Hydroxylamine surfactant composition

Abstract

The surfactant composition comprises 60% or more by weight, based on the total weight of the surfactant composition, of a surfactant; and 0.01% to 5% by weight, based on the total weight of the surfactant composition, of a hydroxylamine having Structure (I), wherein R1, R2, and R3 of Structure (I) are independently selected from the group consisting of H, an alkanolamine, or a hydroxylalkyl group having a straight or branched carbon chain having from 1 to 8 carbons; and R4 of Structure (I) is selected from the group consisting of an alkanolamine, or a hydroxylalkyl group having a straight or branched carbon chain having from 1 to 8 carbons.

Description

Technical Field

[0001] The present disclosure relates to surfactant compositions, and more particularly, to surfactant compositions containing hydroxylamine and showing a reduction in the concentration of volatile organic compounds.

Background Art

[0002] Introduction Volatile organic compounds (“VOCs”) are compounds having a high vapor pressure. VOCs are introduced into products and compositions in various ways. For example, the manufacture of a product may leave VOCs that release gas over time in the product. Additionally or alternatively, VOCs may be generated during storage of the product as a result of oxidation or exposure to high temperature conditions. Examples of VOCs include aldehydes, ketones, and various forms of acids. VOCs are typically released as gas from products, which can cause unpleasant odors and other problems. Considering these concerns, consumers and manufacturers pay high attention to the removal or reduction of VOCs in products.

[0003] Attempts have been made to address common VOCs. For example, World Intellectual Property Organization Publication 2018148898 (“Publication ’898”) discloses the use of polyurethane foams showing reduced levels of formaldehyde and acetaldehyde emissions. As shown in Tables 1 and 3 of Publication ’898, the use of 2-amino-2(hydroxymethyl)propane-1,3-diol (i.e., Example 2) has the effect of reducing acetaldehyde, but the effect on other existing VOCs is limited. Similar to Publication ’898, U.S. Patent No. 8,007,545 (“Patent ’545”) discloses a deodorant composition using 2-amino-2-hydroxymethyl-1,3-propanediol. As shown by Table 1 of Patent ’545, the deodorant composition was able to reduce the aldehyde odor, but it was not below the detectable threshold for the human nose.

[0004] Considering the above, it is remarkable to discover compositions utilizing amine compounds that can simultaneously and significantly reduce the concentrations of aldehydes, ketones, esters, alcohols, and acidic VOCs. [Overview of the project]

[0005] The inventors of this application have discovered a composition that, as a result of containing a hydroxylamine compound, exhibits a significantly reduced total VOC content while simultaneously reducing aldehydes, ketones, esters, alcohols, and acidic VOCs. The inventors of this application have discovered that by incorporating 0.01% by weight ("wt%) to 5% by weight of hydroxylamine having structure (I) into a surfactant composition containing 60% by weight or more of a surfactant, aldehydes, ketones, esters, alcohols, and acidic VOCs are simultaneously reduced. Such results are advantageous in that they enable the production and distribution of surfactant compositions that do not significantly contribute to the total VOC content of downstream products. In addition, the inventors of this disclosure have also discovered that the addition of sodium bisulfite to surfactant compositions can also help reduce various VOCs.

[0006] The present invention is particularly useful in cleaning, coating, and adhesive applications.

[0007] According to the first feature of this disclosure, the surfactant composition comprises 60% by weight or more of a surfactant based on the total weight of the surfactant composition, and 0.01% to 5% by weight of a hydroxylamine having structure (I) based on the total weight of the surfactant composition, wherein R1, R2 and R3 are independently selected from the group consisting of H, alkanolamines, or hydroxylalkyl groups having a linear or branched carbon chain having 1 to 8 carbon atoms, and R4 is selected from the group consisting of alkanolamines or hydroxylalkyl groups having a linear or branched carbon chain having 1 to 8 carbon atoms.

[0008] According to the second feature of this disclosure, the surfactant composition contains 75% by weight or more of the surfactant based on the total weight of the surfactant composition.

[0009] According to the third feature of this disclosure, the surfactant composition contains 0.01% to 1% by weight of hydroxylamine based on the total weight of the surfactant composition.

[0010] According to the fourth feature of this disclosure, the surfactant is an ethoxylated nonionic surfactant, and the surfactant contains an average of 8 moles or 9 moles of ethylene oxide.

[0011] According to the fifth feature of this disclosure, the surfactant composition further comprises sodium bisulfite.

[0012] According to the sixth feature of this disclosure, the surfactant composition contains 0.01% to 0.5% by weight of sodium bisulfite based on the total weight of the surfactant composition.

[0013] According to the seventh feature of this disclosure, the surfactant has structure (II), and n of structure (II) is between 3 and 11.

[0014] According to the eighth feature of this disclosure, the surfactant has structure (III), where x of structure (III) is 2 to 8 and y of structure (III) is 3 to 40.

[0015] According to the ninth feature of this disclosure, the hydroxylamine is selected from the group consisting of tris(hydroxyl-methyl)aminomethane, diethanolamine, and combinations thereof.

[0016] According to the tenth feature of this disclosure, hydroxylamine is diethanolamine.

[0017] Surfactant composition This disclosure relates to surfactant compositions. The surfactant compositions comprise a surfactant and hydroxylamine. The surfactant compositions may also comprise sodium bisulfite. As will be described in more detail below, the introduction of antioxidants and hydroxylamine helps to reduce and / or remove various VOCs from the surfactant compositions so that they do not significantly contribute to the VOC content of downstream applications.

[0018] Hydroxylamine The surfactant composition contains hydroxylamine. As used herein, the term "hydroxylamine" means a chemical compound having both an amine and a hydroxyl group, a functional group, or a moiety. Hydroxylamine is characterized by structure (I).

[0019] [ka] In the structure, R1, R2, and R3 are independently selected from the group consisting of H, alkanolamines, or hydroxylalkyl groups having a linear or branched carbon chain with 1 to 8 carbon atoms, and R4 is selected from the group consisting of alkanolamines or hydroxylalkyl groups having a linear or branched carbon chain with 1 to 8 carbon atoms. The hydroxylamines may be selected from the group consisting of diethanolamine, tris(hydroxyl-methyl)aminomethane, aminoethylethanolamine, diisopropanolamine, 2-amino-1-butanol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, 2-amino-1-methyl-1,3-propanediol, N-methylethanolamine, N-butylethanolamine, monoisopropanolamine, mono-sec-butanolamine, di-sec-butanolamine, other hydroxylamines, and combinations thereof.

[0020] The surfactant composition may contain 0.01% to 5% by weight of hydroxylamine based on the total weight of the surfactant composition. For example, the surfactant composition may contain 0.01% or more by weight, or 0.05% or more by weight, or 0.10% or more by weight, or 0.25% or more by weight, or 0.50% or more by weight, or 0.75% or more by weight, or 1.00% or more by weight, or 1.50% or more by weight, or 2.00% or more by weight, or 2.50% or more by weight, or 3.00% or more by weight, or 3.50% or more by weight, or 4.00% or more by weight, or 4.50% or more by weight, based on the total weight of the surfactant composition. It may contain hydroxylamine in amounts of 5.00% by weight or less, or 4.50% by weight or less, or 4.00% by weight or less, or 3.50% by weight or less, or 3.00% by weight or less, or 2.50% by weight or less, or 2.00% by weight or less, or 1.50% by weight or less, or 1.00% by weight or less, or 0.75% by weight or less, or 0.50% by weight or less, or 0.25% by weight or less, or 0.10% by weight or less, or 0.05% by weight or less.

[0021] surfactant As described above, surfactant compositions include surfactants. As used herein, the term “surfactant” means a compound that reduces the interfacial tension between two immiscible phases of different chemicals. Surfactants may be ionic or nonionic. Surfactants may be alkoxylated with one or more ethylene oxide (i.e., ethoxylated), propylene oxide (i.e., propoxylated), and / or butylene oxide (i.e., butoxylated) components. Surfactants may have structure (II).

[0022] [ka] For Structure (II), n is 3 or more, or 4 or more, or 5 or more, or 6 or more, or 7 or more, or 8 or more, or 9 or more, or 10 or more, and at the same time, 11 or less, or 10 or less, or 9 or less, or 8 or less, or 7 or less, or 6 or less, or 5 or less, or 4 or less. The variable "n" represents the average molar unit of oxyethylene in Structure (II). As defined herein, the n value is tested and determined by proton nuclear magnetic resonance spectroscopy and carbon-13 nuclear magnetic resonance spectroscopy. The surfactant may have Structure (III).

[0023] [Chemical formula] For Structure (III), y is 3 or more, or 4 or more, or 5 or more, or 10 or more, or 15 or more, or 20 or more, or 25 or more, or 30 or more, or 35 or more, and at the same time, 40 or less, or 35 or less, or 30 or less, or 25 or less, or 20 or less, or 15 or less, or 10 or less, or 5 or less, or 4 or less. X in Structure (III) is 2 or more, or 3 or more, or 4 or more, or 5 or more, or 6 or more, or 7 or more, and at the same time, 8 or less, or 7 or less, or 6 or less, or 5 or less, or 4 or less, or 3 or less. The variable "x" represents the average molar unit of oxypropylene used in Structure (III), and the variable "y" represents the average molar unit of oxyethylene in Structure (III). As defined herein, the x and y values are tested and determined by proton nuclear magnetic resonance spectroscopy and carbon-13 nuclear magnetic resonance spectroscopy. The surfactant may be a blend of surfactants such as Structure (II), Structure (III) and / or other surfactants.

[0024] The surfactant composition contains 60% by weight or more of a surfactant based on the total weight of the surfactant composition. For example, the surfactant composition contains 60% by weight or more, or 61% by weight or more, or 62% by weight or more, or 63% by weight or more, or 64% by weight or more, or 65% by weight or more, or 66% by weight or more, or 67% by weight or more, or 68% by weight or more, or 69% by weight or more, or 70% by weight or more, or 71% by weight or more, or 72% by weight or more, or 73% by weight or more, or 74% by weight or more, or 75% by weight or more, or 76% by weight or more, or 77% by weight or more, or 78% by weight or more, or 79% by weight or more, or 80% by weight or more, or 81% by weight or more, or 82% by weight or more, or 83% by weight or more, or 84% by weight or more, or 85% by weight or more, or 86% by weight or more, or 87% by weight or more, or 88% by weight or more, or 89% by weight or more, or 90% by weight or more, or 91% by weight or more, or 92% by weight or more, or 93% by weight or more, or 94% by weight or more, or 95% by weight or more, or 96% by weight or more, or 97% by weight or more, or 98% by weight or more, or 99% by weight or more. At the same time, it may contain 99.98% by weight or less, or 99% by weight or less, or 98% by weight or less, or 97% by weight or less, or 96% by weight or less, or 95% by weight or less, or 94% by weight or less, or 93% by weight or less, or 92% by weight or less, or 91% by weight or less, or 90% by weight or less, or 89% by weight or less, or 88% by weight or less, or 87% by weight or less, or 86% by weight or less, or 85% by weight or less, or 84% by weight or less, or 83% by weight or less, or 82% by weight or less, or 81% by weight or less, or 80% by weight or less, or 79% by weight or less, or 78% by weight or less, or 77% by weight or less, or 76% by weight or less, or 75% by weight or less, or 74% by weight or less, or 73% by weight or less, or 72% by weight or less, or 71% by weight or less, or 70% by weight or less, or 69% by weight or less, or 68% by weight or less, or 67% by weight or less, or 66% by weight or less, or 65% by weight or less, or 64% by weight or less, or 63% by weight or less, or 62% by weight or less, or 61% by weight or less.

[0025] Sodium bisulfite The surfactant composition may contain sodium bisulfite. Sodium bisulfite has the CAS number 7631-90-5. The surfactant composition may contain 0.01% to 0.50% by weight of sodium bisulfite. For example, the surfactant composition may contain 0.01% or more by weight, or 0.02% or more by weight, or 0.04% or more by weight, or 0.06% or more by weight, or 0.08% or more by weight, or 0.10% or more by weight, or 0.20% or more by weight, or 0.30% or more by weight, or 0.40% or more by weight, and simultaneously contain 0.50% or less by weight, or 0.40% or less by weight, or 0.30% or less by weight, or 0.20% or less by weight, or 0.10% or less by weight, or 0.08% or less by weight, or 0.06% or less by weight, or 0.04% or less by weight, or 0.02% or less by weight of sodium bisulfite, based on the total weight of the surfactant composition. The surfactant composition may have a weight ratio of hydroxylamine to sodium bisulfite of 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, and simultaneously, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1. [Examples]

[0026] material The following materials were used in the examples.

[0027] Surfactant 1 has structure (III) with x = 5, y = 9, and CAS number 64366-70-7. Surfactant 1 contains 99% or more active material by weight and is available from The Dow Chemical Company (Midland, MI, USA).

[0028] Surfactant 2 has structure (II) with n = 3 and CAS number 60828-78-6. Surfactant 2 is available in a composition containing 90% by weight of the active substance and 10% by weight of the aqueous composition from The Dow Chemical Company (Midland, MI, USA).

[0029] DEA is a diethanolamine with CAS number 111-42-2 and is commercially available from The Dow Chemical Company (Midland, MI, USA).

[0030] TAM is tris(hydroxymethyl)aminomethane with CAS number 77-86-1 and is commercially available from Sigma-Aldrich (St. Louis, MO, USA).

[0031] NAS is an aqueous solution of 25% by weight sodium bisulfite. Sodium bisulfite has the CAS number 7631-90-5 and is commercially available from Sigma-Aldrich (St. Louis, MO).

[0032] Sample preparation and testing Comparative examples ("CE") and examples of the present invention ("IE") were prepared by first combining the specified components in a sample container. The container was then placed on a shaking platform at 300 rpm for 2 hours. All samples showed a homogeneous appearance at the end of shaking. Prior to headspace gas chromatography-mass spectrometry ("HS GCMS") analysis of the examples, the comparative examples and examples of the present invention were heated at 70°C for 24 hours. A control sample of pure surfactant 2 was placed in a container and maintained at approximately 23°C for 24 hours.

[0033] The data in Table 2 were analyzed using the following method: The examples were analyzed using an Agilent 7890A gas chromatograph, an Agilent 5975C mass spectrometer, and an Agilent 7697A headspace autosampler. The gas chromatograph column was a SolGel-wax column with dimensions of 30 mm × 250 μm × 1 μm. The carrier gas used was helium at a constant flow rate of 1.0 mL / min. The gas chromatograph oven was programmed to maintain a temperature of 50°C for 5 minutes, then increase the temperature to 250°C at 10°C / min, and maintain for 3 minutes. The gas chromatograph was set to scan mode with a source temperature of 230°C and an MSQuad temperature of 150°C, and to collection scan mode searching for masses between 29 and 400 Daltons. The headspace oven was heated to 130°C for 15 minutes. HS GC-MS was performed on 20-30 mg samples placed in 20 mL headspace vials for analysis. All samples were prepared in double batches, and the average results are shown. All VOCs were semi-quantified using toluene as an equivalent, and their response coefficient to toluene was considered to be "1". Aliquots of 2.0 μg of toluene were injected into headspace vials, and the peak area of ​​toluene was used for semi-quantification.

[0034] The data in Tables 3 and 4 were analyzed using the following method: The examples were analyzed using an Agilent 7890A gas chromatograph, an Agilent 5975C mass spectrometer, and an Agilent 7697A headspace autosampler. The gas chromatograph column was an Agilent DB-5MS column (J&W123-5533) with dimensions of 30 mm × 320 μm × 1 μm. The carrier gas used was helium at a constant flow rate of 1.5 mL / min. The gas chromatograph oven was programmed to maintain a temperature of 50°C for 5 minutes, then increase the temperature to 250°C at a rate of 10°C / min, and maintain the temperature for 3 minutes. The gas chromatograph was set to scan mode with a source temperature of 230°C and an MSQuad temperature of 150°C, and to collection scan mode searching for masses between 29 and 400 Daltons. The headspace oven was heated to 130°C for 15 minutes. The sample preparation procedure was the same as described above.

[0035] result Table 1 provides the compositions of CE1-CE5, IE1-IE5, and the control sample.

[0036] [Table 1]

[0037] Tables 2 and 3 show the effects of adding hydroxylamine to surfactant 1.

[0038] [Table 2]

[0039] [Table 3]

[0040] Table 4 shows the effects of adding hydroxylamine alone or in combination with sodium bisulfite to surfactant 2.

[0041] [Table 4]

[0042] As can be seen from Tables 2 to 4, the addition of hydroxylamine alone or in combination with sodium bisulfite favorably reduces the total VOC content in the examples. Compared to CE1, IE1 demonstrates that the inclusion of only 0.2% by weight of tris(hydroxymethyl)aminomethane is sufficient to produce a surfactant composition with less than half the VOC of the sample without tris(hydroxymethyl)aminomethane (e.g., CE1). Compared to CE2, IE2 demonstrates that the inclusion of only 0.1% by weight of diethanolamine is sufficient to produce a surfactant composition with less than 15% of the VOC of the sample without diethanolamine (e.g., CE2).

[0043] Referring here to Table 4, a control of surfactant 2, which was not subjected to thermal aging for reference purposes, is provided. As can be seen, IE3–IE5 perform significantly better than the control and CE3–CE5 in removing total VOC content, thereby demonstrating that the introduction of hydroxylamine is beneficial in VOC removal. IE3–IE5 also show lower VOC numbers than the control samples, indicating that the introduction of hydroxylamine is beneficial even when dealing with VOCs already present in the surfactant from manufacturing. IE5 shows that the combination of sodium bisulfite and hydroxylamine is even more effective in reducing the total VOC number than the use of hydroxylamine alone. This result is surprising because hydroxylamine and sodium bisulfite exhibit a synergistic effect in reducing the total VOCs present in the surfactant composition.

Claims

1. A surfactant composition, Based on the total weight of the surfactant composition, 60% by weight or more of the surfactant, Based on the total weight of the surfactant composition, 0.01% to 5% by weight of a hydroxylamine having structure (I) Includes: 【Chemistry 1】 In the structure, R １ , R ２ and R ３ R is independently selected from the group consisting of H, alkanolamines, or hydroxylalkyl groups having a linear or branched carbon chain having 1 to 8 carbon atoms, ４ In a surfactant composition, the surfactant is selected from the group consisting of alkanolamines or hydroxylalkyl groups having a linear or branched carbon chain having 1 to 8 carbon atoms, The surfactant has structure (II) 【Chemistry 2】 In structure (II), n is 3 to 11, or The surfactant has structure (III) 【Transformation 3】 In structure (III), x is between 2 and 8, and y is between 3 and 40. A surfactant composition characterized by the following features.

2. The surfactant composition according to claim 1, wherein the surfactant composition contains 75% by weight or more of the surfactant based on the total weight of the surfactant composition.

3. The surfactant composition according to claim 2, wherein the surfactant composition contains 0.01% to 1% by weight of the hydroxylamine based on the total weight of the surfactant composition.

4. The surfactant composition according to claim 1, wherein the surfactant is an ethoxylated nonionic surfactant, and the surfactant contains an average of 8 moles or 9 moles of ethylene oxide.

5. The surfactant composition according to claim 1, further comprising sodium bisulfite.

6. The surfactant composition according to claim 5, wherein the surfactant composition contains 0.01% to 0.5% by weight of the sodium bisulfite based on the total weight of the surfactant composition.

7. The surfactant composition according to any one of claims 1 to 6, wherein the hydroxylamine is selected from the group consisting of tris(hydroxyl-methyl)aminomethane, diethanolamine, and combinations thereof.

8. The surfactant composition according to claim 7, wherein the hydroxylamine is diethanolamine.

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