CN115477580A - A kind of environment-friendly synthetic method and application of 3-hydroxyl-2-naphthoic acid methyl ester - Google Patents
A kind of environment-friendly synthetic method and application of 3-hydroxyl-2-naphthoic acid methyl ester Download PDFInfo
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- CN115477580A CN115477580A CN202111505329.XA CN202111505329A CN115477580A CN 115477580 A CN115477580 A CN 115477580A CN 202111505329 A CN202111505329 A CN 202111505329A CN 115477580 A CN115477580 A CN 115477580A
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- YVVBECLPRBAATK-UHFFFAOYSA-N methyl 3-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC=C2C=C(O)C(C(=O)OC)=CC2=C1 YVVBECLPRBAATK-UHFFFAOYSA-N 0.000 title claims description 38
- 238000010189 synthetic method Methods 0.000 title abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 22
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 22
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001308 synthesis method Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract 4
- 238000007599 discharging Methods 0.000 claims abstract 2
- 238000001914 filtration Methods 0.000 claims abstract 2
- 239000011148 porous material Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000002440 industrial waste Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 238000003756 stirring Methods 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000012452 mother liquor Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RTBQQRFTCVDODF-UHFFFAOYSA-N 3-methoxynaphthalene-2-carboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(OC)=CC2=C1 RTBQQRFTCVDODF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ester compound Chemical class 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域technical field
本发明涉及C07C67/08的IPC技术领域，具体涉及到一种3-羟基-2-萘甲酸甲酯的环保型合成方法及其应用。The invention relates to the IPC technical field of C07C67/08, in particular to an environment-friendly synthesis method of methyl 3-hydroxy-2-naphthoate and its application.
背景技术Background technique
3-羟基-2-萘甲酸甲酯是新型橡胶功能助剂3-羟基-2-萘甲酰腙(BMH)的关键中间体，可以用来制备BMH，用于改善轮胎的生热性以及促使白炭黑分散性。3-羟基-2-萘甲酸甲酯是一种酯类化合物，可以通过传统的酯化反应制备得到，例如采用3-羟基-2-萘甲酸与甲醇的酯化反应。例如，中国专利CN106608821A中公开了一种3-羟基-2-萘甲酸甲酯生产工艺，其中采用3-甲氧基-2-萘甲酸与过量的甲醇在浓硫酸的催化下反应得到所述3-羟基-2-萘甲酸甲酯。然而这些传统的工艺中酯化反应往往需要进行24小时以上，而且反应不完全，大量未反应的3-羟基-2-萘甲酸需用碱水处理，原料损失大且有大量废水、废盐产生。实际生产中，为了提高反应程度，往往使用大量硫酸催化，生产一吨产品需0.51吨硫酸，同时还要采用大量液碱中和，产生大量废水及工业废盐。因此，传统的上述工艺一方面生产效率较低，而且生产不环保，需要进一步改进。3-Hydroxy-2-naphthoic acid methyl ester is the key intermediate of the new rubber functional additive 3-hydroxy-2-naphthoylhydrazone (BMH), which can be used to prepare BMH for improving the heat generation of tires and promoting Silica dispersibility. 3-Hydroxy-2-naphthoic acid methyl ester is a kind of ester compound, which can be prepared by traditional esterification reaction, such as the esterification reaction of 3-hydroxy-2-naphthoic acid and methanol. For example, Chinese patent CN106608821A discloses a 3-hydroxy-2-naphthoic acid methyl ester production process, wherein 3-methoxy-2-naphthoic acid is reacted with excess methanol under the catalysis of concentrated sulfuric acid to obtain the 3 -Hydroxy-2-naphthoic acid methyl ester. However, in these traditional processes, the esterification reaction often needs to be carried out for more than 24 hours, and the reaction is not complete. A large amount of unreacted 3-hydroxy-2-naphthoic acid needs to be treated with alkaline water, and the loss of raw materials is large and a large amount of waste water and waste salt are generated. . In actual production, in order to increase the degree of reaction, a large amount of sulfuric acid is often used for catalysis, and 0.51 tons of sulfuric acid is required to produce one ton of product. At the same time, a large amount of liquid caustic soda is used for neutralization, resulting in a large amount of waste water and industrial waste salt. Therefore, on the one hand, the traditional above-mentioned process has low production efficiency, and the production is not environmentally friendly, and needs further improvement.
发明内容Contents of the invention
针对上述技术问题，本发明的第一方面提供了一种3-羟基-2-萘甲酸甲酯的环保型合成方法，其包括如下步骤：将3-羟基-2-萘甲酸与甲醇加入到反应釜中，加入催化剂后升温进行反应，反应时间为8～12小时，然后冷却滤除催化剂，反应体系恢复至室温后冷却出料即得；其中反应温度不低于100℃。For the problems of the technologies described above, the first aspect of the present invention provides an environment-friendly synthetic method of 3-hydroxyl-2-naphthoic acid methyl ester, which comprises the steps of: adding 3-hydroxyl-2-naphthoic acid and methyl alcohol to the reaction In the kettle, after adding the catalyst, the temperature is raised to react, the reaction time is 8-12 hours, then the catalyst is cooled and filtered, the reaction system returns to room temperature, and then the material is cooled and discharged; wherein the reaction temperature is not lower than 100°C.
本发明的3-羟基-2-萘甲酸甲酯是反应单体3-羟基-2-萘甲酸(CAS：92-70-6)与甲醇在催化剂作用下，高温条件下脱水缩合反应制备得到。其中1摩尔的3-羟基-2-萘甲酸与1摩尔的甲醇反应，使3-羟基-2-萘甲酸结构中的羧基与甲醇结构中的羟基之前缩合，脱去一摩尔的水，制备得到所述3-羟基-2-萘甲酸甲酯。其中，为了使3-羟基-2-萘甲酸单体充分反应，其中的甲醇用量过量。The 3-hydroxy-2-naphthoic acid methyl ester of the present invention is prepared by the dehydration condensation reaction of the reaction monomer 3-hydroxy-2-naphthoic acid (CAS: 92-70-6) and methanol under the action of a catalyst under high temperature conditions. Wherein 1 mole of 3-hydroxy-2-naphthoic acid reacts with 1 mole of methanol to condense the carboxyl group in the 3-hydroxy-2-naphthoic acid structure with the hydroxyl group in the methanol structure, and remove one mole of water to prepare The 3-hydroxyl-2-naphthoic acid methyl ester. Wherein, in order to make the 3-hydroxyl-2-naphthoic acid monomer react fully, the amount of methyl alcohol used therein is excessive.
在一些实施方式中，所述3-羟基-2-萘甲酸单体与甲醇的质量比例可以为100：(250～400)，可示例的，其质量比例可以为100:250、100:260、100:270、100:280、100:290、100:295、100:300、100:302、100:305、100:310、100:320、100:330、100:340、100:350、100:360、100:370、100:380、100:390、100:400等。In some embodiments, the mass ratio of the 3-hydroxy-2-naphthoic acid monomer to methanol can be 100:(250-400), for example, the mass ratio can be 100:250, 100:260, 100:270, 100:280, 100:290, 100:295, 100:300, 100:302, 100:305, 100:310, 100:320, 100:330, 100:340, 100:350, 100: 360, 100:370, 100:380, 100:390, 100:400, etc.
本申请中的3-羟基-2-萘甲酸与甲醇是在高温条件下进行酯化反应，其反应温度不低于100℃。作为本发明一种优选的技术方案，所述反应温度为100～120℃。由于3-羟基-2-萘甲酸与甲醇之间的脱水缩合反应的吸热反应，因此加热在一定程度上有助于提高反应程度的提高。The esterification reaction between 3-hydroxy-2-naphthoic acid and methanol in this application is carried out under high temperature conditions, and the reaction temperature is not lower than 100°C. As a preferred technical solution of the present invention, the reaction temperature is 100-120°C. Due to the endothermic reaction of the dehydration condensation reaction between 3-hydroxy-2-naphthoic acid and methanol, heating helps to some extent to increase the degree of reaction.
然而，由于3-羟基-2-萘甲酸在常温下是浅黄色晶体，甲醇的液体，因此如果反应温度过高，高于甲醇的沸点时，甲醇会气化，影响反应程度，而且由于甲醇气化使反应压力升高，可能出现安全性事故。本发明的酯化反应是在高压反应釜中进行，将3-羟基-2-萘甲酸与甲醇混合溶解，然后升温至100～120℃下反应，可以在一定程度上加快反应程度，缩短反应时间，使之在12小时以内即可实现更高的收率，反应12小时后的收率可以达到95％。Yet, because 3-hydroxyl-2-naphthoic acid is pale yellow crystal at normal temperature, the liquid of methanol, so if the reaction temperature is too high, when higher than the boiling point of methanol, methanol will gasify, affecting the degree of reaction, and due to methanol gas The reaction pressure will be increased, which may lead to safety accidents. The esterification reaction of the present invention is carried out in a high-pressure reactor, 3-hydroxy-2-naphthoic acid and methanol are mixed and dissolved, and then the temperature is raised to 100-120°C for reaction, which can accelerate the reaction degree to a certain extent and shorten the reaction time , so that a higher yield can be realized within 12 hours, and the yield after 12 hours of reaction can reach 95%.
本发明中，3-羟基-2-萘甲酸与甲醇的酯化反应是在高压条件下进行的，为了不保证反应单体的充分转化，申请人发现在提升反应的温度的同时，进一步提高反应釜的压力，使之不低于0.3MPa，更有利于在短的反应时间内提升收率。作为本发明一种优选的技术方案，所述反应过程中反应压力不低于0.3MPa。进一步优选的，所述反应过程中反应压力为0.3～0.5MPa。In the present invention, the esterification reaction of 3-hydroxy-2-naphthoic acid and methanol is carried out under high pressure conditions. In order not to ensure the full conversion of the reaction monomer, the applicant finds that while raising the reaction temperature, the reaction temperature can be further improved. The pressure of the kettle is not lower than 0.3MPa, which is more conducive to improving the yield in a short reaction time. As a preferred technical solution of the present invention, the reaction pressure during the reaction is not lower than 0.3 MPa. Further preferably, the reaction pressure during the reaction is 0.3-0.5 MPa.
3-羟基-2-萘甲酸与甲醇在高温高压条件下完成酯化反应后，冷却反应体系的温度至60℃左右，过滤离子交换树脂，进行洗涤干燥等处理后可以重复使用。此外，通过常压蒸馏等方式将体系中多余的甲醇蒸馏出来，可以进一步重复使用。将过滤得到的母液冷却至室温，烘干即可得到3-羟基-2-萘甲酸甲酯产品。After completing the esterification reaction between 3-hydroxy-2-naphthoic acid and methanol under high temperature and high pressure conditions, cool the temperature of the reaction system to about 60°C, filter the ion exchange resin, wash and dry it, and then reuse it. In addition, excess methanol in the system is distilled out by means of atmospheric distillation and the like, which can be further reused. Cool the filtered mother liquor to room temperature and dry to obtain the 3-hydroxy-2-naphthoic acid methyl ester product.
本发明中，3-羟基-2-萘甲酸与甲醇的酯化反应是在适量催化剂下反应的，作为本发明一种优选的技术方案，所述催化剂为浓硫酸和/或离子交换树脂。本发明中所述催化剂的用量不能太高，尤其是在浓硫酸作为催化剂时，其用量过高则造成大量的工业废盐。而若其用量过少则影响其反应速度。In the present invention, the esterification reaction of 3-hydroxy-2-naphthoic acid and methanol is reacted under an appropriate amount of catalyst. As a preferred technical scheme of the present invention, the catalyst is concentrated sulfuric acid and/or ion exchange resin. The consumption of catalyst described in the present invention can't be too high, especially when concentrated sulfuric acid is used as catalyst, its consumption too high will cause a large amount of industrial waste salts. And if its dosage is too little, it will affect its reaction speed.
本发明中，所述催化剂的用量为所述3-羟基-2-萘甲酸质量的3.5～7wt％，可示例的，其用量可以为3.5wt％、3.8wt％、4.0wt％、4.2wt％、4.5wt％、4.8wt％、5.0wt％、5.2wt％、5.4wt％、5.5wt％、5.7wt％、5.9wt％、6.0wt％、6.2wt％、6.5wt％、6.8wt％、7.0wt％等。本发明中档所述催化剂为浓硫酸时，其是指浓度为98％的浓硫酸。In the present invention, the dosage of the catalyst is 3.5-7wt% of the mass of the 3-hydroxyl-2-naphthoic acid, for example, the dosage can be 3.5wt%, 3.8wt%, 4.0wt%, 4.2wt% , 4.5wt%, 4.8wt%, 5.0wt%, 5.2wt%, 5.4wt%, 5.5wt%, 5.7wt%, 5.9wt%, 6.0wt%, 6.2wt%, 6.5wt%, 6.8wt%, 7.0 wt% etc. When the catalyst described in the mid-range of the present invention is concentrated sulfuric acid, it refers to concentrated sulfuric acid with a concentration of 98%.
本发明中优选采用离子交换树脂作为反应催化剂。作为本发明一种优选的技术方案，所述离子交换树脂的平均孔径为
作为本发明一种优选的技术方案，所述离子交换树脂的比表面积不低于40m2/g。进一步优选的，所述离子交换树脂的比表面积为50～60m2/g；可示例的，其比表面积可以为50m2/g、50.5m2/g、51m2/g、51.5m2/g、52m2/g、52.5m2/g、53m2/g、53.5m2/g、54m2/g、54.5m2/g、55m2/g、55.5m2/g、56m2/g、56.5m2/g、57m2/g、57.5m2/g、58m2/g、58.5m2/g、59m2/g、59.5m2/g、60m2/g等。本发明中所述的比表面积是用以表征微粒尺寸大小的物理量，可以根据常规的方式进行测试得到即可。As a preferred technical solution of the present invention, the specific surface area of the ion exchange resin is not less than 40m 2 /g. Further preferably, the specific surface area of the ion exchange resin is 50-60m 2 /g; for example, the specific surface area may be 50m 2 /g, 50.5m 2 / g , 51m 2 /g, 51.5m 2 /g , 52m 2 /g, 52.5m 2 /g, 53m 2 /g, 53.5m 2 /g, 54m 2 /g, 54.5m 2 /g, 55m 2 /g, 55.5m 2 /g, 56m 2 /g, 56.5m 2 /g, 57m 2 /g, 57.5m 2 /g, 58m 2 /g, 58.5m 2 /g, 59m 2 /g, 59.5m 2 / g, 60m 2 /g, etc. The specific surface area described in the present invention is a physical quantity used to characterize the particle size, which can be obtained by testing in a conventional manner.
作为本发明一种优选的技术方案，所述离子交换树脂的孔体积为0.2～0.5ml/g。可示例的，其孔体积可以为0.2ml/g、0.25ml/g、0.28ml/g、0.3ml/g、0.32ml/g、0.35ml/g、0.38ml/g、0.4ml/g、0.42ml/g、0.45ml/g、0.48ml/g、0.5ml/g等。As a preferred technical solution of the present invention, the pore volume of the ion exchange resin is 0.2-0.5 ml/g. Exemplary, its pore volume can be 0.2ml/g, 0.25ml/g, 0.28ml/g, 0.3ml/g, 0.32ml/g, 0.35ml/g, 0.38ml/g, 0.4ml/g, 0.42 ml/g, 0.45ml/g, 0.48ml/g, 0.5ml/g, etc.
本发明中对满足上述要求的离子交换树脂的具体来源并不做特殊限定，可以选用本领域技术人员所熟知的而各类相关离子交换树脂产品，包括但不限于罗门哈斯A15树脂(15WET催化树脂)等。In the present invention, the specific source of the ion-exchange resin that meets the above requirements is not particularly limited, and various related ion-exchange resin products well known to those skilled in the art can be selected, including but not limited to Rohm and Haas A15 resin (15WET catalytic resin), etc.
申请人在完成本发明的过程中发现，在本申请的3-羟基-2-萘甲酸与甲醇的酯化反应中，在保证0.3～0.5MPa的反应压力下，提升反应温度至100～120℃范围内，有利于提高反应的收率。尤其是当采用适量的上述特定孔径、特定比表面积和特定孔体积的离子交换树脂作为催化剂使用时，能够在只反应12小时左右的时间，就能实现95％的收率，而且能够保证产物中3-羟基-2-萘甲酸甲酯的含量(级纯度)高于98％。申请人推测在100～120℃条件下，甲醇能够气化并充分的附着在上述特定的离子交换树脂多孔结构中，并且利用其孔径、比表面积等特性，使体系中的3-羟基-2-萘甲酸能够与甲醇更充分的接触，从而有助于提高反应程度，缩短反应时间。然而并非比表面积越大，孔径越小，其反应程度就越高，申请人发现若其孔径过小，比表面积过大，反应的程度和收率反而下降。可能是由于其孔径过小，阻碍体系中的3-羟基-2-萘甲酸与甲醇的接触。During the process of completing the present invention, the applicant found that in the esterification reaction of 3-hydroxy-2-naphthoic acid and methanol of the present application, under the reaction pressure of 0.3-0.5 MPa, the reaction temperature should be raised to 100-120°C In the range, it is beneficial to improve the yield of the reaction. Especially when using an appropriate amount of the ion exchange resin with the above-mentioned specific pore diameter, specific specific surface area and specific pore volume as a catalyst, the yield of 95% can be realized in only about 12 hours of reaction time, and the product can be guaranteed The content (grade purity) of methyl 3-hydroxy-2-naphthoate was higher than 98%. The applicant speculates that under the condition of 100-120°C, methanol can be vaporized and fully attached to the above-mentioned specific ion-exchange resin porous structure, and utilize its pore size, specific surface area and other characteristics to make the 3-hydroxyl-2- Naphthoic acid can be more fully contacted with methanol, thereby helping to improve the degree of reaction and shorten the reaction time. However, the larger the specific surface area and the smaller the pore size, the higher the degree of reaction. The applicant found that if the pore size is too small and the specific surface area is too large, the degree of reaction and the yield will decrease instead. It may be because the pore size is too small, hindering the contact of 3-hydroxy-2-naphthoic acid and methanol in the system.
本发明的第二个方面提供了如上所述的环保型合成方法制备得到的3-羟基-2-萘甲酸甲酯在橡胶领域中的应用。The second aspect of the present invention provides the application of methyl 3-hydroxy-2-naphthoate prepared by the above-mentioned environment-friendly synthesis method in the field of rubber.
本发明提供的技术方案具有如下有益效果： The technical scheme provided by the invention has the following beneficial effects :
本发明提供的合成3-羟基-2-萘甲酸甲酯的方法中不采用大量的浓硫酸作为催化剂，浓硫酸的用量至多为3-羟基-2-萘甲酸质量的5％，不产生大量的酸性工业废盐，生产方式环保、安全。此外本发明中通过采用特定结构的离子交换树脂作为催化剂，并与之搭配使用缩短其反应时间，使之在12小时左右的反应时间内，实现95％左右的收率，而且保证其产物中的3-羟基-2-萘甲酸甲酯含量不低于98％，适合工业化生产。In the method for the synthesis of 3-hydroxyl-2-naphthoic acid methyl ester provided by the invention, do not adopt a large amount of vitriol oil as catalyzer, the consumption of vitriol oil is at most 5% of 3-hydroxyl-2-naphthoic acid quality, does not produce a large amount of Acidic industrial waste salt, the production method is environmentally friendly and safe. In addition, in the present invention, the ion-exchange resin with specific structure is used as the catalyst, and its reaction time is shortened by using it in conjunction with it, so that it can achieve a yield of about 95% within a reaction time of about 12 hours, and ensure that the The content of methyl 3-hydroxy-2-naphthoate is not less than 98%, which is suitable for industrial production.
具体实施方式detailed description
实施例1Example 1
本实施例公开了一种3-羟基-2-萘甲酸甲酯的环保型合成方法，其包括如下步骤：在500ml高压釜中加入100克3-羟基-2-萘甲酸、300克甲醇和5克A15树脂(罗门哈斯15WET催化树脂)，搅拌混合25min后，升高体系的温度至110℃，调节反应釜压力至0.4MPa，并在此条件下搅拌反应12小时；然后冷却至60℃，过滤滤出A15树脂(下一批反应中重复使用)；将体系中的滤液在常压下蒸馏，蒸馏出甲醇克左右的150(下一批反应中重复使用)；然后将过滤后的母液冷至室温过滤，烘干，洗涤干燥得淡黄色固体3-羟基-2-萘甲酸甲酯102克(收率95％)，产物中3-羟基-2-萘甲酸甲酯含量98.2％。The present embodiment discloses an environment-friendly synthetic method of 3-hydroxyl-2-naphthoic acid methyl ester, which comprises the steps of: adding 100 grams of 3-hydroxyl-2-naphthoic acid, 300 grams of methanol and 5 Gram A15 resin (Rohm and Haas 15WET catalytic resin), after stirring and mixing for 25min, raise the temperature of the system to 110°C, adjust the pressure of the reactor to 0.4MPa, and stir and react under this condition for 12 hours; then cool to 60°C , filter out the A15 resin (reuse in the next batch of reactions); distill the filtrate in the system under normal pressure, distill out 150 grams of methanol (reuse in the next batch of reactions); then filter the mother liquor Cool to room temperature, filter, dry, wash and dry to obtain 102 grams of light yellow solid methyl 3-hydroxy-2-naphthoate (yield 95%), and the content of methyl 3-hydroxy-2-naphthoate in the product is 98.2%.
实施例2Example 2
本实施例公开了一种3-羟基-2-萘甲酸甲酯的环保型合成方法，其包括如下步骤：在500ml高压釜中加入100克3-羟基-2-萘甲酸、300克甲醇和5克98％硫酸，搅拌混合25min后，升高体系的温度至110℃，调节反应釜压力至0.4MPa，并在此条件下搅拌反应12小时；将反应体系中的物料中常压蒸馏出150克甲醇(下一批反应中重复使用)，然后将过滤后的母液冷至室温过滤，烘干得淡黄色固体3-羟基-2-萘甲酸甲酯100克(收率93％)，产物中3-羟基-2-萘甲酸甲酯含量97.2％。The present embodiment discloses an environment-friendly synthetic method of 3-hydroxyl-2-naphthoic acid methyl ester, which comprises the steps of: adding 100 grams of 3-hydroxyl-2-naphthoic acid, 300 grams of methanol and 5 gram of 98% sulfuric acid, after stirring and mixing for 25min, raise the temperature of the system to 110°C, adjust the pressure of the reactor to 0.4MPa, and stir and react under this condition for 12 hours; Methanol (reuse in the next batch of reactions), then the filtered mother liquor is cooled to room temperature and filtered, and dried to obtain 100 grams (yield 93%) of light yellow solid 3-hydroxyl-2-naphthoic acid methyl ester, 3 in the product -Hydroxy-2-naphthoic acid methyl ester content 97.2%.
实施例3Example 3
本实施例公开了一种3-羟基-2-萘甲酸甲酯的环保型合成方法，其包括如下步骤：在500ml高压釜中加入100克3-羟基-2-萘甲酸、300克甲醇和5克离子交换树脂(
实施例4Example 4
本实施例公开了一种3-羟基-2-萘甲酸甲酯的环保型合成方法，其包括如下步骤：在500ml高压釜中加入100克3-羟基-2-萘甲酸、300克甲醇和5克A15树脂(罗门哈斯15WET催化树脂)，搅拌混合25min后，升高体系的温度至135℃，调节反应釜压力至0.4MPa，并在此条件下搅拌反应12小时；然后冷却至60℃，过滤滤出A15树脂(下一批反应中重复使用)；将体系中的滤液在常压下蒸馏，蒸馏出甲醇克左右的150(下一批反应中重复使用)；然后将过滤后的母液冷至室温过滤，烘干，洗涤干燥得淡黄色固体3-羟基-2-萘甲酸甲酯102克(收率93％)，产物中3-羟基-2-萘甲酸甲酯含量98.3％。The present embodiment discloses an environment-friendly synthetic method of 3-hydroxyl-2-naphthoic acid methyl ester, which comprises the steps of: adding 100 grams of 3-hydroxyl-2-naphthoic acid, 300 grams of methanol and 5 Gram A15 resin (Rohm and Haas 15WET catalytic resin), after stirring and mixing for 25min, raise the temperature of the system to 135°C, adjust the pressure of the reactor to 0.4MPa, and stir and react under this condition for 12 hours; then cool to 60°C , filter out the A15 resin (reuse in the next batch of reactions); distill the filtrate in the system under normal pressure, distill out 150 grams of methanol (reuse in the next batch of reactions); then filter the mother liquor Cool to room temperature, filter, dry, wash and dry to obtain 102 g of light yellow solid methyl 3-hydroxy-2-naphthoate (yield 93%), and the content of methyl 3-hydroxy-2-naphthoate in the product is 98.3%.
实施例5Example 5
本实施例公开了一种3-羟基-2-萘甲酸甲酯的环保型合成方法，其包括如下步骤：在500ml高压釜中加入100克3-羟基-2-萘甲酸、300克甲醇和5克A15树脂(罗门哈斯15WET催化树脂)，搅拌混合25min后，升高体系的温度至75℃，调节反应釜压力至0.4MPa，并在此条件下搅拌反应12小时；然后冷却至60℃，过滤滤出A15树脂(下一批反应中重复使用)；将体系中的滤液在常压下蒸馏，蒸馏出甲醇克左右的150(下一批反应中重复使用)；然后将过滤后的母液冷至室温过滤，烘干，洗涤干燥得淡黄色固体3-羟基-2-萘甲酸甲酯102克(收率88％)，产物中3-羟基-2-萘甲酸甲酯含量93.4％。The present embodiment discloses an environment-friendly synthetic method of 3-hydroxyl-2-naphthoic acid methyl ester, which comprises the steps of: adding 100 grams of 3-hydroxyl-2-naphthoic acid, 300 grams of methanol and 5 Gram A15 resin (Rohm and Haas 15WET catalytic resin), after stirring and mixing for 25min, raise the temperature of the system to 75°C, adjust the pressure of the reactor to 0.4MPa, and stir and react under this condition for 12 hours; then cool to 60°C , filter out the A15 resin (reuse in the next batch of reactions); distill the filtrate in the system under normal pressure, distill out 150 grams of methanol (reuse in the next batch of reactions); then filter the mother liquor Cool to room temperature, filter, dry, wash and dry to obtain 102 grams of light yellow solid methyl 3-hydroxy-2-naphthoate (yield 88%), and the content of methyl 3-hydroxy-2-naphthoate in the product is 93.4%.
从上述实验结果中够可以看出，本发明的3-羟基-2-萘甲酸甲酯的合成方法中生产工艺环保，不采用大量的浓硫酸，从而不产生大量的酸性工业废盐。而且，通过对其中的催化剂、反应温度、反应压力等条件的优化改性，在保证高的收率和纯度的同时，显著缩短了反应时间，大大提升了生产效率。Enough can be seen from above-mentioned experimental result, in the synthetic method of 3-hydroxyl-2-naphthoic acid methyl ester of the present invention, production technology environmental protection, do not adopt a large amount of vitriol oil, thereby do not produce a large amount of acidic industrial waste salts. Moreover, by optimizing and modifying the catalyst, reaction temperature, reaction pressure and other conditions, while ensuring high yield and purity, the reaction time is significantly shortened and the production efficiency is greatly improved.
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