WO2024020776A1

WO2024020776A1 - Low odor silicone polyether type surfactants and their use in polyurethane compositions

Info

Publication number: WO2024020776A1
Application number: PCT/CN2022/107872
Authority: WO
Inventors: Zhengming TANG; Jian Zou; Tengfei LIU; Haiying Li; Shuyu DUAN; Canzheng CAI; Shaoguang Feng; Ping Zhang
Original assignee: Dow Global Technologies Llc
Priority date: 2022-07-26
Filing date: 2022-07-26
Publication date: 2024-02-01

Abstract

The present disclosure relates to low odor silicone polyether surfactants and their use in polyurethane compositions. The present disclosure provides a method of stabilizing an SPE surfactant formed by grafting a vinyl polyether onto a silicone backbone, comprising, pre-treating the SPE surfactant with a basic compound having a pKb of from 1.0 to 9.0. The present disclosure also provides an SPE surfactant obtained by the described method and its use in polyurethane compositions.

Description

LOW ODOR SILICONE POLYETHER TYPE SURFACTANTS AND THEIR USE IN POLYURETHANE COMPOSITIONS

FIELD OF THE DISCLOSURE

The present disclosure relates to silicone polyether (SPE) type surfactants. More specifically, the present disclosure relates to low odor stable silicone polyether type surfactants, their preparation, and their use in polyurethane compositions.

BACKGROUND

Over the years, molecules such as aldehydes and cyclic ethers have been identified as undesirable odorants in various polyurethane products, including formulated polyols, and flexible polyurethane foams. Examples of cyclic ethers that may be present in polyurethane foams include trioxocane, 2-ethyl-4-methyl-1, 3-dioxolane (2-EMD) and 2, 4-dimethyl-1, 3-dioxolane (2-DMD) .

An analytical work performed with the objective of identifying the causes of musty odor in flexible polyurethane foam demonstrated that trioxocane and its isomers are among the root causes of malodor (see, e.g., S. H. Harris et al., “Characterization of Polyurethane Foam Odor Bodies, ” Polyurethanes World Congress 1987, Aachen, Germany, pages 848-851) . This is surprising in consideration of the relatively high boiling point of trioxocane (220 ℃) , and it underlines the strong olfactory power associated with this type of molecules.

The problem of malodor in polyurethane foam has become an industry challenge. There are various solutions that have been proposed, such as the use of reactive amine catalysts (see, e.g., US8563676B2) , or the use of formulation ingredients that have been synthesized in a way that reduces the presence of volatile species (see, e.g., CN111247188A) . However, the contribution of aldehydes and cyclic ethers to the overall smell of polyurethane products has so far not been fully understood. People have some knowledge in how cyclic ethers are formed, but specifically for polyurethane system the understanding is limited, and consequently no effective solutions have been proposed to address this challenge.

Accordingly, there is still a need for a polyurethane composition having low odor.

SUMMARY OF THE DISCLOSURE

In an aspect, the present disclosure provides a method of stabilizing an SPE surfactant formed by grafting a vinyl polyether onto a silicone backbone, comprising, pre-treating the SPE surfactant with a basic compound having a pKb of from 1.0 to 9.0.

In a further aspect, the present disclosure provides a stabilized SPE surfactant that is obtained by the method described herein.

In a further aspect, the present disclosure provides polyurethane composition, comprising,

(A) a polyol component comprising one or more polyols selected from the group consisting of a polyester polyol, a polyether polyol, and the combination thereof, and

(B) an isocyanate component comprising one or more isocyanate compounds,

wherein the (A) polyol component and/or the (B) isocyanate component comprises a stabilized SPE surfactant obtained by the method of stabilizing an SPE surfactant described herein.

In a further aspect, the present disclosure provides a polyurethane product formed using the polyurethane composition described herein.

In a further aspect, the present disclosure provides use of the stabilized SPE surfactant described herein in the manufacture of a polyurethane composition.

In a further aspect, the present disclosure provides use of the stabilized SPE surfactant described herein in the manufacture of a polyurethane product.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

DETAILED DESCRIPTION OF THE DISCLOSURE

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Also, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.

As disclosed herein, “and/or” means “and, or as an alternative” . All ranges include endpoints unless otherwise indicated.

As disclosed herein, all percentages mentioned herein are by weight, and temperatures in ℃, unless specified otherwise.

A. Stabilization of SPE surfactants

Odor issues in polyurethane foams have long been an unresolved problem in the art, and understanding of the causes has been quite limited.

After a long root cause analysis, the inventors have discovered that silicone polyether (SPE) type surfactants (also referred to herein as "SPE surfactants" ) are an important contributing source of odorous components in polyurethane foams, especially in the flexible polyurethane foams for furniture and bedding applications.

SPE surfactants are widely used as surfactants in flexible and rigid polyurethane foams. They are generally formed by grafting a vinyl polyether onto a silicone backbone. It is found by the inventors that the manufacturing of SPE surfactants during which some materials (such as vinyl polyethers) may be used in excess to ensure the completeness of the hydrosilylation reaction may lead to the consequence that the produced SPE surfactants contain unsaturated species that can degrade during storage, to form aldehydes and cyclic ethers, leading to odor issue in polyurethane foams. This implies that the use of SPE surfactants can have varying effects on the final odor of the polyurethane foam, depending on the amount of unsaturated species that are initially present in the SPE surfactants as well as on the storage time and storage conditions of the SPE surfactants. The finding is surprising, since SPE surfactants are generally present in an amount of only around 1%in the full flexible polyurethane formulation and their impact on the final foam smell was expected to be negligible. Contrary to the previous understanding, the inventors have demonstrated that SPE surfactants, even though used at low level, can still lead to the formation of substantial amount of odor components in the final polyurethane foams.

As used herein, "SPE surfactants" typically are silicone surfactants having siloxane backbones and polyether pendant groups. The SPE surfactants can be nonhydrolyzable or hydrolyzable. The nonhydrolyzable surfactants, in which the polyether pendant groups are attached to the siloxane backbone by Si-C bonds, are generally believed to have high potency but produce "tight" polyurethane foams with poor breathability. Hydrolyzable surfactants, in which the polyether pendant groups are attached to the siloxane backbone by Si-bonds, are generally believed to have less potency but offer good processing characteristics, and produce polyurethane foams with good breathability. In some embodiments, the SPE surfactants can be obtained by the reaction of a hydrogen siloxane (for example, an organohydrogensiloxane) and a polyether compound having an aliphatically unsaturated group, in the presence of a hydrosilylation catalyst. The methods for preparing SPE surfactants are known in the art and can be found in vast literature, for example, EP Patent No. EP1081182 (B1) , which is incorporated herein by reference in its entirety.

In some embodiments, pre-treating the SPE surfactant with a basic compound comprises combining (for example, mixing) the SPE surfactant with the basic compound.

In some embodiments, the amount of the basic compound used to pre-treat the SPE surfactant is from 0.01%to 15%, by weight of the SPE surfactant. In some embodiments, the amount of the basic compound used to pre-treat the SPE surfactant is within the range obtained by combining any two of the following endpoints: 0.01%, 0.05%, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, and 15%, by weight of the SPE surfactant. In an exemplary embodiment, the amount of the basic compound used to pre-treat the SPE surfactant is from 0.05%to 15%, from 0.1%to 15%, from 0.01%to 14%or from 0.05%to 14%, by weight of the SPE surfactant.

In some embodiments, the basic compound is liquid at room temperature with a melting point below 20 ℃.

In some embodiments, the basic compound has a pKb of from 1.0 to 9.0. In some embodiments, the basic compound has a pKb within the range obtained by combining any two of the following endpoints: 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0 and 9.0. In an exemplary embodiment, the basic compound has a pKb of from 2.0 to 9.0, from 2.0 to 8.0, from 2.0 to 6.0, from 2.0 to 5.0, from 2.5 to 5.0, from 2.8 to 5.0 or from 3.0 to 5.0.

In some embodiments, the basic compound comprises an amine.

As used herein, the term "amine" refers to a compound in which one or more hydrogen atoms of ammonia are substituted by hydrocarbon residues, and the number of hydrocarbon residues may be one, two, or three. The hydrocarbon residue may be a part of linear or branched aliphatic hydrocarbon structure, or a part of aliphatic hydrocarbon structure in which a cyclic structure such as a five-membered ring and a six-membered ring is formed, or an aromatic hydrocarbon. Further, halogens such as fluorine, chlorine, and bromine and functional groups such as a hydroxy group and a nitrile group may be combined with these aliphatic hydrocarbon residues or aromatic hydrocarbon residues.

In some embodiments, the amine can be selected from the group consisting of primary amines, secondary amines, tertiary amines, and any mixture thereof. The term "primary amine" refers to amines having an ammonia molecule in which only one of the hydrogen atoms in the ammonia molecule has been replaced. The term "secondary amine" refers to amines having an ammonia molecule in which two of the hydrogen atoms in the ammonia molecule have been replaced. The term "tertiary amine" refers to amines having an ammonia molecule in which three of the hydrogen atoms in the ammonia molecule have been replaced. In a particular embodiment, the amine comprises a tertiary amine.

In some embodiments, the amine can be selected from amine additives (for example, amine catalysts) that are used in polyurethane foam formulations. In some embodiments, the amine can be selected from primary amine catalysts, secondary amine catalysts, tertiary amine catalysts, or any mixture thereof. In some embodiments, the amine comprises a tertiary amine catalyst. Tertiary amine catalysts include organic compounds that contain at least one tertiary nitrogen atom and are capable of catalyzing the hydroxyl/isocyanate reaction between the polyol component and the isocyanate component. In some embodiments, the amine catalysts have zero or at most one hydroxyl group.

Exemplary amine additives can include, but are not limited to, 1-butyl amine, di-n-butyl amine, triethylenediamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, piperazine, tetramethylbutanediamine, pentamethyldiethylenetriamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, N, N-dimethylpiperazine, morpholine, N-ethylmorpholine, N-coco-morpholine, bis(dimethylaminoethyl) ether, N-methylmorpholine, N-ethylpiperidine, 2-methylpropanediamine, methyltriethylenediamine, 2, 4, 6-tridimethylamino-methyl) phenol, 1, 3-bis- (dimethylamino) -2-propanol, N, N-dimethylcyclohexylamine, N-cetyl N, N-dimethyl amine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1, 4-butanediamine, N, N, N'-trimethyl-N'-hydroxyethyl bis (aminoethyl) ether, N, N-bis (3-dimethylaminopropyl) N-isopropanolamine, (N, N-dimethyl) amino-ethoxy ethanol, N, N, N', N'-tetramethyl hexane diamine, 1, 8-diazabicyclo-5, 4, 0-undecene-7, 2, 4, 6-tris (dimethylaminomethyl) phenol, N, N-dimorpholinodiethyl ether, N-methyl imidazole, dimethyl aminopropyl dipropanolamine, bis (dimethylaminopropyl) amino-2-propanol, tetramethylamino bis (propylamine) , (dimethyl (aminoethoxyethyl) ) ( (dimethyl amine) ethyl) ether, tris (dimethylamino propyl) amine, dicyclohexyl methyl amine, bis (N, N-dimethyl-3-aminopropyl) amine, 1, 2-ethylene piperidine, methylhydroxy ethyl piperazine, pentamethyldiethylene triamine, 1, 4-diazobicyclo-2, 2, 2-octane, dimethylalkylamines where the alkyl group contains 4 to 18 carbon atoms, dimethylethanol amine (DMEA) , tetramethyliminobispropyl amine (e.g., Polycat15) , N, N-dimethylcyclohexyl amine (DMCHA) , tetraethylenediamine (e.g., Dabco/TEDA) , 2- [2- (dimethylamino) ethoxy] ethanol (DMEE) , and N, N-bis (3-dimethylaminopropyl) -N-isopropanol amine (e.g., JEFFCAT ZR-50) , and mixtures thereof.

As used herein, "pre-treatment" or "pre-treating" of an SPE surfactant means that the SPE surfactant is treated before its subsequent application (for example, in a polyurethane composition) . In some embodiments, the pre-treating or stabilizing of the SPE surfactant with a basic compound as described herein is carried out after the SPE surfactant is synthesized or prepared. In other words, the basic compound is added to the SPE surfactant after the synthesis or preparation of the SPE surfactant is completed. One or more basic compounds generally used during the synthesis or preparation of the SPE surfactant are not sufficient to be considered as the pre-treating or stabilizing described herein. In some embodiments, the pre-treating or stabilizing is carried out after the preparation of the SPE surfactant is completed and before it is packaged or stored.

It is found by the inventors that by pre-treating SPE surfactants according to the present disclosure, the SPE surfactants can be stabilized and the degradation of SPE surfactants during storage can be minimized. Much lower levels of cyclic ethers and aldehydes can be observed in the so-treated SPE surfactants in accelerated ageing test (to simulate prolonged storage) .

B. Stabilized SPE surfactant

In a further aspect, the present disclosure provides a stabilized SPE surfactant that is obtained by the method described above.

The "stabilized SPE surfactant" refers to an SPE surfactant that is pre-treated or stabilized with a basic compound, as described above. In some embodiments, the stabilized SPE surfactant comprises an SPE surfactant mixed with a basic compound. In some embodiments, the basic compound is mixed with the SPE surfactant after the synthesis or preparation of the SPE surfactant is completed.

In some embodiments, the amount of the basic compound comprised in the stabilized SPE surfactant is from 0.01%to 15%, by weight of the SPE surfactant. In some embodiments, the amount of the basic compound used to pre-treat the SPE surfactant is within the range obtained by combining any two of the following endpoints: 0.01%, 0.05%, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, and 15%, by weight of the SPE surfactant. In an exemplary embodiment, the amount of the basic compound used to pre-treat the SPE surfactant is from 0.05%to 15%, from 0.1%to 15%, from 0.01%to 14%or from 0.05%to 14%, by weight of the SPE surfactant.

In some embodiments, the amount of odorous components generated from the stabilized SPE surfactant is lower (for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%or more lower) than that of the same SPE surfactant except that it is not stabilized according to the present disclosure, after a duration of storage of about 14 days at 25℃, or after accelerated ageing at 80 ℃ for more than 5 days. The odorous components can be one or more selected from aldehydes (e.g., propionaldehyde) , cyclic ethers (e.g., trioxocane, EMD, DMD) , or a mixture thereof.

The SPE surfactants and basic compounds of the stabilized SPE surfactant are as described in the "A. Stabilization of SPE surfactants" portion above.

C. Polyurethane composition

(B) an isocyanate component comprising one or more isocyanate compounds,

The polyurethane composition according to the present disclosure is a two-component composition comprising (A) a polyol component and (B) an isocyanate component. In some embodiments, the polyurethane composition is a polyurethane foam composition.

As used herein, the term "two-component" means that the polyurethane foam composition is provided in parts separated from each other before use. Typically, the composition according to the present disclosure can include at least a first component comprising one or more polyols selected from the group consisting of a polyester polyol, a polyether polyol, and the combination thereof (also referred to herein as a "polyol component" , "polyol component (A) " , or "OH component" ) , and a second component comprising one or more isocyanate compounds (also referred to herein as an "isocyanate component" , "isocyanate component (B) " , or "NCO component" ) . The polyol component and the isocyanate component can be prepared, stored, transported and served separately, and combined shortly or immediately before being applied to, for example, products to be potted. It is contemplated that when these two components are brought into contact, a curing reaction begins in which the polyol groups react with the isocyanate groups to form urethane links. The reactive polyurethane dispersion formed by bringing the two components into contact can be referred to as a "reaction mixture" or a "curable mixture. "

In some embodiments, the NCO/OH ratio of the isocyanate component to the polyol component comprised in the polyurethane foam composition can be within the range of from 0.5: 1 to 5: 1. In some embodiments, NCO/OH ratio of the isocyanate component to the polyol component can be within the range obtained by combining any two of the following endpoints: 0.5: 1, 0.8: 1, 1: 1, 1.2: 1, 1.5: 1, 1.8: 1, 2: 1, 2.2: 1, 2.5: 1, 3: 1, 4: 1, and 5: 1. In some specific embodiments, the NCO/OH ratio of the isocyanate component to the polyol component can be within the range of from 0.5: 1 to 4: 1, or from 0.5: 1 to 3: 1, preferably from 0.5: 1 to 2.5: 1, from 0.8: 1 to 3: 1, from 0.8: 1 to 2.5: 1, from 1: 1 to 2.5: 1, from 1.2: 1 to 2.2: 1, or from 0.8: 1 to 2.0: 1; and more preferably from 0.8: 1 to 1.8: 1, from 1: 1 to 2: 1, from 1.2: 1 to 2: 1, or from 1: 1 to 1.8: 1.

As used herein, the term "NCO/OH ratio" refers to the ratio of the number of isocyanate groups to the number of hydroxyl groups in the polyurethane foam composition; or more specifically, the ratio between the number of isocyanate groups in the isocyanate component and the number of hydroxyl groups in the polyol component, of the polyurethane composition.

In some embodiments, the polyurethane composition further comprises one or more catalysts, including amine compounds (for example, tertiary amine compounds) , organometallic compounds, and any combination thereof. Exemplary tertiary amine compounds include triethylenediamine, N-methylmorpholine, N, N-dimethylcyclohexylamine, N, N', N'-dimethylaminopropylhexahydrotriazine, 2-hydroxy-N, N, N-trimethylpropan-1-aminium formate, pentamethyldiethylenetriamine, tetramethylethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine, N, N-dimethyl-N', N'-dimethyl isopropylpropylenediamine, N, N-diethyl-3-diethylaminopropylamine and dimethylbenzylamine. Exemplary organometallic catalysts include organomercury, organolead, organoferric and organotin catalysts. Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyltin di-laurate, as well as other organometallic compounds such as are disclosed in U.S. Patent 2,846,408. A catalyst for the trimerization of polyisocyanates, resulting in a polyisocyanurate, such as an alkali metal alkoxide may also optionally be employed herein. Such catalysts are used in an amount which measurably increases the rate of polyurethane formation. The one or more catalysts can be comprised in either or both of the polyol component and the isocyanate component. Typical amounts are 0.001 to 3 parts by weight of catalyst per 100 parts by weight the polyol component. In some embodiments, the polyurethane composition comprises amine catalysts, tin catalysts, or a mixture thereof.

In some embodiments, the polyurethane composition further comprises one or more blowing agents. The blowing agent used in the polyurethane composition includes at least one physical blowing agent which is selected from a hydrocarbon, hydrofluorocarbon, hydrochlorofluorocarbon, fluorocarbon, dialkyl ether or fluorine-substituted dialkyl ether, or any combination thereof. Blowing agents of these types include propane, isopentane, n-pentane, n-butane, isobutane, isobutene, cyclo-pentane, dimethyl ether, 1, 1-dichloro-l-fluoroethane (HCFC-141b) , chlorodifluoromethane (HCFC-22) , l-chloro-l, l-difluoroethane (HCFC-142b) , 1, 1, 1, 2-tetrafluoroethane (HFC-134a) , 1, 1, 1, 3, 3-pentafluorobutane (HFC-365mfc) , 1, 1-difluoroethane (HFC-152a) , 1, 1, 1, 2, 3, 3, 3-heptafluoropropane (HFC-227ea) , 1, 1, 1, 3, 3-pentafluoropropane (HFC-245fa) , hydrofluoroolefin (HCFO) , hydrofluoroolefin (HFO) such as LBA, and any combination thereof. The polyurethane composition can also comprise a chemical blowing agent, such as water, carboxylic acid, formic acid, and any combination thereof. The one or more blowing agents can be comprised in either or both of the polyol component and the isocyanate component. In some embodiments, the one or more blowing agents are comprised in the polyol component. Typically, the blowing agent constitutes from 1 to 20 parts by weight per 100 parts by weight the polyol component.

Optionally, the polyurethane composition further comprises one or more chain extension and or cross linkage materials. Examples of such materials include but are not limited to ethylene glycol, diethylene glycol, triethylene glycol, propylene oxide, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-butane diol, 1, 6-hexane diol, 1, 8-octane diol, cyclohexane dimethanol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol and sucrose, as well as alkoxylates, diethanol amine, monoethanol amine, triethanol amine, mono-, di-or tri (isopropanol) amine, glycerine, trimethylol propane, and combinations thereof.

Optionally, the polyurethane composition further comprises one or more additives such as fillers, anti-oxidants, preservatives, pigments, colorants, and flame retardant additives.

(A) The polyol component

The polyol component comprised in the polyurethane composition comprises one or more polyols. The one or more polyols comprised in the polyurethane composition can be selected from the group consisting of polyester polyols, polyether polyols, and any combination thereof.

In some embodiments, the polyol component comprises the SPE surfactant described herein. In some embodiments, the polyol component comprises from 0.01%to 10%, for example, from 0.01%, 0.05%0.1%, 0.5%, or 0.8%, to 1%, 1.2%, 1.5%, 2%, 5%, 8%or 10%, of the SPE surfactant described herein, by weight of the polyol component.

As used herein, the term "polyol" refers to a compound with two or more hydroxyl groups. A polyol is a "diol" when it has exactly two hydroxyl groups, a "triol" when it has exactly three hydroxyl groups, a "tetraol" when it has exactly four hydroxyl groups, a "pentanol" when it has exactly five hydroxyl groups, and so on.

In some embodiments, the one or more polyols in the polyol component have an average hydroxyl group functionality of from 2 to 8, for example, from 2 to 7, or from 3 to 6.

In some embodiments, the one or more polyols in the polyol component have an average hydroxyl group number from 25 to 1000 mg KOH/g, for example, from 25 to 900 mg KOH/g, from 28 to 1000 mg KOH/g, or from 28 to 900 mg KOH/g.

In some embodiments, the polyol component can comprise a polyester polyol. A compound that contains two or more ester linkages in the same linear chain of atoms is known herein as a "polyester. " A compound that is a polyester and a polyol is known herein as a "polyester polyol. "

The polyester polyols employed in the polyurethane composition can have a molecular weight not to exceed 10,000 g/mol.

In some embodiments, the polyester polyols can have a hydroxyl group functionality of at least 2 (i.e., f ≥ 2) . In some embodiments, the polyester polyols can have a hydroxyl group functionality of not to exceed 10 (i.e., f ≤ 10) . In some embodiments, the polyester polyols can have a hydroxyl group functionality within the range of from 2 to 8, from 2 to 7, from 3 to 7, from 3 to 6, or from 3 to 5.

In some embodiments, the polyester polyols can have a hydroxyl group number of greater than 25 mg KOH/g. In some embodiments, the polyester polyols can have a hydroxyl group number of smaller than 1,000 mg KOH/g. In some embodiments, the polyester polyols can have an average hydroxyl group number of from 25 to 950 mg KOH/g, from 25 to 900 mg KOH/g, from 27 to 1000 mg KOH/g, from 27 to 950 mg KOH/g, from 28 to 1000 mg KOH/g, or from 28 to 950 mg KOH/g.

In some embodiments, the polyester polyols include, but are not limited to, polycondensates of diols and also, optionally, polyols (e.g., triols, tetraols) , and of dicarboxylic acids and also, optionally, polycarboxylic acids (e.g., tricarboxylic acids, tetracarboxylic acids) or hydroxycarboxylic acids or lactones. The polyester polyols can also be derived from, instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides, or corresponding polycarboxylic esters of lower alcohols.

Suitable diols include, but are not limited to, ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, pentylene glycol, hexalene glycol, polyalkylene glycols, such as polyethylene glycol, and also 1, 2-propanediol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, and neopentyl glycol. If a polyester polyol functionality greater than 2 is to be achieved, polyols having a functionality of 3 or greater can optionally be included in the polyol composition (e.g., trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate) .

Suitable dicarboxylic acids include, but are not limited to, aliphatic acids, aromatic acids, and combinations thereof. Examples of suitable aromatic acids include phthalic acid, isophthalic acid, terephthalic acid, and tetrahydrophthalic acid. Examples of suitable aliphatic acids include hexahydrophthalic acid, cyclohexane dicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methyl succinic acid, 3, 3-diethyl glutaric acid, 2, 2-dimethyl succinic acid, and trimellitic acid. As used herein, the term “acid” also includes any anhydrides of said acid. Further, monocarboxylic acids, such as benzoic acid and hexane carboxylic acid, should be minimized or excluded from the disclosed compositions. Saturated aliphatic and/or aromatic acids are also suitable for use according to this disclosure, such as adipic acid or isophthalic acid.

In some embodiments the polyol component can comprise a polyether polyol.

A compound that contains two or more ether linkages in the same linear chain of atoms is known herein as a "polyether. " A compound that is a polyether and a polyol is a "polyether polyol. "

The polyether polyols employed in the polyurethane composition can have a molecular weight not to exceed 10,000 g/mol.

In some embodiments, the polyether polyols can have a hydroxyl group functionality of at least 2 (i.e., f ≥ 2) . In some embodiments, the polyether polyols can have a hydroxyl group functionality of not to exceed 10 (i.e., f ≤ 10) . In some embodiments, the polyether polyols can have a hydroxyl group functionality within the range of from 2 to 8, from 2 to 7, from 3 to 7, from 3 to 6, from 3 to 5.

In some embodiments, the polyether polyols can have a hydroxyl group number of greater than 25 mg KOH/g. In some embodiments, the polyether polyols can have a hydroxyl group number of smaller than 1,000 mg KOH/g. In some embodiments, the polyether polyols can have an average hydroxyl group number of from 25 to 950 mg KOH/g, from 25 to 900 mg KOH/g, from 27 to 1000 mg KOH/g, from 27 to 950 mg KOH/g, from 28 to 1000 mg KOH/g, or from 28 to 950 mg KOH/g.

In some embodiments, the polyether polyols for use in the present disclosure are obtained by the addition polymerisation of alkylene oxides with polyhydric alcohol starter compounds. Examples of such polyhydric alcohols include glycerin, sorbitol, sucrose, glucose, fructose, lactose or other sugars. In some embodiments, the starter compound is sorbitol or sucrose. These polyhydric alcohols as well as mixtures of these alcohols with water, glycerol, propylene glycol, ethylene glycol or diethylene glycol, may be used as starter compounds. Examples of suitable sorbitol-or sucrose/glycerine-initiated polyethers that can be used include VORANOL ^TM 360, VORANOL ^TM RN411, VORANOL ^TM RN490, VORANOL ^TM 370, VORANOL ^TM 446, VORANOL ^TM 520, VORANOL ^TM 550, VORANOL ^TM RN 482, TERCAROL ^TM RF 55 or VORANOL ^TM RH 360 polyols, all available from The Dow Chemical Company.

In some embodiments, the polyol component can have a viscosity at 25℃ of from 200 cSt to 38,000 cSt, for example, from 200 cSt to 35,000 cSt, or from 250 cSt to 35,000 cSt, as measured according to ASTM D2196.

(B) The isocyanate component

The isocyanate component comprised in the polyurethane composition comprises one or more isocyanate compounds reactive with the one or more polyols in the polyol component.

In some embodiments, the isocyanate component comprises the SPE surfactant described herein. In some embodiments, the isocyanate component comprises from 0.01%to 10%, for example, from 0.01%, 0.05%0.1%, 0.5%, or 0.8%, to 1%, 1.2%, 1.5%, 2%, 5%, 8%or 10%, of the SPE surfactant described herein, by weight of the isocyanate component.

In some embodiments, the isocyanate compound can be one or more selected from isocyanate monomers, isocyanate prepolymers, modified isocyanates and combination thereof.

As used herein, an "isocyanate monomer" is any compound that contains two or more isocyanate groups. An "aromatic isocyanate" is an isocyanate that contains one or more aromatic rings. An "aliphatic isocyanate" contains no aromatic rings. In some embodiments, the isocyanate compound comprises an aromatic isocyanate.

Isocyanate monomers suitable for use according to the disclosure can be selected from the group consisting of aromatic isocyanates, aliphatic isocyanates, carbodiimide modified isocyanates, and the combinations thereof. Examples of aromatic isocyanates suitable for use according to the disclosure include, but are not limited to, isomers of methylene diphenyl dipolyisocyanate ( "MDI" ) such as 4, 4-MDI, 2, 4-MDI and 2, 2’-MDI, or modified MDI such as carbodiimide modified MDI or urethane modified MDI or allophanate modified MDI; isomers of toluene-dipolyisocyanate ( "TDI" ) such as 2, 4-TDI, 2, 6-TDI, isomers of naphthalene-dipolyisocyanate ( "NDI" ) such as 1, 5-NDI, and the combinations thereof. Examples of aliphatic isocyanates suitable for use according to this disclosure include, but are not limited to, isomers of hexamethylene dipolyisocyanate ( "HDI" ) , isomers of isophorone dipolyisocyanate ( "IPDI" ) , isomers of xylene dipolyisocyanate ( "XDI" ) , isomers of methylene-bis- (4-cyclohexylisocyanate) ( "HMDI" ) , and the combinations thereof. In some embodiments, the isocyanate monomers comprises diisocyanate monomers selected from the group consisting of isophorone diisocyanate (IPDI) , methylene-bis- (4-cyclohexylisocyanate) (HMDI) , hexamethylene diisocyanate (HDI) , methylene diphenyl diisocyanate (MDI) , toluene diisocyanate (TDI) , and the combination thereof.

In some embodiments, the isocyanate component of the polyurethane composition can be prepared using any organic polyisocyanates, modified polyisocyanates, isocyanate based prepolymers, and mixtures thereof. These can include aliphatic and cycloaliphatic isocyanates, but aromatic and especially multifunctional aromatic isocyanates such as 2, 4-and 2, 6-toluenediisocyanate and the corresponding isomeric mixtures; 4, 4'-, 2, 4'-and 2, 2'-diphenyl-methanediisocyanate (MDI) and the corresponding isomeric mixtures; mixtures of 4, 4'-, 2, 4'-and 2, 2'-diphenylmethanediisocyanates and polyphenyl polymethylene polyisocyanates (PMDI) ; and mixtures of PMDI and toluene diisocyanates are preferred. Most preferably, the polyisocyanate used to prepare the prepolymer formulation of the present invention is MDI or PMDI or crude mixtures of any of these.

In some embodiments, the isocyanate component can have a viscosity at 25℃ of from 50 mPa·s to 20,000 mPa·s, from 50 mPa·s to 18,000 mPa·s, or from 100 mPa·s to 18,000 mPa·s, as measured according to ASTM D2196.

In some embodiments, the amount of odorous components generated from the polyol component and/or the isocyanate component comprising the stabilized SPE surfactant is lower (for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%or more lower) than that of the polyol component and/or the isocyanate component comprising the same SPE surfactant except that it is not stabilized according to the present disclosure, after a duration of storage of about 14 days at 25℃, or after accelerated ageing at 80 ℃ for more than 5 days. The odorous components can be one or more selected from aldehydes (e.g., propionaldehyde) , cyclic ethers (e.g., trioxocane, EMD, DMD) , or a mixture thereof.

D. Polyurethane product

In a further aspect, the present disclosure provides a polyurethane product formed using the polyurethane composition described above.

In some embodiments, the polyurethane product is polyurethane foam.

Generally, the polyurethane foam can be formed by (i) providing the polyurethane composition comprising (A) a polyol component and (B) an isocyanate component as described; (ii) forming a reaction mixture by mixing the (A) polyol component with the (B) isocyanate component; (iii) subjecting the reaction mixture to conditions such that reacts, expands, and cures to form a polyurethane foam.

The (A) polyol component and the (B) isocyanate component are as described in the "C. Polyurethane composition" portion above.

In some embodiments, the reaction mixture reacts, expands and cures within an enclosed space to form polyurethane foam within said enclosed space. In some embodiments, the reaction mixture is allowed to react, expand and cure at room temperature or higher.

In some embodiments, the amount of odorous components generated from the polyurethane product manufactured using the stabilized SPE surfactant is lower (for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%or more lower) than that of the polyurethane product manufactured using the same SPE surfactant except that it is not stabilized according to the present disclosure, after a duration of storage of about 14 days at 25℃, or after accelerated ageing at 80 ℃ for more than 5 days. The odorous components can be one or more selected from aldehydes (e.g., propionaldehyde) , cyclic ethers (e.g., trioxocane, EMD, DMD) , or a mixture thereof.

E. Uses and Applications

In some embodiments, the polyurethane composition is a polyurethane foam composition.

In some embodiments, the polyurethane product is polyurethane foam.

EXAMPLES

Some embodiments of the invention will now be described in the following Examples, wherein all parts and percentages are by weight unless otherwise specified.

1. Reagents and Chemicals

Structures of some of the exemplary pre-treating additives listed above are shown below.

2. Sample preparing

2.1 Preparation of the formulated polyol used to manufacture the Foam

The detailed formulations are described in Examples CE10 and IE10.

a. The additives, described above, were firstly mixed with SPE surfactant or polyols based on the formulations in examples table below (see below formulations for each result) .

b. The mixture of surfactant or polyols with additives was stored at 25 ℃ overnight.

c. The above mixture was added with the other components and then mixed by a stirrer for 3 minutes at a speed of 3000 RPM to get formulated polyols as part A. Then the formulated polyols were stored at 25 ℃ for 12-24 hrs before foaming.

2.2 Foaming procedure

An aliquot of 106.69 g formulated polyol was mixed with 58.4 g of TDI isocyanate to prepare the foam sample. After foaming, the foam sample was packaged with aluminum foil. The gas bag analysis was conducted within 7 days after foam sample was prepared.

3.Quantification of odorants in SPE surfactants and foam

3.1 Sample preparation

The samples (0.3 g) were put into a 20 mL headspace GC-MS vial for analysis.

3.2 SPME (solid phase micro-extraction) GC-MS method parameters

SPME GC-MS analysis was conducted on an Agilent 7890 gas chromatograph coupled with a mass spectrometry detector (Agilent 5975C MSD) . The GC conditions are listed below. Semi-quantification was conducted by a reference standard (5 ppm of each, prepared in polyol 8010) . The LOQ (limit of quantitation or limit of detection) of the method for various cyclic ethers is ～ 0.01 ppm.

[Oven program]

Initial temp: 50℃ (On) Maximum temp: 325℃

Initial time: 4.00 min Equilibration time: 0.50 min

Ramps:

#Rate Final temp Final time Cryo (N2)

1 16 250 2 Cryo: Off

2 0.0 (Off) Cryo fault: Off

Run time: 18.50 min Ambient temp: 25℃

[SPME condition] : PDMS/DVB SPME fiber from Supleco Co. Ltd

Incubation Temp.: 75℃

Incubation Time: 5.00 min

Extraction Time: 30 min

[Column]

Agilent 19091S-433, HP-5MS, 5%Phenyl Methyl Silox, 30 m x 250 μm, 0.25 μm film thickness

Mode: constant pressure

Pressure: 7.6522 psi

Nominal initial flow: 1 mL/min

Average velocity: 36.445 cm/sec

[MS SCAN and SIM parameters]

DMD/EMD quantification:

Resolution: Low

Group Start Time: 2.30

Plot 1 Ion: 72.00

Ions/Dwell In Group (Mass, Dwell) (Mass, Dwell) (Mass, Dwell)

(59.00, 30) (72.00, 30) (87.00, 30)

Trioxocane quantification:

Resolution: Low

Group Start Time: 8.00

Plot 1 Ion: 101.00

Ions/Dwell In Group (Mass, Dwell) (Mass, Dwell) (Mass, Dwell)

(59.00, 30) (101.00, 30) (130.00, 30)

4. Examples and testing

4.1 Comparison between commercial SPE and pre-treated SPE

Amine catalysts were tested to validate the concept of using them to pre-treat the surfactant NIAX ^TM Silicone L-650 to reduce the formation of cyclic ethers during storage of the surfactant. Thus, the surfactant was compared with various pre-treated versions, and Table 1 shows the stability of the commercial SPE grade compared with pre-treated SPE grades, after accelerated ageing to simulate prolonged storage.

Thus, comparative example 1 (CE1) corresponding to the commercial SPE grade shows substantial formation of cyclic ethers after accelerated ageing, with DMD level increasing from 0.01 ppm at time zero, to 0.11 ppm after 6 days at 80 ℃.

Comparative example 2 (CE2) , corresponding to the commercial SPE pre-treated with water, shows a formation of cyclic ethers after ageing that is similar to CE1. Of the three cyclic ethers, trioxocane formation is now increasing faster during the initial part of the test, reflecting the impact of water presence. Pre-treatment of the SPE with antioxidant AO1135 (CE3) has some effect in reducing the formation of cyclic ethers after ageing, in comparison with CE1 the cyclic ether levels are lower, however the impact is limited and may be insufficient in addressing the issue of smell.

The most dramatic impact on the formation of cyclic ethers after ageing is associated with Inventive example 1 (IE1) corresponding to the SPE pre-treated with the amine catalyst Jeffcat ^TM ZR50. It shows that the amount of cyclic ethers is almost unchanged after accelerated ageing for 6 days at 80 ℃.

Table 1. Cyclic ethers formed during storage

4.2 Comparison between commercial SPE and SPEs pre-treated using different amines

SPE pre-treated with different amines were evaluated and compared with the commercial SPE. Acetic acid, frequently observed in SPE surfactants (from acetaldehydes oxidation) , was included among the pre-treating agent. Note that most of the amines used here are typical amine catalysts used in PU foam formulations.

In Table 2, CE4 corresponds to the commercial SPE while CE5 corresponding to the commercial SPE pre-treated with water, hence these two examples replicate compositions identical to those already mentioned in Table 1, however the difference now is the type of ageing treatment (16 hours at 80 ℃) and the type of testing (head-space SMPE) .

CE6 and CE7 correspond to SPEs pre-treated with acetic acid. The amount of generated degradation products, and particularly of odorous components such as propionaldehyde and of cyclic ethers increases substantially after ageing, indicating that pre-treatment with an acid will cause a worsening in the formation of odorous components after ageing of the SPE.

The inventive examples IE2, IE3, and IE4 correspond to the SPE pre-treated with different levels of JEFFCAT ^TM ZR-50, with or without water. The results after accelerated ageing show a substantial reduction in the detected amount of propionaldehyde.

The inventive examples IE5, IE6, IE7 correspond to the SPE pre-treated with other amines, again compared with the comparative examples, after accelerated ageing the inventive examples show a substantial reduction in the detected amount of propionaldehyde.

The samples were aged at 80 ℃ for 16 hours before testing. In spite of the relatively short accelerated ageing time, the benefits of using the inventive concept is confirmed by the experimental data, which were limited in this experiment to propionaldehyde quantitation.

The pre-treatment of the SPE with basic compounds such as those considered in the inventive examples reported in Table 2, can stabilize the SPE so that the formation of odorous components during storage is substantially reduced.

The example IE4 is of particular interest because it shows that the amount of basic compound is effective even when used at low level. In fact IE4 corresponds to the SPE surfactant pre-treated with only 1%of basic compound.

Also note that typically, the formulated polyols will also contain amine catalysts. However, these amine catalysts may not have much effect in stabilizing SPE surfactants as most of cyclic ethers may have already formed during shipping and storage of the surfactant.

Table 2. Cyclic ethers and propionaldehyde formed during storage

Remarks: For propionaldehyde the results are reported as peak area, as conversion of the peak area into ppm could not be accurately performed, hence it was decided to leave the results expressed as peak area as they were better reflecting the concentration of odorous species in the sample.

4.3 Commercial SPE unstabilized or stabilized with amines: polyol and foam testing

In the previous examples, it has been shown that commercial SPE may show degradation during storage, leading to the formation of odorous components. It has also been shown that pre-treated SPE with basic compounds may substantially reduce the speed of degradation, thus leading to a pre-treated SPE that has a smaller content of odorous components.

We now show that the amount of odorous degradation products that are present in the SPE may have a direct impact on the presence of odorous components in the final PU foam.

Thus Table 3 shows that after accelerated ageing at 80 ℃ for 10 days, the commercial SPE surfactant contained a substantial amount of propionaldehyde and a substantial amount of cyclic ethers (see CE8) . These same odorous components are present in a much smaller amount when considering the same SPE surfactant pre-treated with the stabilizer (see IE8) .

Table 4 shows the detected amounts of propionaldehyde and of cyclic ethers present in the formulated polyol prepared using the commercial SPE or the pre-treated SPE that were described in Table 3. Data show that the larger amount of propionaldehyde and of cyclic ethers associated with the aged commercial SPE grade, is reflected in proportionally larger amounts of the same odorous components in the formulated polyol.

Formulated polyol sample was prepared as follows. The various formulation ingredients (see recipe below) are mixed with a stirrer for 3 minutes at a speed of 3000 RPM. Then the two formulated polyols were stored at 25 ℃ for about 2 days before testing for degradation products.

Table 5 shows the detected amounts of propionaldehyde and of cyclic ethers present in the PU foam prepared using the formulated polyols from Table 4. Data show that the larger amount of propionaldehyde and of cyclic ethers associated with the aged commercial SPE grade, is reflected in proportionally large amounts of the same odorous components in the final foam.

Foaming procedure is as follows. An aliquot of 106.69 g formulated polyol was mixed with 58.4 g of Isocyanate 1 with a stirrer for 1 minute at a speed of 3000 RPM to prepare the foam sample. After foaming, the foam sample was packaged with aluminum foil. The gas bag analysis was conducted 3 days after foam sample was prepared.

	Name	Content (g)
Polyol	Polyol 1	100
H ₂O	Distilled water	4.6
Surfactant	see example CE8 or example IE8	1.6
Catalyst	JEFFCAT ^TM ZR-50	0.21
Catalyst	Catalyst T-9	0.28
TDI	Isocyanate 1	58.4

Table 3. Cyclic ethers in commercial SPE or pre-treated SPE, after ageing

Table 4. Cyclic ethers in formulated polyol containing aged commercial SPE or aged pre-treated SPE

Table 5. Cyclic ethers in PU foam prepared using formulated polyol containing aged commercial SPE or aged pre-treated SPE

Data in Table 5 show that, in spite that the amount of SPE surfactant is only about 1%of the total PU foam mass, the quality of the SPE can have a substantial impact on the amount of odorous components that are present in the foam. Use of pre-treated SPE surfactant allows to reduce the amount of odorous components, in particular of trioxocane.

Table 6. Expanded study on the stability of Niax L650, not pre-treated or pre-treated with various basic compounds with different pKb

Remarks: Data in Table 6 are expanding on the type of testing already described in Table 1. In particular, the samples were tested within 24 hours after samples were prepared (fresh prepared) , and analyzed after stored at R. T for 2 weeks. The LOQ of the method was 0.01 ppm. Detection was limited to only trioxocane.

Various amines with different pKb were selected for this study. It is indicated that most of amines showed similar behavior in suppressing the degradation of unsaturation and formation of trioxocane. Too strong basicity showed negative effect, such as KOH. pKb from 2.8 to 5.0 showed the best performances. Higher pKb such as aniline and diphenylamine showed effect, but not as good as the others.

Table 7. Expanded study on loading ratio of ZR-50 and Polyol 2

Remarks: The samples were tested within 24 hours after samples were prepared (fresh prepared) , and, analyzed after stored at R. T for 2 weeks.

Polyol 2 and ZR-50 were selected to study the impact of loading ratio. For ZR-50, the suppressing effect can be maintained until 0.01%, though the effect decreased with lower loading ratio. The two runs with Polyol 2 show that it also works, as it contains a tertiary amino structure, however compared with ZR-50 there is a difference in equivalent weight, the difference being a factor of approximately 10. Hence the wt %loading level of polyol 2 in the surfactant must be about 10 times higher than the loading level of ZR-50, to have similar impact on the stability. Higher ratio of amine led to better suppressing performances, but need to balance the performances and potential side effect from amines.

Claims

A method of stabilizing a silicone polyether (SPE) surfactant formed by grafting a vinyl polyether onto a silicone backbone, comprising, pre-treating the SPE surfactant with a basic compound having a pKb of from 1.0 to 9.0.
The method according to claim 1, wherein the amount of the basic compound used to pre-treat the SPE surfactant is from 0.01%to 15%, by weight of the SPE surfactant.
The method according to claim 1, wherein the basic compound comprises an amine.
The method according to claim 3, wherein the amine is selected from the group consisting of primary amines, secondary amines, tertiary amines and any mixture thereof.
The method according to claim 3, wherein the amine has a pKb of from 2.8 to 5.0.
The method according to claim 3, wherein the amine has at most one hydroxyl group.
The method according to claim 1, wherein the pre-treating of the SPE surfactant with a basic compound having a pKb of from 1.0 to 9.0 is carried out after the SPE surfactant is synthesized.
A stabilized SPE surfactant obtained by the method according to claim 1.
A polyurethane composition, comprising,

(A) a polyol component comprising one or more polyols selected from the group consisting of a polyester polyol, a polyether polyol, and the combination thereof, and

(B) an isocyanate component comprising one or more isocyanate compounds,

wherein the (A) polyol component and/or the (B) isocyanate component comprises a stabilized SPE surfactant obtained by the method according to claim 1.
The polyurethane composition of claim 9, which is a polyurethane foam composition.