CN109970552B - 一种苯甲酸甲酯和苯甲酸乙酯的联产方法 - Google Patents
一种苯甲酸甲酯和苯甲酸乙酯的联产方法 Download PDFInfo
- Publication number
- CN109970552B CN109970552B CN201910242140.2A CN201910242140A CN109970552B CN 109970552 B CN109970552 B CN 109970552B CN 201910242140 A CN201910242140 A CN 201910242140A CN 109970552 B CN109970552 B CN 109970552B
- Authority
- CN
- China
- Prior art keywords
- benzoate
- methyl
- ethyl
- ethylene
- furoate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 title claims abstract description 44
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229940095102 methyl benzoate Drugs 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- HDJLSECJEQSPKW-UHFFFAOYSA-N Methyl 2-Furancarboxylate Chemical compound COC(=O)C1=CC=CO1 HDJLSECJEQSPKW-UHFFFAOYSA-N 0.000 claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006709 oxidative esterification reaction Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 abstract 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 3
- -1 benzonitrile compound Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzenecarbonitrile Natural products N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种苯甲酸甲酯和苯甲酸乙酯的联产方法，本发明采用一锅法将糠酸甲酯和乙烯经加成‑酯交换‑脱水反应联产苯甲酸甲酯和苯甲酸乙酯。反应原料均可由木质纤维素制得，其中，糠酸甲酯可由糠醛氧化酯化制备，乙烯可由生物乙醇脱水制备。本发明工艺过程绿色环保，具有较强的创新性和应用推广价值。
Description
技术领域
本发明属于能源化工技术领域，具体涉及一种苯甲酸甲酯和苯甲酸乙酯的联产方法。
背景技术
苯甲酸酯类化合物广泛存在于天然产物中，在工业上可用作有机合成中间体、增塑剂、香料和溶剂，并且在生物化工、农药和功能材料等方面也有重要的应用价值。其中，苯甲酸甲酯和苯甲酸乙酯最为常见。苯甲酸甲酯，又名安息香酸甲酯，具有浓郁的果香味，不仅可以用于配制香水香精和人造精油，还能用作纤维素醚、纤维素酯、合成树脂和橡胶的溶剂。苯甲酸乙酯的性质和应用领域与苯甲酸甲酯相似。
目前苯甲酸酯类化合物主要是以苯甲酸和醇直接进行酯化反应制得(CN106631786A，CN106674006A，CN107954874A)，此法所采用的原料苯甲酸主要通过氧化甲苯得到，而后者多由石油催化重整和烃类裂解制得。此外，利用苯甲酸盐和卤代烃制取苯甲酸酯，会副产大量盐，污染严重，后续处理复杂(CN108047036A)。以铜催化剂在氧气氛围中催化苄腈类化合物与醇或酚类制取苯甲酸酯类化合物，原料成本高且氧气氧化具有一定的危险性(CN104892408A)。因此，亟待建立一条易操作、无污染且不依赖化石资源的合成路径以制备苯甲酸酯类化合物。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种苯甲酸甲酯和苯甲酸乙酯的联产方法。
本发明的技术方案如下：
一种苯甲酸甲酯和苯甲酸乙酯的联产方法，其特征在于：其糠醛甲酯的转化率为19.9-95.0％，苯甲酸甲酯的选择性为6.5-40.0％，苯甲酸乙酯的选择性为0.9-43.0％，
包括：将糠酸甲酯、乙酸乙酯和硅铝比为5-300的分子筛催化剂加入到密闭高压反应釜中，用氮气充分置换密闭高压反应釜中的空气后，再充入乙烯，于150-250℃搅拌反应1-24h。
在本发明的一个优选实施方案中，所述分子筛催化剂包括H-β、H-Y、H-USY和H-ZSM-5。
在本发明的一个优选实施方案中，所述分子筛催化剂的硅铝比为6-150。
在本发明的一个优选实施方案中，充入乙烯至压力为1-4MPa。
在本发明的一个优选实施方案中，所述糠酸甲酯由糠醛氧化酯化制备。
在本发明的一个优选实施方案中，所述乙烯由生物乙醇脱水制备。
在本发明的一个优选实施方案中，所述糠酸甲酯、酯类有机溶剂和分子筛催化剂的比例为0.1-1mmol∶10-15mL∶0.1-0.2g。
本发明的有益效果是：本发明采用一锅法将糠酸甲酯和乙烯经加成-酯交换-脱水反应联产苯甲酸甲酯和苯甲酸乙酯。反应原料均可由木质纤维素制得，其中，糠酸甲酯可由糠醛氧化酯化制备，乙烯可由生物乙醇脱水制备。本发明工艺过程绿色环保，具有较强的创新性和应用推广价值。
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。
实施例1
将0.36mmol糠酸甲酯、10mL乙酸乙酯和0.1g H-β(Si/Al＝25)加入密闭高压反应釜中，用氮气置换空气3次后再充入2MPa乙烯，在190℃下加热搅拌反应6h。反应结束后，取少量液相产品进行检测。经过气相色谱分析，糠酸甲酯的转化率为94.8％，苯甲酸甲酯的选择性为6.7％，苯甲酸乙酯的选择性为31.8％。
实施例2
将0.36mmol糠酸甲酯、10mL乙酸乙酯和0.1g H-β(Si/Al＝25)加入密闭高压反应釜中，用氮气置换空气3次后再充入2MPa乙烯，在210℃下加热搅拌反应6h。反应结束后，取少量液相产品进行检测。经过气相色谱分析，糠酸甲酯的转化率为85.2％，苯甲酸甲酯的选择性为12.8％，苯甲酸乙酯的选择性为23.5％。
实施例3
将0.36mmol糠酸甲酯、10mL乙酸乙酯和0.1gH-β(Si/Al＝25)加入密闭高压反应釜中，用氮气置换空气3次后再充入2MPa乙烯，在210℃下加热搅拌反应12h。反应结束后，取少量液相产品进行检测。经过气相色谱分析，糠酸甲酯的转化率为94.4％，苯甲酸甲酯的选择性为11.8％，苯甲酸乙酯的选择性为42.9％。
实施例4
将1.0mmol糠酸甲酯、10mL乙酸乙酯和0.2g H-β(Si/Al＝25)加入密闭高压反应釜中，用氮气置换空气3次后再充入2MPa乙烯，在230℃下加热搅拌反应6h。反应结束后，取少量液相产品进行检测。经过气相色谱分析，糠酸甲酯的转化率为83.7％，苯甲酸甲酯的选择性为18.0％，苯甲酸乙酯的选择性为29.4％。
实施例5
将0.98mmol糠酸甲酯、10mL乙酸乙酯和0.15g H-β(Si/Al＝25)加入密闭高压反应釜中，用氮气置换空气3次后再充入2MPa乙烯，在250℃下加热搅拌反应10h。反应结束后，取少量液相产品进行检测。经过气相色谱分析，糠酸甲酯的转化率为84.5％，苯甲酸甲酯的选择性为9.2％，苯甲酸乙酯的选择性为19.3％。
实施例6
将0.60mmol糠酸甲酯、10mL乙酸乙酯和0.2g H-β(Si/Al＝146)加入密闭高压反应釜中，用氮气置换空气3次后再充入2MPa乙烯，在190℃下加热搅拌反应14h。反应结束后，取少量液相产品进行检测。经过气相色谱分析，糠酸甲酯的转化率为43.5％，苯甲酸甲酯的选择性为39.9％，苯甲酸乙酯的选择性为7.4％。
实施例7
将0.87mmol糠酸甲酯、10mL乙酸乙酯和0.15g H-USY(Si/Al＝6)加入密闭高压反应釜中，用氮气置换空气3次后再充入1.5MPa乙烯，在200℃下加热搅拌反应16h。反应结束后，取少量液相产品进行检测。经过气相色谱分析，糠酸甲酯的转化率为19.9％，苯甲酸甲酯的选择性为0.9％，苯甲酸乙酯的选择性为11.0％。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
Claims (3)
1.一种苯甲酸甲酯和苯甲酸乙酯的联产方法，其特征在于：其糠酸甲酯的转化率为83.7%%，苯甲酸甲酯的选择性为18.0%，苯甲酸乙酯的选择性为29.4%，
包括：将糠酸甲酯、乙酸乙酯和硅铝比为25的分子筛催化剂加入到密闭高压反应釜中，用氮气充分置换密闭高压反应釜中的空气后，再充入乙烯至压力为2MPa，于230℃搅拌反应6h；分子筛催化剂为H-β；糠酸甲酯、乙酸乙酯和分子筛催化剂的比例为1mmol: 10mL:0.2g。
2.如权利要求1所述的联产方法，其特征在于：所述糠酸甲酯由糠醛氧化酯化制备。
3.如权利要求1所述的联产方法，其特征在于：所述乙烯由生物乙醇脱水制备。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910242140.2A CN109970552B (zh) | 2019-03-28 | 2019-03-28 | 一种苯甲酸甲酯和苯甲酸乙酯的联产方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910242140.2A CN109970552B (zh) | 2019-03-28 | 2019-03-28 | 一种苯甲酸甲酯和苯甲酸乙酯的联产方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109970552A CN109970552A (zh) | 2019-07-05 |
| CN109970552B true CN109970552B (zh) | 2021-02-19 |
Family
ID=67081063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910242140.2A Active CN109970552B (zh) | 2019-03-28 | 2019-03-28 | 一种苯甲酸甲酯和苯甲酸乙酯的联产方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109970552B (zh) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7385081B1 (en) * | 2007-11-14 | 2008-06-10 | Bp Corporation North America Inc. | Terephthalic acid composition and process for the production thereof |
| US9321714B1 (en) * | 2014-12-05 | 2016-04-26 | Uop Llc | Processes and catalysts for conversion of 2,5-dimethylfuran derivatives to terephthalate |
-
2019
- 2019-03-28 CN CN201910242140.2A patent/CN109970552B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109970552A (zh) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chan-Thaw et al. | New generation biofuels: γ-valerolactone into valeric esters in one pot | |
| Sha et al. | Metal-free benzannulation of yne-allenone esters for atom economical synthesis of functionalized 1-naphthols | |
| CN102206142B (zh) | 一种3-甲氧基-3-甲基-1-丁醇的制备方法 | |
| CN108774130B (zh) | 一种合成气一步法制乙酸甲酯的方法 | |
| CN110227558A (zh) | 一种用于制备缩醛/酮的固体酸催化剂及其制备方法和应用 | |
| CN101580462B (zh) | 一种2，3-丁二醇高效脱水制甲乙酮的方法 | |
| CN108947943B (zh) | 一种固体磷钨酸直接催化5-甲基糠醇二聚的方法 | |
| KR101862042B1 (ko) | 폴리옥시메틸렌 디메틸 에테르 카보닐 화합물 및 메틸 메톡시아세테이트의 제조방법 | |
| CN109970552B (zh) | 一种苯甲酸甲酯和苯甲酸乙酯的联产方法 | |
| CN103203248B (zh) | 一种zsm-35分子筛羰基化催化剂的制备方法 | |
| CN103880661B (zh) | 一种催化乙醇直接脱氢制备乙酸乙酯的方法 | |
| CN114315532B (zh) | 一种2,2-二烷氧基乙醛合成1,1,4,4-四烷氧基-2-丁烯的方法 | |
| CN107540520B (zh) | 一种由频那醇制备均苯四甲酸或偏苯三甲酸的方法 | |
| CN113045375A (zh) | 一种由二戊基蒽烷基转移制备2-戊基蒽的方法 | |
| CN117304087B (zh) | 1,1,3,3-四甲丁基过氧化氢的制备方法 | |
| CN109867614B (zh) | 一种4,4-二烷硫-1-苯基-3-丁烯-1-酮衍生物及合成方法 | |
| CN110841716A (zh) | 用于脱氢芳樟醇重排反应制备柠檬醛的催化剂及其制备方法、制备柠檬醛的方法 | |
| CN112679296B (zh) | 一种叔丁醇直接转化生产丙烯的方法 | |
| CN109851487B (zh) | 一种负载型碳化钼催化柑青醛选择环化制备环柑青醛的方法 | |
| CN116217523B (zh) | 一种制备5，5’-二乙酰基-2，2’-联呋喃的方法 | |
| CN109651327B (zh) | 一种无催化剂条件下制备氧杂蒽酮的工艺方法 | |
| CN1781899A (zh) | 一种由乙醇制备乙酸乙酯的方法 | |
| CN116554131B (zh) | 一种由乙酰丙酸无溶剂加氢得到γ-戊内酯的制备方法 | |
| CN117417313B (zh) | 一种5-甲基四氢糠醇的制备方法 | |
| WO2015095999A1 (zh) | 制备聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |