A composite thickener for quaternary ammonium salt system in weak acid environment

Abstract

The present application provides a kind of composite thickening agent for quaternary ammonium salt system in weak acid environment, belongs to the field of thickening agent;The formula includes cationic guar gum, silicone oil, cationic cellulose, zwitterionic buffer.The present application solves the problem of thickening and quaternary ammonium salt bactericide compatibility in weak acid system of quaternary ammonium salt-containing organic acid pickling agent by charge synergy of cationic guar gum and ester quaternary ammonium salt, network strengthening of cationic cellulose and pH stability of zwitterionic buffer.

Description

Technical Field

[0001] This invention relates to the field of thickener technology, and more particularly to a composite thickener that can be used in quaternary ammonium salt systems under weakly acidic conditions. Background Technology

[0002] Pickling agents, as the core preparations for industrial cleaning and metal surface treatment, are mainly divided into three categories: inorganic acids, organic acids, and composite types.

[0003] Inorganic acids (such as hydrochloric acid, sulfuric acid, and nitric acid) can quickly dissolve metal oxides and stubborn scale due to their strong acidity. For example, hydrochloric acid can efficiently remove rust, while sulfuric acid accelerates the reaction at high temperatures. However, its strong corrosiveness can easily damage the metal substrate (especially stainless steel and aluminum, which may cause pitting or stress corrosion). Moreover, cleaning waste liquid often contains toxic components such as chloride ions and nitrites, so corrosion inhibitors are needed and operating conditions must be strictly controlled.

[0004] In contrast, organic acids (such as citric acid, EDTA, and glycolic acid) are mild and dissolve metal oxides through complexation, significantly reducing the risk of substrate corrosion. For example, citric acid achieves gentle rust removal in boiler cleaning by complexing iron ions, while aminosulfonic acid does not corrode galvanized metals, making it the only choice for cleaning galvanized materials.

[0005] The core advantages of organic acids lie in their environmental friendliness and material compatibility: their waste liquids have low toxicity and are partially biodegradable (such as glycolic acid), meeting green industrial standards; they are also more adaptable to sensitive materials such as stainless steel and copper alloys. For example, citric acid does not damage the passivation layer when cleaning austenitic steel, and EDTA can complete cleaning and passivation in one step, reducing secondary corrosion. Furthermore, organic acids can be compounded to enhance their functionality (e.g., mixing glycolic acid and formic acid enhances their scale-dissolving ability) and meet the stringent hygiene requirements of the food and medical fields (e.g., food-grade CIP cleaning agents). Although organic acids are more expensive, their low pollution and high safety characteristics make them more competitive in precision instruments and environmentally sensitive applications. In the future, with advancements in compound formulation technology, they will further balance efficiency and sustainability needs, becoming the mainstream direction for high-end manufacturing and green cleaning.

[0006] Thickeners are added to pickling agents to increase viscosity and enhance the adhesion of the liquid to vertical surfaces, thus extending the contact time between the acid and dirt or rust and improving cleaning efficiency. At the same time, it reduces the risk of acid mist splashing and spraying, improving operational safety.

[0007] However, the acidic thickeners currently used in commercial formulations are mainly designed for thickening strong acids such as hydrochloric acid. To address the issue of decreased antibacterial efficacy when replacing strong acids with weak ones, quaternary ammonium salts are commonly used in combination. However, this combination approach presents new challenges for the formulation thickeners:

[0008] 1) Traditional acidic thickeners, such as oleamine polyoxyethylene ethers, only have a good thickening effect on strong acids. After thickening, the system is stable and does not easily become thinner during storage (the main mechanism is that under strong acid conditions, oleamine polyoxyethylene ethers form stable chemical bonds with acids, and the intermolecular forces are strong, which can resist the influence of external factors and maintain the viscosity and performance stability of the system). However, in weak acid systems, the thickening effect is very weak because the hydrogen ion concentration of weak acids is low, and the interaction with oleamine polyoxyethylene ethers is not as strong as that of strong acids. The resulting micelle structure is unstable, resulting in low thickening degree and poor stability. With the passage of time or changes in the environment, phenomena such as viscosity reduction and stratification may occur.

[0009] 2) Most formulas on the market that use weak acids as pickling agents employ hydrophilic colloids as thickeners. However, when compounded with quaternary ammonium salt bactericides, most hydrophilic polymer thickeners are incompatible with quaternary ammonium salts because they have anionic functional groups in their structure.

[0010] Currently, there are no thickeners on the market that are completely compatible with the same formulation scenarios. For example, in the case of organic acid systems, anionic colloids such as xanthan gum are generally used as thickeners, but the formulations used cannot contain cationic components such as quaternary ammonium salts. Because weak acids themselves have weak bactericidal ability, their bactericidal and sterilization effects in bathrooms and other places are limited. Compounding with quaternary ammonium salts can greatly compensate for this effect, but it is incompatible with anionic colloids such as xanthan gum. Therefore, organic acid pickling agents can only be compounded with quaternary ammonium salts but have no viscosity, or have high viscosity but cannot be compounded with quaternary ammonium salts. There is currently no perfect solution. Summary of the Invention

[0011] This invention provides a composite thickener that can be used in quaternary ammonium salt systems under weakly acidic conditions, thereby filling the current market gap.

[0012] In a first aspect, the present invention provides a composite thickener containing, by weight percentage, the following components:

[0013] 36-48% cationic guar gum

[0014] 24-35% silicone oil

[0015] 3.6-5% cationic cellulose

[0016] 0.18-0.45% zwitterionic buffer;

[0017] The thickener is dissolved in an alcohol solvent.

[0018] The silicone oil is either cationic or nonionic.

[0019] Preferably, the silicone oil is a cationic silicone oil.

[0020] More preferably, the silicone oil is an uncapped cationic silicone oil.

[0021] More preferably, the silicone oil is an amino silicone oil.

[0022] Preferably, the alcohol solvent is a C2-C9 alcohol.

[0023] More preferably, the alcohol solvent is a C7-C9 long-chain alcohol.

[0024] Preferably, the zwitterionic buffer is 2-morpholine ethanesulfonic acid and / or 3-morpholine propanesulfonic acid.

[0025] Secondly, the present invention also provides the application of the aforementioned composite thickener in organic acid pickling agents containing quaternary ammonium salt disinfectants.

[0026] Preferably, it is added to the organic acid pickling agent in the form of a pre-dissolved alcohol solvent.

[0027] Preferably, the amount added in this invention is 0.1-1.5% of the total mass of the pickling agent, in order to adjust the viscosity to within 100-2000 mPa·s.

[0028] This invention uses cationic guar gum and ester-based quaternary ammonium salts as core thickening components, both of which are cationic or nonionic structures. This avoids the charge conflict problem between traditional anionic thickeners and quaternary ammonium salts, achieving efficient compounding of quaternary ammonium salt bactericides in weak acid systems and solving the pain point that "thickening and bactericidal cannot coexist".

[0029] Cationic guar gum binds to negatively charged fibers or particles (such as quaternary ammonium salt bactericides) through the positive charge of its quaternary ammonium groups, forming a stable hydrogen bond and electrostatic adsorption network. Its mannose-galactose backbone provides physical cross-linking points, enhancing system viscosity; it is charge-compatible with quaternary ammonium salt bactericides, avoiding the precipitation problems of traditional anionic thickeners (such as xanthan gum). Simultaneously, the quaternary ammonium groups in pickling agents synergistically form a cationic network with cationic guar gum, improving viscosity stability; the hydrogen bonds between the quaternary ammonium groups and guar gum are complementary, forming a three-dimensional network; and the hydroxyethyl group enhances water solubility and improves low-temperature stability.

[0030] Cationic silicone oils remain stable even under acidic conditions of pH 4-6. They adsorb positively charged bands onto metal surfaces, forming a dense film structure that improves thickening efficiency and durability.

[0031] Nonionic silicone oils offer advantages such as wide pH adaptability, no charge limitation, compatibility with anionic / cationic systems without charge repulsion issues, and suitability for complex formulations. Different silicone oils can be selected based on the specific pH and concentration of the pickling agent.

[0032] The active groups at the ends of the uncapped silicone oil molecular chains (such as hydroxyl and amino groups) can crosslink rapidly, and adding a small amount can significantly improve viscosity; moreover, the flowability and anti-splatter properties are better after thickening.

[0033] Amphoteric buffers maintain charge balance through the buffering effect of sulfonic acid groups and morpholine rings, preventing the aggregation of cationic components due to pH fluctuations and ensuring the charge stability of cationic components under weakly acidic conditions.

[0034] Alcohols are used as solvents to pre-dissolve the components, ensuring that the thickener dissolves quickly in acidic media and avoiding problems such as local clumping or uneven viscosity. At the same time, if long-chain alcohols are used, they also have an antifoaming effect, which breaks down the foam film by reducing surface tension and reducing the negative impact on viscosity.

[0035] This invention solves the problem of compatibility between thickening agents and quaternary ammonium salt bactericides in weak acid systems by utilizing the charge synergy between cationic guar gum and ester-based quaternary ammonium salts, the network reinforcement of cationic cellulose, and the pH stabilization of zwitterionic buffers. Attached Figure Description

[0036] Figure 1 This describes the effect of the composite thickener provided in Example 1 of the present invention when added to an organic acid pickling agent.

[0037] Figure 2 This describes the effect of the composite thickener provided in Example 7 of the present invention when added to an organic acid pickling agent.

[0038] Figure 3 This describes the effect of the composite thickener provided in Example 8 of the present invention when added to an organic acid pickling agent. Detailed Implementation

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] Unless otherwise specified, the experimental methods used in the specific implementation methods are all conventional methods, and the materials and reagents used are all commercially available unless otherwise specified.

[0041] In this invention, unless otherwise specified, "%" represents a percentage by mass; the raw materials and reagents used are all commercially available products.

[0042] The guar gum used in this invention is guar hydroxypropyltrimethylammonium chloride (cationic type) and carboxymethyl guar gum (anionic type).

[0043] The silicone oils used in this invention are hydroxyl silicone oil (nonionic), amino silicone oil (cationic), and polydimethylsiloxane alcohol (anionic).

[0044] The alcohols used in this invention are ethanol (C2), n-heptanol (C7), isohexanediol (C8), 1-nonanol (C9), and n-undecyl alcohol (C1). 11 ).

[0045] The cellulose used in this invention is cationic cellulose and carboxymethyl cellulose, respectively.

[0046] The organic acid pickling agent used in this invention comprises the following components:

[0047] 15% citric acid

[0048] 3% succinic acid

[0049] 2% oxalic acid

[0050] 0.4% of decyl dimethyl ammonium chloride

[0051] Water balance.

[0052] Example 1

[0053] A method for preparing a composite thickener includes the following steps:

[0054] S1 Weighing: Weigh each component according to the following mass fractions:

[0055] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0056] 24 parts amino silicone oil

[0057] 3.6 parts cationic cellulose

[0058] 0.18 parts of 2-morpholinoethanesulfonic acid

[0059] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0060] Example 2

[0061] A method for preparing a composite thickener includes the following steps:

[0062] S1 Weighing: Weigh each component according to the following mass fractions:

[0063] 42 parts guar gum hydroxypropyltrimethylammonium chloride

[0064] 30 parts amino silicone oil

[0065] 4.2 parts cationic cellulose

[0066] 0.32 parts of 3-morpholinopropanesulfonic acid

[0067] S2 Mixing: Take n-heptanol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of iso-n-heptanol to other components is 1:1; after mixing, seal for later use.

[0068] Example 3

[0069] A method for preparing a composite thickener includes the following steps:

[0070] S1 Weighing: Weigh each component according to the following mass fractions:

[0071] 48 parts of guar gum hydroxypropyltrimethylammonium chloride

[0072] 35 parts amino silicone oil

[0073] 5.0 parts cationic cellulose

[0074] 0.45 parts of 3-morpholinopropanesulfonic acid

[0075] S2 Mixing: Take 1-nonanol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of 1-nonanol to other components is 1:1; after mixing, seal and store for later use.

[0076] Example 4

[0077] A method for preparing a composite thickener includes the following steps:

[0078] S1 Weighing: Weigh each component according to the following mass fractions:

[0079] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0080] 24 parts hydroxy silicone oil

[0081] 3.6 parts cationic cellulose

[0082] 0.18 parts of 2-morpholinoethanesulfonic acid

[0083] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0084] Example 5

[0085] A method for preparing a composite thickener includes the following steps:

[0086] S1 Weighing: Weigh each component according to the following mass fractions:

[0087] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0088] 24 parts amino silicone oil

[0089] 3.6 parts cationic cellulose

[0090] 0.18 parts of 2-morpholinoethanesulfonic acid

[0091] S2 Mixing: Take ethanol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of ethanol to other components is 1:1; after mixing, seal and store for later use.

[0092] Example 6

[0093] A method for preparing a composite thickener includes the following steps:

[0094] S1 Weighing: Weigh each component according to the following mass fractions:

[0095] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0096] 24 parts amino silicone oil

[0097] 3.6 parts cationic cellulose

[0098] 0.18 parts of 2-morpholinoethanesulfonic acid

[0099] S2 Mixing: Take n-undecyl alcohol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of n-undecyl alcohol to other components is 1:1; after mixing, seal and store for later use.

[0100] Example 7

[0101] A method for preparing a composite thickener includes the following steps:

[0102] S1 Weighing: Weigh each component according to the following mass fractions:

[0103] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0104] 24 parts amino silicone oil

[0105] 3.6 parts carboxymethyl cellulose

[0106] 0.18 parts of 2-morpholinoethanesulfonic acid

[0107] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0108] Example 8

[0109] A method for preparing a composite thickener includes the following steps:

[0110] S1 Weighing: Weigh each component according to the following mass fractions:

[0111] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0112] 24 parts of polydimethylsiloxane alcohol

[0113] 3.6 parts cationic cellulose

[0114] 0.18 parts of 2-morpholinoethanesulfonic acid

[0115] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0116] Example 9

[0117] A method for preparing a composite thickener includes the following steps:

[0118] S1 Weighing: Weigh each component according to the following mass fractions:

[0119] 36 parts carboxymethyl guar gum

[0120] 24 parts amino silicone oil

[0121] 3.6 parts cationic cellulose

[0122] 0.18 parts of 2-morpholinoethanesulfonic acid

[0123] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0124] Example 10

[0125] A method for preparing a composite thickener includes the following steps:

[0126] S1 Weighing: Weigh each component according to the following mass fractions:

[0127] 24 parts amino silicone oil

[0128] 3.6 parts cationic cellulose

[0129] 0.18 parts of 2-morpholinoethanesulfonic acid

[0130] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0131] Example 11

[0132] A method for preparing a composite thickener includes the following steps:

[0133] S1 Weighing: Weigh each component according to the following mass fractions:

[0134] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0135] 3.6 parts cationic cellulose

[0136] 0.18 parts of 2-morpholinoethanesulfonic acid

[0137] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0138] Example 12

[0139] A method for preparing a composite thickener includes the following steps:

[0140] S1 Weighing: Weigh each component according to the following mass fractions:

[0141] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0142] 24 parts amino silicone oil

[0143] 0.18 parts of 2-morpholinoethanesulfonic acid

[0144] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0145] Example 13

[0146] A method for preparing a composite thickener includes the following steps:

[0147] S1 Weighing: Weigh each component according to the following mass fractions:

[0148] 36 parts guar gum hydroxypropyltrimethylammonium chloride

[0149] 24 parts amino silicone oil

[0150] 3.6 parts cationic cellulose

[0151] S2 Mixing: Take isohexyl glycol and add the aforementioned components while stirring slowly until a homogeneous emulsion is formed; the mass ratio of isohexyl glycol to other components is 1:1; after mixing, seal and store for later use.

[0152] After adding the aforementioned embodiment to the pickling agent, a corresponding viscosity test was performed. The test method is as follows:

[0153] Test Standard: GB / T 15357-2014 Surfactants and Detergents - Determination of Viscosity and Flow Properties of Liquid Products by Rotation Viscometer

[0154] Test environment: Standard atmospheric pressure, 25℃

[0155] Test sample: A certain amount of the example was added to the aforementioned pickling agent, stirred for 1 minute and then allowed to stand for 30 minutes.

[0156] The results are shown in Table 1.

[0157] Table 1

[0158]

[0159]

[0160] According to the results in Table 1, when the addition amount of the present invention is 0.2-3% (half of which is solvent), the viscosity of the system is within 300-1000 (Examples 1, 2, and 3), which meets the normal usage requirements of pickling agents. However, when the addition amount reaches 3%, the viscosity is too high, which is a special requirement under specific scenarios. Generally speaking, there are currently no usage scenarios for organic acid pickling agents with a viscosity above 1800. Figure 1 The results are from Example 1 at an addition amount of 3%; it can be seen that at this addition amount, the organic acid detergent remains transparent and exhibits wall adhesion (a phenomenon at a certain viscosity).

[0161] Example 4 used hydroxyl silicone oil, Example 5 used short-chain alcohol ethanol, and Example 6 used n-11 alcohol, the longest-chain alcohol that is liquid at room temperature; their viscosity data differed significantly but were still within a suitable viscosity range, proving that the present invention has wide applicability.

[0162] Example 7 uses carboxymethyl cellulose, an anionic compound. In the system, electrostatic attraction between the anions and cations occurs, forming a white, insoluble complex precipitate (e.g., ...). Figure 2 As shown in the figure, this leads to a significant decrease in viscosity, making it impossible to achieve the thickening effect.

[0163] Example 8 uses polydimethylsiloxane alcohol (anionic silicone oil) and cationic guar gum to form a three-dimensional physical cross-linked network, forming a gel-like substance that causes a sharp increase in viscosity (e.g. Figure 3 (As shown).

[0164] Example 9 used carboxymethyl guar gum and exhibited the same phenomenon as in Example 8.

[0165] Examples 10, 11, 12, and 13 show the experimental results of systems lacking guar gum, silicone oil, cellulose, and 2-morpholine ethanesulfonic acid, respectively. It can be seen that the absence of any one of these components will result in a slight decrease in viscosity.

[0166] In summary, based on the experimental data in Table 1, since all examples 1-13 were dissolved in the same mass of alcohol, the actual concentration was half of that in Table 1. Therefore, in practical applications, the addition amount of this invention is within a reasonable range of 0.1-1.5%.

[0167] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A composite thickener, characterized in that, It contains the following components by mass percentage: 36-48% cationic guar gum 24-35% silicone oil 3.6-5% cationic cellulose 0.18-0.45% zwitterionic buffer; The silicone oil is either a cationic silicone oil or a nonionic silicone oil; The thickener is dissolved in an alcohol solvent; The cationic guar gum is guar gum hydroxypropyltrimethylammonium chloride; The alcohol solvent is a C2-C9 alcohol; The zwitterionic buffer is 2-morpholinoethanesulfonic acid and / or 3-morpholinopropanesulfonic acid.

2. The composite thickener according to claim 1, characterized in that, The silicone oil is a cationic silicone oil.

3. The composite thickener according to claim 2, characterized in that, The silicone oil is an uncapped cationic silicone oil.

4. The composite thickener according to claim 3, characterized in that, The silicone oil is an amino silicone oil.

5. The composite thickener according to claim 1, characterized in that, The alcohol solvent is a long-chain alcohol of C7-C9.

6. The use of the composite thickener according to any one of claims 1-5 in an organic acid pickling agent containing quaternary ammonium salt disinfectant.

7. The application of the composite thickener according to claim 6 in organic acid pickling agents containing quaternary ammonium salt disinfectants, characterized in that, It is added to the organic acid pickling agent in the form of a pre-dissolved alcohol solvent.

8. The application of the composite thickener according to claim 6 in organic acid pickling agents containing quaternary ammonium salt disinfectants, characterized in that, The amount of the composite thickener added to the organic acid pickling agent containing quaternary ammonium salt disinfectant is 0.1-1.5 wt% of the total mass of the pickling agent.

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