Ester-based quaternary ammonium salt with condensed ring structure, preparation method thereof and film

Abstract

The present invention relates to the technical field of ester quaternary ammonium salts, and more particularly to an ester quaternary ammonium salt with a condensed ring structure, a preparation method thereof, and a film. The ester quaternary ammonium salt with a condensed ring structure can better combine with polycyclic musk aromatic compounds based on the principle of like dissolves like, thereby increasing the retention time of the polycyclic musk aromatic compound essence in the film or fabric and improving the fragrance retention effect.

Description

Technical Field

[0001] The present invention relates to the technical field of ester quaternary ammonium salts, in particular to an ester quaternary ammonium salt with a condensed ring structure, a preparation method thereof and a film. Background Art

[0002] Polycyclic musk aromatic compounds are a class of synthetic fragrances with complex fused ring structures. They are widely used in perfumes, detergents, and personal care products due to their excellent fragrance retention and distinctive musk aroma. The molecular structure of these compounds typically contains multiple fused ring systems (such as benzene, cycloalkanes, or heterocycles), with characteristic substituents such as tert-butyl and methoxy groups to enhance stability and aroma intensity.

[0003] Esterquats are cationic surfactants with numerous industrial applications. Among them, they can be used in fabric finishing to reduce the friction coefficient between fibers, making fabrics softer, smoother, and fluffier, enhancing the feel and wearing comfort of fabrics. Esterquats are essential components of film. Incorporating polycyclic musk aromatic compounds into film can imbue the film with additional functionality. For example, using film to finish fabrics can impart a musky aroma. Summary of the Invention

[0004] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide an ester-based quaternary ammonium salt with a condensed ring structure, a preparation method thereof, and a film, aiming to give the film more functionality.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The present invention provides an ester-based quaternary ammonium salt with a condensed ring structure, wherein the ester-based quaternary ammonium salt contains a naphthyl group and an alkyl group with 12 to 22 carbon atoms;

[0007] The ester group quaternary ammonium salt comprises compound A, compound B and compound C;

[0008] The general formulas of compound A, compound B and compound C are as follows:

[0009]

[0010] In the general formula, each R is the same or different, and the R represents an alkyl group or a naphthyl group having 12 to 22 carbon atoms, the alkyl group is a substituted or unsubstituted alkyl group, and the naphthyl group is a substituted or unsubstituted naphthyl group;

[0011] X - Represents anions that are compatible with softeners.

[0012] The ester quaternary ammonium salt with a condensed ring structure, wherein the anion compatible with the softener is a halogen, CH3SO4 or C2H5SO4.

[0013] A second aspect of the present invention provides a method for preparing an ester quaternary ammonium salt, which is used to prepare the ester quaternary ammonium salt with a fused ring structure as described above, comprising the steps of:

[0014] Transesterification reaction: Add an alcoholamine, fatty acid methyl ester, naphthoate, and catalyst solution to a reactor equipped with a mechanical stirrer; the molar ratio of alcoholamine, fatty acid methyl ester naphthoate, and naphthoic acid is 1:(0.4-1.2):(0.4-1.2); purge with nitrogen, and heat the reaction mixture to 91°C-105°C over 30 minutes under a vacuum pressure of 200 mbar. React for 1-1.5 hours until the reaction mixture no longer releases low-boiling substances to obtain an amine ester, and then cool to 60°C.

[0015] Quaternization reaction: Add a solvent to a reactor, heat to 78-80°C, slowly dropwise add a quaternizing agent to the system, and the molar ratio of the quaternizing agent to the amine ester is (0.95-1):1; after the dropwise addition is completed, keep the temperature at 78-80°C for 1.5-2 hours until the amine value of the reaction mixture reaches a minimum constant value, thereby obtaining an ester-based quaternary ammonium salt with a fused ring structure.

[0016] The preparation method of the ester quaternary ammonium salt, wherein the alcoholamine is selected from triethanolamine.

[0017] The preparation method of the ester quaternary ammonium salt, wherein the fatty acid methyl ester is selected from at least one of C12-C22 acid methyl esters; and the C12-C22 acid is a saturated acid or an unsaturated acid.

[0018] The preparation method of the ester quaternary ammonium salt, wherein the naphthoic acid ester is selected from at least one of ethyl 1-naphthoate, methyl α-naphthoate, and methyl 5-hydroxy-1-naphthoate.

[0019] The preparation method of the ester quaternary ammonium salt, wherein the catalyst is selected from at least one of sodium methoxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, and sodium borohydride.

[0020] The preparation method of the ester-based quaternary ammonium salt, wherein the quaternizing agent is selected from at least one of dimethyl sulfate, methyl chloride, dimethyl carbonate, and trimethyl phosphate.

[0021] The preparation method of the ester quaternary ammonium salt, wherein the solvent is selected from at least one of C1-C6 alcohols, diols, fatty acids, monoglycerides, diglycerides, and triglycerides.

[0022] A third aspect of the present invention provides a film comprising the above-mentioned ester quaternary ammonium salt with a condensed ring structure and a polycyclic musk aromatic compound.

[0023] Beneficial Effects: The present invention provides an ester-based quaternary ammonium salt with a condensed ring structure. The ester-based quaternary ammonium salt has a similar structure to polycyclic musk aromatic compounds. Based on the principle of like dissolves like, the polycyclic musk aromatic compounds can be better incorporated into the ester-based quaternary ammonium salt, thereby imparting a unique fragrance to the film.

[0024] The present invention also provides a film comprising the aforementioned ester-based quaternary ammonium salt with a fused ring structure and a polycyclic musk aromatic compound. Compared to conventional films, the film of the present invention provides an additional fragrance, resulting in a long-lasting aroma. Furthermore, due to the presence of the fused ring structure, the polycyclic musk aromatic compound in the film is less likely to evaporate and escape, resulting in a more lasting aroma. DETAILED DESCRIPTION

[0025] The present invention provides an ester group quaternary ammonium salt with a fused ring structure, a preparation method thereof, and a film. To make the purpose, technical solution, and effects of the present invention clearer and more specific, the present invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely for explaining the present invention and are not intended to limit the present invention.

[0026] The present invention provides an ester-based quaternary ammonium salt with a condensed ring structure, wherein the ester-based quaternary ammonium salt contains a naphthyl group and an alkyl group with 12 to 22 carbon atoms;

[0027] The ester group quaternary ammonium salt comprises compound A, compound B and compound C;

[0028] The general formulas of compound A, compound B and compound C are as follows:

[0029]

[0030] In the general formula, each R is the same or different, and the R represents an alkyl group or a naphthyl group having 12 to 22 carbon atoms, the alkyl group is a substituted or unsubstituted alkyl group, and the naphthyl group is a substituted or unsubstituted naphthyl group;

[0031] X - Represents anions that are compatible with softeners.

[0032] Preferably, the anion compatible with the softener may be halogen, CH3SO4 or C2H5SO4.

[0033] The ester-based quaternary ammonium salt of the present invention has a condensed ring structure, which is similar to the condensed ring structure of polycyclic musk aromatic compounds. According to the principle of like dissolves like, similar properties enable polycyclic musk aromatic compounds to be well combined in the ester-based quaternary ammonium salt.

[0034] When polycyclic musk fragrances are used, the ester-quaternary ammonium salts with condensed ring structures in the film can reduce the volatilization of the fragrance during storage. During use, after the ester-quaternary ammonium salts form a uniform, soft film on the fiber surface, the polycyclic musk fragrance can also be better retained on the fabric through the ester-quaternary ammonium salts with condensed ring structures, achieving a longer-lasting fragrance effect.

[0035] A second aspect of the present invention provides a method for preparing an ester quaternary ammonium salt, which is used to prepare the ester quaternary ammonium salt with a fused ring structure as described above, comprising the steps of:

[0036] Transesterification reaction: Add an alcoholamine, fatty acid methyl ester, naphthoate, and catalyst solution to a reactor equipped with a mechanical stirrer; the molar ratio of alcoholamine, fatty acid methyl ester naphthoate, and naphthoic acid is 1:(0.4-1.2):(0.4-1.2); purge with nitrogen, and heat the reaction mixture to 91°C-105°C over 30 minutes under a vacuum pressure of 200 mbar. React for 1-1.5 hours until the reaction mixture no longer releases low-boiling substances to obtain an amine ester, and then cool to 60°C.

[0037] Quaternization reaction: Add a solvent to a reactor, heat to 78-80°C, slowly dropwise add a quaternizing agent to the system, and the molar ratio of the quaternizing agent to the amine ester is (0.95-1):1; after the dropwise addition is completed, keep the temperature at 78-80°C for 1.5-2 hours until the amine value of the reaction mixture reaches a minimum constant value, thereby obtaining an ester-based quaternary ammonium salt with a fused ring structure.

[0038] Preferably, the alcoholamine is selected from triethanolamine.

[0039] Preferably, the fatty acid methyl ester is selected from at least one of C12-C22 acid methyl esters; the C12-C22 acid is a saturated acid or an unsaturated acid.

[0040] Specifically, the C12 to C22 acids can be selected from the following acids: oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, cetanoic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, octadecatrienoic acid, punicic acid, α-eleostearic acid, β-eleostearic acid, arachidonic acid, eicosapentaenoic acid, ichthyoleic acid, and docosahexaenoic acid.

[0041] Preferably, the naphthoic acid ester is selected from at least one of ethyl 1-naphthoate, methyl α-naphthoate, and methyl 5-hydroxy-1-naphthoate.

[0042] Preferably, the catalyst is selected from at least one of sodium methoxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, and sodium borohydride.

[0043] Preferably, the quaternizing agent is selected from at least one of dimethyl sulfate, methyl chloride, dimethyl carbonate, and trimethyl phosphate.

[0044] Preferably, the solvent is selected from at least one of C1-C6 alcohols, diols, fatty acids, monoglycerides, diglycerides, and triglycerides.

[0045] A third aspect of the present invention provides a film comprising the above-mentioned ester quaternary ammonium salt with a condensed ring structure and a polycyclic musk aromatic compound.

[0046] Specifically, the polycyclic musk aromatic compound is at least one selected from musk deodorant, musk cymbidium, musk wanshan and musk galaxolide.

[0047] Example 1

[0048] An ester quaternary ammonium salt with a condensed ring structure, and its preparation method is as follows:

[0049] Transesterification: 149.2 g (1 mol) of triethanolamine, 240 g (0.8 mol) of methyl stearate, 160 g (0.8 mol) of ethyl 1-naphthoate, and 8.8 g of a 25% methanol solution of sodium methoxide were introduced into a reactor equipped with a mechanical stirrer. The reaction mixture was heated to 95°C over 30 minutes under a vacuum pressure of 200 mbar under nitrogen. The reaction was allowed to proceed for 1 hour until the reaction mixture ceased releasing low-boiling substances, yielding an amine ester. The amine ester was then cooled to 60°C.

[0050] Quaternization reaction: Slowly add 120 g of isopropanol to the above reactor, heat to 78-80°C, and slowly add 120 g (0.95 mol) of dimethyl sulfate dropwise to the system. After the addition is completed, keep the temperature at 78-80°C for 100 minutes until the amine value of the reaction mixture reaches the minimum. Cool to room temperature to obtain an ester quaternary ammonium salt with a fused ring structure.

[0051] Example 2

[0052] An ester quaternary ammonium salt with a condensed ring structure, and its preparation method is as follows:

[0053] Transesterification: 149.2 g (1 mol) of triethanolamine, 232.34 g (0.8 mol) of methyl punicate, 151.34 g (0.8 mol) of methyl 5-hydroxy-1-naphthoate, and 8.8 g of a 25% sodium methoxide solution in methanol were introduced into a reactor equipped with a mechanical stirrer. The reaction mixture was heated to 105°C over 30 minutes under a vacuum pressure of 200 mbar and allowed to react for 1.2 hours until the reaction mixture ceased releasing low-boiling products, yielding the amine ester. The amine ester was then cooled to 60°C.

[0054] Quaternization reaction: Slowly add 120 g of isopropanol to the above reactor, heat to 78-80°C, and slowly add 117.87 g (0.95 mol) of trimethyl phosphate dropwise to the system. After the addition is completed, keep the temperature at 78-80°C for 100 minutes, at which time the amine value of the reaction mixture has reached the minimum. Cool to room temperature to obtain an ester-based quaternary ammonium salt with a condensed ring structure.

[0055] Example 3

[0056] An ester quaternary ammonium salt with a condensed ring structure, and its preparation method is as follows:

[0057] Transesterification: 149.2 g (1 mol) of triethanolamine, 235.57 g (0.8 mol) of methyl linoleate, 160 g (0.8 mol) of ethyl 1-naphthoate, and 8.8 g of a 25% sodium methoxide solution in methanol were introduced into a reactor equipped with a mechanical stirrer. The reaction mixture was heated to 95°C over 30 minutes under a vacuum pressure of 200 mbar and allowed to react for 1 hour. When the reaction mixture no longer released low-boiling products, an amine ester was obtained, which was then cooled to 60°C.

[0058] Quaternization reaction: Slowly add 120 g of isopropanol to the above reactor, heat to 78-80°C, and slowly add 120 g (0.95 mol) of dimethyl sulfate dropwise to the system. After the addition is completed, keep the temperature at 78-80°C for 100 minutes until the amine value of the reaction mixture reaches the minimum. Cool to room temperature to obtain an ester quaternary ammonium salt with a fused ring structure.

[0059] Example 4

[0060] An ester-based quaternary ammonium salt with a fused ring structure, the preparation method of which differs from that of Example 1 in that the transesterification reaction is different;

[0061] In this example, the transesterification reaction was performed by introducing 149.2 g (1 mol) of triethanolamine, 142.23 g (0.4 mol) of methyl stearate, 228.23 g (1.2 mol) of ethyl 1-naphthoate, and 8.8 g of a 25% sodium methoxide solution in methanol into a reactor equipped with a mechanical stirrer. The reaction mixture was heated to 95°C over 30 minutes under a vacuum pressure of 200 mbar under nitrogen. The reaction was allowed to proceed for 1 hour until the reaction mixture ceased releasing low-boiling substances, yielding an amine ester, which was then cooled to 60°C.

[0062] Example 5

[0063] An ester-based quaternary ammonium salt with a fused ring structure, the preparation method of which differs from that of Example 1 in that the transesterification reaction is different;

[0064] In this example, the transesterification reaction was performed by introducing 149.2 g (1 mol) of triethanolamine, 341.36 g (1.2 mol) of methyl stearate, 76.08 g (0.4 mol) of ethyl 1-naphthoate, and 8.8 g of a 25% sodium methoxide solution in methanol into a reactor equipped with a mechanical stirrer. The reaction mixture was heated to 95°C over 30 minutes under a vacuum pressure of 200 mbar under nitrogen. The reaction was allowed to proceed for 1 hour until the reaction mixture ceased releasing low-boiling substances, yielding an amine ester, which was then cooled to 60°C.

[0065] Comparative Example 1

[0066] An ester-based quaternary ammonium salt with a fused ring structure, the preparation method of which differs from that of Example 1 in that the transesterification reaction is different;

[0067] In this comparative example, the transesterification reaction was performed by introducing 149.2 g (1 mol) of triethanolamine, 455.15 g (1.6 mol) of methyl stearate, and 8.8 g of a 25% sodium methoxide solution in methanol into a reactor equipped with a mechanical stirrer. The reaction mixture was heated to 95°C over 30 minutes under a vacuum pressure of 200 mbar under nitrogen. The reaction was allowed to proceed for 1 hour until the reaction mixture ceased releasing low-boiling products, yielding an amine ester, which was then cooled to 60°C.

[0068] Comparative Example 2

[0069] An ester-based quaternary ammonium salt with a fused ring structure, the preparation method of which differs from that of Example 1 in that the transesterification reaction is different;

[0070] In this example, the transesterification reaction was performed by introducing 149.2 g (1 mol) of triethanolamine, 304.30 g (1.2 mol) of ethyl 1-naphthoate, and 8.8 g of a 25% sodium methoxide solution in methanol into a reactor equipped with a mechanical stirrer. The reaction mixture was heated to 95°C over 30 minutes under a vacuum pressure of 200 mbar under nitrogen. The reaction was allowed to proceed for 1 hour until the reaction mixture ceased releasing low-boiling products, yielding an amine ester, which was then cooled to 60°C.

[0071] Example 6

[0072] A soft film is composed of 4 parts of the ester quaternary ammonium salt of Example 1 and 2 parts of musk deodorant, calculated by weight.

[0073] Example 7

[0074] A soft film is composed of 4 parts of the ester quaternary ammonium salt of Example 2 and 2 parts of musk deodorant, calculated by weight.

[0075] Example 8

[0076] A soft film is composed of 4 parts of the ester quaternary ammonium salt of Example 3 and 2 parts of musk deodorant, calculated by weight.

[0077] Example 9

[0078] A soft film is composed of 4 parts of the ester quaternary ammonium salt of Example 4 and 2 parts of musk deodorant, calculated by weight.

[0079] Example 10

[0080] A soft film is composed of 4 parts of the ester quaternary ammonium salt of Example 5 and 2 parts of musk deodorant, calculated by weight.

[0081] Comparative Example 3

[0082] A soft film is composed of 4 parts by weight of the ester quaternary ammonium salt of Comparative Example 1 and 2 parts of musk deodorant.

[0083] Comparative Example 4

[0084] A soft film is composed of 4 parts of the ester quaternary ammonium salt of Comparative Example 2 and 2 parts of musk deodorant, calculated by weight.

[0085] The fragrance retention of fabrics washed with the above-mentioned soft sheets was tested to evaluate the fragrance retention of the soft sheets. The specific test steps are based on the "Evaluation Method for the Fragrance Retention of Detergents (Long-Lasting)".

[0086] The results are shown in Table 1.

[0087] Table 1

[0088]

[0089] In Table 1, “√” means that more than 80% of the subjects smelled the fragrance of the fabric, and “×” means that less than 80% of the subjects smelled the fragrance of the fabric.

[0090] To improve accuracy, if the result is "×", the test is continued for one more day. The above results show that, compared with the ester quaternary ammonium salt without a condensed ring structure (Comparative Example 1), the ester quaternary ammonium salt with a condensed ring structure (Examples 6-10) of the present invention can significantly prolong the fragrance duration of musk pink on fabrics.

[0091] Further comparison of the results of Examples 6-8 shows that the fragrance lasting time of Example 6 is longer than that of Examples 7 and 8, reflecting that the ester quaternary ammonium salts with condensed rings of different structures have different binding abilities to musk deodorant, and thus the fragrance lasting time in the fabric is also different.

[0092] The difference of embodiment 6, embodiment 9, embodiment 10 is, the consumption of methyl stearate and 1-ethyl naphthoate is different during transesterification reaction, and it is found that when the mol ratio of methyl stearate and 1-ethyl naphthoate is 1:1, the ester group quaternary ammonium salt obtained is the best. The reason is that alkyl and fabric acting force are strong, and when consumption is on the small side, the ester group quaternary ammonium salt left on the fabric will be few, thereby the essence of combination will also be less. And naphthyl is a condensed ring structure, is mainly used in better combining with polycyclic musk aromatic compounds, and when content is insufficient, the amount of naturally combined polycyclic musk aromatic compounds is just less. When the content of naphthyl and alkyl is moderate, best use effect can be achieved.

[0093] The films in Comparative Examples 3 and 4 use ester-based quaternary ammonium salts containing only alkyl and naphthyl groups. As can be seen, both films lack the fragrance retention effect of Examples 6-10. This is because when containing only alkyl groups, the polycyclic musk aromatic compound fragrance cannot be well bound to the fabric. When containing only naphthyl groups, the polycyclic musk aromatic compound fragrance lacks a medium to bind to the fabric and is also easily lost.

[0094] Rewetting performance: Fabric softener products were tested for rewetting performance according to QB / T4309-2012, "Determination of Rewetting Performance of Fabric Softeners." Three test pieces were tested in parallel for each sample, and the results were averaged. The shorter the test time, the better the rewetting performance. The results are shown in Table 2.

[0095] Table 2

[0096]

[0097] It can be seen from the results in Table 2 that the rewettability of the film of the present invention can reach the level of the prior art and has application value.

[0098] It is understandable that those skilled in the art can make equivalent substitutions or changes based on the technical solution and inventive concept of the present invention, and all these changes or substitutions should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A method for preparing an ester quaternary ammonium salt, characterized in that: The steps include: Transesterification reaction: Add an alcoholamine, fatty acid methyl ester, naphthoate, and a catalyst solution to a reactor equipped with a mechanical stirrer; the molar ratio of alcoholamine, fatty acid methyl ester, and naphthoate is 1:(0.4-1.2):(0.4-1.2); purge with nitrogen, and heat the reaction mixture to 91°C-105°C over 30 minutes under a vacuum pressure of 200 mbar. React for 1-1.5 hours until the reaction mixture no longer releases low-boiling substances to obtain an amine ester, and then cool to 60°C. Quaternization reaction: Add a solvent to a reactor, heat to 78-80°C, slowly dropwise add a quaternizing agent to the system, and the molar ratio of the quaternizing agent to the amine ester is (0.95-1):1; after the dropwise addition is completed, the reaction mixture is kept at 78-80°C for 1.5-2 hours until the amine value of the reaction mixture reaches a minimum constant value, thereby obtaining an ester-based quaternary ammonium salt with a condensed ring structure; The alcoholamine is selected from triethanolamine; The fatty acid methyl ester is selected from at least one of C12-C22 acid methyl esters; the C12-C22 acid is a saturated acid or an unsaturated acid; The naphthoic acid ester is selected from at least one of ethyl 1-naphthoate, methyl α-naphthoate, and methyl 5-hydroxy-1-naphthoate.

2. The method for preparing an ester group quaternary ammonium salt according to claim 1, wherein The catalyst is selected from at least one of sodium methoxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, and sodium borohydride.

3. The preparation method of the ester group quaternary ammonium salt according to claim 1, wherein The quaternizing agent is selected from at least one of dimethyl sulfate, methyl chloride, dimethyl carbonate, and trimethyl phosphate.

4. The method for preparing an ester quaternary ammonium salt according to claim 1, wherein The solvent is selected from at least one of C1-C6 alcohols, diols, fatty acids, monoglycerides, diglycerides, and triglycerides.

5. A film, characterized in that: The invention comprises an ester-based quaternary ammonium salt with a condensed ring structure and a polycyclic musk aromatic compound; the ester-based quaternary ammonium salt with a condensed ring structure is prepared by the preparation method of the ester-based quaternary ammonium salt according to any one of claims 1 to 4; and the polycyclic musk aromatic compound is selected from at least one of musk demerara, musk cymbidium, musk wanshanensis, and musk galaxolide.

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