CN110963990A - Preparation method of musk C-14 - Google Patents
Preparation method of musk C-14 Download PDFInfo
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- CN110963990A CN110963990A CN201911353255.5A CN201911353255A CN110963990A CN 110963990 A CN110963990 A CN 110963990A CN 201911353255 A CN201911353255 A CN 201911353255A CN 110963990 A CN110963990 A CN 110963990A
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- depolymerization
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
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Abstract
A method for preparing musk C-14 comprises the following steps: performing polycondensation reaction; carrying out depolymerization reaction; carrying out reduced pressure distillation; and (4) fractional distillation. According to the invention, by adopting a one-pot method, the depolymerization catalyst is directly added to carry out depolymerization reaction without refining after the polycondensation reaction is finished, so that the process operation is simplified, and the production cost is reduced; polymerization inhibitor is added in the polymerization process, the polymerization degree of the intermediate is effectively controlled, byproducts such as high polymer and the like are prevented from being generated, and the utilization rate of raw materials is obviously improved; in the depolymerization process, an independently developed efficient nontoxic depolymerization catalyst is added, so that the intermediate product is completely depolymerized, and the yield of the product is improved; the post-treatment process of the crude product is free of the washing process, so that the operation process is simplified, the production period is shortened, the production efficiency is improved, no process wastewater is generated in the production process, and the process is green and environment-friendly; the product distillation adopts fractional distillation, and impurity removal, rectification and recovery are completed by using the same kettle, so that the production energy consumption is reduced, the yield of finished products is improved, and the production cost is reduced to a greater extent.
Description
Technical Field
The invention relates to the technical field of essence and spice processing, and particularly relates to a preparation method of musk C-14.
Background
Musk C-14 is a colorless or yellowish viscous liquid which is widely used in the markets of high-grade perfumes, cosmetics, soaps, hair care products and personal care products, and has been approved for use in the fields of medicines and food additives. Musk C-14 is a cyclic macromolecular compound without nitro group, its structure is similar to that of natural musk, and it is a cyclic compound containing 14 carbon atoms, and its synthesis method is that firstly, the dibasic acid and glycol are undergone the process of polycondensation reaction to produce linear polyester, then under the action of catalyst the linear polyester is depolymerized and cyclized to form macrocyclic diester.
At present, when linear polyester depolymerization is carried out in the production process of musk C-14, chain growth reaction is carried out due to crosslinking action, so that the viscosity of a medium is increased, the heat transfer efficiency is deteriorated, and the medium presents a plastic state after a certain time of reaction. If the viscosity is reduced by increasing the reaction temperature, the carbonization of the reactor wall material is accelerated, and a large amount of reaction by-products are formed, which is a main reason for influencing the product quality and yield. Although certain process and engineering measures may improve this situation to some extent, the results are not satisfactory.
Disclosure of Invention
Based on the situation, the invention aims to provide a preparation method of musk C-14, which is low in cost and high in preparation efficiency.
The invention provides a preparation method of musk C-14, which comprises the following steps:
and (3) polycondensation reaction: adding ethylene glycol into a polycondensation reaction kettle, stirring, gradually adding dodecanedioic acid and a polymerization inhibitor, decompressing and vacuumizing the polycondensation reaction kettle, introducing nitrogen for replacement, heating to a first preset temperature, and performing polycondensation reaction to generate linear polyester;
depolymerization reaction: adding a depolymerization catalyst into the linear polyester, heating to a second preset temperature, vacuumizing the polycondensation reaction kettle to enable the polycondensation reaction kettle to be in a negative pressure state, and carrying out depolymerization reaction to obtain a crude product reaction liquid;
and (3) reduced pressure distillation: transferring the crude product reaction liquid into a fractionation reaction kettle after cooling, controlling the temperature to a third preset temperature, and carrying out reduced pressure distillation to obtain a crude product;
fractional distillation: and controlling the temperature to a fourth preset temperature, and carrying out fractional distillation to obtain a finished product and a byproduct.
The preparation method of the musk C-14 adopts a one-pot method, and directly adds a depolymerization catalyst to carry out depolymerization reaction without refining after the polycondensation reaction is finished, thereby simplifying the process operation and reducing the production cost; polymerization inhibitor is added in the polymerization process, the polymerization degree of the intermediate is effectively controlled, byproducts such as high polymer and the like are prevented from being generated, and the utilization rate of raw materials is obviously improved; in the depolymerization process, an independently developed efficient nontoxic depolymerization catalyst is added, so that the intermediate product is completely depolymerized, and the yield of the product is improved; the post-treatment process of the crude product is free of the washing process, so that the operation process is simplified, the production period is shortened, the production efficiency is improved, no process wastewater is generated in the production process, and the process is green and environment-friendly; the product distillation adopts fractional distillation, and impurity removal, rectification and recovery are completed by using the same kettle, so that the production energy consumption is reduced, the yield of finished products is improved, and the production cost is reduced to a greater extent.
The preparation method of the musk C-14, wherein after the step of polycondensation reaction, the preparation method further comprises the following steps: recovering the unreacted ethylene glycol under reduced pressure.
The preparation method of the musk C-14, wherein after the fractional distillation step, the preparation method further comprises the following steps:
the by-products are recovered for feeding to the next batch of polymeric material for depolymerization.
The preparation method of the musk C-14 comprises the step of polycondensation, wherein in the step of polycondensation, the input mass ratio of the n-dodecanedioic acid to the ethylene glycol is 1:05-1:0.6, the input amount of the polymerization inhibitor is 1.5-2% of the total amount of the n-dodecanedioic acid and the ethylene glycol, and the polymerization degree of an intermediate is 5-15.
The preparation method of the musk C-14 comprises the steps of introducing nitrogen for replacement for not less than 3 times in the step of polycondensation reaction, and continuously introducing nitrogen after replacement.
The preparation method of the musk C-14 comprises the step of polycondensation, wherein in the step of polycondensation, the first preset temperature is 230 +/-10 ℃, and the thermal insulation polycondensation is carried out for 5 hours.
The preparation method of the musk C-14 comprises the following steps of (1) in a depolymerization reaction step, adding a depolymerization catalyst which is a high-activity composite depolymerization catalyst in an amount which is 2.5-3% of that of the n-dodecanedioic acid;
the second preset temperature is 320 +/-10 ℃, and the depolymerization reaction time is 6 hours.
The musk C-14 preparation method, wherein the depolymerization catalyst is prepared from aluminum carbonate, p-toluenesulfonic acid, silicotungstomolybdic acid, anhydrous copper sulfate and water according to the weight ratio of 1.5: 1: dissolving at a ratio of 1:0.5:6, adding granular silicon dioxide with the same mass as the dissolved solution, completely adsorbing, placing in an oven, and drying at 105 ℃ to obtain the product.
The preparation method of the musk C-14, wherein in the step of reduced pressure distillation, the third preset temperature is 180 +/-10 ℃.
The preparation method of the musk C-14, wherein in the step of fractional distillation, the fourth preset temperature is 200 ℃.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a flow chart of a process for preparing musk C-14 according to an embodiment of the invention;
FIG. 2 is a reaction formula of the polycondensation reaction of the present invention;
FIG. 3 is a reaction scheme of the depolymerization reaction of the present invention.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1 to 3, the present invention provides a method for preparing musk C-14, including steps S10-S40:
step S10, polycondensation reaction: adding ethylene glycol into a polycondensation reaction kettle, stirring, gradually adding dodecanedioic acid and a polymerization inhibitor, decompressing and vacuumizing the polycondensation reaction kettle, introducing nitrogen for replacement, heating to a first preset temperature, and performing polycondensation reaction to generate linear polyester;
in another preferred embodiment of the present invention, after the polycondensation reaction step, the preparation method further comprises: recovering the unreacted ethylene glycol under reduced pressure. Namely, a one-pot method is adopted, unreacted ethylene glycol is recycled after the polycondensation reaction is finished, and a depolymerization catalyst is directly added without refining for depolymerization reaction, so that the process operation is simplified, and the production cost is reduced.
In the polycondensation step, the n-dodecanedioic acid and the ethylene glycol are added in a mass ratio of 1:05 to 1:0.6 so that the n-dodecanedioic acid is completely reacted. The input amount of the polymerization inhibitor is 1.5-2% of the total amount of the n-dodecanedioic acid and the ethylene glycol, the polymerization degree range of the intermediate is 5-15, byproducts such as high polymers can be effectively prevented from being generated, and the utilization rate of raw materials is remarkably improved.
Furthermore, in the step of polycondensation reaction, the number of times of introducing nitrogen for replacement is not less than 3, and the nitrogen is continuously introduced for protection after replacement is finished, so as to prevent oxygen in the air from causing side reactions such as oxidation, cracking and the like.
Specifically, in the polycondensation reaction step, the first preset temperature is 230 ± 10 ℃, and the thermal insulation polycondensation reaction is 5 hours, so that the n-dodecanedioic acid is completely reacted.
Step S20, depolymerization reaction: adding a depolymerization catalyst into the linear polyester, heating to a second preset temperature, vacuumizing the polycondensation reaction kettle to enable the polycondensation reaction kettle to be in a negative pressure state, and carrying out depolymerization reaction to obtain a crude product reaction liquid;
the depolymerization catalyst is a high-efficiency nontoxic depolymerization catalyst independently developed by the applicant, so that an intermediate product can be completely depolymerized, and the yield of the product is improved. Further, in the depolymerization step, as the reaction proceeds, the viscosity of the material increases and the heat transfer effect becomes poor, and it is necessary to increase the temperature continuously to ensure the progress of the depolymerization reaction. Specifically, in this step, the second preset temperature is 320 ± 10 ℃, and the depolymerization reaction time is 6 hours, so that the depolymerization reaction is completely performed.
In another preferred embodiment of the present invention, the depolymerization catalyst is a high-activity composite depolymerization catalyst, and the input amount of the depolymerization catalyst is 2.5-3% of the input amount of the n-dodecanedioic acid.
It is to be understood that, in the present invention, the depolymerization catalyst is prepared from aluminium carbonate and p-toluene sulphonic acid, silicotungstomolybdic acid, anhydrous copper sulphate and water in a ratio of 1.5: 1: dissolving at a ratio of 1:0.5:6, adding granular silicon dioxide with the same mass as the dissolved solution, completely adsorbing, placing in an oven, and drying at 105 ℃ to obtain the product.
Step S30, reduced pressure distillation: transferring the crude product reaction liquid into a fractionation reaction kettle after cooling, controlling the temperature to a third preset temperature, and carrying out reduced pressure distillation to obtain a crude product;
in another preferred embodiment of the present invention, after the step of fractional distillation, the preparation method further comprises:
the by-products are recovered for feeding to the next batch of polymeric material for depolymerization. Not only reduces the production cost, but also reduces the discharge of three wastes, and obviously improves the economic and social benefits.
It should be noted that, in the course of the after-treatment of the crude product, the washing process is eliminated, so that the operation process is simplified, the production period is shortened, the production efficiency is improved, no process wastewater is generated in the production process, and the process is green and environment-friendly. Specifically, in the reduced pressure distillation step, the third preset temperature is 180 ± 10 ℃.
Step S40, fractional distillation: and controlling the temperature to a fourth preset temperature, and carrying out fractional distillation to obtain a finished product and a byproduct.
In the invention, the impurity removal, rectification and recovery set are all completed by a fractionation reaction kettle, so that the production energy consumption is reduced, the yield of finished products is improved, and the production cost is reduced to a greater extent. Specifically, in the step of fractional distillation, the fourth preset temperature is 200 ℃.
In addition, through the transformation to production facility, partial key equipment adopts self-control equipment, and this equipment structure is reasonable, the dependable performance, convenient operation, and it is safe in utilization, energy-conservation is showing.
In conclusion, the preparation method of the musk C-14 provided by the invention adopts a one-pot method, and directly adds a depolymerization catalyst to carry out depolymerization reaction without refining after the polycondensation reaction is finished, so that the process operation is simplified, and the production cost is reduced; polymerization inhibitor is added in the polymerization process, the polymerization degree of the intermediate is effectively controlled, byproducts such as high polymer and the like are prevented from being generated, and the utilization rate of raw materials is obviously improved; in the depolymerization process, an independently developed efficient nontoxic depolymerization catalyst is added, so that the intermediate product is completely depolymerized, and the yield of the product is improved; the post-treatment process of the crude product is free of the washing process, so that the operation process is simplified, the production period is shortened, the production efficiency is improved, no process wastewater is generated in the production process, and the process is green and environment-friendly; the product distillation adopts fractional distillation, and impurity removal, rectification and recovery are completed by using the same kettle, so that the production energy consumption is reduced, the yield of finished products is improved, and the production cost is reduced to a greater extent.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the musk C-14 is characterized by comprising the following steps:
and (3) polycondensation reaction: adding ethylene glycol into a polycondensation reaction kettle, stirring, gradually adding dodecanedioic acid and a polymerization inhibitor, decompressing and vacuumizing the polycondensation reaction kettle, introducing nitrogen for replacement, heating to a first preset temperature, and performing polycondensation reaction to generate linear polyester;
depolymerization reaction: adding a depolymerization catalyst into the linear polyester, heating to a second preset temperature, vacuumizing the polycondensation reaction kettle to enable the polycondensation reaction kettle to be in a negative pressure state, and carrying out depolymerization reaction to obtain a crude product reaction liquid;
and (3) reduced pressure distillation: transferring the crude product reaction liquid into a fractionation reaction kettle after cooling, controlling the temperature to a third preset temperature, and carrying out reduced pressure distillation to obtain a crude product;
fractional distillation: and controlling the temperature to a fourth preset temperature, and carrying out fractional distillation to obtain a finished product and a byproduct.
2. The process for the preparation of musk C-14 according to claim 1, wherein after the step of polycondensation, the process further comprises: recovering the unreacted ethylene glycol under reduced pressure.
3. The process for the preparation of musk C-14 according to claim 1, wherein after the step of fractional distillation the process further comprises:
the by-products are recovered for feeding to the next batch of polymeric material for depolymerization.
4. The process for preparing musk C-14, as claimed in claim 1, wherein in the polycondensation step, the n-dodecanedioic acid and ethylene glycol are added in a mass ratio of 1:05 to 1:0.6, the amount of the polymerization inhibitor is 1.5 to 2% of the total amount of the n-dodecanedioic acid and ethylene glycol, and the polymerization degree of the intermediate is in the range of 5 to 15.
5. The process for producing musk C-14C according to claim 1, wherein in the polycondensation step, the nitrogen gas is introduced not less than 3 times for substitution, and the introduction of the nitrogen gas is continued after the substitution.
6. The process for preparing musk C-14, according to claim 1, wherein the first predetermined temperature is 230 ± 10 ℃ and the polycondensation reaction is maintained for 5 hours in the polycondensation step.
7. The method for preparing musk C-14, as claimed in claim 1, wherein in the depolymerization step, the depolymerization catalyst is a high-activity composite depolymerization catalyst, and the dosage of the depolymerization catalyst is 2.5-3% of the dosage of the n-dodecanedioic acid;
the second preset temperature is 320 +/-10 ℃, and the depolymerization reaction time is 6 hours.
8. The process for the preparation of musk C-14 according to claim 7, wherein the depolymerization catalyst is prepared from aluminium carbonate and p-toluene sulphonic acid, silicotungstomolybdic acid, anhydrous copper sulphate and water in a ratio of 1.5: 1: dissolving at a ratio of 1:0.5:6, adding granular silicon dioxide with the same mass as the dissolved solution, completely adsorbing, placing in an oven, and drying at 105 ℃ to obtain the product.
9. The process for the preparation of musk C-14 according to claim 1, wherein the third predetermined temperature is 180 ± 10 ℃ during the vacuum distillation step.
10. The process for the preparation of musk C-14 according to claim 1, wherein the fourth predetermined temperature is 200 ℃ during the step of fractional distillation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499609A (en) * | 2020-04-26 | 2020-08-07 | 绵阳三香汇生物科技有限公司 | Preparation method of Kunlun musk |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803288A (en) * | 1986-03-20 | 1989-02-07 | Nisso Petrochemical Industries Co., Ltd. | Process for producing macrocyclic ester compounds |
| CN1228428A (en) * | 1998-03-03 | 1999-09-15 | 希尔斯股份公司 | Method for preparing macrocyclic ester or lactone |
| CN104693165A (en) * | 2013-12-10 | 2015-06-10 | 上海凯赛生物技术研发中心有限公司 | Method for producing long-chain diacid cyclic ethylene ester |
| CN105884742A (en) * | 2016-05-06 | 2016-08-24 | 江西黄岩香料有限公司 | Preparation method of musk-T |
-
2019
- 2019-12-25 CN CN201911353255.5A patent/CN110963990A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803288A (en) * | 1986-03-20 | 1989-02-07 | Nisso Petrochemical Industries Co., Ltd. | Process for producing macrocyclic ester compounds |
| CN1228428A (en) * | 1998-03-03 | 1999-09-15 | 希尔斯股份公司 | Method for preparing macrocyclic ester or lactone |
| CN104693165A (en) * | 2013-12-10 | 2015-06-10 | 上海凯赛生物技术研发中心有限公司 | Method for producing long-chain diacid cyclic ethylene ester |
| CN105884742A (en) * | 2016-05-06 | 2016-08-24 | 江西黄岩香料有限公司 | Preparation method of musk-T |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499609A (en) * | 2020-04-26 | 2020-08-07 | 绵阳三香汇生物科技有限公司 | Preparation method of Kunlun musk |
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Application publication date: 20200407 |