A rheology modifier for a hand sanitizer system, and its preparation method and application

Abstract

The present invention provides a rheology modifier for a hand sanitizer system, a preparation method thereof, and an application thereof. The rheology modifier comprises a component A and a component B; wherein the component A comprises a copolymer backbone of a polyisocyanate and a polyether polyol, and its chain ends are capped by an amino-containing cationic end-capping agent, and its structure is shown in the following formula 1: #imgabs0# The component B comprises a copolymer backbone of a polyisocyanate and a polyether polyol, and its chain ends are capped by a carboxylate-containing anionic end-capping agent, and its structure is shown in the following formula 2: #imgabs1# When the rheology modifier of the present invention is added to a high ethanol system, the positive and negative ions in the components A and B attract and bind to each other through charge interaction, establishing a three-dimensional network structure in the entire system, reducing the movement of free molecules in the system, greatly improving the viscosity of the product, and meeting the viscosity requirements for the use of the hand sanitizer. In addition, adding a small amount of this product to the formula system can achieve an ideal viscosity.

Description

Technical Field

[0001] The present invention relates to the field of polymer material preparation, and in particular to a combined rheology modifier containing AB two components for a wash-free hand sanitizer system, and a preparation method and application thereof. Background Art

[0002] Hand sanitizers are hand sanitizers that don't require running water for rinsing. They eliminate the need for towels, water, or soap. With society advocating for water conservation and environmental protection, their role is growing. Composed primarily of cleaning ingredients and volatile solvents, they effectively kill germs on hands and other surfaces, providing a disinfecting and cleansing effect. They have a 99.99% kill rate against over 200 bacterial species, including Escherichia coli, Staphylococcus aureus, Candida albicans, and Pseudomonas aeruginosa.

[0003] Commonly used hand sanitizers on the market are primarily alcohol-based, typically composed of water, alcohol, and a thickener. 75% alcohol is the primary disinfectant, making it similar to a solvent-based system. This makes it difficult for conventional rheology modifiers used in aqueous systems to achieve effective thickening. These rheology modifiers are primarily classified into two categories: water-soluble polymers and associative rheology modifiers.

[0004] Water-soluble polymer rheology modifiers, such as cellulose (HEC) and acrylic thickeners (ASE), have completely hydrophilic molecular structures and contain no hydrophobic structures. These thickeners thicken the aqueous phase by forming hydrogen bonds with water molecules in the system. Carbomer thickeners, homopolymers or heteropolymers of acrylic acid, are a very important class of rheology modifiers. Neutralized carbomers form excellent gel matrices, exhibiting superior thickening, suspending, and emulsifying properties and good compatibility with other excipients. They are often used as adhesives, pharmaceutical excipients, and nutritional supplements, and are particularly widely used in lotions, creams, and gels. They can also be used in hand sanitizers, but they are expensive and inconvenient to use.

[0005] Associative rheology modifiers are primarily polyurethane or polyether-based, water-soluble oligomers containing hydrophobic groups. Their primary structure consists of a hydrophilic, solvated segment in the middle and a hydrophobic endcapping structure at the end. In aqueous systems, the hydrophilic portion of these thickeners forms hydrogen bonds with water, ensuring the dissolution or dispersion of the thickener molecules. In aqueous systems, the hydrophobic portion of the thickener bridges the hydrophobic association with the emulsion, solid particles, and micelles in the aqueous system, forming a three-dimensional network structure and thickening the aqueous system.

[0006] CN112831010A relates to a polyurethane thickener with an ionized multi-arm star structure. The thickener molecule has ionic branched arms. The anionic groups on these arms make the thickener easier to emulsify and disperse, while the cationic groups impart certain anti-electrolyte properties. Furthermore, the multi-branched structure and the longer branched chains on the thickener enhance its thickening ability, provide a more complete associative structure, and save on dosage. However, the hydrophobic structure of this polyurethane thickener prevents association in a high-ethanol-content disposable hand sanitizer system, rendering it incapable of thickening such a system.

[0007] CN108299608 describes an alkali-swellable associative thickener, which is prepared by emulsion polymerization from methacrylic acid, ethyl acrylate, a polyurea crosslinking monomer, a hydrophobic associating monomer, an anionic surfactant, a nonionic surfactant, and an initiator. This thickener is not susceptible to the effects of residual solvent in the aqueous system, additives such as dispersants, and the system's ion concentration, and exhibits excellent stability. However, the backbone of this alkali-swellable thickener shrinks in high-ethanol-content hand sanitizer systems due to reduced polarity, resulting in very low thickening efficiency and failure to meet performance requirements.

[0008] CN101407624B describes a thickener mixture composition and a method for thickening an aqueous system comprising an associative thickener. In the associative thickener, the properties of identical groups attached to or within the associative thickener backbone can be reversibly switched between hydrophilic and hydrophobic. When the groups attached to or within the backbone are rendered hydrophilic, the aqueous thickener is pourable and easily incorporated into aqueous polymer compositions. When the groups are rendered hydrophobic, the thickener effectively performs its thickening function. This change can be easily achieved by adjusting the pH of the associative thickener composition and the aqueous polymer composition being thickened. However, the hydrophobic structure of the associative thickener prevents intermolecular association in systems with high ethanol content, and the carboxylic acid backbone forms weak hydrogen bonds with water, resulting in very low thickening efficiency and failing to meet market demand.

[0009] CN103483491 discloses a method for preparing a powdered carbomer. The method involves polymerizing acrylic acid in a mixed solvent of ethyl acetate and cyclohexane using an oil-soluble initiator to produce a white powder of polyacrylic acid, which has a good thickening effect in aqueous phases and personal care applications. However, the main chain of the powdered carbomer is primarily composed of acrylic acid. In a high-concentration ethanol system, the reduced polarity causes the molecular chains to shrink and agglomerate, significantly reducing the thickening efficiency.

[0010] CN111777707A provides a carbomer for high-concentration alcohol gels. The carbomer is obtained by copolymerizing two or more C10-C30 alkyl methacrylates with acrylic acid, adding a dispersant such as anhydrous potassium carbonate. The carbomer can remain in a gel state in 80% by volume ethanol, exhibits high tolerance to dehydration, and maintains a high-transmittance gel state in high-concentration ethanol. While this powdered carbomer meets the performance requirements of hand sanitizers, its production process is complex, production costs are high, and the use of solvents in its preparation poses significant environmental risks.

[0011] Therefore, developing a rheological additive that can meet the needs of high ethanol systems has become the focus of current research. Summary of the Invention

[0012] To address the aforementioned issues in the prior art, the present invention aims to provide a novel rheology modifier and preparation method for hand sanitizer systems, specifically a combined rheology modifier comprising two components, A and B. The present invention utilizes the fundamental principle of large-scale structure formation through the attraction and combination of positive and negative ions, synthesizing the cationic component A and the anionic component B separately.

[0013] When the rheology modifier is added to a high-ethanol system, the positive and negative ions in components A and B attract and bind to each other through charge interaction, forming a three-dimensional network structure throughout the system. This reduces the movement of free molecules within the system and significantly increases the product's viscosity, meeting the viscosity requirements for hand sanitizers. Furthermore, adding a small amount of this product to a formulation can achieve the desired viscosity.

[0014] In order to achieve the above-mentioned object of the invention, the technical solution of the present invention is as follows:

[0015] The present invention provides a rheology modifier for a hand sanitizer system, wherein the rheology modifier comprises component A and component B; wherein,

[0016] The component A contains a copolymer backbone of polyurethane polyisocyanate and polyether, and its chain ends are capped by an amino-containing cationic capping agent. The structure is shown in Formula 1 below:

[0017]

[0018] In Formula 1, D is a polyisocyanate residue, E is a polyether polyol residue, M is an amino-containing cationic capping agent residue, and m is any integer from 1 to 5;

[0019] The B component contains a copolymer backbone of polyurethane polyisocyanate and polyether, and the chain ends are capped by a carboxylate-containing anion capping agent, and the structure is shown in Formula 2 below:

[0020]

[0021] In Formula 2, F is a polyisocyanate residue, G is a polyether polyol residue, N is a carboxylate-containing anion capping agent residue, and n is any integer from 1 to 5.

[0022] Preferably, the molecular weight Mw of the component A is 2000-10000, preferably 4000-8000; the molecular weight Mw of the component B is 3000-10000, preferably 4500-7500.

[0023] Preferably, the mass ratio of component A to component B is 1:0.2-2, preferably 1:0.5-1.5.

[0024] The rheology modifier for a hand sanitizer system according to the present invention comprises a cation-containing component A and an anion-containing component B. When the components are added to the hand sanitizer system, the solvated polyether polyol segments thereof freely extend, and the positive and negative ion structures contained at the ends of the components A and B establish a dense three-dimensional network structure in the system through charge attraction. Simultaneously, the solvated segments interact well with water and ethanol in the system through hydrogen bonds, reducing the number of freely moving molecules in the system and effectively increasing the viscosity of the system.

[0025] In the present invention, in the polyisocyanate residue D of component A and the polyisocyanate residue F of component B, the polyisocyanate is a diisocyanate and / or a triisocyanate, preferably a diisocyanate; the polyisocyanates in residues D and F may be the same or different.

[0026] In the present invention, the diisocyanate is selected from any one or a combination of at least two of aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates;

[0027] In some embodiments, preferably, suitable diisocyanates may be 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4'-diphenylmethane diisocyanate, 4,4-bibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of toluene diisocyanate (TDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanatocyclohexane, Any one or a combination of at least two of ester-2,2,4-trimethylhexane, 1-isocyanatomethyl-S-isocyanato-1-trimethylcyclohexane, 4,4'-diisocyanatophenylperfluoroethane, tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocyanate, ethylene diisocyanate, and di-isocyanatoethyl phthalate;

[0028] In some embodiments, the diisocyanate is preferably an aliphatic diisocyanate, more preferably any one of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (HMDI), or a combination of at least two thereof.

[0029] In the present invention, the polyether polyol residue E of component A and the polyether polyol residue G of component B are any one or a combination of at least two of polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene glycol-polypropylene glycol (PEG-PPG), and polybutylene glycol, preferably polyethylene glycol (PEG); the polyether polyols in residues E and G may be the same or different;

[0030] Preferably, the molecular weight of the polyether polyol is 500-10,000 Daltons, more preferably 1,000-4,000 Daltons.

[0031] In the present invention, the amino-containing cationic end-capping agent residue M of component A is selected from a compound containing an amino group and a hydroxyl group, preferably a neutralization product of acetic acid and an amino alcohol, wherein the amino alcohol preferably has 4-12 carbon atoms, and more preferably isobutanolamine, 6-aminohexanol, 8-aminooctanol, 10-amino-n-decanol, and 12-amino-n-dodecanol, or a combination of at least two thereof. The compound containing an amino group and a hydroxyl group described in the present invention is obtained by neutralizing an amino alcohol with acetic acid. It serves as an end-capping substance in component A. After its hydroxyl end is polymerized to the main chain of component A, the end-capping residue M neutralized by acetic acid is ionized to form a cationic charge after being added to the hand sanitizer system.

[0032] In the present invention, the carboxylate-containing anion capping agent residue N of component B is selected from a hydroxyl compound containing a carboxylate, preferably a C4-C12 hydroxycarboxylic acid compound, more preferably any one or a combination of at least two of 4-hydroxydecanoic acid, 5-hydroxylauric acid, 7-hydroxytetradecanoic acid, and 9-hydroxystearic acid. The hydroxyl compound containing a carboxylate in the present invention serves as a capping substance in component B. After its hydroxyl end is polymerized to the main chain of component B, the residual carboxylate ion at the other end is added to the hand sanitizer system, and the cationic charge of component A is attracted by charge to form a larger three-dimensional structure, thereby achieving a thickening effect.

[0033] The present invention also provides a method for preparing the rheology modifier for the aforementioned hand sanitizer system. The preparation method can be achieved by solution polymerization, wherein the solvent is a solvent that does not contain active H, including but not limited to any one or a combination of at least two of benzene, toluene, xylene, ethylbenzene, chloroform, acetone, and butyl acetate. The preparation method can also be achieved by bulk polymerization. The present invention preferably uses bulk polymerization, which does not contain organic solvents, is more economical and environmentally friendly, and has a lower irritation to the human body when used in the hand sanitizer system.

[0034] In some embodiments, the method for preparing the rheology modifier of the present invention comprises the following steps:

[0035] 1) dehydrating the polyether polyol 1, then adding the catalyst 1 and the polyisocyanate 1 thereto in an inert gas environment to carry out a polymerization reaction, and then adding an amino-containing cationic end-capping agent to carry out an end-capping reaction to obtain component A;

[0036] 2) The polyether polyol 2 is subjected to a dehydration treatment, and then, under an inert gas environment, a catalyst 2 and a polyisocyanate 2 are added thereto for polymerization reaction, and then a carboxylate anion-containing capping agent is added for capping reaction to obtain component B.

[0037] In the method of the present invention, in step 1), the amino-containing cationic end-capping agent is a neutralization product of acetic acid and an amino alcohol. In some specific implementation methods, the preparation method of the amino-containing cationic end-capping agent is preferably: mixing acetic acid and an amino alcohol compound at a mass ratio of 1:1.7-3.5, and then neutralizing and reacting at 20-40° C. for 0.5-1.5 h to obtain the amino-containing cationic end-capping agent;

[0038] Preferably, the amino-containing cationic end-capping agent obtained above is dehydrated to control the water content to be less than 300 ppm before being added to the system in step 1); preferably, vacuum heating dehydration is adopted, the vacuum degree during dehydration is 2-5 KPa, the temperature is 45-50° C., and the dehydration time is 1-3 h.

[0039] In the method of the present invention, in steps 1) and 2), the basic method for preparing the polyurethane resin by polymerization reaction of polyisocyanate and polyether polyol is known in the prior art and can be prepared by various methods, such as solution synthesis or bulk synthesis. The method of the present invention preferably adopts bulk synthesis.

[0040] The polymerization reaction of the present invention is preferably carried out in the absence of water. For example, in some embodiments, azeotropic dehydration or vacuum heating dehydration can be used. During the reaction, nitrogen is used for protection to prevent water vapor from entering.

[0041] In the method of the present invention, in steps 1) and 2), the polyether polyol 1 and the polyether polyol 2 are preferably dehydrated by vacuum heating until the water content is less than 300 ppm; the vacuum degree during dehydration is 2-5 KPa, the temperature is 105-115° C., and the dehydration time is 1-3 h.

[0042] In the method of the present invention, in steps 1) and 2), the polymerization reaction is carried out under catalyst conditions, and the catalyst is any one or a combination of at least two of an organic metal catalyst and / or an amine catalyst; wherein, preferably, the organic metal catalyst is any one or a combination of at least two of dibutyltin dilaurate, stannous octoate, bismuth decanoate, bismuth octoate, and a silver-containing catalyst, and the amine catalyst is triethylamine and / or 1,4-diazabicyclo[2.2.2]octane; the catalyst 1 and the catalyst 2 may be the same or different.

[0043] Preferably, the amount of the catalyst added in steps 1) and 2) is 0.08-0.12% of the mass of the polyisocyanate, and the amounts added in the two steps can be the same or different.

[0044] In the method of the present invention, in steps 1) and 2), the molar ratio of the polyisocyanate to the polyether polyol is 1-2.5:1, preferably 1.2-2:1, and the molar ratios of the two can be the same or different.

[0045] In the method of the present invention, in step 1), the amount of the amino-containing cationic capping agent added is 8-15% of the mass of the polyether polyol 1; and in step 2), the amount of the carboxylate-containing anionic capping agent added is 6-12% of the mass of the polyether polyol 2.

[0046] In the method of the present invention, in steps 1) and 2), the polymerization reaction temperature is not strictly limited and can be selected from 40-130°C, preferably 50-120°C, and more preferably 70-110°C. The two can be the same or different. Selecting the optimal reaction temperature can effectively reduce the formation of by-products and improve the quality of the product;

[0047] The end-capping reaction temperature is 40-130°C, preferably 50-120°C, more preferably 70-110°C;

[0048] Preferably, in steps 1) and 2), the polymerization reaction time is 1-3 hours, and the end-capping reaction time is 1-3 hours.

[0049] In the method of the present invention, in steps 1) and 2), the polymerization reaction adopts a bulk polymerization mode. During the polymerization reaction, an inert gas needs to be used for protection. The inert gas is nitrogen and / or helium, preferably nitrogen.

[0050] In the method of the present invention, in steps 1) and 2), after the reaction is completed, a water dispersion operation may be further included. In some embodiments, the specific method is to cool the system to 50-55° C. after the reaction is completed, add water thereto, and fully mix and disperse to obtain viscous solutions containing component A and component B, respectively;

[0051] Preferably, in steps 1) and 2), the amount of water added is 59-61% of the mass of the system, and the viscosity of the viscous solutions containing component A and component B obtained respectively is 300-2000 cp, preferably 500-1200 cp.

[0052] The present invention also provides a use of the rheology modifier, which can be used as a thickener for a hand sanitizer system, preferably a hand sanitizer system with a high ethanol content, wherein the high ethanol content means that the mass percentage of ethanol in the system is not less than 60%.

[0053] The present invention also provides a hand sanitizer composition, comprising the rheology modifier of the present invention, wherein the content of the rheology modifier is 0.5-1.5%, preferably 0.95-1.05%, based on the total mass of the hand sanitizer composition being 100%.

[0054] Preferably, the mass ratio of component A to component B in the rheology modifier is 1:0.2-2, preferably 1:0.5-1.5.

[0055] In some embodiments, the raw material composition of the hand sanitizer provided by the present invention includes:

[0056]

[0057] In some embodiments, the hand sanitizer of the present invention can be prepared by the following method, comprising the steps of: first, mixing olive oil and glycerin, heating to 30-35° C., then adding a mixture of water and ethanol, stirring evenly, and cooling to 20-25° C., and then adding a rheology modifier and mixing evenly to obtain the hand sanitizer.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] The present invention provides a combined rheology modifier containing two components, A and B. The basic principle of forming a large-scale structure by attracting and combining positive and negative ions is adopted to separately synthesize a cation-containing component A and anion-containing component B. When simultaneously added to a high-ethanol system, the positive and negative ions attract and combine with each other through charge interaction, establishing a three-dimensional network structure in the entire system. This reduces the movement of free molecules in the system, greatly improves the viscosity of the product, and meets the viscosity requirements for the use of wash-free hand sanitizers. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 This is the GPC spectrum of component A prepared in Example 1;

[0061] Figure 2 This is the GPC spectrum of component B prepared in Example 1. DETAILED DESCRIPTION

[0062] In order to better implement the present invention, the present invention is further described below with reference to the embodiments, but the embodiments are not intended to limit the present invention.

[0063] Commercially available polyurethane thickener C1 and powdered carbomer C2 were selected as comparative examples and compared with the products made in the following examples in different formulas of hand sanitizers.

[0064] The polyurethane thickener C1 selected is DOW Chemical RM-12W, C1 is a traditional linear thickener, mainly composed of polyethylene glycol, polyisocyanate and blocked alkyl chain polymerization; this product has high market recognition, and its main parameters are as follows:

[0065] Appearance: transparent to milky white liquid;

[0066] Chemical type: non-ionic;

[0067] Density: 1.038g / cm 3 ;

[0068] Viscosity: ≤4000cp;

[0069] Solid content: 19.0%;

[0070] Solvent: water.

[0071] The selected carbomer thickener C2 is Lubrizol's Carbopol Ultrez 20. C2 is a highly cross-linked polyacrylic acid. This product has high market recognition. Its main parameters are as follows:

[0072] Appearance: white loose powder;

[0073] Chemical type: polyacrylate cross-linked copolymer;

[0074] Viscosity (0.5% aqueous dispersion): 30,000-50,000 mPas;

[0075] Contains carboxylic acid groups: 56-68%.

[0076] The main raw materials used in the examples of the present invention are as follows. Other materials are common commercially available unless otherwise specified:

[0077]

[0078]

[0079] Example 1

[0080] The rheology modifier P1 for the hand sanitizer system was prepared, and its synthetic formula was as follows:

[0081] Table 1

[0082]

[0083] The steps for synthesizing the modifier for the hand sanitizer system using this formula are as follows:

[0084] 1) Preparation of an amine-containing cationic end-capping agent: 5.81 g of 8-aminooctanol was mixed with 2.4 g of acetic acid, and the mixture was neutralized at 25° C. for 1 h, and vacuum dehydrated at 45° C. (pressure 2-5 kPa) for 1.5 h until the water content was less than 300 ppm to obtain an amine-containing cationic end-capping agent, which was set aside;

[0085] 2) Preparation of Component A: 100 g (0.1 mol) of polyethylene glycol 1000 (PEG1000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet. The mixture was dehydrated at 110°C for 2 h under negative pressure (pressure 2-5 kPa) until the water content was less than 300 ppm. The temperature was lowered to 80°C, and nitrogen was introduced into the three-necked flask to release the pressure. 0.01615 g of 8108R and 20.18 g (0.12 mol) of HDI were added to the three-necked flask to initiate polymerization. The reaction was continued at 80°C for 2 h.

[0086] Then, 8.21 g of the amino-containing cationic end-capping agent prepared in step 1) was added to the three-necked flask, and the end-capping reaction was maintained at 80°C for 2 hours. After the reaction was fully completed, the temperature was lowered to 50-55°C. 193.4 g of water was added thereto, and the mixture was mixed and dispersed thoroughly to obtain a viscous liquid containing component A. The viscosity of component A was 830 cp and the molecular weight Mw was 6384. The GPC spectrum is shown in FIG. Figure 1 The peak 6384 on the right side of the figure is proved to be component A, and its structure is shown in Formula 1.

[0087] 3) Preparation of component B): 100 g (0.1 mol) of polyethylene glycol 1000 (PEG1000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet, and water was removed at 110° C. for 2 h until the water content was less than 300 ppm under negative pressure (pressure 2-5 kPa). The temperature was lowered to 80° C., and nitrogen was introduced into the three-necked flask to release the pressure. 0.02 g of 8108R and 20.18 g (0.12 mol) of HDI were added to the three-necked flask to initiate the polymerization reaction, and the reaction was carried out at 80° C. for 2 h.

[0088] Then add 7.53g of 4-hydroxydecanoic acid to the three-necked flask and keep the end-capping reaction at 80℃ for 2h. After the reaction is fully completed, cool it to 50-55℃; add 191.5g of water and mix and disperse thoroughly to obtain a viscous liquid containing component B. The viscosity of component B is 720cp and the molecular weight Mw is 6386. The GPC spectrum is as follows Figure 2 The peak 6386 on the right side of the figure is confirmed to be component B, and its structure is shown in Formula 2.

[0089] Example 2

[0090] The rheology modifier P2 for the hand sanitizer system was prepared, and its synthetic formula was as follows:

[0091] Table 2

[0092]

[0093] The steps for synthesizing the modifier for the hand sanitizer system using this formula are as follows:

[0094] 1) Preparation of an amino-containing cationic end-capping agent: 5.86 g of 6-aminohexanol was mixed with 3.0 g of acetic acid, and the mixture was neutralized at 40° C. for 0.5 h. The mixture was then vacuum-dehydrated at 50° C. (pressure 2-5 kPa) for 1 h until the water content was less than 300 ppm, thereby obtaining an amino-containing cationic end-capping agent for later use.

[0095] 2) Preparation of Component A: 100 g (0.025 mol) of polyethylene glycol 4000 (PEG4000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet. The mixture was dehydrated at 105°C for 3 h under negative pressure (pressure 2-5 kPa) until the water content was less than 300 ppm. The temperature was lowered to 90°C, and nitrogen was introduced into the three-necked flask to release the pressure. 0.01312 g of 8108R and 13.12 g (0.05 mol) of HMDI were added to the three-necked flask to initiate polymerization. The reaction was continued at 90°C for 1.5 h.

[0096] To the three-necked flask, add 8.86 g of the amino-containing cationic end-capping agent prepared in step 1) and maintain the end-capping reaction at 90°C for 1.5 hours. After the reaction is fully completed, cool to 50-55°C. Add 182.4 g of water and mix thoroughly to obtain a viscous liquid containing component A. Component A has a viscosity of 560 cp and a molecular weight (Mw) of 4608.

[0097] 3) Preparation of component B): 100 g (0.025 mol) of polyethylene glycol 4000 (PEG4000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet. The mixture was dehydrated at 115° C. for 1.2 h until the water content was less than 300 ppm under negative pressure (pressure 2-5 kPa). The temperature was lowered to 80° C., and nitrogen was introduced into the three-necked flask to release the pressure. 0.01443 g of 8108R and 13.12 g (0.05 mol) of HMDI were added to the three-necked flask to initiate a polymerization reaction. The reaction was continued at 80° C. for 2 h.

[0098] Then, 10.82 g of 5-hydroxylauric acid was added to the three-necked flask. The end-capping reaction was maintained at 80°C for 2 hours. After the reaction was fully completed, the temperature was lowered to 50-55°C. 185.3 g of water was added and mixed thoroughly to obtain a viscous liquid containing component B. Component B had a viscosity of 620 cp and a molecular weight (Mw) of 4957.

[0099] Example 3

[0100] The rheology modifier P3 for the hand sanitizer system was prepared, and its synthetic formula is as follows:

[0101] Table 3

[0102]

[0103]

[0104] The steps for synthesizing the modifier for the hand sanitizer system using this formula are as follows:

[0105] 1) Preparation of an amino-containing cationic end-capping agent: 6.93 g of 10-amino-n-decanol was mixed with 2.4 g of acetic acid, and the mixture was neutralized at 20° C. for 1.5 h. The mixture was then vacuum-dehydrated at 45° C. (pressure 2-5 kPa) for 3 h until the water content was less than 300 ppm, thereby obtaining an amino-containing cationic end-capping agent for later use.

[0106] 2) Preparation of component A: 100 g (0.05 mol) of polyethylene glycol 2000 (PEG2000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet. The mixture was dehydrated at 115°C for 1 h until the water content was less than 300 ppm under negative pressure (pressure 2-5 kPa). The temperature was lowered to 70°C, and nitrogen was introduced into the three-necked flask to release the pressure. 0.014 g of 8108R and 15.56 g (0.07 mol) of IPDI were added to the three-necked flask to initiate polymerization. The reaction was continued at 70°C for 3 h.

[0107] To the three-necked flask, add 9.33 g of the amino-containing cationic end-capping agent prepared in step 1) and maintain the end-capping reaction at 70°C for 3 hours. After the reaction is fully completed, cool to 50-55°C. Add 186.8 g of water and mix thoroughly to obtain a viscous liquid containing component A. Component A has a viscosity of 670 cp and a molecular weight (Mw) of 4967.

[0108] 3) Preparation of component B): 100 g (0.033 mol) of polyethylene glycol 3000 (PEG3000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet, and water was removed at 105° C. for 3 h until the water content was less than 300 ppm; while maintaining 105° C., nitrogen was introduced into the three-necked flask to release the pressure, and 0.01 g of 8108R and 8.41 g (0.05 mol) of HDI were added to the three-necked flask to initiate the polymerization reaction, and the reaction was carried out at 105° C. for 1.2 h;

[0109] Then, add 10.02g of 9-hydroxystearic acid to the three-necked flask and maintain the end-capping reaction at 105°C for 1.2 hours. After the reaction is fully completed, cool to 50-55°C. Then, add 178.2g of water and mix thoroughly to obtain a viscous liquid containing component B. Component B has a viscosity of 1080cp and a molecular weight (Mw) of 7105.

[0110] Example 4

[0111] The rheology modifier P4 for the hand sanitizer system was prepared, and its synthetic formula was as follows:

[0112] Table 4

[0113]

[0114] The steps for synthesizing the modifier for the hand sanitizer system using this formula are as follows:

[0115] 1) Preparation of an amino-containing cationic end-capping agent: 10.74 g of 12-amino-n-dodecanol was mixed with 3.2 g of acetic acid, and the mixture was neutralized at 35° C. for 1 h, and vacuum-dehydrated at 48° C. (pressure 2-5 kPa) for 2 h until the water content was less than 300 ppm to obtain an amino-containing cationic end-capping agent, which was set aside;

[0116] 2) Preparation of Component A: 100 g (0.033 mol) of polyethylene glycol 3000 (PEG3000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet. The mixture was dehydrated at 108°C for 1.5 h until the water content was less than 300 ppm under negative pressure (pressure 2-5 kPa). The temperature was then lowered to 85°C, and nitrogen was introduced into the three-necked flask for decompression. 0.01574 g of 8108R and 15.74 g (0.06 mol) of HMDI were added to the three-necked flask, and the polymerization reaction was initiated at 85°C for 1.8 h.

[0117] To the three-necked flask, add 13.94 g of the amino-containing cationic end-capping agent prepared in step 1). Maintain the end-capping reaction at 85°C for 1.5 hours. After the reaction is fully complete, cool to 50-55°C. Add 194.3 g of water and mix thoroughly to obtain a viscous liquid containing component A. Component A has a viscosity of 1130 cp and a molecular weight (Mw) of 7461.

[0118] 3) Preparation of component B): 100 g (0.05 mol) of polyethylene glycol 2000 (PEG2000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet. The mixture was dehydrated at 112° C. for 1.5 h until the water content was less than 300 ppm under negative pressure (pressure 2-5 kPa). The temperature was lowered to 95° C., and nitrogen was introduced into the three-necked flask to release the pressure. 0.01445 g of 8108R and 14.45 g (0.065 mol) of IPDI were added to the three-necked flask to initiate a polymerization reaction. The reaction was continued at 95° C. for 1.6 h.

[0119] Then, 6.49 g of 5-hydroxylauric acid was added to the three-necked flask. The end-capping reaction was maintained at 95°C for 1.6 hours. After the reaction was fully completed, the temperature was lowered to 50-55°C. 181.3 g of water was added and mixed thoroughly to obtain a viscous liquid containing component B. Component B had a viscosity of 570 cp and a molecular weight (Mw) of 4838.

[0120] Example 5

[0121] The rheology modifier P5 for the hand sanitizer system was prepared, and its synthetic formula is as follows:

[0122] Table 5

[0123]

[0124] The steps for synthesizing the modifier for the hand sanitizer system using this formula are as follows:

[0125] 1) Preparation of an amine-containing cationic end-capping agent: 5.81 g of 8-aminooctanol was mixed with 2.4 g of acetic acid, and the mixture was neutralized at 30° C. for 1.2 h. The mixture was then vacuum-dehydrated at 47° C. (pressure 2-5 kPa) for 2 h until the water content was less than 300 ppm, thereby obtaining an amine-containing cationic end-capping agent for later use.

[0126] 2) Preparation of component A: 100 g (0.033 mol) of polyethylene glycol 3000 (PEG3000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet. The mixture was dehydrated at 110°C for 2 h under negative pressure (pressure 2-5 kPa) until the water content was less than 300 ppm. The temperature was lowered to 80°C, and nitrogen was introduced into the three-necked flask to release the pressure. 0.00987 g of 8108R and 8.97 g (0.053 mol) of HDI were added to the three-necked flask to initiate the polymerization reaction. The reaction was carried out at 80°C for 2 h.

[0127] To the three-necked flask, add 8.21 g of the amino-containing cationic end-capping agent prepared in step 1) and maintain the end-capping reaction at 80°C for 2 hours. After the reaction is fully completed, cool to 50-55°C. Add 175.9 g of water and mix thoroughly to obtain a viscous liquid containing component A. Component A has a viscosity of 980 cp and a molecular weight (Mw) of 6988.

[0128] 3) Preparation of component B): 100 g (0.033 mol) of polyethylene glycol 3000 (PEG3000) was added to a 500 ml three-necked flask equipped with an electromagnetic stirrer and a nitrogen inlet, and water was removed at 110° C. for 2 h until the water content was less than 300 ppm under negative pressure (pressure 2-5 kPa). The temperature was lowered to 80° C., and nitrogen was introduced into the three-necked flask to release the pressure. 0.00987 g of 8108R and 8.97 g (0.053 mol) of HDI were added to the three-necked flask to initiate the polymerization reaction, and the reaction was carried out at 80° C. for 2 h.

[0129] Then, add 69.77g of 7-hydroxytetradecanoic acid to the three-necked flask and maintain the end-capping reaction at 80°C for 2 hours. After the reaction is fully completed, cool to 50-55°C. Then, add 178.4g of water and mix thoroughly to obtain a viscous liquid containing component B. Component B has a viscosity of 1160cp and a molecular weight (Mw) of 7125.

[0130] Comparative Example 1

[0131] Referring to the method of Example 1, comparative rheology modifiers C1-C7 were prepared according to the following conditions:

[0132] C1: Refer to Example 1, except that the rheology modifier only uses component A prepared in step 2) without adding component B.

[0133] C2: Refer to Example 1, except that the rheology modifier is only component B prepared in step 3) without adding component A.

[0134] C3: Referring to Example 1, the difference is that in step 2), when preparing component A, the amino-containing cationic capping agent prepared in step 1) is not added for end-capping.

[0135] C4: Referring to Example 1, the difference is that in step 2), when preparing component A, the amino-containing cationic capping agent prepared in step 1) is replaced with 2-hydroxyethylamine.

[0136] C5: Refer to Example 1, except that the B component is not capped with a carboxylate-containing anion capping agent (4-hydroxydecanoic acid).

[0137] C6: Refer to Example 1, except that the carboxylate-containing anion capping agent (4-hydroxydecanoic acid) in component B is replaced by hydroxypropionic acid.

[0138] C7: Referring to Example 1, component A was replaced with a star-shaped polyurethane thickener prepared by the method provided in Example 1 of CN112831010A.

[0139] C8: Referring to Example 1, component B was replaced with an associative polyurethane thickener prepared by the method provided in Example 1 of CN101407624A.

[0140] The following Examples 6-7 are application examples of the rheology modifiers P1-P5 prepared in Examples 1-5 for the hand sanitizer system, and are compared with commercially available thickeners B1 and B2, and the rheology modifiers C1-C8 prepared in Comparative Example 1.

[0141] The required test items and methods are as follows:

[0142] 1) Thickening efficiency: Add the same amount of thickener to the system and examine the system's viscosity at 20 rpm (unit: cp);

[0143] 2) Transparency test: measured using a Unicolor 7200 spectrophotometer, with 100% being optimal;

[0144] 3) Storage stability: The finished paint was placed in a 50°C oven for 14 days to observe the change in viscosity of the hand sanitizer. Judgment criteria: good storage stability was scored as 5 points, and poor storage stability was scored as 1 point.

[0145] Example 6

[0146] Comparisons are shown for rheology modifiers P1-P5 prepared in Examples 1-5 of the present invention for use in hand sanitizer systems, rheology modifiers C1-C8 prepared in Comparative Example 1, and commercially available thickeners B1 and B2 at a relatively high ethanol content (approximately 75% by mass). Simply mix the following ingredients.

[0147] Table 6

[0148] serial number raw material Mass / g 1 water 29 2 ethanol 70 3 thickener 1

[0149] According to the above formula test performance, the following table results are obtained:

[0150] Table 7

[0151] Test items Viscosity / cp transparency / % Storage stability / min B1 76 78 4 B2 3860 91 3 C1 66 90 4 C2 68 91 3 C3 63 90.7 4 C4 72 90.2 4 C5 63 90.7 4 C6 69 91.2 3 C7 72 83 3 C8 71 82 3 P1 4355 93 4 P2 4400 94 5 P3 4378 93 5 P4 4510 94.20 5 P5 4677 95.10 5

[0152] As can be seen from Table 7, the combined rheology modifier containing two components, AB, for use in a hand sanitizer system according to the present invention has high thickening efficiency in a high ethanol content system, as well as good transparency and storage stability, meeting the performance requirements of hand sanitizers.

[0153] Example 7

[0154] The rheology modifiers P1-P5 for the hand sanitizer system prepared in the embodiment of the present invention were used to prepare a hand sanitizer, and compared with the rheology modifiers C1-C8 prepared in Comparative Example 1 and commercially available thickener products B1 and B2.

[0155] The formula of the wash-free hand sanitizer used in the present invention is as follows:

[0156] Table 8

[0157] serial number raw material Mass / g 1 water 23.5 2 ethanol 62 3 glycerin 2 4 olive oil 1.5 5 Rheology modifiers / thickeners 1.0

[0158] The hand sanitizer preparation steps include: firstly mixing olive oil and glycerin, heating to 30-35°C, then slowly adding a mixture of water and ethanol, stirring evenly and cooling to 20-25°C, and then slowly adding a rheology modifier (or thickener) and mixing evenly to obtain the hand sanitizer.

[0159] The performance test of the hand sanitizer system prepared according to the above formula was carried out, and the results were as follows:

[0160] Table 9

[0161]

[0162]

[0163] As can be seen from Table 9, the combined rheology modifier containing the AB two-components for the hand-free hand sanitizer system of the present invention also has good thickening efficiency in the conventional hand-free hand sanitizer formula on the market, while not affecting the transparency and storage stability.

[0164] The above embodiments are preferred implementation methods of the present invention, but the present invention is not limited to the above implementation methods. Any other changes, modifications, simplifications, and replacements made without departing from the spirit and principles of the present invention should be considered equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A rheology modifier for a hand sanitizer system, characterized in that: The rheology modifier comprises component A and component B; wherein, The component A contains a copolymer backbone of polyisocyanate and polyether polyol, and the chain ends are capped by an amino-containing cationic capping agent. The structure is shown in Formula 1 below: In Formula 1, D is a polyisocyanate residue, E is a polyether polyol residue, M is an amino-containing cationic capping agent residue, and m is any integer from 1 to 5; The amino-containing cationic end-capping agent is selected from the neutralization product of acetic acid and amino alcohols, and the amino alcohols have 4 to 12 carbon atoms; The B component contains a copolymer backbone of polyisocyanate and polyether polyol, and the chain ends are capped by a carboxylate-containing anion capping agent, and the structure is shown in Formula 2 below: In formula 2, F is a polyisocyanate residue, G is a polyether polyol residue, N is a carboxylate anion capping agent residue, and n is any integer from 1 to 5; The carboxylate-containing anion capping agent is selected from any one of C4-C12 hydroxycarboxylic acid compounds, 7-hydroxytetradecanoic acid, and 9-hydroxystearic acid, or a combination of at least two thereof.

2. The rheology modifier according to claim 1, characterized in that The molecular weight Mw of the A component is 2000-10000; the molecular weight Mw of the B component is 3000-10000.

3. The rheology modifier according to claim 2, characterized in that The molecular weight Mw of the A component is 4000-8000.

4. The rheology modifier according to claim 2, characterized in that The molecular weight Mw of the B component is 4500-7500.

5. The rheology modifier according to claim 1, characterized in that The mass ratio of component A to component B is 1:0.2-2.

6. The rheology modifier according to claim 5, characterized in that The mass ratio of component A to component B is 1:0.5-1.

5.

7. The rheology modifier according to claim 1, characterized in that In the polyisocyanate residue D of component A and the polyisocyanate residue F of component B, the polyisocyanate is a diisocyanate and / or a triisocyanate; the polyisocyanates in residues D and F may be the same or different; and / or In the polyether polyol residue E of component A and the polyether polyol residue G of component B, the polyether polyol is any one of polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol, and polybutylene glycol, or a combination of at least two thereof; the polyether polyols in residues E and G may be the same or different.

8. The rheology modifier according to claim 7, characterized in that The diisocyanate is selected from any one of aliphatic diisocyanate and aromatic diisocyanate, or a combination of at least two thereof.

9. The rheology modifier according to claim 8, characterized in that The diisocyanate is 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4-bibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of toluene diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethyl Any one or a combination of at least two of hexane, 1-isocyanatemethyl-S-isocyanate-1-trimethylcyclohexane, 4,4'-diisocyanatephenylperfluoroethane, tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocyanate, ethylene diisocyanate, and di-isocyanateethyl phthalate.

10. The rheology modifier according to claim 8, characterized in that The diisocyanate is an aliphatic diisocyanate.

11. The rheology modifier according to claim 10, characterized in that The diisocyanate is any one of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate, or a combination of at least two thereof.

12. The rheology modifier according to claim 7, characterized in that The molecular weight of the polyether polyol is 500-10000 Daltons.

13. The rheology modifier according to claim 12, characterized in that The molecular weight of the polyether polyol is 1000-4000 Daltons.

14. The rheology modifier according to claim 1, characterized in that In the amino-containing cationic capping agent residue M of component A, the amino alcohol is selected from any one of isobutanolamine, 6-aminohexanol, 8-aminooctanol, 10-aminodecanol, and 12-aminododecanol, or a combination of at least two thereof.

15. The rheology modifier according to claim 1, characterized in that In the carboxylate-containing anion capping agent residue N of component B, the carboxylate-containing anion capping agent is selected from any one of 4-hydroxydecanoic acid and 5-hydroxylauric acid, or a combination of at least two thereof.

16. A method for preparing a rheology modifier for a hand sanitizer system according to any one of claims 1 to 15, characterized in that the steps include: 1) dehydrating the polyether polyol 1, then adding the catalyst 1 and the polyisocyanate 1 thereto in an inert gas environment to carry out a polymerization reaction, and then adding an amino-containing cationic end-capping agent to carry out an end-capping reaction to obtain component A; 2) The polyether polyol 2 is subjected to a dehydration treatment, and then, under an inert gas environment, a catalyst 2 and a polyisocyanate 2 are added thereto for polymerization reaction, and then a carboxylate anion-containing capping agent is added for capping reaction to obtain component B.

17. The preparation method according to claim 16, characterized in that In step 1), the amino-containing cationic capping agent is a neutralization product of acetic acid and an amino alcohol, and the preparation method is: acetic acid and an amino alcohol compound are mixed at a mass ratio of 1:1.7-3.5, and then neutralized at 20-40° C. for 0.5-1.5 hours to obtain the amino-containing cationic capping agent; In steps 1) and 2), the polyether polyol 1 and the polyether polyol 2 are both dehydrated by vacuum heating until the water content is less than 300 ppm; the vacuum degree during dehydration is 2-5 KPa, the temperature is 105-115° C., and the dehydration time is 1-3 h; In steps 1) and 2), the polymerization reaction is carried out under catalyst conditions, and the catalyst is any one or a combination of at least two of an organic metal catalyst and / or an amine catalyst; the catalyst 1 and the catalyst 2 may be the same or different; The amount of the catalyst added in steps 1) and 2) is 0.08-0.12% of the mass of the polyisocyanate, and the amounts added can be the same or different; In steps 1) and 2), the molar ratio of the polyisocyanate to the polyether polyol is 1-2.5:1, and the molar ratios of the two can be the same or different; In step 1), the amount of the amine-containing cationic capping agent added is 8-15% by mass of the polyether polyol 1; in step 2), the amount of the carboxylate-containing anionic capping agent added is 6-12% by mass of the polyether polyol 2; In steps 1) and 2), the polymerization reaction temperature is 40-130°C, and the two can be the same or different; The end-capping reaction temperature is 40-130°C; In steps 1) and 2), the polymerization reaction time is 1-3 hours, and the end-capping reaction time is 1-3 hours; In steps 1) and 2), the polymerization reaction is carried out in bulk polymerization. During the polymerization reaction, an inert gas is used for protection, and the inert gas is nitrogen and / or helium.

18. The preparation method according to claim 17, characterized in that The amino-containing cationic end-capping agent is dehydrated to control the water content to be less than 300 ppm, and then added to the system in step 1); Vacuum heating dehydration is adopted, the vacuum degree during dehydration is 2-5Kpa, the temperature is 45-50℃, and the dehydration time is 1-3h.

19. The preparation method according to claim 17, characterized in that The organic metal catalyst is any one of dibutyltin dilaurate, stannous octoate, bismuth decanoate, bismuth octoate, and a silver-containing catalyst, or a combination of at least two thereof; the amine catalyst is triethylamine and / or 1,4-diazabicyclo[2.2.2]octane.

20. The preparation method according to claim 17, characterized in that The molar ratio of the polyisocyanate to the polyether polyol is 1.2-2:

1.

21. The preparation method according to claim 17, characterized in that The polymerization reaction temperature is 50-120°C.

22. The preparation method according to claim 21, characterized in that The polymerization reaction temperature is 70-110°C.

23. The preparation method according to claim 17, characterized in that The end-capping reaction temperature is 50-120°C.

24. The preparation method according to claim 23, characterized in that The end-capping reaction temperature is 70-110°C.

25. The preparation method according to claim 16, characterized in that In steps 1) and 2), after the reaction is completed, a water dispersion operation is further included. The method is to cool the system to 50-55° C., add water thereto, and fully mix and disperse to obtain viscous solutions containing component A and component B, respectively.

26. The preparation method according to claim 25, characterized in that In steps 1) and 2), the amount of water added is 59-61% of the mass of the system, and the viscosity of the viscous solutions containing component A and component B obtained respectively is 300-2000 cp.

27. The preparation method according to claim 26, characterized in that The viscosity of the viscous solution containing component A and component B is 500-1200 cp.

28. Use of the rheology modifier according to any one of claims 1 to 15 or the rheology modifier prepared by the method according to any one of claims 16 to 27, characterized in that: Thickener for hand sanitizer systems.

29. The use according to claim 28, characterized in that A hand sanitizer system for a high ethanol content system, wherein the high ethanol content means that the mass percentage of ethanol in the system is not less than 60%.

30. A hand sanitizer composition, characterized in that: The rheology modifier comprises the rheology modifier according to any one of claims 1 to 15 or the rheology modifier prepared by the method according to any one of claims 16 to 27, wherein the content of the rheology modifier is 0.5-1.5% based on the total mass of the hand sanitizer composition being 100%.

31. The hand sanitizer composition according to claim 30, characterized in that The content of the rheology modifier is 0.95-1.05%.

32. The hand sanitizer composition according to claim 30, characterized in that The mass ratio of component A to component B in the rheology modifier is 1:0.2-2.

33. The hand sanitizer composition according to claim 32, characterized in that The mass ratio of component A to component B in the rheology modifier is 1:0.5-1.

5.

34. The hand sanitizer composition according to claim 30, characterized in that The raw materials of the hand sanitizer are as follows:

35. The hand sanitizer composition according to claim 34, characterized in that The raw materials of the hand sanitizer are as follows:

36. The hand sanitizer composition according to claim 30, characterized in that The hand sanitizer is prepared by the following method, comprising the steps of: firstly mixing olive oil and glycerin, heating to 30-35° C., then adding a mixture of water and ethanol, stirring evenly, and cooling to 20-25° C., and then adding a rheology modifier and mixing evenly to obtain the hand sanitizer.

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