CN117547471B - L-menthol composition with improved cool feeling and hair permeability and application thereof - Google Patents

L-menthol composition with improved cool feeling and hair permeability and application thereof Download PDF

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CN117547471B
CN117547471B CN202410039117.4A CN202410039117A CN117547471B CN 117547471 B CN117547471 B CN 117547471B CN 202410039117 A CN202410039117 A CN 202410039117A CN 117547471 B CN117547471 B CN 117547471B
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menthol
neoisomenthol
mass content
mass
product
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CN117547471A (en
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于磊
刘家邑
吴庆海
李康
刘英俊
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Wanhua Chemical Group Co Ltd
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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    • A61K31/00—Medicinal preparations containing organic active ingredients
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/24—Thermal properties
    • A61K2800/244—Endothermic; Cooling; Cooling sensation

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Abstract

The invention relates to the technical field of L menthol products, and provides an L menthol composition with improved cool feeling and hair penetration and application thereof. The L menthol composition mainly comprises L menthol, D menthol, L neoisomenthol and D neoisomenthol; the sum of the mass content of the L-menthol and the D-menthol is > 99.50% and the mass content of L-menthol is > 99.00% based on the total mass of the composition; the mass content of the L-new isomenthol is more than or equal to 0.004%, and the sum of the mass content of the L-new isomenthol and the mass content of the D-new isomenthol is 0.005% -0.050%, wherein the mass content of the L-new isomenthol is larger than the mass content of the D-new isomenthol, and the difference between the mass content of the L-new isomenthol and the mass content of the D-new isomenthol is more than 0.001%.

Description

L-menthol composition with improved cool feeling and hair permeability and application thereof
Technical Field
The invention relates to the technical field of L menthol products, and further relates to an L menthol composition with improved cool feeling and hair permeability and application thereof.
Background
Menthol, also known as menthol, is a terpenoid organic compound and has wide application in the fields of oral care, tobacco, food and medicine. Menthol has eight isomers in total, but only the L menthol configuration has the purest mint flavor and cool feeling, and as the physical properties among different menthol isomers are quite similar, the complete separation of the isomers is difficult, so that the commercial L menthol products often contain various menthol isomers, and even trace isomer residues have extremely great influence on the sense as the characteristic flavor and cool feeling experience of each isomer are different, so that the cool feeling and the transmitting property of the commercial L menthol products are uneven.
The structural formula of the eight isomers of menthol is shown below,
How to improve the cool feeling of the L menthol product is still one of the technical problems to be broken through in the field.
Disclosure of Invention
Aiming at the technical problem of how to improve the cool feeling and the hair penetration of an L menthol product, the invention provides an L menthol composition with improved cool feeling and hair penetration and application thereof.
The invention provides the following technical scheme for achieving the purpose:
In one aspect, the present invention provides an L-menthol composition having improved cool feeling and hair transmission, the L-menthol composition consisting essentially of L-menthol, D-menthol, L-neoisomenthol, and D-neoisomenthol;
The sum of the mass content of the L-menthol and the D-menthol is > 99.50% and the mass content of L-menthol is > 99.00% based on the total mass of the composition;
The mass content of the L-new isomenthol is more than or equal to 0.004%, and the sum of the mass content of the L-new isomenthol and the mass content of the D-new isomenthol is 0.005% -0.050%, wherein the mass content of the L-new isomenthol is larger than the mass content of the D-new isomenthol, and the difference between the mass content of the L-new isomenthol and the mass content of the D-new isomenthol is more than 0.001%.
The inventors found that among the above-mentioned compositions having the main components of L-menthol, D-menthol, L-neo-isophthol and D-neo-isophthol, a composition having the contents of L-menthol, D-menthol, L-neo-isophthol and D-neo-isophthol satisfying the above-mentioned content requirements has significantly improved cool feeling and hair penetration, and is a high-quality L-menthol composition product.
In some embodiments, the sum of the mass content of L menthol and D menthol in the L menthol composition is, for example, 99.51%, 99.60%, 99.65%, 99.70%, 99.80%, 99.87%, 99.90%, or 99.95%, etc.; the mass content of the L menthol is, for example, 99.01%, 99.20%, 99.30%, 99.40%, 99.50%, 99.55%, 99.60%, 99.67%, 99.79% or 99.90%. In some embodiments, the mass content of L neoisomenthol in the L menthol composition is, for example, 0.004%, 0.010%, 0.020%, 0.030%, 0.035%, 0.040%, etc.; the sum of the mass contents of L neoisomenthol and D neoisomenthol is, for example, 0.005%, 0.006%, 0.010%, 0.020%, 0.025%, 0.030%, 0.035%, 0.045% or 0.050% or the like; the difference between the mass content of L-neoisomenthol and the mass content of D-neoisomenthol is, for example, 0.002%, 0.004%, 0.005%, 0.015%, 0.020%, 0.023%, 0.025%, 0.030%, 0.040% or 0.045%, etc.
In some preferred embodiments, the L-menthol is present in an amount of > 99.60%, preferably > 99.70% by mass, and the composition meeting the preferred content requirements has further improved cool feel transmission.
In some preferred embodiments, the difference between the mass content of said L neoisomenthol and the mass content of said D neoisomenthol is > 0.005%, preferably > 0.016%. Compositions meeting this preferred level requirement have further improved cool feel transmission.
In some preferred embodiments, the sum of the mass contents of the L menthol and the D menthol is 99.60-99.95%, and the mass content of the L menthol is 99.30-99.80%, preferably 99.60-99.80%;
The mass content of the L-neoisomenthol is 0.004-0.040%, the sum of the mass content of the L-neoisomenthol and the mass content of the D-neoisomenthol is 0.005-0.050%, and the mass content of the L-neoisomenthol is larger than the mass content of the D-neoisomenthol, and the difference between the mass content of the L-neoisomenthol and the mass content of the D-neoisomenthol is 0.002-0.025%, preferably 0.010-0.025%. The composition meeting the preferred content requirements has a further improved cool feel profile.
Specifically, the L menthol composition may further contain other components including, for example, isopulegol, menthone, isomenthone, neomenthol, and/or isomenthol, etc., in a balance, for example, a total content of these components by mass of < 0.5%, for example, 0.4%, 0.2%, 0.1%, 0.05%, 0.03%, etc., for example < 0.4%, for example < 0.2%, for example < 0.1%, etc. In some examples, the L menthol composition comprises, in mass percent, 0.020-0.240% isopulegol, 0.005-0.070% menthone, 0.004-0.025% isomenthone, 0.003-0.007% neomenthol, and 0.003-0.008% isomenthol.
The second aspect of the present invention provides the use of the above-described L-menthol composition in the preparation of a cosmetic or pharmaceutical product, which gives these products a better cooling sensation by adding the above-described L-menthol composition provided by the present invention to the cosmetic or pharmaceutical product.
A third aspect of the present invention provides the use of an L-menthol composition as described above for enhancing the cooling sensation of a product, including a cosmetic or pharmaceutical product.
The "cosmetics" mentioned above may be, for example, toothpastes, skin care products, hair care products, shaving foams, etc., and medical products such as antipyretics, mouthwashes, cooling oils, etc., and there is no particular limitation on the specific type of products, and the above-mentioned compositions provided by the present invention can be applied to products requiring improvement of cooling feeling.
In a fourth aspect, the present invention provides a method of improving cool feeling and hair transmission of an L-menthol product, the L-menthol product comprising L-menthol, D-menthol, L-neo-iso-menthol, and D-neo-iso-menthol, by making the mass content of L-menthol, D-menthol, L-neo-iso-menthol in the L-menthol product satisfy the following conditions (I) and (II) to improve cool feeling and hair transmission of the L-menthol product:
(I) The sum of the mass content of L menthol and D menthol is > 99.50% based on the total mass of the L menthol product, and the mass content of L menthol is > 99.00%;
(II) based on the total mass of the L menthol product, the mass content of L neoisomenthol is greater than or equal to 0.004%, and the sum of the mass contents of L neoisomenthol and D neoisomenthol is 0.005% to 0.050%, the mass content of L neoisomenthol being greater than the mass content of D neoisomenthol, the difference between the mass contents of L neoisomenthol and D neoisomenthol being > 0.001%.
The present inventors have found that by satisfying the above-described conditions (I) and (II) in an L-menthol product whose main components are L-menthol, D-menthol, L-neo-isophthol and D-neo-isophthol, the quality of the L-menthol product in terms of cool feeling and hair permeability can be significantly improved. The manner in which the contents of L menthol, D menthol, L neoisophthol and D neoisophthol satisfy the above-described conditions (I), (II) may be varied, for example, by formulating the corresponding components while satisfying the above-described conditions (I), (II), or may be obtained by purifying crude L menthol, for example, by subjecting the crude L menthol to purification processes well known in the art such as distillation, rectification, crystallization and/or extraction, and the like, and a person skilled in the art may obtain a product satisfying the target conditions by adjusting the process conditions and/or the operation steps and the like in the purification process, and select a portion satisfying the above-described conditions (I) and (II) as the L menthol product of the present invention in the purification process.
In some preferred embodiments, in the condition (I), the L menthol is more than 99.60% by mass, preferably more than 99.70% by mass.
In some preferred embodiments, in the condition (II), the difference between the mass content of the L neoisomenthol and the mass content of the D neoisomenthol is > 0.005%, preferably > 0.016%.
In some preferred embodiments, in the condition (I), the sum of the mass contents of the L menthol and the D menthol is 99.60 to 99.95%, and the mass content of the L menthol is 99.30 to 99.80%, preferably 99.60 to 99.80%;
In the condition (II), the mass content of the L neoisomenthol is 0.004-0.040%, the sum of the mass content of the L neoisomenthol and the mass content of the D neoisomenthol is 0.005-0.050%, and the mass content of the L neoisomenthol is larger than the mass content of the D neoisomenthol, and the difference between the mass content of the L neoisomenthol and the mass content of the D neoisomenthol is 0.002-0.025%, preferably 0.010-0.025%.
In some examples, the L menthol products obtained by the above methods, in addition to L menthol, D menthol, L neo-iso-menthol, D neo-iso-menthol satisfying the conditions (I) and (II), contain the balance of other components, including, for example, isopulegol, menthone, isomenthone, neomenthol, and/or iso-menthol, etc., e.g., the total content by mass of these components is < 0.5%, e.g., 0.4%, 0.2%, 0.1%, 0.05%, 0.03%, etc., e.g., < 0.4%, e.g., < 0.2%, e.g., < 0.1%, etc. In some examples, the resulting L menthol product comprises, in mass percent, 0.020-0.240% isopulegol, 0.005-0.070% menthone, 0.004-0.025% isomenthone, 0.003-0.007% neomenthol, and 0.003-0.008% isomenthol.
Further, the crystallization is, for example, solution crystallization or melt crystallization, preferably melt crystallization, more preferably static melt crystallization. The static melt crystallization may be performed in a static melt crystallizer known in the art, for example, a static melt crystallizer having a plurality of heat exchange walls therein, which may be cooled or heated by circulating a refrigerant or a heating medium.
In some embodiments, the crude L menthol is purified by static melt crystallization, specifically comprising the steps of:
(1) Heating and melting crude L menthol in a static melting crystallizer, cooling to separate out crystals, and discharging uncrystallized residual liquid;
Preferably, the temperature of the heating and melting is 43-50 ℃;
preferably, the cooling comprises cooling to 40-42 ℃ at a cooling rate of 0.2-1.0 ℃/h, and then maintaining for 1-3h; then cooling to 41.2-41.5 ℃ at a cooling rate of 0.03-0.06 ℃/h;
(2) Heating up and sweating the crystal, continuously discharging the generated distillate in the sweating process, continuously monitoring the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol in the distillate, and collecting the distillate part meeting the conditions (I) and (II) as an L menthol product when the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol meets the conditions (I) and (II);
preferably, the heating rate of the heating sweating is 0.05-0.08 ℃/h.
The static melt crystallization step and conditions described above are an example, and one skilled in the art may also obtain an L-menthol product satisfying the conditions (I) and (II) by other crystallization processes or by adjusting the crystallization process according to the difference of crude L-menthol.
In some embodiments, the L-menthol products satisfying the conditions (I) and (II) are obtained by rectifying crude L-menthol. The rectification comprises the following steps:
And (3) rectifying the crude L menthol in a rectifying tower, continuously monitoring the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol in the distillate extracted from the top of the rectifying tower, and collecting the distillate part with the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol meeting the conditions (I) and (II) as the L menthol product.
In some embodiments, the operating conditions of the rectification column include: the temperature of the tower bottom is 100-130 ℃, the temperature of the tower top is 40-60 ℃, the pressure of the tower top is 0.5-5KPa absolute, and the reflux ratio is 5:1-15:1. the above is an example of a rectifying column operating condition, and a person skilled in the art may also adjust the specific rectifying column operating condition according to the actual situation.
In some embodiments, the sum of the mass content of L-menthol and D-menthol in the crude L-menthol used to prepare the L-menthol product is > 95.00%, e.g., 95.10%, 95.50%, 96.00%, 96.50%, 97.00%, 98.00%, etc.; wherein the mass content of L-menthol is > 90.00% (e.g., 90.10%, 93.00%, 95.00%, 95.70%, 96.00%, 97.00%, 98.00%, etc.), and the sum of the mass contents of L-neo-isophthol and D-neo-isophthol is 0.01% -0.60% (e.g., 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, etc.), wherein the mass content of L-neo-isophthol is > 0.005% (e.g., 0.006%, 0.010%, 0.100%, 0.200%, 0.300%, 0.330%, 0.350%, 0.400%, 0.500%, 0.550%, etc.).
Cool feeling and hair-penetrating property means: the diffusion and penetration properties of the cooling sensation exhibited by the L menthol product or L menthol composition the quality of the composition in terms of the cooling sensation was evaluated by comparing the closeness of the L menthol composition to the cooling sensation after application of the L menthol reference sample to the skin. Specific evaluation methods are described below.
The technical scheme provided by the invention has the following beneficial effects:
The main components of the L-menthol composition provided by the invention, namely L-menthol, D-menthol, L-neo-isomenthol and D-neo-isomenthol, have specific content requirements, and the composition has obviously improved cool feeling and hair penetration. The invention also provides a method for improving the cool feeling and the hair penetration of the L-menthol product, which ensures that the main components of L-menthol, D-menthol and L-neo-iso-menthol in the L-menthol product meet specific content requirements and has obviously improved cool feeling and hair penetration compared with the L-menthol product which does not meet the requirements.
Detailed Description
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples. It should be understood that the following examples are only for better understanding of the present invention and are not meant to limit the present invention to the following examples.
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.
Where specific experimental steps or conditions are not noted in the examples, they may be performed according to the operations or conditions of the corresponding conventional experimental steps in the art. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The crystallizers used in the following examples and comparative examples were static melt crystallizers with a heating/cooling medium of an aqueous ethylene glycol solution (ethylene glycol to water mass ratio of 1:1) and a temperature control accuracy of.+ -. 0.5 ℃.
The main raw materials used in the following examples and comparative examples:
Crude L menthol, wherein the sum of the mass contents of L menthol and D menthol is 96.50%, the mass content of L menthol is 95.70%, the sum of the mass contents of L neoisomenthol and D neoisomenthol is 0.51%, and the mass content of L neoisomenthol is 0.33%, from the SIGMAALDRICH reagent network.
In the following examples, the "the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol in the liquid distillate satisfies the content requirement" means that the following condition is satisfied: (I) The sum of the mass contents of L menthol and D menthol is more than 99.50%, and the mass content of L menthol is more than 99.00%; (II) the mass content of L-neoisomenthol is not less than 0.004%, the sum of the mass content of L-neoisomenthol and the mass content of D-neoisomenthol is in the range of 0.005% -0.050%, the mass content of L-neoisomenthol is greater than the mass content of D-neoisomenthol, and the difference between the mass content of L-neoisomenthol and the mass content of D-neoisomenthol is > 0.001%.
The composition analysis method of the L menthol product is described as follows: chromatographic column model: alpha-DEX-120, column length 30m, column inner diameter 0.25mm, vaporization chamber temperature: 220 ℃, detector temperature: 300 ℃, sample injection amount: 0.2 microliter, split ratio: 100: column temperature procedure: the initial temperature was maintained at 85℃for 55min, then at 20℃per min to 130℃for 15min.
Example 1
Adding 2kg of crude L menthol into a melting crystallizer, raising the temperature of the system to 45 ℃ at the speed of 10 ℃/h, maintaining the temperature at 45 ℃ for 5 hours to completely melt the crude L menthol, then starting cooling at the speed of 0.5 ℃/h, maintaining the temperature stable after cooling to 42.0 ℃, starting slowly cooling at the speed of 0.05 ℃/h after 2 hours, continuing cooling to 41.5 ℃, and then opening a bottom valve to discharge the uncrystallized residual liquid; and then starting to slowly raise the temperature at the speed of 0.05 ℃/h to sweat the crystal, continuously discharging the liquid distillate generated in the sweating process, continuously taking the liquid distillate to carry out composition analysis, taking the liquid distillate meeting the content requirement as an L menthol product after the mass content of the L menthol, the D menthol and the L neoisomenthol in the liquid distillate meets the content requirement, sampling and carrying out cooling evaluation, and recording the composition and cooling evaluation results of the L menthol product in Table 1.
Example 2
Adding 2kg of crude L menthol into a melting crystallizer, raising the temperature of the system to 45 ℃ at the speed of 10 ℃/h, maintaining the temperature at 45 ℃ for 5 hours to completely melt the crude L menthol, then starting cooling at the speed of 0.5 ℃/h, maintaining the temperature stable after cooling to 42.0 ℃, starting slowly cooling at the speed of 0.05 ℃/h after 3 hours, continuing cooling to 41.5 ℃, and then opening a bottom valve to discharge the uncrystallized residual liquid; and then starting to slowly raise the temperature at the speed of 0.06 ℃/h to sweat the crystal, continuously discharging the liquid distillate generated in the sweating process, continuously taking the liquid distillate to carry out composition analysis, taking the liquid distillate meeting the content requirement as an L menthol product after the mass content of the L menthol, the D menthol and the L neoisomenthol in the liquid distillate meets the content requirement, sampling and carrying out cooling evaluation, and recording the composition and cooling evaluation results of the L menthol product in Table 1.
Example 3
Adding 2kg of crude L menthol into a melting crystallizer, raising the temperature of the system to 45 ℃ at the speed of 10 ℃/h, maintaining the temperature at 45 ℃ for 5 hours to completely melt the crude L menthol, then starting cooling at the speed of 0.5 ℃/h, maintaining the temperature stable after cooling to 42.0 ℃, starting slowly cooling at the speed of 0.06 ℃/h after 2 hours, continuing cooling to 41.5 ℃, and then opening a bottom valve to discharge the uncrystallized residual liquid; and then starting to slowly raise the temperature at the speed of 0.07 ℃/h to sweat the crystal, continuously discharging the liquid distillate generated in the sweating process, continuously taking the liquid distillate to carry out composition analysis, taking the liquid distillate which meets the content requirement as an L menthol product after the mass content of the L menthol, the D menthol and the L neoisomenthol in the liquid distillate meets the content requirement, sampling and carrying out cooling evaluation, and recording the composition and cooling evaluation results of the L menthol product in Table 1.
Comparative example 0
Adding 2kg of crude L menthol into a melt crystallizer, wherein the operation and condition parameters of the melting process, the cooling crystallization process and the sweating process are the same as those of the embodiment 3, continuously discharging liquid distillate generated in the sweating process, continuously taking the liquid distillate for composition analysis, continuously performing the sweating process after the mass contents of the L menthol, the D menthol and the L neo-isomenthol in the liquid distillate are the same as those of the L menthol product collected in the embodiment 3, sampling and analyzing, recording the composition results obtained by sampling and analyzing the liquid distillate taken after 20min in Table 1, taking the liquid distillate as the L menthol product of the comparative example, and performing cooling sensation evaluation, and recording the results in Table 1.
Comparative example 1
Adding 2kg of crude L menthol into a melting crystallizer, raising the temperature of the system to 45 ℃ at the speed of 10 ℃/h, maintaining the temperature at 45 ℃ for 5 hours to completely melt the crude L menthol, then starting cooling at the speed of 0.5 ℃/h, maintaining the temperature stable after cooling to 42.0 ℃, starting slowly cooling at the speed of 0.02 ℃/h after 6 hours, continuing cooling to 41.5 ℃, and then opening a bottom valve to discharge the uncrystallized residual liquid; then, the crystallization was subjected to perspiration by starting a slow temperature rise at a rate of 0.04 ℃/h, the liquid distillate produced during the perspiration was continuously discharged, while the liquid distillate was continuously taken for composition analysis, and after the mass contents of L menthol, D menthol, L neo-isopulegol and D neo-isopulegol in the liquid distillate reached the desired levels, the composition of the liquid distillate was recorded, which was taken as the L menthol product of this comparative example, sampled for cooling sensation evaluation, and the results were recorded in table 1.
Comparative example 2
Adding 2kg of crude L menthol into a melting crystallizer, raising the temperature of the system to 45 ℃ at the speed of 10 ℃/h, maintaining the temperature at 45 ℃ for 5 hours to completely melt the crude L menthol, then starting cooling at the speed of 0.5 ℃/h, maintaining the temperature stable after cooling to 42.0 ℃, starting slowly cooling at the speed of 0.06 ℃/h after 3 hours, continuing cooling to 41.0 ℃, and then opening a bottom valve to discharge the uncrystallized residual liquid; then, the crystallization was subjected to perspiration by starting a slow temperature rise at a rate of 0.05 ℃/h, the liquid distillate produced during the perspiration was continuously discharged, while the liquid distillate was continuously taken for composition analysis, and after the mass contents of L menthol, D menthol, L neo-isopulegol and D neo-isopulegol in the liquid distillate reached the desired levels, the composition of the liquid distillate was recorded, which was taken as the L menthol product of this comparative example, sampled for cooling sensation evaluation, and the results were recorded in table 1.
Comparative example 3
2Kg of crude L menthol is taken and added into a melting crystallizer, the temperature of the system is increased to 45 ℃ at the speed of 10 ℃/h, the crude L menthol is completely melted at 45 ℃ for 5 hours, then the materials in the melting crystallizer are completely discharged to be used as L menthol products, the compositions of the L menthol products are analyzed, and the samples are sampled for cooling evaluation, and the results are shown in table 1.
Example 4
Adding 1kg of crude L menthol into a tower kettle of a rectifying tower, starting rectifying operation, continuously collecting distillate from the tower top, analyzing the mass content of L menthol, D menthol, L new isomenthol and D new isomenthol, collecting the distillate with the mass content meeting the content requirement of the L menthol, D menthol, L new isomenthol and D new isomenthol as an L menthol product, sampling, and evaluating the cooling effect, wherein the result is shown in table 1.
The rectification column operating conditions were as follows:
the temperature of the tower bottom is 101-110 ℃, the temperature of the tower top is 45-60 ℃, the pressure of the tower top is 1-3KPa (absolute pressure), and the reflux ratio is 10:1.
The rectification apparatus parameters were as follows:
The packing is 3*3 triangular spiral packing, the inner diameter of the rectifying tower is 50mm, and the packing height is 1.2m.
Comparative example 4
Adding 1kg of crude L menthol into a tower kettle of a rectifying tower, starting rectifying operation, continuously collecting distillate from the tower top, analyzing the mass content of L menthol, D menthol, L new isomenthol and D new isomenthol in the distillate, continuously sampling and analyzing the tower top after the mass content of L menthol, D menthol and L new isomenthol in the distillate is the same as that of the L menthol product collected in the embodiment 4, recording the composition obtained by sampling and analyzing the tower top after 20min in table 1, taking part of the distillate as the L menthol product of the comparative example, and carrying out cooling evaluation, and recording the result in table 1.
The operating conditions and the equipment parameters of the rectifying tower are the same as those of the embodiment 4.
The results of composition analysis of the L-menthol products obtained in each of the examples and comparative examples are shown in Table 1 below.
Cool feeling evaluation method
In evaluating the quality of the L-menthol products of examples and comparative examples, the reference sample used was a crude L-menthol raw material sample used in the examples. The specific scoring process is as follows:
5 panelists with secondary flavoring agents are used for forming a panelist, the panelist is responsible for scoring the samples, and after the scoring is finished, the average score is taken as the final score of the test samples.
The cool feeling and hair penetration evaluation method comprises the following steps: the standard sample and the sample to be tested are respectively diluted to the concentration of 1wt% by using a solvent (double dealdehyding alcohol), and then are smeared on the inner sides of elbow joints at two sides of a panelist, the score is given according to the cool feeling degree, the score of the standard sample is 5.0 points, the higher the score is, the higher the cool feeling transmission degree is, and the score grade is as follows: the hair is transparent (9.1-10 min), and can be used for treating hair (8.1-9.0 min), hair (7.1-8.0 min), hair (6.1-7.0 min), hair passing (5.0-6.0 min) and hair failing (less than 5.0 min).
The evaluation results are shown in the following table 1:
TABLE 1
From the above experimental results, it is apparent that the L menthol products of the examples of the present invention have the main components L menthol, D menthol, L neoisomenthol and D neoisomenthol in comparison with the products of the comparative examples, while satisfying the conditions that "the sum of the mass contents of L menthol and D menthol is > 99.50%, and the mass contents of L menthol is > 99.00%" and "the sum of the mass contents of L neoisomenthol is not less than 0.004%, the sum of the mass contents of L neoisomenthol and D neoisomenthol is 0.005% -0.050%, the mass contents of L neoisomenthol is greater than the mass content of D neoisomenthol, and the difference of the mass contents of L neoisomenthol and D neoisomenthol is > 0.001%", and the L menthol products provided in the examples have significantly improved cool feeling and hair permeability compared with the comparative examples.
The products of examples 2 and 3 further improved the cool feel and the hair transmission of the L menthol product as compared with example 1. The product of example 3 has more excellent cool feeling and hair permeability than the product of example 2.
It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (16)

1. An L-menthol composition having improved cool feeling and hair transmission, characterized in that said L-menthol composition mainly comprises L-menthol, D-menthol, L-neo-isomenthol and D-neo-isomenthol;
The sum of the mass contents of the L menthol and the D menthol is 99.60-99.95% based on the total mass of the composition, and the mass content of the L menthol is 99.30-99.80%;
The mass content of the L-neoisomenthol is 0.004-0.040%, the sum of the mass content of the L-neoisomenthol and the mass content of the D-neoisomenthol is 0.005-0.050%, and the mass content of the L-neoisomenthol is greater than the mass content of the D-neoisomenthol, and the difference between the mass content of the L-neoisomenthol and the mass content of the D-neoisomenthol is 0.002-0.025%.
2. The L-menthol composition according to claim 1, wherein the mass content of the L-menthol is 99.60 to 99.80%;
the difference between the mass content of L neoisomenthol and the mass content of D neoisomenthol is 0.010-0.025%.
3. The L-menthol composition according to claim 1 or 2, wherein the L-menthol composition further comprises a balance of other components, said other components comprising isopulegol, menthone, isomenthone, neomenthol and/or isomenthol; the total mass content of the other components in the L menthol composition is less than 0.5 percent.
4. Use of the L-menthol composition according to any one of claims 1 to 3, wherein said composition is used in the preparation of a cosmetic or pharmaceutical product.
5. Use of an L-menthol composition according to any one of claims 1 to 3, for enhancing the cooling sensation of a product, wherein said product comprises a cosmetic or pharmaceutical product.
6. A method of improving cool feeling and hair transmission of an L-menthol product, wherein the L-menthol product comprises L-menthol, D-menthol, L-neo-isophthol, and D-neo-isophthol, and the cool feeling and hair transmission of the L-menthol product is improved by making the mass content of L-menthol, D-menthol, L-neo-isophthol, and D-neo-isophthol in the L-menthol product satisfy the following conditions (I) and (II):
(I) The sum of the mass contents of the L menthol and the D menthol is 99.60-99.95% based on the total mass of the L menthol product, and the mass content of the L menthol is 99.30-99.80%;
(II) the mass content of L neoisomenthol is 0.004-0.040%, the sum of the mass content of L neoisomenthol and the mass content of D neoisomenthol is 0.005-0.050%, and the mass content of L neoisomenthol is greater than the mass content of D neoisomenthol, the difference between the mass content of L neoisomenthol and the mass content of D neoisomenthol is 0.002-0.025%, based on the total mass of the L menthol product.
7. The process according to claim 6, wherein the L-menthol product satisfying the conditions (I) and (II) is obtained by subjecting crude L-menthol to purification comprising distillation, rectification, crystallization and/or extraction of the crude L-menthol.
8. The method of claim 7, wherein the crystallization is solution crystallization or melt crystallization.
9. The method of claim 8, wherein the crystallization is melt crystallization.
10. The method of claim 9, wherein the melt crystallization is static melt crystallization.
11. The method according to claim 10, characterized in that the crude L menthol is purified by static melt crystallization, in particular comprising the steps of:
(1) Heating and melting crude L menthol in a static melting crystallizer, cooling to separate out crystals, and discharging uncrystallized residual liquid;
(2) Heating up and sweating the crystal, continuously discharging the generated distillate in the sweating process, continuously monitoring the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol in the distillate, and collecting the distillate part meeting the conditions (I) and (II) as an L menthol product when the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol meets the conditions (I) and (II).
12. The method of claim 11, wherein the elevated melting temperature is 43-50 ℃;
The cooling comprises cooling to 40-42 ℃ at a cooling rate of 0.2-1.0 ℃/h, and then keeping for 1-3h; then cooling to 41.2-41.5 ℃ at a cooling rate of 0.03-0.06 ℃/h.
13. The method of claim 11 wherein the elevated temperature sweat rate is from 0.05 to 0.08 ℃/h.
14. The method of claim 7, wherein the rectifying comprises the steps of:
And (3) rectifying the crude L menthol in a rectifying tower, continuously monitoring the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol in the distillate extracted from the top of the rectifying tower, and collecting the distillate part with the mass content of L menthol, D menthol, L neoisomenthol and D neoisomenthol meeting the conditions (I) and (II) as the L menthol product.
15. The method of claim 14, wherein the operating conditions of the rectification column include: the temperature of the tower bottom is 100-130 ℃, the temperature of the tower top is 40-60 ℃, the pressure of the tower top is 0.5-5KPa absolute, and the reflux ratio is 5:1-15:1.
16. The method according to any one of claims 7-15, wherein the sum of the mass contents of L menthol and D menthol in the crude L menthol is > 95.00% and 98.00%, wherein the mass content of L menthol is > 90.00% and 98.00%, and the sum of the mass contents of L neoisomenthol and D neoisomenthol is 0.01% -0.60%, wherein the mass content of L neoisomenthol is > 0.005% and 0.550%.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5663460A (en) * 1994-07-29 1997-09-02 Takasago International Corporation Liquid l-n-menthol composition and process for preparing the same
CN104684412A (en) * 2012-10-05 2015-06-03 小川香料株式会社 Powdery refreshing composition
CN104812732A (en) * 2012-11-27 2015-07-29 巴斯夫欧洲公司 Composition of menthol and menthyl lactate, its preparation and its use as a cooling, flavouring and/or fragrance agent
CN104829422A (en) * 2015-04-10 2015-08-12 湖南利洁生物化工有限公司 Method for splitting D,L-menthol
CN105461516A (en) * 2015-11-20 2016-04-06 安徽海华科技股份有限公司 A synthetic process of L-menthol
CN108853105A (en) * 2012-12-12 2018-11-23 西姆莱斯股份公司 Cosmetic composition, composite medicine and food compositions
CN116554003A (en) * 2023-04-27 2023-08-08 安徽海华科技集团有限公司 L-menthol purifying process
CN117305022A (en) * 2023-11-29 2023-12-29 万华化学集团股份有限公司 Method for improving quality of L menthol product

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10239274A1 (en) * 2002-08-22 2004-03-04 Symrise Gmbh & Co. Kg Process for the production of menthol
BRPI0419195A (en) * 2004-10-13 2007-12-18 Symrise Gmbh & Co Kg menthol lactate composition and a mixture of menthol isomers
US8785698B2 (en) * 2009-02-17 2014-07-22 Nagaoka & Co., Ltd. Methods and apparatus for production of natural L-menthol
EP3093002B1 (en) * 2015-05-15 2018-04-25 Symrise AG Liquid cooling compositions
EP3388411A1 (en) * 2017-04-13 2018-10-17 Sulzer Chemtech AG A process for purifying a crude composition including a monoterpene compound, such as a monocyclic monoterpene alcohol, by layer melt crystallization

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5663460A (en) * 1994-07-29 1997-09-02 Takasago International Corporation Liquid l-n-menthol composition and process for preparing the same
CN104684412A (en) * 2012-10-05 2015-06-03 小川香料株式会社 Powdery refreshing composition
CN104812732A (en) * 2012-11-27 2015-07-29 巴斯夫欧洲公司 Composition of menthol and menthyl lactate, its preparation and its use as a cooling, flavouring and/or fragrance agent
CN108853105A (en) * 2012-12-12 2018-11-23 西姆莱斯股份公司 Cosmetic composition, composite medicine and food compositions
CN104829422A (en) * 2015-04-10 2015-08-12 湖南利洁生物化工有限公司 Method for splitting D,L-menthol
CN105461516A (en) * 2015-11-20 2016-04-06 安徽海华科技股份有限公司 A synthetic process of L-menthol
CN116554003A (en) * 2023-04-27 2023-08-08 安徽海华科技集团有限公司 L-menthol purifying process
CN117305022A (en) * 2023-11-29 2023-12-29 万华化学集团股份有限公司 Method for improving quality of L menthol product

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘锐锋 ; .清凉香料应用研究进展.特种经济动植物.2020,(第08期),26-28页. *
清凉香料应用研究进展;刘锐锋;;特种经济动植物;20200810(第08期);26-28页 *

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