Sustainable polyester polyols and their uses

Abstract

The present disclosure provides an isocyanate-reactive hydrogen composition that includes an increased amount of a sustainable polyester polyol. The isocyanate-reactive hydrogen composition can be combined with a polyisocyanate composition to form a reactive system that can be reacted and expanded to form a flexible foam. The flexible foam produced can be used in a variety of applications, such as automotive and furniture seating.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Patent Application No. 63 / 316,548, filed March 4, 2022, which is incorporated herein by reference.

[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT Not applicable.

[0003] Field The present disclosure relates generally to isocyanate-reactive compositions comprising at least 15% by weight of a sustainable polyester polyol, processes for producing flexible foams by reaction of the polyol composition with a polyisocyanate composition, and flexible foams obtained from such processes. [Background technology]

[0004] Flexible polyurethane foams are widely used in a variety of applications requiring the unique mechanical, sound absorption, load bearing, and / or other properties that this material offers. Flexible polyurethane foams are made by the reaction of at least one polyisocyanate containing isocyanate (NCO) groups with at least one polyol containing hydroxyl (OH) groups in the presence of a blowing agent, a surfactant, a catalyst, and other optional additives. The most commonly used blowing agent is water.

[0005] The flexible foam industry has seen a significant increase in the use of sustainable and / or bio-based polyols, which are incorporated into formulations in exchange for petroleum-based polyether polyols. The ability to claim a level of bio-renewable content in a foam provides a market competitive advantage over those that do not incorporate such polyols.

[0006] However, the use of bio-based polyols as raw materials in the manufacture of polyurethane foam products is not without its challenges. Specifically, when bio-based polyols are used in existing polyurethane foam formulations at levels greater than 10% by weight, certain physical properties (e.g., humid aged tensile, wet compression set, hysteresis loss, etc.) are degraded compared to foams made solely with petroleum-based polyols. These losses in physical properties significantly limit the amount of bio-based polyol that can be incorporated into a flexible foam or formulation.

[0007] In view of the above, developments that improve the mechanical strength properties of flexible foams made with sustainable and / or bio-based polyols and allow for the use of higher concentrations of such sustainable and / or bio-based polyols without resulting in a loss of mechanical strength properties would be a significant improvement in the art. Summary of the Invention

[0008] The present disclosure describes an isocyanate-reactive hydrogen composition comprising at least 15% by weight of a sustainable polyester polyol based on the total weight of isocyanate-reactive hydrogen-containing components present in the composition, the sustainable polyester polyol being derived from (i) a thermoplastic polyester, (ii) a hydroxylated material, and (iii) a hydrophobic material. The primary hydroxyl content can be at least about 30%, calculated from the number of primary and secondary hydroxyl groups in the ol.

[0009] The present disclosure also provides a reaction system containing a polyisocyanate composition and an isocyanate-reactive composition, the isocyanate-reactive composition including a sustainable polyester polyol and a first polyether polyol, the first polyether polyol having polyether chains containing at least about 50% by weight ethylene oxide (EO), based on the total weight of the first polyether polyol and water.

[0010] In yet another embodiment, provided is a process for producing flexible foams by reacting and expanding the above-described reactive system. Flexible foams can be used in a variety of applications, such as for seating surfaces in automobiles and furniture, or for automobile carpeting, dash insulation, steering wheels, or instrument panels, etc. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present disclosure provides an isocyanate-reactive hydrogen composition containing a sustainable polyol and its use in flexible foam production. One advantage of the isocyanate-reactive hydrogen composition of the present disclosure is that at least 15% by weight of a petroleum-based polyol can be replaced with a sustainable polyester polyol (i.e., a polyester polyol made with sustainable materials, and in some embodiments, sustainable and bio-based materials), and can be used to produce flexible foams that do not exhibit the degradation of mechanical strength properties typically seen when prior art bio-based polyols are used at similar levels. The term "bio-based" materials, as used herein, refer to materials derived from plant, animal, or microbial sources. Preferably, they are derived from plant sources. The term "sustainable" means that the materials used to produce the polyester polyols of the present disclosure are produced from raw materials that are sustainable over a long period of time (i.e., from renewable or regenerated raw materials).

[0012] When used herein, the term "comprising" and its derivatives are not intended to exclude the presence of any additional elements, steps, or procedures, whether or not they are disclosed herein. For the avoidance of any doubt, all compositions claimed herein through the use of the term "comprising" may include any additional additives, adjuvants, or compounds, unless stated to the contrary. In contrast, the term "consisting essentially of," when used herein, excludes any other elements, steps, or procedures from any subsequent recitation unless they are essential to operability, and the term "consisting of," when used, excludes any element, step, or procedure not specifically delineated or listed. The terms "or" and "and / or" refer to the recited members individually as well as in any combination, unless otherwise indicated. For example, the phrase A and / or B refers to A alone, B alone, or both A and B.

[0013] The articles "a" and "an" are used herein to refer to one or more than one (i.e., at least one) of the grammatical object of the article. By way of example, "a polyisocyanate" means one polyisocyanate or more than one polyisocyanate. The phrases "in one embodiment," "according to one embodiment," and the like generally mean that the particular feature, structure, or characteristic that follows the phrase is included in at least one embodiment of the present disclosure, and may also be included in more than one embodiment of the present disclosure. Importantly, such phrases are not necessarily referring to the same embodiment. As used herein, the term "polyisocyanate" refers to one or more polyisocyanates. When "may," "can," "could," or "might" is used to describe that a feature is included or has a certain characteristic, it does not require that particular element or feature be included or have the certain characteristic.

[0014] The terms "preferred" and "preferably" refer to embodiments that may provide certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or different circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the present disclosure.

[0015] The term "about," as used herein, allows for a degree of variability in values ​​or ranges, for example, the degree can be within 10%, within 5%, or within 1% of the stated value or of the stated range limit.

[0016] Values ​​expressed in range format should be interpreted in an open manner, not only to include the numerical values ​​specified as the limits of the range, but also to include all individual numerical values ​​or subranges subsumed within that range, as if each numerical value and subrange were specifically stated. For example, a range such as 1 to 6 should be considered to specifically disclose subranges such as 1 to 3, 2 to 4, 3 to 6, etc., as well as the individual numbers subsumed within that range, e.g., 1, 2, 3, 4, 5, and 6. This is true regardless of the breadth of the range.

[0017] The term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes both the occurrence and non-occurrence of the event or circumstance.

[0018] "Isocyanate Index" or "NCO Index" or "Index" refers to the ratio of NCO groups to isocyanate-reactive hydrogen atoms present in the formulation, given as a percentage: [NCO] x 100 / [active hydrogen] (%). In other words, NCO Index represents the percentage of isocyanate actually used in the formulation relative to the amount of isocyanate theoretically required to react with the amount of isocyanate-reactive hydrogen used in the formulation. Of course, Isocyanate Index as used herein is considered in the context of the actual foam-forming process involving isocyanate components and isocyanate-reactive components. Any isocyanate groups consumed in the preliminary steps to produce modified polyisocyanates (including isocyanate derivatives such as those referred to in the art as prepolymers), nor any active hydrogens consumed in the preliminary steps (e.g., reacting with isocyanates to produce modified polyols or polyamines) are not taken into account when calculating Isocyanate Index. Only the free isocyanate groups and free isocyanate-reactive hydrogens (including hydrogens of water) present at the actual foam formation stage are taken into consideration.

[0019] The expression "isocyanate-reactive hydrogens" as used herein refers to the sum of the active hydrogen atoms of the hydroxyl and amine groups present in the isocyanate-reactive hydrogen composition for purposes of calculating the Isocyanate Index, which means that one hydroxyl group is considered to have one reactive hydrogen, one primary amine group is considered to have one reactive hydrogen, and one water molecule is considered to have two active hydrogens for purposes of calculating the Isocyanate Index of the actual foam-forming process.

[0020] The term "isocyanate-reactive hydrogen-containing component" refers to a compound that has an isocyanate-reactive hydrogen.

[0021] The term "reactive system" refers to a combination of components, in this case polyisocyanates. , are maintained in one or more containers separate from the isocyanate-reactive hydrogen components.

[0022] The expression "polyurethane foam", as used herein, refers to a porous product as obtained by reacting a polyisocyanate with an isocyanate-reactive hydrogen component using a foam-forming agent, and in particular to a porous product obtained using water (which is involved in a reaction in which water and isocyanate groups react to give urea bonds and carbon dioxide to produce a polyurea-urethane foam) and polyols as reactive foam-forming agents, and optionally amino alcohols and / or polyamines as isocyanate-reactive hydrogen components.

[0023] The term "hydroxyl value" refers to the concentration of hydroxyl groups capable of reacting with isocyanate groups per unit weight of polyol. The hydroxyl number is reported in mg KOH / g and can be measured according to ASTM D 1638 standard.

[0024] The terms "average functionality" or "average hydroxyl functionality" of a polyol refer to the average number of OH groups per molecule. The average functionality of an isocyanate refers to the average number of --NCO groups per molecule.

[0025] The term "substantially free" refers to a composition in which a particular component or moiety is present in an amount that does not significantly affect the overall composition. In some embodiments, "substantially free" can refer to a composition in which a particular component or moiety is present in an amount of less than about 5% by weight, or less than about 4% by weight, or less than about 3% by weight, or less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, or less than 0.05% by weight, or even less than 0.01% by weight, based on the total weight of the composition, or the absence of the amount of the particular component or moiety present in the respective composition.

[0026] Accordingly, the present disclosure provides an isocyanate-reactive hydrogen composition comprising one or more isocyanate-reactive hydrogen-containing components. In one embodiment, the isocyanate-reactive composition comprises at least about 15 wt% of a sustainable polyester polyol, where the wt% is based on the total weight of the isocyanate-reactive hydrogen-containing components.

[0027] The sustainable polyester polyol can be derived from (i) a thermoplastic polyester, (ii) a hydroxylated material, and (iii) a hydrophobic material. In one embodiment, the sustainable polyester polyol has a primary hydroxyl content of at least about 30%, or at least 35%, or at least 40%, or at least 45%, calculated based on the number of primary and secondary hydroxyl groups of the polyester polyol. In other embodiments, the sustainable polyester polyol has a primary hydroxyl content of at least about 50%, or at least about 55%, or at least about 60%, or at least about 65%, or at least about 70%, or at least about 75%, or at least about 80%, or at least about 85%, or at least about 90%, or at least about 95%, calculated based on the number of primary and secondary hydroxyl groups of the polyester polyol. In yet other embodiments, the sustainable polyester polyols have a primary hydroxyl content of about 35%-100%, or about 40%-97%, or about 45%-95%, or about 55%-90%, or about 60%-85%, calculated based on the number of primary and secondary hydroxyl groups in the polyester polyol. In yet other embodiments, the sustainable polyester polyols are substantially free of secondary hydroxyl groups.

[0028] Thermoplastic polyesters that can be used to make sustainable polyester polyols are It is well known in the art. Such thermoplastic polyesters are condensation polymers resulting from the reaction of glycols with aromatic dicarboxylic acids or acid derivatives. Examples include, but are not limited to, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), glycol modified polyethylene terephthalate (PETG), copolymers of terephthalic acid and 1,4-cyclohexanedimethanol (PCT), PCTA (isophthalic acid modified PCT), polyhydroxyalkanoates such as polyhydroxybutyrate, copolymers of diols and 2,5-furandicarboxylic acid or dialkyl 2,5-furandicarboxylate such as polyethylene furanoate, copolymers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and isophthalic acid derivatives, terephthalic acid derivatives, or orthophthalic acid derivatives, dihydroferulic acid polymers, and mixtures thereof. In one embodiment, the thermoplastic polyester comprises virgin polyester, recycled polyester, or mixtures thereof. Polyethylene terephthalate is particularly preferred, with recycled polyethylene terephthalate (rPET), virgin PET, and mixtures thereof being particularly preferred. Further examples of suitable thermoplastic polyesters can be found in U.S. Patent Application Publication No. 2009 / 0131625, the disclosure of which is incorporated herein by reference.

[0029] The thermoplastic polyester component of the sustainable polyester polyol can, for example, comprise from about 5% to about 50% by weight of the total weight of the sustainable polyester polyol. In other embodiments, the sustainable polyester polyol can, for example, comprise from about 15% to about 40% by weight, or from about 20% to about 35% by weight of the total weight of the sustainable polyester polyol.

[0030] The hydroxylated material of the sustainable polyester polyol can be, for example, at least one aliphatic diol, at least one derivative thereof, or a combination thereof.

[0031] In one embodiment, the hydroxylated material can be an aliphatic diol having the formula: H.O.R. 1 -OH In the formula, R 1 is a divalent radical selected from the group consisting of: (a) an alkylene radical having 2 to 12 carbon atoms, (b) a radical having the formula: -(R 2 O) n -R 2 - In the formula, R 2 is an alkylene radical having 2 to 4 carbon atoms and n is an integer from 1 to 20; and (c) mixtures thereof.

[0032] Examples of suitable aliphatic diols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, butylene glycol, polyethylene glycol, 1,2-cyclohexanediol, and poly(oxyalkylene) polyols containing 2 to 4 alkylene radicals derived from the condensation of ethylene oxide, propylene oxide, or any combination thereof. As will be appreciated by those skilled in the art, in preparing mixed poly(oxyethylene-oxypropylene) polyols, ethylene oxide and propylene oxide can be added to the starting hydroxyl-containing reactant either as a mixture or sequentially. Mixtures of such diols can be used if desired.

[0033] In one embodiment, the hydroxylated material is, for example, diethylene glycol, glycerol, polyethylene glycol, trimethylolpropane, pentaerythritol, ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, butylene glycol, 1,2-cyclohexanediol, hexanediol, pentanediol, polyoxyalkylene diols (eg, tri- and tetraethylene glycol), derivatives thereof, and combinations thereof are possible.

[0034] The hydroxylated material of the sustainable aromatic polyester polyol can, for example, comprise about 30% to about 80% by weight of the total weight of the sustainable aromatic polyester polyol. Alternatively, the hydroxylated material of the sustainable aromatic polyester polyol can comprise about 35% to about 65% by weight of the total weight of the sustainable aromatic polyester polyol. Alternatively, the hydroxylated material of the sustainable aromatic polyester polyol can comprise about 40% to about 60% by weight of the total weight of the sustainable aromatic polyester polyol.

[0035] The hydrophobic material can include, for example, natural oils (e.g., triglycerides (especially fats and oils)) derived from renewable sources. The natural oils can be unmodified (e.g., do not contain hydroxyl functional groups), functionalized natural oil polyols, or combinations thereof. Suitable natural oils include, for example, triglyceride oil, coconut oil, cochin oil, corn oil, cottonseed oil, linseed oil, olive oil, palm oil, palm kernel oil, peanut oil, soybean oil, sunflower oil, tall oil, tallow, lesquerella oil, tung oil, whale oil, tea seed oil, sesame seed oil, safflower oil, rapeseed oil, fish oil, derivatives thereof, and combinations thereof. Suitable derivatives of natural oils include, but are not limited to, fatty acids, fatty acid methyl esters, and fatty acid alkanolamides. Examples of fatty acids include, but are not limited to, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and mixtures thereof. Another suitable fatty acid is 2-ethylhexanoic acid. Examples of fatty acid methyl esters include, but are not limited to, methyl caproate, methyl caprylate, methyl caprate, methyl laurate, methyl myristate, methyl palmitate, methyl oleate, methyl stearate, methyl linoleate, methyl linolenate, and mixtures thereof. Examples of fatty alkanolamides include, but are not limited to, tall oil fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid monoethanolamide. These suitable natural oils can be functionalized by epoxidation and / or hydroxylation reactions.

[0036] In some embodiments, the natural oil component can be, for example, castor oil, corn oil, soybean oil, functionalized castor oil, functionalized coconut oil, functionalized cochin oil, functionalized corn oil, functionalized cottonseed oil, functionalized linseed oil, functionalized olive oil, functionalized palm oil, functionalized palm kernel oil, functionalized peanut oil, functionalized soybean oil, functionalized sunflower oil, functionalized tall oil, functionalized tallow, functionalized lesquerella oil, functionalized tung oil, functionalized whale oil, functionalized tea seed oil, functionalized sesame seed oil, functionalized safflower oil, functionalized rapeseed oil, functionalized fish oil, and combinations thereof.

[0037] In some embodiments, the natural oil polyol is a functionalized natural oil that can be prepared by epoxidizing natural oil and then reacting the epoxidized oil with water and / or hydroxylated materials to convert the epoxy groups to OH groups.The epoxidized natural oil is commercially available, or alternatively, can be prepared by reacting an unsaturated natural oil with a peracid to form an epoxidized oil.Various methods for preparing epoxidized oil have been described in the art, including, for example, those described in U.S. Pat. Nos. 6,107,433, 6,433,121, 6,573,354, and 6,686,435.Suitable materials used to convert the epoxy groups to OH groups include any of the following: Reactive hydrogen compounds such as hydrogen, water, lithium aluminum hydride, sodium borohydride, ammonia, or aliphatic or aromatic amines, aliphatic or aromatic alcohols and their alkoxides (monofunctional), glycols, triols, tetraols, sugars, carboxylic acids, mineral acids including, for example, hydrochloric acid, sulfuric acid, and phosphoric acid. The amount of hydroxylating material is that amount that will react with enough epoxidized triglyceride oil to convert about 10% to about 100% of the epoxy groups to hydroxy groups.

[0038] Hydroxylation of the epoxidized natural oil can occur at a temperature range of about 50° C. to about 250° C. and a pressure range of 0 psi to about 4000 psi. The resulting natural oil-based polyols can have OH values ​​ranging from about 25 mg KOH / g to about 500 mg KOH / g and acid values ​​ranging from about 0 mg KOH / g to about 10 mg KOH / g.

[0039] In some embodiments, the hydrophobic material may comprise from about 1% to about 50% by weight of the total weight of the sustainable polyester polyol, or alternatively from about 5% to about 40% by weight of the total weight of the sustainable polyester polyol, or alternatively from about 10% to about 30% by weight of the total weight of the sustainable polyester polyol.

[0040] The sustainable polyester polyols can be made by placing components (i)-(iii) in a reaction vessel and subjecting the reactive mixture to esterification / transesterification reaction conditions at a temperature range of about 50° C. to about 300° C. for about 1 hour to about 48 hours (e.g., about 5 hours to about 24 hours). Any volatile by-products of the reaction, such as water, methanol, or ethylene glycol, can be removed from the process site, thereby forcing the ester interchange reaction to completion. The synthesis of the sustainable bio-based polyester polyols can occur under reduced pressure, atmospheric pressure, or elevated pressure. In some embodiments, components (i) and (ii) can be pre-reacted with each other and combined to form an intermediate product by removing the volatile by-products. The intermediate product can then be reacted with the remaining component (iii) through esterification / transesterification reaction conditions to form the sustainable polyester polyol.

[0041] During synthesis, an esterification / transesterification catalyst can be used to increase the reaction rate. Examples of suitable esterification / transesterification catalysts include tin catalysts (e.g., FASCAT® catalyst, available from Arkema, Inc.), titanium catalysts (e.g., TYZOR® TBT catalyst, TYZOR® TE catalyst, both available from Dork Ketal Chemical LLC), alkali catalysts (e.g., sodium hydroxide, potassium hydroxide, sodium alkoxide, and potassium alkoxide), acid catalysts (e.g., sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acid), enzymes, or combinations thereof. The esterification / transesterification catalyst can be present in an amount ranging from about 0.001% to about 0.2% by weight, based on the total weight of the sustainable polyester polyol.

[0042] According to one embodiment, the sustainable polyester polyols can have an acid value (mg KOH / g) of about <5.0, or about <2.0, or about <1.75, or about <1.5. In another embodiment, the sustainable polyester polyols can have a hydroxyl number (mg KOH / g) of about 10 to about 200, or about 25 to 100, or about 50 to about 65, or about 55 to about 60. In yet another embodiment, the sustainable polyester polyols can have a viscosity (centipoise at 25° C.) of about 200 to about 100,000, or about 1,000 to about 10,000, or about 3,000 to about 5,500, or about 3,500 to about 5,000. In yet another embodiment, the sustainable polyester polyols can have a water content (wt %) of about <0.5, or about <0.2, or about <0.1.

[0043] In one embodiment, the sustainable polyester polyol is present in the isocyanate-reactive hydrogen composition in an amount of at least about 16% by weight, or at least about 17% by weight, or at least about 18% by weight, or at least about 19% by weight, or at least about 20% by weight, or at least about 21% by weight, or at least about 22% by weight, or at least about 23% by weight, or at least about 24% by weight, or at least about 25% by weight, or at least about 26% by weight, or at least about 27% by weight, or at least about 28% by weight, or at least about 29% by weight, or at least about 30% by weight, about 31% by weight, or at least about 32% by weight, or at least about 33% by weight, or at least about 34% by weight, or at least about 35% by weight, based on the total weight of the isocyanate-reactive hydrogen-containing components.

[0044] In another embodiment, the sustainable polyester polyol is present in the isocyanate-reactive hydrogen composition in a range from about 15% to about 45% by weight, or from about 18% to about 40% by weight, or from about 20% to about 35% by weight, based on the total weight of the isocyanate-reactive hydrogen-containing component.

[0045] In another embodiment, the isocyanate-reactive hydrogen composition also includes a first polyether polyol having a polyether chain containing at least about 50 wt% ethylene oxide (EO), based on the total weight of the first polyether polyol. In some embodiments, the first polyether polyol can have a polyether chain containing at least about 60 wt%, or at least about 65 wt%, or at least about 70 wt%, or at least about 75 wt%, or at least about 80 wt%, or at least about 85 wt%, or at least about 90 wt%, or at least about 95 wt%, based on the total weight of the first polyether polyol. In yet other embodiments, the first polyether polyol can have an EO content of at least about 50 wt% to 100 wt%, or at least about 60 wt% to 90 wt%, or at least about 65 wt% to 85 wt%, based on the total weight of the polyether polyol.

[0046] Preferably, the remainder of the alkylene oxide content of the polyether chains of the first polyether polyol is derived from propylene and / or butylene oxide. More preferably, the remainder of the alkylene oxide content of the polyether chains of the first polyether polyol is derived from propylene oxide. Thus, the polyether chains of the first polyether polyol preferably have a propylene oxide content of about 50% by weight or less, more preferably a propylene oxide content of about 35% by weight or less, and even more preferably a propylene oxide content of about 30% by weight or less, based on the total weight of the first polyether polyol.

[0047] The distribution of the oxyethylene groups and other oxyalkylene groups (if present) along the polyether chain can be a random distribution, a block copolymer distribution, or a combination thereof.

[0048] The first polyether polyol can suitably be based on a hydroxyl-containing starting compound having hydroxyl groups in the range of 2 to 8, for example one or more polyfunctional alcohols. Polyether polyols based on a mixture of such hydroxyl-containing starting compounds can also be used as the first polyether polyol. Examples of suitable polyfunctional alcohols include glycol, glycerol, pentaerythritol, trimethylolpropane, triethanolamine, sorbitol, and mannitol. Advantageously, the first polyether polyol is based on a starting compound selected from glycerol or a mixture of propylene glycol (MPG) and glycerol.

[0049] In some embodiments, the first polyether polyol can have an average nominal functionality of at least 1.5, or at least 2, or at least 2.5, or at least 3. The average nominal functionality of the first polyether polyol can be up to 8, or up to 6. In other embodiments, the first polyether polyol can have an average equivalent weight of 200-2000 Da, preferably 200-1800 Da, and a molecular weight of 600-8000 Da, preferably 600-5000 Da. In yet other embodiments, the first polyether polyol can have a hydroxyl value of at least 28, while in other embodiments the hydroxyl value is up to 48.

[0050] The first polyether polyol can be prepared by any suitable process known in the art, such as by ring-opening polymerization of an alkylene oxide to a hydroxyl-containing starting material in the presence of a multimetal cyanide complex catalyst or a KOH catalyst.

[0051] In some embodiments, the first polyether polyol can be present in the isocyanate-reactive hydrogen composition in an amount of at least about 40% by weight, or at least about 45% by weight, or at least about 50% by weight, or at least about 55% by weight, based on the total weight of the isocyanate-reactive hydrogen-containing components. In other embodiments, the first polyether polyol can be present in the isocyanate-reactive hydrogen composition in an amount of from about 35% to 70% by weight, or from about 40% to 65% by weight, or from about 45% to 55% by weight, based on the total weight of the isocyanate-reactive hydrogen-containing components.

[0052] According to another embodiment, the isocyanate-reactive composition can include other isocyanate-reactive hydrogen-containing components, which can be present in an amount of 0 to 15 weight percent, based on the total weight of the isocyanate-reactive hydrogen-containing components. Such other isocyanate-reactive hydrogen-containing components can be selected from chain extenders, crosslinkers, polyether polyamines, polyols different from the sustainable polyester polyols and the first polyether polyol of the present disclosure, water, and mixtures thereof.

[0053] The chain extender has two (2) isocyanate reactive hydrogens and can be selected from amines, aminoalcohols, and diols, of which diols are preferably used. Further, the chain extender can be aromatic, cycloaliphatic, araliphatic, and aliphatic, of which aliphatic ones are preferably used. The chain extender can have an average equivalent weight of less than 150. Most preferred are aliphatic diols such as ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,2-hexanediol, 3-methylpentane-1,5-diol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, and tripropylene glycol, and aromatic diols and their propoxylated and / or ethoxylated products.

[0054] The crosslinker is an isocyanate-reactive hydrogen component containing 3 to 8 isocyanate-reactive hydrogens, and preferably has an average equivalent weight of less than 150. Examples of such crosslinkers include glycerol, trimethylolpropane, pentaerythritol, triethanolamine, polyoxyethylene polyols having an average nominal functionality of 3 to 8 and an average equivalent weight of less than 150 (such as ethoxylated glycerol, trimethylolpropane, and pentaerythritol having an equivalent weight of less than 150), and polyether triamines having an equivalent weight of less than 150.

[0055] Polyether polyamines are polyoxypropylene polyamines, polyoxyethylene polyamines, The polyether polyamines may be selected from polyoxypropylene polyoxyethylene polyamines, and polyoxypropylene polyoxyethylene polyamines, preferably having an equivalent weight (number average molecular weight divided by the number of amine groups at the polymer chain ends) of 150 to 3000. Such polyether polyamines are known in the art and include Jeffamine® ED2003 and T5000 amines.

[0056] The polyol can be a polyester polyol (different from the sustainable polyester polyol of the present disclosure), a polythioether, a polycarbonate, a polyacetal, a polyolefin, a polysiloxane, or a polyether (different from the first polyether polyol).Polyester polyols that can be used include hydroxyl-terminated reaction products of dihydric alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, or cyclohexanedimethanol, or mixtures of such dihydric alcohols, and dicarboxylic acids or their ester-forming derivatives, such as succinic acid, glutaric acid, and adipic acid, or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, or dimethyl terephthalate, or mixtures thereof.Polythioether polyols that can be used include products obtained by condensing thiodiglycol alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols, or aminocarboxylic acids. Usable polycarbonate polyols include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, or tetraethylene glycol with diaryl carbonates such as diphenyl carbonate, or with phosgene. Usable polyacetal polyols include those prepared by reacting glycols such as diethylene glycol, triethylene glycol, or hexanediol with formaldehyde. Suitable polyacetals can also be prepared by polymerization of cyclic acetals. Suitable polyolefin polyols include hydroxy-terminated butadiene homopolymers and copolymers, and suitable polysiloxane polyols include polydimethylsiloxane diols.The polyether polyol different from the first polyether polyol can have an EO content of less than about 50 wt. % based on the total weight of the polyether polyol, an average equivalent weight of 150-4000, more preferably 150-2500, and preferably an average functionality of 2-4. Such polyols include polyoxyethylene polyoxypropylene polyols in which the oxyethylene and oxypropylene units are distributed randomly, in blocks, or in combinations thereof, as well as polyoxypropylene polyols and / or polyoxyethylene polyols, and polyoxyethylene glycols having a molecular weight of 600-1000. The polyols can also include dispersions or solutions containing addition or condensation polymers in the above types of polyols. Such modified polyols, often referred to as "polymer polyols," have been well described in the prior art and include products obtained by in situ polymerization of one or more vinyl monomers, such as styrene and / or acrylonitrile, in the above polyether polyols, or by in situ reaction of polyisocyanates with amino- and / or hydroxy-functional compounds, such as triethanolamine, in the above polyols. Polyoxyalkylene polyols containing 1 to 50% by weight of dispersed polymer may be particularly useful. The particle size of the dispersed polymer is preferably less than 50 microns.

[0057] The isocyanate-reactive hydrogen composition may also include one or more known additives, such as catalysts that enhance the formation of urethane bonds, e.g., tin catalysts such as stannous ethylhexanoate and dibutyltin dilaurate, tertiary amine catalysts, e.g., dibutyltin dilaurate, diphenyl ether catalysts ... These include, but are not limited to, triethylenediamine and imidazoles, such as methylimidazole, and other catalysts, such as maleates and acetates; non-ionic surfactants; silicon-based surfactants; flame retardants; smoke suppressants; UV stabilizers; colorants; microbial inhibitors; fillers; internal release agents (such agents can be used to further enhance the release of the produced material, but are not required) and external release agents (such agents are preferably used only at the start of the initial molding, as described below).

[0058] A particularly suitable class of catalysts are the alkali metal or alkaline earth metal carboxylates. The catalyst can be a salt of any metal in Groups IA and IIA of the Periodic Table, but generally alkali metal salts such as potassium and sodium salts, especially potassium salts, are preferred. Mixtures of salts can be used, such as mixtures of potassium and sodium salts, if desired.

[0059] The carboxylate may be selected from aliphatic carboxylates having 2 to 10 carbon atoms, such as acetates, hexanoates, 2-ethylhexanoates, and octanoates. In particular, the carboxylate may be selected from those having the following formula: REA-COO-, In the formula, A is a hydrocarbon radical having 1 to 6, preferably 1 to 3, carbon atoms; E is -O- or [ka] and R is X-R1-(OR2) n -, in which X is CH3- or OH-, R1 is a hydrocarbon radical having 1 to 8, preferably 1 to 4, carbon atoms, R2 is a hydrocarbon radical having 2 to 4, preferably 2 or 3 carbon atoms, and n is an integer from 0 to 10, preferably 0 to 5.

[0060] In some embodiments, A can be selected from diradicals such as -CH2, -CH2CH2-, -CH2CH2CH2-, -CH=CHCH2-, -CH2-CH=CH, and -CH=CH-.

[0061] In some embodiments, R1 can be selected from those diradicals mentioned for A, as well as from the radicals obtained by removing two hydrogen atoms from, for example, butane, pentane, hexane, and octane. The most suitable radicals for R1 are methylene, ethylene, trimethylene, tetramethylene, and propylene.

[0062] In some embodiments, R2 can be selected from ethylene, trimethylene, tetramethylene, ethylethylene, and propylene. The most preferred groups are ethylene and propylene.

[0063] Such catalysts and their preparation are known (i.e. EP 294161, EP 220697, and EP 751114). Examples of catalysts include sodium acetate, potassium acetate, potassium hexanoate, potassium 2-ethylhexanoate, potassium ethoxyacetate, sodium ethoxyacetate, maleic acid and ethoxyethane, ethoxyethoxyethane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene ... dipropylene glycol, tripropylene glycol, ethylene glycol, dipropylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, dipropylene glycol, dipropylene glycol, dipropylene Examples of suitable catalysts include potassium salts of hemiesters of hydroxy-containing compounds with ethanol, methanol, ethanol, propanol, or butanol, and potassium salts of hemiesters of such hydroxy-containing compounds with malonic acid, succinic acid, glutaric acid, adipic acid, or fumaric acid. Mixtures of such catalysts can be used as well. The catalysts can typically be used in small amounts, for example, about 0.0015 parts by weight to about 5 parts by weight or about 0.1 parts by weight to about 0.5 parts by weight of each catalyst per 100 parts by weight of the isocyanate-reactive hydrogen-containing component.

[0064] Water can be used as a blowing agent, optionally in combination with other blowing agents known in the art, such as hydrocarbons, so-called CFCs and HCFCs, N2, and CO2. Most preferably, water is used as the blowing agent, optionally in combination with CO2. The amount of blowing agent will depend on the density desired for the flexible foam. In some embodiments, the amount of blowing agent present in the isocyanate-reactive hydrogen composition can be about 0.8% to 5% by weight, based on the total weight of the isocyanate-reactive hydrogen-containing component.

[0065] In accordance with another embodiment, provided is a reaction system comprising an isocyanate-reactive hydrogen composition of the present disclosure and a polyisocyanate composition.

[0066] In one embodiment, the polyisocyanate composition comprises an organic polyisocyanate, which may be: (1) diphenylmethane diisocyanate, comprising at least 40% by weight, preferably at least 50% by weight, or at least 60% by weight, and most preferably at least 85% by weight of 4,4'-diphenylmethane diisocyanate (4,4'-MDI); (2) carbodiimide and / or uretonimine modified variants of diphenylmethane diisocyanate (1), having an NCO value of 20% by weight or more; (3) urethane modified variants of diphenylene diisocyanate (1), having an NCO value of 20% by weight or more, which are reaction products of excess diphenylmethane diisocyanate (1) with a polyol having an average nominal hydroxyl functionality of 2 to 4 and an average molecular weight of up to 1000, such as: (4) prepolymers, having an NCO value of 20% by weight or more, and having an excess of the above. A reaction product of any of the organic polyisocyanates (1) to (3) with a polyol having an average nominal hydroxyl functionality of 2 to 6, an average molecular weight of 2000 to 12000, and preferably a hydroxyl value of 15 to 60 mg KOH / , the polyol being, for example, a petroleum-based polyester polyol and a polyether polyol, in particular a polyoxyethylene polyoxypropylene polyol, having an average nominal hydroxyl functionality of 2 to 4, an average molecular weight of 2500 to 8000, and preferably a hydroxyl value of 15 to 60, and preferably an oxyethylene content of 5 to 25% by weight (the oxyethylene is preferably at the polymer chain end) or an oxyethylene content of 50 to 90% by weight (the oxyethylene is preferably randomly distributed over the polymer chain), or (5) a mixture of any of the above organic polyisocyanates. The organic polyisocyanates (1) and (2) and mixtures thereof are suitable as the organic polyisocyanate.

[0067] The organic polyisocyanate may be blended with one or more other polyisocyanates that are not any of the organic polyisocyanates (1)-(4) above. When present, such other polyisocyanates may comprise, for example, up to 25% by weight, or up to 10% by weight, or up to 5% by weight, based on the total weight of the polyisocyanate composition. The other polyisocyanates may be aliphatic polyisocyanates, cycloaliphatic polyisocyanates, araliphatic polyisocyanates, and preferably aromatic polyisocyanates, such as toluene diisocyanate in the form of the 2,4 and 2,6-isomers and mixtures thereof, as well as prepolymerizations of toluene diisocyanate with natural fat / oil derived polyols, polyoxyalkylene polyols having alkylene oxides that have been subjected to ring-opening addition polymerization with natural fat / oil derived polyols, or petroleum derived polyoxyalkylene polyols. You can choose from the following:

[0068] According to another embodiment, provided is a process for producing flexible foam by reacting and expanding a polyisocyanate composition and an isocyanate-reactive hydrogen composition of a reaction system. The reaction can be carried out at an NCO index of 40 to 120, preferably 70 to 110. Flexible foams can have a density of about 15 kg / m. 3 ~Approx. 150kg / m 3 , preferably about 15 kg / m 3 ~Approx. 54kg / m 3 , and most preferably about 25 kg / m 3 ~about 50kg / m 3 (ASTM D 3574, Test A). In another embodiment, provided is a flexible foam made according to the process of the present disclosure.

[0069] The molding process can be performed with or without limited foam expansion. Unlimited foam expansion includes providing the polyisocyanate composition and the isocyanate-reactive hydrogen composition in an open container and forming and expanding the foam without a top-closing lid. The expanding foam will expand vertically against the weight of the atmosphere and / or the weight of a thin film. One such example in which a free rise process may be performed is by dispensing the reaction system into a trough where it expands and cures. Limited foam expansion includes expanding the foam in a container that imparts weight to the expanding foam, or expanding the foam in a closed mold where the expansion is constrained by the internal dimensions of the cavity, producing a foam with dimensions and shape corresponding to those of the mold cavity.

[0070] Preferably, the reaction is carried out in a closed mold, with limited foam rise. This process can be carried out in any type of mold known in the art. Examples of such molds include, but are not limited to, molds used commercially to make polyurethane furniture parts, automobile seats and other automobile parts, such as armrests and headrests, bedding, mattresses, etc. Mold materials can be made of, for example, metals, such as steel, aluminum, and epoxy resins.

[0071] The molding process can be a so-called cold cure molding process, in which the polyisocyanate composition and the isocyanate-reactive hydrogen composition used to make the foam are fed to a mold at a temperature between ambient and up to about 80° C., preferably up to about 70° C., and during the process the mold is maintained at a temperature between ambient and up to 80° C., preferably up to 70° C. After demolding, the foam is optionally cured at a temperature between ambient and about 100° C., preferably between ambient and about 70° C., for a period of between 1 hour and 2 days.

[0072] The various components of the reaction system can be mixed in any order, although it is preferred to add the components of the polyisocyanate composition last or simultaneously with the other components of the isocyanate-reactive hydrogen composition to avoid premature reactions before the remainder of the components can be added. The various components that make up the isocyanate-reactive hydrogen composition can all be mixed prior to forming the reaction system. Alternatively, the various components of the isocyanate-reactive hydrogen composition can be mixed simultaneously when mixing with the components that make up the polyisocyanate composition. It is also possible to have various subcombinations of the components of the isocyanate-reactive hydrogen composition and mix these subcombinations together at the same time that the polyisocyanate composition is added.

[0073] The flexible foams of the present disclosure may be useful in a variety of applications, such as automobile seating, carpeting, dashboards, steering wheels or instrument panels, bedding, carpet underlay, flexible packaging foams, acoustic foams, furniture seating, and other "comfort" applications. Comfort applications include those in which the foam absorbs the heat of the user's body or water vapor that evaporates from the body during use. The foam or foam-containing article in such applications will often support at least a portion of the user's weight and will be compressed during use. Examples of such comfort applications include pillows, mattress tops, mattresses, comforters, quilting, insulation fabrics, and the like. Thus, according to another embodiment, an article can be provided that includes the flexible foam of the present disclosure. The article can be, but is not limited to, a seat cushion or seat back for use in a vehicle or in furniture.

[0074] The following examples are provided to illustrate the disclosure and are not intended to limit the scope of the disclosure. EXAMPLES

[0075] Example 1 Synthesis of sustainable polyester polyols according to the present disclosure A round-bottom reactor was fitted with a distillation column, condenser and vacuum pump, to which polyethylene terephthalate (PET) pellets, diethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol 400 (PEG 400) and Tyzor® TE catalyst were added. The reaction mixture was heated to 230° C. to digest the solid PET pellets. After all the solid PET pellets were dissolved, the temperature was increased to 240° C. and vacuum was applied, starting at 200 torr. By-product ethylene glycol (EG) was collected and the vacuum was gradually increased to 10 torr near the end of the reaction. The vacuum was then stopped when the head temperature dropped to 70° C. Soybean oil (SBO) and epoxidized soybean oil (ESBO) were then added to the reactor and the reaction was maintained at 240° C. for at least 2 hours until the material was clear and no haze remained. A sample was taken to ensure that the acid number was less than 1.5 mg KOH / g, and the initial OH number was also measured. Optionally, glycol can be added to the reactor to adjust the OH number of the final product to the desired specifications. The final sustainable polyester polyol was then cooled to room temperature and transferred to a container. Various systems containing an isocyanate-reactive hydrogen composition and a polyisocyanate composition were then prepared and reacted to produce flexible foams. The reaction systems and foams produced therefrom in the examples were as follows: [Table 1] 1 6000MW EO triol (75% EO), OHv=36 2 6000MW EO triol (28% EO), OHv=28 * At 2000MW, it has a calculated primary OH content of 60% 4 Approximately 930MW with 100% secondary OH content 5 1,3-Propanediamine, N'-(3-(dimethylamino)propyl)-N,N-dimethyl 6 N(3-Dimethylaminopropyl)-N,N-diisopropanolamine Dent after 10 minutes = (foam height at the end of initial expansion - foam height 10 minutes after the end of initial expansion) / (foam height at the end of initial expansion)

[0076] Typical 10 minute dent values ​​for molded seat foams are usually in the range of 1-3%. As shown in Table 1 above, foam quality and stability deteriorates as the primary OH content of the bio-based polyester polyol in the formulation decreases. Commercially available bio-based polyols with no primary OH content show significant deterioration in terms of dent and foam quality.

[0077] While the forgoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, the scope of which will now be set forth in the following claims. This is determined by the scope of the request.

Claims

1. 1. An isocyanate-reactive hydrogen composition comprising at least 15 weight percent of a sustainable polyester polyol derived from (i) a thermoplastic polyester, (ii) a hydroxylated material, and (iii) a hydrophobic material, the sustainable polyester polyol having a primary hydroxyl content of at least about 30 percent, calculated from the number of primary and secondary hydroxyl groups in the polyester polyol, and the weight percent is based on the total weight of isocyanate-reactive hydrogen-containing components present in the composition.

2. 10. The isocyanate-reactive hydrogen composition of claim 1, further comprising a first polyether polyol having polyether chains containing at least about 50 weight percent ethylene oxide (EO), based on the total weight of the first polyether polyol.

3. 3. The isocyanate-reactive hydrogen composition of claim 2, wherein the polyether polyol has at least about 70 weight percent EO-containing polyether chains, based on the total weight of the first polyether polyol.

4. 2. The isocyanate-reactive hydrogen composition of claim 1, wherein the thermoplastic polyester is a recycled polyester.

5. The hydroxylated material is selected from (1) an aliphatic diol having the formula: HO-R １ -OH In the formula, R １ is defined as: (a) an alkylene radical having 2 to 12 carbon atoms, (b) a radical of the formula: -(R ２ O) ｎ -R ２ - In the formula, R ２ is an alkylene radical having 2 to 4 carbon atoms and n is an integer from 1 to 20, and (c) mixtures thereof. is a divalent radical selected from the group consisting of 2. The isocyanate-reactive hydrogen composition of claim 1.

6. 10. The isocyanate-reactive hydrogen composition of claim 1, wherein the hydrophobic material is a natural oil, a functionalized natural oil, or a combination thereof.

7. 3. The isocyanate-reactive hydrogen composition of claim 2, wherein the first polyether polyol is present in the isocyanate-reactive hydrogen composition in an amount of about 35% to 70% by weight, based on the total weight of the isocyanate-reactive hydrogen-containing components.

8. 10. The isocyanate-reactive hydrogen composition of claim 1 further comprising water and optionally one or more of a catalyst, a non-ionic surfactant, a silicon based surfactant, a flame retardant, a smoke suppressant, a UV stabilizer, a colorant, a microbial inhibitor, a filler, an internal mold release agent, and an external mold release agent.

9. 2. The isocyanate-reactive hydrogen composition of claim 1, wherein the sustainable polyester polyol has a primary hydroxyl content of at least about 45%, calculated from the number of primary and secondary hydroxyl groups in the polyester polyol.

10. A reactive system comprising: (a) a polyisocyanate composition comprising an organic polyisocyanate; and (b) an isocyanate-reactive composition comprising: (b1) at least 15% by weight of: (i) a thermoplastic polyester; (ii) a hydroxyl group; the reactive system comprising: a silylating material; and (iii) a sustainable polyester polyol derived from a hydrophobic material, the sustainable polyester polyol having a primary hydroxyl content of at least about 30%, calculated from the number of primary and secondary hydroxyl groups in the polyester polyol, said weight percent being based on the total weight of isocyanate-reactive hydrogen components present in the composition; (b2) a first polyether polyol having polyether chains containing at least about 50 weight percent ethylene oxide (EO), based on the total weight of the first polyether polyol; and (b3) water.

11. 11. The reactive system of claim 10, wherein the organic polyisocyanate is selected from: (1) diphenylmethane diisocyanate comprising at least 40 wt.% 4,4'-diphenylmethane diisocyanate (4,4'-MDI), based on the total weight of diphenylmethane diisocyanate; (2) carbodiimide and / or uretonimine modified variants of diphenylmethane diisocyanate (1) having an NCO value of 20 wt.% or greater; and (3) mixtures thereof.

12. The reactive system of claim 11, wherein the organic polyisocyanate is diphenylmethane diisocyanate containing at least 50% by weight of 4,4'-MDI.

13. 11. The reaction system of claim 10, wherein the isocyanate-reactive hydrogen composition further comprises a catalyst.

14. 11. The reactive system of claim 10, wherein the sustainable polyester polyol has a primary hydroxyl content of at least about 45%, calculated from the number of primary and secondary hydroxyl groups in the polyester polyol.

15. A process for producing a flexible foam comprising reacting the polyisocyanate composition and the isocyanate-reactive hydrogen composition of the reaction system of claim 10 and expanding and molding the composition.

16. The process of claim 15, wherein the reaction is carried out at an NCO index of 40 to 120.

17. 16. A flexible foam produced according to the process of claim 15.

18. 20. An article comprising the flexible foam of claim 17.

19. 20. The article of claim 18 which is a seat cushion or backrest for use in a vehicle or in furniture.

20. 20. The article of claim 19, for use in automotive carpeting, dash insulation, steering wheel, or instrument panel.

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