阅读说明：本技术 一种三环癸烯酯的制备方法 (Preparation method of tricyclodecenyl ester ) 是由 邵洪东 陈彩玲 陈雄毅 左洪亮 刘阳 杨璧逢 黄永东 曾显淦 林放 于 2021-09-23 设计创作，主要内容包括：本发明香料的制备方法,更具体地说,它涉及一种三环癸烯酯的制备方法,包括将羧酸加热升温除水,随后加入负载型固体催化剂并升温,再滴加双环戊二烯进行反应,反应完毕后过滤并在负压下蒸馏获得粗产品,将所述粗产品通过减压蒸馏制备获得三环癸烯酯,所述羧酸包括乙酸、丙酸和异丁酸中的一种或多种,所述负载型固体催化剂为沸石负载磷钨酸。本发明采用负载型固体催化剂作为反应的催化剂,负载型固体催化剂可以循环使用,有效地降低了生产成本,且相对于液体酸催化剂难以进行回收,采用负载型固体催化剂可避免反应后的中和水洗步骤,从而减少了大量废水的产生,避免污染环境。(The invention relates to a preparation method of a spice, in particular to a preparation method of tricyclodecenyl ester, which comprises the steps of heating carboxylic acid to raise the temperature and remove water, then adding a supported solid catalyst and raising the temperature, then dropwise adding dicyclopentadiene to react, filtering after the reaction is finished, distilling under negative pressure to obtain a crude product, and distilling under reduced pressure to prepare the tricyclodecenyl ester, wherein the carboxylic acid comprises one or more of acetic acid, propionic acid and isobutyric acid, and the supported solid catalyst is zeolite supported phosphotungstic acid. The invention adopts the supported solid catalyst as the catalyst for the reaction, the supported solid catalyst can be recycled, the production cost is effectively reduced, and compared with the liquid acid catalyst, the supported solid catalyst is difficult to recycle, and the supported solid catalyst can avoid the step of neutralization and water washing after the reaction, thereby reducing the generation of a large amount of waste water and avoiding the environmental pollution.)

1. A preparation method of tricyclodecenyl ester is characterized by comprising the steps of heating carboxylic acid to remove water, adding a supported solid catalyst, heating, dropwise adding dicyclopentadiene to react, filtering after the reaction is finished, distilling under negative pressure to obtain a crude product, and distilling the crude product under reduced pressure to obtain the tricyclodecenyl ester, wherein the carboxylic acid comprises one or more of acetic acid, propionic acid and isobutyric acid, and the supported solid catalyst is zeolite supported phosphotungstic acid.

2. The method of claim 1, wherein the carboxylic acid is present in excess.

3. The method of claim 1 or 2, wherein the molar ratio of the carboxylic acid to the dicyclopentadiene is 2-3: 1.

4. The method of claim 3, wherein the molar ratio of the carboxylic acid to the dicyclopentadiene is 2.5-3: 1.

5. The method for preparing tricyclodecenyl ester according to claim 1, wherein a supported solid catalyst is added and heated to 50-170 ℃.

6. The method for preparing tricyclodecenyl ester according to claim 1, wherein the dropping time of dicyclopentadiene is 7-17 h, and the reaction temperature is controlled to be 60-170 ℃ during the dropping process.

7. The method for preparing tricyclodecenyl ester according to claim 1, wherein the dicyclopentadiene reacts for 10-20 h at constant temperature after being added dropwise.

8. The method of claim 1, wherein the dicyclopentadiene has a purity of 90-95% and the carboxylic acid has a purity of 80-95%.

Technical Field

The invention relates to a preparation method of a spice, and more particularly relates to a preparation method of tricyclodecenyl ester.

Background

Tricyclodecenyl esters, particularly carboxylic acid esters derived from dicyclopentadiene, are a ubiquitous fragrance ingredient in detergents, shampoos, deodorants, hard-surface cleaners, and other applications.

The tricyclodecenyl acetate includes tricyclodecenyl acetate, tricyclodecenyl propionate and tricyclodecenyl butyrate, and the tricyclodecenyl acetate is a colorless to pale yellow viscous liquid, has strong and durable fragrance and woody fragrance, can be used in cosmetics, can be used as soap or detergent perfume due to its stability in alkaline medium, and can also be used as a pharmaceutical intermediate. The tricyclodecenyl propionate is widely used in various essence formulas in daily chemical essence, commonly exists in essence such as surface cleaning agent, shampoo, deodorant, detergent, soap and the like, and has sweet fruity fragrance accompanied with fragrance of jasmine and fennel.

Problems with current aromas in processing include: (1) in the production process, a liquid catalyst such as trifluoromethanesulfonic acid and the like is adopted for catalytic reaction, and neutralization and water washing are needed in the reaction process for neutralizing acid in a reaction product, so that a large amount of wastewater is generated; (2) due to the presence of a portion of the water in the liquid acid, this water is very likely to destroy the activity of the catalyst, resulting in a reduction in the catalytic effect.

Disclosure of Invention

In view of the above problems, an object of the present invention is to provide a method for preparing tricyclodecenyl ester, wherein a supported solid catalyst is used as a reaction catalyst, the supported solid catalyst can be recycled, the production cost is effectively reduced, the supported solid catalyst is difficult to recover relative to a liquid acid catalyst, and the supported solid catalyst can be used to avoid neutralization and water washing after the reaction, so that the generation of a large amount of waste water is reduced, and the environmental pollution is avoided.

The technical purpose of the invention is realized by the following technical scheme, and the preparation method of the tricyclodecenyl ester comprises the steps of heating carboxylic acid to remove water, adding a supported solid catalyst, heating, dropwise adding dicyclopentadiene to react, filtering after the reaction is finished, distilling under negative pressure to obtain a crude product, and distilling under reduced pressure to prepare the tricyclodecenyl ester, wherein the carboxylic acid comprises one or more of acetic acid, propionic acid and isobutyric acid, and the supported solid catalyst is zeolite supported phosphotungstic acid. The invention adopts carboxylic acid and dicyclopentadiene as raw materials, carboxylic acid is added to carbon-carbon double bonds of the dicyclopentadiene through electrophilic addition under the action of a supported solid catalyst, and the supported solid catalyst can generate hydrolysis reaction with moisture in a solution system, so that the carboxylic acid is heated before the carboxylic acid and the dicyclopentadiene are mixed for reaction, a small amount of residual moisture in the carboxylic acid is removed, the catalytic activity of the catalyst is prevented from being damaged, and the reuse rate of the catalyst is reduced. Because excessive carboxylic acid is added in the reaction, after the reaction is finished, the excessive carboxylic acid is recovered by reducing pressure and raising temperature, the recovered carboxylic acid can be reused, the production cost is reduced, and the distilled crude product is subjected to reduced pressure distillation to prepare the tricyclodecenyl ester product.

In the present invention, the carboxylic acid is in excess. The excessive carboxylic acid is added in the reaction, which is favorable for the full reaction and improves the reaction conversion rate.

In the invention, the molar ratio of the carboxylic acid to the dicyclopentadiene is 2-3: 1.

In the invention, the molar ratio of the carboxylic acid to the dicyclopentadiene is 2.5-3: 1.

In the invention, a supported solid catalyst is added and the temperature is raised to 50-170 ℃.

In the invention, the dripping time of the dicyclopentadiene is 7-17 h, and the reaction temperature is controlled to be 60-170 ℃ in the dripping process.

In the invention, after the dicyclopentadiene is dripped, the reaction is carried out for 10-20 h at constant temperature.

In the invention, the purity of the dicyclopentadiene is 90-95%, and the purity of the carboxylic acid is 80-95%. The purity of the dicyclopentadiene and the carboxylic acid is controlled, impurities such as acetic anhydride and acetic ester possibly existing in the raw materials are reduced to pollute the raw materials, side reaction and byproducts are reduced, and the yield of the product is ensured.

The invention has the following beneficial effects:

(1) the invention adopts the supported solid catalyst to replace the liquid acid catalyst, and the supported solid catalyst can be recycled, thereby effectively reducing the production cost;

(2) the supported solid catalyst can perform hydrolysis reaction with water in a solution system, so that before the carboxylic acid and the dicyclopentadiene are mixed and reacted, the carboxylic acid is heated to remove a small amount of residual water in the carboxylic acid, the catalytic activity of the catalyst is prevented from being damaged, and the reuse rate of the catalyst is reduced;

(3) the invention adopts the supported solid catalyst, which can avoid the step of neutralization and water washing after the reaction, thereby reducing the generation of a large amount of waste water and avoiding the pollution to the environment;

(4) the purity of dicyclopentadiene and carboxylic acid in the reaction is controlled, impurities such as acetic anhydride and acetic ester in the raw materials are reduced to pollute the raw materials, side reactions and byproducts are reduced, and the yield of the tricyclodecenyl ester is ensured.

Detailed Description

Example 1

The preparation method of the embodiment comprises the following steps:

(1) acid addition and water removal: adding 70 parts of excessive carboxylic acid into the reaction kettle, heating to remove water, and analyzing the moisture content in the carboxylic acid to ensure that the moisture is completely removed;

(2) and (3) catalytic reaction: after the acid with water removed in the step (1) is fully stirred, adding 0.5 part of supported solid catalyst, slowly heating to 50 ℃, wherein the supported solid catalyst is zeolite supported phosphotungstic acid, then starting to dropwise add dicyclopentadiene, controlling the temperature in the dropwise adding process to be 60 ℃, controlling the dropwise adding time of 50 parts of dicyclopentadiene to be 7 hours, and carrying out constant-temperature reaction for 10 hours after the dropwise adding of the dicyclopentadiene is finished until the sampling analysis is qualified;

(3) and (3) recovering carboxylic acid: filtering after the reaction in the step (2) is finished, transferring filtrate to a raw material recovery kettle, and heating and recovering excessive carboxylic acid under negative pressure to obtain a crude product;

(4) product treatment: and refining the crude product by reduced pressure distillation to obtain a tricyclodecenyl ester product.

Among them, dicyclopentadiene has a purity of 90%, carboxylic acid has a purity of 80%, and further, carboxylic acid is acetic acid.

Wherein the molar ratio of the carboxylic acid to the dicyclopentadiene is 2: 1.

The content of tricyclodecenyl ester in the tricyclodecenyl ester product prepared in this example was measured by gas chromatography and reached 87%.

Example 2

The preparation method of this example differs from that of example 1 in that: the purity of the carboxylic acid in the step (1) is 95%, and the carboxylic acid is propionic acid; in the step (2), adding a supported solid catalyst, slowly heating to 170 ℃, keeping the purity of dicyclopentadiene at 95%, dropwise adding for 17h, controlling the temperature in the dropwise adding process to 170 ℃, and reacting at constant temperature for 20h after the dropwise adding of dicyclopentadiene is finished, wherein the molar ratio of carboxylic acid to dicyclopentadiene is 3: 1.

The content of the tricyclodecenyl ester in the prepared tricyclodecenyl ester product is up to 92% by adopting gas chromatography detection.

Example 3

The preparation method of this example differs from that of example 1 in that: the purity of the carboxylic acid in the step (1) is 90%, and the carboxylic acid is isobutyric acid; in the step (2), a supported solid catalyst is added, the temperature is slowly raised to 100 ℃, the purity of the dicyclopentadiene is 95%, the dripping time is 15 hours, the temperature is controlled to be 150 ℃ in the dripping process, the dicyclopentadiene reacts for 15 hours at constant temperature after the dripping is finished, and the molar ratio of the carboxylic acid to the dicyclopentadiene is 2.5: 1.

The content of the tricyclodecenyl ester in the prepared tricyclodecenyl ester product is 91% by adopting gas chromatography detection.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is conceivable, and the examples presented herein demonstrate the results of applicants' actual experiments. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.