Surfactant composition containing hydrazide

Abstract

The surfactant composition comprises 60% by weight or more of a surfactant and 0.01% by weight to 1% by weight of a hydrazide antioxidant, based on the total weight of the surfactant composition.

Description

Technical Field

[0001] The present disclosure relates to surfactant compositions, and more particularly to surfactant compositions containing hydrazide antioxidants.

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 in the product that release gas over time. Additionally or alternatively, VOCs can be generated during 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, generating unpleasant odors and causing 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 ("'898 Publication") discloses the use of polyurethane foams that exhibit reduced levels of formaldehyde and acetaldehyde emissions. '898 Publication also discloses the use of antioxidants in attempts to reduce VOCs. As seen in Tables 1 and 3 of '898 Publication, the use of antioxidants alone has the effect of increasing all measured VOCs (i.e., formaldehyde, acetaldehyde, and acrolein) rather than reducing them. In contrast to '898 Publication, Chinese Patent No. 107335320(B) ("'320 Patent") discloses an odor and formaldehyde removal composition. The composition of '320 Patent utilizes antioxidants in the form of carbohydrazides bonded to graphene oxide and titanium dioxide to neutralize and capture formaldehyde. Carbohydrazides are compounds belonging to a broader chemical class of hydrazides. Comparative Example 9 of the 320 patent demonstrates that the formaldehyde reduction ability of a composition is largely unaffected when a carbohydrazide is removed from a graphene oxide-nanotitanium dioxide compound. This result suggests that the effect of carbohydrazides on the formaldehyde exclusion properties of carbohydrazide-modified graphene and titanium oxide is minimal, if any.

[0004] Considering the above, the discovery of compositions utilizing hydrazide antioxidant compounds that exhibit reduced concentrations of not only aldehydes and ketone VOCs, but also esters, alcohols, and acid VOCs, is remarkable. [Overview of the project]

[0005] The inventors of this application have discovered compositions using hydrazide antioxidant compounds that exhibit reduced concentrations of esters, alcohols, and acidic VOCs, as well as aldehydes and ketones. The inventors found that by incorporating 0.01% by weight ("wt%) to 1% by weight of a hydrazide antioxidant 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 remarkable in that a significant impact on the total VOCs present in the surfactant composition is achieved despite relatively small amounts of hydrazide antioxidants. Furthermore, these effects are remarkable given that prior art has demonstrated a tendency for antioxidants to increase VOCs or have only a slight effect on their presence. The VOC-reducing ability of hydrazide antioxidants is advantageous in that it enables 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 and 0.01% to 1% by weight of a hydrazide antioxidant, based on the total weight of the surfactant composition.

[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 is a nonionic surfactant and contains an average of 8 or 9 moles of ethylene oxide.

[0011] According to the fifth feature of this disclosure, the surfactant has structure (I), and n of structure (I) is 3 to 11.

[0012] According to the sixth feature of this disclosure, the surfactant has structure (II), where x of structure (II) is 2 to 8 and y of structure (II) is 3 to 40.

[0013] According to the seventh feature of this disclosure, the surfactant composition contains 75% by weight or more of surfactant based on the total weight of the surfactant composition.

[0014] According to the eighth feature of this disclosure, the surfactant composition contains 0.01% to 0.5% by weight of a hydrazide antioxidant based on the total weight of the surfactant composition.

[0015] According to the ninth feature of this disclosure, the hydrazide antioxidant is a carbohydrazide.

[0016] According to the tenth feature of this disclosure, the surfactant composition essentially consists of a surfactant, water, and a carbohydrazide. [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. A surfactant composition comprises a surfactant and a hydrazide antioxidant. In various examples, a surfactant composition essentially consists of a surfactant and a hydrazide antioxidant and does not contain other compounds that substantially affect the properties of the surfactant composition. As will be described in more detail below, the introduction of a hydrazide antioxidant helps to reduce and / or remove various VOCs from the surfactant composition so that the surfactant composition does not significantly contribute to the VOC content of downstream applications.

[0023] 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 (I),

[0024] [Chemical formula] n in structure (I) 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. At the same time, it is 11 or less, 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 (I). 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 (II),

[0025] [Chemical formula] In structure (II), y is 3 or greater, or 4 or greater, or 5 or greater, or 10 or greater, or 15 or greater, or 20 or greater, or 25 or greater, or 30 or greater, or 35 or greater, while simultaneously being 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. In structure (II), X is 2 or greater, or 3 or greater, or 4 or greater, or 5 or greater, or 6 or greater, or 7 or greater, while simultaneously being 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 (II), and the variable "y" represents the average molar unit of oxyethylene in structure (II). 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 (I), structure (II), and / or other surfactants.

[0026] 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. On the other hand, 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.

[0027] Hydrazide antioxidant The surfactant composition contains a hydrazide antioxidant. As defined herein, a "hydrazide antioxidant" is a compound containing a hydrazide functional group. Examples of hydrazide antioxidants include carbohydrazide, acetohydrazide, propanohydrazide, malonic acid dihydrazide, adipic acid dihydrazide, sebacate acid dihydrazide, succinic acid dihydrazide, tartrate dihydrazide, diphenylhydrazide, other hydrazides, and combinations thereof. The surfactant composition contains 0.01% to 1.00% by weight of the hydrazide antioxidant. For example, the surfactant composition contains 0.01% by weight or more, or 0.05% by weight or more, or 0.10% by weight or more, or 0.20% by weight or more, or 0.30% by weight or more, or 0.40% by weight or more, or 0.50% by weight or more, or 0.60% by weight or more, or 0.70% by weight or more, or 0.80% by weight or more, or 0.90% by weight or more, on the other hand, 1.00% by weight or less, or 0.90% by weight or less, or 0.80% by weight or less, or 0.70% by weight or less, or 0.60% by weight or less, or 0.50% by weight or less, or 0.40% by weight or less, or 0.30% by weight or less, or 0.20% by weight or less, or 0.10% by weight or less of a hydrazide antioxidant. [Examples]

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

[0029] Surfactant 1 has structure (II) 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 (I) with n = 3 and CAS number 60828-78-6. Surfactant 2 is a 90% by weight active substance in a 10% by weight aqueous composition, and is available from The Dow Chemical Company, Midland, MI, USA.

[0031] CBH is a 5% by weight aqueous solution of carbohydrazide. Carbohydrazide has the CAS number 497-18-7 and is commercially available from Sigma-Aldrich (St. Louis, Missouri).

[0032] Sample preparation and testing Comparative examples ("CE") and inventive examples ("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. CE1, CE2, IE1, and IE2 were heated at 54°C for 24 hours, after which headspace gas chromatography-mass spectrometry ("HS_GCMS") was performed on the samples. IE3-IE6 were aged at approximately 23°C for 48 hours. All control examples were 100% by weight of surfactant 1 or surfactant 2 and were left at approximately 23°C, while the other samples were aged.

[0033] The headspace of the container was 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 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 program was to hold at 50°C for 5 minutes, increase the temperature to 250°C at a rate of 10°C / min, and hold for 3 minutes. The gas chromatograph was set to the scan mode with a source temperature of 230°C, a MSQuad temperature of 150°C, and the collection scan mode to search for masses from 29 daltons to 400 daltons. The headspace oven was heated at 130°C for 15 minutes. HS GCMS was performed on 20 - 30 mg of the sample placed in a 20 mL headspace vial for analysis. All samples were prepared in duplicate and the average results are shown. Toluene was used as a standard to semi - quantify all VOCs. An aliquot of 2.0 μg of toluene was injected into the headspace vial, and the peak area of toluene was used for semi - quantification.

[0034] Results Table 1 provides the compositional data of the samples containing Surfactant 1 and Surfactant 2. To ensure the calculation of appropriate removal rates, each set of experiments had a control sample to establish the baseline VOC concentration, from which the removal rate was calculated by dividing the total impurities in the example by the total impurities in the control. In the table, the entry “ND” means not detected, and “<LOQ (Limit Of Quantification)” indicates that the specific VOC concentration was significantly low and could not be reliably reported. The reduction of VOC was calculated by subtracting the quotient of dividing the total VOC of the sample by the total control VOC from 1 and multiplying the result by 100. The VOC concentration is provided in parts per million (PPM). Tables 2 and 3 provide the test results of the VOCs present in the control and the examples.

[0035]

Table 1

[0036] [Table 2]

[0037] [Table 3]

[0038] Referring to Tables 1 to 3, it is clear that the introduction of a hydrazide antioxidant into either surfactant 1 or surfactant 2 reduces the total VOC concentration of the surfactant composition. Compared with CE1 and control 1, IE1 demonstrates that the hydrazide antioxidant can reduce the initially present VOCs in surfactant 1 by more than 86% and resist the formation of new VOCs after thermal aging. Compared with CE2 and control 2, IE2 demonstrates that the hydrazide antioxidant can reduce the initially present VOCs in surfactant 2 by more than 75% and resist the formation of new VOCs after thermal aging. IE1 and IE2 demonstrate that the use of hydrazide antioxidants effectively reduces VOCs present in various types of surfactants and surfactant compositions. Tables 1 to 3 further demonstrate that hydrazide antioxidants are particularly effective in reducing ketone and aldehyde-based VOCs.

[0039] Referring to Table 4, aldehyde VOC removal data for IE3 to IE6 is provided.

[0040] [Table 4]

[0041] Table 4 demonstrates that hydrazide antioxidants are effective removers of aldehyde-based VOCs from both types of surfactants tested. Each of IE4–6 provides a VOC reduction of over 90%, while IE3 still provides an acceptable VOC reduction of over 70%.

Claims

1. A surfactant composition, Based on the total weight of the surfactant composition, 60% by weight or more of the surfactant, A surfactant composition comprising 0.01% to 1% by weight of a hydrazide antioxidant, The surfactant has structure (I), 【Chemistry 1】 In structure (I), n is 3 to 11, or The surfactant has structure (II), 【Chemistry 2】 In structure (II), 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 is an alkoxylated surfactant.

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

4. The surfactant composition according to claim 2, wherein the surfactant is a nonionic surfactant and contains an average of 8 or 9 moles of ethylene oxide.

5. 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.

6. The surfactant composition according to claim 5, wherein the surfactant composition comprises 0.01% to 0.5% by weight of the hydrazide antioxidant based on the total weight of the surfactant composition.

7. The surfactant composition according to any one of claims 1 to 6, wherein the hydrazide antioxidant is a carbohydrazide.

8. The surfactant composition according to claim 7, wherein the surfactant composition essentially consists of the surfactant, water, and the carbohydrazide.

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