • surfactant AK8850
  • PEG-400 pore opener
  • blowing agent distilled water
  • the apparent density of the PU foam was measured according to the displacement method.
  • the cellular structure of the samples was investigated using a field emission scanning electron microscopy instrument (JEOL IT300 SEM) operated at 15 kV.
  • the TGA test was conducted under TA5500. Samples with a weight of approximately 4 mg were heated from room temperature to 800°C at a rate of 20 °C/min in air.
  • CE-6 was a complete petroleum-based PU foam formulation where no bio-based polyols were used.
  • IE-11 to IE-14 were polyurethane foam formulations incorporating 11-49 wt. %of bio-based polyester polyols, which showed similar foam density and thermal conductivity, but significantly improved thermal stability (indicated by the increased temperatures of 50 wt. %loss by TGA) , compared to CE-6.
  • CE-7 was a biomass-containing polyurethane foam formulation, based on an incumbent bio-based polyol, castor oil.
  • IE-12 was based on the bio-based polyol of IE-7 with similar molecular weight and functionality to castor oil.
  • CE-7 showed too long gelling time, probably attributed to its secondary OH groups which hampered its reactivity.
  • IE-7 showed significantly improved compatibility (indicated by lower Ra 2 values of Hansen solubility parameters in Table 4) with petroleum-based polyols, which will benefit future technology proliferations in more polyurethane systems by providing better storage stability and processibility.
  • IE-12 Compared to CE-6 and CE-7, IE-12 also showed improved foam structures (indicated by the reduced cell size and size distribution variations) , as revealed by the SEM images in Figure 1 and foam size analysis of the SEM images in Table 5.
  • the Hansen solubility parameters were tested for CP450, IE-7 and castor oil.
  • the polyols were blended in various common organic solvents (24 types) with well-known parameters.
  • a predetermined amount of 50 wt%polyols was mixed with organic solvents.
  • the mixture was sealed and mixed vigorously for 2 h. Then, the solubility was measured by using PICA HTR.
  • solubility sphere of CP450, IE-7 and castor oil on three mutually perpendicular axes were shown in Figure 2, where triangles represent solvents with Hansen solubility parameter outside solubility sphere, and circles represent solvents with Hansen solubility parameters inside solubility sphere.
  • the solubility parameters and the interaction radius for CP450 were obtained as 16.98, 8.50 and 12.02 (Mpa) 1/2 (for solubility parameters ⁇ D , ⁇ P , ⁇ H , respectively) .
  • Mpa 1/2 for solubility parameters ⁇ D , ⁇ P , ⁇ H , respectively
  • IE-7 they were determined as 17.45, 7.25 and 9.31 (Mpa) 1/2 (for solubility parameters ⁇ D , ⁇ P , ⁇ H , respectively) .
  • Ra 2 4 ( ⁇ D A - ⁇ D B ) 2 + ( ⁇ P A - ⁇ P B ) 2 + ( ⁇ H A - ⁇ H B ) 2
  • OH# is titrated according to ASTM D4274.
  • Acid# is titrated by according to ASTM D4662.
  • Brookfield Viscosity is measured by a Brookfield viscometer DVII+ with spindle #27 at modified temperature at 50 °C according to ASTM D4287.
  • Polyol, BDO were stored at 90 °C.
  • MDI was stored at 60 °C.
  • Index between -NCO and -OH was kept as 1.03 all the time.
  • Total amount of the reactants was fixed at 100 g.
  • the molar ratio between BDO and various polyols was fixed at 3.49, respectively.
  • Time was recorded immediately after mixing of the three components and viscosity was monitored after ca. 10 s of mixing of 2000 rpm. Reactivity was recorded as second (s) when the viscosity reached 2000 mPa*s(environmental temperature is 23 °C;no additional temperature control was applied) .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un polyester polyol d'origine biologique, son procédé de préparation ainsi que son utilisation dans une mousse de polyuréthane. Le procédé de préparation de polyester polyol d'origine biologique consiste à (1) prendre un mélange d'au moins un acide carboxylique difonctionnel en C4-C20 d'origine biologique, d'au moins un polyol d'origine biologique et d'au moins un monoacide d'origine biologique ; (2) chauffer le mélange jusqu'à une température se trouvant entre 160°C et 175°C avec une augmentation graduelle de ≤ 30°C par heure ; (3) chauffer le mélange jusqu'à une température se trouvant entre plus de 175°C et 200°C avec une augmentation graduelle de ≤ 30°C par heure après que le mélange de l'étape (2) ait été maintenu entre 160°C et 175°C pendant un temps de digestion supérieur ou égal à 0,5 heure ; et (4) former le polyester polyol d'origine biologique à une température se trouvant entre plus de 175°C et 250°C pendant un temps de digestion supérieur ou égal à 0,5 heure, éventuellement en présence de catalyseurs. Le polyol d'origine biologique a une faible fonctionnalité qui permet une plus grande liberté de formulation de solutions d'origine biologique, et le procédé de préparation du polyol d'origine biologique est rentable.
PCT/CN2024/107157 2024-07-24 2024-07-24 Polyester polyol d'origine biologique, procédé de préparation associé et mousse de polyuréthane Pending WO2026020341A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150299373A1 (en) * 2012-10-26 2015-10-22 Bayer Materialscience Ag Method for producing soft polyurethane foam based on polyester polyols
US10472454B2 (en) * 2012-01-18 2019-11-12 Basf Se Preparing rigid polyurethane foams
EP4186936A1 (fr) * 2021-11-26 2023-05-31 Selena Industrial Technologies Sp. z o.o. Polyols de polyester d'origine biologique, mousse de polyuréthane polyol de polyester monocomposant d'origine biologique ou composition adhésive en mousse et utilisation de polyol de polyester d'origine biologique pour la fabrication d'une mousse de construction monocomposant ou adhésif en mousse
EP4286438A1 (fr) * 2022-05-31 2023-12-06 Covestro Deutschland AG Mousse dure pur/pir comprimée à cellules ouvertes et à cellules fines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10472454B2 (en) * 2012-01-18 2019-11-12 Basf Se Preparing rigid polyurethane foams
US20150299373A1 (en) * 2012-10-26 2015-10-22 Bayer Materialscience Ag Method for producing soft polyurethane foam based on polyester polyols
EP4186936A1 (fr) * 2021-11-26 2023-05-31 Selena Industrial Technologies Sp. z o.o. Polyols de polyester d'origine biologique, mousse de polyuréthane polyol de polyester monocomposant d'origine biologique ou composition adhésive en mousse et utilisation de polyol de polyester d'origine biologique pour la fabrication d'une mousse de construction monocomposant ou adhésif en mousse
EP4286438A1 (fr) * 2022-05-31 2023-12-06 Covestro Deutschland AG Mousse dure pur/pir comprimée à cellules ouvertes et à cellules fines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WOODS, G.: "The ICI Polvurethanes Book", 1990, ICI POLYURETHANES

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