Biodegradable multi-block copolymer surfactants

Abstract

A surfactant composition comprises one or more multi-block copolymer surfactants having the general formula: R-O-[AO] x [AOa EOb] y [EO] c, wherein R is a linear or branched, saturated or unsaturated C6 to C18 carbon chain; aO is a C3 to C6 alkylene oxide, and x ranges from 0 to 5; y is at least 1, [AOa EOb] represents a block copolymer wherein a ranges from 1 to 20 and b ranges from 0.5 to 3.5; and c ranges from 1 to 50. A process includes polymerizing one or more C3 to C6 alkylene oxides in the presence of an alcohol R-OH to produce a first product; polymerizing a mixture of one or more alkylene oxides and ethylene oxide in the presence of the first product to form a block [AOa EOb] and produce a second product; and polymerizing ethylene oxide in the presence of the second product to produce the multi-block copolymer surfactant.

Description

Technical Field

[0001] The implementation plan involves multiblock copolymer surfactants, their preparation methods, and their usage methods. Background Technology

[0002] Surfactants are used for a variety of purposes in the chemical and manufacturing industries. These purposes include, for example, imparting or enhancing the wetting and detergency of products, including wetting agents, emulsifiers, rinsing aids, defoamers / low-foaming agents, spray cleaners, drug delivery agents, emulsifiers for herbicides and pesticides, metal cleaners, paints, coatings, agricultural sprays and crop growth promoters, latex, stabilizers for paints and paper products, etc. A broad class of surfactants includes nonionic surfactants, which are generally considered to produce less foam than their ionic counterparts. Nonionic surfactants are often chosen for their biodegradability and low aquatic toxicity, making them suitable for a wide range of applications such as coatings, crop applications, and industrial cleaning. However, properties such as high critical micelle concentration (CMC) and suboptimal cleaning performance hinder the widespread adoption of nonionic surfactants across various industries. Summary of the Invention

[0003] In one aspect, the embodiments disclosed herein include surfactant compositions having one or more multiblock copolymer surfactants having the general formula: RO-[AO] x [AO a EO b ] y [EO] c Where R is a straight-chain or branched, saturated or unsaturated C6 to C18 carbon chain; AO is a C3 to C6 epoxide alkane, and x ranges from 0 to 5; y is at least 1, [AO a EO b ] represents a block copolymer, wherein a ranges from 1 to 20, b ranges from 0.5 to 3.5, and c ranges from 1 to 50.

[0004] On the other hand, the method includes: polymerizing one or more C3 to C6 alkylene oxides in the presence of an alcohol R-OH to generate a first product; and polymerizing a mixture of one or more alkylene oxides and ethylene oxide in the presence of the first product to form a block [AO] a EO b And generate a second product; and in the presence of the second product, polymerize ethylene oxide to generate a multiblock copolymer surfactant. Detailed Implementation

[0005] The embodiments relate to multiblock copolymer surfactants, their preparation methods, and their applications. The multiblock copolymer surfactants disclosed herein can be prepared by addition polymerization of alkylene oxide blocks containing one or more comonomers onto C6 to C18 alcohol starting compounds. The surfactants also contain one or more random and / or gradient copolymer blocks, which improve biodegradability while also reducing CMC and foaming properties. The hydrophilicity and biodegradability of the random and gradient copolymer blocks can be tuned by incorporating ethylene oxide (EO) into blocks of one or more alkylene oxide (AO) comonomers (AO / EO molar equivalent ratio of 2 to 30).

[0006] Poly(alkylene oxides) are widely used as nonionic surfactants and in the production of fatty alcohol-based surfactants, exhibiting cleaning efficiency for hard surfaces, high solubility in water, auxiliary properties in agrochemicals, and low foaming properties. Typically, AO comonomers with 3 or more carbon atoms are added to the starting alcohol to increase the surfactant's hydrophobicity, thereby reducing the CMC and enhancing detergent properties. However, with increasing AO comonomer content and block size (e.g., PO blocks > 6 molar equivalents), biodegradability begins to decrease, potentially falling below international regulatory standards (e.g., OECD requirements for biodegradability and aggregation).

[0007] To overcome these challenges, addition polymerization of hydrophilic EO blocks can be introduced to allow for higher PO (and larger carbon number AO) content, thereby disrupting the PO blocks and improving biodegradability. However, the introduction of EO comonomers and blocks can alter hydrophobicity and the resulting cleaning efficiency, and balancing surfactant performance and biodegradability is crucial for surfactant design.

[0008] The multiblock copolymer surfactants disclosed herein may comprise alkyl alcohols modified with a plurality of epoxy alkane blocks, including at least one block incorporating an EO via random or gradient polymerization. The multiblock copolymer surfactants disclosed herein offer low CMC as well as enhanced biodegradability and surfactant properties in a variety of applications such as laundry, hard surface cleaning, and dishwashing. The surfactant compositions disclosed herein can be prepared by adding epoxy alkane, which serves as a copolymer block, to a C8 to C18 alcohol starting compound in the presence of a catalyst.

[0009] The alkyl alcohol starting compound can be a straight-chain or branched primary or secondary C6-C18 alcohol, such as hexanol, octanol, nonanol, decanol, 2-ethylhexanol, 2-propylheptanol, a mixture of C8-C10 straight-chain alcohols, tridecanool, isotrigineol, etc. Polymerization onto the alkyl alcohol may include modification with at least one AO ​​block, which includes C3 to C6 epoxides, such as propylene oxide, butane oxide, etc.

[0010] Block copolymers may comprise a mixture of AO and EO comonomers, wherein the EO is introduced via random or gradient polymerization. Random block polymerization involves co-feeding a primary comonomer (i.e., AO) and a secondary comonomer (i.e., EO) at a fixed AO / EO ratio during polymerization. The resulting random block comprises secondary comonomers (typically EO) randomly spaced throughout the block.

[0011] The preparation of AOEO blocks may also include the formation of gradient copolymers, wherein the concentration of secondary comonomers introduced into the reaction (and into the extended polymer chains) varies as polymerization proceeds. Control of the gradient concentration of secondary comonomers can be achieved by any suitable method, including changing the feed rate of one or more comonomers, introducing comonomers with different reactivity, or changing the total time period for feeding the corresponding comonomers into the polymerization zone (e.g., in a batch or continuous reactor). For example, the formation of gradient copolymer blocks [AOEO] may include co-feeding one or more alkyl oxidases (e.g., PO) as the primary feed stream and EO as the secondary feed stream into the polymerization zone, wherein the feeding time from the secondary EO feed stream is shorter than the feeding time from the primary AO feed stream, resulting in a gradual decrease in the concentration of free EO during polymerization. For example, gradient block polymerization may include addition polymerization, wherein a certain concentration of AO is fed within 180 minutes from the start of the reaction, while the secondary (or secondary) comonomer EO is fed within 23 minutes from the start. During gradient polymerization, the feed rate (e.g., weight / minute) can be the same or different.

[0012] After generating random and / or gradient [AOEO] blocks, the multiblock surfactant composition can be capped with additional AO or EO blocks. For example, a multiblock surfactant can be prepared in which [EOPO] undergoes random polymerization followed by addition of EO (e.g., 9 moles) to prepare the target surfactant.

[0013] Multiblock copolymer surfactants may comprise at least one random or graded block copolymer containing one or more EO comonomers and one or more AO comonomers. Multiblock copolymer surfactants also include surfactants “terminated” with EO. The multiblock copolymer surfactants disclosed herein may have the following general formula:

[0014] RO-[AO] x [AO a EO b ] y [EO] c

[0015] Where R is a straight-chain or branched, saturated or unsaturated C6 to C18 carbon chain; AO is a C3 to C6 epoxide alkane, and x ranges from 0 to 10; y is at least 1, [AO aEO b ] represents a block copolymer, wherein a ranges from 1 to 20, b ranges from 0.3 to 3.5, and c ranges from 1 to 50.

[0016] In some cases, multiblock copolymer surfactants have the following general formula:

[0017] R-O-[PO] a EO b ] y [EO] c

[0018] Wherein R is a straight or branched, saturated or unsaturated C6 to C18 carbon chain; y is at least 1 and represents a block copolymer of PO and EO; a ranges from 1 to 20; b ranges from 0.5 to 3.5; and the ratio a / b ranges from 2 to 30; and c ranges from 1 to 50.

[0019] Multiblock copolymer surfactants can have number average molecular weights ranging from 30 Da to 4000 Da or from 30 Da to 3000 Da.

[0020] The multiblock copolymer surfactants disclosed herein may have an average number of hydroxyl groups (OH count) in the range of 20 mg KOH / g to 100 mg KOH / g, 25 mg KOH / g to 90 mg KOH / g, or 25 mg KOH / g to 80 mg KOH / g as defined in ASTM D4274-21.

[0021] The multiblock copolymer surfactants disclosed herein may have a CMC of 1000 ppm or less, 500 ppm or less, or 250 ppm or less.

[0022] The cloud point of the multiblock copolymer surfactants disclosed herein in water can be 30°C or higher, 40°C or higher, or 50°C or higher. In some cases, the multiblock copolymer surfactants disclosed herein may have a cloud point in the range of 30°C to 120°C, 35°C to 100°C, or 40°C to 100°C.

[0023] Applications of multiblock copolymer surfactants include a wide range of formulations and products used for: detergents, washing agents, hard surface cleaning agents, polyurethanes, epoxy resins, thermoplastics, paints, coatings, metal products, agricultural products including herbicides and pesticides, oilfield and mining products, pulp and paper products, textiles, water treatment products, flooring products, inks, colorants, pharmaceuticals, cleaning products, personal care products, lubricants, and combinations thereof. In the preparation of these and other types of formulations and products, multiblock copolymer surfactants can contribute to or enhance desired properties such as surface activity, detergency, wetting, rewetting, defoaming, additive stability, latex stability, drug delivery capabilities, emulsification, rinsing, plasticizing, reactive dilution, rheology modification, suspension, pseudoplasticizing, thickening, curing, impact modification, lubrication, emulsification and microemulsification, and combinations thereof.

[0024] Examples of these applications include: as a general-purpose surfactant; as a low-foaming surfactant for household and commercial cleaning; as a low-foaming surfactant in mechanical cleaning processes; as a reactive diluent in casting, encapsulation, flooring, potting, adhesives, laminating materials, reinforcing plastics, and filament winding; as a coating; as a wetting agent; as a rinsing aid; as a defoamer / low-foaming agent; as a spray cleaner; as an emulsifier for herbicides and pesticides; as a metal cleaner; as a suspending agent and emulsifier for paints and coatings; as a mixing enhancer in the preparation of micro-heterogeneous mixtures of organic compounds in polar and non-polar carrier fluids for agricultural sprays and crop growth promoters; as a latex stabilizer; as a microemulsifier for pulp and paper products; and so on.

[0025] The surfactant of the present invention can be used as a component in a fully formulated detergent in hard surface cleaning preparations, such as dishwashing detergent for automatic dishwashers. To use the surfactant of the present invention as a dishwasher detergent, a detergent composition containing the surfactant is placed in an automatic dishwasher.

[0026] Although the formulation components and properties have been disclosed individually, it is contemplated that component elements can be included, excluded, or combined in any manner or sub-combination using any of the above concentration ranges and nested sub-ranges therein. Furthermore, the formulation properties can be similarly achieved through various combinations of the components within the said ranges.

[0027] The numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, and all values ​​between the lower limit and the upper limit. Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are by weight, and all test methods are current methods as of the date of this disclosure.

[0028] Example

[0029] The following examples are provided to illustrate embodiments of the invention, but are not intended to limit the scope of the invention. Table 1 provides the materials used in the following examples.

[0030]

[0031] Example 1: Synthesis of Multiblock Copolymer Surfactants

[0032] Surfactant 1 of the present invention: A multiblock copolymer surfactant containing random EOPO blocks having a 2EH+[r-1.5EO9PO]+9EO structure was prepared as follows. 500.9 g of 2-ethylhexanol and 14.31 g of a 45% potassium hydroxide aqueous solution were loaded into a 15 L conical reaction vessel equipped with a magnetically coupled stirrer head and a temperature controller. The solution was stirred at 200 rpm and heated to 105 °C. A vacuum was applied to maintain the solution at 30 mBar to remove water. After two hours under the above conditions, the residual water was measured to be 510 ppm using a Karl Fischer titration apparatus. The solution was cooled to 100 °C and nitrogen gas was introduced into the reactor to release the vacuum.

[0033] The alkoxylation reaction was carried out in two steps. In the first step, 2008 g of 1,2-propane oxide and 254 g of ethylene oxide were co-fed into the solution at 135 °C over 240 minutes with stirring at 320 rpm. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 8 hours to digest all the oxides present. In the second step, 1523 g of ethylene oxide was fed at 135 °C at a constant feed rate over 390 minutes. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 4 hours to digest all the oxides present. Throughout both steps, the pressure in the reaction vessel was closely monitored, and the oxide feed was appropriately limited so that the pressure did not exceed 3.5 bar. The solution was then cooled to 80 °C, and 10.2 g of a 70% aqueous solution of acetic acid was added. The solution was stirred at 350 rpm for 1 hour.

[0034] Surfactant 2 of the present invention: A multiblock copolymer surfactant containing random EOPO blocks having a 2EH+[r-3.0EO9PO]+9EO structure was prepared as follows. 215.3 g of 2-ethylhexanol and 6.6 g of a 45% potassium hydroxide aqueous solution were loaded into a 15 L conical reaction vessel equipped with a magnetically coupled stirrer head and a temperature controller. The solution was stirred at 200 rpm and heated to 105 °C. A vacuum was applied to maintain the solution at 30 mBar to remove water. After two hours under the above conditions, the residual water was measured to be 1060 ppm using a Karl Fischer titration apparatus. The solution was cooled to 100 °C and nitrogen gas was introduced into the reactor to release the vacuum.

[0035] The alkoxylation reaction was carried out in two steps. In the first step, 863 g of 1,2-propane oxide and 218 g of ethylene oxide were co-fed into the solution at 135 °C over 180 minutes with stirring at 320 rpm. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 6 hours to digest all the oxides present. In the second step, 614.6 g of ethylene oxide was fed at 135 °C at a constant feed rate over 360 minutes. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 4 hours to digest all the oxides present. Throughout both steps, the pressure in the reaction vessel was closely monitored, and the oxide feed was appropriately limited so that the pressure did not exceed 3.5 bar. The solution was then cooled to 80 °C, and 4.6 g of 70% aqueous acetic acid was added. The solution was stirred at 350 rpm for 1 hour.

[0036] Surfactant 3 of the present invention: A multi-block copolymer surfactant containing gradient EOPO blocks having a structure of 2EH+4PO+[g-1.5EO5PO]+9EO is prepared as follows. 212.7 g of 2-ethylhexanol and 6.1 g of a 45% potassium hydroxide aqueous solution are loaded into a 15 L conical reaction vessel equipped with a magnetically coupled stirrer head and a temperature controller. The solution is stirred at 200 rpm and heated to 105 °C. A vacuum is applied to maintain the solution at 30 mBar to remove water. After two hours under the above conditions, the residual water content is measured to be 500 ppm using a Karl Fischer titration apparatus. The solution is cooled to 100 °C and nitrogen gas is introduced into the reactor to release the vacuum.

[0037] The alkoxylation reaction was carried out in three steps. In the first step, 367.7 g of propylene oxide was fed into the solution at 135 °C over 60 minutes with stirring at 320 rpm. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 0.5 hours to digest some of the remaining oxides. In the second step, 460 g of 1,2-propylene oxide and 105 g of ethylene oxide were co-fed into the solution at 135 °C with stirring at 320 rpm. In this step, both oxides were fed simultaneously at the same feed rate. Ethylene oxide was added over 25 minutes, while the propylene oxide feed was completed over 110 minutes. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 6 hours to digest all the remaining oxides.

[0038] In the third step, 627.6 g of ethylene oxide was fed at a constant feed rate over 360 minutes at 135 °C. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 4 hours to digest all the oxides present. Throughout both steps, the pressure in the reaction vessel was closely monitored, and the oxide feed was appropriately limited so that the pressure did not exceed 3.5 bar. The solution was then cooled to 80 °C, and 4.3 g of a 70% aqueous solution of acetic acid was added. The solution was stirred at 350 rpm for 1 hour.

[0039] Surfactant 4 of the present invention: A multiblock copolymer surfactant containing gradient EOPO blocks having a structure of 2EH+4PO+[g-3EO5PO]+9EO was prepared as follows. 218.6 g of 2-ethylhexanol and 6.7 g of a 45% potassium hydroxide aqueous solution were loaded into a 15 L conical reaction vessel equipped with a magnetically coupled stirrer head and a temperature controller. The solution was stirred at 200 rpm and heated to 105 °C. A vacuum was applied to maintain the solution at 30 mBar to remove water. After two hours under the above conditions, the residual water was measured to be 830 ppm using a Karl Fischer titration apparatus. The solution was cooled to 100 °C and nitrogen gas was introduced into the reactor to release the vacuum.

[0040] The alkoxylation reaction was carried out in three steps. In the first step, 389.5 g of propylene oxide was fed into the solution at 135 °C over 90 minutes with stirring at 320 rpm. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 0.5 hours to digest some of the remaining oxides. In the second step, 487 g of 1,2-propylene oxide and 222 g of ethylene oxide were co-fed into the solution at 135 °C with stirring at 320 rpm. In this step, the two oxides were fed simultaneously at the same feed rate. Ethylene oxide was added over 50 minutes, while the propylene oxide feed was completed over 110 minutes. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 6 hours to digest all the remaining oxides. In the third step, 627.3 g of ethylene oxide was fed at 135 °C over 360 minutes at a constant feed rate. After all oxides were fed, the reaction was allowed to proceed at 135°C for 4 hours to digest all present oxides. During both steps, the pressure in the reaction vessel was closely monitored, and the oxide feed was appropriately limited so that the pressure did not exceed 3.5 bar. The solution was then cooled to 80°C, and 4.8 g of a 70% aqueous solution of acetic acid was added. The solution was stirred at 350 rpm for 1 hour.

[0041] Surfactant 5 of the present invention: A multi-block copolymer surfactant containing gradient EOPO blocks having a 2EH+[g-1.5EO5PO]+9EO structure was prepared as follows. 226.1 g of 2-ethylhexanol and 6.5 g of a 45% potassium hydroxide aqueous solution were loaded into a 15 L conical reaction vessel equipped with a magnetically coupled stirrer head and a temperature controller. The solution was stirred at 200 rpm and heated to 105 °C. A vacuum was applied to maintain the solution at 30 mBar to remove water. After two hours under the above conditions, the residual water was measured to be 580 ppm using a Karl Fischer titration apparatus. The solution was cooled to 100 °C and nitrogen gas was introduced into the reactor to release the vacuum.

[0042] The alkoxylation reaction was carried out in two steps. In the first step, 898 g of 1,2-propane oxide and 114 g of ethylene oxide were co-fed into the solution at 135 °C with stirring at 320 rpm. The two oxides were fed simultaneously at the same feed rate. Ethylene oxide was added within 23 minutes, while the propylene oxide feed was completed within 180 minutes. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 6 hours to digest all present oxides. In the second step, 681 g of ethylene oxide was fed at 135 °C at a constant feed rate over 360 minutes. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 4 hours to digest all present oxides. Throughout both steps, the pressure in the reaction vessel was closely monitored, and the oxide feed was appropriately limited so that the pressure did not exceed 3.5 bar. The solution was then cooled to 80 °C, and 4.6 g of a 70% aqueous solution of acetic acid was added. The solution was stirred at 350 rpm for 1 hour.

[0043] Surfactant 5 of the present invention: A multiblock copolymer surfactant containing gradient EOPO blocks having a 2EH+[g-3.0EO5PO]+9EO structure was prepared as follows. 221.7 g of 2-ethylhexanol and 6.7 g of a 45% potassium hydroxide aqueous solution were loaded into a 15 L conical reaction vessel equipped with a magnetically coupled stirrer head and a temperature controller. The solution was stirred at 200 rpm and heated to 105 °C. A vacuum was applied to maintain the solution at 30 mBar to remove water. After two hours under the above conditions, the residual water was measured to be 750 ppm using a Karl Fischer titration apparatus. The solution was cooled to 100 °C and nitrogen gas was introduced into the reactor to release the vacuum.

[0044] The alkoxylation reaction was carried out in two steps. In the first step, 889 g of 1,2-propane oxide and 225 g of ethylene oxide were co-fed into the solution at 135 °C with stirring at 320 rpm. The two oxides were fed simultaneously at the same feed rate. Ethylene oxide was added within 46 minutes, while the propylene oxide feed was completed within 180 minutes. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 6 hours to digest all present oxides. In the second step, 634 g of ethylene oxide was fed at 135 °C at a constant feed rate over 360 minutes. After all oxides were fed, the reaction was allowed to proceed at 135 °C for 4 hours to digest all present oxides. Throughout both steps, the pressure in the reaction vessel was closely monitored, and the oxide feed was appropriately limited so that the pressure did not exceed 3.5 bar. The solution was then cooled to 80 °C, and 4.7 g of a 70% aqueous solution of acetic acid was added. The solution was stirred at 350 rpm for 1 hour.

[0045] The physical properties of the surfactant of this invention were then investigated, as shown in Table 2. The number of hydroxyl groups (in KOH) was measured using ASTM D4274D. The number-average molecular weight was calculated as: 56100 / number of OH groups * polymer functionality (one in this case).

[0046]

[0047] Example 2: Surfactant Performance

[0048] In this embodiment, the properties of the surfactant were analyzed to quantify the performance of the surfactant of the present invention relative to a comparative sample. The results are shown in Table 3. The surfactant performance was first evaluated by measuring the cloud point and critical micelle concentration (CMC) of each alkoxylated product at a 1 wt% aqueous solution concentration.

[0049] Table 1 summarizes the results. The new series of 2EH+[ ]+9EO surfactants exhibits a low CMC of approximately 100 ppm, significantly lower than that of the comparative surfactant 1. This new approach allows for a reduction of approximately one order of magnitude in CMC while maintaining similar surfactant properties, such as surface tension, pour point, solubility, and contact angle.

[0050]

[0051] Example 3: Biodegradability Test

[0052] The biodegradability of these novel surfactants was assessed according to OECD Guideline 301D: Respiration Measurement Tests. Biodegradation was evaluated in duplicate reaction mixtures containing a defined mineral culture medium inoculated with activated sludge biosolids (30 mg / L dry weight) from a wastewater treatment plant in the City of Midland (Michigan, USA). Biodegradation of a reference substance (aniline) was also measured in duplicate to assess inoculum viability and determine the accuracy of the respiration measurements. Oxygen consumption and carbon dioxide release in the continuously stirred (22°C) reaction mixture were measured at 6-hour intervals during a 28-day test period using a respiration meter. Respiration in the biodegradation reaction was corrected for respiration occurring in an inoculated blank containing only the inoculated mineral culture medium, and this net respiration was compared to the ThOD and theoretical carbon dioxide production (ThCO2) of each substance to determine the percentage of biodegradation based on oxygen consumption (DO2) and carbon dioxide release (DCO2).

[0053] The surfactants of this invention reach a level (60% DO2) within 28 days, indicating that these materials meet the OECD standard currently classified as "biodegradable".

[0054] Example 4: Clothing Washing Application Test

[0055] In this embodiment, a surfactant formulation was prepared and its ability to remove sebum from fabrics was analyzed. A primary cleaning test was performed using a staining tester with six parallel 2L drums, each filled with 1L of 120ppm Ca:Mg 3:1 hardness-adjusted water, and the washing temperature was set to 86℉ (30°C). The test detergent formulation was added at a dosage level of 0.3g / L, and the spindle speed of the staining tester was adjusted to 85rpm. Four 5cm × 5cm test fabrics from PC-S-94 dust and sebum samples were added to each drum and washed for 30 minutes. The fabrics were then removed, the washing solution drained, and hardness-adjusted water was added to the drums. The washed fabrics were returned to the drums and rinsed for 3 minutes. They were then removed and dried in a dryer at a "warm" setting for 60 minutes.

[0056] Color space analysis was used to determine the effectiveness of stain removal. The L*, a*, and b* values ​​of the stained fabric were measured before washing (US) and after washing (WS) using a Mach 5 spectrophotometer from Colour Consult. The L*, a*, and b* values ​​of unwashed, unstained polyester-cotton fabric (UF) were measured below for SRI calculation:

[0057]

[0058] Where: US = unwashed soiled area, UF = unwashed (unsoiled) fabric area, WS = washed soiled area. ΔE (US−UF) = ΔE color difference between the unwashed stain and the unwashed fabric, where ΔE (WS−UF) = ΔE color difference between the washed stain and the unwashed fabric. The ΔE* value is calculated as: ΔE* = (ΔL) / (W-UF) * UF / (W-UF) = ΔE / UF. 2 + Δa 2 + Δb 2 ) 0.5

[0059] The test was repeated twice, and the data from the two tests were combined to compare the performance of detergents with different test surfactants.

[0060] The unit dosage formulation for laundry detergents, with ingredients listed in the order of addition, is provided in Table 4, wherein the active ingredient comprises 55% and the pH is adjusted to approximately 8-8.5. The results are shown in Tables 5 and 6.

[0061]

[0062]

[0063]

[0064] Example 5: Hard Surface Cleaning Test

[0065] In this embodiment, a surfactant is used to generate a cleaning formulation for removing dirt from a hard surface (i.e., vinyl tile), and the results are evaluated according to the Gardner scrubbing test (as outlined in ASTM D-2486). The results are quantified by the grayscale value of the scrubbed area after treatment. The cleaning percentage is calculated as (grayscale value after cleaning - grayscale value of the contaminated tile) / (grayscale value of the uncontaminated tile - grayscale value of the contaminated tile) × 100%.

[0066] The staining formulation contained 8.15 wt% soybean oil, 27.62 wt% triglycerides, 3.17 wt% carbon black, and 61.06 wt% VM&P naphtha. The stain was applied to tiles and tested as non-crosslinked (drying at room temperature (25°C) for 12–24 hours) or crosslinked (oven drying at 71°C for 18 hours, then cooling to room temperature). Cleaning formulations were prepared based on the general formulations shown in Table 7, and their stability was then visually observed and tested via a scrubbing test. The results are shown in Table 8.

[0067]

[0068]

[0069] For hard surface cleaning applications, comparative surfactant 1 is used as a commercial benchmark for hard surface cleaning performance. A higher cleaning percentage value indicates higher cleaning efficiency. For both non-crosslinked and crosslinked ceramic tiles, the surfactants of the present invention containing random or gradient copolymer blocks exhibit comparable or improved cleaning performance relative to comparative surfactant 1, with surfactant 5 of the present invention exhibiting the best cleaning performance.

[0070] While the foregoing relates to exemplary embodiments, other and additional embodiments may be devised without departing from the basic scope of the invention, the scope of which is defined by the appended claims.

Claims

1. A surfactant composition comprising: One or more multiblock copolymer surfactants having the following general formula RO-[AO] x [TO THE a AND THE b ] y [AND THE] c Where R is a straight-chain or branched, saturated or unsaturated C6 to C18 carbon chain; AO is a C3 to C6 epoxide alkane, and x ranges from 0 to 5; y is at least 1, [AO a EO b ] represents a block copolymer, wherein a ranges from 1 to 20, b ranges from 0.5 to 3.5, and c ranges from 1 to 50.

2. The composition according to claim 1, wherein [AO] a EO b [ ] is a gradient block copolymer.

3. The composition according to claim 1, wherein [AO] a EO b [ ] is a random block copolymer.

4. The composition according to claim 1, wherein the a / b ratio of the one or more multiblock copolymer surfactants ranges from 2 to 30.

5. The composition according to claim 1, wherein the one or more multiblock copolymer surfactants have the following general formula: R- O-[PO a IS b ] y [IS] c Wherein R is a straight or branched, saturated or unsaturated C6 to C18 carbon chain; y is at least 1 and represents a block copolymer of PO and EO; a ranges from 1 to 20; b ranges from 0.5 to 3.5; and the ratio a / b ranges from 2 to 30; and c ranges from 1 to 50.

6. The composition according to claim 1, wherein the one or more multiblock copolymer surfactants are generated by: In the presence of alcohol R-OH, one or more C3 to C6 epoxides are polymerized to generate the first product; In the presence of the first product, a mixture of one or more alkyl oxidants and ethylene oxides is polymerized to generate r, wherein the one or more alkyl oxidants and ethylene oxides are co-fed at an a / b ratio of 2 to 30 to generate the second product; and Ethylene oxide is polymerized in the presence of the second product.

7. A method of using a surfactant according to any of the preceding claims, the method comprising using the composition to clean a substrate.

8. The method of claim 7, wherein the substrate is a textile or a solid surface.

9. A method for preparing a multiblock copolymer surfactant, wherein the multiblock copolymer surfactant has the following general formula: R- O-[AO] x [TO THE a AND THE b ] y [AND THE] c Where R is a straight-chain or branched, saturated or unsaturated C6 to C18 carbon chain; AO is a C3 to C6 epoxide alkane, and x ranges from 0 to 5; y is at least 1, [AO a EO b ] indicates a block copolymer, wherein a ranges from 1 to 20, b ranges from 0.5 to 3.5, and c ranges from 1 to 50; The method includes: In the presence of alcohol R-OH, one or more C3 to C6 epoxides are polymerized to generate the first product; In the presence of the first product, a mixture of one or more alkyl oxidants and ethylene oxide is polymerized to form a block [AO] a EO b And generate a second product; as well as In the presence of the second product, ethylene oxide is polymerized to generate the multiblock copolymer surfactant.

10. The method of claim 9, wherein the mixture of one or more alkyl oxidants and ethylene oxide is polymerized to form block [AO] a EO b This includes co-feeding the one or more alkyl oxidants as the main feed stream and the ethylene oxide as the secondary feed stream into the polymerization zone, wherein the feeding time from the secondary feed stream is shorter than the feeding time from the main feed stream.

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