Depolymerization of polyurethanes, polyureas or polyisocyanurates to polyol products

Abstract

Reacting a waste polymeric product comprising a thermoset having urethane bonds, urea bonds, and / or isocyanurate bonds; a polycarboxylic acid or anhydride; a first polyether polyol having number average molecular weight of from 800 to 5000 grams / mole, and an average of at least 2 hydroxyl groups per molecule wherein at least 50%, hydroxyl groups are primary alcohol; a second a second polyether polyol having a number average molecular weight less than 350 grams / mole, and, optionally, a third polyether polyol having an average of from 1.8 to 7 hydroxyl groups per molecule and having a number average molecular weight of greater than 350 up to 1000 grams / mole can form a reaction product composition directly useful in forming new polyurethane materials.

Description

86172-WO-PCT (DC200018PCT)DEPOLYMERIZATION OF POLYURETHANES, POLYUREAS OR POL YISOCYANUR ATES TO POLYOL PRODUCTSFIELD OF THE INVENTION

[0001] This invention relates to a method of recycling polyurethanes, polyureas or polyisocyanurates, particularly polyurethane foams.BACKGROUND OF THE INVENTION

[0002] Recycling of polymeric materials can be an important approach to reducing polymer (e.g., plastic) waste and also reducing raw material supply demand.

[0003] Recycling of thermosetting material, such as polymers that have both urethane, urea, and / or isocyanurate linkages typically involves chemolysis (i.e., chemical decomposition to simpler and / or smaller compounds). These polymers may be, for example polyurethanes, polyureas, polyisocyanurates, polyurethane / ureas (having both urethane and urea linkages), polyurethane / isocyanurates (having both urethane and isocyanurates linkages), polyurethane / urea / isocyanurates (having urethane, urea and isocyanurates linkages), and polyurea / isocyanurates (having urea and isocyanurate linkages).100041 Past approaches to chemolysis of polyurethanes and polyureas typically involve forming a liquid, dispersion, or paste-like reaction mixture including reagents and fragments of polyurethane products to be recycled. The reagent(s) react with the polyurethane to break down the polyurethane. The reaction product mixture tends to be multi -phase and / or unstable over time (i.e., lack shelf stability). The reaction product can further include primary amine by-products that can interfere with desired reactions when the reaction product is used in forming new polyurethane products. Accordingly, these processes typically include separation and / or purification steps to isolate the desired reaction products before the reaction products can then be used in subsequent chemical processes.

[0005] Certain chemolysis reactions may produce reaction products that have high hydroxyl number (or OH number) and / or primary amine byproducts from the waste polymer having urethane, urea, and / or isocyanurate linkages, making them less ideal or unsuitable for many end use applications. Products from a recycling process having moderate OH number are highly desirable for manufacturing of subsequent polyurethane products such as rigid polyurethane foams.

[0006] It would be desirable to have an efficient, simple, and / or rapid means of converting waste thermosetting polymeric materials having urethane, urea, and / or isocyanurate linkages by chemolysis to form a reaction product composition which can be used in forming new products. It would also be desirable to have a reaction product86172-WO-PCT (DC200018PCT) composition characterized by one or more of the following: having good stability (e.g., good shelf life without macroscopic phase separation); having low amount of primary amines; suitable for being directly used in subsequent reaction with other materials to form new and useful polymeric articles without the need for costly, cumbersome, lengthy or time consuming separation of the reaction products; and / or having a moderate OH number. SUMMARY OF THE INVENTION

[0007] A method comprising forming a reaction mixture. The reaction mixture comprises a waste polymeric product comprising a thermoset having urethane bonds, urea bonds, isocyanurate bonds, or a combination of two or more urethane, urea or isocyanurate bonds; a polycarboxylic acid or anhydride; a first polyether polyol having number average molecular weight of from 800 to 5000, preferably 1000 to 4000, more preferably 1200 to 3000 grams / mole and having an average of at least 2 hydroxyl groups per molecule wherein at least 50%, preferably at least 60%, more preferably at least 70%, yet more preferably at least 80%, and most preferably at least 90% of the hydroxyl are primary alcohol; a second polyether polyol having a number average molecular weight less than 350, preferably less than 300, grams / mole, and, optionally, a third poly ether polyol having an average of from 1.8 to 7 hydroxyl groups per molecule and having a number average molecular weight of greater than 350, preferably greater than 400 grams / mole, up to 1000, or up to 800 grams / mole. Reacting the reaction mixture to chemolyze (decompose) the waste polymeric product to form a reaction product composition.DETAILED DESCRIPTION OF THE INVENTION

[0008] The present inventors discovered that it is beneficial, in chemolysis of a waste thermosetting polymeric material that comprises urethane, urea, and / or isocyanurate linkages, to use of a mixture of a first polyether polyol having a relatively high molecular weight and comprising primary alcohol groups, a second polyether polyol having a lower molecular weight, and, optionally, a third a polyether polyol having a relatively high molecular weight and comprising secondary alcohol groups. Particularly, the reaction product composition formed from this chemolysis can have good shelf stability and / or can be substantially homogeneous and can comprise low amount of primary amine by-products, such that the reaction product composition can be directly used to form new polyurethane products. Furthermore, if at least a portion of the polyether polyols include polyols having three or more hydroxyl groups per molecule, the reaction product can have an OH number and average hydroxyl (OH) functionality (i.e., functionality is number of OH groups per molecule) in a desirable range for forming future cross-linked polyurethanes by reacting the86172-WO-PCT (DC200018PCT) reaction product composition with a polyisocyanate to produce a new polyurethane product, such as a rigid polyurethane foam.

[0009] Particularly, the present inventors also found that if a low molecular weight primary alcohol polyether polyol is present in significant amounts in the reaction mixture in combination with a high molecular weight polyether polyol having secondary alcohol groups, the residue of the waste thermosetting polymeric material (e.g., waste polyurethane, waste polyurethane / urea, waste polyurethane / isocyanurate, waste polyurethane / isocyanurate / urea, waste polyurea, waste polyurea / isocyanurate, or waste polyisocyanurate), may not be fully dispersed in the reaction product composition, as evidenced by phase separation and / or precipitation. By “residue” is meant a portion (i.e., chemical group or moiety) of the original waste thermosetting polymeric material after the breaking of the urethane, isocyanurate, and / or urea bonds. Without wishing to be bound by theory, it is believed that a higher molecular weight polyether polyol better facilitates dispersion of the residue of the waste thermosetting polymeric material (e.g., waste polyurethane, waste polyurethane / urea, waste polyurethane / isocyanurate, waste polyurethane / isocyanurate / urea, waste polyurea, waste polyurea / isocyanurate, or waste polyisocyanurate) by reacting with the residue to form a dispersible component in the reaction product mixture. However, low molecular weight polyether polyols, particularly those with a majority of their hydroxyl groups being a primary alcohol group, can react more quickly with the residue but will not provide dispersibility of the residue. The present inventors discovered that when using a higher molecular weight polyether polyol that comprises a majority of primary alcohol groups, the reaction rates of the lower molecular weight polyether polyol and the higher molecular weight polyether polyol is better balanced providing more residue bonded to higher molecular weight polyether polyols thereby providing better dispersion of the residue of the thermosetting polymeric material (e.g., waste polyurethane, waste polyurethane / urea, waste polyurethane / isocyanurate, waste polyurethane / isocyanurate / urea, waste polyurea, waste polyurea / isocyanurate, or waste polyisocyanurate). This leads to a reaction product mixture that is more homogeneous and / or has better shelf stability.

[0010] The waste polymeric product comprises as the major component a thermoset polymer comprising urethane, urea, and / or isocyanurate bonds. For example, the waste polymeric product can comprise a polyurethane, a polyurethane / urea, a polyurethane / isocyanurate, a polyurethane / urea / isocyanurate, a polyurea, a polyurea / isocyanurate, or a polyisocyanurate. For example, the waste polymeric product can comprise greater than 50, greater than 60, greater than 70, greater than 80, or greater than 9086172-WO-PCT (DC200018PCT) and up to 100, up to 99, up to 98, up to 97, up to 96, or up to 95 weight percent (wt%) of the thermoset polymer comprising urethane, urea, and / or isocyanurate bonds (e.g. waste polyurethane, waste polyurethane / urea, waste polyurethane / isocyanurate, waste polyurethane / isocyanurate / urea, waste polyurea, waste polyurea / isocyanurate, or waste polyisocyanurate) based on total weight of the waste product. The remainder of the waste product may include one or more additives (e.g., fillers, catalysts, surfactants, pigments, etc.); impurities; other polymers that had been mixed or blended with the polyurethane; residual amounts from adjacent layers adhered to the polyurethane waste product such as metal foils, craft paper, or polymers, or moisture.

[0011] The waste polymeric product comprising a thermoset polymer comprising urethane, urea, and / or isocyanurate bonds can be any such product which is desired to be recycled. For example, the waste polymeric product can comprise a polyurethane based on any common polyols such as a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyacrylate polyol, a copolymer polyol, a dispersed polyol, a natural oil derived polyol, or a mixture of these types of polyols. As another example, the waste polymeric product to be recycled can be, for example, a flexible polyurethane foam. Notably flexible polyurethane foams typically include both urethane and urea linkages and can be considered a polyurethane / urea. Rigid polyurethane or polyisocyanurate foams can include isocyanurate linkages in addition to urethane and urea linkages.

[0012] While not required, to increase surface area for reaction, the waste polymeric product can be provided in the form of fragments. For example, a polyurethane source (e.g., a polyurethane foam, such as a flexible polyurethane foam) can be cut into pieces and then shredded or chopped to form fragments. The size of the fragments can be, for example, from 0.1, from 0.5, or from 1 up to 100, up to 50, up to 10, or to up 5 millimeters. The waste polymeric product to be converted can initially be in solid form and, if initially in the form of a low density foam, can be pre-processed into a higher density or more compact form to facilitate its loading into a reaction vessel.

[0013] The waste polymeric product can be present in an amount of from 5, from 10, from 20, or from 30 up to 70, up to 60, up to 55, or up to 50 weight percent based on total weight of the reaction mixture. The reaction mixture includes the waste product, the polycarboxylic acid or anhydride, the first polyether polyol, the second polyether polyol, optionally, a third polyether polyol, and any additional optional ingredients. The entire waste polymeric product can be present in the reaction mixture at the beginning of the process or the waste polymeric product can be added in aliquots over time. The latter approach can86172-WO-PCT (DC200018PCT) facilitate better wetting of the waste polymeric product during a decomposition process. The “initial stage’- of the process includes the time up until the entire charge of the waster polymeric product has been added to the reaction mixture.

[0014] The polycarboxylic acid or anhydride thereof can be, for example, phthalic anhydride, phthalic acid, maleic anhydride, maleic acid, fumaric acid, succinic anhydride, succinic acid, alkenylsuccinic anhydrides and acids, (e.g., dodecenyls uccinic anhydride), tetrahydrophthalic anhydride, tetrahydrophthalic acid, methyl tetrahydrophthalic anhydride, methyl tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, methyl hexahydrophthalic anhydride, methyl hexahydrophthalic acid, nadic anhydride, nadic acid, methyl nadic anhydride, methyl nadic acid, citric acid, isocitric acid, or mixtures of two or more thereof. The amount of the polycarboxylic acid or anhydride thereof can be from 1 , from 3, from 5, or from 7 up to 20, up to 17, or up to 15 weight percent based on total weight of the total reaction mixture including the initial reaction mixture, and if later charges are used, the total reaction mixture including initial and subsequent charges of reactants. The polycarboxylic acid or anhydride or a portion of the total amount thereof is provided in the initial stage of the process. However, a portion the polycarboxylic acid or anhydride can be added, for example as a second aliquot, after the initial stage, (e.g., after the final charge of the waste polymeric product, such as 30 minutes, 1 hour or 2 hours after the final charge of the waste polymeric product , or at a time for example, from 2, from 3, from 4, from 5 hours after the beginning of the reaction up to for example about 8 hours after the beginning of the reaction). For example, from 1, from 5, from 10, from 15 or from 20 up to 40, up to 35, up to 30 weight percent of the polycarboxylic acid or anhydride based on total weight of the polycarboxylic acid or anhydride used in the chemolysis process can be added at such a later time in the process. For example, when a second portion of the polycarboxylic acid or anhydride is added after the initial stage, (e.g., after the final charge of the waste polymeric product, such as 30 minutes, 1 hour or 2 hours after the final charge of the waste polymeric product , or at a time for example, from 2, from 3, from 4, from 5 hours after the beginning of the reaction up to for example about 8 hours after the beginning of the reaction) the weight ratio of the polycarboxylic acid or anhydride in the initial stage of the reaction to the second portion provided after the initial stage can be from 99:1 , from 95:5, from 90:10, or from 80:20 up to 60:40, up to 65:35 or up to 70:30. This later addition (e.g., charge or aliquot) can facilitate reduction of aromatic amine content by reaction of the acid or anhydride with the amine that may form during chemolysis reactions.86172-WO-PCT (DC200018PCT)

[0015] The first polyether polyol comprises hydroxyl groups that are primary alcohols. For example, at least 50, at least 60, at least 70, at least 80, at least 90, at least 95 up to 100 or up to 99% on the hydroxyl groups are primary alcohols. The number average molecular weight of the first polyether polyol can be for example from 800, or from 1000 up to 5000, up to 4000 or up to 3000 grams per mole. The first polyether polyol can be a block polymer or oligomer.

[0016] The first polyether polyol can have the structure:where “m” is independently in each occurrence an integer of from 1, from 2, from 3 up to 57, up to 30, up to 15, or up to 8; “n” is independently in each occurrence an integer of from 0, from 1, from 5 or from 10 up to 36, up to 24, or up to 15; p is an integer of 2, 3, 4, 5, or 6, preferably 2 or 3, more preferably 2; a, b, and c are independently in each occurrence an integer of 0, from 1, from 2, from 3, or from 4, up to 57, up to 50, up to 40, up to 30, or up to 20; Ri is an alkyl group of 1-3 carbon atoms, preferably 1 carbon atom; and A is a direct bond or is a multi- valent (i.e., p- valent) radical group of alkyl, aryl, alkylaryl, or cycloalkyl. In this structure, from 15, from 20, from 25 or from 30 mole% up to 100, up to 80, up to 60, up to 40, or up to 35mole% of the alkyl-oxide) repeat units can be ethylene oxide (i.e., - (CH2CH2O)- oxide with the remainder being propylene oxide -(CsHeO)- or butylene oxide - (C4HSO)- based on total number of alkyl oxide repeat units. In this structure (m+a*n) / (m+a*n+b*n+c*n) can be from 0.15, from 0.2 from 0.25 or from 0.3 up to 1, up to 0.9 or up to 0.8, up to 0.6, up to 0.4, or up to 0.35.

[0017] The first polyether polyol can have the structure (HO-CH2-R2)q-(YO) wherein YO is a polyether group, R2is a direct bond or an alkyl group of 1, 2 or 3 carbon atoms, and q is an integer of 2, 3, 4, 5, 6 preferably 2 or 3, more preferably 2. YO can comprise at least 15, at least 20, at least 25 or at least 30 mole% up to 100, up to 80, up to 60, up to 40 or up to 35 mole percent of repeat units of ethylene oxide, based on total repeat units in the first polyether polyol. Additional repeat units of propylene oxide and / or butylene oxide preferably can be included.

[0018] For example, YO can comprise a block of ethylene oxide repeat units and a block propylene oxide (or butylene oxide) repeat units. For example, the structure of Y O can be ethylene oxide capped polypropylene oxide. Alternatively, Y O could comprise a block of86172-WO-PCT (DC200018PCT) propylene oxide repeat units or a block of butylene oxide repeat units. For example the first polyether polyol can have a structureEO Cap PO Block PO Block EO Cap where x and y are integers of 1 or more and are selected to provide the desired molecular weight and 0.18<x / y<2.5.

[0019] The first polyether polyol can be present in the reaction mixture in an amount of from 5, from 8, or from 10 up to 40, up to 30, up 25, or up to 23 weight percent based on total weight of the reaction mixture. However, at higher molecular weights, such as number average molecular weights above 1000, or above 1500 grams per mole particularly for an EO capped PO structure (e.g., an ethylene oxide (EO) capped polyether polyol comprising a majority of a propylene oxide block), the first poly ether polyol may be desirably present in amounts of no more than 26 or no more than 25 weight percent. The first polyether polyol can be present in an amount such that it contains of from 1 , from 2, or from 3 up to 20, up to 15, up to 10 or up to 7 mole% of the total hydroxyl equivalents from all polyols in the reaction mixture including the initial reaction mixture, and if later charges are used, the total reaction mixture including initial and subsequent charges of reactants. However, for the first polyether polyol having relatively high molecular weights, such as number average molecular weights above 1000, or above 1500 grams per mole, particularly for example, an EO capped PO structure, the first poly ether polyol may be desirably present in amounts of 1 to 10 mol % of the total hydroxyl equivalents from all polyols in the reaction mixture including the initial reaction mixture, and if later charges are used, the total reaction mixture including initial and subsequent charges of reactants.

[0020] The second polyether polyol has a number average molecular weight of from 120, from 130, form 140, from 150, from 160, from 170, from 180, from 190 or from 200 up to 350, up to 330, up to 320, up to 310, up to 300, up to 290, or up to 280 grams per mole. The second polyether polyol can have an OH number of, for example, from 650, from 660, from 670, from 680, from 690, or from 700 up to 1500, up to 1200, up to 1100, or up to 1050. The second polyether polyols can have ethyloxy, propyloxy or butyloxy groups with the hydroxyl group on the second carbon atom. The second polyether polyols can, for example be diols such as diethylene glycol or dipropylene glycol. The second polyether polyol can be, for example, tripropylene glycol. The second polyether polyol can be for example a triol86172-WO-PCT (DC200018PCT) such as a polyether polyol prepared by propoxylating glycerin. Other specific examples include polyethylene glycol with a number average molecular weight of 200 (PEG 200), propylene glycol (provided the hydroxyl group meets the limits of being secondary alcohol as discussed above) and VORANOL™ CP260 (from Dow Inc.). The second polyether polyol can be present in an amount of from 5, from 8, from 10, from 12 or from 14 up to 40, up to 35, up to 30, or up to 20 weight percent based on total weight of the total reaction mixture including the initial reaction mixture, and if later charges are used, the total reaction mixture including initial and subsequent charges of reactants. The second polyether polyol can be present in an amount of from 20, from 30, from 40, or from 55 up to 80, up to 75, up to 70, up to 65 or up to 60 mole% of the total hydroxyl equivalents from all polyols in the reaction mixture including the initial reaction mixture, and if later charges are used, the total reaction mixture including initial and subsequent charges of reactants (e.g. the first and second polyether polyols and any optional polyether polyolsused in the chemolysis process. The second polyether polyol or a portion of the total amount thereof is provided in the initial reaction mixture. However, a portion of the second polyether polyol can be added, for example as a second aliquot, after the initial stage of the reaction, (e.g., after the final charge of the waste polymeric product, such as 30 minutes, 1 hour or 2 hours after the final charge of the waste polymeric product , or at a time for example, from 2, from 3, from 4, from 5 hours after the beginning of the reaction up to for example about 8 hours after the beginning of the reaction), the weight ratio of the second polyether polyol added in the initial stage of the reaction to the second portion provided after the initial stage can be from 90:10, from 80:20, or from 75:25 up to 50:50, up to 55:45 or up to 60:40 This later addition (e.g., charge or aliquot) can facilitate esterification of any unreacted acid that may otherwise be in the reaction product.

[0021] The optional third polyether polyol can have an average from 1.8, from 1.9, from 2, from 2.5, or from 3 up to 7, up to 6, up to 5, or up to 4 hydroxyl groups per molecule and having a number average molecular weight of greater than 350, or greater than 400 grams / mole up to 1000, up to 900, up to 800 gram. The third polyether polyol includes secondary alcohol groups in amounts of more than 50, more than 60, more than 70, more than 80 up to 100, up to 98, up to 95 mole% of based on total number of alcohol groups of the third polyether polyol. For example, the third polyether polyol can be or can include a poly(propylene ether) polyol. For example, the third polyether polyol can be or can include a triol. The third polyether polyol, can be for example a glycerine propoxylated polyether triol. The third polyether polyol can be present in an amount of from 0, from 5, from 10, from 1586172-WO-PCT (DC200018PCT) up to 80 up to 70, up to 60, up to 50, up to 40, up to 30, or up to 25 weight percent based on total weight of the reaction mixture. The third polyether polyol can be present in an amount of 0, of greater than 0, of from 5, from 10, from 20 or from 35 up to 70, up to 50, or up to 40 mole% of the total hydroxyl equivalents from all polyols in the reaction mixture including the initial reaction mixture, and if later charges are used, the total reaction mixture including initial and subsequent charges of reactants. The molecular weight can be determined for example by gel permeation chromatography as described ASTM D5296-19 using a polyethylene glycol calibration standard and uninhibited THF solvent. Note, however, that molecular weight of polyether polyol reactants can alternatively be the nominal molecular weight specified by the vendor or calculated from the average hydroxyl number and the average hydroxyl functionality of a polyol specified by the vendor.

[0022] The reaction mixture can exclude grafted polyether polyols.

[0023] No catalyst is required for the reaction. However, there can be a catalyst preferably in amounts of from 0.01, from 0.05, from 0.1, or from 0.2 up to 5, up to 4, up to 3, up to 2, up to 1, or up to 0.7 weight percent based on total weight of the reaction mixture. The catalyst can be, for example a metal salt of an organic acid, such a Group 1 metal of an organic acid preferably having 5-10 carbon atoms, or, as a specific example, potassium octoate; a metal carboxylate, or a metal hydroxide. Other choices for catalyst may include: tin(II) salts of organic carboxylic acids (e.g. tin(II) diacetate); bismuth salts of organic carboxylic acids (e.g. bismuth octanoate); cyclic and / or linear tertiary amines and / or long chain amines (e.g., bis-(2-dimethylaminoethyl)ether; N,N,N',N", N"-pentamethyldiethylene- triamine, triethyl amine, tributyl amine; N,N-dimethylaminopropylamine, dimethylethanolamine, N,N,N',N'-tetramethylethylenediamine, dimethylbenzylamine, triethylenediamine); tetraalkylammonium hydroxides (e.g., tetramethylammonium hydroxide); alkali metal hydroxides (e.g., sodium hydroxide); alkali metal alkoxides (e.g., sodium methoxide); and combinations thereof. Some commercially available depolymerization catalysts include POLYCAT® 5, POLYCAT® 8, DABCO® 33-LV, and DABCO® T-12, DABCO® TMR-2, DABCO® TMR-20, DABCO® TMR-30, DABCO® TMR-7, DABCO® K 2097; DABCO® KI 5, POLYCAT® 41, and POLYCAT® 46 all available from Evonik. The reaction mixture can be free of halide containing catalysts.

[0024] The process according to the invention can be carried out, for example, in a corrosion resistant vessel. The vessel can be constructed, for example, from glass or stainless steel. The reaction can be carried out at ambient pressure, so the vessel need not be designed to resist pressures above ambient. The vessel can be equipped with mechanical stirring, for86172-WO-PCT (DC200018PCT) example an impeller type overhead stirrer. The vessel can be equipped with a fractionation or distillation device, for example a distillation column.

[0025] In the process according to the invention, the reaction components (e.g., first polyether polyol, first portion of second polyether polyol, first portion of dicarboxylic acid, and any optional components) can be heated to an initial temperature from 120, from 140, or from 160 up to 230, up to 220, or up to 210°C. The thermoset polymer waste (e.g. polyurethane, polyurethane / urea, polyurethane / isocyanaurate)can be metered in to the heated mixture to form the reaction mixture. During the metering process, the reaction mixture can be maintained at a temperature of from 120, from 140, or from 160 up to 230, up to 220, or up to 210°C. After all thermoset polymer waste is added to the reactor, the reaction mixture can be heated and stirred for an additional 30 minutes, 1 hour or 2 hours, or until a time for example, from 2, from 3, from 4, from 5 hours after the beginning of the reaction up to for example about 8 hours after the beginning of the reaction). During this step the reaction temperature can be maintained at a level from 140, from 150, from 160, or from 17 up to 240, or up to 230°C . At this point a portion of the second polyether polyol can be added, for example as a second aliquot. In addition, a portion of the polycarboxylic acid or anhydride can be added, for example as a second aliquot. After this, the reaction mixture can be heated for from 15, from 30, or from 60 minutes up to 4, up to 3, or up to 2.5 hours. During this step the reaction temperature can maintained at a level from 140, from 150, from 160, or from 170 up to 240, or up to 230°C. After this, the reaction mixture can be allowed to cool to room temperature and may be directly used in subsequent polymerization reactions (such as forming a new polyurethane foam) without further purification.

[0026] The reaction mixture can be free of or substantially free of water. For example, the reaction mixture can have less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, or less than or equal to 0.05 weight percent water, based on total weight of the reaction mixture. The method can be run without the addition of water.

[0027] The reactants can be heated by any suitable means, including convection, conduction, radiation or a combination thereof. No radiation (e.g., microwave radiation) is needed for a rapid acidolysis of the polyurethane. The reaction temperature can be from 120, from 130, from 140, from 150, from 160, or from 170 up to 240, up to 230, or up to 220°C.

[0028] The reaction product mixture is preferably homogeneous or substantially homogeneous liquid (solution or dispersion). The reaction product mixture can preferably86172-WO-PCT (DC200018PCT) include the following imides species, and / or

[0029] wherein where R3 is a bond (could be a single or double bond), an aromatic group (e.g., having 5 to 12 carbon atoms, preferably linked in the ortho position to the adjacent N atoms, a cycloaliphatic group (e.g., having 3, 4, 5, 6, 7, 8, 9, 10, 1 1, or 12 carbon atoms) and preferably linked to the adjacent atoms at 1,2 positions, or an aliphatic group (e.g., having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. R3 can be the same or can be different in different occurrences within the molecule and where R4 is a group originating from the isocyanate(s) used in preparing the polyurethane, polyurethane / urea, or polyurea of the waste product. R4 can include aromatic, cycloaliphatic, and / or aliphatic groups such as, for example, divalent radicals of benzene, toluene, tetramethylxylene, naphthalene, (poly)methylenediphenyl, (poly)dicyclohexylmethane, hexane, cyclohexane, or isophorone. R4 can be the same or can be different in different occurrences within the molecule. The reaction product will also include various polyol species that do not include imide structures such as, for example polyols liberated from the polyurethane / polyurea waste product, polyether polyol reactants or polyols form be reaction thereof.

[0030] The reaction product mixture can have a viscosity of from 100, from 2000, or from 3000 up to 50000, up to 40000, up to 30000, or up to 20000 centipoise at 25°C. The viscosity can be measured on a cone and plate viscometer such as a Brookfield DV-II+ viscometer with revolution per minute (rpm) chosen such that the torque of the viscometer is between 10 and 90% of its operating range, preferably 50%. according to ASTM D4878-23.

[0031] The reaction product mixture can have a number average molecular weight of from 300, or from 350 up to 1000, up to 800 or up to 700 g / mol; a weight average molecular weight of from 600 up to 5000 g / mol, and a z average molecular weight of from 1500 up to 30,000 g / mol.

[0032] Number average molecular weight (Mn), weight average molecular weight (Mw), z average molecular weight (Mz) and polydispersity index (PDI) = Mw / Mn)) are determined according to the procedure described in ASTM D5296-19. This method uses Gel Permeation Chromatography (GPC); an Agilent 1200 HPLC system with a PLgel Guard86172-WO-PCT (DC200018PCT)Column and four PLgel narrow porosity columns (5 pm, 300 mm x 7.5 mm) (50 Angstrom (A); 100 A; 1,000 A; and 10,000 A); and a ReadyCal Polyethylene Glycol Calibrant Set (44000-238 Mp) utilizing uninhibited tetrahydrofuran (THF). The samples used for the molecular weight measurement were prepared at a concentration of 0.1 g / 10 mL THF.

[0033] The reaction product mixture can have less than 5000, less than 4000, less than 3000, or less than 2000 parts by weight per million of water based on total weight of the reaction product mixture. Water content can be measured by coulometric titration according to ASTM D4672-24.

[0034] The reaction product mixture can have an OH number of from 100 or from 125 or from 150 up to 375 or up to 350 or up to 300 mg KOH / gram. OH number or hydroxyl number (OH#) is determined according to the procedure described in ASTM El 899- 16 for the standard test method for hydroxyl groups using reaction with p-toluenesulfonyl isocyanate and potentiometric titration with a Mettler T70 titration system using tetrabutylammonium hydroxide.

[0035] The reaction product mixture can have a basic amine content (indicative of the amount of undesirable primary amines) of less than 0.7, less than 0.6, less than 0.5, less than 0.4, less than 0.3, less than 0.2, or less than 0.1 milliequivalents per gram as measured according to ASTM D6979-18. The measurement can be made utilizing, for example, a Mettler T7 Titration System.

[0036] The reaction product mixture can show good shelf life stability. For example, the reaction product mixture can show no macroscopic (visual inspection) phase separation when inspected in a 10 ml graduated cylinder after aging at 55°C for 30 days. For example, stability of recycled polyols can be assessed by evaluating macroscopic phase separation of samples aged in graduated cylinders and recording relative volumes of top and bottom phases. Recycled polyol blends can be mixed in a FlackTek™ speedmixer at 1500 rpm for 30 seconds. Approximately 8 mL of polyol can be then immediately poured into a 10 mL graduated cylinder. The samples can be then placed in a 55 °C oven to further accelerate aging. After 30 days at 55 °C, phase separation can be evaluated by visual inspection for these samples.

[0037] The reaction product mixture can be reacted with a polyisocyanate to form a new polyurethane based product. For example, a reaction product mixture as disclosed herein having, for example, an OH number of from 100 or from 125 or from 150 up to 375 or up to 350 or up to 300 mg KOH / gram can be reacted with a polyisocyanate such as86172-WO-PCT (DC200018PCT) polymethylene polyphenylisocyanate in the presence of other optionally additives known to skilled in the art such as a blowing agent, a surfactant, a catalyst, a flame retardant, a filler, a pigment, etc. to form a rigid polyurethane or polyisocyanurate insulating foam. The stoichiometric ratio of the isocyanate groups in the polyisocyanate component to the hydroxyl groups from the reaction product mixtures and other optional components (e.g., an additional polyol, water, and the like) can be between 1.0 and 6. This ratio multiplied by 100 is typically referred as isocyanate index. The isocyanate index of the foam-forming composition comprising the reaction product mixture of the present invention can he from 100, from 120, from 150, from 175, from 200, or from 250 up to 600, up to 575, up to 550, up to 500, up to 475, or up to 450.

[0038] As a specific example of such subsequent reaction, the reaction product mixture can be used to produce a rigid polyurethane foam product. The rigid polyurethane foam can have a density of, for example, from 20, from 25, or from 30 kg / m3up to 200, up to 150, up to 100, up to 75, or up to 60 kg / m3in one general embodiment. Some of the advantageous properties exhibited by the resulting foam product produced according to the present invention, can include, for example: good thermal insulation, good mechanical strength and toughness, and high recycling content.

[0039] The rigid polyurethane foam product can exhibit a low thermal conductivity (or “K-factor”) and can for example have a K-factor of less than or equal to 28, less than or equal to 25, or less than or equal to 22 mW / m-K, at 10°C. K-factor is measured on foam specimens having dimensions of 20 cm x 20 cm x 2.5 cm at 50 °F (10 °C) according to ASTM C518-04 (2010). The insulating foam can have a compression strength of at least 80 kPa as measured according to ASTM D-1621-16.86172-WO-PCT (DC200018PCT)EXAMPLESIngredients

[0040] VORANOL™ 8136 (from DOW Inc.) is a glycerine-initiated, hetereopolymer triol with hydroxyl number of 54 mg KOH / g for use in preparing flexible polyurethane slabstock foams

[0041] Water, deionized

[0042] VORASURF™ DC 5986 (from DOW Inc.) is a silicone surfactant for use with flexible polyurethane slahstock foam formulations

[0043] DABCO™ 33LV (from EVONIK) is 33% triethylenediamine in dipropylene glycol; catalyst

[0044] DABCO™ BL11 (from EVONIK) is 70% bis(N,N-dimethylaminoethyl)ether in dipropylene glycol; blowing agent catalyst for foam

[0045] DABCO™ T-9 (from EVONIK) is stannous octoate; catalyst for foam

[0046] VORANATE™ T80 (from DOW Inc.) is ablend of toluene diisocyanate isomers100471 Voranol™ CP450 (from DOW Inc.) is a glycerine initiated propoxylated poly ether polyol having a functionality of 3.0 and a hydroxyl number of 383 mg KOH / g.

[0048] Polyethylene glycol 200 (PEG 200) (TCI America) is polyethylene glycol with molecular weight of 200;

[0049] Diethylene glycol

[0050] DABCO™ K15 (EVONIK) is 70% potassium octoate in diethylene glycol;

[0051] 30% Hydrogen peroxide

[0052] Phthalic anhydride

[0053] Maleic anhydride

[0054] Tripropylene glycol

[0055] Dipropylene glycol

[0056] Polyether polyol 1 A - an ethylene oxide (EO) capped, block copolymer with propylene oxide (PO) with about 27 weight% of the repeat units being ethylene oxide and having an average of 2 hydroxyl groups per molecule and a Hydroxyl number of 61 mg KOH / g

[0057] Polyether polyol IB - - a linear block polyether polyol copolymer of EO / PO (EO capped) with about 27 weight% of the repeat units being ethylene oxide and having a hydroxyl number of 45 mg KOH / g.86172-WO-PCT (DC200018PCT)

[0058] Poly ether polyol 1 Comp - a poly ether diol based on propylene oxide with ethylene oxide capping with about 12 weight% of the repeat units being ethylene oxide and having a hydroxyl number of 56 mg KOH / g.

[0059] Polyether polyol 2 comp is a propylene glycol initiated, polypropylene oxide diol with hydroxyl number of 56 mg KOH / g

[0060] Polyester A is an aromatic polyester polyol having a functionality of 2.0 and a hydroxyl number of 220 mg KOH / g.

[0061] Polyester B is an aromatic polyester polyol having a functionality of 2.4 and a hydroxyl number of 315 mg KOH / g.

[0062] Catalyst 1, 2, 3 and 4 are Polycat™ 5, TMR™ 31, Polycat™ 8 and Dabco™ K2097, respectively, all available from Evonik.

[0063] Additive 1 is a flame retardant, tris(chloropropyl) phosphate (TCPP), available as Fyrol™ PCF from ICL.

[0064] Isocayanate 1 is polymethylene polyphenylisocyanate with number average molecular weight of 360 g / mol and average isocyanate functionality of 2.7 (Voranate M229)Example 1 - Preparation of Flexible Foam (a polyurethane / urea) pieces for recycling

[0065] A flexible foam sheet of 2.54 cm thickness was densified as 125°C and 20 tons of pressure for 5 minutes and then cut into rectangular pieces with largest dimension of approximately 7 mm for subsequent chemolysis. The flexible foam had been prepared from the following ingredients: 100 parts VORANOL™ 8136, 4.5 parts water, 0.8 parts VORASURF™ DC 5986, 0.11 parts DABCO™ 33LV - 33% triethylenediamine in dipropylene glycol, 0.04 parts DABCO™ BL11 — 70% bis(N,N-dimethylaminoethyl)ether in dipropylene glycol, 0.20 parts DABCO™ T-9 - stannous octoate, 56.08 parts VORANATE™ T80 toluene diisocyanate.Example 2 - Chemolysis procedure

[0066] Into a 4 neck, 500 mL glass reactor was loaded 80% of the phthalic anhydride; VORANOL™ CP 450; PEG 200 or tripropylene glycol; Polyether polyol 1 A, IB, or 1 Comp; optional 30% hydrogen peroxide; and DABCO™ KI 5 catalyst with overhead turbine-type blade stirrer and stir bearing inserted along with stopper, N2 inlet adaptor, Dean-Stark type distillation trap (heat traced & insulated) & condenser, with gentle N2 sweep via inlet adaptor and exiting through trap and condenser. The reactor was warmed by temperature controlled86172-WO-PCT (DC200018PCT) oil bath and held at 65°C for 1.5 hours, then ramped to 180-190°C and the addition of the pieces of the densified foam from Example 1 began in 1 to 3 gram aliquots. Upon completing foam addition, temperature was increased to 210°C and held for 2 hours. The remaining 20% of the phthalic anhydride, maleic anhydride, and diethylene glycol or dipropylene glycol were added to the reactor with reaction continuing another 2 hours at 210°C before cooling and transferring warm with subsequent characterization. Ratios of components and characterization of re-polyol products summarized in Table 1 for Comparative and Inventive Examples.

[0067] The reaction product mixture was characterized and tested for viscosity, molecular weight, OH number, nitrogen content, amount residual water, and shelf stability as described herein. Notably the inventive examples 1-5 all show initial single phase and after aging, while the comparative examples all showed two phases initially and after aging.86172-US-PSP (DC200018US)TABLE 1.86172-US-PSP (DC200018US)Example 3 - Preparation of Rigid Foam using reaction product mixture

[0068] Foams are made from formulations as set forth in Table 2. In all cases, a recycled polyol, i.e., a reaction product mixture of this invention, is mixed with other polyols, surfactant, water, catalysts and flame retardant additive using a high-speed laboratory mixer. For comparative foam F-B, the reaction mixture from Comparative A of Example 2 and Table 1 was mixed in a FlackTek™ mixer before combining with the other ingredients. The physical blowing agent (cyclopentane) is then mixed in, followed by the addition of a polyisocyanate. The resulting reaction mixture is mixed at high speed for 5 seconds and then immediately poured into a vertically oriented 30 cm x 20 cm x 5 cm mold which is preheated to 55°C. The reaction mixture is permitted to react in the mold for 20 minutes, at which time the resulting foam is demolded.

[0069] Test specimens were cut from the middle interior section of each foam for testing after the foams are conditioned overnight in room temperature air. Foam core density is calculated on the basis of weight and physical dimensions of specimens used for K-factor measurements. K-factor is measured according to ASTM C518-21. Compressive strength is measured according to ASTM D1621-16. Results of the property testing are as indicated in Table 2.86172-US-PSP (DC200018US)Table 2

[0070] This disclosure further encompasses the following aspects.

[0071] Aspect 1 : A method comprising forming a reaction mixture which comprises a waste polymeric product comprising a thermoset having urethane bonds, urea bonds, isocyanurate bonds, or a combination of two or more thereof, a polycarboxylic acid or anhydride, a first polyether polyol having number average molecular weight of from 800 to 5000, preferably from 1000 to 4000, more preferably from 1050 to 3500, even more preferably from 1200 to 3000 g / mols and having an average of at least 2 hydroxyl groups per molecule wherein at least 50%, preferably at least 60%, more preferably at least 70%, yet more preferably at least 80%, and most preferably at least 90% of the hydroxyl groups are primary alcohol, a second polyether polyol having a number average molecular weight less than 350, preferably less than 330, more preferably less than 300, grams / mole, and, optionally, a third polyether polyol having an average of from 1 .8 to 7 hydroxyl groups per molecule and having a number average molecular weight of greater than 350, preferably86172-US-PSP (DC200018US) greater than 400 grams / mole, up to 1000, or up to 800 grams / mole; and reacting the reaction mixture to decompose the waste polymeric product to form a reaction product composition.

[0072] Aspect 2. The method of Aspect 1 wherein the first polyether polyol has the structurewhere “m” is independently in each occurrence an integer of from 1 , preferably from 2, more preferably from 3 up to 57, preferably up to 30, more preferably up to 15, or most preferably up to 8; “n” is independently in each occurrence an integer of 0, preferably from 1, more preferably from 5, or most preferably from 10 up to 36, preferably up to 24, or up to 15; p is an integer of 2, 3, 4, 5, or 6, preferably 2 or 3, more preferably 2; a, b, and c are independently in each occurrence an integer of from 0, preferably from 1 , more preferably from 2, still more preferably from 3, or most preferably from 4, up to 57, preferably up to 50, more preferably up to 40, still more preferably up to 30, or most preferably up to 20; Ri is an alkyl group of 1-3 carbon atoms, preferably 1 carbon atom; and A is a direct bond or is a multi-valent (i.e., p-valent) radical group of alkyl, aryl, alkylaryl, or cycloalkyl.Aspect 3. The method of Aspect 2 wherein (m+a*n) / (m-i-a*n-i-b*n-i-c*n) is from 0.15, from 0.2 from 0.25 or from 0.3 up to 1, up to 0.9 or up to 0.8, up to 0.6, up to 0.4, or up to 0.35.

[0073] Aspect 4. The method of Aspect 1 wherein the first polyether polyol has a structure (HO-CH2-R2)q-(YO) wherein YO is a polyether group, R2is a direct bond or an alkyl group of 1 to 3 carbon atoms, and q is an integer of 2, 3, 4, 5, or 6, preferably 2 or 3, more preferably 2, wherein YO comprises at least 15 mole% of repeat units of ethylene oxide, based on total repeat units in the first polyether polyol and wherein the HO-CH2-R2- groups are each bonded to a block of ethylene oxide repeat units.

[0074] Aspect 5. The method of Aspect 1 wherein the first polyether polyol comprises a block of propylene oxide repeat units end capped with a block of ethylene oxide repeat units.

[0075] Aspect 6. The method of any of the previous claims wherein, after an initial reaction phase, an additional portion of the carboxylic acid or anhydride thereof or an additional portion of the second polyether polyol, or both are added.

[0076] Aspect 7. The method of any of the previous claims wherein the polycarboxylic acid or anhydride is selected from phthalic anhydride, phthalic acid, maleic anhydride, maleic acid, fumaric acid, succinic anhydride, succinic acid, alkenylsuccinic anhydrides and acids, (i.e. dodecenylsuccinic anhydride), tetrahydrophthalic anhydride,86172-US-PSP (DC200018US) tetrahydrophthalic acid, methyl tetrahydrophthalic anhydride, methyl tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, methyl hexahydrophthalic anhydride, methyl hexahydrophthalic acid, nadic anhydride, nadic acid, methyl nadic anhydride, methyl nadic acid, citric acid, isocitric acid, or mixtures of two or more thereof.

[0077] Aspect 8. The method of any of the previous claims wherein the reaction mixture includes catalyst.

[0078] Aspect 9. The method of any of the previous claims wherein the reaction mixture is free of halide-containing catalyst.

[0079] Aspect 10. The method of any of the previous claims wherein the reaction occurs at a temperature of 140 to 240°C.

[0080] Aspect 11. The method of any one of the preceding claims wherein in the waste polymeric product comprises a flexible polyurethane foam.

[0081] Aspect 12. The method of any one of the preceding claims wherein an amount of water present in the reaction mixture is less than 0.15, preferably less than 0.1, more preferably less than 0.05 weight percent based on total weight of the reaction mixture.100821 Aspect 13. The method any one of the preceding claims wherein no water is added to the reaction mixture.

[0083] Aspect 14. The method of any one of the preceding claims wherein the reaction product composition has an OH number of from 100 to 375, preferably 125 to 350 mg KOH per gram.

[0084] Aspect 15. The method of any one of the preceding claims wherein the amount of basic nitrogen in the reaction produce is less than 0.7, preferably less than 0.6, more preferably less than 0.5, still more preferably less than 0.4, yet more preferably less than 0.3, even more preferably less than 0.2 milliequivalents per gram.

[0085] Aspect 16. The method of any one of the preceding claims wherein the reaction product composition is shelf stable as indicated by no macroscopic phase separation after aging at 55 °C for 30 days.

[0086] Aspect 17. The method of any one of the preceding claims wherein at least a portion of the first, second and third polyether polyols have at least 3 hydroxyl groups per molecule.

[0087] Aspect 18. The method of any one of the preceding claims wherein the reaction mixture based on total weight of the reaction mixture comprises from 5 to 60 weight percent of the waste polymeric product, from 1 to 20 weight percent of the polycarboxylic acid or the anhydride thereof, from 5 to 40, preferably from 8 to 30 and more preferably from86172-US-PSP (DC200018US)10 to 25 weight percent of the first polyether polyol, from 5 to 40, preferably from 8 to 35, more preferably from 10 to 30, yet more preferably from 12 to 25, and most preferably from 14 to 20 weight percent of the second polyether polyol, and from 5 to 80, preferably 10 to 70, more preferably 20 to 60 and most preferably 30 to 50 weight percent of the third polyether polyol.

[0088] Aspect 19. The method of Aspect 18 wherein a first portion of the polycarboxylic acid or the anhydride is provided in an initial reaction stage and a second portion of the polycarboxylic acid or the anhydride is provided after the reacting the initial reaction mixture for a period at least one hour after a final addition of the polymeric waste product and where a weight ratio of the first portion to the second portion is from 99:1 to 60:40.

[0089] Aspect 20. The method of Aspect 18 or 19 wherein first portion of the second polyether polyol is provided in an initial reaction stage and a second portion of the second polyether polyol is provided after the reacting the initial reaction mixture for a period at least one hour after a final addition of the polymeric and where a weight ratio of the first portion to the second portion is from 90:10 to 50:50

[0090] Aspect 21. The method of any one of the preceding claims further comprising reacting the reaction product composition with a polyisocyanate to form a new polyurethane product.

[0091] Aspect 22. The method of Aspect 21 wherein the new polyurethane product is a rigid polyurethane or polyisocyanurate foam.

[0092] Aspect 23. A composition made by the method of any one of claims 1-20.

[0093] Aspect 24. An article made by the method of Aspect 20 or 21.

[0094] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt.%, or, more specifically, 5 wt.% to 20 wt.%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt.% to 25 wt.%,” etc.). Moreover, stated upper and lower limits can be combined to form ranges (e.g., “at least 1 or at least 2 weight percent” and “up to 10 or 5 weight percent” can be combined as the ranges “1 to 10 weight percent”, or “1 to 5 weight percent” or “2 to 10 weight percent” or “2 to 5 weight percent”).

[0095] The disclosure may alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed. The disclosure may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are86172-US-PSP (DC200018US) otherwise not necessary to the achievement of the function and / or objectives of the present disclosure.

[0096] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0097] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

Claims

86172-US-PSP (DC200018US)What is claimed is:

1. A method comprising forming a reaction mixture comprising a) a waste polymeric product comprising a thermoset having urethane bonds, urea bonds, isocyanurate bonds, or a combination of two or more thereof, b) a polycarboxylic acid or anhydride, c) a first polyether polyol having number average molecular weight of from 800 to 5000 grams per mole and having an average of at least 2 hydroxyl groups per molecule wherein at least 50% of the hydroxyl groups based on total number of hydroxyl groups on the first polyether polyol are primary alcohols, d) a second polyether polyol having a number average molecular weight of less than 350 grams / mole, and, e) optionally, a third polyether polyol having an average of from 1.8 to 7 hydroxyl groups per molecule and having a number average molecular weight of greater than 350 up to 1000 grams / mole; and reacting the reaction mixture to decompose the waste polymeric product to form a reaction product composition.

2. The method of claim 1 wherein the first polyether polyol has the structurewhere “m” is independently in each occurrence an integer of from 1 up to 57; “n” is independently in each occurrence an integer of from 0 up to 36; p is an integer of 2, 3, 4, 5, or 6; a, b, and c are independently in each occurrence an integer of from 0 up to 57; Ri is an alkyl group of 1-3 carbon atoms, preferably 1 carbon atom; and A is a direct bond or is a p- valent radical group of alkyl, aryl, alkylaryl, or cycloalkyl.

3. The method of claim 2 wherein (m+a*n) / (m+a*n+b*n+c*n) is from 0.15 up to 1.

4. The method of claim 1 wherein the first polyether polyol has a structure (HO-CH2- R2)q-(YO) wherein YO is a poly ether group, R2is a direct bond or an alkyl group of 1 to 3 carbon atoms, and q is an integer of 2, 3, 4, 5, or 6, wherein YO comprises at least 15 mole%86172-US-PSP (DC200018US) of repeat units of ethylene oxide, based on total repeat units in the first polyether polyol and wherein the “HO-CH2-R2-“ groups are each bonded to a block of ethylene oxide repeat units.

5. The method of claim 1 wherein the first polyether polyol comprises a block of propylene oxide repeat units end capped with a block of ethylene oxide repeat units.

6. The method of any of the previous claims wherein, after an initial reaction phase, an additional portion of the carboxylic acid or anhydride thereof or an additional portion of the second poly ether polyol, or both are added.

7. The method of any of the previous claims wherein the polycarboxylic acid or anhydride is selected from phthalic anhydride, phthalic acid, maleic anhydride, maleic acid, fumaric acid, succinic anhydride, succinic acid, an alkenylsuccinic anhydride, (i.e. dodecenylsuccinic anhydride), an alkenyl succinic acid, tetrahydrophthalic anhydride, tetrahydrophthalic acid, methyl tetrahydrophthalic anhydride, methyl tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, methyl hexahydrophthalic anhydride, methyl hexahydrophthalic acid, nadic anhydride, nadic acid, methyl nadic anhydride, methyl nadic acid, citric acid, isocitric acid, or mixtures of two or more thereof.

8. The method of any one of the preceding claims wherein in the waste polymeric product comprises a flexible polyurethane foam.

9. The method of any one of the preceding claims wherein the reaction product composition has an OH number of from 100 to 375 mg KOH per gram.

10. The method of any one of the preceding claims wherein the amount of basic nitrogen in the reaction produce is less than 0.7 milliequivalents per gram.

11. The method of any one of the preceding claims wherein the reaction product composition is shelf stable as indicated by no macroscopic phase separation after aging at 55°C for 30 days.

12. The method of any one of the preceding claims wherein at least a portion of the first, second and third polyether polyols have at least 3 hydroxyl groups per molecule.

13. The method of any one of the preceding claims wherein the reaction mixture based on total weight of the reaction mixture comprises from 5 to 60 weight percent of the waste polymeric product, from 1 to 20 weight percent of the polycarboxylic acid or the anhydride thereof, from 5 to 40, preferably from 8 to 30 and more preferably from 10 to 25 weight percent of the first polyether polyol,86172-US-PSP (DC200018US) from 5 to 40, preferably from 8 to 35, more preferably from 10 to 30, yet more preferably from 12 to 25, and most preferably from 14 to 20 weight percent of the second polyether polyol, and from 5 to 80, preferably 10 to 70, more preferably 20 to 60 and most preferably 30 to 50 weight percent of the third polyether polyol.

14. The method of claim 13 wherein a first portion of the polycarboxylic acid or the anhydride is provided in an initial reaction stage and a second portion of the polycarboxylic acid or the anhydride is provided after the reacting the initial reaction mixture for a period at least one hour after a final addition of the polymeric waste product and where a weight ratio of the first portion to the second portion is from 99: 1 to 60:40.

15. The method of claim 13 or 14 wherein first portion of the second polyether polyol is provided in an initial reaction stage and a second portion of the second polyether polyol is provided after the reacting the initial reaction mixture for a period at least one hour after a final addition of the polymeric and where a weight ratio of the first portion to the second portion is from 90:10 to 50:50.

16. The method of any one of the preceding claims further comprising reacting the reaction product composition with a polyisocyanate to form a new polyurethane product.

17. The method of claim 16 wherein the new polyurethane product is a rigid polyurethane or polyisocyanurate foam.

18. A composition made by the method of any one of claims 1-15.

19. An article made by the method of claim 17 or 18.