WO2021133281A1 - Mousses de polyuréthane basse densité obtenues à partir de formulations de polyols incorporées à des monoesters de polysorbate - Google Patents

Mousses de polyuréthane basse densité obtenues à partir de formulations de polyols incorporées à des monoesters de polysorbate Download PDF

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WO2021133281A1
WO2021133281A1 PCT/TR2019/051238 TR2019051238W WO2021133281A1 WO 2021133281 A1 WO2021133281 A1 WO 2021133281A1 TR 2019051238 W TR2019051238 W TR 2019051238W WO 2021133281 A1 WO2021133281 A1 WO 2021133281A1
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polysorbate
foam
polyol
low
polyol formulation
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Talat PINARER
Alpay Taralp
Hüseyin KOÇ
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Özerden Plasti̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇
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Priority to PCT/TR2019/051238 priority Critical patent/WO2021133281A1/fr
Publication of WO2021133281A1 publication Critical patent/WO2021133281A1/fr

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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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3278—Hydroxyamines containing at least three hydroxy groups
    • C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide 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
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484—Polysaccharides and derivatives 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
    • C08G18/6535—Compounds of group C08G18/3271
    • 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
    • C08G2110/0041—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

  • This invention relates to improvements in the area of two-component one-shot polyurethane systems.
  • this invention depicts a process of preparing low-density foam bodies by admixing isocyanate and polyol components, the latter being a polyol-based formulation chiefly comprising of one or more low-cost commodity polyols and one or more polysorbate monoes ters.
  • said polysorbate monoesters contribute both as crosslinkable co-building blocks of the newly arising foam body, and as foam-formation facilitators, enabling commodity polyols of said formulation to effectively partake as low-cost foam co-building blocks.
  • the invention is especially related to preparing and utilizing polyol formulations comprising of (i) polysorbate monoesters such as polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80, or combinations thereof as polyurethane foam body co-building blocks, (ii) small molecular weight commodity polyols as inexpensive polyurethane foam body co-building blocks, (iii) water as carbon dioxide gas precursor, (iv) foam formation catalysts, (v) foam stabilizers, and optionally (vi) small molecular weight polyethylene glycols as a polyurethane foam compliancy potentiating agent.
  • polysorbate 20 laurate
  • 40 palmitate
  • 60 stearate
  • 80 oleate
  • 20 laurate
  • 40 palmitate
  • 60 stearate
  • 80 oleate
  • the aldehyde functional group of glucose is reduced, yielding sorbitol.
  • Sorbitol is converted primarily to a cyclic 1 ,4-sorbitan via acid-catalyzed dehydrative ether formation.
  • This cyclic etherification step is never ideal, so said “sorbitan” mixture actually comprises 1 ,4-sorbitan as the main product, plus minor amounts of 1 ,5-sorbitan, 2,5-sorbitan, isosorbide and sorbitol starting material.
  • This mixture is subsequently esterified at the C6 hydroxyl group of sorbitan (Concurrent etherification/esterification of sorbitol is practiced in certain proprietary processes). Said esterification at the C6 position is regioselective because the C6 primary hydroxyl group of sorbitan is more reactive compared to the other groups, which are secondary hydroxyls.
  • sorbitan monoester is exhaustively reacted with ethylene oxide via ring-opening polymerization to the extent that an average of 20 ethylene oxides react per molecule of sorbitan monoester, yielding a multiply oxyethylated (i.e., ethoxylated) C6 monoester of sorbitan.
  • the commercially prepared polysorbate monoesters listed above may be regarded as a mix of sorbitan derivatives of which the multiply oxyethylated C6 monoester of 1 ,4-sorbitan depicts the major product and product name ((Anarjan & Tan (2013); Cottrell & van Peij (2004); Cottrell & van Peij (2015); van Haften (1979); Hasenhuettl (2008)).
  • trademark names such as Polysorbate 20, 40, etc.
  • commercial polysorbate monoesters are also marketed as Tween (Tween 20, 40, etc.).
  • Polysorbates are used in the packaging of materials to prevent fogging.
  • edible products like bread, ice-cream, chewing gum, and gelatin all contain polysorbates as additives.
  • Various medicinal formulations incorporate them as a helper ingredient to prompt proper dispersion of pills in the stomach.
  • Polysorbates are also used in the cosmetics industry in order to solubilize or blend ingredients together. A major growth in polysorbate production is anticipated, attributable to the high demand for beauty and personal care products, as well as to the ever-increasing application of sorbitan ester ethoxylates in the pharmaceutical industry.
  • polysorbate monoesters in particular have been added in small amounts to polyol formulations used for polyurethane foam formation. Said polysorbates appear to have been used almost exclusively for their favorable surfactant traits. Very few academic or commercial examples in the prior art have cited the use of polysorbate monoesters for their potential to physically participate as a building block base resin material for construction of the foam body. This negligible use of polysorbate monoesters as a base resin material in polyurethane foam-targeted polyol formulations depicts one application, which lacks visibility and merits further development, particularly in the case of low- density polyurethane foams, where said use of polysorbate monoesters is entirely lacking.
  • polysorbate monoesters as base resin materials in polyurethane “B Component” polyol formulations has not been developed to the extent that one might anticipate.
  • these ethoxylated and propoxylated sorbitol-based polyetherpolyols depict well- established commercial building blocks for the routine preparation of low, medium and high density polyurethane foams. As such, perhaps there has been some reluctance to investigate and further develop alternative polyols such as polysorbate monoester base resins.
  • substantially polysorbate monoester-based polyol formulations have not been used to prepare low density foam products even though said formulations have been used to prepare medium density (referring to free-rise densities on the order of 32 kg/m 3 ) products. No connection was made even though one presumably could suppose that the simple use of more water as gas precursor should yield lighter foams. Even proprietary polyetherpolyol formulations loaded with water are routinely used to obtain low-density foams; in spite of common structural features, no investigation was made on polysorbate monoesters.
  • Polyetherpolyols differ from polysorbate monoesters in that they are based out of alkoxylated but non-esterified sugar alcohols. As such, proprietary polyetherpolyols cannot undergo ester hydrolysis, whereas the same cannot be de facto supposed for polysorbate monoesters. Perhaps the possibility of encountering problematic ester hydrolysis in highly water-loaded formulations was a discouraging factor leading to said apparent lack of polysorbate monoester formulations for preparing low-density foams. Indeed, Andrew et at. (2014) affirmed that polyester polyols are prone to hydrolysis, which directly affects the storage life of the formulation.
  • polyester polyols were treated at 120°C in the presence of wet organic solvents and tertiary amines for a two-week period, leading to incremental and substantial hydrolysis of the fatty acids.
  • the hydrolysis observed by Andrew et at. was attributed to general base catalysis (i.e., amine-prompted generation of hydroxide nucleophile) as opposed to nucleophilic catalysis (i.e., direct nucleophilic attack of the ester carbonyl carbon by amine).
  • This claim was supported by Kirby (1972) and Bender (1960), who investigated the hydrolysis of esters prepared from aliphatic carboxylic acids and fairly non-acidic aliphatic alcohols.
  • polysorbate monoesters were discouraging. For instance, the large fatty acid chain might have been deemed simply too hydrophobic for applications, which require high water loadings. Perhaps the incorporation of a monoesterfied building block was regarded as being antithetical to the goal of achieving good crosslinking, as such polysorbate monoesters would necessarily bear less hydroxyl groups per molecule compared to the commercially established, structurally related polyetherpolyol base resins, which are typically unesterified or otherwise unblocked at all of their terminal hydroxyl groups.
  • Inexpensive commodity polyols have not escaped attention in low-density foam products, but they certainly have escaped emphasis.
  • Commodity polyols generally appear in combination with expensive specialty polyols such as polyetherpolyols, the latter being the major contributor to the polyol formulation.
  • polyetherpolyols the latter being the major contributor to the polyol formulation.
  • no commercial polyol formulations have entailed the use of inexpensive commodity polyols as the exclusive or near exclusive base resin material for preparing low-density polyurethane foams.
  • the end product has always been a medium density or high density (referring to free-rise densities of 3 48 kg/m 3 ) polyurethane foam.
  • Figure 2 Typical misrepresentation (top) and correct structure (bottom) of polysorbate monoester, which is formed by esterifying sorbitan at the C6 position, followed by exhaustive oxyethylation of the resultant sorbitan monoester intermediate.
  • Said polysorbate monoester when admixed with low-cost commodity polyols, and possibly low-molecular-weight PEGs (Fig. 1), forms an isocyanate-reactive base resin material for constructing polyurethane foam bodies.
  • w + x + y (+ z) - a such that 16 £ a £ 22, and a is typically targeted as 20 (z applies to the incorrect top representation).
  • R may be any saturated or unsaturated hydrocarbon radical having 11 -17 carbon atoms.
  • polysorbate monoesters are often preferred. These include polysorbate 20, polysorbate 40, polysorbate 60 and polysorbate 80.
  • Emmrich-Smolczyk etal. (2014) reported the use of polysorbate-related sorbitan monoesters in preparing structurally robust foams for panel applications. Water was present and foam densities consistently exceeded 40 kg/m 3 .
  • specialty starting materials such as proprietary polyetherpolyols will remain a cornerstone of the low-density polyurethane foam industry until the problem of preparing an inexpensive and adequately performing commodity polyol formulation can preclude any further need of said specialty polyetherpolyols.
  • the invention relates to a single-phase polyol formulation used for the synthesis of low-density polyurethane foams in one-shot two-component polyurethane systems.
  • the invention also relates to a process of preparing low-density foams by admixing a commercially available isocyanate, as the A Component, and a polyol formulation comprising of polysorbate monoesters and low-cost commodity polyols, as the B Component.
  • Said invention detracts from the aforementioned disadvantages/dearth of knowledge in the area of low density polyurethane foams and brings along additional advantages, thus supplementing the prior art and precluding any need for specialty starting materials such as expensive proprietary polyetherpolyols.
  • the main purpose of the invention is to prepare low-density polyurethane foam bodies by combining an isocyanate component and a polyol formulation, the latter comprising of inexpensive commodity polyols, polysorbate monoesters, and water as a safe and convenient precursor to generate carbon dioxide.
  • a second major purpose is to preclude any need for costly proprietary polyetherpolyols, as well as flammable/possibly harmful blowing agents such as pentane, cyclopentane, freons or hydrolytically unstable organics such as methyl formate.
  • Another purpose of the invention is to further lower production costs by maximizing the weight percentage use of inexpensive commodity polyol types while minimizing the weight percentage use of said intermediate-cost polysorbate monoester in the polyol formulation.
  • Another purpose of the invention is to raise the total water content of the commodity polyol- polysorbate monoester polyol formulation to such a level (i.e., 3 20 wt%) that tree-rise foam densities ranging from 6-10 kg/m 3 can be attained and material costs can be minimized.
  • Another purpose of the invention is to optionally incorporate a low-molecular-weight polyethylene glycol as co-additive in the polyol formulation to better fine-tune the mechanical traits of the final foam body.
  • a further purpose of this invention is to prepare a foam product, which on the basis of customer needs can be made to display either a spongy resilience, which imparts tolerance to repeated compression, or a plastic-deformability, lending itself well to single-use cushioning applications.
  • Another purpose of the invention is to yield a shaped body out of the foam and to use said shaped body as protective equipment, sound insulation and thermal insulation.
  • a further purpose is to fine-tune the cure time by appropriately selecting the loading, hydroxyl value and hydroxyl composition of the commodity polyols, favoring more hydroxyls and primary alcohols when curing speed and strength is desired, more hydroxyls and secondary alcohols when strength but slower curing is required, and less hydroxyls in all cases where strength is not a priority and mechanical compliance is preferred.
  • a further purpose is to ensure that a foam body with acceptable physico-chemico-mechanical traits can be prepared by admixing the isocyanate and polyol formulation. Said acceptable traits should be reproducible over a reasonable range of production temperatures and mixing approaches.
  • a further purpose, implied and certainly known to those skilled in the art, is to afford acceptable foam bodies by addressing potential drawbacks relating to (i) poor stability, reconstitutability and shelf life of the polyol formulation in high-water-content environments, (ii) foam rupture, bleeding and shrinkage during foam body formation, (iii) poor flow traits during foam body formation, and (iv) poor mechanical traits of the ensuing foam body.
  • a further purpose is to prepare a polyol formulation such that the ester components present in said formulation are substantially stable over the shelf-life of the polyol formulation in spite of the presence of tertiary amines and substantial water.
  • a further purpose is to prepare a polyol stock formulation in the form of a metastable dispersion.
  • Said metastable dispersion is easily reconstitutable prior to use via mild stirring, and does not phase-separate when being applied.
  • An ideal extension of said purpose is to prepare a polyol formulation in the form of a solution/stable dispersion. Said solution/stable dispersion does not phase-separate into aqueous and organic layers over the course of its storage lifetime and requires no periodic mixing to reconstitute the compounds making up said formulation.
  • a further purpose is to prepare a polyol formulation, which does not contain potentially harmful transition metal catalysts.
  • a further purpose is to prepare a polyol formulation utilizing tap water such that said polyol formulation reproducibly displays good foaming traits irrespective of the tap water source, and as such, said formulation requires no expensive distilled or deionized water.
  • a further purpose is to lower production costs by utilizing only one tertiary amine catalyst in the polyol formulation.
  • the reactive mixture formed by admixing said formulation and isocyanate displayed excellent flow, foaming and gelation traits.
  • Other polyol formulations comprising primarily of polysorbate monolaurate and selected commodity polyols were similarly tested.
  • inexpensive low-molecular weight polyethylene glycols were also introduced.
  • the resultant foam bodies displayed free-rise densities of 6-10 kg/m 3 , rapid tack-free times and fast onset of load-bearing traits. All formulations tested qualified as low-cost alternatives to proprietary polyetherpolyol formulations optimized for foam-in-place applications.
  • Most of the polyol formulations also displayed excellent flow traits when admixed with isocyanate, lending themselves well to molding foam applications.
  • the test formulations - comprising chiefly of only commodity-type polyols - failed to yield the desired foam bodies.
  • formulations comprising of glycerol, triethanolamine, PEG400 and substantial water experienced catastrophic boiling in spite of the use of additional foam stabilizer.
  • high- water formulations comprising of substantial non-polysorbate polyester polyols and glycerol yielded foams with a grainy, sandy feeling and poor mechanical traits.
  • High-water formulations utilizing sorbitol as the exclusive polyol base material rose well upon mixing with isocyanate, but the free-rising foam quickly tore itself apart before the onset of gelation.
  • high-water formulations using PEG400 in high amounts yielded a foam, which did not set quickly, which shrank, and was too soft for mechanically-demanding applications such as packaging. As such, a marginal “polysorbate” contribution at best, positive or otherwise, was forecast.
  • foam bodies displayed good mechanical strength and resiliency. It appeared that the combination of polysorbate monoester, low-molecular weight polyols, water and isocyanate had struck a good balance, prompting optimal crosslinking density/rates, foaming volume, foam rise and gelation times, cellular dynamics and cell stability. Such a counter-intuitive yet pleasant outcome raised new possibilities for the routine tandem use of readily-available, inexpensive commodity polyols and polysorbate monoesters in low- density foam-in-place as well as molding foam commercial applications.
  • the cheapest of commodity polyols were used in the largest of possible weight fractions.
  • This approach served to minimize the average cost of the commodity polyols as well as to limit the weight fraction of the more costly polysorbate monoester building block.
  • the approach succeeded to the extent that unit costs had decreased to a level acceptable for commercial production purposes.
  • unit costs dipped well below the purchase costs of commercial polyetherpolyols.
  • the unit costs were on par, but the invention still benefited from easy access to starting materials.
  • ester hydrolysis was anticipated on the basis of: (i) The catalytic action of a tertiary amine, (ii) the high water content of said formulation, and (iii) the work of researchers such as Andrew et al. (2014), who presented hydrolytic data of comparable esters in aqueous systems. Remarkably, neither a loss of ester functionality, nor an inconsistency in foam formation was apparent for polyol formulations stored over a 12- month period at room temperature. Foam bodies derived from polyol formulations kept in storage for 12 months revealed no decrease of product quality.
  • the most commonly used commercial catalysts continue to be triethylenediamine for gelation (i.e., polyurethane bond formation), and bis(2-dimethylaminoethyl)ether for carbon dioxide gas formation.
  • bis(2-dimethylaminoethyl)ether typically sold in 30 wt% dipropylene glycol as DABCO BL11
  • DABCO BL11 dipropylene glycol
  • the invention has extended the application of commodity polyol formulations to the area of two-component (one-shot), low-density polyurethane foam systems.
  • the invention resolves problems highlighted in the technical field by providing an easily- accessible, cost-effective commercial alternative to specialty polyetherpolyols for preparing low density foam bodies.
  • the principle outcome of said invention is an economic low-density foam body, formed by admixing commodity polyol formulations containing substantial polysorbate monoester and water, and an isocyanate component. Urethane and urea bonding is initiated, leading to eventual gelation, and gas is liberated, affording low foam body densities.
  • the invention underscores the merit of polysorbate monoester incorporation as a strategy to enable the effective utilization of very common low- cost commodity polyols. Accordingly, said invention entails the preparation of a polyol formulation comprising of
  • said invention embodies a polysorbate monoester-incorporated commodity polyol formulation for use in one-shot two-component polyurethane systems, characterized in that said polyol formulation comprises of
  • the invention further embodies a process to prepare a polysorbate monoester-incorporated commodity polyol formulation characterized in that said formulation is prepared by mechanically admixing, in no mandatory order; one or more types of polysorbate monoesters; one or more types of low-cost commodity polyols; water as gas generator; one or more types of tertiary amine foam formation catalysts; and one or more types of foam stabilizers in a weight ratio of 17-38% / 35-61% / 20-25% / 0.9-1.5% / 0.65-0.71% respectively, until a homogeneous dispersion is observed.
  • the invention further embodies a process to prepare a low-density, polysorbate monoester- incorporated polyurethane foam material/body characterized in that said foam is prepared by combining, at a specific weight ratio and temperature,
  • Said co-building block is optional and is utilized only where certain foam body traits are desired; (b) preparation of the polysorbate monoester-incorporated commodity polyol formulation (i.e., Component B) by admixing polysorbate monoester with inexpensive commodity polyols, amongst which ricinoleic acid polyhydroxyldiethanolamide may or may not partake, water, catalysts, foam stabilizers and possibly auxiliaries; and (c) application of said polysorbate monoester-incorporated commodity polyol formulation (i.e., Component B) by admixing it with isocyanate (i.e., Component A), thereby inducing foam formation and gelation to yield a polyurethane foam body.
  • isocyanate i.e., Component A
  • This invention relates to a process of preparing cost-effective low-density polyurethane foam bodies by admixing (i) a high-water-content polyol formulation comprising of polysorbate monoesters and low-cost commodity polyols, and (ii) a commercial isocyanate component.
  • the commodity polyols and polysorbate monoesters may be regarded as a dynamic system of polyols, which act to mutually complement one another’s weaknesses, thereby serving to reduce production costs without compromising foam formation traits and foam body performance.
  • the reactive admixture comprising of polysorbate monoester, commodity polyol, water (said admixture contains no gas-forming agent other than water, which is present in large amounts to prompt low-density foam body formation), and isocyanate, flows and therefore can be shaped into foam bodies utilizing molds. Once formed, said foam bodies retain their mechanical properties to the extent that they do not notably shrink following preparation, and serve well in packaging/cushioning applications.
  • PEG may be included in the polyol formulation to better fine-tune the mechanical traits of the resultant foam body.
  • low-density foam bodies are those with a free-rise density of 6 £ 10 kg/m3, whereas medium and high-density foam bodies display free-rise densities on the order of 32 and 3 48 kg/m3, respectively.
  • Low, medium and high density foams differ in their open-cell/closed-cell ratio; low density foams are primarily open-celled, medium density foams are typically 95% closed-celled, and high-density foams are essentially entirely closed-celled.
  • the size, structure and connectivity of cells in foam influences other foam body traits such as thermal insulation, sound isolation, etc.
  • the A Component is any commercially available isocyanate and the B Component is the polyol formulation (a mixture of polysorbate monoester polyols, low- molecular-weight commodity polyols, foam formation catalysts, water as blowing agent precursor, foam stabilizers, and optional auxiliary molecules, specifically low-molecular weight polyethylene glycols).
  • the polyol formulation a mixture of polysorbate monoester polyols, low- molecular-weight commodity polyols, foam formation catalysts, water as blowing agent precursor, foam stabilizers, and optional auxiliary molecules, specifically low-molecular weight polyethylene glycols.
  • wt% refers to percentage weight, weight percent or % by weight.
  • quantities expressed as “one” or “one or more” respectively imply “one type of” or “one or more types of’, and not “one unit of quantity” or “one or more units of quantity” (i.e., not “one” molecule, “one or more” moles, etc.).
  • the polysorbate monoester is an oxyethylated 1 ,4-sorbitan C6 monoester (i.e., an oxyethylated 1 ,4-sorbitan structure with a fatty acid ester bond at the C6 position of sorbitan).
  • said polysorbate monoester is a polyhydroxy sorbitan ester derivative (or group of different ester derivatives) formed by condensing the C6 hydroxyl functional group of sorbitan and the carboxylic acid functional group of a saturated or unsaturated fatty acid (or group of the corresponding different carboxylic acids) of the form RCOOFI, where R is a hydrocarbon radical of 11-17 carbon units in length, followed by repeated oxyethylation of the resultant sorbitan ester intermediate or corresponding sorbitan ester intermediates.
  • R is a hydrocarbon radical of 11-17 carbon units in length
  • crosslinkers have three or more hydroxyl groups per molecule (e.g., polysorbate monoester, sorbitol, glycerol, triethanolamine, ricinoleic acid diethanolamide) and no other reactive group.
  • Linkers have two hydroxyl groups per molecule (e.g., neopentyl glycol, linear alkyl glycols with the alkyl chain ranging from C2 to C6, and low-molecular-weight PEGs) and no other reactive group.
  • the quality of being chemically “reactive” herein pertains to the scope of isocyanate chemistry.
  • Auxiliaries herein are defined as optional and pertain to low- molecular-weight PEG linkers.
  • Foam-formation catalysts refer to those tertiary amine based catalysts, which prompt carbon dioxide gas generation (via reaction of water with isocyanate, followed by decomposition of the ensuing carbamic acid intermediate to liberate carbon dioxide and primary amine) and urethane bond formation (foam gelation). Foam formation catalysts should not be inadvertently misconstrued solely with the act of gas generation/foaming, implying only the former event. Urea bonding occurs in parallel to gas generation and urethane bonding. Urea bonding proceeds without a catalyst via direct interaction of primary amino groups and isocyanate.
  • the base resin or base resin material refers to the sum of all different types of polyols in the polyol formulation.
  • said polyols comprise polysorbate monoester admixed with low-cost commodity polyols and optionally low- molecular-weight auxiliary PEG. Said polyols serve as structural building blocks of the foam.
  • low-molecular-weight polyethylene glycol refers to any PEG from PEG100 through to and including PEG600.
  • commodity polyols are monomer-sized crosslinkers possessing at least three hydroxyl functions. All such monomeric building blocks may be regarded as low- molecular-weight compounds.
  • Said commodity polyols may be glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, triethanolamine, pentaerythritol, erythritol, tris(hydroxymethyl)methane, N-acetylglucosamine, xylitol, mannitol, sorbitol, fructose, glucose, xylose 1 ,1 ,1-tris(hydroxymethyl)ethane, and 1 ,1 ,1-tris(hydroxymethyl)propane. Combinations may be employed. Amongst this group, the natural sugars are less preferred because they are more easily degraded by microorganisms over the course of time.
  • the term single-phase relates to a homogeneously-mixed polyol formulation.
  • a homogenous mixture refers to a solution, stable dispersion or metastable dispersion of said formulation.
  • solutions and stable dispersions retain their homogeneity indefinitely.
  • a metastable dispersion refers to polyol formulations, which do not phase-separate into a top and bottom layer over the period of a typical workday.
  • metastable dispersions do phase-separate into two layers, but for purposes herein, said two distinct layers can be conveniently remixed prior to reuse, once again forming a metastable dispersion amenable for reaction with isocyanate.
  • surrogate refers to a combination of polysorbate monoester, commodity polyol, and optionally low-molecular-weight PEG, which can be used to replace an equivalent mass of the costly/proprietary specialty polyetherpolyol without compromising the convenience of the production process or traits of the ensuing foam body.
  • enabling reflects the non-obvious ability of polysorbate monoesters to improve the foam-formation traits of substantially commodity polyol- based formulations. To qualify as “enabling”, said improvement must occur to the extent that admixtures of polysorbate monoester and commodity polyol can (i) suppress those pitfalls established for commodity polyol-only base resins, 1 and (ii) function as a specialty polyetherpolyol surrogate, permitting the preparation of good-quality, low-density foam bodies at a relatively reduced cost.
  • spongy resilience refers to the quality of being compliant but not necessarily visco-elastic.
  • the A & B Components may be admixed batchwise, via hand, manual device, or batch mixer. Alternatively said Components may be admixed continuously, whereof the A & B Components are brought together using calibrated pumps. In either case, effective and rapid mixing is achieved by applying turbulence/shear forces. In batch/manual foam preparation processes, the turbulence of mixing is loosely related to the mechanical shear experienced by the admixture. In continuous flow production processes, the turbulence of mixing is more easily related to the flux value. Flux is defined as the flow rate of material exiting the spray gun nozzle divided by the cross-sectional area of the nozzle opening. In continuous flow applications, devices utilizing impingement mixing within the nozzle of the spray gun have become the standard practice.
  • mass loss is an important consideration. Mass loss is not very substantial in denser foams, however, the open-celled structure of low-density foam provides ample routes for gas liberation, leading to reduced mass and the concerns over substantially lowered %yields.
  • the mass of starting materials can be calculated from the flow rate exiting the spray gun nozzle (i.e., grams/second) multiplied by the spray period (in seconds).
  • the weight of gas or material lost during foam formation will only be ascertained using direct massing on a standard balance, as theoretical treatments are not nearly as accurate to ascertain such details in this polyurethane system. While the gas volume liberated clearly reflects the water content of the system, estimating the volume of gas lost or predicting the %yield is another matter, which goes well beyond the water concentration of the polyol formulation. For instance, surface bleeding/out-gassing is commonly observed near the end of the gelation process in said low-density foam bodies.
  • Water in the polyol formulation contributes to the traits of the resultant foam body in three ways:
  • foam bodies with tree-rise densities between 6-8 kg/m3 exhibit an early onset of plastic deformation, while those ranging between 7-10 kg/m3 display a substantial and atypical degree of repeatable compressibility prior to failure.
  • the mechanical compliancy and resiliency of the latter case may be used to advantage in selected sectors, which utilize low- density polyurethane foam products for repeated cushioning.
  • the relative ratio and specific structure of polysorbate monoester versus commodity polyol can be varied to fine-tune the traits of the final foam body.
  • the compounds making up said polyol formulation are: (1) An ethoxylated sorbitan monoester structure (i.e., polysorbate monoester), which bears at the C6 hydroxyl a laurate (polysorbate 20), palmitate (polysorbate 40), stearate (polysorbate 60), oleate (polysorbate 80) or non-commercially utilized fatty acid carboxylate radical, as well as combinations thereof; (2) a low-cost commodity polyol such as glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, triethanolamine, tris(hydroxymethyl)methane, 1 ,1 ,1- tris(hydroxymethyl)ethane, 1 ,1 ,1
  • Said compounds preside in the above formulation at a weight ratio of 17-38% / 35-61% / 20-25% / 0.9-1.5% / 0.65-0.71% / 1-10%, respectively, with respect to the weight of the final polyol formulation.
  • Polyol percentages herein refer to dry weights; in cases where 70 wt% sorbitol syrup is utilized, for instance, the total mass delivered to the formulation will not correspond to sorbitol, as water comprises 30 wt% of said total. Accordingly, care should be exercised to avoid concentration errors when preparing said formulations. Concentrations lying outside the prescribed range may also form foams useful for specific applications (e.g., medium-density or high-density foams utilizing less water and more polyol) but for purposes of said invention, the wt% range shown above is prescribed.
  • the addition order of the above compounds is not important, but as a rule of thumb water is added second-to-last and incrementally so as to not inadvertently surpass the water solubility of the system. If higher foam compliancy is desired in the finished body, less water can be added to the polyol formulation.
  • the temperature of admixing is not crucial, but for convenience, stirring can be performed about room temperature. Gas bubbles form during the addition of water, imparting a notable murkiness, but the solution itself remains homogenous so long as the water content is not saturating (experience shows that gas bubbles and murkiness vanish overnight).
  • addition of the silicone foam stabilizer sometimes yields an indefinitely stable hazy dispersion or false appearance of a dispersion.
  • the total weight fraction of polysorbate monoester or monoesters used in the formulation should range from 17-38 wt%. Beneath the lower limit, the problematic traits of the low- molecular-weight polyols (i.e., catastrophic bleeding, grainy/sandy foam formation, rupture prior to foam gelation) will become more apparent due to the relative lack of polysorbate monoester, which acts positively to ameliorate such events. Above the upper limit, the cost savings will likely not be substantial enough to warrant commercial scale production.
  • the commodity polyols of said invention should total 35-61 wt% of the polyol formulation. Loadings beneath 35 wt% will limit the cost savings advantage, whereas loadings higher than 65 wt% could prompt previously established problems such as rapid phase separation of the polyol formulation, unfavorable foaming traits, and related negative traits in the final foam body.
  • the size of the polyol as well as the number of hydroxyl groups in the polyol can be intelligently adjusted to fine-tune the crosslinking density and gelling time of the newly-forming foam body.
  • An increased abundance of hydroxyl groups for a given molecular weight polyol can prompt faster gelling and higher crosslink densities (e.g., compare 4 hydroxyl groups per pentaerythritol versus 3 hydroxyl groups per 1 ,1 ,1- tris(hydroxymethyl)ethane). With the hydroxyl group number-to-molecular weight fixed, a higher molecular weight polyol will also prompt similar results.
  • a formulation containing sorbitol would be expected to gel slower and yield a softer foam compared to an equal weight of the larger lactitol molecule.
  • molecules with differing primary/secondary hydroxyl ratios can be used to adjust the curing time, as secondary hydroxyl groups are less reactive towards isocyanate (e.g., pentaerythritol versus erythritol).
  • the sole blowing agent to be used in said invention is carbon dioxide for reasons of economics, operator safety, and environmental safety.
  • the sole precursor of carbon dioxide in said invention is water for reasons of economics, operator safety, miscibility with other formulation compounds, and desirable reaction chemistry.
  • the reaction chemistry of water is particularly attractive in that it not only contributes to gas formation/foaming (carbon dioxide is generated in situ during the reaction of water and isocyanate), but also to gelation via urea bond formation; in this process, water adds across the isocyanate bond, generating a thermally-labile carbamic acid, which rapidly decomposes to the primary amine, concomitantly losing carbon dioxide in the process.
  • a “water-blown” polyurethane foam is thus a misnomer in the sense that such foams are primarily constructed via urethane as well as urea bonds.
  • the amount of foam formation catalyst can range from 0.9 to 1.5 wt% with respect to the weight of the polyol formulation. Using less than 0.9 wt% catalyst delays foam gelation excessively, leading to structural shrinkage and higher free-rise densities in the final foam product. Excessive use of catalyst (> 1.5 wt%) leads to rapid foaming, which proves hard to physically manage during application. The excessive catalyst also adds unnecessarily to the overall material costs.
  • the foam formation catalyst can be any suitable tertiary amine or collection of different suitable tertiary amines. Said catalysts should be appropriately chosen such that the reactive mixture yields good flow, foaming and gelling traits during reaction, as well as shock-absorbing traits in the finished foam body. While combinations of said commercial catalysts are commonly practiced, the invention stipulates the use of one catalyst type in order to limit production costs. Tin-based catalysts are excluded from said invention in keeping with environmental and personal safety considerations. Other metal-based catalysts have also been excluded for similar reasons. Suitable tertiary amines should display low volatility. Triethylamine for instance, is unsuitable for the reason that it will produce an unacceptably strong stench during application.
  • Triethanolamine is much better in that it is nonvolatile, but its basicity is curbed to such an extent by the inductive electron withdrawal of three oxygen atoms that large amounts must be utilized in order to yield an appreciable rate (also, triethanolamine experiences intramolecular hydrogen bonding, which reduces the nucleophilicity of the nitrogen atom).
  • Suitable amines for said invention are triethylenediamine, bis(2-dimethylaminoethyl)ether, a combination thereof, or other suitably designed tertiary amines.
  • bis(2- dimethylaminoethyl)ether typically sold in 30 wt% dipropylene glycol under the name of DABCO BL11
  • DABCO BL11 dipropylene glycol
  • bis(2-dimethylaminoethyl)ether can be employed alone to achieve a good foam product. While the inventors prefer said catalyst, any catalyst or group of catalysts can be utilized as long as sufficient activity and good balance is observed in mediating gas generation and foam gelation.
  • a foam stabilizer contributes by stabilizing the foam formation event.
  • Foam stabilizers greatly reduce the likelihood of premature boiling (i.e., a catastrophic discharge/out-bleeding of gas) by suppressing cell coalescence during foam formation. As such, the cells remain stable long enough for gelation to occur.
  • the polyurethane foam stabilizer is a commercially available compound comprising of a co-polymer or selection of co polymers.
  • the building blocks of said stabilizer comprise of PDMS, PEG and PPG.
  • Commercial brands suitable for said invention include one or a combination of Momentive Niax Silicone L6900, Siltech Silstab 2755, and Siltech Silstab 2791 , to name a few.
  • Auxiliaries herein are non-mandatory, optional co-additives. Auxiliaries are not added in the absence of low-molecular-weight commodity polyols. Auxiliaries typically denote dihydroxy linkers such as low-molecular-weight PEGs (PEG100 through to PEG600). Outside the scope of said invention, linkers have also included neopentyl glycol, tripropylene glycol, dibutylene glycol and tributylene glycol, to name a few. Said hydroxyl-pendent linkers primarily impart compliancy to the final foam. Their effect becomes more pronounced as the length of the linker increases.
  • Said linkers may be desired to facilitate foam formation in cases where a freely- rising foam is seen to “tear itself up” and bleed-out before reaching maximum volume.
  • Linkers may also be prescribed in order to fine-tune the softness traits of the finished foam product. Excess use of the auxiliary can potentially reduce crosslinking, delay the setting time, and yield a product, which is deemed too weak or malleable for the intended application; amounts not exceeding 10 wt% of the polyol formulation are acceptable. Amounts under 1 wt% may be regarded as being inconsequential with respect to their effect on the finished foam traits.
  • any commercially available diisocyanate, triisocyanate or polymeric isocyanate can in principle be utilized as the isocyanate component (i.e., Component A).
  • the commercially available isocyanate products some include MDI, PMDI, TDI, HDI, NDI, HMDI, IPDI, and dimeryldiisocyanate, to name a few.
  • PMDI is preferred herein for reasons of cost, local availability, low volatility, and effectiveness.
  • Dimeryldiisocyanate refers to the isocyanate obtained following the interaction of phosgene and dimeracid amines (i.e., aminated derivatives of thermally dimerized/partly trimerized fatty acids).
  • the polyol formulation (B Component) and isocyanate (A Component) are combined batch-wise or via a continuous flow system in a weight ratio of 1 :0.8 to 1 :1.5 and preferably 1 :1 to 1 :1.4 (polyol/isocyanate).
  • polyol/isocyanate a weight ratio of 1 :0.8 to 1 :1.5 and preferably 1 :1 to 1 :1.4
  • isocyanate and polyol components are strongly admixed, gas liberation as well as urethane and urea bonding proceed. All events proceed at appropriate rates, yielding a reactive, free- flowing foamy mass that conforms well to the shape of a mold, and subsequently gels and solidifies into a material, which is neither too soft & compliant, nor too mechanically rigid & plastically deforming. If the relative amount of isocyanate is too high (i.e., 1 : >1.5), an overly rigid foam will be obtained. Conversely, exceedingly low relative amounts of isocyan
  • Batch reactions can be performed by strongly mixing either the isocyanate component or polyol formulation (preferably the polyol formulation), and rapidly adding the other thereon.
  • turbulent mixing is continued for another 2-5 seconds and the mixture is poured into a mold or left idle to rise. Strong mixing is beneficial and should be continued for as long a time as practically possible; ideally, mixing should be ceased just before the onset of foaming so as to not disturb formation of cellular structures.
  • the isocyanate and polyol components must make effective contact.
  • Mixing should be designed such that the isocyanate component and polyol formulation experience strong turbulent mixing at the instant they are combined. If such is not the case, the majority of polyol and isocyanate molecules will not come into intimate contact; a spatially heterogeneous lag time at the onset of combining the two Components will be operative, giving rise to spatiotemporal heterogeneities in the distribution of reactive materials. Consequently local reactions will differ from region to region, giving rise to irreproducible physico-chemical heterogeneities in the product foam.
  • Fine temperature control before combining the polyol formulation and isocyanate stock is also crucial to obtain reproducible foaming and foam body formation.
  • precise temperature control is more crucial for ensuring product reproducibility when the A and B Components are combined at elevated temperatures. If the A and B Components are to be administered above 45°C, fine temperature control may be regarded as mandatory.
  • the polyol formulation and isocyanate are separately pre-heated to a temperature ranging between 55°C to 75°C.
  • the A and B Components may be preheated to a common temperature or to different temperatures. In the experience of the inventors, the optimum temperature prior to impingement mixing is on the order of 60-70°C/60-70°C (referring to A/B Components).
  • a higher pre-reaction temperature improves the cell structure by enhancing mass transfer events, improving the mixing of reaction participants.
  • a fringe benefit of using higher temperatures is that less foam stabilizer is needed to prevent cellular coalescence and collapse.
  • higher pre-reaction temperatures typically give rise to pleasantly small and uniform cells.
  • the converse scenario applies at lower pre-reaction temperatures.
  • descending below 55°C/55°C typically gives rise to noticeably coarser cells.
  • low pre-reaction temperatures may prove advantageous in the exceptional case of when extremely low-viscosity polyol formulations are used in continuous foam systems. In such cases, problematic splashing will be markedly reduced if the reactive mixture is jetted-out at temperatures somewhat cooler than the norm.
  • a last convenience of said invention is that the mass lost following foam formation appears to be predictable. Of all formulations tested, free-rise foam body masses and hence product yields were remarkably consistent, residing within the range of 85 ⁇ 2%. Accordingly it would appear that untested alternative polyol formulations, prepared within the scope of said invention, will also display the same yields. Such established consistency carries along a measure of practical convenience, as profits for formulations prepared within the context of said invention can be readily forecast, unlike certain proprietary polyetherpolyol-based formulations, which are prone to yield variations. While non-mass-measurement approaches to ascertain %yield have been attempted in said invention, these efforts were abandoned in view that all estimates were grossly in error.
  • the conceptual exercise attempts to highlight the potential complexities involved in estimating mass losses as opposed to applying direct measurement. For the sake of argument, said exercise is arbitrarily focused on estimating the amount of carbon dioxide gas, which might be liberated on the basis of water levels in the polyol formulation and the reaction between isocyanate and water.
  • the mole fraction of total nucleophiles transforming into carbon dioxide gas can be theorized as the mole fraction of water (i.e., number of moles of water divided by the total molar sum of all isocyanate-reactive groups such as water, primary hydroxyl, secondary hydroxyl, and in situ generated primary amino groups;
  • XH2 O n H 2o/ni 0taiNu ) multiplied by the rate of water reacting with isocyanate (r H 2o), divided by the sum of the different molar fractions of all isocyanate-reactive nucleophiles (i.e., moles of each nucleophile type divided by the total molar sum of all isocyanate-reactive nucleophiles;
  • XN n H 2o/ni 0taiNu
  • the total gas created can be estimated as the product of the mole fraction of total nucleophiles converted into carbon dioxide multiplied by the moles of isocyanate present.
  • R FI or alkyl
  • each different type of nucleophile is expected to respond differently to time- dependent changes of viscosity over the course of reaction; arbitrarily assuming equivalent time-course perturbations of the different nucleophile rate constants would depict an overly optimistic and very unlikely view.
  • water is likely to be the least affected by increases of viscosity, as its smaller size should allow for easier diffusion - hydrophobic “pinning” potentials notwithstanding - compared to other reacting groups.
  • a 100L reactor equipped with mechanical stirring and heating bands featuring temperature feedback and control circuitry is charged with synthesis grade castor oil and pre-warmed liquid diethanolamine in a 1 :3 molar ratio.
  • the reactor lid is closed (but not sealed) in order to minimize air exchange with the outside and heating is commenced.
  • the reaction attains 130°C and the two-phase mixture become one-phase.
  • the temperature is stabilized at 130°C for another hour and heating is subsequently shut off, allowing the stirred solution to return to room temperature overnight.
  • the resultant one-phase product can be described as a homogenous solution comprising of free glycerol and ricinoleic acid diethanolamide in a 1 :3 molar ratio.
  • the combined mixture was mechanically stirred until a slightly hazy homogeneous dispersion was observed.
  • the above polyol formulation was combined with PMDI in a 1 :1.35 (wt/wt) ratio utilizing impingement mixing.
  • the polyol and isocyanate streams were each pre-heated to 70°C.
  • the resulting mixture was allowed to tree-rise, yielding a low-density foam with a pleasant and unusual resiliency for foams of the low-density class.
  • the molding and flow traits of the reactive mixture were satisfactory, yielding a molded foam body with desirable mechanical traits.
  • the early onset of load-bearing traits permitted said formulation to be used as an alternative to commercial foam-in-place and molding foam B Components. Said formulation was metastable, requiring brief mixing just prior to use.
  • Example 3 Preparation and Application of the Component B Polyol Formulation To a mixing vessel, the following items were added in no particular mandatory order:
  • the above polyol formulation was combined with PMDI in a 1 :1.35 (wt/wt) ratio utilizing continuous-flow impingement mixing.
  • the polyol and isocyanate streams were each pre-heated to 70°C.
  • the resulting mixture was allowed to free-rise, yielding a low-density foam with a pleasant and unusual resiliency for foams of the low-density class.
  • the molding and flow traits of the reactive mixture were satisfactory, yielding a molded foam body with desirable mechanical traits.
  • the early onset of load-bearing traits permitted said formulation to be used as an alternative to commercial foam-in-place and molding foam B Components. Said formulation was metastable, requiring brief mixing just prior to use.
  • the combined mixture was mechanically stirred until a homogeneous solution was observed.
  • the above polyol formulation was combined with PMDI in a 1 :1.35 (wt/wt) ratio utilizing continuous-flow impingement mixing.
  • the polyol and isocyanate streams were each pre-heated to 70°C.
  • the resulting mixture was allowed to tree-rise, yielding a low-density foam with a pleasant and unusual resiliency for foams of the low-density class.
  • the molding and flow traits of the reactive mixture were satisfactory, yielding a molded foam body with desirable mechanical traits.
  • the early onset of load-bearing traits permitted said formulation to be used as an alternative to commercial foam-in-place and molding foam B Components. Said formulation was stable and had not phase separated even after a year of storage.
  • Example 5 Preparation and Application of the Component B Polyol Formulation To a mixing vessel, the following items were added in no particular mandatory order:
  • the combined mixture was mechanically stirred until a homogenous solution was noted.
  • the above polyol formulation was combined with PMDI in a 1 :1.35 (wt/wt) ratio utilizing continuous-flow impingement mixing.
  • the polyol and isocyanate streams were each pre-heated to 60°C or 70°C.
  • the resulting mixture was allowed to free-rise, yielding a low-density foam.
  • the molding and flow traits of the reactive mixture were not as satisfactory as the previous examples, implying that molding foam applications might take second priority in the case of this formulation.
  • the early onset of load-bearing traits permitted said formulation to be used as an alternative to commercial foam-in-place B Components. Said formulation was stable and had not phase separated even after a year of storage. Said formulation was clearly the most cost-effective of the four examples herein.

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Abstract

La présente invention concerne la préparation de corps en mousse de polyuréthane basse densité par mélange d'isocyanate avec des formulations de polyols comprenant (i) des monoesters de polysorbate tels que le polysorbate 20, le polysorbate 40, le polysorbate 60, le polysorbate 80, ou leurs combinaisons en tant que blocs de co-construction des corps en mousse, (ii) des polyols d'usage courant en tant que blocs de co-construction des corps en mousse économiques, (iii) de l'eau en tant que précurseur de dioxyde de carbone, (iv) des catalyseurs de formation de mousse, (v) des stabilisateurs de mousse et, éventuellement, (vi) des polyéthylèneglycols de faible poids moléculaire en tant qu'agent de potentialisation de la complaisance des corps en mousse.
PCT/TR2019/051238 2019-12-27 2019-12-27 Mousses de polyuréthane basse densité obtenues à partir de formulations de polyols incorporées à des monoesters de polysorbate WO2021133281A1 (fr)

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