Surfactant composition with reduced volatile organic compounds

Abstract

To provide a surfactant composition with reduced levels of volatile organic compounds. [Solution] The surfactant composition comprises 60% by weight or more of a surfactant based on the total weight of the surfactant composition, 0.01% to 1% by weight of an antioxidant, 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 of structure (I) 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 of structure (I) is selected from the group consisting of alkanolamines or hydroxylalkyl groups having a linear or branched carbon chain having 1 to 8 carbon atoms.

Description

Technical Field

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

Background Art

[0002] Introduction Volatile organic compounds ("VOCs") are compounds that have a high vapor pressure. VOCs are introduced into products and compositions in various ways. For example, the manufacture of a product may leave VOCs in the product that release gas over time. Additionally or alternatively, VOCs can be generated during the storage of a 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 bad odors and other problems. In view of these concerns, consumers and manufacturers are paying 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 that exhibit reduced levels of formaldehyde and acetaldehyde release. Publication '898 discloses in Tables 1 and 3 that the use of about 0.1 wt% of an amino alcohol alone removed 30% of the aldehydes, the use of 1.5% of an antioxidant alone resulted in a 53.41% increase in aldehydes present, and the combination of 0.1 wt% of an amino alcohol and 1.5 wt% of an antioxidant reached an aldehyde removal rate of 54.38%. The antioxidant used was a blend of a hindered phenolic antioxidant and butylated hydroxytoluene. Despite the apparent interaction effect between the amino alcohol and the hindered phenolic and butylated hydroxytoluene antioxidants, a significant amount of aldehydes and other VOCs were present in the compositions of Publication '898.

[0004] Considering the above, it is remarkable to discover compositions utilizing amine compounds and antioxidants that can reduce the total VOC concentration of aldehydes, ketones, esters, alcohols, and acids by more than 70%. [Overview of the project]

[0005] The inventors of this application have discovered compositions utilizing amine compounds and antioxidants that can reduce the total VOC concentration of aldehydes, ketones, esters, alcohols, and acids by more than 70%. The inventors found that by incorporating 0.01% ("wt%) to 1% by weight of antioxidants and 5% by weight or less of structure (I) hydroxylamine into a surfactant composition containing 60% by weight or more of surfactant, aldehydes, ketones, esters, alcohols, and acids are simultaneously reduced, resulting in a reduction of more than 70% in total VOC content. Such results are remarkable in that a significant impact on the total VOC present in the surfactant composition is achieved despite relatively small amounts of antioxidants and hydroxylamine. Even more remarkable is the functionality of such combinations, considering the uncertainty introduced by using hydroxylamines, antioxidants, and systems different from those demonstrated in the prior art. These 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.

[0006] The present invention is particularly useful in coating, cleaning, 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, 0.01% to 1% by weight of an antioxidant, 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 of structure (I) 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 of structure (I) 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 is an alkoxylated surfactant.

[0009] According to the third feature of this disclosure, the surfactant is an ethoxylated nonionic surfactant.

[0010] According to the fourth feature of this disclosure, the surfactant has structure (II) in which n is 3 to 11.

[0011] According to the fifth feature of this disclosure, n in structure (II) is between 7 and 9.

[0012] According to the sixth 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.

[0013] According to the seventh feature of this disclosure, the surfactant composition comprises 0.01% to 0.1% by weight of an antioxidant and 0.01% to 0.1% by weight of a hydroxylamine based on the total weight of the surfactant composition.

[0014] According to the eighth feature of this disclosure, the hydroxylamine is selected from the group consisting of diethanolamine, aminoethylethanolamine, diisopropanolamine, or a combination thereof.

[0015] According to the ninth feature of this disclosure, the antioxidant is selected from the group consisting of hydrazine, phenylhydrazine, semicarbazide, carbohydrazide, DL-α-tocopherol, tetramethyl-4-piperidinol, propyl gallate, and combinations thereof.

[0016] According to the tenth feature of this disclosure, the antioxidant is DL-α-tocopherol, and the hydroxylamine is aminoethylethanolamine. [Modes for carrying out the invention]

[0017] As used herein, the term "and / or" means, when used in the enumeration of two or more items, that any one of the enumerated items may be used on its own, or any combination of two or more of the enumerated items may be used. For example, if a composition is described as containing components A, B, and / or C, the composition may contain A alone, B alone, C alone, A and B in combination, A and C in combination, B and C in combination, or A, B, and C in combination.

[0018] Unless otherwise stated, all ranges include the endpoint.

[0019] Unless the date is indicated by a hyphenated two-digit number in the test method number, the test method refers to the most recent test method as of the priority date of this document. References to test methods include both references to the testing association and the test method number. Test method organizations are referred to by one of the following abbreviations: ASTM refers to ASTM International (formerly the American Society for Testing and Materials), IEC refers to the International Electrotechnical Commission, EN refers to the European Norm, DIN refers to the Deutsches Institut für Normung, and ISO refers to the International Organization for Standards.

[0020] As used herein, the term weight percentage ("weight %) refers to the percentage by weight of an ingredient relative to the total weight of a polymer composition, unless otherwise specified.

[0021] Where used herein, a Chemical Abstract Services registration number ("CAS#") refers to the unique numerical identifier last assigned to a chemical compound by Chemical Abstract Services as of the priority date of this document.

[0022] Surfactant composition This disclosure relates to surfactant compositions. The surfactant compositions comprise a surfactant, an antioxidant, and hydroxylamine. 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. The surfactant compositions may be used in coating, cleaning, and adhesive applications.

[0023] Hydroxylamine The surfactant composition contains hydroxylamine. As used herein, the term "hydroxylamine" means an amine and a chemical compound having a hydroxyl group, a functional group, or a moiety. Hydroxylamine is characterized by structure (I). [ka] In the formula, 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. The hydroxylamine 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.

[0024] 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% by weight or more, or 0.05% by weight or more, or 0.10% by weight or more, or 0.25% by weight or more, or 0.50% by weight or more, or 0.75% by weight or more, or 1.00% by weight or more, or 1.50% by weight or more, or 2.00% by weight or more, or 2.50% by weight or more, or 3.00% by weight or more, or 3.50% by weight or more, or 4.00% by weight or more, or 4.50% by weight or more. On the other hand, at the same time, it may contain 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 of hydroxylamine.

[0025] Surfactant As described above, the surfactant composition contains a surfactant. As used herein, the term "surfactant" means a compound that reduces the interfacial tension between two immiscible phases of different chemical substances. The surfactant may be ionic or non-ionic. The surfactant 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. The surfactant may have structure (II),

Chemical formula

[0026] The surfactant composition contains 60% by weight or more of 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 or 78% by weight or 79% by weight or 80% by weight or 81% by weight or 82% by weight or 83% by weight or 84% by weight or 85% by weight or 86% by weight or 87% by weight or 88% by weight or 89% by weight or 90% by weight or 91% by weight or 92% by weight or 93% by weight or 94% by weight or 95% by weight or 96% by weight or 97% by weight or 98% by weight or 99% or more by weight, while simultaneously 99.98% or less by weight, or 99% or less by weight, or 98% or less by weight, or 97% or less by weight, or 96% or less by weight, or 95% or less by weight, or 94% or less by weight, or 93% or less by weight, or 92% or less by weight, or 91% or less by weight, or 90% or less by weight, or 89% or less by weight, or 88% or less by weight, or 87% or less by weight, or 86% or less by weight, or 85% or less by weight, or 84% or less by weight, or 83% or less by weight, or 82% or less by weight, or 81% or less by weight. It may include less than or equal to % by weight, 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.

[0027] Antioxidant The surfactant composition contains an antioxidant. The antioxidant is selected from the group consisting of hydrazine, phenylhydrazine, semicarbazide, carbohydrazide, DL-α-tocopherol, tetramethyl-4-piperidinol, propyl gallate, other antioxidants, and combinations thereof. The surfactant composition contains 0.01% to 1.00% by weight of the antioxidant. For example, a surfactant composition may contain, based on the total weight of the surfactant composition, 0.01% or more by weight, or 0.05% 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, or 0.50% or more by weight, or 0.60% or more by weight, or 0.70% or more by weight, or 0.80% or more by weight, or 0.90% or more by weight, while simultaneously containing 1.00% or less by weight, or 0.90% or less by weight, or 0.80% or less by weight, or 0.70% or less by weight, or 0.60% or less by weight, or 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 of an antioxidant. [Examples]

[0028] material The following materials were used in the examples.

[0029] 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).

[0030] Surfactant 2 has structure (II) with n = 8 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).

[0031] DEA is a diethanolamine with CAS number 111-42-2 and is commercially available from The Dow Chemical Company, Midland, MI, USA.

[0032] AEEA is an aminoethylethanolamine with CAS number 111-41-1, and is commercially available from The Dow Chemical Company, Midland, MI, USA.

[0033] DIPA is a diisopropanolamine with CAS number 110-97-4 and is commercially available from The Dow Chemical Company, Midland, MI, USA.

[0034] TMP is tetramethyl-4-piperidinol with CAS number 2403-88-5 and is available from Shanghai Energy Chemicals Co. Ltd. (Shanghai, China).

[0035] CBH is a 5 wt% aqueous solution of carbohydrazide. Carbohydrazide has the CAS number 497-18-7 and is commercially available from Sigma-Aldrich (St. Louis, Missouri).

[0036] SVE is a synthetic vitamin E, also known as DL-α-tocopherol, with CAS number 10191-41-0, and is available from Sigma-Aldrich (St. Louis, Missouri).

[0037] 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 table at 300 rpm for 2 hours. All samples showed a homogeneous appearance at the end of shaking. After holding the samples at approximately 23°C for 48 hours, headspace gas chromatography-mass spectrometry ("HSGC-MS") analysis was performed on the samples.

[0038] 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 (sn. 1297586B08, p / n 054787) with dimensions of 30 m × 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 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. HSGC-MS was performed on 20 mg to 30 mg samples placed in 20 mL headspace vials for analysis. All samples were prepared in double-cycles, 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 the headspace vials, and the peak area of ​​toluene was used for semi-quantification.

[0039] result Table 1 provides compositional and performance data for compositions containing surfactant 1. Hydroxylamine ("HA") and antioxidant ("AO") are provided along with their respective amounts. The remainder of the sample is surfactant 1. Table 2 provides compositional and performance data for examples containing surfactant 2. Hydroxylamine and antioxidant are provided in their respective amounts. The remainder of the sample is surfactant 2. For both Tables 1 and 2, each set of experiments had a control sample ("cont") to establish a baseline VOC concentration. The removal rate was calculated by subtracting the quotient obtained by dividing the total VOC of the example by the total VOC of the control from 1, and then multiplying the result by 100. The column "Group" indicates which control sample and which example correspond to each other. VOC and total VOC values ​​are provided in ppm. [Table 1] [Table 2]

[0040] As can be seen from Tables 1 and 2, CE1 to CE12 yield various different VOC removal rates depending on the hydroxylamine or antioxidant used. Comparing CE1 to CE6 with CE7 to CE12, the removal rate appears to depend on the type of surfactant used. Despite the suggestions from the prior art, the combination of both hydroxylamine and antioxidants in surfactant compositions can surprisingly reduce aldehydes, ketones, esters, alcohols, and acid VOCs simultaneously, reducing the total VOC content by more than 70%. For example, each of IE1 to IE5 can reduce the total VOC content in the surfactant composition by more than 70%. Particularly noteworthy is IE5, which demonstrates that while DIPA and SVE alone could not achieve a 70% removal rate (see CE8 and CE11), the combination of DIPA and SVE additives can achieve a removal rate of more than 70%. Furthermore, several combinations of hydroxylamine and antioxidants show synergistic results. For example, DIPA and TMP showed relatively low efficiencies of 59.75% (CE3) and 3.60% (CE5), respectively, but the combination of these two additives achieved a removal rate of 75.10% in IE2, demonstrating a significant synergistic effect.

Claims

1. A surfactant composition, Based on the total weight of the surfactant composition, 60% by weight or more of the surfactant, 0.01% to 1% by weight of antioxidant, 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 formula, 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 The surfactant composition is selected from the group consisting of alkanolamines or hydroxylalkyl groups having a linear or branched carbon chain having 1 to 8 carbon atoms.

2. The surfactant composition according to claim 1, wherein the surfactant is an alkoxylated surfactant.

3. The surfactant composition according to claim 2, wherein the surfactant is an ethoxylated nonionic surfactant.

4. The surfactant has structure (II), 【Chemistry 2】 The surfactant composition according to claim 3, wherein n in structure (II) is 3 to 11.

5. The surfactant composition according to claim 4, wherein n in structure (II) is 7 to 9.

6. The surfactant has structure (III), 【Transformation 3】 The surfactant composition according to claim 1, wherein x in structure (III) is 2 to 8 and y in structure (III) is 3 to 40.

7. The surfactant composition Based on the total weight of the surfactant composition, 0.01% to 0.1% by weight of the antioxidant, and Based on the total weight of the surfactant composition, 0.01% to 0.1% by weight of hydroxylamine, A surfactant composition according to claim 1, comprising:

8. The surfactant composition according to any one of claims 1 to 7, wherein the hydroxylamine is selected from the group consisting of diethanolamine, aminoethylethanolamine, diisopropanolamine, or a combination thereof.

9. The surfactant composition according to any one of claims 1 to 7, wherein the antioxidant is selected from the group consisting of hydrazine, phenylhydrazine, semicarbazide, carbohydrazide, DL-α-tocopherol, tetramethyl-4-piperidinol, propyl gallate, and combinations thereof.

10. The surfactant composition according to any one of claims 1 to 7, wherein the antioxidant is DL-α-tocopherol and the hydroxylamine is aminoethylethanolamine.

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