阅读说明：本技术 一种玫瑰香精包埋香料的制备方法以及二氧化碳可控释放玫瑰香精的方法 (Preparation method of rose essence embedded spice and method for releasing rose essence by carbon dioxide ) 是由 史清照 张启东 华辰凤 徐秀娟 胡军 毛健 柴国璧 范武 宋瑜冰 刘俊辉 屈展 于 2020-12-03 设计创作，主要内容包括：本发明属于香料的制备领域,具体涉及一种玫瑰香精包埋香料的制备方法以及二氧化碳可控释放玫瑰香精的方法。该方法包括：1)将玫瑰精油、N-烷基咪唑和水混合,制备混合液；2)将混合液和二氧化碳混合,形成聚集体溶液体系。本发明中,通过在水体系中N-烷基咪唑和二氧化碳反应,生成具有表面活性的N-烷基咪唑碳酸氢盐,N-烷基咪唑碳酸氢盐能够以聚集体形式包埋玫瑰香精,并形成稳定的聚集体溶液体系,从而构建常态下稳定的玫瑰香精包埋香料。利用N-烷基咪唑碳酸氢盐在水体系中对CO-2的敏感性,可以实现N-烷基咪唑碳酸氢盐逆向转变为N-烷基咪唑,N-烷基咪唑没有表面活性,从而实现包埋体系的控制释放。(The invention belongs to the field of preparation of perfumes, and particularly relates to a preparation method of a perfume embedded with a rose essence and a method for releasing the rose essence under the control of carbon dioxide. The method comprises the following steps: 1) mixing rose essential oil, N-alkyl imidazole and water to prepare a mixed solution; 2) and mixing the mixed solution with carbon dioxide to form an aggregate solution system. In the invention, N-alkyl imidazole bicarbonate with surface activity is generated by the reaction of N-alkyl imidazole and carbon dioxide in a water system, and the N-alkyl imidazole bicarbonate can embed the rose essence in an aggregate form and form a stable aggregate solution system, thereby constructing the stable rose essence embedded spice under a normal state. CO-pairs in aqueous systems using N-alkylimidazolium bicarbonates 2 The N-alkyl imidazole bicarbonate can be reversely converted into the N-alkyl imidazole due to the sensitivity of the N-alkyl imidazole bicarbonate, and the N-alkyl imidazole has no surface activity, so that the controlled release of an embedding system is realized.)

1. The preparation method of the rose essence embedded spice is characterized by comprising the following steps:

1) mixing rose essential oil, N-alkyl imidazole and water to prepare a mixed solution; the alkyl in the N-alkyl imidazole is C_10-12The linear alkyl group of (1);

2) and mixing the mixed solution with carbon dioxide to form an aggregate solution system.

2. The method for preparing encapsulated rose essence according to claim 1, wherein in step 1), the amount of rose essential oil is 0.1-0.2g and the amount of N-alkylimidazole is 0.1-0.4g per 50ml of water.

3. The method for preparing encapsulated rose essence according to claim 1, wherein in step 1), the N-alkyl imidazole is prepared by a method comprising the steps of: reacting beta-cyanoethylimidazole with bromoalkane in a solvent at the temperature of 100-120 ℃, removing the solvent after reaction, adding alkali liquor and chloroform for mixing, separating an organic phase and carrying out aftertreatment.

4. The method for preparing encapsulated rose essence according to claim 1, which is characterized in thatCharacterized in that in the step 2), the mixing of the mixed solution and the carbon dioxide comprises introducing CO into the mixed solution₂Gas or CO₂High CO concentration of at least 80%₂Mixing the gas, and/or adding dry ice to the mixed solution.

5. The method for preparing encapsulated rose essence of claim 4, wherein CO is introduced₂Gas or said high concentration CO₂The velocity of the mixed gas is 0.05-0.5L/min.

6. The method for preparing the encapsulated rose essence of claim 5, wherein CO is introduced into 50ml of the mixed solution₂Gas or said high concentration CO₂The time of mixing gas is 10-60 min.

7. The method for preparing a rose essence embedded flavor according to any one of claims 1 to 6, wherein the average particle size of the aggregate solution system is 100-300 nm.

8. The method for releasing the rose essence under the control of carbon dioxide is characterized by comprising the following steps:

1) mixing rose essential oil, N-alkyl imidazole and water to prepare a mixed solution; the alkyl in the N-alkyl imidazole is C_10-12The linear alkyl group of (1);

2) mixing the mixed solution with carbon dioxide to form an aggregate solution system;

3) using lean CO₂The gas destroys the aggregate solution system, releasing rose essential oil; the lean CO₂The gas does not contain CO₂Or is CO₂Low concentration CO of not more than 20%₂A gas.

9. The method for controlled release of rose essence with carbon dioxide according to claim 8, wherein in step 3), the CO-poor is used₂The gas destroying the aggregate solution system comprises introducing a CO-lean stream into the aggregate solution system₂Gas, fed with CO lean₂The gas rate is 0.05-0.5L/min.

10. The method for controlled release of rose essence with carbon dioxide according to claim 8 or 9, characterized in that the CO-lean is₂The gas is selected from one or more of nitrogen, air and argon.

Technical Field

The invention belongs to the field of preparation of perfumes, and particularly relates to a preparation method of a perfume embedded with a rose essence and a method for releasing the rose essence under the control of carbon dioxide.

Background

The rose essential oil is a rare natural spice and is mainly used in the fields of food, health care products, daily chemicals and the like. However, the rose essential oil is insoluble in water, has the characteristics of strong volatility, light and heat sensitivity and the like, so that the rose essential oil is easily lost and damaged under the conditions of storage and application, and the application of the rose essential oil is greatly limited.

At present, the rose essential oil is often processed by adopting an embedding technology to enhance the solubility and stability of the rose essential oil in water. Xueshitao et al, using saccharified glass as wall material, homogenizing, freezing, drying, and pulverizing to obtain oleum Rosae Rugosae microcapsule (preparation of microcapsule oleum Rosae Rugosae and its perfuming evaluation of cigarettes [ J ]. school news of Yunnan university (Nature edition), 2013, 35(S1): 293-. The technical research on the preparation of microcapsule essence by using beta-cyclodextrin to include rose essential oil (beta-cyclodextrin to include rose essential oil [ J ]. applied chemical industry, 2011, 40(03):510-512) in Taoyang et al.

The embedding modes achieve the aims of improving the dispersibility in an aqueous solution system and enhancing the stability to a certain extent, but the release capacity of most of the embedding modes is poor, so that the application effect of the rose essential oil is limited.

Disclosure of Invention

The invention aims to provide a preparation method of rose essence embedded spice, which realizes the uniform dispersion of rose essential oil in an aqueous solution system and enhances the stability and has the function of controlled release.

The second purpose of the invention is to provide a method for releasing the rose essence by controlling carbon dioxide.

In order to realize the purpose, the technical scheme of the preparation method of the rose essence embedded spice is as follows:

a preparation method of rose essence embedded spice comprises the following steps:

1) mixing rose essential oil, N-alkyl imidazole and water to prepare a mixed solution; the alkyl in the N-alkyl imidazole is C_10-12The linear alkyl group of (1);

2) and mixing the mixed solution with carbon dioxide to form an aggregate solution system.

According to the preparation method of the rose essence embedded spice, N-alkyl imidazole bicarbonate with surface activity is generated by the reaction of N-alkyl imidazole and carbon dioxide in a water system, and the rose essence can be embedded in the N-alkyl imidazole bicarbonate in an aggregate form to form a stable aggregate solution system, so that the stable rose essence embedded spice under a normal state is constructed. CO-pairs in aqueous systems using N-alkylimidazolium bicarbonates₂The N-alkyl imidazole bicarbonate can be reversely converted into the N-alkyl imidazole due to the sensitivity of the N-alkyl imidazole bicarbonate, and the N-alkyl imidazole has no surface activity, so that the controlled release of an embedding system is realized.

In the step 1), the dosage of the rose essential oil is 0.1-0.2g and the dosage of the N-alkyl imidazole is 0.1-0.4g per 50ml of water.

The N-alkylimidazole can be prepared according to the prior art method, and in order to improve the reaction yield, preferably, the N-alkylimidazole is prepared by the method comprising the following steps: reacting beta-cyanoethylimidazole with bromoalkane in a solvent at the temperature of 100-120 ℃, removing the solvent after reaction, adding alkali liquor and chloroform for mixing, separating an organic phase and carrying out aftertreatment.

Beta-cyanoethylimidazole can be prepared by reacting imidazole and acrylonitrile in a solvent at 50-60 deg.C for 2-5 h. The molar ratio of imidazole and acrylonitrile can be controlled to be 1: 1-1.5.

When the beta-cyanoethylimidazole reacts with the alkyl bromide, the reaction is carried out for 10 to 20 hours under the conditions of 100 ℃ and 120 ℃. The mol ratio of bromoalkane to imidazole can be controlled to be 1: 1-1.5.

The introduction of CO into the mixed liquor may be carried out in a manner well known in the art₂For example, the method may be performed by introducing gas or adding dry ice.

Preferably, in the step 2), the mixing the mixed solution and the carbon dioxide comprises introducing CO into the mixed solution₂Gas or CO₂High CO concentration of at least 80%₂Mixing the gas, and/or adding dry ice to the mixed solution. Further preferably, CO is introduced₂Gas or said high concentration CO₂The velocity of the mixed gas is 0.05-0.5L/min. Introducing CO into every 50ml of mixed solution₂Gas or said high concentration CO₂The time of mixing gas is 10-60 min.

By CO₂The amount of (b) is sufficient to form a stable aggregate solution, and the stability of the system can be evaluated by the average particle size of the aggregate solution system, which is preferably 100-300 nm.

The technical scheme of the method for releasing the rose essence by controlling the carbon dioxide comprises the following steps:

the method for releasing the rose essence under the control of carbon dioxide comprises the following steps:

1) mixing rose essential oil, N-alkyl imidazole and water to prepare a mixed solution; the alkyl in the N-alkyl imidazole is C₁₂The linear alkyl group of (1);

2) mixing the mixed solution with carbon dioxide to form an aggregate solution system;

3) using lean CO₂The gas destroys the aggregate solution system, releasing rose essential oil; the lean CO₂The gas does not contain CO₂Or is CO₂Concentration of not higher than20% low concentration CO₂A gas.

In aqueous systems, N-alkylimidazoles with CO₂The process of forming N-alkyl imidazole bicarbonate is a reversible process, when carbon dioxide-poor gas is introduced into the system, the introduced gas will react with CO₂Compete for CO in the system₂The reaction to form N-alkyl imidazole bicarbonate is driven out in the reverse direction, the surface active N-alkyl imidazole bicarbonate returns to the non-surface active N-alkyl imidazole form, the aggregates are destroyed, and the encapsulated rose essence is released.

The controlled release method of rose essence of the invention, CO₂The device has the function of controlling a release switch of an embedding system, the original rose essence embedding system can be destroyed by introducing the poor carbon dioxide gas, the rose essence is separated from the system, and the controllable release of the perfume is realized.

In step 3), the utilization is lean of CO₂The gas destroying the aggregate solution system comprises introducing a CO-lean stream into the aggregate solution system₂Gas, fed with CO lean₂The gas rate is 0.05-0.5L/min. Preferably, the lean CO₂The gas is selected from one or more of nitrogen, air and argon.

Drawings

FIG. 1 shows the results of particle size analysis of rose essence embedded flavor in example 1 of the present invention;

FIG. 2 is the analysis result of particle size after the destruction of the encapsulating system of the rose essence-embedded spice in example 6 of the present invention;

FIG. 3 shows the introduction of CO into the N-dodecyl imidazole/water system₂And analyzing the particle size of the post solution.

Detailed Description

The following examples are provided to further illustrate the practice of the invention.

First, the specific embodiment of the preparation method of the rose essence embedded spice of the invention

Example 1

The preparation method of the rose essence embedded spice comprises the following steps:

1) 6.8g of imidazole and 8.0g of acrylonitrile were added to 25ml of methanol, the mixture was reacted at 60 ℃ for 3 hours, the solvent was distilled off under reduced pressure to obtain β -cyanoethylimidazole, the β -cyanoethylimidazole was dissolved in 30ml of acetonitrile, 22.1g of bromododecane was added, the mixture was reacted at 100 ℃ for 15 hours, the acetonitrile was distilled off under reduced pressure, 50ml of 15 wt% NaOH solution and 30ml of chloroform were added, and the mixture was kept at 25 ℃ for 1 hour. Separating out an organic phase; the organic phase was washed with 30ml of deionized water to neutrality, and the chloroform solvent was removed by distillation under reduced pressure to obtain N-dodecyl imidazole.

2) Mixing 0.1g rose essential oil, 0.1g N-dodecyl imidazole, and 50ml water to form a mixed solution, and introducing CO into the mixed solution at a rate of 0.25L/min₂And (5) gas is used for 30min, so that the stable rose essence-embedded water solution (forming a stable aggregate solution system) can be obtained.

Example 2

The preparation method of the rose essence embedded spice comprises the following steps:

1) 6.8g of imidazole and 8.0g of acrylonitrile were added to 30ml of methanol, and the mixture was reacted at 50 ℃ for 4 hours, the solvent was distilled off under reduced pressure to obtain β -cyanoethylimidazole, which was dissolved in 25ml of acetonitrile, 22g of bromododecane was added, the mixture was reacted at 110 ℃ for 11 hours, the acetonitrile was distilled off under reduced pressure, 50ml of a 15 wt% NaOH solution and 30ml of chloroform were added, and the mixture was kept at 25 ℃ for 1 hour. Separating out an organic phase; the organic phase was washed with 30ml of deionized water to neutrality, and the chloroform solvent was removed by distillation under reduced pressure to obtain N-dodecyl imidazole.

2) Mixing 0.1g rose essential oil, 0.1g N-dodecyl imidazole and 50ml water to form a mixed solution, and introducing CO into the mixed solution at a rate of 0.10L/min₂And (5) gas is used for 1h, so that the aqueous solution for stably embedding the rose essence can be obtained.

Example 3

The preparation method of the rose essence embedded spice comprises the following steps:

1) 6.8g of imidazole and 8.0g of acrylonitrile were added to 25ml of methanol, the mixture was reacted at 60 ℃ for 3 hours, the solvent was distilled off under reduced pressure to obtain β -cyanoethylimidazole, the β -cyanoethylimidazole was dissolved in 30ml of acetonitrile, 22.1g of bromododecane was added, the mixture was reacted at 115 ℃ for 15 hours, the acetonitrile was distilled off under reduced pressure, 50ml of 15 wt% NaOH solution and 30ml of chloroform were added, and the mixture was kept at 25 ℃ for 1 hour. Separating out an organic phase; the organic phase was washed with 30ml of deionized water to neutrality, and the chloroform solvent was removed by distillation under reduced pressure to obtain N-dodecyl imidazole.

2) Mixing 0.15g rose essential oil, 0.15g N-dodecyl imidazole and 50ml water to form a mixed solution, and introducing CO into the mixed solution at a rate of 0.25L/min₂And (5) gas is used for 50min to obtain the stable rose essence embedded aqueous solution.

Example 4

The preparation method of the rose essence embedded spice comprises the following steps:

1) 6.8g of imidazole and 8.0g of acrylonitrile were added to 25ml of methanol, and the mixture was reacted at 60 ℃ for 3 hours, the solvent was distilled off under reduced pressure to obtain β -cyanoethylimidazole, which was dissolved in 30ml of acetonitrile, 21.5g of bromodecane was added, the mixture was reacted at 100 ℃ for 17 hours, the acetonitrile was distilled off under reduced pressure, 50ml of a 15 wt% NaOH solution and 30ml of chloroform were added, and the mixture was held at 25 ℃ for 1 hour. Separating out an organic phase; the organic phase was washed with 30ml of deionized water to neutrality, and the chloroform solvent was removed by distillation under the reduced pressure to obtain N-decylimidazole.

2) Mixing 0.15g rose essential oil, 0.15g N-decyl imidazole and 50ml water to obtain a mixture, and introducing CO into the mixture at a rate of 0.33L/min₂And (5) gas is used for 35min, so that the aqueous solution for stably embedding the rose essence can be obtained.

Example 5

The preparation method of the rose essence embedded spice comprises the following steps:

1) 6.8g of imidazole and 8.0g of acrylonitrile were added to 25ml of methanol, the mixture was reacted at 60 ℃ for 3 hours, the solvent was distilled off under reduced pressure to obtain β -cyanoethylimidazole, the β -cyanoethylimidazole was dissolved in 30ml of acetonitrile, 22.1g of bromododecane was added, the mixture was reacted at 115 ℃ for 15 hours, the acetonitrile was distilled off under reduced pressure, 50ml of 15 wt% NaOH solution and 30ml of chloroform were added, and the mixture was kept at 25 ℃ for 1 hour. Separating out an organic phase; the organic phase was washed with 30ml of deionized water to neutrality, and the chloroform solvent was removed by distillation under reduced pressure to obtain N-dodecyl imidazole.

2) Mixing 0.15g rose essential oil, 0.30g N-dodecyl imidazole and 50ml water to form a mixed solution, and introducing CO into the mixed solution at a rate of 0.25L/min₂Gas is used for 50min to obtain stably embedded roseAqueous solution of rose essence.

In other embodiments of the method for preparing the rose essence-embedded flavor of the present invention, dry ice can be optionally added to obtain a stable aggregate solution.

Secondly, the method for releasing the rose essence with controllable carbon dioxide

Example 6

The method for releasing the rose essence by controlling the carbon dioxide comprises the following steps:

air was introduced into the aggregate solution system obtained in example 1 at a flow rate of 0.20L/min for 5min, and the embedded system was destroyed and changed from clear to transparent to turbid, releasing rose essence.

Example 7

The method for releasing the rose essence by controlling the carbon dioxide comprises the following steps:

n was introduced into the aggregate solution system obtained in example 2 at a flow rate of 0.20L/min₂When the gas is aerated for 1min, the embedding system is damaged and changes from clear and transparent state to turbid state, and the rose essence is released.

Example 8

The method for releasing the rose essence by controlling the carbon dioxide comprises the following steps:

ar gas is introduced into the aggregate solution system obtained in example 3 at a flow rate of 0.20L/min for 10min, and the embedding system is damaged, so that the transparent state is changed into a turbid state, and the rose essence is released.

Example 9

The method for releasing the rose essence by controlling the carbon dioxide comprises the following steps:

ar gas is introduced into the aggregate solution system obtained in example 4 at a flow rate of 0.15L/min for 20min, and the embedding system is damaged, so that the transparent state is changed into a turbid state, and the rose essence is released.

Example 10

The method for releasing the rose essence by controlling the carbon dioxide comprises the following steps:

to the aggregate solution system obtained in example 5N is introduced at a flow rate of 0.25L/min₂And (4) aerating for 15min to destroy the embedding system, so that the embedding system is changed from a clear and transparent state to a turbid state, and the rose essence is released.

In other embodiments of the method for controllably releasing rose essence by carbon dioxide, the flow rate and time of the introduced gas can be adjusted within the preferable range of the invention, and the experimental effect equivalent to that of the embodiments can be obtained.

Third, Experimental example

Experimental example 1 particle size analysis

The particle size analysis of the rose essence embedded flavor obtained in example 1 is shown in fig. 1, and it can be seen that most of the aggregate size is distributed around 188.5nm, and a stable aggregate solution system is formed.

After the rose essence is released by using the method of example 6, the particle size analysis result of the system is shown in fig. 2, and it can be seen that the aggregate size of the system is obviously increased, 52.4% of the aggregate size is about 2.1 microns, and the stability is greatly reduced.

For comparison, in the same manner as in example 1, CO was introduced into the mixed solution of example 1 without adding N-dodecyl imidazole and in the same ratio of N-dodecyl imidazole to water₂Thereafter, as a result of the particle size analysis shown in FIG. 3, it can be seen that the particle size of the aggregates was concentrated at 159.5 nm.

The comparison shows that the particle size of the system for embedding the perfume in the rose essence is small, and the rose essence is favorable for obtaining good stability.

Experimental example 2 analysis of Rose essence concentration

Citronellol is the main component of rose essence, and the concentration of citronellol in the system is quantified through GC-MS.

For the rose essence embedded fragrance of example 1 and the rose essence embedded fragrance destroyed by the method of example 6, the samples were taken from the middle of the solution system (after the embedded system was destroyed, part of the rose essence would be layered, the samples were taken from the aqueous phase, the evaluation results showed that the concentration of the rose essence stably existing in the aqueous phase), 1ml of the samples were taken, 5ml of acetone solution with internal standard (internal standard: sudachi and balsamic acid ester; concentration: 1.0 μ g/ml) was added, the solution was dried with anhydrous sodium sulfate, filtered and diluted 40 times with the internal standard solution for quantitative analysis by GC-MS, the GC-MS conditions were: a chromatographic column: DB-WAXetr (60 m.times.0.25 mm.times.0.25 μm); carrier gas: he; column flow rate: 1 mL/min; sample inlet temperature: 250 ℃; temperature programming: 50 deg.C (0min),3 deg.C/min → 250 deg.C (5 min); a non-shunting mode; GC/MS transmission line temperature: 250 ℃, EI ion source temperature: 230 ℃, quadrupole temperature: 150 ℃; EI ionization energy: 70 eV; scanning mode: an ion scan (138, 123, 109; 178, 122, 105) is selected.

In example 1, the concentration of citronellol was 0.271 mg/mL. After disruption of the embedding system as in example 6, the concentration of citronellol was 0.012 mg/mL.

In example 2, the concentration of citronellol was 0.343 mg/mL. After disruption of the embedding system as in example 7, the concentration of citronellol was 0.010 mg/mL.

In example 3, the concentration of citronellol was 0.315 mg/mL. After disruption of the embedding system as in example 8, the concentration of citronellol was 0.004 mg/mL.

In example 4, the concentration of citronellol was 0.300 mg/mL. After disruption of the encapsulation system as in example 9, the concentration of citronellol was 0.006 mg/mL.

In example 5, the concentration of citronellol was 0.438 mg/mL. After disruption of the embedding system as in example 10, the concentration of citronellol was 0.003 mg/mL.

Through the above experiments, it was demonstrated that the controlled release of the rose essence embedded fragrance can be achieved according to the method of the examples.

Experimental example 3 stability

This example performed stability testing of the rose essence encapsulated fragrance of example 1.

The aqueous solution obtained in step 2) of example 3 was left at room temperature, and samples were taken after 1 day, 2 days, 3 days, 5 days, 10 days, and 30 days, respectively, and the concentration of p-citronellol in the solution was measured by the method of example 2), and the measurement results are shown in table 1. Wherein the comparative example is an aqueous rose essence solution prepared by mixing rose essence and water, and the initial concentration of the rose essence is the same as that of example 3.

TABLE 1 citronellol content in Rose essence embedding solution

As can be seen from Table 1, compared with a system without surfactant embedding, the content of citronellol, which is the main component of the rose essence, in the system is not obviously reduced in the process of placing at room temperature, which indicates that the embedded rose essence has higher stability.