Polyurethane foam composition, foams prepared therefrom and methods thereof

Abstract

A polyurethane foam composition and method of preparation. The composition includes at least one volatility control agent. In an embodiment, the composition includes at least one volatility control agent selected from the group consisting of: (i) phosphorus-containing groups; (ii) thiocarbamates; (iii) nitrogen-containing compounds; (iv) phenolic antioxidants; or combinations of two or more thereof. The present invention also relates to a method of controlling the volatility of at least one aldehyde species that may be generated in raw materials used in the foam composition or during the foam formation or foam curing or foam aging process.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of Indian Provisional Application No. 202111039327, filed on August 31, 2021, the entire disclosure of which is incorporated herein by reference.

[0002] The present invention relates to compositions for polyurethane foams (PU), polyurethane foams prepared from the compositions, and methods for preparing such foams. In particular, the present invention relates to polyurethane foam compositions that provide reduced volatile emissions and therefore reduced undesirable odors. [Background technology]

[0003] Polyurethane foams are well known for their wide variety of applications. Traditionally, these foams emit volatile organic compounds (VOCs), including, for example, low molecular weight volatile aldehydes and amines, which may be present in the raw materials used to make the foam, or may be generated during the foaming process, or may result from aging, and which may contribute to odor and volatility profiles in consumer goods prepared from the foam. Examples of such low molecular weight aldehydes include formaldehyde, acetaldehyde, propionaldehyde, and acrolein.

[0004] Previous attempts have been made to use additives in polyurethane foams to eliminate the emission of volatile compounds to provide materials useful in the interior of automobile passenger compartments, which may be provided as part of separate devices, such as air purification devices in vehicle interiors, homes, buildings, fired heaters, luggage, furniture, etc. Summary of the Invention

[0005] The following is a summary of the present disclosure to provide a basic understanding of some aspects of VOC emissions from certain PU foam compositions. This summary is not intended to identify key or critical components, nor is it intended to define any limitations to the embodiments or claims. Furthermore, this summary may provide a simplified overview of some aspects, which may be described in more detail in other parts of the present disclosure.

[0006] In one embodiment, provided is a composition for preparing a polyurethane foam, the composition comprising at least one compound suitable for controlling the emission of one or more volatile compounds. In particular, provided is a composition comprising at least one compound capable of controlling the emission of at least one aldehyde species that may be generated in raw materials used in the foam composition or during the foam formation or foam curing or foam aging process.

[0007] In another aspect, provided is a process for preparing a polyurethane foam from the composition.

[0008] In one embodiment, provided is a composition including: (a) at least one blowing reactant; (b) at least one volatility control agent selected from the group consisting of (i) a phosphorus-containing group; (ii) a thiocarbamate; (iii) a nitrogen-containing group; (iv) a phenolic antioxidant; or a combination of two or more thereof; and (c) a catalyst.

[0009] In one embodiment, the at least one volatility control agent is a phosphite triester, a diorganophosphite, an organodiphosphite, a polyolefin with phosphite substituents, a CH or CH bonded to phosphorus. 2 The compound includes a phosphorus-containing group (i) selected from phosphonates, phosphonium compounds, and phosphazenes having a moiety.

[0010] In one embodiment, the at least one volatility control agent is selected from one or more compounds of Formula (I), Formula (II), Formula (Vi), Formula (V-ii), Formula (V-iii); Formula (V-iv), Formula (Vv), and / or Formula (V-vi): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] R in the formula 1 is C6 to C30 aryl, or -N(R 5 )R 6 is selected from, where R 5 and R 6 are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety that is preferably bonded through a carbon atom and does not contain an acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R 5 and R 6 can be taken together to form a 5- to 10-membered ring; R 2 is C6-C30 aryl, -N(R5 )R 6 , and -OR 7 is selected from, where R 5 and R 6 are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety that is preferably bonded through a carbon atom and does not contain an acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R 5 and R 6 can be joined together to form a 5- to 10-membered ring, and R 7 is selected from C1-C10 alkyl; R 3 is C6-C30 aryl, -N(R 5 )R 6 , and -OR 8 is selected from, where R 5 and R 6 are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety that is preferably bonded through a carbon atom and does not contain an acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R 5 and R 6 can be joined together to form a 5- to 10-membered ring, and R 8 is selected from C1-C10 alkyl; R 4 Ha-CH 2 -R 9 or =NR 10 is selected from, where R 9 -C(O)-O x R 11 , -CN, -R 12 CN, or -R 13 -CH 2 -PR 1 R 2 R 3 is selected from, where R 11 is H, C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy; R 12 and R 13are each selected from C1-C10 alkyl or C6-C30 aryl, x is 0 or 1, and R 1 , R 2 , and R 3 is as defined above; and R 10 is selected from C1-C10 alkyl or C6-C30 aryl; A - is selected from organic or inorganic anions, where R 4 =NR 10 In this case, the P atom in formula (I) is pentavalent and has a positive charge and a counter ion A - does not have; R in the formula 14 , R 15 , and R 16 are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group, and combinations thereof; R in the formula 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 32 , R 33 , R 38 , R 39 , R 41 , R 42 , R 43 , R 44 , R 50 , and R 51 are each independently selected from monovalent C1-C30 alkyl, C2-C30 alkene containing one or more points of unsaturation, C4-C30 cycloalkyl, C2-C30 ether group, C2-C30 alkylene glycol, C2-C30 polyalkylene glycol, C6-C30 aryl, C7-C30 arylalkyl, and C7-C30 alkylaryl; R 31 , R 47 , and R 49 are each independently selected from C1 to C30 alkylene, C4 to C30 cycloalkylene, C6 to C30 arylene, C7 to C30 arylalkylene, and C7 to C30 alkylarylene; R40 , R 45 , R 46 , R 52 , R 53 , and R 54 are each independently selected from hydrogen, a monovalent C1-C30 alkyl, a C2-C30 alkene containing one or more points of unsaturation, a C4-C30 cycloalkyl, a C2-C30 ether group, a C6-C30 aryl, a C7-C30 arylalkyl, and a C7-C30 alkylaryl; and X is C(O)-R 48 , C1-C30 alkyl, C6-C30 aryl optionally substituted with cyano, OH, where R 48 is selected from C1 to C30 alkyl.

[0011] In one embodiment, the volatility control agent is selected from compounds of formula (I), where R 1 , R 2 , and R 3 are each independently selected from C6 to C30 aryl, and R 4 Ha-CH 2 -R 9 ;=NR 10 where R 9 -C(O)-O x R 11 , -CN, or -R 12 Selected from CN;R 11 is C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy; R 12 is selected from C1-C10 alkyl or C6-C30 aryl; and x is 0 or 1.

[0012] In one embodiment, the volatility control agent is selected from compounds of formula (I), where R 1 , R 2 , and R 3 are each independently -N(R 5 )R 6 is selected from, where R 5 and R 6 are each independently a C1 to C10 alkyl group; and R 4=NR 10 is selected from, where R 10 is selected from C1 to C10 alkyl or C6 to C30 aryl.

[0013] In one embodiment, the volatility control agent is selected from compounds of formula (I), where R 1 is R 2 -OR 7 ;R 3 -OR 8 where R 7 and R 8 are each independently C1 to C10 alkyl; R 4 Ha-CH 2 -R 9 where R 9 -C(O)-O x R 11 is selected from, where R 11 is H, C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy.

[0014] In one embodiment, the volatility control agent is selected from a compound of formula (II) and wherein R 14 , R 15 , and R 16 are each selected from C1 to C10 alkyl. 14 , R 15 , and R 16 are each methyl.

[0015] In one embodiment, the volatility control agent is (cyanomethyl)-triphenylphosphonium chloride, (methoxycarbonylmethyl)-triphenylphosphonium bromide, tertiary butylimino-tris(dimethylamino)phospholene (phosphazene-based P- 1 -t-Bu), tertiary butylimino-tri(pyrrolidino)phosphorane [phosphazene base P 1 -t-Bu-tris(tetramethylene)], tertiary octylimino-tris(dimethylamino)phosphorane (phosphazene-based P 1-t-Oct), 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-bis(diethylphosphonomethyl)biphenyl, diethyl-4-cyanobenzylphosphonate, N-methoxy-N-methyl In some embodiments, the phosphonic acid ester is selected from one or more of methyl(triphenylphosphoranylidene)acetamide, dimethyl(2-oxopropyl)phosphonate, diethyl(2-oxopropyl)phosphonate, dimethyl(2-oxoheptyl)phosphonate, diethyl(2-oxoheptyl)phosphonate, diethylcarboxymethylphosphonate, diethyl(2-oxo-2-phenylethyl)phosphonate, diethyl(methylthiomethyl)phosphonate, methyl(triphenylphosphoranylidene)acetate, diethylphosphonoacetic acid, and 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide.

[0016] In one embodiment, the volatility control agent comprises a phosphite triester of formula (Vi), where R 24 , R 25 and R 26 Each is C1-C30 alkyl. In one embodiment, R 24 , R 25 , and R 26 is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, decyl, isodecyl, dodecyl, isododecyl, tridecyl, isotridecyl, lauryl, and 2-ethylhexyl.

[0017] In one embodiment, the volatility control agent comprises a phosphite of formula (Vi), where R 24 , R25 , and R 26 are each C6-C30 aryl, C7-C30 arylalkyl, or C7-C30 alkylaryl. 24 , R 25 , and R 26 is selected from phenyl, tosyl, methylphenyl, and 6-tert-butyl-3-methylphenyl.

[0018] In one embodiment, the volatility control agent comprises a phosphite triester of formula (Vi), where R 24 , R 25 and R 26 is a C2 to C30 alkylene glycol or a C2 to C30 polyalkylene glycol. 24 , R 25 and R 26 are each selected from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, or tripropylene glycol. The volatility control agent is a diorganophosphite of formula (V-ii) or a tautomer thereof (R 27 O)P(OH)(OR 28 ), where R 27 and R 26 are each independently selected from C1 to C10 alkyl, and C6 to C30 aryl.

[0019] In one embodiment, the volatility control agent comprises an organodiphosphate of formula (V-iii), where R 29 , R 30 , R 32 , and R 33 is selected from monovalent C1-C30 alkyl or C2-C30 ether groups, C2-C30 alkenes containing one or more points of unsaturation, C6-C30 aryls, C7-C30 arylalkyls, and C7-C30 alkylaryls; and R 31is selected from C1 to C30 alkylene, a divalent C2 to C30 ether-containing group, a C4 to C30 cycloalkylene, a C6 to C30 arylene, a C7 to C30 arylalkylene, and a C7 to C30 alkylarylene.

[0020] In one embodiment, the volatility control agent is selected from alkylphenol diisodecyl phosphite, dimethyl phosphite, triethyl phosphite, diphenyl phosphite, triphenyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, diisodecyl phenyl phosphite, tris(nonylphenyl)phosphite, tetraphenyl dipropylene glycol diphosphate, poly(dipropylene glycol) phenyl phosphite, triisooctyl phosphite, trilauryl phosphite, triisodecyl phosphite, tristridecyl phosphite, triisotridecyl phosphite, phosphonic acid di-9-octadecen-1-yl ester, 4,4'-butylidene bis(6-tertiary butyl-3-methylphenyl ditridecyl phosphite), tris(dipropylene glycol) phosphite and diisodecyl phenyl phosphite, or a combination of two or more thereof.

[0021] In one embodiment, the volatility control agent comprises a thiocarbamate. In one embodiment, the thiocarbamate is tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetrabutylthiuram disulfide, tetradecylthiuram disulfide, tetrahexadecylthiuram disulfide, tetracosylthiuram disulfide, 1-methyl-1-propyl-6-butyl-6-methylthiuram disulfide, 1-propyl-1-butyl-6-methyl-6-t-butylthiuram disulfide, dihexamethylenethiuram disulfide, dipentamethylthiuram disulfide, tetra ... Methylene thiuram disulfide, tetrabenzyl thiuram disulfide, piperazinium pentamethylene dithiocarbamate, piperazinium dibutyl dithiocarbamate, piperazinium dicyclohexyl dithiocarbamate, piperazinium di(3-oxycyclohexyl) dithiocarbamate, ammonium dipropyl dithiocarbamate, metal thiocarbamates such as nickel dipropyl dithiocarbamate, nickel dibutyl dithiocarbamate, nickel didecyl dithiocarbamate, zinc dimethyl dithiocarbamate , zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate, zinc dihexyl dithiocarbamate, zinc dibenzyl dithiocarbamate, sodium dimethyl dithiocarbamate, sodium diethyl dithiocarbamate, sodium dibutyl dithiocarbamate, sodium dibenzyl dithiocarbamate, copper dimethyl dithiocarbamate, copper dibutyl dithiocarbamate, copper diethyl dithiocarbamate, copper diamyl dithiocarbamate, copper dioctadecyl dithiocarbamate, copper diphenyl dithiocarbamate, copper di Benzyl dithiocarbamate, copper di(orthotolylaminoethyl)dithiocarbamate, copper dicyclohexyldithiocarbamate, potassium dihexyldithiocarbamate, calcium dihexyldithiocarbamate, zirconium diethyldithiocarbamate, tellurium diethyldithiocarbamate, cobalt dibutyldithiocarbamate, antimony dibutyldithiocarbamate, bismuth dimethyldithiocarbamate, lead dimethyldithiocarbamate, tin dibutyldithiocarbamate, copper dicyclopentyldithiocarbamate,The copper dithiocarbamate is selected from copper 1-butyl-1-cyclohexyl-7-butyl-7-cyclohexyldithiocarbamate, copper di(3-oxacyclohexyl)dithiocarbamate, copper di(4-oxacyclohexyl)dithiocarbamate, copper di(3-thiocyclohexyl)dithiocarbamate, copper di(4-azacyclohexyl)dithiocarbamate, copper 1-butyl-1-(3-oxacyclohexyl)-7-butyl-7-(3-oxacyclohexyl)dithiocarbamate, copper di(4-pyridyl)dithiocarbamate, copper di(4-N,N-dimethylanilino)dithiocarbamate, copper di(4-anisyl)dithiocarbamate, copper di(4-thioanisyl)dithiocarbamate, and copper di(3-furanyl)dithiocarbamate.

[0022] In one embodiment, the volatility control agent is a nitrogen compound selected from compounds of formula (III), formula (IV), -OH, -NH, or -NH 2 Functionalized pyrrolidine, -OH, -NH, or -NH 2 Functionalized pyrazolidines, -OH, -NH, or -NH 2 Functionalized imidazolidine, -OH, -NH, or -NH 2 Functionalized imidazolidinone, and / or -OH, -NH, or -NH 2 tetrahydropyrimidinone, or a combination of two or more of these, a nitrogen-containing compound selected from one or more of: [ka] [ka] R in the formula 17 , R 18 , and R 19 are each independently H, a C1-C20 alkyl group optionally substituted with one or more hydroxyl groups, -R 20 -OH, or -R 21 -C(O)OH, where R 20 and R 21are each independently selected from a divalent C1 to C20 hydrocarbon group, a C4 to C30 cyclic hydrocarbon group, and a divalent C6 to C30 aryl group, each of which may be optionally substituted with a heteroatom-containing group; or R 17 , R 18 , and R 19 two of may form a 5-12 membered ring, which may optionally contain one or more heteroatoms in the ring, such as N, O, and which may be substituted with a hydroxy functional group, provided that the compound contains at least one -OH or at least one -C(O)OH functional group; and 22 is hydrogen or a linear or branched C1-C24 alkyl, aryl, heteroalkyl, or alkylaryl group; R 23 is hydrogen or a straight or branched chain C1 to C24 alkyl, heteroalkyl, or alkylaryl group.

[0023] In one embodiment, the volatility control agent is selected from compounds of formula (III) and R 17 -R 21 -C(O)OH, where R 20 and R 21 are independently selected from a divalent C1 to C20 hydrocarbon group, a C4 to C30 cyclic hydrocarbon group, and a divalent C6 to C30 aryl group, each of which may be optionally substituted with a heteroatom-containing group.

[0024] In one embodiment, the volatility control agent is selected from one or more of nicotinic acid, arginine, asparagine, cysteine, glutamine, histidine, methionine, serine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, tryptophan, and tyrosine.

[0025] In one embodiment, -OH, -NH, or NH 2 A functionalized pyrrolidine, pyrazolidine, imidazolidine, or imidazolidinone contains an alcohol, a primary amine, a secondary amine, or a carboxylic acid functional group attached directly or through a linking group to one of the nitrogen atoms.

[0026] In one embodiment, the volatility control agent is an -OH functionalized imidazolidinone or pyrimidinone selected from N-substituted (hydroxyalkyl) imidazolidinones of formula (VI) or N-substituted (hydroxyalkyl functionalized) tetrahydro-2-pyrimidinones of formula (VII). [ka] R in the formula 34 , R 35 , and R 37 are each independently selected from hydrogen or a straight or branched chain C1-C24 alkyl, C4-C30 cycloalkyl, C6-C30 aryl, C1-C24 heteroalkyl, C7-C30 alkaryl, or C7-C30 arylalkyl group; and R 36 is selected from a C1 to C24 alkylene, a C4 to C30 cycloalkylene, a C6 to C30 arylene, a C1 to C24 heteroalkylene, a C7 to C30 alkarylene, or a C7 to C30 arylalkylene group.

[0027] In one embodiment, the volatility control agent is selected from one or more of 1-(hydroxymethyl)imidazolidinone, 1-(2-hydroxyethyl)imidazolidinone, 1-(2-hydroxypropyl)imidazolidinone, and 1-(2-hydroxyethyl)-2-imidazolidinone, tetrahydro-1-(2-hydroxyethyl)-2(1H)-pyrimidinone.

[0028] In one embodiment, the volatility control agent is selected from alkaline earth metal salts of alkylphenol thioesters, sulfurized alkylphenols, metal salts of sulfurized alkylphenols, metal salts of non-sulfurized alkylphenols, oil soluble phenates, and sulfurized phenates.

[0029] In one embodiment, the volatility control agent comprises an alkylated phenothiazine selected from monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monononylphenothiazine, dinonylphenothiazine, monooctylphenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, distyrylphenothiazine, butyloctylphenothiazine, and styryloctylphenothiazine.

[0030] In one embodiment according to any of the preceding embodiments, the volatility control agent is present in an amount from about 0.05 parts per 100 parts polyol to about 10 parts per 100 parts polyol.

[0031] In one embodiment according to any of the preceding embodiments, the volatility control agent is provided as a separate component.

[0032] In one embodiment according to any of the preceding embodiments, the volatility control agent is provided in a mixture with the catalyst, water, plasticizer, natural oil, glycol, chain extender, and alkoxylated monoalcohol.

[0033] In one embodiment according to any of the preceding embodiments, the at least one blowing reactant is selected from (i) an isocyanate and (ii) a polyether polyol, a polyester polyol, a polyamine, a polyether amine.

[0034] In one embodiment according to any of the preceding embodiments, the volatility control agent is provided in admixture with an isocyanate and / or in admixture with a polyether polyol, a polyamine, and / or a polyester polyol.

[0035] In another embodiment, provided is a process for preparing a polyurethane foam from the composition of any of claims 1-32, comprising contacting at least one blowing reactant with a volatility control agent.

[0036] In yet another embodiment, provided is a polyurethane foam formed by this method, hi one embodiment, the foam has a concentration of at least one aldehyde species that is at least 10% to 99.5% lower than that of a foam formed from the same composition without the volatility control agent.

[0037] In one embodiment, the at least one aldehyde species is present in a concentration that is less than in the same composition lacking the volatility control agent.

[0038] In yet another embodiment, provided is a method for reducing emissions from a polyurethane foam, the method comprising contacting at least one foaming reactant with at least one volatility control agent according to any of the preceding embodiments.

[0039] The following description discloses various exemplary embodiments. Some improvements and novel aspects may be explicitly identified and others may be apparent from the description. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0040] Reference is made below to exemplary embodiments. As will be understood, other embodiments may be utilized, and structural and functional changes may be made. Furthermore, features of the various embodiments may be combined or modified. Thus, the following description is provided merely as an example, and is not intended to limit in any way the various changes and modifications that may be made to the described embodiments. In this disclosure, a number of specific details are set forth to provide a thorough understanding of the subject disclosure. It should be understood that the embodiments of the present disclosure may be practiced with other embodiments, which may not necessarily include all embodiments described herein.

[0041] As used herein, the term "foaming reactant" refers to a compound that participates as a reactant to produce polyurethane foam. Examples of such foaming reactants include organic isocyanates and isocyanate-reactive compounds selected from the group consisting of polyether polyols, polyester polyols, primary and secondary polyamines, or mixtures or hybrids thereof.

[0042] As used herein, the term "volatility control agent" refers to a compound that can control the release of odor-causing volatile compounds. In one embodiment, the term "volatility control agent" refers to a compound that can reduce the content of aldehyde species in the composition and / or prevent the formation of aldehyde species during the foaming process or in the finished foamed product.

[0043] As used herein, the terms "example" and "exemplary" mean illustrative or illustrative. The terms "example" and "exemplary" do not indicate required or preferred implementations or embodiments. The term "or" is intended to be inclusive rather than exclusive, unless the context indicates otherwise. For example, the phrase "A uses B or C" includes any inclusive permutation (e.g., A uses B; A uses C; or A uses both B and C). As another matter, the articles "a" and "an" are generally intended to mean "one or more," unless the context indicates otherwise.

[0044] The term "alkyl" includes straight-chain, branched-chain, and cyclic monovalent hydrocarbon groups, which may be substituted with a heteroatom or heteroatom-containing group. In embodiments, the term alkyl may include C1-C30 alkyl groups. Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl, isooctyl, and 2-ethylhexyl, nonyl such as n-nonyl, and decyl such as n-decyl, among others.

[0045] The term "alkoxy" as used herein refers to a monovalent group of the group --O-alkyl, where alkyl is defined above.

[0046] The term "alkylene" includes straight-chain, branched-chain, and cyclic divalent hydrocarbon groups, which may be substituted with heteroatoms or heteroatom-containing groups. In embodiments, the term alkylene includes C1-C30 alkylene groups. Examples of alkylene include, but are not limited to, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tertiary butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and the like.

[0047] The term "aryl" includes any monovalent aromatic hydrocarbon or heteroaromatic group, which may be substituted with a heteroatom or heteroatom-containing group. The term also includes fused systems containing aromatic groups and groups with several aryl groups joined by a bond or linking group. In embodiments, the term aryl includes C5-C30 aryl groups, fused aryl groups containing two or more C5-C20 aryl groups, and multiple aryl group structures containing two or more C5-C20 aryl groups joined by a linking group. Illustrative examples of aryl include phenyl, naphthalenyl, benzyl, phenethyl, o-, m-, and p-tolyl, and xylyl.

[0048] The term "arylene" includes any divalent aromatic hydrocarbon, which may be substituted with a heteroatom or heteroatom-containing group, and the term also includes fused systems containing aromatic groups. In embodiments, the term aryl includes C5-C20 arylene groups, fused arylene groups containing two or more C5-C20 aryl groups, and multiple arylene group structures containing two or more C5-C20 aryl groups joined by a linking group.

[0049] The term "aralkyl" includes straight-chain, branched-chain and cyclic monovalent hydrocarbon radicals, optionally substituted with aryl substituents. The term "aralkylene" refers to a divalent aralkyl group.

[0050] The term "alkaryl" includes aryl groups substituted with one or more alkyl substituents. The term "alkarylene" refers to a divalent alkaryl group.

[0051] The term "cyclic" as used herein refers to a compound containing any molecule having at least three atoms joined together to form a ring (excluding phenyl rings). The term "cyclo" or "cyclic" includes monovalent cyclic hydrocarbons, including monocyclic, bicyclic, tricyclic, and more ring structures, as well as bridged, fused, and fused rings, including at least one bridged ring. The rings may be, for example, 3-10 membered, specifically 4-8 membered, and more specifically 4-, 5-, 6-, 7-, or 8-membered. In embodiments, cyclic alkyl includes C3-C20 cyclic alkyl groups. Examples of suitable cyclic groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, bicyclo[2.2.2]nonane, adamantyl, or tetrahydronaphthyl (tetralin).

[0052] The term "cyclo" or "cyclic" alkylene includes divalent cyclic hydrocarbons, including monocyclic, bicyclic, tricyclic, and higher cyclic structures, as well as bridged cyclic, fused cyclic, and fused cyclic groups, including at least one bridged cyclic group. In embodiments, cyclic alkylene includes C3-C20 cyclic alkylene groups.

[0053] The term "alkynyl" is defined as a C2-C10 branched or straight chain unsaturated aliphatic hydrocarbon group having one or more triple bonds between two or more carbon atoms. Examples of alkynes include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl and nonynyl.

[0054] The term "substituted" means that one or more hydrogens, portions of a molecule, or atoms on a molecule have been replaced by a substituent, provided that the normal valence is not exceeded. The substituent can be a heteroatom. The term "hetero" as used herein refers to atoms such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, etc., or to groups containing such atoms in conjunction with another group or containing such atoms. Examples of suitable substituents include, but are not limited to, -OR, -NR'R, -C(O)R, -SR, -halo, -CN, -NO 2 , -SO 2 , phosphoryl, imino, thioester, carbocyclic, aryl, heteroaryl, alkyl, alkenyl, bicyclic and tricyclic groups. When a substituent is a keto group (i.e., =O), two hydrogens on the atom are replaced. Keto substituents are not found on aromatic moieties. The terms R and R' refer to alkyl groups, which may be the same or different.

[0055] Compositions and methods are provided for reducing emissions from polyurethane foams. In accordance with the present technology, compositions are provided that include at least one blowing reactant, a volatility control agent, and a catalyst. In one embodiment, the volatility control agent is selected from (i) phosphorus-containing compounds; (ii) thiocarbamates; (iii) nitrogen-containing compounds; (iv) phenolic antioxidants; or combinations of two or more thereof. Non-limiting examples of suitable materials include, but are not limited to, amino alcohols, amino acids, alkaline earth metal salts of alkylphenol thioesters; sulfurized alkylphenols; metal salts of sulfurized alkylphenols; metal salts of non-sulfurized alkylphenols; oil-soluble phenates; sulfurized phenates; phosphite triesters (e.g., P(OR) 3 Compounds having the structure: 2 Compounds with the structure OH or their tautomers HP(OR) 2 O); Organodiphosphite [(OR) 2 PZP(OR) 2 ], thiocarbamate, -OH, -NH, or -NH 2 Functionalized pyrrolidine, -OH, -NH, or -NH 2 Functionalized pyrazolidines, -OH, -NH, or -NH 2 Functionalized imidazolidine, -OH, -NH, or -NH 2 Functionalized imidazolidinone, and / or -OH, -NH, or -NH 2 tetrahydropyrimidinones or combinations of two or more of these.

[0056] In one embodiment, the volatility control agent is selected from at least one compound of the group consisting of: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0057] In one embodiment, the volatility control agent is a phosphorus-based material selected from phosphonium compounds of formula (I): [ka] R in the formula 1 is C6 to C30 aryl, or -N(R 5 )R 6 is selected from, where R 5 and R 6 are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety that is preferably bonded through a carbon atom and does not contain an acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R 5 and R 6can be taken together to form a 5- to 10-membered ring; R 2 is C6-C30 aryl, -N(R 5 )R 6 , and -OR 7 is selected from, where R 5 and R 6 are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety that is preferably bonded through a carbon atom and does not contain an acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R 5 and R 6 can be joined together to form a 5- to 10-membered ring, and R 7 is selected from C1-C10 alkyl; R 3 is C6-C30 aryl, -N(R 5 )R 6 , and -OR 8 is selected from, where R 5 and R 6 are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety that is preferably bonded through a carbon atom and does not contain an acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R 5 and R 6 can be joined together to form a 5- to 10-membered ring, and R 8 is selected from C1-C10 alkyl; R 4 Ha-CH 2 -R 9 or =NR 10 is selected from, where R 9 -C(O)-O x R 11 , -CN, -R 12 CN, or -R 13 -CH 2 -PR 1 R 2 R 3 is selected from, where R 11is C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy; R 12 and R 13 are each selected from C1-C10 alkyl or C6-C30 aryl, x is 0 or 1, and R 1 , R 2 , and R 3 is as defined above; and R 10 is selected from C1-C10 alkyl or C6-C30 aryl; A - is selected from organic or inorganic anions and has a valence that opposes the charge of the phosphorus atom.

[0058] In one embodiment, R 5 and R 6 are each independently selected from H and C1-C10 alkyl, or C6-C30 aryl.

[0059] As will be understood, the phosphorus atom is R 1 ~R 4 Depending on the substituents selected for the group, it may carry a positive charge. If the phosphorus atom carries a positive charge, the compound may be provided with an appropriate counter ion (A - The counter ion is not particularly limited and may be selected as desired. In embodiments, the counter ion is selected from organic or inorganic anions. Examples of suitable anions include F - , Cl - , I - , or Br - Such as halides, hydroxides, carbonates, sulfates, carboxylates, acetates, mesylates, tosylates, alcoholates, perchlorates, and the like.

[0060] As will be understood, R 4 =NR 10 In the above case, the P atom in formula (I) is pentavalent and does not have a positive charge, so that the counter ion A - is not required.

[0061] In one embodiment, R 1 ~R 3 are each C6 to C30 aryl, and R 4 Ha-CH 2 -R 9 where R 9 is -CN. In one embodiment, R 1 ~R 3 are each phenyl.

[0062] In one embodiment, the volatility control agent is selected from compounds of formula (I), where R 1 , R 2 , and R 3 are each independently selected from C6 to C30 aryl, and R 4 Ha-CH 2 -R 9 , =NR 10 where R 9 -C(O)-O x R 11 , -CN, or -R 12 Selected from CN;R 11 is C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy; R 12 is selected from C1-C10 alkyl or C6-C30 aryl; and x is 0 or 1.

[0063] In one embodiment, the volatility control agent is selected from compounds of formula (I), where R 1 , R 2 , and R 3 are each independently -N(R 5 )R 6 is selected from, where R 5 and R 6 are each independently a C1 to C10 alkyl group; and R 4 =NR 10 is selected from, where R 10 is selected from C1 to C10 alkyl or C6 to C30 aryl.

[0064] In one embodiment, the volatility control agent is selected from compounds of formula (I), where R 1 is R 2 -OR 7 ;R 3 -OR 8 where R 7 and R 8 are each independently C1 to C10 alkyl; R 4 Ha-CH 2 -R 9 Here, R 9 -C(O)-O x R 11 is selected from, where R 11 is H, C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy.

[0065] As will be appreciated, when the phosphorus atom in the compound of formula (I) is in a 4-coordinated state, the phosphorus atom carries a positive charge, and the compound is provided with a suitable anion to balance the charge. This anion may be any anion desirable for a particular purpose or intended application. Examples of suitable anions include chloride, bromide, iodide, hexafluorophosphate, acetate, and the like.

[0066] In another embodiment, the phosphorus-based compound is a phosphazene compound of formula (II): [ka] R in the formula 14 , R 15 , and R 16 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur, preferably bonded through a carbon atom, in the form of a group or moiety that does not contain an acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof (hydrogen is less preferred). The organic and heteroorganic groups preferably have from 1 to about 20 carbon atoms (more preferably from 1 to about 10 carbon atoms; most preferably from 1 to about 6 carbon atoms).

[0067] Examples of phosphorus-based compounds suitable as volatility control agents include, but are not limited to, (cyanomethyl)-triphenylphosphonium chloride, (methoxycarbonylmethyl)-triphenylphosphonium bromide, tertiary butylimino-tris(dimethylamino)phospholene (phosphazene-based P- 1 -t-Bu), tertiary butylimino-tri(pyrrolidino)phosphorane [phosphazene base P 1 -t-Bu-tris(tetramethylene)], tertiary octylimino-tris(dimethylamino)phosphorane (phosphazene-based P 1 -t-Oct), 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-bis(diethylphosphonomethyl)biphenyl, diethyl-4-cyanobenzylphosphonate, N-methoxy -N-methyl(triphenylphosphoranylidene)acetamide, dimethyl(2-oxopropyl)phosphonate, diethyl(2-oxopropyl)phosphonate, dimethyl(2-oxoheptyl)phosphonate, diethyl(2-oxoheptyl)phosphonate, diethylcarboxymethylphosphonate, diethyl(2-oxo-2-phenylethyl)phosphonate, diethyl(methylthiomethyl)phosphonate, methyl(triphenylphosphoranylidene)acetate, diethylphosphonoacetic acid, 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide, and others.

[0068] Amino alcohol compounds, which may also be referred to as alkanolamines, can be selected from primary, secondary, and / or tertiary cyclic amines containing a hydroxy (i.e., alcohol) functionality. Amino acid compounds contain one amino group and one carboxyl (-C(O)OH) group as well as thio- (-SH, such as cysteine), -SR (such as methionine), amide (-C(O)NH 2 , asparagine), primary amino (such as lysine), heterocyclic groups (such as histidine, tryptophan), and phenolic groups (such as tyrosine). Amino compounds suitable for use as volatility control agents include, but are not limited to, compounds of formula (III): [ka] R in the formula 17 , R 18 , and R 19 are each independently H, a C1-C20 alkyl group optionally substituted with one or more hydroxyl groups, -R 20 -OH, or -R 21 -C(O)OH, where R 20 and R 21 are each independently selected from a divalent C1-C20 hydrocarbon group, a C4-C30 cyclic hydrocarbon group, and a divalent C6-C30 aryl group, each of which may be optionally substituted with a heteroatom-containing group (e.g., an amino group); wherein compound (III) is not selected from diethanolamine or triethanolamine; or R 17 , R 18 , and R 19 Two of the may form a 5-12 membered ring, which may optionally contain one or more heteroatoms in the ring, such as N, O, and which may be substituted with a hydroxy functional group, provided that the compound contains at least one -OH or at least one -C(O)OH functional group.

[0069] Examples of suitable amino alcohols or amino acids include, but are not limited to, 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidinemethanol, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine ... N-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide, 2-(1-piperazinyl)ethanol, 2-(4-amino-1-piperazinyl)ethanol, 2-piperidinemethanol, and others.

[0070] Examples of suitable amino acid compounds include, but are not limited to, nicotinic acid, arginine, asparagine, cysteine, glutamine, histidine, methionine, serine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, tryptophan, tyrosine, and others.

[0071] Still other compounds suitable for use as volatility control agents can be selected from a variety of materials including, but not limited to, sulfurized hindered phenols, alkaline earth metal salts of alkylphenol thioesters having C5 to C12 alkyl side chains, sulfurized alkylphenols, metal salts of sulfurized or non-sulfurized alkylphenols such as nonylphenol calcium sulfide, oil-soluble phenates, and sulfurized phenates, phosphorus sulfurized or sulfurized hydrocarbons, phosphate esters, and thiocarbamates.

[0072] In one embodiment, the volatility control agent is selected from a phenothiazine or an alkylated phenothiazine having the formula (IV): [ka] R in the formula 22 is hydrogen or a linear or branched C1-C24 alkyl, aryl, heteroalkyl, or alkylaryl group, and R 23 is hydrogen or a straight or branched C1-C24 alkyl, heteroalkyl, or alkylaryl group. The alkylated phenothiazine may be selected from the group consisting of monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monononylphenothiazine, dinonylphenothiazine, monooctylphenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, distyrylphenothiazine, butyloctylphenothiazine, and styryloctylphenothiazine.

[0073] In one embodiment, the volatility control agent is a material selected from thiocarbamates. Examples of suitable thiocarbamates include, but are not limited to, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetrabutylthiuram disulfide, tetradecylthiuram disulfide, tetrahexadecylthiuram disulfide, tetracosylthiuram disulfide, 1-methyl-1-propyl-6-butyl-6-methylthiuram disulfide, 1-propyl-1-butyl-6-methyl-6-t-butylthiuram disulfide, dihexamethylenethiuram disulfide ...methylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram Sulfides, dipentamethylene thiuram disulfide, tetrabenzyl thiuram disulfide, piperazinium pentamethylene dithiocarbamate, piperazinium dibutyl dithiocarbamate, piperazinium dicyclohexyl dithiocarbamate, piperazinium di(3-oxycyclohexyl) dithiocarbamate, ammonium dipropyl dithiocarbamate, metal thiocarbamates such as nickel dipropyl dithiocarbamate, nickel dibutyl dithiocarbamate, nickel didecyl dithiocarbamate, zinc Dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dihexyldithiocarbamate, zinc dibenzyldithiocarbamate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, sodium dibenzyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, copper diamyldithiocarbamate, copper dioctadecyldithiocarbamate, copper di Phenyldithiocarbamate, copper dibenzyldithiocarbamate, copper di(orthotolylaminoethyl)dithiocarbamate, copper dicyclohexyldithiocarbamate, potassium dihexyldithiocarbamate, calcium dihexyldithiocarbamate, zirconium diethyldithiocarbamate, tellurium diethyldithiocarbamate, cobalt dibutyldithiocarbamate, antimony dibutyldithiocarbamate, bismuth dimethyldithiocarbamate, lead dimethyldithiocarbamate, tin dibutyldithiocarbamate,Copper dicyclopentyldithiocarbamate, copper 1-butyl-1-cyclohexyl-7-butyl-7-cyclohexyldithiocarbamate, copper di(3-oxacyclohexyl)dithiocarbamate, copper di(4-oxacyclohexyl)dithiocarbamate, copper di(3-thiocyclohexyl)dithiocarbamate, copper di(4-azacyclohexyl)dithiocarbamate, copper 1-butyl-1-(3-oxacyclohexyl)-7-butyl-7-(3-oxacyclohexyl)dithiocarbamate, copper di(4-pyridyl)dithiocarbamate, copper di(4-N,N-dimethylanilino)dithiocarbamate, copper di(4-anisyl)dithiocarbamate, copper di(4-thioanisyl)dithiocarbamate, and copper di(3-furanyl)dithiocarbamate.

[0074] The volatility control agent may also be selected from a phosphite or phosphonate. In one embodiment, the phosphite is selected from a phosphite triester, a diorganophosphite, an organodiphosphite, or a phosphite-substituted polymer. As will be appreciated, a diorganophosphite can be represented by the general formula HP(OR) 2 O and the tautomer P(OR) 2 In one embodiment, the phosphonates have a CH or CH bonded to the phosphorus atom. 2 The moiety can be selected from phosphonates.

[0075] In one embodiment, the volatility control agent is selected from compounds of formula (Vi), (V-ii), (V-iii), (V-iv), (Vv), and / or (V-vi): [ka] [ka] [ka] [ka] [ka] [ka] R in the formula 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 32 , R 33 , R 38 , R 39 , R 41 , R 42 , R 43 , R 44 , R 50 , and R 51 are each independently selected from monovalent C1-C30 alkyl, C2-C30 alkene containing one or more points of unsaturation, C4-C30 cycloalkyl, C2-C30 ether group, C2-C30 alkylene glycol, C2-C30 polyalkylene glycol, C6-C30 aryl, C7-C30 arylalkyl, and C7-C30 alkylaryl; R 31 , R 47 , and R 49 are each independently selected from C1 to C30 alkylene, C4 to C30 cycloalkylene, C6 to C30 arylene, C7 to C30 arylalkylene, and C7 to C30 alkylarylene; R 40 , R 45 , R 46 , R 52 , R 53 , and R 54are each independently selected from hydrogen, a monovalent C1-C30 alkyl, a C2-C30 alkene containing one or more points of unsaturation, a C4-C30 cycloalkyl, a C2-C30 ether group, a C6-C30 aryl, a C7-C30 arylalkyl, and a C7-C30 alkylaryl; X is optionally cyano, C(O)-R substituted with OH; 48 , C1-C30 alkyl, C6-C30, where R 48 is selected from C1-C30 alkyl. In compounds (Vi), (V-ii), (V-iii), (V-iv), and (Vv), each R group may be the same or different from each other. In one embodiment, each R group in the phosphite is the same. In one embodiment, the two R groups in the phosphite are the same. In another embodiment, each R group in the phosphite is different. As will be understood, the alkyl and alkene groups can be straight or branched chain. They may also optionally contain one or more heteroatoms in the chain and include functional groups such as OH, amine, -SH, and others. In addition, the carbon atom number of the cycloalkyl and aryl groups can refer to the number of atoms in the ring structure, or it can refer to the total number of carbons in the compound, i.e., it can include the size of the ring and the groups attached to the ring. The cycloalkyl and aryl groups can also include functional groups such as OH, amine, -SH, and others; m is 1-4, 2-3, and in one embodiment 2; n is 0-3, p is 0-3, and q is 0-3; where m+n+p+q is 4; and n+p+q is 0-3.

[0076] R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 32 , R 33 , R 38 , R 39 , R 41 , R42 , R 43 , and R 44 Examples of suitable groups for include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, decyl, isodecyl, dodecyl, isododecyl, tridecyl, isotridecyl, lauryl, 2-ethylhexyl, phenyl, tosyl, methylphenyl, 6-tertiary butyl-3-methylphenyl, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and the like.

[0077] Some examples of suitable phosphites include, but are not limited to, alkylphenol diisodecyl phosphite, dimethyl phosphite, triethyl phosphite, diphenyl phosphite, triphenyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, diisodecyl phenyl phosphite, tris(nonylphenyl) phosphite, tetraphenyl dipropylene glycol diphosphate, poly(dipropylene glycol) phenyl phosphite, triisooctyl phosphite, trilauryl phosphite, triisodecyl phosphite, tristridecyl phosphite, triisotridecyl phosphite, phosphonic acid di-9-octadecen-1-yl ester, 4,4'-butylidene bis(6-tert-butyl-3-methylphenyl ditridecyl phosphite, tris(dipropylene glycol) phosphite, and diisodecyl phenyl phosphite.

[0078] Examples of suitable phosphonates include, but are not limited to, dimethyl(2-oxypropyl)phosphonate, dimethyl(2-oxoethyl)phosphonate, diethyl(2-oxopropyl)phosphonate, diethyl(4-cyanoethyl)phosphonate, and 4,4'-bis(diethylphosphomethyl)biphenyl.

[0079] In one embodiment, the phosphite can be provided as a polymer substituted with a phosphite group. For example, the polymer can be a polyolefin polymer, in which one or more hydrogen atoms on the carbon can be substituted with a phosphite group. The polymer can be a random or block copolymer with the phosphite substituents. Examples include, but are not limited to, polyethylene, polypropylene, polybutylene, and others. Non-limiting examples of phosphite-substituted polymers include those having the repeating unit: [ka] where R 55 is a bond, C1-C30 alkylene, C4-C30 cycloalkylene, C6-C30 arylene, C7-C30 arylalkylene, and C7-C30 alkylarylene; and R 56 and R 57 are independently selected from monovalent C1-C30 alkyl, C2-C30 alkene containing one or more points of unsaturation, C4-C30 cycloalkyl, C2-C30 ether group, C6-C30 aryl, C7-C30 arylalkyl, and C7-C30 alkylaryl.

[0080] The volatility control compound can also be selected from pyrrolidines, pyrazolidines, imidazolidines, imidazolidinones, pyrimidinones, and the like, where the compound preferably has an alcohol, a carboxylic acid functionality, an -NH group, or an -NH bonded directly or through a linking group to one of the nitrogen atoms. 2 Non-limiting examples of such compounds include, for example, 1-(hydroxymethyl)imidazolidinone, 1-(2-hydroxyethyl)imidazolidinone, 1-(2-hydroxypropyl)imidazolidinone, 1-(2-hydroxyethyl)-2-imidazolidinone, and the like.

[0081] In one embodiment, the volatility control agent is -OH, -NH, or -NH 2Functionalized pyrrolidine, -OH, -NH, or -NH 2 Functionalized pyrazolidines, -OH, -NH, or -NH 2 Functionalized imidazolidine, -OH, -NH, or -NH 2 Functionalized imidazolidinone, and / or -OH, -NH, or -NH 2 tetrahydropyrimidinones.

[0082] In one embodiment, the volatility control agent is an —OH functional imidazolidinone or pyrimidinone selected from N-substituted (hydroxyalkyl) imidazolidinones of formula (VI) or N-substituted (hydroxyalkyl functionalized) tetrahydro-2-pyrimidinones of formula (VII): [ka] R in the formula 34 , R 35 , and R 37 are each independently hydrogen or a straight or branched C1-C24 alkyl 、 selected from a C4-C30 cycloalkyl, a C6-C30 aryl, a C1-C24 heteroalkyl, a C7-C30 alkaryl, or a C7-C30 arylalkyl group; and R 36 is selected from a C1 to C24 alkylene, a C4 to C30 cycloalkylene, a C6 to C30 arylene, a C1 to C24 heteroalkylene, a C7 to C30 alkarylene, or a C7 to C30 arylalkylene group.

[0083] Typically, the volatility control agent is a component of the composition used for foaming. The volatility control agent is in the polyol portion of the composition used for foaming, or in the isocyanate portion of the composition used for foaming, or in a mixture of polyols or isocyanates, or added with the catalyst. Alternatively, the volatility control agent is added separately into the composition for foaming during the foaming process. Typically, the volatility control agent is used in an amount of about 0.05 to about 10 parts per 100 parts polyol (pphp), about 0.1 to about 7.5 pphp, about 0.5 to about 5 pphp, or about 1 to about 3 pphp.

[0084] The composition for preparing polyurethane foams is not particularly limited and can be selected as desired for a particular purpose or intended use. The wide variety of compositions that can be used include, but are not limited to, high resilience foams, flexible foams, viscoelastic foams, microcellular foams, rigid foams, and others. High resilience polyurethane foams are produced by reacting an isocyanate with an isocyanate-reactive compound containing two or more reactive sites, typically in the presence of a blowing agent(s), catalysts, surfactants, and other auxiliary additives. The isocyanate-reactive compound is typically a polyether polyol, polyester polyol, primary and secondary polyamines, or water. The catalyst used in preparing polyurethane foams promotes the two main reactions between the reactants: gelation and blowing. These reactions must proceed simultaneously and at competitively balanced rates during the process to produce polyurethane foams with the desired physical characteristics. Flexible molded polyurethane molded foams must have a certain degree of open cell, and additional processing, such as crushing the foam, may be required to reach the desired cell openness.

[0085] Examples of suitable polyols for preparing polyurethane foams are those having an average number of hydroxyl groups per molecule of at least 2, typically about 2 to about 3.5 hydroxyl groups per molecule. Useful polyols include hydroxyl-terminated polyolefin polyols such as polyether diols and triols, polyester diols and triols, and polybutadiene diols. Other useful polyols include copolymers in which polymeric materials are grafted onto a polyol backbone, such as, for example, SAN (styrene / acrylonitrile) or AN (acrylonitrile) grafted polyether polyols, commonly referred to as copolymer polyols, polyols derived from natural substances such as castor oil, chemically modified soybean oil or other chemically modified fatty acid oils, and polyols obtained by alkoxylation of natural substances such as castor oil or soybean oil.

[0086] Exemplary polyols are polyether diols and triols, particularly those derived from one or more alkylene oxides, phenyl-substituted alkylene oxides, phenyl-substituted alkylene oxides and / or ring-opened cyclic ethers such as ethylene oxide, propylene oxide, styrene oxide, tetrahydrofuran and others, advantageously having a number average molecular weight of from 1000 to 6000, and preferably a weight average molecular weight of from 2500 to 4000.

[0087] Examples of polyisocyanates used to prepare polyurethane foams include, but are not limited to, toluene diisocyanate (TDI) including the 2,4 and 2,6 isomers, isocyanate prepolymers of TDI made from the reaction of TDI with polyols, or other aromatic or aliphatic isocyanates, and the foam index is typically 60 to 130. According to one embodiment of the invention, the polyisocyanate can be a hydrocarbon diisocyanate (e.g., alkylene diisocyanates and arylene diisocyanates), such as toluene diisocyanate including polymeric forms, diphenylmethane isocyanate, and combinations thereof. In yet another embodiment of the invention, the polyisocyanate includes the above isomers, such as methylene diphenyl diisocyanate (MDI) and 2,4- and 2,6-toluene diisocyanate (TDI), as well as the known triisocyanates and polymethylene poly(phenylene isocyanate), also known as polymeric MDI or crude MDI, and combinations thereof. Non-limiting examples of isomeric 2,4- and 2,6-toluene diisocyanates include Mondur TM TD80 or Papi TM 27 and combinations thereof. TM is a registered trademark of Covestro. TM is a registered trademark of The Dow Chemical Company.

[0088] The composition of the present invention may additionally contain a surfactant. The surfactants typically used in the composition are not particularly limited and may be selected as desired for a particular purpose or intended use. Examples of surfactants include, but are not limited to, polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylate, copolymers of ethylene oxide (EO) and propylene oxide (PO) and copolymers of silicone and polyether (silicone polyether copolymers), silicone copolymers, dimethyl silicone oil, and copolymers of ethylene oxide and propylene oxide and mixtures thereof. Examples of suitable surfactants include those available from Momentive Performance Materials under the trade name NIAX. TMThe catalysts used in the compositions of the present invention are not particularly limited and may be selected as desired for a particular purpose or intended use. Examples of suitable catalysts include, but are not limited to, 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, 2-[2-(dimethylamino)ethoxy]ethanol, 2-[2-(dimethylamino)ethyl-methyl-amino]ethanol, 3,3'-iminobis(N,N-dimethylpropylamine), dimethylaminoethanol, 3-(dimethylamino)-1-propylamine, 3-(diethylamino)-1-propylamine, 2-[2-[2-(dimethylamino)ethoxy]ethyl-methylamino]ethanol, 3-{[3-(dimethylamino)propyl]-methylamino}propanol, 2-{[3 -(dimethylamino)propyl]-methyl-amino}ethanol, 2-[2-(dimethylamino)ethoxy]ethanol, 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, 2-{[2-(dimethylamino)ethyl]-methylamino}ethanol, bis-(2-dimethylaminoethyl)ether; short chain tertiary amines or tertiary amines containing at least oxygen, such as pentamethyldiethylenetriamine, triethylamine, tributylamine, N,N-dimethylaminopropylamine, dimethylethanolamine, N,N,N',N'-tetramethylethylenediamine, or urea. Further examples of suitable catalysts include, but are not limited to, amidines, organometallic compounds, and combinations thereof. These may include amidines such as, but are not limited to, 1,8-diazabicyclo[5.4.0]undec-7-ene and 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, and salts thereof.

[0089] Organometallic compounds may include organotin compounds such as, but not limited to, tin(II) salts of organic carboxylic acids, such as tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate. Bismuth salts of organic carboxylic acids, such as bismuth octanoate, may also be selected. Organometallic compounds may be selected for use alone or in combination, or in some embodiments, in combination with one or more of the highly basic amines described above.

[0090] Examples of catalysts capable of accelerating both the foaming and curing reactions are cyclic tertiary amines or long chain amines containing several nitrogen atoms, such as dimethylbenzylamine, N-methyl-, N-ethyl-, and N-cyclohexylmorpholine, N,N,N',N'-tetramethylbutanediamine and N,N,N',N'-hexanediamine, bis(dimethylaminopropyl)urea, dimethylpiperazine, dimethylcyclohexylamine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane, triethylenediamine (TEDA), etc. In one embodiment, 1,4-diazabicyclo[2.2.2]octane (TEDA) is used.

[0091] Another class of catalysts for both the foaming and curing reactions may also be selected, such as alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine, and dimethylethanolamine. Combinations of any of the above may also be used effectively. Some of these catalysts also act as crosslinkers when they contain more than one reactive hydrogen. This is the case, for example, for triethanolamine.

[0092] An example of a suitable catalyst is available from Momentive Performance Materials, Inc. under the trade name NIAX TM These include those commercially available under:

[0093] The composition of the present invention may additionally contain a number of property enhancers. Examples of such property enhancers used in compositions for preparing polyurethane foams include, but are not limited to, blowing agents, organic flame retardants; antiozonants, antioxidants; thermal or thermo-oxidative degradation inhibitors, UV stabilizers, UV absorbers, or any agent that, when added to a foam-forming composition, inhibits thermal, photo, and / or chemical degradation of the resulting foam. Also contemplated herein for use in the compositions of the present invention are any known conventional bacteriostatic, antimicrobial, and gas fade inhibitors.

[0094] Blowing agents can be of the physical and / or chemical type. Typical physical blowing agents are methylene chloride, hydrofluoroolefins, hydrofluorocarbons, chlorofluorocarbons, alkanes or CO used to provide expansion in the foaming process. 2 A typical chemical blowing agent is water, which reacts with the isocyanate in the foam to form a reaction mixture that produces carbon dioxide gas.

[0095] Other optional component(s) that may be used to prepare the compositions of the present invention are known in the art and include fillers, such as inorganic fillers or combinations of fillers. Fillers may include, for example, calcium carbonate (limestone) and other fillers to reduce the cost of the produced foam, aluminum trihydrate and other flame retardant fillers, barium sulfate (barite) and other high density fillers used for sound absorption, microspheres of materials such as glass or polymers that may further reduce the density of the foam, and other improvements including density modification, mechanical property or physical property modification such as sound absorption, flame retardancy, or other benefits that may accompany economic improvement. High aspect ratio fillers used to modify mechanical properties such as foam stiffness or flexural modulus include: synthetic fibers such as milled glass or graphite fibers; natural mineral fibers such as wollastonite; natural animal fibers such as wool or vegetable fibers such as cotton; synthetic platelet fillers such as ground glass; natural platelet mineral fibers such as mica; and the possible addition of any pigment, dye, or colorant.

[0096] These optional ingredients include other polyhydroxyl terminated materials, such as those having 2 to 8 hydroxyl groups per molecule and molecular weights of 62 to 500, which function as crosslinkers or chain extenders. Examples of useful chain extenders with 2 hydroxyl groups include dipropylene glycol, diethylene glycol, 1,4-butanediol, ethylene glycol, 2,3-butanediol, and neopentyl glycol. Crosslinkers with 3 to 8 hydroxyl groups include glycerin, diethanolamine, pentaerythritol, mannitol, and others.

[0097] The foams may be prepared by reacting the foaming reactants under suitable conditions to prepare the foam.

[0098] The volatility control agent likely removes the emission-generating agent. Examples of such emission-generating agents include volatile substances, including but not limited to formaldehyde, acetaldehyde, propionaldehyde, acrolein, and others. The volatility control agent can be added to the mixture of foaming reactants. Alternatively, the volatility control agent can be added to a separate composition that includes one or more components used in the composition to prepare the foam. In one embodiment, the volatility control agent is added to the mixture of polyol, surfactant(s), chain extender(s), crosslinker(s) and catalyst(s) prior to blending or mixing with the remaining components of the composition.

[0099] In a further embodiment, the present invention provides a method for controlling emissions from polyurethane foams. The method may include contacting at least one foaming reactant with a volatility control agent, including one or more of any of the volatility control agents described herein above. In one embodiment, the method includes contacting at least one foaming reactant with a volatility control agent selected from the group consisting of: [ka] [ka] [ka] [ka] Phosphites of formula (Vi), (V-ii), (V-iii), (V-iv), (Vv) and / or (V-vi) [ka] [ka] [ka] [ka] [ka] [ka] N-substituted (hydroxyalkyl)imidazolidinones of formula (VI) or N-substituted (hydroxyalkyl-functionalized) tetrahydro-2-pyrimidinones of formula (VII): [ka] where each R group is as defined herein.

[0100] The composition containing the volatility control agent has a reduced aldehyde content compared to the same composition without the volatility control agent. For purposes of the present technology, a reduced aldehyde content is provided, where at least one aldehyde species is reduced relative to a composition without the volatility control agent. It is also understood that the aldehyde content of the foam composition may vary depending on the region or area, where the foam is produced or used based on different specifications of raw materials that may be used or accepted in different regions / countries. Regardless of the specifications of the starting materials, the composition of the present invention provides a reduction of one or more aldehyde species relative to the same composition without the volatility control agent.

[0101] In one embodiment, the composition and / or foams made from such compositions have a concentration of at least one aldehyde species that is at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 75%, at least 80%, at least 90%, or even at least 95% lower than the concentration in the same composition without the volatility control agent. In one embodiment, the composition and / or foams made from such compositions have a concentration of at least one aldehyde species that is about 5% to about 95%, about 10% to about 90%, about 20% to about 80%, about 25% to about 75%, about 30% to about 60%, or about 40% to about 50% lower than the concentration in the same composition without the volatility control agent. In one embodiment, at least the formaldehyde content of the composition or foams made from the composition is lower than that of the same composition without the volatility control agent.

[0102] It will be further understood that a composition of the present invention may be considered effective if the concentration of one or more aldehyde species is reduced compared to a composition not containing a volatility control agent or foam formed from the composition, even if the concentration of one or more other aldehyde species is not reduced or is increased.

[0103] In addition, it will be appreciated that the volatility control agent may be one that effectively reduces or at least prevents the growth of one or more aldehyde species in the final foam product on an ongoing basis.

[0104] Aspects and embodiments of the present technology will be further understood with reference to the following examples.

[0105] Working Example

[0106] The following polyol blends A, B and C were used in combination with a volatility control agent to prepare compositions of the present invention: CARADOL SA34-05 is a propylene oxide and ethylene oxide based polyether triol for producing flexible polyurethane foams such as high resilience slabstock or low temperature cure molded parts. [Table 0]

[0107] 0.5 to 5.0 pphp of volatility control agent was added to 10 grams of Polyol Blend A or B, and the mixture was sealed and heated in an oil bath to 150°C for 30 minutes. The sample was then allowed to cool to room temperature, and then 3 ml of 2,4-dinitrophenylhydrazine phosphate solution (0.2M concentration, Sigma-Aldrich, CAS number 125038-14-4) was injected. The sample was heated to 50°C for 30 minutes and subsequently analyzed by HPLC for the presence of residual aldehydes.

[0108] A control test was run without the volatility control agent. The amounts of aldehydes present in the polyol blend were approximately 10 ppm formaldehyde, 20 ppm acetaldehyde, and 500 ppm propionaldehyde.

[0109] The volatility control agents were dissolved in a suitable solvent prior to testing. Polyol Blend A was used to compare the effectiveness of the volatility control agent, using a commercial sample, Jeffadd TM AS-53 (available from Huntsman Polyurethanes Shanghai China Co., Ltd.) and Milliguard TM AS-88 (available from Milliken Shanghai China Co., Ltd.) Table 1 shows the effect of volatile control agents (ECAs) relative to a control that did not contain these agents. [Table 1]

[0110] Examples 1 to 16

[0111] (2,8,9-Trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane) (CAS number: 120666-13-9) was purchased from Sigma-Aldrich.

[0112] (Cyanomethyl)triphenylphosphonium chloride (CAS number: 4336-70-3) was purchased from TCI Chemicals.

[0113] (Methoxycarbonylmethyl)triphenylphosphonium bromide (CAS number: 1779-58-4) was purchased from TCI Chemicals.

[0114] Tertiary butylimino-tris(dimethylamino)phosphorane (CAS number: 81675-81-2) was purchased from Sigma-Aldrich.

[0115] 4,4-Bis(diethylphosphonomethyl)biphenyl (BEDP) (CAS number: 17919-34-5) was purchased from TCI Chemicals.

[0116] Dimethyl(2-oxopropyl)phosphonate (CAS number: 4202-14-6) was purchased from TCI Chemicals.

[0117] Diethyl (4-cyanobenzyl)phosphonate (CAS number: 1552-41-6) was purchased from TCI Chemicals.

[0118] Diethyl (2-oxopropyl)phosphonate (CAS number: 1067-71-6) was purchased from Sigma-Aldrich.

[0119] Diethylphosphonoacetate (CAS number: 3095-95-2) was purchased from Sigma-Aldrich.

[0120] Dimethyl 2-oxoheptylphosphonate (CAS number: 36969-89-8) was purchased from Sigma-Aldrich.

[0121] Dimethyl phosphite (CAS number: 868-85-9) was purchased from Sigma-Aldrich.

[0122] Diphenyl phosphite (CAS number: 4712-55-4) was purchased from Sigma-Aldrich.

[0123] Triethyl phosphite (CAS number: 122-52-1) was purchased from Sigma-Aldrich.

[0124] Triphenyl phosphite (CAS number: 101-02-0) was purchased from Sigma-Aldrich.

[0125] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (CAS number: 35948-25-5) (DOPO) was purchased from TCI Chemicals.

[0126] Tris(dipropylene glycol) phosphite (CAS number: 36788-39-3) is available from Momentive Performance Materials, Inc.

[0127] Doverphos TM LGP-11 is a proprietary high molecular weight phosphite available from Dover Chemical Company.

[0128] Doverphos TM LGP-12LV is a high molecular weight phosphite available from Dover Chemical Company.

[0129] Doverphos TM DP-253 (CAS number: 64051-29-2) is dioleyl hydrogen phosphite available from Dover Chemical Company.

[0130] Doverphos TM 374 is an alkyl diisodecyl phosphite available from Dover Chemical Company.

[0131] L-Lysine (CAS number: 56-87-1) was purchased from Sigma-Aldrich.

[0132] 2-Piperidinemethanol (CAS number: 3433-37-2) was purchased from Sigma-Aldrich.

[0133] 1-(2-Hydroxyethyl)-2-imidazolidinone (CAS number: 3699-54-5) and cyanoacetamide (CAS number: 107-91-5) were purchased from Sigma-Aldrich.

[0134] 1-(2-Hydroxyethyl)pyrrolidine (CAS number: 3699-54-5) was purchased from Sigma-Aldrich.

[0135] Copper diethyldithiocarbamate (CAS number: 13681-87-3) was purchased from TCI Chemicals.

[0136] 10H-Phenothiazine (CAS number: 92-84-2) was purchased from Sigma-Aldrich.

[0137] L-(+)-Arginine (CAS number: 74-79-3), L-cysteine ​​(CAS number: 52-90-4), L-glutamine (CAS number: 56-85-9), L-serine (CAS number: 56-45-1), and L-(-)-tyrosine (CAS number: 60-18-4) were purchased from TCI Chemicals.

[0138] Compositions including Examples 1 to 5 were prepared using Polyol Blend A and a phosphorus-based material as a volatility control agent. The results are presented in Table 2A. The amount of aldehydes present in Polyol Blend A was 10 ppm formaldehyde, 20 ppm acetaldehyde, and 500 ppm propionaldehyde. Of the compositions tested, those containing (2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane) and cyanomethyltriphenylphosphonium chloride as volatility control agents showed at least HCHO and CH 3The composition containing methoxycarbonylmethyltriphenylphosphonium bromide showed good volatilization control for HCHO, whereas 4,4 bis(diethylphosphonomethyl)biphenyl (BEDP) reduced emissions of HCHO to 4.1 ppm and CH 3 For CHO, efficacy was demonstrated up to 13.1 ppm. [Table 2A]

[0139] Furthermore, compositions including Examples 6-10 were prepared using Polyol Blend B and other phosphorus-based materials as volatility control agents. The results are presented in Table 2B. The amount of aldehydes present in Polyol Blend B is about 9 ppm formaldehyde, 15 ppm acetaldehyde, and 489 ppm propionaldehyde. As is evident from Comparative Examples 6-10, the phosphorus-based additives tested tended to reduce the levels of aldehydes. [Table 2B]

[0140] As is evident from Comparative Examples 10A to 10D, the tested tri- and di-substituted phosphite additives tended to reduce the levels of aldehydes. Compositions including Examples 10A, 10B (diorganophosphites) and Examples 10C, 10D (phosphite triesters) were prepared using Polyol Blend A as a volatility control agent. The results are presented in Table 2C. Polyol Blend A was tested with the diorganophosphites of Examples 10A, 10B and the phosphite triesters of Examples 10C, 10D, both of which acted as volatility control agents, reducing the levels of acetaldehyde and especially formaldehyde, compared to the control sample (Polyol Blend A without ECA). [Table 2C]

[0141] A composition containing 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide of Example 10E was prepared as a volatility control agent using Polyol Blend A. The detected amounts of aldehydes present in Polyol Blend A were 11.2 ppm formaldehyde, 17.8 ppm acetaldehyde, and 522.4 ppm propionaldehyde. Acting as a volatility control agent, Example 10E reduced the levels of propionaldehyde, and especially formaldehyde and acetaldehyde, compared to the control sample (Polyol Blend A without ECA). The results are presented in Table 2D. [Table 2D]

[0142] 0.1 to 1.0 pphp of tris(dipropylene glycol) phosphite (a volatility control agent) was added to 10 grams of polyol blend C (Table 4A), the mixture was sealed and kept in a shaker for 30 minutes, and then heated in an oil bath at 150°C for 30 minutes. The sample was then allowed to cool to room temperature, followed by injection of 3 ml of DNPH phosphoric acid solution (prepared in the laboratory to a DNPH concentration of 0.1 M). The sample was heated at 50°C for 60 minutes and analyzed by HPLC for the presence of residual aldehydes. A control run was run without the volatility control agent. The amount of aldehydes present in the polyol blend was approximately 31 ppm formaldehyde (Table 2E), 16 ppm acetaldehyde, and 197 ppm propionaldehyde.

[0143] Compositions including Example 10F were prepared using Polyol Blend C and tris(dipropylene glycol) phosphite as the volatility control agent, and the results are presented in Table 2E. [Table 2E] Among the different compositions of 0.1, 0.5, and 1.0 pphp tris(dipropylene glycol) phosphite tested in Polyol Blend C, compositions containing 0.5 and 1.0 pphp tris(dipropylene glycol) phosphite as a volatility control agent provided a significant reduction in formaldehyde levels and a partial reduction in acetaldehyde levels compared to the control sample.

[0144] Examples 10G to 10I

[0145] Doverphos in 1.0pphp TM The material (volatility control agent) was added to 10 grams of Polyol Blend C, the mixture was sealed and kept in a shaker for 30 minutes, and then heated in an oil bath at 150°C for 30 minutes. The sample was then allowed to cool to room temperature, followed by injection of 3 ml of DNPH phosphoric acid solution (prepared in the laboratory to a DNPH concentration of 0.1 M). The sample was heated at 50°C for 60 minutes and analyzed by HPLC for the presence of residual aldehydes. A control run was run without the volatility control agent. The amount of aldehydes present in the Polyol Blend was approximately 6.3 ppm formaldehyde, 7.3 ppm acetaldehyde, and 187.2 ppm propionaldehyde.

[0146] Compositions using Examples 10G-10I were prepared using Polyol Blend C as the volatility control agent. The results are presented in Table 2F. [Table 2F]

[0147] The amounts of aldehydes detected in Polyol Blend C were 6.3 ppm formaldehyde, 7.3 ppm acetaldehyde, and 187.2 ppm propionaldehyde. TM Among the materials, Doverphos TM LGP-11(10G) and Doverphos TMLGP-12LV(10H) provided a significant reduction in formaldehyde to 1.6 ppm and 0.5 ppm, respectively. TM DP253(10I) showed a reduction in formaldehyde levels to 3.7 ppm.

[0148] Compositions containing amino acids, amino alcohols, and hydroxy-functionalized imidazolidinone (Examples 11-14) were also tested for release using Polyol Blend A. The results obtained are shown in Table 3. Among the compositions tested, those containing L-lysine, 2-piperidinemethanol, 1-(2-hydroxyethyl)-2-imidazolidinone, and 1-(2-hydroxyethyl)pyrrolidine as ECAs showed good effect on formaldehyde release (1.3, 6.7, 2.6, and 3.0 ppm, respectively). Compositions containing L-lysine or 2-piperidinemethanol also showed good control on acetaldehyde release (5.4 and 6.0 ppm, respectively). All the additives tested (Examples 11-14) reduced the propionaldehyde level from 500 ppm to 340-390 ppm. [Table 3]

[0149] Compositions containing copper salts and phenothiazine derivatives as ECAs (Examples 15-16). The results obtained from these compositions are shown in Table 4. Among the compositions tested, the composition containing copper(II) diethyldithiocarbamate showed good release control for formaldehyde (0.1 ppm). Interestingly, copper(II) diethyldithiocarbamate showed good effect in reducing acetaldehyde (2.4 ppm) and propionaldehyde (150 ppm). 10H-phenothiazine surprisingly also reduced the levels of formaldehyde, acetaldehyde, and propionaldehyde. [Table 4]

[0150] Examples 17A to 17G

[0151] The following Polyol Blend C was used in combination with a volatility control agent to prepare compositions of the present invention. [Table 4A]

[0152] 0.5 to 1.0 pphp of amino acid (volatility control agent) was dissolved in 0.5 ml to 1.0 ml of water. The dissolved or partially dissolved amino acid was added to 10 grams of Polyol Blend C, the mixture was sealed and kept in a shaker for 30 minutes, and then heated in an oil bath at 150°C for 30 minutes. The sample was then allowed to cool to room temperature, followed by injection of 3 ml of DNPH phosphoric acid solution (prepared in the laboratory to a DNPH concentration of 0.1 M). The sample was heated at 50°C for 60 minutes and analyzed by HPLC for the presence of residual aldehydes. A control run was run without the volatility control agent. The amount of aldehydes present in the polyol blend was approximately 10 ppm formaldehyde, 10 ppm acetaldehyde, and 300 ppm propionaldehyde.

[0153] The compositions of Examples 17A to 17F and 17G are prepared by mixing Polyol Blend C and an amino acid-based material or Doverphos TM 374 as a volatility control agent. The results are presented in Table 4B. [Table 4B]

[0154] The amount of aldehydes present in the polyol blend is approximately 10 ppm formaldehyde, 10 ppm acetaldehyde, and 300 ppm propionaldehyde. Among the compositions tested for different active site amino acids, compositions containing L-cysteine ​​(17B), L-lysine (17D), and L-(-)-tyrosine (17F) as volatility control agents recorded significant reductions in formaldehyde levels compared to the control sample. Furthermore, compositions containing L-(+)-arginine (17A), L-glutamine (17C), and L-serine (17E) moderately reduced formaldehyde levels compared to the control sample. Doverphos TM 374 (alkylaryl phosphite) acted as a volatility control agent and recorded the lowest emissions for HCHO.

[0155] Evaluation of polyurethane foams

[0156] The following exemplary polyurethane foams were made according to the formulations outlined in Tables 5 through 14.

[0157] KONIX FA-703 is a glycerin-derived base polyether polyol with a molecular weight Mw of 5,100, purchased from KPX Chemical (Nanjing) Co., Ltd.

[0158] KONIX FA-3630S is a polymer polyol with a solid content of 30% and was purchased from KPX Chemical (Nanjing) Co., Ltd.

[0159] Hyperlite TM E-833 polyol is a base polyether polyol purchased from Covestro.

[0160] Hyperlite TM E-852 polyol is a copolymer polyol purchased from Covestro.

[0161] DEOA is the abbreviation for diethanolamine (CAS number: 111-42-2), which is a chemical that is a viscous liquid at room temperature (purity ≥ 99.0%, produced by supercooling technology), purchased from Shanghai Lin Gaofeng Chemical Reagents Co., Ltd. and added directly into the formulation.

[0162] Niax TM DEOA-LF is an 85 wt% aqueous solution of diethanolamine available from Momentive Performance Materials.

[0163] Niax TM Catalyst A-1 is a conventional blowing catalyst available from Catalyst Momentive Performance Materials, Inc.

[0164] Niax TM Catalyst A-33 is a gelling catalyst available from Momentive Performance Materials.

[0165] Niax TM Catalyst DMEE is a reactive PU catalyst available from Momentive Performance Materials.

[0166] Niax TM Catalyst EF-150 is a low volatility blowing catalyst available from Momentive Performance Materials, Inc.

[0167] Niax TM Catalyst EF-100 is a reduced volatility blowing catalyst available from Momentive Performance Materials, Inc.

[0168] Niax TM Catalyst EF-600 is a balanced, low odor, reduced volatility catalyst available from Momentive Performance Materials, Inc.

[0169] Jeffcat TM Catalyst ZR-50 is a reactive, reduced volatility gelling catalyst available from Huntsman Polyurethanes (China) Company.

[0170] Niax TM Silicone L-3641 is a highly active silicone surfactant suitable for TM formulations available from Momentive Performance Materials.

[0171] Niax TM Silicone L-3185 is a highly active silicone surfactant suitable for TM or TDI formulations available from Momentive Performance Materials.

[0172] TM20 (TDI 80%, MDI 20%, NCO 44.89) is a mixture of 80wt% Lupranat T80 (purchased from BASF) and 20wt% Desmodur TM It is a self-blended isocyanate containing 44V20L (purchased from Covestro).

[0173] Mondur TM TD80 Grade A is a mixture of the 2,4- and 2,6-isomers of toluene diisocyanate (TDI) in an 80 / 20 (w / w) ratio and is available from Covestro.

[0174] MT30 (TDI 30%, MDI 70%, NCO% 37.36) is 30wt% Lupranate TM T80 (purchased from BASF) and 70wt% Desmodur TM It is a self-blended isocyanate containing 3133 (purchased from Covestro).

[0175] Dipropylene glycol (DPG, CAS number: 25265-71-8) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0176] Diethylene glycol (DEG, CAS number: 111-46-6) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0177] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (CAS number: 35948-25-5) (DOPO) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. and used as a solution in DEG.

[0178] Sodium diethyldithiocarbamate trihydrate (SDETC) (CAS number: 20624-25-3) was purchased from Shanghai McKin Biochemical Technology Co., Ltd. and used as a solution in DPG.

[0179] Copper(II) diethyldithiocarbamate (CDEDTC) (CAS number: 13681-87-3) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. and used as a solution in DPG.

[0180] Polyurethane foams were prepared according to the following procedure: For each of the foam series presented in each of the tables, first, base polyether polyols and polymer polyols such as KONIX FA-703 / KONIX FA-3630S in Tables 5-13, and Hyperlite E-833 / Hyperlite E-852 in Table 14, crosslinker Niax®, TM DEOA or Niax TM DEOA-LF, Silicone stabilizer Niax TM Silicone L-3641 or Niax TM Premixes of L-3185 were prepared according to the ratios listed in the table. The premixes were mixed for 5 minutes at 4,000 rpm using a Pendraulik dissolver LR75. Then, proprietary catalyst-water-catalyst blends were prepared by mixing the prescribed amounts of water with the corresponding amine catalyst as follows: a) Water / Niax TM Catalyst A-1 / Niax TM Catalyst A-33 [C-1, C-2, C-4, C-5, C-9, C-13D, Examples 18-21, 26, 30-31, 33G], b) Water / Niax TM Catalyst EF-150 / Niax TM Catalyst A-33 [C-3, C-13B, Examples 22-25, 33B, 33C], c) Water / Niax TM Catalyst DMEE / NiaxTM Catalyst A-33 [C-6, C-7, C-8, C-10, C-11, and Examples 27-29, 32], d) Water / Niax EF-100 / Jeffcat ZR-50 [C-12, C-13, and Example 33], e) Water / Niax TM EF-150 / Niax TM EF-600 [C-13, Examples 33D to 33F] and f) water / Niax TM EF-100 / Niax TM EF-600 [C-14, Examples 34-35]. A predetermined amount of polyol premix was transferred to a plastic container according to the quantities summarized in Tables 5-14, then a predetermined amount of water / amine mixture was added, and the resulting mixture was mixed for 45 seconds at 4,000 rpm using a Pendraulik mixer. A predetermined amount of volatility control agent (ECA) or ECA solution was then added to the blend and mixed for an additional 30 seconds. Finally, a predetermined amount of isocyanate (TM20 in Tables 5-12, MT30 in Table 13, or TDI in Table 14) was added, and the resulting mixture was mixed for an additional 4 seconds. The mixture was then poured into a 30 cm x 30 cm x 10 cm thermostated (65°C) aluminum mold and the mold was closed. The mold lid was equipped with four vents (1 mm diameter) located at each corner. The mixture expanded and filled the mold cavity to produce the molded foam specimens. After counting 5 minutes from the addition of TM20, the mold was opened and a square PU foam pad measuring 30 cm x 30 cm x 10 cm was demolded and used for the physical property evaluations listed in the table. The following processing and physical properties of the foam were evaluated: Exit time was the time recorded from the end of mixing the polyol blend and isocyanate to the first extrusion of foam from one of the vent holes.

[0181] The force to crush (FTC) is the peak force required to deflect the foam pad to 50% (FTC-50) or 75% (FTC-75) of its original thickness within 1 minute after demolding using a flat, 203 mm diameter standard circular indenter. It is measured using a load tester with the same settings as used for foam hardness measurements. A crosshead speed of 200 mm / min is used for the load tester. The FTC value is a good relevant measurement of the open cell characteristics (continuity) of the foam, the lower the value the more open the foam.

[0182] Hot indentation load deflection (hot ILD) is measured within 3 minutes after demolding on the same pad used for FTC measurement. Following FTC measurement, the foam pad is completely crushed in a crusher before taking the Hot ILD50% (50% compression) or Hot ILD75% (75% compression) measurements. The Hot ILD value is a good relevant measurement of the degree of cure of the foam 3 minutes after demolding. The higher the Hot ILD value, the more cured the foam.

[0183] Indentation Force Deflection (IFD-25%) is a parameter that provides information about the firmness of the foam. The higher the IFD value, the firmer the foam. The detailed test procedure for IFD is described in ASTM D3574 test B1.

[0184] The aldehyde emission results in polyurethane foams are measured according to the recommendations of Toyota TSM0508G method: a volatile content measurement method using a sampling bag. The polyurethane foams must be produced within 14 days before the test and must be crushed to open the air bubbles before being cut into the specified cubes of 30 grams of test specimens. The test specimens are weighed and then placed in a specified 10 L Tedlar gas bag (GL Sciences SMAETBAG) that has been previously treated with the hot washing method and has passed the blank value limit requirements. The bag containing the foam specimens is sealed and then filled with approximately 5 L of nitrogen gas. In the next step, the nitrogen gas is removed by suction and checked for possible leaks. The bag is then filled with 5 L of nitrogen gas, accurately measured by a gas flow meter, and the stop valve connected to the Tedlar bag is closed. The bag containing the foam specimens is placed in a constant temperature oven maintained at 65 °C. Under these conditions, the bag is held at 65°C for 2 hours, then the bag is pumped out through a 300 mg 2,4-dinitrophenylhydrazine (DNPH) cartridge to capture the carbonyl compounds. The gas sampled on the DNPH cartridge is extracted using acetonitrile as a solvent. The extracted acetonitrile solution was analyzed using an Agilent HPLC 1200 equipped with a UV-Visible spectrophotometer (G1315B DAD, 360 nm). The injection volume was 5 μL onto an Agilent Poroshell 120EC-C18 75 x 4.6 mm, 2.7 μm chromatography column, and an acetonitrile:water gradient elution was used to quantify each of the DNPH-hydrazones.

[0185] The formaldehyde, acetaldehyde, and propionaldehyde emissions for each of the comparative examples and examples are listed in Tables 5 through 12. Testing of the foam series in each table was performed on the same day, and the foams were processed in the same manner to present representative characteristics. [Table 5]

[0186] Data shown in Table 5 compares Example C1 with Examples 18-20, and shows that formaldehyde emissions ranged from 0.045 to 0.023 mg / m when 0.1 pphp of diethyl (2-oxopropyl) phosphonate was added. 3 and the most significant reduction in formaldehyde emissions was achieved with the addition of 1.0 pphp: 0.013 mg / m 3 It can be seen that this is achieved by using diethyl (2-oxopropyl) phosphonate. Meanwhile, the results of the evaluation parameters of the molded foam, such as exit time, FTC, hot ILD, and IFD-25%, show that diethyl (2-oxopropyl) phosphonate has no negative effect on both the molding process and the mechanical properties of the foam. [Table 6]

[0187] Table 6 shows that dimethyl (2-oxoheptyl) phosphonate acts as a volatility control agent, reducing formaldehyde emissions from 0.0634 to 0.0336 mg / m compared to the reference sample. 3 and had only a slight effect on the foaming process and no effect on the mechanical properties of the foam, resulting in reduced FTC-75% values ​​and comparable IFD-25% values ​​compared to the reference sample. [Table 7]

[0188] 4,4-Bis(diethylphosphonomethyl)biphenyl was used in the formulation as a 20 wt % solution in gamma-butyrolactone.

[0189] As can be seen from the data listed in Table 7, 4,4-bis(diethylphosphonomethyl)biphenyl provides efficient formaldehyde emission control behavior in molded TM20 polyurethane foam applications, ranging from 0.0533 to 0.0210 mg / m 3Furthermore, 4,4-bis(diethylphosphonomethyl)biphenyl was shown to have no effect on exit time, FTC-75% values, hot ILD-75% and IFD-25%, and no negative effect on foaming characteristics and foam mechanical properties.

[0190] Applicants have found that phosphorus-based volatility control agents advantageously make no contribution to objectionable foam odor, unlike the cyanoacetoacetamide and diethyl malonate described in U.S. Patent Publication 2016 / 0304686A1. [Table 8]

[0191] 1-(2-hydroxyethyl)-2-imidazolidinone was used in the foam formulation as a 75 wt% solution in water. Table 8 shows that 1-(2-hydroxyethyl)-2-imidazolidinone reduced formaldehyde emissions from 0.0462 to 0.0186 mg / m compared to the reference sample. 3 The results show that the foaming process was reduced to 100%. Applicant observed a slight negative impact on the foaming process, but no impact on the mechanical properties of the foam (reduced FTC-75% values ​​and comparable IFD-25% values ​​compared to the reference). Example C-5 is a comparative example, which includes the addition of cyanoacetoacetamide, as described in US Patent Publication 2016 / 0304686A1. As shown in Table 8, cyanoacetoacetamide had a large negative impact on the foaming process, and the addition of cyanoacetoacetamide (as a 15 wt % aqueous solution) resulted in complete foam collapse (Example C-5). [Table 9]

[0192] (Cyanomethyl)triphenylphosphonium chloride was used as a 2.12 wt% solution in DMEE. The amount of DMEE added in formulations C-6, C-7, Examples 27 and 28 is constant. The calculated use level of (cyanomethyl)triphenylphosphonium chloride obtained in the foam formulation was 0.05 pphp. As shown in Table 9, two experiments were performed for this comparative example. In contrast to Examples C-6 and C-7, the addition of (cyanomethyl)triphenylphosphonium chloride leads to a reduction in the emission of formaldehyde, acetaldehyde and acrolein from the foam samples. As shown in Table 9, the exit time, FTC-50%, hot ILD-50% and pad weight show no significant effect on the foam properties and foaming process, providing additional improvements over current technology. [Table 10]

[0193] (Methoxycarbonylmethyl)triphenylphosphonium bromide was also used as a solution in DMEE (5.21 wt%). The DMEE usage level in formulation C-8 and Example 29 is constant. The calculated loading of (methoxycarbonylmethyl)triphenylphosphonium bromide in the formulation was 0.027 pphp. As shown by comparing inventive Example 29 and reference sample C-8 (Table 10), (methoxycarbonylmethyl)triphenylphosphonium bromide reduced formaldehyde and acetaldehyde emissions from 0.1030 to 0.0417 mg / m, respectively. 3 , and 0.0870 to 0.0550 mg / m 3 Both were reduced to 0.01%. A reduction in the amount of acrolein and propionaldehyde emissions from the foam specimens was also observed when compared to the reference samples. The exit time, FTC-50% and hot ILD-50% results indicated that (methoxycarbonylmethyl)triphenylphosphonium bromide had a slight detrimental effect on the foaming process and foam properties. [Table 11]

[0194] Dimethyl 2-oxopropylphosphonate is a liquid and therefore was applied neat directly to the formulation. The data in Table 11 compares Example C-9 with Examples 30-31 and shows that formaldehyde emissions are reduced when 0.5 pphp of dimethyl 2-oxopropylphosphonate is added to the formulation. Table 11 shows that foam samples prepared with dimethyl 2-oxopropylphosphonate have reduced FTC and hot ILD values, which indicate undesirable interference with the foaming process. [Table 12]

[0195] Diethyl (4-cyanobenzyl) phosphonate was applied as a solution in propylene carbonate (PC) (9.82 wt%) and used at 0.1 pphp in the foam formulation. As shown in the data in Table 12, diethyl (4-cyanobenzyl) phosphonate reduced formaldehyde emissions in polyurethane foam formulations molded with TM20 compared to reference samples C-10 and C-11. In addition, no negative effects on the foaming process were observed in foam samples prepared with diethyl (4-cyanobenzyl) phosphonate. [Table 13A]

[0196] 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide was used as a solution in diethylene glycol (DEG) (10 wt%). As shown in the data in Table 13A comparing Example C-1 with Example 33, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide can be seen to provide formaldehyde emission control in MT30 molded polyurethane applications, resulting in a reduction in formaldehyde emissions of 0.2074 to 0.1742 mg / m2 in the final formulated product when 1.0 pphp of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide solution was used (calculated 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide loading of 0.1 pphp). 3 Meanwhile, the results of the evaluation parameters of the molded foam, such as exit time, FTC, hot ILD, and IFD-25%, show that 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide has no adverse effect on the foaming process and the mechanical properties of the foam.

[0197] 7-[2-(2-hydroxymethylethoxy)methylethoxy]tetramethyl-3,6,8,11-tetraoxa-7-phosphatridecane-1,13-diol (CAS number: 36788-39-3) is a liquid and therefore was applied neat directly to the formulations in amounts of 0.1 and 0.5 pphp (Table 13B). [Table 13B]

[0198] As shown by comparing Example 33B with Reference Sample C-13B in Table 13B, the addition of 0.1 pphp of tris(dipropylene glycol) phosphite (CAS number: 36788-39-3) reduced formaldehyde emissions from 0.0442 to 0.0292 mg / m 3 , and 0.0383 to 0.0258 mg / m 3Increasing the amount of this additive from 0.1 to 0.5 pphp further reduced the formaldehyde level by 0.0258 mg / m 3 On the other hand, the exit time was not affected, whereas the FTC and hot ILD results showed that tris(dipropylene glycol) phosphite contributed to the increase in the FTC and hot ILD values.

[0199] In an additional series of experiments (Table 13C, Examples 33D and 33E), the phosphite Doverphos TM DP253 and Doverphos TM With the addition of LGP11, the formaldehyde levels of the comparative foams went from 0.1620 to 0.1439 mg / m 3 and 0.1133 mg / m 3 The addition of tris(dipropylene glycol) phosphite reduced formaldehyde levels from 0.1620 to 0.0435 mg / m 3 was significantly reduced to [Table 13C]

[0200] The beneficial effect of tris(dipropylene glycol) phosphite was also observed from the comparative example shown in Table 13D, where the addition of tris(dipropylene glycol) phosphite (Example 33G) reduced formaldehyde levels to 0.0556 mg / m 3 to undetectable range 0mg / m 3 A controlled release of acetaldehyde was also observed, with the release decreasing from 0.0561 to 0.0400 mg / m 3 has been reduced to. [Table 13D]

[0201] Sodium diethyldithiocarbamate trihydrate (SDETC) and copper(II) diethyldithiocarbamate (CDEDTC) were solids and dissolved in DPG at room temperature with stirring to give concentrations of 1.22 and 2.54 wt% in DPG, respectively. The calculated loadings of SDETC and CDEDTC in the formulation were 0.012 and 0.025 pphp, corresponding to 100 ppm in the final foam specimens. [Table 14]

[0202] As shown by a comparison of Examples 34, 35, and Reference Sample C-14 in Table 14, both SDETC and CDEDTC reduced formaldehyde emissions from 0.0980 to 0.0718 mg / m 3 , and 0.0980 to 0.0428 mg / m 3 Meanwhile, the results of exit time, FTC and hot ILD indicated that neither SDETC nor CDEDTC had any detrimental effect on the foaming process and foam properties.

[0203] The above description includes examples according to the present specification. Of course, it is not possible to describe all possible combinations of components or methods for the purpose of describing the present specification, but one skilled in the art may recognize that many other combinations and permutations are possible herein. Therefore, the present specification is intended to embrace all changes, modifications, and variations that are included within the spirit and scope of the claims. Furthermore, when the term "comprises" is used in the detailed description of the invention or the claims, the term "comprises" is intended to be inclusive in a manner similar to the way that the term "comprises" is interpreted when "comprises" is used as a transitional term in the claims.

[0204] The above description identifies various non-limiting embodiments of the method for treating a composition that contains one or more aldehyde species to reduce the concentration of at least one of the one or more aldehyde species.Modifications may occur to those skilled in the art and those who may make and use the invention.The disclosed embodiments are merely for illustrative purposes and are not intended to limit the scope of the invention or the subject matter described in the following claims.

Claims

1. 1. A composition comprising: a) at least one foaming reactant; b) at least one volatility control agent selected from the group consisting of: (i) a phosphorus-containing group; (ii) a thiocarbamate; (iii) a nitrogen-containing compound; (iv) a phenolic antioxidant; or a combination of two or more thereof; and c) catalyst A composition comprising:

2. The at least one volatility control agent is a phosphite triester, a diorganophosphite, an organodiphosphite, a polyolefin with phosphite substituents, a CH or CH bonded to phosphorus, ２ 10. The composition of claim 1, comprising a phosphorus-containing group (i) selected from phosphonates, phosphonium compounds, and phosphazenes having a moiety.

3. The at least one volatility control agent is selected from one or more compounds of formula (I), formula (II), (Vi), (V-ii), (V-iii); (V-iv), (V-v), and / or (V-vi): 【Chemistry 46】 【Chemistry 47】 【Chemistry 48】 【Chemistry 49】 【Chemistry 50】 【Chemistry 51】 【Chemistry 52】 【Chemistry 53】 In the formula R １ is a C6 to C30 aryl, or —N(R ５ ) R ６ where R ５ and R ６ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety, preferably bonded through a carbon atom, and not containing acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R ５ and R ６ can be taken together to form a 5- to 10-membered ring; R ２ is C6 to C30 aryl, —N(R ５ ) R ６ , and -OR ７ where R ５ and R ６ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety, preferably bonded through a carbon atom, and not containing acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R ５ and R ６ can be taken together to form a 5- to 10-membered ring, and R ７ is selected from C1-C10 alkyl; R ３ is C6 to C30 aryl, —N(R ５ ) R ６ , and -OR ８ where R ５ and R ６ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety, preferably bonded through a carbon atom, and not containing acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R ５ and R ６ can be taken together to form a 5- to 10-membered ring, and R ８ is selected from C1-C10 alkyl; R ４ Ha-CH ２ -R ９ or =N-R １０ where R ９ is -C(O)-O ｘ R １１ , -CN, -R １２ CN or -R １３ -CH ２ -PR １ R ２ R ３ where R １１ is H, C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy; R １２ and R １３ are each selected from C1-C10 alkyl or C6-C30 aryl, x is 0 or 1, and R １ , R ２ , and R ３ is as defined above; and R １０ is selected from C1-C10 alkyl or C6-C30 aryl; A － is selected from organic or inorganic anions, where R ４ =N-R １０ In this case, the P atom in formula (I) is pentavalent and has a positive charge and a counter ion A － does not have In the formula R １４ , R １５ , and R １６ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group, and combinations thereof; In the formula R ２４ , R ２５ , R ２６ , R ２７ , R ２８ , R ２９ , R ３０ , R ３２ , R ３３ , R ３８ , R ３９ , R ４１ , R ４２ , R ４３ , R ４４ , R ５０ , and R ５１ are each independently selected from monovalent C1-C30 alkyl, C2-C30 alkene containing one or more points of unsaturation, C4-C30 cycloalkyl, C2-C30 ether group, C2-C30 alkylene glycol, C2-C30 polyalkylene glycol, C6-C30 aryl, C7-C30 arylalkyl, and C7-C30 alkylaryl; R ３１ , R ４７ , and R ４９ are each independently selected from C1 to C30 alkylene, C4 to C30 cycloalkylene, C6 to C30 arylene, C7 to C30 arylalkylene, and C7 to C30 alkylarylene; R ４０ , R ４５ , R ４６ , R ５２ , R ５３ , and R ５４ are each independently selected from hydrogen, a monovalent C1-C30 alkyl, a C2-C30 alkene containing one or more points of unsaturation, a C4-C30 cycloalkyl, a C2-C30 ether group, a C6-C30 aryl, a C7-C30 arylalkyl, and a C7-C30 alkylaryl; and X is C(O)-R ４８ , C1-C30 alkyl, C6-C30 aryl optionally substituted with cyano, OH, where R ４８ The composition of claim 1, wherein is selected from C1 to C30 alkyl.

4. The volatility control agent is selected from compounds of formula (I), wherein R １ , R ２ , and R ３ are each independently selected from C6 to C30 aryl, and R ４ Ha-CH ２ -R ９ ;=N-R １０ where R is selected from ９ is -C(O)-O ｘ R １１ , -CN, or -R １２ CN; R １１ is a C1-C10 alkyl, a C1-C10 alcohol, or a C1-C10 alkoxy; R １２ is selected from C1-C10 alkyl or C6-C30 aryl; and x is 0 or 1.

5. The volatility control agent is selected from compounds of formula (I), wherein R １ , R ２ , and R ３ are each independently -N(R ５ ) R ６ where R ５ and R ６ are each independently a C1 to C10 alkyl group; and R ４ is = N-R １０ where R １０ The composition of claim 3, wherein is selected from C1 to C10 alkyl or C6 to C30 aryl.

6. The volatility control agent is selected from compounds of formula (I), wherein R １ is R ２ Ha-OR ７ and R ３ Ha-OR ８ where R ７ and R ８ are each independently C1-C10 alkyl; R ４ Ha-CH ２ -R ９ where R ９ is -C(O)-O ｘ R １１ where R １１ The composition of claim 3, wherein is H, C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy.

7. The volatility control agent is selected from compounds of formula (II), wherein R １４ , R １５ , and R １６ The composition of claim 3, wherein each is selected from C1 to C10 alkyl.

8. R １４ , R １５ , and R １６ The composition of claim 7, wherein each is methyl.

9. The volatility control agent is (cyanomethyl)-triphenylphosphonium chloride, (methoxycarbonylmethyl)-triphenylphosphonium bromide, tertiary butylimino-tris(dimethylamino)phosphorene (phosphazene base P- １ -t-Bu), tertiary butylimino-tri(pyrrolidino)phosphorane [phosphazene base P １ -t-Bu-tris(tetramethylene)], tertiary octylimino-tris(dimethylamino)phosphorane (phosphazene base P １ -t-Oct), 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-bis(diethylphosphonomethyl)biphenyl, diethyl-4-cyanobenzylphosphonate, N-methoxy-N-methyl(trimethylsilyl)biphenyl 2. The composition of claim 1, wherein the methyl phosphonate is selected from one or more of: methyl(triphenylphosphoranylidene)acetamide, dimethyl(2-oxopropyl)phosphonate, diethyl(2-oxopropyl)phosphonate, dimethyl(2-oxoheptyl)phosphonate, diethyl(2-oxoheptyl)phosphonate, diethylcarboxymethylphosphonate, diethyl(2-oxo-2-phenylethyl)phosphonate, diethyl(methylthiomethyl)phosphonate, methyl(triphenylphosphoranylidene)acetate, diethylphosphonoacetic acid, and 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide.

10. The volatility control agent has the formula: 【Chemical 54】 wherein R ２４ , R ２５ and R ２６ The composition of claim 3, wherein each is a C1 to C30 alkyl.

11. R ２４ , R ２５ , and R ２６ 11. The composition of claim 10, wherein is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, decyl, isodecyl, dodecyl, isododecyl, tridecyl, isotridecyl, lauryl, and 2-ethylhexyl.

12. The volatility control agent has the formula: 【Chemistry 55】 wherein R ２４ , R ２５ , and R ２６ is each a C6 to C30 aryl, a C7 to C30 arylalkyl, or a C7 to C30 alkylaryl.

13. R ２４ , R ２５ , and R ２６ The composition of claim 12, wherein is selected from phenyl, tosyl, methylphenyl, and 6-tert-butyl-3-methylphenyl.

14. The volatility control agent has the formula: 【Chemical Formula 56】 wherein R ２４ , R ２５ and R ２６ and each is a C2 to C30 alkylene glycol or a C2 to C30 polyalkylene glycol.

15. R ２４ , R ２５ and R ２６ and each are selected from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, or tripropylene glycol.

16. The volatility control agent is a diorganophosphite of formula (V-ii) or its tautomer (R ２７ O)P(OH)(OR ２８ ): 【Chemical 57】 where R ２７ and R ２６ are each independently selected from C1 to C10 alkyl, and C6 to C30 aryl.

17. The volatility control agent is an organodiphosphite of formula (V-iii): 【Chemistry 58】 wherein R ２９ , R ３０ , R ３２ , and R ３３ is selected from monovalent C1-C30 alkyl or C2-C30 ether groups, C2-C30 alkenes containing one or more points of unsaturation, C6-C30 aryls, C7-C30 arylalkyls, and C7-C30 alkylaryls; and R ３１ is selected from C1 to C30 alkylene, a C2 to C30 divalent ether-containing group, a C4 to C30 cycloalkylene, a C6 to C30 arylene, a C7 to C30 arylalkylene, and a C7 to C30 alkylarylene.

18. 2. The composition of claim 1, wherein the volatility control agent is selected from alkylphenol diisodecyl phosphite, dimethyl phosphite, triethyl phosphite, diphenyl phosphite, triphenyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, diisodecyl phenyl phosphite, tris(nonylphenyl) phosphite, tetraphenyl dipropylene glycol diphosphate, poly(dipropylene glycol) phenyl phosphite, triisooctyl phosphite, trilauryl phosphite, triisodecyl phosphite, tristridecyl phosphite, triisotridecyl phosphite, phosphonic acid di-9-octadecen-1-yl ester, 4,4'-butylidenebis(6-tert-butyl-3-methylphenyl ditridecyl phosphite), tris(dipropylene glycol) phosphite, and diisodecyl phenyl phosphite, or a combination of two or more thereof.

19. 10. The composition of claim 1, wherein the volatility control agent comprises a thiocarbamate.

20. Thiocarbamates include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetrabutylthiuram disulfide, tetradecylthiuram disulfide, tetrahexadecylthiuram disulfide, tetracosylthiuram disulfide, 1-methyl-1-propyl-6-butyl-6-methylthiuram disulfide, 1-propyl-1-butyl-6-methyl-6-t-butylthiuram disulfide, dihexamethylenethiuram disulfide, dipentamethylenethiuram disulfide, tetraben Dithiuram disulfide, piperazinium pentamethylenedithiocarbamate, piperazinium dibutyldithiocarbamate, piperazinium dicyclohexyldithiocarbamate, piperazinium di(3-oxycyclohexyl)dithiocarbamate, ammonium dipropyldithiocarbamate, metal thiocarbamates such as nickel dipropyldithiocarbamate, nickel dibutyldithiocarbamate, nickel didecyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate dithiocarbamate, zinc dihexyldithiocarbamate, zinc dibenzyldithiocarbamate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, sodium dibenzyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, copper diamyldithiocarbamate, copper dioctadecyldithiocarbamate, copper diphenyldithiocarbamate, copper dibenzyldithiocarbamate, copper di(ortho-tolylaminoethyl)dithiocarbamate dithiocarbamate, copper dicyclohexyldithiocarbamate, potassium dihexyldithiocarbamate, calcium dihexyldithiocarbamate, zirconium diethyldithiocarbamate, tellurium diethyldithiocarbamate, cobalt dibutyldithiocarbamate, antimony dibutyldithiocarbamate, bismuth dimethyldithiocarbamate, lead dimethyldithiocarbamate, tin dibutyldithiocarbamate, copper dicyclopentyldithiocarbamate, copper 1-butyl-1-cyclohexyl-7-butyl-7-cyclohexyldithiocarbamate,20. The composition of claim 19, wherein the dithiocarbamate is selected from copper di(3-oxacyclohexyl)dithiocarbamate, copper di(4-oxacyclohexyl)dithiocarbamate, copper di(3-thiocyclohexyl)dithiocarbamate, copper di(4-azacyclohexyl)dithiocarbamate, copper 1-butyl-1-(3-oxacyclohexyl)-7-butyl-7-(3-oxacyclohexyl)dithiocarbamate, copper di(4-pyridyl)dithiocarbamate, copper di(4-N,N-dimethylanilino)dithiocarbamate, copper di(4-anisyl)dithiocarbamate, copper di(4-thioanisyl)dithiocarbamate, and copper di(3-furanyl)dithiocarbamate.

21. The volatility control agent is a nitrogen compound selected from the compounds of formula (III), formula (IV), -OH, -NH, or -NH ２ Functionalized pyrrolidine, —OH, —NH, or —NH ２ Functionalized pyrazolidines, -OH, -NH, or -NH ２ Functionalized imidazolidine, —OH, —NH, or —NH ２ Functionalized imidazolidinone, and / or —OH, —NH, or —NH ２ tetrahydropyrimidinone, or a combination of two or more thereof; 【Chemical Formula 59】 【Chemistry 60】 In the formula R １７ , R １８ , and R １９ are each independently H, a C1 to C20 alkyl group optionally substituted with one or more hydroxyl groups, -R ２０ -OH or -R ２１ —C(O)OH, where R ２０ and R ２１ are each independently selected from a divalent C1 to C20 hydrocarbon group, a C4 to C30 cyclic hydrocarbon group, and a divalent C6 to C30 aryl group, each of which may optionally be substituted with a heteroatom-containing group; or R １７ , R １８ , and R １９ two of may form a 5-12 membered ring, which may optionally contain one or more heteroatoms in the ring, such as N, O, and which may be substituted with a hydroxy functional group, provided that the compound contains at least one —OH or at least one —C(O)OH functional group; and wherein R ２２ is hydrogen or a straight or branched chain C1 to C24 alkyl, aryl, heteroalkyl, or alkylaryl group, and R ２３ 10. The composition of claim 1, wherein is hydrogen or a straight or branched chain C1 to C24 alkyl, heteroalkyl, or alkylaryl group.

22. The volatility control agent is selected from compounds of formula (III) and R １７ Ha-R ２１ —C(O)OH, where R ２０ and R ２１ are independently selected from a divalent C1 to C20 hydrocarbon group, a C4 to C30 cyclic hydrocarbon group, and a divalent C6 to C30 aryl group, each of which may optionally be substituted with a heteroatom-containing group.

23. 23. The composition of claim 22, wherein the volatility control agent is selected from one or more of nicotinic acid, arginine, asparagine, cysteine, glutamine, histidine, methionine, serine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, tryptophan, and tyrosine.

24. -OH, -NH, or NH ２ 22. The composition of claim 21, wherein the functionalized pyrrolidine, pyrazolidine, imidazolidine, or imidazolidinone contains an alcohol, primary amine, secondary amine, or carboxylic acid functional group attached directly or through a linking group to one of the nitrogen atoms.

25. The volatility control agent is an —OH functionalized imidazolidinone or pyrimidinone selected from N-substituted-(hydroxyalkyl)imidazolidinones of formula (VI) or N-substituted-(hydroxyalkyl-functionalized)tetrahydro-2-pyrimidinones of formula (VII): 【Hua 61】 In the formula R ３４ , R ３５ , and R ３７ are each independently selected from hydrogen or a straight or branched chain C1-C24 alkyl, C4-C30 cycloalkyl, C6-C30 aryl, C1-C24 heteroalkyl, C7-C30 alkaryl, or C7-C30 arylalkyl group; and R ３６ is selected from a C1 to C24 alkylene, a C4 to C30 cycloalkylene, a C6 to C30 arylene, a C1 to C24 heteroalkylene, a C7 to C30 alkarylene, or a C7 to C30 arylalkylene group.

26. 24. The composition of claim 23, wherein the volatility control agent is selected from one or more of 1-(hydroxymethyl)imidazolidinone, 1-(2-hydroxyethyl)imidazolidinone, 1-(2-hydroxypropyl)imidazolidinone, and 1-(2-hydroxyethyl)-2-imidazolidinone, tetrahydro-1-(2-hydroxyethyl)-2(1H)-pyrimidinone.

27. 10. The composition of claim 1, wherein the volatility control agent is selected from alkaline earth metal salts of alkylphenol thioesters, sulfurized alkylphenols, metal salts of sulfurized alkylphenols, metal salts of non-sulfurized alkylphenols, oil-soluble phenates, and sulfurized phenates.

28. 10. The composition of claim 1, wherein the volatility control agent comprises an alkylated phenothiazine selected from monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monononylphenothiazine, dinonylphenothiazine, monooctylphenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, distyrylphenothiazine, butyloctylphenothiazine, and styryloctylphenothiazine.

29. 29. The composition of any of claims 1 to 28, wherein the volatility control agent is present in an amount of from about 0.05 parts per 100 parts polyol to about 10 parts per 100 parts polyol.

30. 29. The composition of any of claims 1 to 28, wherein the volatilization control agent is provided as a separate component.

31. 29. The composition of any of claims 1 to 28, wherein the volatility control agent is provided in admixture with the catalyst, water, plasticizer, natural oil, glycol, chain extender, and alkoxylated monoalcohol.

32. 29. The composition of any of claims 1 to 28, wherein the at least one blowing reactant is selected from (i) an isocyanate and (ii) a polyether polyol, a polyester polyol, a polyamine, a polyether amine.

33. 33. The composition of claim 32, wherein the volatility control agent is provided in admixture with an isocyanate and / or in admixture with a polyether polyol, a polyamine, and / or a polyester polyol.

34. 29. A process for preparing a polyurethane foam from the composition of any of claims 1 to 28, comprising contacting at least one blowing reactant with a volatility control agent.

35. 35. A polyurethane foam formed by the method of claim 34.

36. 36. The polyurethane foam of claim 35, wherein the foam has a concentration of the at least one aldehyde species that is at least 10% to 99.5% lower than that of a foam formed from the same composition without the volatility control agent.

37. 37. The polyurethane foam of claim 36, wherein the at least one aldehyde species is present in a concentration that is less than in the same composition lacking the volatility control agent.

38. 1. A method for reducing emissions from polyurethane foam, comprising contacting at least one blowing reactant with at least one volatility control agent selected from the group consisting of: (i) phosphorus-containing groups; (ii) thiocarbamates; (iii) nitrogen-containing compounds; (iv) phenolic antioxidants; or combinations of two or more thereof.

39. The at least one volatility control agent is a phosphite triester, a diorganophosphite, an organodiphosphite, a polyolefin with phosphite substituents, a CH or CH bonded to phosphorus, ２ 39. The method of claim 38, comprising a phosphorus-containing group (i) selected from a phosphonate, a phosphonium compound, or a phosphazene having a moiety.

40. The at least one volatility control agent is selected from one or more compounds of formula (I), formula (II), (Vi), (V-ii), (V-iii); (V-iv), (V-v), and / or (V-vi): 【Hua 62】 【Chemistry 63】 【Hua 64】 【Chemistry 65】 【Hua 66】 【Hua 67】 【Chemistry 68】 【Chemical Formula 69】 In the formula R １ is a C6 to C30 aryl, or —N(R ５ ) R ６ where R ５ and R ６ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety, preferably bonded through a carbon atom, and not containing acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R ５ and R ６ can be taken together to form a 5- to 10-membered ring; R ２ is C6 to C30 aryl, —N(R ５ ) R ６ , and -OR ７ where R ５ and R ６ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety, preferably bonded through a carbon atom, and not containing acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R ５ and R ６ can be taken together to form a 5- to 10-membered ring, and R ７ is selected from C1-C10 alkyl; R ３ is C6 to C30 aryl, —N(R ５ ) R ６ , and -OR ８ where R ５ and R ６ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., containing nitrogen, oxygen, phosphorus, silicon, or sulfur in the form of a group or moiety, preferably bonded through a carbon atom, and not containing acid functionality such as carboxylic acid or sulfonic acid), and combinations thereof; or R ５ and R ６ can be taken together to form a 5- to 10-membered ring, and R ８ is selected from C1-C10 alkyl; R ４ Ha-CH ２ -R ９ or =N-R １０ where R ９ is -C(O)-O ｘ R １１ , -CN, -R １２ CN or -R １３ -CH ２ -PR １ R ２ R ３ where R １１ is H, C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy; R １２ and R １３ are each selected from C1-C10 alkyl or C6-C30 aryl, x is 0 or 1, and R １ , R ２ , and R ３ is as defined above; and R １０ is selected from C1-C10 alkyl or C6-C30 aryl; A － is selected from organic or inorganic anions, where R ４ =N-R １０ In this case, the P atom in formula (I) is pentavalent and has a positive charge and a counter ion A － does not have In the formula R １４ , R １５ , and R １６ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group, and combinations thereof; In the formula R ２４ , R ２５ , R ２６ , R ２７ , R ２８ , R ２９ , R ３０ , R ３２ , R ３３ , R ３８ , R ３９ , R ４１ , R ４２ , R ４３ , R ４４ , R ５０ , and R ５１ are each independently selected from monovalent C1-C30 alkyl, C2-C30 alkene containing one or more points of unsaturation, C4-C30 cycloalkyl, C2-C30 ether group, C2-C30 alkylene glycol, C2-C30 polyalkylene glycol, C6-C30 aryl, C7-C30 arylalkyl, and C7-C30 alkylaryl; R ３１ , R ４７ , and R ４９ are each independently selected from C1 to C30 alkylene, C4 to C30 cycloalkylene, C6 to C30 arylene, C7 to C30 arylalkylene, and C7 to C30 alkylarylene; R ４０ , R ４５ , R ４６ , R ５２ , R ５３ , and R ５４ are each independently selected from hydrogen, a monovalent C1-C30 alkyl, a C2-C30 alkene containing one or more points of unsaturation, a C4-C30 cycloalkyl, a C2-C30 ether group, a C6-C30 aryl, a C7-C30 arylalkyl, and a C7-C30 alkylaryl; and X is C(O)-R ４８ , C1-C30 alkyl, C6-C30 aryl optionally substituted with cyano, OH, where R ４８ 39. The method of claim 38, wherein is selected from C1 to C30 alkyl.

41. The volatility control agent is selected from compounds of formula (I), wherein R １ , R ２ , and R ３ are each independently selected from C6 to C30 aryl, and R ４ Ha-CH ２ -R ９ ;=N-R １０ where R is selected from ９ is -C(O)-O ｘ R １１ , -CN, or -R １２ CN; R １１ is a C1-C10 alkyl, a C1-C10 alcohol, or a C1-C10 alkoxy; R １２ is selected from C1-C10 alkyl or C6-C30 aryl; and x is 0 or 1.

42. The volatility control agent is selected from compounds of formula (I), wherein R １ , R ２ , and R ３ are each independently -N(R ５ ) R ６ where R ５ and R ６ are each independently a C1 to C10 alkyl group; and R ４ is = N-R １０ where R １０ is selected from C1-C10 alkyl or C6-C30 aryl.

43. The volatility control agent is selected from compounds of formula (I), wherein R １ is R ２ Ha-OR ７ and R ３ Ha-OR ８ where R ７ and R ８ are each independently C1-C10 alkyl; R ４ Ha-CH ２ -R ９ where R ９ is -C(O)-O ｘ R １１ where R １１ is H, C1-C10 alkyl, C1-C10 alcohol, or C1-C10 alkoxy.

44. The volatility control agent is selected from compounds of formula (II), wherein R １４ , R １５ , and R １６ 41. The method of claim 40, wherein each is selected from C1 to C10 alkyl.

45. R １４ , R １５ , and R １６ 45. The method of claim 44, wherein each is methyl.

46. The volatility control agent is (cyanomethyl)-triphenylphosphonium chloride, (methoxycarbonylmethyl)-triphenylphosphonium bromide, tertiary butylimino-tris(dimethylamino)phosphorene (phosphazene base P- １ -t-Bu), tertiary butylimino-tri(pyrrolidino)phosphorane [phosphazene base P １ -t-Bu-tris(tetramethylene)], tertiary octylimino-tris(dimethylamino)phosphorane (phosphazene base P １ -t-Oct), 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 4,4'-bis(diethylphosphonomethyl)biphenyl, diethyl-4-cyanobenzylphosphonate, N-methoxy-N-methyl(triphenyl 41. The method of any of claims 38 to 40, wherein the methyl group is selected from one or more of methyl(triphenylphosphoranylidene)acetamide, dimethyl(2-oxopropyl)phosphonate, diethyl(2-oxopropyl)phosphonate, dimethyl(2-oxoheptyl)phosphonate, diethyl(2-oxoheptyl)phosphonate, diethylcarboxymethylphosphonate, diethyl(2-oxo-2-phenylethyl)phosphonate, diethyl(methylthiomethyl)phosphonate, methyl(triphenylphosphoranylidene)acetate, diethylphosphonoacetic acid, and 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide.

47. The volatility control agent has the formula: 【Chemistry 70】 wherein R ２４ , R ２５ and R ２６ and each is a C1 to C30 alkyl.

48. R ２４ , R ２５ , and R ２６ is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, decyl, isodecyl, dodecyl, isododecyl, tridecyl, isotridecyl, lauryl, and 2-ethylhexyl.

49. The volatility control agent has the formula: 【Chemical 71】 wherein R ２４ , R ２５ , and R ２６ is each a C6 to C30 aryl, a C7 to C30 arylalkyl, or a C7 to C30 alkylaryl.

50. R ２４ , R ２５ , and R ２６ 50. The method of claim 49, wherein is selected from phenyl, tosyl, methylphenyl, and 6-tert-butyl-3-methylphenyl.

51. The volatility control agent has the formula: 【Chemical Formula 72】 wherein R ２４ , R ２５ and R ２６ and each is a C2 to C30 alkylene glycol or a C2 to C30 polyalkylene glycol.

52. R ２４ , R ２５ and R ２６ 52. The method of claim 51, wherein each of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, or tripropylene glycol is selected from the group consisting of propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol.

53. The volatility control agent is a diorganophosphite of formula (V-ii) or its tautomer (R ２７ O)P(OH)(OR ２８ ): [Chemical Formula 73] where R ２７ and R ２６ are each independently selected from C1 to C10 alkyl, and C6 to C30 aryl.

54. The volatility control agent is an organodiphosphite of formula (V-iii): 【Chemical Formula 74】 wherein R ２９ , R ３０ , R ３２ , and R ３３ is selected from monovalent C1-C30 alkyl or C2-C30 ether groups, C2-C30 alkenes containing one or more points of unsaturation, C6-C30 aryls, C7-C30 arylalkyls, and C7-C30 alkylaryls; and R ３１ is selected from C1 to C30 alkylene, a C2 to C30 divalent ether-containing group, a C4 to C30 cycloalkylene, a C6 to C30 arylene, a C7 to C30 arylalkylene, and a C7 to C30 alkylarylene.

55. 41. The method of claim 40, wherein the volatility control agent is selected from alkylphenol diisodecyl phosphite, dimethyl phosphite, triethyl phosphite, diphenyl phosphite, triphenyl phosphite, isodecyl diphenyl phosphite, 2-ethylhexyl diphenyl phosphite, diisodecyl phenyl phosphite, tris(nonylphenyl) phosphite, tetraphenyl dipropylene glycol diphosphate, poly(dipropylene glycol) phenyl phosphite, triisooctyl phosphite, trilauryl phosphite, triisodecyl phosphite, tristridecyl phosphite, triisotridecyl phosphite, phosphonic acid di-9-octadecen-1-yl ester, 4,4'-butylidenebis(6-tert-butyl-3-methylphenyl ditridecyl phosphite), tris(dipropylene glycol) phosphite, and diisodecyl phenyl phosphite, or a combination of two or more thereof.

56. 41. The method of claim 40, wherein the volatility control agent comprises a thiocarbamate.

57. Thiocarbamates include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetrabutylthiuram disulfide, tetradecylthiuram disulfide, tetrahexadecylthiuram disulfide, tetracosylthiuram disulfide, 1-methyl-1-propyl-6-butyl-6-methylthiuram disulfide, 1-propyl-1-butyl-6-methyl-6-t-butylthiuram disulfide, dihexamethylenethiuram disulfide, dipentamethylenethiuram disulfide, tetraben Dithiuram disulfide, piperazinium pentamethylenedithiocarbamate, piperazinium dibutyldithiocarbamate, piperazinium dicyclohexyldithiocarbamate, piperazinium di(3-oxycyclohexyl)dithiocarbamate, ammonium dipropyldithiocarbamate, metal thiocarbamates such as nickel dipropyldithiocarbamate, nickel dibutyldithiocarbamate, nickel didecyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate dithiocarbamate, zinc dihexyldithiocarbamate, zinc dibenzyldithiocarbamate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, sodium dibenzyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, copper diamyldithiocarbamate, copper dioctadecyldithiocarbamate, copper diphenyldithiocarbamate, copper dibenzyldithiocarbamate, copper di(ortho-tolylaminoethyl)dithiocarbamate dithiocarbamate, copper dicyclohexyldithiocarbamate, potassium dihexyldithiocarbamate, calcium dihexyldithiocarbamate, zirconium diethyldithiocarbamate, tellurium diethyldithiocarbamate, cobalt dibutyldithiocarbamate, antimony dibutyldithiocarbamate, bismuth dimethyldithiocarbamate, lead dimethyldithiocarbamate, tin dibutyldithiocarbamate, copper dicyclopentyldithiocarbamate, copper 1-butyl-1-cyclohexyl-7-butyl-7-cyclohexyldithiocarbamate,57. The method of claim 56, wherein the dithiocarbamate is selected from copper di(3-oxacyclohexyl)dithiocarbamate, copper di(4-oxacyclohexyl)dithiocarbamate, copper di(3-thiocyclohexyl)dithiocarbamate, copper di(4-azacyclohexyl)dithiocarbamate, copper 1-butyl-1-(3-oxacyclohexyl)-7-butyl-7-(3-oxacyclohexyl)dithiocarbamate, copper di(4-pyridyl)dithiocarbamate, copper di(4-N,N-dimethylanilino)dithiocarbamate, copper di(4-anisyl)dithiocarbamate, copper di(4-thioanisyl)dithiocarbamate, and copper di(3-furanyl)dithiocarbamate.

58. The volatility control agent is a nitrogen compound selected from the compounds of formula (III), formula (IV), -OH, -NH, or -NH ２ Functionalized pyrrolidine, —OH, —NH, or —NH ２ Functionalized pyrazolidines, -OH, -NH, or -NH ２ Functionalized imidazolidine, —OH, —NH, or —NH ２ Functionalized imidazolidinone, and / or —OH, —NH, or —NH ２ tetrahydropyrimidinone, or a combination of two or more thereof; 【Chemistry 75】 【Chemical 76】 In the formula R １７ , R １８ , and R １９ are each independently H, a C1 to C20 alkyl group optionally substituted with one or more hydroxyl groups, -R ２０ -OH or -R ２１ —C(O)OH, where R ２０ and R ２１ are each independently selected from a divalent C1 to C20 hydrocarbon group, a C4 to C30 cyclic hydrocarbon group, and a divalent C6 to C30 aryl group, each of which may optionally be substituted with a heteroatom-containing group; or R １７ , R １８ , and R １９ two of may form a 5-12 membered ring, which may optionally contain one or more heteroatoms in the ring, such as N, O, and which may be substituted with a hydroxy functional group, provided that the compound contains at least one —OH or at least one —C(O)OH functional group; and wherein R ２２ is hydrogen or a straight or branched chain C1 to C24 alkyl, aryl, heteroalkyl, or alkylaryl group, and R ２３ is hydrogen or a straight or branched chain C1 to C24 alkyl, heteroalkyl, or alkylaryl group.

59. The volatility control agent is selected from compounds of formula (III) and R １７ Ha-R ２１ —C(O)OH, where R ２０ and R ２１ are independently selected from a divalent C1 to C20 hydrocarbon group, a C4 to C30 cyclic hydrocarbon group, and a divalent C6 to C30 aryl group, each of which may optionally be substituted with a heteroatom-containing group.

60. 60. The method of claim 59, wherein the volatility control agent is selected from one or more of nicotinic acid, arginine, asparagine, cysteine, glutamine, histidine, methionine, serine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, tryptophan, and tyrosine.

61. -OH, -NH, or NH ２ 59. The method of claim 58, wherein the functionalized pyrrolidine, pyrazolidine, imidazolidine, or imidazolidinone contains an alcohol, primary amine, secondary amine, or carboxylic acid functional group attached directly or through a linking group to one of the nitrogen atoms.

62. The volatility control agent is an —OH functionalized imidazolidinone or pyrimidinone selected from N-substituted-(hydroxyalkyl)imidazolidinones of formula (VI) or N-substituted-(hydroxyalkyl-functionalized)tetrahydro-2-pyrimidinones of formula (VII): [Chemical 77] In the formula R ３４ , R ３５ , and R ３７ are each independently selected from hydrogen or a straight or branched chain C1-C24 alkyl, C4-C30 cycloalkyl, C6-C30 aryl, C1-C24 heteroalkyl, C7-C30 alkaryl, or C7-C30 arylalkyl group; and R ３６ is selected from a C1 to C24 alkylene, a C4 to C30 cycloalkylene, a C6 to C30 arylene, a C1 to C24 heteroalkylene, a C7 to C30 alkarylene, or a C7 to C30 arylalkylene group.

63. 63. The method of any of claims 60 to 62, wherein the volatility control agent is selected from one or more of 1-(hydroxymethyl)imidazolidinone, 1-(2-hydroxyethyl)imidazolidinone, 1-(2-hydroxypropyl)imidazolidinone, and 1-(2-hydroxyethyl)-2-imidazolidinone, tetrahydro-1-(2-hydroxyethyl)-2(1H)-pyrimidinone.

64. 41. The method of claim 40, wherein the volatility control agent is selected from alkaline earth metal salts of alkylphenol thioesters, sulfurized alkylphenols, metal salts of sulfurized alkylphenols, metal salts of non-sulfurized alkylphenols, oil-soluble phenates, and sulfurized phenates.

65. 41. The method of claim 40, wherein the volatility control agent comprises an alkylated phenothiazine selected from monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monononylphenothiazine, dinonylphenothiazine, monooctylphenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, distyrylphenothiazine, butyloctylphenothiazine, and styryloctylphenothiazine.

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