1, 3-butanediol product and application thereof

Abstract

The invention relates to the technical field of 1, 3-butanediol products, and provides a 1, 3-butanediol product and application thereof.The 1, 3-butanediol product has improved odor and low skin irritation, and the crotonaldehyde content of the 1, 3-butanediol product can still be kept at a low level after long-time storage. One aspect of the present invention provides a 1, 3-butanediol product in which, when the relative retention time corresponding to the peak appearance position of 1, 3-butanediol is set to 1.0 in gas chromatography analysis, the sum of the area ratios of peaks appearing within the relative retention time range of 1.32-1.38 is > 0 and < = 750 ppm.

Description

Technical Field

[0001] The invention relates to a 1,3-butanediol product and application thereof. Background Art

[0002] 1,3-Butanediol is a colorless and odorless liquid with good moisturizing properties and low skin irritation. It is widely used in cosmetics as a moisturizer and solvent.

[0003] There are many processes and methods for producing 1,3-butanediol. (1) British patent GB853266A discloses a method of using acetaldehyde as a raw material to generate 3-hydroxybutyraldehyde through aldol condensation in an alkaline solution, and then hydrogenating 3-hydroxybutyraldehyde to generate 1,3-butanediol. (2) Chinese patent CN103102229B9 discloses a method of using formaldehyde and propylene as raw materials to prepare 1,3-butanediol through Prins reaction in the presence of an acidic oxide catalyst. (3) Japanese patent JP3290 466B2 discloses a method for preparing 1,3-butanediol by a three-step process, which comprises condensing acetaldehyde to form 2,6-dimethyl-1,3-dioxane-4-ol (aldoxane), then decomposing 2,6-dimethyl-1,3-dioxane-4-ol to obtain dimeric meta-hydroxybutyraldehyde (paraldol), and then hydrogenating to obtain 1,3-butanediol; (4) Canadian patent CA2759994C discloses a method for synthesizing 1,3-butanediol using non-natural microorganisms. In addition, there are: (5) laser irradiation of ethanol containing hydrogen peroxide and saturated with nitrogen to directly synthesize 1,3-butanediol; (6) acrolein reacts with 2,2-dimethyl-1,3-propanediol, the product is hydrolyzed after carbonyl synthesis, and hydrogenated to obtain 1,3-butanediol.

[0004] Considering factors such as economy and product quality, most of the preparation methods currently adopted are (1) acetaldehyde condensation hydrogenation method, and the specific process is as follows:

[0005] 1) Acetaldehyde condensation: In alkaline solution, acetaldehyde condenses to produce 3-hydroxybutyraldehyde;

[0006] 2) Hydrogenation process: 3-hydroxybutyraldehyde is hydrogenated to produce 1,3-butanediol;

[0007] 3) Separation and purification: extraction, distillation and other processes to remove impurities;

[0008] Chinese patent application CN110790634A discloses a method that uses segmented hydrogenation and hydrogenation catalysts to add modifiers to obtain 1,3-butanediol with a purity greater than 99.5%, wherein the content of the odor-producing impurity 1,3-dioxane can be reduced to less than 0.01wt%. Chinese patent application CN117940397A uses a heating method to remove the odorous substance methyl vinyl ketone. Chinese patent application CN117940396A uses Pd / C catalytic hydrogenation to reduce the odorous substance 6-hydroxy-2-hexanone.

[0009] Whether there is an odor is an important indicator for the application of 1,3-butanediol in cosmetics, but more importantly, cosmetics need to contact the skin, and even be used in the mouth, tableware cleaning, etc., and may enter the human digestive system; therefore, safety is also a more important indicator for the application of cosmetics. Although the above patents control the impurities that produce odor, they do not consider the impact of residual impurities on human safety. In the current production methods of 1,3-butanediol, whether it is acetaldehyde condensation method, propylene carbonylation method, or 2,6-dimethyl-1,3-dioxane-4-ol decomposition method, the intermediate product 3-hydroxybutyraldehyde will be produced, accompanied by a small amount of crotonaldehyde. 3-Hydroxybutyraldehyde is easily dehydrated to produce crotonaldehyde. The LC50 of crotonaldehyde is 240mg / kg (oral in mice), and it is irritating to the human eye above 45ppm. China's "Cosmetic Technical Specifications-2015" lists it as a prohibited substance.

[0010] Chinese patent application CN114340586A provides a 1,3-butanediol product, defines 3-hydroxybutyraldehyde and acetal of 1,3-butanediol, and the provided 1,3-butanediol product is colorless and transparent, and has little color change over time. Summary of the invention

[0011] The present invention provides a 1,3-butanediol product and application thereof. The 1,3-butanediol product provided by the present invention has improved odor and lower skin irritation, and its crotonaldehyde content can still be maintained at a lower level after being stored for a long time.

[0012] To achieve the purpose, the present invention provides the following technical solutions:

[0013] In one aspect, the present invention provides a 1,3-butanediol product. In a gas chromatography analysis of the 1,3-butanediol product, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing in the range of relative retention time of 1.32-1.38 is greater than 0 and less than or equal to 750 ppm;

[0014] The analysis conditions of the gas chromatography are as follows:

[0015] Gas chromatograph: Agilent 7890 gas chromatograph;

[0016] Detector: flame ionization detector (FID);

[0017] Chromatographic column: HP-VOC chromatographic column, column length 60m×inner diameter 0.32mm×film thickness 1.8μm;

[0018] Carrier gas: nitrogen, flow rate 1.5 ml / min;

[0019] Column temperature: initial temperature 50℃, maintained for 2 min, then increased to 80℃ at 5℃ / min, then increased to 270℃ at 15℃ / min and maintained for 10 min;

[0020] Vaporization chamber temperature: 260℃;

[0021] Detector temperature: 280°C.

[0022] Preferably, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing within the relative retention time range of 1.32-1.38 is 5-700 ppm, for example, 10-700 ppm.

[0023] Furthermore, after a 50 wt % aqueous solution of the 1,3-butanediol product is adjusted to pH 6 and placed at 50° C. for 90 days, the mass content of crotonaldehyde does not exceed 10 ppm.

[0024] Another aspect of the present invention provides a moisturizer comprising the above-mentioned 1,3-butanediol preparation.

[0025] Another aspect of the present invention provides a cosmetic comprising the moisturizing agent described above.

[0026] In another aspect, the present invention provides a method for improving the odor and / or skin irritation of a composition to which a 1,3-butanediol product is added. The 1,3-butanediol product added must meet the following requirements to improve the odor and / or skin irritation of the composition:

[0027] In the gas chromatography analysis of the 1,3-butanediol product, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0,

[0028] The sum of the area ratios of the peaks appearing in the relative retention time range of 1.32-1.38 is >0 and ≤750 ppm;

[0029] The analysis conditions of the gas chromatography are as follows:

[0030] Gas chromatograph: Agilent 7890 gas chromatograph;

[0031] Detector: flame ionization detector (FID);

[0032] Chromatographic column: HP-VOC chromatographic column, column length 60m×inner diameter 0.32mm×film thickness 1.8μm;

[0033] Carrier gas: nitrogen, flow rate 1.5 ml / min;

[0034] Column temperature: initial temperature 50℃, maintained for 2 min, then increased to 80℃ at 5℃ / min, then increased to 270℃ at 15℃ / min and maintained for 10 min;

[0035] Vaporization chamber temperature: 260℃;

[0036] Detector temperature: 280°C.

[0037] Preferably, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing within the relative retention time range of 1.32-1.38 is 5-700 ppm, for example, 10-700 ppm.

[0038] The present invention also provides a method for preparing the 1,3-butanediol product described above, comprising the following steps:

[0039] S1, using a feed liquid containing 3-hydroxybutyraldehyde as a hydrogenation raw material liquid, and performing a hydrogenation reaction to obtain a reaction liquid containing 1,3-butanediol;

[0040] S2, separating and refining the reaction solution containing 1,3-butanediol to obtain a 1,3-butanediol product;

[0041] Wherein, in step S1, before the hydrogenation reaction, the acid value of the hydrogenation raw material liquid is controlled to be 5-200 ppm;

[0042] Preferably, in the 3-hydroxybutyraldehyde-containing liquid, the content of 3-hydroxybutyraldehyde is >20wt%, preferably >55wt%;

[0043] Preferably, the water content in the 3-hydroxybutyraldehyde-containing liquid is 1-42 wt%, preferably 5-42 wt%.

[0044] The technical solution provided by the present invention has the following beneficial effects:

[0045] The 1,3-butanediol product that meets the specific peak area ratio requirements of the present invention has significantly improved odor and significantly reduced skin irritation, and during a long storage period, there is no significant increase in the crotonaldehyde content, and the crotonaldehyde content can still be maintained at a low level. DETAILED DESCRIPTION

[0046] In order to facilitate the understanding of the present invention, the present invention will be further described below in conjunction with examples. It should be understood that the following examples are only for a better understanding of the present invention and do not mean that the present invention is limited to the following examples.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the invention belongs. The term "and / or" as may be used herein includes any and all combinations of one or more of the associated listed items.

[0048] The present invention provides a 1,3-butanediol product. In gas chromatography analysis of the 1,3-butanediol product, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of peaks appearing within the relative retention time range of 1.32-1.38 is greater than 0 and less than or equal to 750 ppm;

[0049] The analysis conditions of the gas chromatography are as follows:

[0050] Gas chromatograph: Agilent 7890 gas chromatograph;

[0051] Detector: flame ionization detector (FID);

[0052] Chromatographic column: HP-VOC chromatographic column, column length 60m×inner diameter 0.32mm×film thickness 1.8μm;

[0053] Carrier gas: nitrogen, flow rate 1.5 ml / min;

[0054] Column temperature: initial temperature 50℃, maintained for 2 min, then increased to 80℃ at 5℃ / min, then increased to 270℃ at 15℃ / min and maintained for 10 min;

[0055] Vaporization chamber temperature: 260℃;

[0056] Detector temperature: 280°C.

[0057] In some examples, in the gas chromatography analysis of 1,3-butanediol products, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32-1-38 is 1ppm, 5ppm, 10ppm, 20ppm, 50ppm, 100ppm, 150ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 750ppm, etc. More preferably, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32-1.38 is 5-700ppm, for example, 10-700ppm.

[0058] Specifically, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the molecular weight of the substance in the range of the relative retention time of 1.32-1.35 is 188, which is an acetal formed by 3-hydroxybutyraldehyde and a saturated six-carbon diol, and has the following structural formula (I) or (II):

[0059]

[0060] Specifically, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the molecular weight of the substance in the range of the relative retention time of 1.35-1.38 is 186, which is an acetal formed by 3-hydroxybutyraldehyde and an unsaturated six-carbon diol, and has the following structural formula (III) or (IV):

[0061]

[0062] Generally, in the production process of 1,3-butanediol, especially the process of acetaldehyde condensation hydrogenation is used to prepare 1,3-butanediol. The production process involves acetaldehyde, 3-hydroxybutyraldehyde, and by-products such as formaldehyde, acetone, butyraldehyde, crotonaldehyde, methyl vinyl ketone, 6-hydroxy-2-hexanone, methyl hydroxyethyl ketone and other carbonyl-containing substances. These substances will have a negative effect on the smell, color, skin irritation, etc. of the product. The content of these substances is reduced through subsequent hydrogenation and separation processes. For example, the boiling points of crotonaldehyde and 3-hydroxybutyraldehyde are quite different from those of 1,3-butanediol, and they are easy to separate through distillation processes. In addition, butyraldehyde and acetaldehyde, crotonaldehyde and acetaldehyde will react to produce 1,3-dihydroxy diols, which are easy to react with the above-mentioned carbonyl-containing compounds to produce acetal ketal substances containing 1,3-dioxane structures such as structural formulas (I)-(IV). The inventors have found that these substances are difficult to separate and remove by hydrogenation or distillation in subsequent processes, and will be contained in 1,3-butanediol and introduced into cosmetics with the use of 1,3-butanediol in downstream applications. Moreover, these substances are unstable, especially in acidic conditions, and are easily decomposed to produce aldehydes and ketones, which affect the odor, color, skin irritation, etc. of 1,3-butanediol products. The inventors found that, according to the above-mentioned gas chromatography analysis conditions, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratio of the peak appearing in the relative retention time range of 1.32-1.35 and the area ratio of the peak appearing in the relative retention time range of 1.35-1.38 is greater than 0 and does not exceed 750ppm, that is, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32-1.38 is greater than 0 and does not exceed 750ppm, for example, 5-750ppm, 5-700ppm, 10-750ppm, 10-700ppm, for example, <500ppm, preferably <50ppm; such 1,3-butanediol products have significantly improved odor and significantly reduced skin irritation compared to products with higher peak area ratios within the above-mentioned relative retention time range, wherein the improved odor is specifically manifested as significantly reducing or weakening the pungent odor.

[0063] The 1,3-butanediol product provided by the present invention does not show a significant increase in the crotonaldehyde content during a long storage period, and can still maintain a low content level. Specifically, after a 50wt% aqueous solution of the 1,3-butanediol product provided by the present invention is adjusted to pH 6 and placed at 50°C for 90 days, the mass content of crotonaldehyde does not exceed 10ppm, and more preferably does not exceed 1ppm.

[0064] In this article, “peak area ratio” refers to the ratio of a specific peak area to the total peak area;

[0065] Among them, "specific peak area" refers to the integrated area of ​​the peak corresponding to a relative retention time in the gas chromatography test; "total peak area" refers to the sum of the integrated areas of all peaks in the gas chromatography test.

[0066] In the 1,3-butanediol product of the present invention, when tested under the above-mentioned gas chromatography analysis conditions, the peak area ratio of 1,3-butanediol is preferably greater than 99.5%, more preferably greater than 99.7%, and even more preferably greater than 99.8%.

[0067] The 1,3-butanediol product provided by the invention is particularly suitable for use in moisturizers and cosmetics, and has obvious improvements in terms of odor and skin irritation.

[0068] The present invention also provides a moisturizer, comprising the 1,3-butanediol preparation described above.

[0069] The present invention also provides a cosmetic comprising the moisturizing agent described above.

[0070] The present invention also provides a method for improving the odor and / or skin irritation of a composition to which a 1,3-butanediol product is added. The added 1,3-butanediol product must meet the following requirements to improve the odor and / or skin irritation of the composition:

[0071] In the gas chromatography analysis of the 1,3-butanediol product, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32-1.38 is greater than 0 and less than or equal to 750 ppm;

[0072] The analysis conditions of the gas chromatography are as follows:

[0073] Gas chromatograph: Agilent 7890 gas chromatograph;

[0074] Detector: flame ionization detector (FID);

[0075] Chromatographic column: HP-VOC chromatographic column ((6%-cyanopropyl-phenyl)-methylpolysiloxane chromatographic column), column length 60m×inner diameter 0.32mm×film thickness 1.8μm;

[0076] Carrier gas: nitrogen, flow rate 1.5 ml / min;

[0077] Column temperature: initial temperature 50℃, maintained for 2 min, then increased to 80℃ at 5℃ / min, then increased to 270℃ at 15℃ / min and maintained for 10 min;

[0078] Vaporization chamber temperature: 260℃;

[0079] Detector temperature: 280°C.

[0080] Furthermore, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing within the relative retention time range of 1.32-1.38 is 5-700 ppm, for example, 10-700 ppm.

[0081] The present invention also provides a method for preparing the 1,3-butanediol product described above, comprising the following steps:

[0082] S1, using a feed liquid containing 3-hydroxybutyraldehyde as a hydrogenation raw material liquid, and performing a hydrogenation reaction to obtain a reaction liquid containing 1,3-butanediol;

[0083] S2, separating and refining the reaction solution containing 1,3-butanediol to obtain a 1,3-butanediol product;

[0084] Wherein, in step S1, before the hydrogenation reaction, the acid value of the hydrogenation raw material liquid is controlled to be 5-200 ppm.

[0085] The preparation of 1,3-butanediol by hydrogenation of 3-hydroxybutyraldehyde is well known in the art. The main improvement of the above preparation method of the present invention is that the inventors have found that by controlling the acid value of the hydrogenation raw liquid in step S1 to 5-200 ppm, it is beneficial to obtain a 1,3-butanediol product that meets the above-mentioned specific peak area ratio requirements of the present invention. The above acid values ​​are all calculated based on acetic acid content.

[0086] In some examples, the acid value of the hydrogenation feed liquid is controlled to be 5 ppm, 10 ppm, 20 ppm, 30 ppm, 50 ppm, 70 ppm, 90 ppm, 100 ppm, 120 ppm, 150 ppm, 170 ppm, 200 ppm, etc.

[0087] There is no particular limitation on the composition of the hydrogenation feed liquid, which may be an acetaldehyde condensation liquid, or a reaction liquid (i.e., a stripping liquid) obtained by stripping the acetaldehyde condensation liquid, or a 3-hydroxybutyraldehyde solution, or refined 3-hydroxybutyraldehyde. The stripping liquid obtained by stripping the condensation liquid containing 3-hydroxybutyraldehyde obtained by acetaldehyde condensation or acetaldehyde condensation mainly includes 3-hydroxybutyraldehyde, and may also include one or more of 2,6-dimethyl-1,3-dioxane-4-ol (aldoxane), di-polybutyraldehyde, and may further include condensation by-products such as crotonaldehyde, butyraldehyde, and acetaldehyde. Preferably, the hydrogenation feed liquid is a reaction mixture containing 3-hydroxybutyraldehyde obtained by acetaldehyde condensation, and the stripping liquid after stripping to remove unreacted acetaldehyde can recover unreacted acetaldehyde by stripping, which is beneficial to reducing manufacturing costs.

[0088] In some examples, the step of preparing 1,3-butanediol products includes an acetaldehyde condensation step, and the hydrogenation raw material liquid is obtained by the acetaldehyde condensation step. In the acetaldehyde condensation step, a reaction mixture containing 3-hydroxybutyraldehyde is prepared by a condensation reaction of acetaldehyde, and the reaction mixture is preferably removed from the unreacted acetaldehyde and used as a hydrogenation raw material liquid. In the acetaldehyde condensation step, it can be carried out in the presence of an alkaline catalyst, and the alkaline catalyst can use a corresponding catalyst suitable for use in the art, and there is no particular limitation on this. For example, as long as the system can be controlled under alkaline conditions, an inorganic base such as sodium hydroxide, sodium carbonate, etc. can be selected; an organic quaternary ammonium base can also be selected, and further, a solid composite catalyst such as MgO-MgAl2O4 solid composite catalyst can also be selected. For the condensation reactor, a kettle reactor can be selected, and a fixed bed reactor can also be selected. Relative to the mass of acetaldehyde, the amount of the alkaline catalyst can be 0.05-5%, preferably 0.5-2%. In the condensation reaction, the condensation reaction temperature can be 0-30°C, preferably 10-15°C (e.g., 12°C, 13°C, 14°C); the reaction time can be 2-20h, preferably 3-10h. The unreacted acetaldehyde can be removed by stripping, such as nitrogen stripping, or short-path evaporation.

[0089] The hydrogenation reaction can be carried out in the presence of a hydrogenation catalyst, and a corresponding catalyst suitable in the art can be selected, without particular limitation. For example, a catalyst containing nickel or cobalt, such as Raney nickel, can be selected; there are no particular limitations on the hydrogenation reaction pressure, the amount of catalyst, etc., and the conventional process conditions in the art can be used; specifically, for example, the temperature of the hydrogenation reaction is 80-140° C., more preferably 90-120° C., and further preferably 100-120° C.; the reaction pressure can be 2-20 MPa (gauge pressure); relative to the mass of 3-hydroxybutyraldehyde, the amount of catalyst can be 1-5%.

[0090] The separation and purification steps used in step S2 may be selected from but not limited to dehydration process, desalination process, extraction process, heavy removal process, and light removal process; further, adsorption, stripping and other processes may be selected.

[0091] In some examples, in step S2, separation and purification are performed by the following method:

[0092] The reaction liquid obtained by the hydrogenation reaction is distilled and separated. The number of plates of the distillation tower is 20-40. First, low-boiling point compounds such as ethanol and water are removed at a pressure of 5-50KPa. After the removal is completed, the pressure is reduced to 0.5-3kPa to collect products with a purity of ≥99.7%;

[0093] The 1,3-butanediol obtained by distillation separation is extracted, specifically, 1,3-butanediol, water and methyl isobutyl ketone are mixed and shaken, the weight of water can be 1-5 times relative to the weight of 1,3-butanediol, and the weight of methyl isobutyl ketone can be 0.2-3 times; then stand to separate the water layer from the organic layer. Methyl isobutyl ketone is further added to the separated water phase, the weight of the added methyl isobutyl ketone is 0.02-1 times relative to the weight of the water phase, and the aforementioned shaking, standing and phase separation operations are repeated once or multiple times. After extraction, the water layer material is dehydrated and concentrated to obtain a 1,3-butanediol product.

[0094] In the production process of preparing 1,3-butanediol by acetaldehyde condensation and hydrogenation, acetaldehyde is condensed and hydrogenated to produce 1,3-butanediol, which is also accompanied by many side reactions and generates many unfavorable substances. For example, 3-hydroxybutyraldehyde is unstable when heated and easily produces crotonaldehyde. Crotonaldehyde is hydrogenated to produce butyraldehyde. Crotonaldehyde and butyraldehyde condense with residual acetaldehyde to produce six-carbon hydroxyaldehyde, which is further hydrogenated to obtain six-carbon diol. The six-carbon diol has a 1,3-dihydroxy structure. In addition, many by-products are produced, such as formaldehyde, acetone, methyl vinyl ketone, methyl hydroxyethyl ketone, 6-hydroxy-2-hexanone, acetic acid and esters of 1,3-butanediol, etc. These substances are easy to remove in the subsequent separation process. Since the six-carbon diol has a 1,3-dihydroxy structure, it is easy to react with aldehydes and ketones to generate stable acetals and ketals with a 1,3-dioxane structure, such as the substances of the above structural formulas (I), (II), (III) and / or (IV). The inventors found that these acetals and ketals are difficult to completely remove in the subsequent separation process, mainly because they have good compatibility with the main product 1,3-butanediol, and the boiling point difference is smaller. Conventional extraction and separation are difficult, resulting in high residues in 1,3-butanediol. When added to cosmetics, they are unstable and easily decomposed to produce aldehydes and ketones and six-carbon diols. Aldehydes and ketones may increase the smell of cosmetics, increase the color of the product, or make the product prone to skin allergy, acne, and carcinogenicity.

[0095] The inventors have found that by controlling the acid value in the hydrogenation raw liquid, the content of the substance with the above-mentioned specific relative retention time in the 1,3-butanediol product of the present invention can be controlled, thereby improving the odor of the obtained product and / or reducing skin irritation. The control of the acid value in the hydrogenation raw liquid can be achieved by using an acidic substance to adjust the acid value of the hydrogenation raw liquid before the hydrogenation reaction, or by adjusting the acid value of the reaction mixture containing 3-hydroxybutyraldehyde obtained by the condensation reaction of acetaldehyde. Preferably, the acid value of the reaction mixture containing 3-hydroxybutyraldehyde is adjusted after the condensation reaction of acetaldehyde is completed. Because the condensation reaction of acetaldehyde uses an alkaline substance as a catalyst, after the reaction is completed, an acidic substance needs to be used to neutralize the condensation reaction liquid to stop the reaction. Adjusting the acid value at this stage can reduce the operation links. Since the condensation reaction liquid needs to be further separated, the separation operation includes but is not limited to the steps of stripping and separating acetaldehyde, dehydration, desalination, etc. Therefore, when the acid value is preferably adjusted in this way, the acid value of the reaction mixture containing 3-hydroxybutyraldehyde is controlled at a higher level, specifically the acid value is controlled at 50ppm-500ppm, preferably 50ppm-200ppm, more preferably 100ppm-200ppm; thereby finally obtaining a hydrogenation raw material liquid with an acid value of 5-200ppm. If the acid value of the hydrogenation raw material liquid is high, the catalyst will be deactivated and the hydrogenation reaction will be hindered; at the same time, when the acid value is high, the aldol condensation reaction will continue, and the aldehyde substances in the hydrogenation raw material liquid will continue to react, thereby causing the above-mentioned (I), (II), (III) and / or (IV) substances in the final product to increase in content.

[0096] The substance used to adjust the acid value is not particularly limited, and one or more organic acids and / or inorganic acids can be used, such as formic acid, acetic acid, etc., and inorganic acids such as hydrochloric acid, sulfuric acid, etc. More preferably, small molecule organic acids such as formic acid and acetic acid are used. Preferably, when the water content in the system is greater than 20wt%, an inorganic acid can be used.

[0097] In the hydrogenation feed liquid, the content of 3-hydroxybutyraldehyde is not particularly limited. From the perspective of the front-end condensation process and subsequent separation, the 3-hydroxybutyraldehyde content is preferably greater than 20wt%, such as 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt%, 95wt%, etc., and can also be greater than 55wt%. In a preferred embodiment, the hydrogenation feed liquid preferably contains 1-42wt% of water, such as 1wt%, 2wt%, 5wt%, 10wt%, 15wt%, 20wt%, 30wt%, 35wt%, 40wt%, 42wt%, etc., for example, more preferably 5-42wt% of water, for example, 10-20wt% of water.

[0098] The present invention is further described below by way of examples, but it should not be understood that the present invention is limited thereto.

[0099] Where specific experimental steps or conditions are not specified in the examples, the corresponding conventional experimental steps or conditions in the art can be used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be purchased commercially.

[0100] The detection methods in the following examples and comparative examples are described as follows:

[0101] The conditions for analyzing 1,3-butanediol products by gas chromatography are as follows:

[0102] Gas chromatograph: Agilent 7890 gas chromatograph;

[0103] Detector: flame ionization detector (FID);

[0104] Chromatographic column: Agilent HP-VOC chromatographic column ((6%-cyanopropyl-phenyl)-methylpolysiloxane chromatographic column), column length 60m×inner diameter 0.32mm×film thickness 1.8μm;

[0105] Carrier gas: nitrogen, flow rate 1.5 ml / min;

[0106] Column temperature: initial temperature 50℃, maintained for 2 min, then increased to 80℃ at 5℃ / min, then increased to 270℃ at 15℃ / min and maintained for 10 min;

[0107] Vaporization chamber temperature: 260℃;

[0108] Detector temperature: 280°C.

[0109] In the gas chromatography analysis, the relative retention time corresponding to the peak position of 1,3-butanediol is set as 1.0, and the area ratio of the peak appearing in the relative retention time range of 1.32-1.35 and the area ratio of the peak appearing in the relative retention time range of 1.35-1.38 are calculated.

[0110] The crotonaldehyde content test method of the 1,3-butanediol products obtained in each embodiment and comparative example after storage:

[0111] (1) Prepare a 50 wt% aqueous solution of 1,3-butanediol sample, adjust the pH to 6 with hydrochloric acid, and place it in a 50°C oven for 90 days as a sample to be tested;

[0112] (2) The crotonaldehyde content was tested using the following HPLC method

[0113] a) Weigh 0.20 g of 2,4-dinitrophenylhydrazine, place in a conical flask, add 40 ml of concentrated hydrochloric acid (concentration: 36.5 wt%) to dissolve, add 60 ml of deionized water, shake well to obtain a 2,4-dinitrophenylhydrazine hydrochloric acid solution, set aside;

[0114] b) Weigh 0.2 g of the sample to be tested, place it in a stoppered test tube, add acetonitrile to 2 ml, add 0.4 ml of 2,4-dinitrophenylhydrazine hydrochloric acid solution, and then add 10 wt % sodium hydroxide aqueous solution to adjust to neutrality, and mix well as the test solution;

[0115] c) preparing crotonaldehyde aqueous solution and measuring by standard curve method, the standard curve concentration is 0.5mg / kg, 1mg / kg, 3mg / kg, 5mg / kg, 7mg / kg, 9mg / kg;

[0116] d) HPLC chromatographic conditions;

[0117] Chromatographic column: C18 column (250mm×4.6mm×5μm, or equivalent);

[0118] Mobile phase: methanol + water (volume ratio of methanol to water is 60:40);

[0119] Flow rate: 1.0 mL / min;

[0120] Detection wavelength: 355nm;

[0121] Column temperature: 25°C;

[0122] Injection volume: 10 μL.

[0123] Product application performance test:

[0124] Odor test method: 1,3-Butanediol product was prepared into a 50wt% aqueous solution, 10 trained personnel were selected to evaluate the odor, and the score was given according to the following evaluation criteria, and the average score was taken as the final result; the evaluation criteria are as follows:

[0125] 5. No smell

[0126] 4: Slight odor

[0127] 3: The smell is acceptable

[0128] 2: The smell is unacceptable

[0129] 1: Obvious pungent smell

[0130] Skin irritation (patch) test method:

[0131] 1) Prepare a 50 wt% aqueous solution of 1,3-butanediol sample, adjust the pH to 6 with hydrochloric acid, and place it in a 50°C oven for 90 days as a sample to be tested;

[0132] 2) Place 0.025 ml of the sample to be tested in the spot tester and apply it to the curved side of the subject's forearm with a hypoallergenic tape. Remove it after 24 hours. Observe the skin reaction 24 hours after removal and record the results according to the skin reaction grading standard. A total of 30 subjects participated in the scoring. The skin reaction grading standard is as follows:

[0133]

[0134] The test result is recorded as n, where n represents the number of scorers of the corresponding scoring level.

[0135] Example 1

[0136] Preparation of hydrogenation raw liquid: 100 g of sodium hydroxide aqueous solution with a mass concentration of 0.5 wt% is added dropwise to 500 g of acetaldehyde for 4 hours, the condensation reaction temperature is controlled at 10-15° C. by a cold bath, the reaction is continued for 3 hours after the addition is completed, acetic acid is added to the system to adjust the acid value of the material to 50 ppm, unreacted acetaldehyde is recovered by short-path evaporation, and a hydrogenation raw liquid (i.e., a condensation liquid containing 3-hydroxybutyraldehyde) is obtained; the obtained hydrogenation raw liquid mainly contains 85.2 wt% of 3-hydroxybutyraldehyde, has a water content of 12.5 wt% and an acid value of 5 ppm.

[0137] Hydrogenation reaction: 300 g of the above hydrogenation raw liquid was added with 8.5 g of Raney nickel catalyst (Raney 6800, purchased from GRACE), the hydrogenation temperature was 80° C., the reaction pressure was 9 MPa (gauge pressure), and the reaction was carried out for 3 hours; after the reaction was completed, a reaction liquid containing 1,3-butanediol was obtained;

[0138] Refining process:

[0139] The reaction liquid containing 1,3-butanediol is distilled and separated. The distillation tower has 30 plates. First, the distillation is carried out at a pressure of 20 KPa to separate low-boiling point compounds such as ethanol and water. Then, the pressure is reduced to 2.0 kPa to collect 1,3-butanediol with a purity of ≥99.7%.

[0140] Then, extraction was performed, and 100 g of 1,3-butanediol, 100 g of water and 60 g of methyl isobutyl ketone obtained by distillation separation were added to a separatory funnel, shaken for 2-3 minutes, and then allowed to stand for 5 minutes to separate the aqueous layer from the organic layer. 6 g of methyl isobutyl ketone was further added to the separated aqueous layer (about 180 g), shaken for 2-3 minutes, and then allowed to stand for 5 minutes to separate the aqueous layer from the organic layer; the same operation was repeated twice for the aqueous layer.

[0141] The aqueous layer after extraction was added to a three-necked flask, and dehydrated and concentrated in an oil bath at 150° C. and 8 kPa for 30 minutes to obtain a 1,3-butanediol product.

[0142] Example 2

[0143] Refer to Example 1, the same points will not be repeated here, and the differences are described below:

[0144] When preparing the hydrogenation raw material liquid, the amount of sodium hydroxide added was adjusted, and 50 g of a sodium hydroxide aqueous solution with a mass concentration of 0.5 wt % was added dropwise for 4 h; the hydrogenation raw material liquid finally obtained mainly contained 91.4 wt % of 3-hydroxybutyraldehyde, had a water content of 5.2 wt % and an acid value of 58 ppm;

[0145] The hydrogenation reaction was carried out with reference to Example 1, except that the hydrogenation temperature was 120°C and the reaction pressure was 12 MPa;

[0146] The refining process is the same as in Example 1.

[0147] Example 3

[0148] Preparation of hydrogenation feed liquid: Take 325g of 3-hydroxybutyraldehyde dimethyl acetal, add 75g of 5wt% hydrochloric acid solution and 200g of water, react at 20-30℃ for 5h, and remove methanol by short-path evaporation. The obtained hydrogenation feed liquid mainly contains 65.3wt% of 3-hydroxybutyraldehyde, 30wt% of water, and the acid value is 102ppm;

[0149] The obtained hydrogenation raw liquid is then subjected to hydrogenation reaction and refining; wherein the hydrogenation reaction is carried out with reference to Example 1, except that the hydrogenation temperature is 140° C.; the refining process is the same as that of Example 1.

[0150] Example 4

[0151] Refer to Example 1, the same points will not be repeated here, and the differences are described below:

[0152] When preparing the hydrogenation raw liquid, 50 g of a 0.5 wt % sodium hydroxide aqueous solution was added dropwise to 800 g of a 60 wt % acetaldehyde aqueous solution for 4 h; the resulting hydrogenation raw liquid mainly contained 58 wt % of 3-hydroxybutyraldehyde, had a water content of 40.6 wt % and an acid value of 196 ppm.

[0153] The hydrogenation reaction was carried out with reference to Example 1, except that the hydrogenation temperature was 110°C;

[0154] The refining process is the same as in Example 1.

[0155] Comparative Example 1

[0156] Preparation of hydrogenation raw liquid: 100 g of sodium hydroxide aqueous solution with a mass concentration of 0.5 wt% is added dropwise to 500 g of acetaldehyde for 4 hours, the condensation reaction temperature is controlled at 10-15° C. by a cold bath, the reaction is continued for 3 hours after the addition is completed, acetic acid is added to the system to adjust the acid value of the material to 32 ppm, unreacted acetaldehyde is recovered by short-path evaporation, and a hydrogenation raw liquid (i.e., a condensation liquid containing 3-hydroxybutyraldehyde) is obtained; the obtained hydrogenation raw liquid mainly contains 84.3 wt% of 3-hydroxybutyraldehyde, the water content is 12.5 wt% and the acid value is 2 ppm.

[0157] The hydrogenation reaction and refining process are the same as those in Example 2.

[0158] Comparative Example 2

[0159] Refer to Example 4, the same points will not be repeated here, and the differences are described below:

[0160] When preparing the hydrogenation raw material liquid, 50 g of a 0.5 wt % sodium hydroxide aqueous solution was added dropwise to 600 g of a 60 wt % acetaldehyde aqueous solution; the hydrogenation raw material liquid finally obtained mainly contained 62 wt % of 3-hydroxybutyraldehyde, had a water content of 36 wt % and an acid value of 245 ppm;

[0161] The hydrogenation reaction was carried out with reference to Example 1, except that the hydrogenation temperature was 110°C;

[0162] The refining process is the same as in Example 1.

[0163] Table 1. Specific peak area ratio, odor evaluation and crotonaldehyde content after storage of 1,3-butanediol products

[0164]

[0165] Table 2 Skin irritation test results

[0166] Rating Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 0 29 29 30 30 12 14 1 1 1 0 0 8 10 2 1 0 0 0 9 6 3 0 0 0 0 1 0 4 0 0 0 0 0 0

[0167] It can be seen that the 1,3-butanediol product of the present invention can significantly reduce the product odor, and the crotonaldehyde content does not increase significantly during long-term storage, but is maintained at a low level; the aqueous solution prepared from the 1,3-butanediol product of the present invention has significantly lower or even no skin irritation.

[0168] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A 1,3-butanediol product, characterized in that: In the gas chromatography analysis of the 1,3-butanediol product, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32-1.38 is greater than 0 and less than or equal to 750 ppm; The analysis conditions of the gas chromatography are as follows: Gas chromatograph: Agilent 7890 gas chromatograph; Detector: flame ionization detector (FID); Chromatographic column: HP-VOC chromatographic column, column length 60m×inner diameter 0.32mm×film thickness 1.8μm; Carrier gas: nitrogen, flow rate 1.5 ml / min; Column temperature: initial temperature 50℃, maintained for 2 min, then increased to 80℃ at 5℃ / min, then increased to 270℃ at 15℃ / min and maintained for 10 min; Vaporization chamber temperature: 260℃; Detector temperature: 280°C.

2. The 1,3-butanediol product according to claim 1, characterized in that When the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32 to 1.38 is 5 to 700 ppm.

3. The 1,3-butanediol product according to claim 2, characterized in that When the relative retention time corresponding to the peak position of 1,3-butanediol is set as 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32 to 1.38 is 10 to 700 ppm.

4. The 1,3-butanediol product according to any one of claims 1 to 3, characterized in that After the pH of a 50 wt % aqueous solution of the 1,3-butanediol product is adjusted to 6, the crotonaldehyde mass content is not more than 10 ppm after being placed at 50° C. for 90 days.

5. A moisturizer comprising the 1,3-butanediol product according to any one of claims 1 to 4. A cosmetic comprising the moisturizing agent according to claim 5 .

7. A method for improving the odor and / or skin irritation of a composition to which a 1,3-butanediol product is added, characterized in that: The added 1,3-butanediol product must meet the following requirements to improve the odor and / or skin irritation of the composition: In the gas chromatography analysis of the 1,3-butanediol product, when the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32-1.38 is greater than 0 and less than or equal to 750 ppm; The analysis conditions of the gas chromatography are as follows: Gas chromatograph: Agilent 7890 gas chromatograph; Detector: flame ionization detector (FID); Chromatographic column: HP-VOC chromatographic column, column length 60m×inner diameter 0.32mm×film thickness 1.8μm; Carrier gas: nitrogen, flow rate 1.5 ml / min; Column temperature: initial temperature 50℃, maintained for 2 min, then increased to 80℃ at 5℃ / min, then increased to 270℃ at 15℃ / min and maintained for 10 min; Vaporization chamber temperature: 260℃; Detector temperature: 280°C.

8. The method according to claim 7, characterized in that When the relative retention time corresponding to the peak position of 1,3-butanediol is set to 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32 to 1.38 is 5 to 700 ppm.

9. The method according to claim 8, characterized in that When the relative retention time corresponding to the peak position of 1,3-butanediol is set as 1.0, the sum of the area ratios of the peaks appearing in the relative retention time range of 1.32 to 1.38 is 10 to 700 ppm.

10. The method for preparing the 1,3-butanediol product according to any one of claims 1 to 9, comprising the following steps: S1, using a feed liquid containing 3-hydroxybutyraldehyde as a hydrogenation raw material liquid, and performing a hydrogenation reaction to obtain a reaction liquid containing 1,3-butanediol; S2, separating and refining the reaction solution containing 1,3-butanediol to obtain a 1,3-butanediol product; in, In step S1, before the hydrogenation reaction, the acid value of the hydrogenation raw material liquid is controlled to be 5-200 ppm; Preferably, in the 3-hydroxybutyraldehyde-containing liquid, the content of 3-hydroxybutyraldehyde is greater than 20wt%; Preferably, the water content in the 3-hydroxybutyraldehyde-containing liquid is 1-42 wt %.

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