Ester quaternary ammonium salt with condensed ring structure, preparation method thereof and soft sheet

Abstract

The invention relates to the technical field of ester-based quaternary ammonium salts, in particular to an ester-based quaternary ammonium salt with a fused ring structure, a preparation method of the ester-based quaternary ammonium salt and a film. The ester quaternary ammonium salt with the fused ring structure can be better combined with the polycyclic musk aromatic compound through a similar dissolves principle, so that the retention time of the polycyclic musk aromatic compound essence in a soft sheet or a fabric is prolonged, and the fragrance retention effect is improved.

Description

Technical Field

[0001] The invention relates to the technical field of ester quaternary ammonium salts, and 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 condensed ring structures. They are widely used in perfumes, detergents and personal care products due to their excellent fragrance retention and unique musk aroma. The molecular structure of these compounds usually contains multiple condensed ring systems (such as benzene rings, cycloalkanes or heterocycles), and has characteristic tert-butyl, methoxy and other substituents to enhance stability and aroma intensity.

[0003] Ester quaternary ammonium salt is a cationic surfactant with many applications in the industrial field. Among them, ester quaternary ammonium salt can be used in the finishing of fabrics to reduce the friction coefficient between fibers, make the fabric softer, smoother and more fluffy, and improve the feel and wearing comfort of the fabric. Ester quaternary ammonium salt is the basic component of film. If polycyclic musk aromatic compounds can be combined with film, the film can be given more functions. For example, when the film is used to finish the fabric, it can also give the fabric a musky fragrance. 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: The present invention provides an ester quaternary ammonium salt with a condensed ring structure, wherein the ester quaternary ammonium salt contains a naphthyl group and an alkyl group with 12 to 22 carbon atoms; The ester group quaternary ammonium salt comprises compound A, compound B and compound C; The general formulas of compound A, compound B and compound C are as follows:

[0006] 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; X - Represents anions that are compatible with softeners.

[0007] The ester quaternary ammonium salt with a condensed ring structure, wherein the anion compatible with the softener is a halogen, CH3SO4 or C2H5SO4.

[0008] The second aspect of the present invention provides a method for preparing an ester quaternary ammonium salt for preparing the ester quaternary ammonium salt with a fused ring structure as described above, comprising the following steps: Transesterification reaction: Add alkanolamine, fatty acid methyl ester, naphthoic acid ester and a catalyst solution into a reactor equipped with a mechanical stirrer; the molar ratio of alkanolamine, fatty acid methyl ester, naphthoic acid ester and naphthoic acid is 1:(0.4 - 1.2):(0.4 - 1.2); Pass nitrogen, heat the reaction mixture to 91°C - 105°C within 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, obtain amine ester, and cool to 60°C; Quaternization reaction: Add a solvent to the reactor, heat to 78 - 80°C, slowly dropwise add a quaternization reagent to the system, and the molar ratio of the quaternization reagent to the amine ester is (0.95 - 1):1; After the dropping is completed, keep the temperature at 78 - 80°C for 1.5 - 2 hours until the amine value of the reaction mixture reaches the minimum constant value, and obtain an ester quaternary ammonium salt with a fused ring structure.

[0009] In the method for preparing the ester quaternary ammonium salt, the alkanolamine is selected from triethanolamine.

[0010] In the method for preparing the ester quaternary ammonium salt, 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.

[0011] In the method for preparing the ester quaternary ammonium salt, the naphthoic acid ester is selected from at least one of ethyl 1-naphthoate, methyl α-naphthylacetate, and methyl 5-hydroxy-1-naphthoate.

[0012] In the method for preparing the ester quaternary ammonium salt, the catalyst is selected from at least one of sodium methoxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, and sodium borohydride.

[0013] In the method for preparing the ester quaternary ammonium salt, the quaternization reagent is selected from at least one of dimethyl sulfate, chloromethane, dimethyl carbonate, and trimethyl phosphate.

[0014] In the method for preparing the ester quaternary ammonium salt, the solvent is selected from at least one of C1 - C6 alcohols, diols, fatty acids, monoglycerides, diglycerides, and triglycerides.

[0015] The third aspect of the present invention provides a soft sheet, which comprises the ester quaternary ammonium salt with a fused ring structure as described above and a polycyclic musk aromatic compound.

[0016] Beneficial effects: The present invention provides an ester quaternary ammonium salt with a fused ring structure. The ester quaternary ammonium salt with a fused ring structure has a similar structure to polycyclic musk aromatic compounds and can, based on the principle of like dissolves like, enable polycyclic musk aromatic compounds to better bind within the ester quaternary ammonium salt, thereby endowing the soft sheet with a unique aroma.

[0017] The present invention also provides a soft sheet, which comprises the above-mentioned ester quaternary ammonium salt with a fused ring structure and polycyclic musk aromatic compounds. Compared with ordinary soft sheets, the soft sheet of the present invention also brings an additional aroma and has a fragrance-retaining effect. In addition, due to the presence of the fused ring structure, the polycyclic musk aromatic compounds in the soft sheet are not easily volatilized and lost, and the fragrance effect is more lasting. Detailed implementation manners

[0018] The present invention provides an ester quaternary ammonium salt with a fused ring structure, a preparation method thereof, and a soft sheet. To make the objectives, technical solutions, and effects of the present invention clearer and more definite, the following examples are given to further elaborate on the present invention in detail. It should be understood that the specific examples described herein are only used to explain the present invention and are not used to limit the present invention.

[0019] The present invention provides an ester quaternary ammonium salt with a fused ring structure, and the ester quaternary ammonium salt contains a naphthyl group and an alkyl group with 12 to 22 carbon atoms; The ester quaternary ammonium salt includes Compound A, Compound B, and Compound C; The general formulas of Compound A, Compound B, and Compound C are as follows:

[0020] In the general formula, each R is the same or different, and R represents an alkyl group with 12 to 22 carbon atoms or a naphthyl group. The alkyl group is a substituted or unsubstituted alkyl group, and the naphthyl group is a substituted or unsubstituted naphthyl group; X - represents an anion compatible with the softener.

[0021] Preferably, the anion compatible with the softener can be halogen, CH3SO4, or C2H5SO4.

[0022] The ester quaternary ammonium salt of the present invention has a fused ring structure, which is similar to the fused ring system structure on polycyclic musk aromatic compounds. According to the principle of like dissolves like, the similar properties enable polycyclic musk aromatic compounds to bind well within the ester quaternary ammonium salt.

[0023] When the fragrance is a polycyclic musk aromatic compound, the ester quaternary ammonium salt with a condensed ring structure in the soft sheet can reduce the volatilization of the fragrance during storage. During use, after the ester quaternary ammonium salt forms a uniform soft film on the fiber surface, the polycyclic musk aromatic compound fragrance can also better remain on the fabric fiber through the ester quaternary ammonium salt with a condensed ring structure, achieving a more lasting fragrance retention effect.

[0024] The second aspect of the present invention provides a preparation method of an ester quaternary ammonium salt for preparing the ester quaternary ammonium salt with a condensed ring structure as described above, including the following steps: Transesterification reaction: Add alkanolamine, fatty acid methyl ester, naphthoic acid ester, and catalyst solution to a reactor equipped with a mechanical stirrer; the molar ratio of alkanolamine, fatty acid methyl ester, naphthoic acid ester, and naphthoic acid is 1:(0.4 - 1.2):(0.4 - 1.2); pass nitrogen, heat the reaction mixture to 91°C - 105°C within 30 minutes under a vacuum pressure of 200 mbar, and react for 1 - 1.5 hours until the reaction mixture no longer releases low-boiling substances to obtain amine ester, and cool to 60°C; Quaternization reaction: Add a solvent to the reactor, heat to 78 - 80°C, slowly dropwise add a quaternization reagent to the system, and the molar ratio of the quaternization reagent to the amine ester is (0.95 - 1):1; after the dropping is completed, keep the temperature at 78 - 80°C for 1.5 - 2 hours until the amine value of the reaction mixture reaches the minimum constant value to obtain the ester quaternary ammonium salt with a condensed ring structure.

[0025] Preferably, the alkanolamine is selected from triethanolamine.

[0026] 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.

[0027] Specifically, the C12 - C22 acid can be selected from the following acids: oleic acid, elaidic acid, isolenic acid, gadoleic acid, eicosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, octadecatrienoic acid, punicic acid, α-eleostearic acid, β-eleostearic acid, arachidonic acid, eicosapentaenoic acid, clupanodonic acid, docosahexaenoic acid.

[0028] Preferably, the naphthoic acid ester is selected from at least one of ethyl 1-naphthoate, methyl α-naphthylacetate, and methyl 5-hydroxy-1-naphthoate.

[0029] Preferably, the catalyst is selected from at least one of sodium methoxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, and sodium borohydride.

[0030] Preferably, the quaternization reagent is selected from at least one of dimethyl sulfate, chloromethane, dimethyl carbonate, and trimethyl phosphate.

[0031] Preferably, the solvent is selected from at least one of C1-C6 alcohols, diols, fatty acids, monoglycerides, diglycerides, and triglycerides.

[0032] The third aspect of the present invention provides a soft film, which comprises the ester quaternary ammonium salt with a fused ring structure and a polycyclic musk aromatic compound as described above.

[0033] Specifically, the polycyclic musk aromatic compound is selected from at least one of tonalide, traseolide, galaxolide, and HHCB.

[0034] Example 1 An ester quaternary ammonium salt with a fused ring structure, and its preparation method is as follows: Transesterification reaction: 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. Nitrogen was passed through, and the reaction mixture was heated to 95 °C within 30 minutes under a vacuum pressure of 200 mbar and reacted for 1 hour until the reaction mixture no longer released low-boiling substances to obtain an amine ester, and the amine ester was cooled to 60 °C.

[0035] Quaternization reaction: 120 g of isopropanol was slowly added to the above reactor, heated to 78-80 °C, and 120 g (0.95 mol) of dimethyl sulfate was slowly added dropwise to the system. After the addition was completed, the mixture was kept at 78-80 °C for 100 minutes. At this time, the amine value of the reaction mixture reached the minimum, and it was cooled to room temperature to obtain an ester quaternary ammonium salt with a fused ring structure.

[0036] Example 2 An ester quaternary ammonium salt with a fused ring structure, and its preparation method is as follows: Transesterification reaction: 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% methanol solution of sodium methoxide were introduced into a reactor equipped with a mechanical stirrer. Nitrogen was passed through, and the reaction mixture was heated to 105 °C within 30 minutes under a vacuum pressure of 200 mbar and reacted for 1.2 hours until the reaction mixture no longer released low-boiling substances to obtain an amine ester, and the amine ester was cooled to 60 °C.

[0037] Quaternization reaction: 120 g of isopropanol was slowly added to the above reactor, heated to 78-80 °C, and 117.87 g (0.95 mol) of trimethyl phosphate was slowly added dropwise to the system. After the addition was completed, the mixture was kept at 78-80 °C for 100 minutes. At this time, the amine value of the reaction mixture had reached the minimum, and it was cooled to room temperature to obtain an ester quaternary ammonium salt with a fused ring structure.

[0038] Example 3 An ester quaternary ammonium salt with a fused ring structure, and its preparation method is as follows: Transesterification reaction: 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 methanol solution of 25% sodium methoxide were introduced into a reactor equipped with a mechanical stirrer. Nitrogen was passed through, and the reaction mixture was heated to 95 °C within 30 minutes under a vacuum pressure of 200 mbar and reacted for 1 hour until the reaction mixture no longer released low-boiling substances to obtain an amine ester, and the amine ester was cooled to 60 °C.

[0039] Quaternization reaction: 120 g of isopropanol was slowly added to the above reactor and heated to 78 - 80 °C. 120 g (0.95 mol) of dimethyl sulfate was slowly added dropwise to the system. After the addition was completed, the mixture was kept at 78 - 80 °C for 100 minutes. At this time, the amine value of the reaction mixture reached the minimum, and it was cooled to room temperature to obtain an ester quaternary ammonium salt with a fused ring structure.

[0040] Example 4 An ester quaternary ammonium salt with a fused ring structure, and the difference in its preparation method from Example 1 lies in the different transesterification reactions; In this example, the transesterification reaction is as follows: 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 methanol solution of 25% sodium methoxide were introduced into a reactor equipped with a mechanical stirrer. Nitrogen was passed through, and the reaction mixture was heated to 95 °C within 30 minutes under a vacuum pressure of 200 mbar and reacted for 1 hour until the reaction mixture no longer released low-boiling substances to obtain an amine ester, and the amine ester was cooled to 60 °C.

[0041] Example 5 An ester quaternary ammonium salt with a fused ring structure, and the difference in its preparation method from Example 1 lies in the different transesterification reactions; In this example, the transesterification reaction is as follows: 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 methanol solution of 25% sodium methoxide were introduced into a reactor equipped with a mechanical stirrer. Nitrogen was passed through, and the reaction mixture was heated to 95 °C within 30 minutes under a vacuum pressure of 200 mbar and reacted for 1 hour until the reaction mixture no longer released low-boiling substances to obtain an amine ester, and the amine ester was cooled to 60 °C.

[0042] Comparative Example 1 An ester quaternary ammonium salt with a condensed ring structure, the difference in its preparation method from that of Example 1 lies in the transesterification reaction being different; In this comparative example, the transesterification reaction is as follows: 149.2 g (1 mol) of triethanolamine, 455.15 g (1.6 mol) of methyl stearate, and 8.8 g of a methanol solution of 25% sodium methoxide were introduced into a reactor equipped with a mechanical stirrer. Nitrogen was passed through, and the reaction mixture was heated to 95 °C within 30 minutes under a vacuum pressure of 200 mbar and reacted for 1 hour until the reaction mixture no longer released low-boiling substances to obtain an amine ester, and the amine ester was cooled to 60 °C.

[0043] Comparative Example 2 An ester quaternary ammonium salt with a condensed ring structure, the difference in its preparation method from that of Example 1 lies in the transesterification reaction being different; In this example, the transesterification reaction is as follows: 149.2 g (1 mol) of triethanolamine, 304.30 g (1.2 mol) of ethyl 1-naphthoate, and 8.8 g of a methanol solution of 25% sodium methoxide were introduced into a reactor equipped with a mechanical stirrer. Nitrogen was passed through, and the reaction mixture was heated to 95 °C within 30 minutes under a vacuum pressure of 200 mbar and reacted for 1 hour until the reaction mixture no longer released low-boiling substances to obtain an amine ester, and the amine ester was cooled to 60 °C.

[0044] Example 6 A soft film, by weight, consists of 4 parts of the ester quaternary ammonium salt of Example 1 and 2 parts of powder musk.

[0045] Example 7 A soft film, by weight, consists of 4 parts of the ester quaternary ammonium salt of Example 2 and 2 parts of powder musk.

[0046] Example 8 A soft film, by weight, consists of 4 parts of the ester quaternary ammonium salt of Example 3 and 2 parts of powder musk.

[0047] Example 9 A soft film, by weight, consists of 4 parts of the ester quaternary ammonium salt of Example 4 and 2 parts of powder musk.

[0048] Example 10 A soft film, by weight, consists of 4 parts of the ester quaternary ammonium salt of Example 5 and 2 parts of powder musk.

[0049] Comparative Example 3 A soft film, by weight, consists of 4 parts of the ester quaternary ammonium salt of Comparative Example 1 and 2 parts of powder musk.

[0050] Comparative Example 4 A soft sheet, by weight, consists of 4 parts of the ester quaternary ammonium salt of Comparative Example 2 and 2 parts of ambrettolide.

[0051] Test the fragrance persistence effect of the fabric washed with the above soft sheet to evaluate the fragrance retention ability of the soft sheet. The specific steps of the test refer to the "Evaluation Method for the Fragrance Retention Ability of Detergents (Long-lasting)".

[0052] The results are shown in Table 1.

[0053] Table 1

[0054] In Table 1, "√" represents that more than 80% of the subjects smelled the fragrance on the fabric. "×" represents that less than 80% of the subjects smelled the fragrance on the fabric.

[0055] To improve the accuracy, when the result is "×", test continuously for one more day. From the above results, it can be seen 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 in the present invention (Examples 6-10) can significantly extend the fragrance retention time of ambrettolide on the fabric.

[0056] Further comparing the results of Examples 6-8, it is found that the fragrance retention time of Example 6 is longer than that of Examples 7 and 8, reflecting that ester quaternary ammonium salts with condensed rings of different structures have different binding abilities to ambrettolide, and thus the fragrance retention times in the fabric are also different.

[0057] The differences between Example 6, Example 9, and Example 10 lie in the different amounts of methyl stearate and ethyl 1-naphthoate used in the transesterification reaction. It is found that when the molar ratio of methyl stearate to ethyl 1-naphthoate is 1:1, the prepared ester quaternary ammonium salt has the best effect. The reason is that the alkyl group has a strong interaction with the fabric. When the amount used is too small, there will not be enough ester quaternary ammonium salt left on the fabric, resulting in less bound fragrance. And the naphthyl group is a condensed ring structure, mainly used for better binding with polycyclic musk aromatic compounds. When the content is insufficient, the amount of polycyclic musk aromatic compounds bound naturally will be less. Only when the contents of the naphthyl group and the alkyl group are appropriate can the best use effect be achieved.

[0058] For the soft sheets of Comparative Example 3 and Comparative Example 4, the ester quaternary ammonium salts used only contain alkyl groups and naphthyl groups. It can be seen that the fragrance retention effects of both are not as good as those of Examples 6-10. The reason is that when only alkyl groups are present, polycyclic musk aromatic compound fragrances cannot be well bound to the fabric. And when only naphthyl groups are present, polycyclic musk aromatic compound fragrances lack a medium to bind to the fabric and are also prone to loss.

[0059] Rewetting property measurement method: According to QB / T 4309-2012 "Determination of the Rewetting Property of Fabric Softeners", the rewetting property of the fabric softener product was measured. Three test pieces were measured in parallel for each sample, and the measurement results were averaged. The shorter the time obtained from the test, the better the rewetting property. The results are shown in Table 2.

[0060] Table 2

[0061] It can be seen from the results in Table 2 that the rewetting property of the soft sheet of the present invention can reach the level of the prior art and has application value.

[0062] It is understandable that for those of ordinary skill in the art, equivalent substitutions or changes can be made according to the technical solution and inventive concept of the present invention, and all such changes or substitutions should fall within the protection scope of the claims appended to the present invention.

Claims

1. An ester quaternary ammonium salt with a fused ring structure, characterized in that, The ester quaternary ammonium salt contains a naphthyl group and an alkyl group with 12 to 22 carbon atoms; The ester quaternary ammonium salt includes Compound A, Compound B, and Compound C; The general formulas of Compound A, Compound B, and Compound C are as follows: In the general formula, each R is the same or different, and R represents an alkyl group with 12 to 22 carbon atoms or a naphthyl group. The alkyl group is a substituted or unsubstituted alkyl group, and the naphthyl group is a substituted or unsubstituted naphthyl group; X - represents an anion compatible with the softener.

2. The ester quaternary ammonium salt with a fused ring structure according to claim 1, characterized in that, The anion compatible with the softener is halogen or CH3SO4.

3. 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 in claim 1 or 2, and is characterized in that, It includes the following steps: Transesterification reaction: Add alkanolamine, fatty acid methyl ester, naphthoic acid ester, and a catalyst solution to a reactor equipped with a mechanical stirrer; the molar ratio of alkanolamine, fatty acid methyl ester, naphthoic acid ester, and naphthoic acid is 1:(0.4 - 1.2):(0.4 - 1.2); Pass nitrogen, heat the reaction mixture to 91°C - 105°C within 30 minutes under a vacuum pressure of 200 mbar, and react for 1 - 1.5 hours until the reaction mixture no longer releases low-boiling substances to obtain amine ester, and cool to 60°C; Quaternization reaction: Add a solvent to the reactor, heat to 78 - 80°C, slowly dropwise add a quaternization reagent to the system, and the molar ratio of the quaternization reagent to the amine ester is (0.95 - 1):1; After the dropping is completed, keep the temperature at 78 - 80°C for 1.5 - 2 hours until the amine value of the reaction mixture reaches the minimum constant value to obtain an ester quaternary ammonium salt with a polycyclic structure.

4. The preparation method of the ester quaternary ammonium salt according to claim 3, characterized in that, The alkanolamine is selected from triethanolamine.

5. The preparation method of the ester quaternary ammonium salt according to claim 3, wherein, 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.

6. The preparation method of the ester quaternary ammonium salt according to claim 3, characterized in that, The naphthoic acid ester is selected from at least one of ethyl 1-naphthoate, methyl α-naphthylacetate, and methyl 5-hydroxy-1-naphthoate.

7. The preparation method of the ester quaternary ammonium salt according to claim 3, characterized in that, The catalyst is selected from at least one of sodium methoxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, and sodium borohydride.

8. The preparation method of the ester quaternary ammonium salt according to claim 3, wherein, The quaternization reagent is selected from at least one of dimethyl sulfate, chloromethane, dimethyl carbonate, and trimethyl phosphate.

9. The preparation method of the ester quaternary ammonium salt according to claim 3, characterized in that, The solvent is selected from at least one of C1 - C6 alcohols, diols, fatty acids, monoglycerides, diglycerides, and triglycerides.

10. A film, characterized in that, It includes the ester quaternary ammonium salt with a polycyclic structure described in Claim 1 or 2 and a polycyclic musk aromatic compound.

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