CN109574847A - A kind of green synthesis process of 11 ester of preservative nipalgin - Google Patents
A kind of green synthesis process of 11 ester of preservative nipalgin Download PDFInfo
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- CN109574847A CN109574847A CN201811519503.4A CN201811519503A CN109574847A CN 109574847 A CN109574847 A CN 109574847A CN 201811519503 A CN201811519503 A CN 201811519503A CN 109574847 A CN109574847 A CN 109574847A
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- nipalgin
- ester
- preservative
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
Abstract
The present invention provides a kind of green synthesis process of 11 ester of preservative nipalgin, using P-hydroxybenzoic acid and positive undecyl alcohol as raw material, using molecular film reactor, the membrane reactor of reaction and membrane separating process coupling can not only be reduced to the dosage of reaction raw materials, and the investment and production energy consumption of equipment can be reduced, the yield of 11 ester of nipalgin is up to 94.9% or more.
Description
Technical field
The present invention relates to preservatives to synthesize field, and in particular to a kind of green syt work of 11 ester of preservative nipalgin
Skill.
Background technique
The quality and nutritive value of food can be improved in food preservative (foodpreservative), improves food
Color shape extends the holding time of food, optimization processing skill etc., these all natural materials added in food or
The effects of chemical synthesis substance, generally all fast light, thermal oxide.Food additives specifically include that edible fragrance, nutrition enhancing
Agent, the basic substance in matrix fructose, food industry auxiliary agent etc..Generally, it is considered that any food preservative is applied to food
In, while capable of effectively killing and inhibit institute microorganism, and there is certain harm to the safety of food.Recently, China is eaten
Product additives industries developing state is fine, and has made some progress and achieve.Economic policy and system reform in China
Under promotion, the enthusiasm of people is improved, so that many small and weak industries have gradually developed, which results in the passes of numerous people
Note.So the condition that food preservative must have are as follows: itself is nontoxic, stability is high, do not have irritant smell and strange taste,
There is bacteriostasis, and bacteriostasis is strong at low concentrations, easy to use, reasonable price in enteron aisle.Paraben esters itself have
The effect for inhibiting bacterial reproduction, preventing fermentation, sterilization, and it is reported that paraben esters have compared with sorbic acid, benzoic acid
There is stronger anti-microbial property.
Paraben esters have significant advantage compared to sorbic acid, benzoic acid as preservative.Paraben esters
It (NipaginEster) is p-hydroxybenzoate (para-hydroxybenzoate, or be abbreviated as paraben) (molecular formula p-
HOC6H4CO2R trade name) is a kind of chemical preservative, is by being chemically synthesized.
The method that the synthesis of paraben esters generallys use are as follows: using P-hydroxybenzoic acid and corresponding alcohol as raw material, with petroleum
Ether, benzene, toluene etc. are azeotropic aqua, and under certain catalyst action, flowing back under certain condition occurs esterification, then after
The methods of processing, purification are refining to obtain product.For example, Dymicky etc. is using P-hydroxybenzoic acid and corresponding alcohol as raw material, with dense
Hydrochloric acid catalysis reaction, then the method for excessive alcohol vacuum distillation removes, and finally makees recrystallization solvent with n-hexane, obtains Buddhist nun
Moor golden ester sterling.Esterification occurs for the sulphuric acid catalysis P-hydroxybenzoic acid such as Lioyd and hexanol or octanol, using benzene as altogether
Boiling agent makes it that esterification occur, then removes excessive pure and mild benzene in reactant with the method that water vapour evaporates, and finally uses petroleum
Ether obtains paraben esters sterling as recrystallization solvent.
However using the concentrated sulfuric acid, concentrated hydrochloric acid catalyst oneself be exposed through out many deficiencies, separated with product it is difficult, to water and heat
Stability is poor, corrosion equipment, pollutes the disadvantages of environment and regeneration are difficult.
Summary of the invention
To solve the above problems, the present invention provides a kind of green synthesis process of 11 ester of preservative nipalgin, feature
Be: using molecular film reactor, the molecular film reactor is direct i.e. in the esterification reaction solution of metathesis reactor
It is placed in tracheary element sieve membrane, molecular sieve membrane tube one end is closed, and the other end connects vacuum plant, and vacuum pump maintenance system vacuum is
50Pa or less；It reacts the water generated and enters cold-trap under negative pressure promotion in a manner of vapor permeable through molecular screen membrane, pass through threeway
Valve is every to be switched every other hour, and is passed through condenser and condensed collection；The operating procedure of esterification is as follows: weighing one by a certain percentage
Quantitative P-hydroxybenzoic acid, undecyl alcohol, solid super acid catalyst and solvent, which is added in molecular film reactor, carries out ester
Change reaction, reaction mixture lotion is filtered after reaction, evaporating solvent under reduced pressure obtains crude product, after crude product is recrystallized
Obtain 11 ester of nipalgin.
Product yield is not only can be improved into the membrane reactor of reaction and membrane separating process coupling, but also the throwing of equipment can be reduced
Money and production energy consumption.Molecular screen membrane is applied in reversible condensation organic reaction, can take off in 0.3~1nm range by molecular sieve bore diameter
Except small molecular by product (removing water in such as esterification), reaction conversion ratio is improved, does not need that water entrainer additionally is added.It is anti-in film
Ying Zhong, since water is continuously removed by membrane module, reaction continues to positive direction movement, therefore almost converts in esterification.
High conversion ratio also may be implemented in the additional amount that alcohol need not be greatly improved in film reaction, saves reaction raw materials and separation costs.
The molar ratio of P-hydroxybenzoic acid and undecyl alcohol of the present invention is 1:1；
The solid super-strong acid is SO4 2--TiO2/Al2O3、SO4 2--ZrO2/Al2O3、SO4 2-/ZrO2Or SO4 2-/TiO2In one
Kind is several, and dosage is 0~1wt%, preferably 0.2~1wt%；Reaction temperature and time are respectively that 60~100 DEG C and 2~20 are small
When, membrane area and reaction solution volume ratio are 0.3~0.6cm2/cm3.Crude product recrystallization solvent used is anhydrous methanol.
The preparation step of the molecular screen membrane is as follows: (1) configuring Synthesis liquid, match as follows: (0.8~1.2) Al2O3:
(1.2~1.5) P2O5: (1.1~1.4) TEA:(100~300) H2O:(0.01~0.03) MnO2；
(2) carrier is placed on bracket made of polytetrafluoroethylene (PTFE), is then placed in the crystallizing kettle of inner liner polytetrafluoroethylene, finally
It is sealed after pouring into a certain amount of prepared Synthesis liquid, crystallizing kettle is put into heating crystallization in the baking oven for reach predetermined temperature；When making
When with microwave heating crystallization, microwave crystallization kettle is put into microwave apparatus, sets heating power as 80~100W, heating time 2
~4h, 180~200 DEG C of heating temperature；It after reaching preset crystallization time, is cooled to room temperature, takes out the molecular screen membrane prepared,
It is rinsed well with deionized water, is then placed in 40 DEG C of oven dryings 48 hours.
It is as follows to obtain configuration step for Synthesis liquid in the step (1): aluminium isopropoxide being added slowly in deionized water, is continued
4h is stirred to hydrolyzing, phosphoric acid is slowly added dropwise, stirs 1h, continues that template, aging 12h is slowly added dropwise.
The carrier that molecular screen membrane uses in the step (2) is homemade porous gamma-Al2O3Piece, with a thickness of 1~3mm,
Diameter is 15~25mm, average pore size is about 0.1~0.35 μm, porosity is about 40~50%, and carrier is polished through No. 1000 sand paper
Smooth, ultrasonic cleaning removes remaining powder and is placed in 60~80 DEG C of baking ovens dry 12h.
By adopting the above-described technical solution, the beneficial effects of the present invention are:
The present invention is using P-hydroxybenzoic acid and positive undecyl alcohol as raw material, using molecular film reactor, by reaction and UF membrane mistake
Product yield not only can be improved in the membrane reactor of journey coupling, but also can reduce the investment and production energy consumption of equipment, nipalgin 11
The yield of ester is up to 94.9% or more；Simultaneously using solid super-strong acid as catalyst, the concentrated sulfuric acid in esterification process can be overcome to make
When for esterification catalyst, raw material is easily carbonized, aoxidizes, being dehydrated, corroding equipment and have the shortcomings that a large amount of spent acid generate, and meets people couple
The requirement of Green Chemistry is a kind of green, economic, efficient, 11 ester of environmentally friendly synthesis nipalgin method.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's every other embodiment obtained without making creative work,
It shall fall within the protection scope of the present invention.
[embodiment 1]
Molecular screen membrane preparation:
The preparation step of the molecular screen membrane is as follows: (1) aluminium isopropoxide being added slowly in deionized water, persistently stir 4h
To hydrolysis, phosphoric acid is slowly added dropwise, stirs 1h, continues that template is slowly added dropwise, aging 12h obtains by adjusting each component ratio
The Synthesis liquid of following mol ratio: 1Al2O3:1.2P2O5:1.5TEA:100H2O:0.01MnO2；
(2) used carrier is homemade porous gamma-Al2O3Piece is about 0.1 μ with a thickness of 1mm, diameter 15mm, average pore size
M, porosity is about 40%, and carrier is polished smooth through No. 1000 sand paper, and ultrasonic cleaning removes remaining powder and is placed on 80 DEG C of baking ovens
Interior dry 12h.Carrier after will be processed is placed on bracket made of polytetrafluoroethylene (PTFE), is then placed in inner liner polytetrafluoroethylene
In crystallizing kettle, is sealed after finally pouring into a certain amount of prepared Synthesis liquid, crystallizing kettle is put into the baking oven for reaching predetermined temperature
Heating crystallization；When using microwave heating crystallization, microwave crystallization kettle is put into microwave apparatus, sets heating power as 100W,
Heating time 4h, 1200 DEG C of heating temperature；It after reaching preset crystallization time, is cooled to room temperature, takes out the molecular sieve prepared
Film is rinsed well with deionized water, is then placed in 40 DEG C of oven dryings 48 hours.
Esterification: 13.8g P-hydroxybenzoic acid, 17.2g undecyl alcohol and 0.55g SO are weighed4 2--TiO2/Al2O3To urge
Agent is added in molecular film reactor, and esterification 4 hours at 70 DEG C control the membrane area and reaction solution of molecular screen membrane
Volume ratio is 0.45cm2/cm3Esterification is carried out, reaction mixture is carried out while hot filtering to obtain crude product after reaction, it will be thick
The 11 ester product 28.2g of nipalgin of product purity >=99.5wt%, coloration < 5 are obtained after product recrystallizing methanol, yield is
96.0%。
[embodiment 2]
Molecular screen membrane preparation:
The preparation step of the molecular screen membrane is as follows: (1) aluminium isopropoxide being added slowly in deionized water, persistently stir 4h
To hydrolysis, phosphoric acid is slowly added dropwise, stirs 1h, continues that template is slowly added dropwise, aging 12h obtains by adjusting each component ratio
The Synthesis liquid of following mol ratio: 1.2Al2O3:1.5P2O5:1.4TEA:300H2O:0.03MnO；
(2) used carrier is homemade porous gamma-Al2O3Piece is about 0.1 μ with a thickness of 2mm, diameter 25mm, average pore size
M, porosity is about 40%, and carrier is polished smooth through No. 1000 sand paper, and ultrasonic cleaning removes remaining powder and is placed on 80 DEG C of baking ovens
Interior dry 12h.Carrier after will be processed is placed on bracket made of polytetrafluoroethylene (PTFE), is then placed in inner liner polytetrafluoroethylene
In crystallizing kettle, is sealed after finally pouring into a certain amount of prepared Synthesis liquid, crystallizing kettle is put into the baking oven for reaching predetermined temperature
Heating crystallization；When using microwave heating crystallization, microwave crystallization kettle is put into microwave apparatus, sets heating power as 100W,
Heating time 4h, 1200 DEG C of heating temperature；It after reaching preset crystallization time, is cooled to room temperature, takes out the molecular sieve prepared
Film is rinsed well with deionized water, is then placed in 40 DEG C of oven dryings 48 hours.
Esterification: 13.8g P-hydroxybenzoic acid, 17.2g undecyl alcohol and 0.55g SO are weighed4 2--TiO2/Al2O3To urge
Agent is added in molecular film reactor, and esterification 4 hours at 70 DEG C control the membrane area and reaction solution of molecular screen membrane
Volume ratio is 0.45cm2/cm3Esterification is carried out, reaction mixture is carried out while hot filtering to obtain crude product after reaction, it will be thick
The 11 ester product 28.7g of nipalgin of product purity >=99.5wt%, coloration < 5 are obtained after product recrystallizing methanol, yield is
97.6%。
[embodiment 3]
Molecular screen membrane preparation:
The preparation step of the molecular screen membrane is as follows: (1) aluminium isopropoxide being added slowly in deionized water, persistently stir 4h
To hydrolysis, phosphoric acid is slowly added dropwise, stirs 1h, continues that template is slowly added dropwise, aging 12h obtains by adjusting each component ratio
The Synthesis liquid of following mol ratio: 1Al2O3:1.2P2O5:1.5TEA:100H2O:0.01MnO2；
(2) used carrier is homemade porous gamma-Al2O3Piece is about 0.1 μ with a thickness of 1mm, diameter 15mm, average pore size
M, porosity is about 40%, and carrier is polished smooth through No. 1000 sand paper, and ultrasonic cleaning removes remaining powder and is placed on 80 DEG C of baking ovens
Interior dry 12h.Carrier after will be processed is placed on bracket made of polytetrafluoroethylene (PTFE), is then placed in inner liner polytetrafluoroethylene
In crystallizing kettle, is sealed after finally pouring into a certain amount of prepared Synthesis liquid, crystallizing kettle is put into the baking oven for reaching predetermined temperature
Heating crystallization；When using microwave heating crystallization, microwave crystallization kettle is put into microwave apparatus, sets heating power as 100W,
Heating time 4h, 1200 DEG C of heating temperature；It after reaching preset crystallization time, is cooled to room temperature, takes out the molecular sieve prepared
Film is rinsed well with deionized water, is then placed in 40 DEG C of oven dryings 48 hours.
Esterification: 13.8g P-hydroxybenzoic acid, 17.2g undecyl alcohol and 0.98g SO are weighed4 2--ZrO2/Al2O3To urge
Agent is added in molecular film reactor, and esterification 4 hours at 70 DEG C control the membrane area and reaction solution of molecular screen membrane
Volume ratio is 0.45cm2/cm3Esterification is carried out, reaction mixture is carried out while hot filtering to obtain crude product after reaction, it will be thick
The 11 ester product 28.6g of nipalgin of product purity >=99.5wt%, coloration < 5 are obtained after product recrystallizing methanol, yield is
97.2%。
[embodiment 4]
Molecular screen membrane preparation:
The preparation step of the molecular screen membrane is as follows: (1) aluminium isopropoxide being added slowly in deionized water, persistently stir 4h
To hydrolysis, phosphoric acid is slowly added dropwise, stirs 1h, continues that template is slowly added dropwise, aging 12h obtains by adjusting each component ratio
The Synthesis liquid of following mol ratio: 1Al2O3:1.2P2O5:1.5TEA:100H2O:0.01MnO2；
(2) used carrier is homemade porous gamma-Al2O3Piece is about 0.1 μ with a thickness of 1mm, diameter 15mm, average pore size
M, porosity is about 40%, and carrier is polished smooth through No. 1000 sand paper, and ultrasonic cleaning removes remaining powder and is placed on 80 DEG C of baking ovens
Interior dry 12h.Carrier after will be processed is placed on bracket made of polytetrafluoroethylene (PTFE), is then placed in inner liner polytetrafluoroethylene
In crystallizing kettle, is sealed after finally pouring into a certain amount of prepared Synthesis liquid, crystallizing kettle is put into the baking oven for reaching predetermined temperature
Heating crystallization；When using microwave heating crystallization, microwave crystallization kettle is put into microwave apparatus, sets heating power as 100W,
Heating time 4h, 1200 DEG C of heating temperature；It after reaching preset crystallization time, is cooled to room temperature, takes out the molecular sieve prepared
Film is rinsed well with deionized water, is then placed in 40 DEG C of oven dryings 48 hours.
Esterification: weighing 13.8g P-hydroxybenzoic acid, 17.2g undecyl alcohol is added in molecular film reactor, 70
Esterification 4 hours at DEG C, the membrane area and reaction solution volume ratio for controlling molecular screen membrane are 0.45cm2/cm3Esterification is carried out,
Reaction mixture is carried out while hot after reaction to filter to obtain crude product, will be obtained after crude product recrystallizing methanol product purity >=
The 11 ester product 27.9g of nipalgin of 99.5wt%, coloration < 5, yield 94.9%.
[comparative example 1]
Weigh 13.8g P-hydroxybenzoic acid, 17.2g undecyl alcohol and 0.55g SO4 2--TiO2/Al2O3For catalyst and 20mL toluene
It is added in reactor, heating reflux reaction 12 hours, reaction mixture is carried out while hot filtering to obtain crude product filter after reaction
Liquid will obtain the 11 ester product 25.3g of nipalgin of product purity >=99.5wt%, coloration < 5 after crude product recrystallizing methanol,
Yield is 86%.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (8)
1. a kind of green synthesis process of 11 ester of preservative nipalgin, it is characterised in that: molecular film reactor is used, it is described
Molecular film reactor is that tracheary element sieve membrane, molecular sieve membrane tube one are directly placed in the esterification reaction solution of metathesis reactor
Hold it is closed, the other end connect vacuum plant, vacuum pump maintain system vacuum be 50Pa；The operating procedure of the esterification is such as
Under: a certain amount of P-hydroxybenzoic acid, undecyl alcohol, solid super acid catalyst and solvent are weighed by a certain percentage is added to molecule
Esterification is carried out in sieve membrane reactor, reaction mixture is carried out filtering to obtain crude product after reaction, after crude product is recrystallized
Obtain 11 ester of nipalgin.
2. the green synthesis process of 11 ester of preservative nipalgin according to claim 1, it is characterised in that: described to hydroxyl
The molar ratio of yl benzoic acid and undecyl alcohol is 1:1.
3. the green synthesis process of 11 ester of preservative nipalgin according to claim 1, it is characterised in that: the solid
Super acids are one or more of phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, and dosage is 0~1wt%.
4. the green synthesis process of 11 ester of preservative nipalgin according to claim 1, it is characterised in that: the esterification
Reaction temperature and time are respectively 60~100 DEG C and 2~20 hours.
5. the green synthesis process of 11 ester of preservative nipalgin according to claim 1, it is characterised in that: the molecule
The membrane area and reaction solution volume ratio of sieve membrane are 0.3~0.6cm2/cm3。
6. the green synthesis process of 11 ester of preservative nipalgin according to claim 1, it is characterised in that: point
The preparation step of sub- sieve membrane is as follows:
(1) Synthesis liquid is configured, is matched as follows: (0.8~1.2) Al2O3: (1.2~1.5) P2O5: (1.1~1.4) TEA:(100~
300) H2O:(0.01~0.03) MnO2；
(2) carrier is placed on bracket made of polytetrafluoroethylene (PTFE), is then placed in the crystallizing kettle of inner liner polytetrafluoroethylene, finally
It is sealed after pouring into a certain amount of prepared Synthesis liquid, crystallizing kettle is put into heating crystallization in the baking oven for reach predetermined temperature；When making
When with microwave heating crystallization, microwave crystallization kettle is put into microwave apparatus, sets heating power as 80~100W, heating time 2
~4h, 180~200 DEG C of heating temperature；It after reaching preset crystallization time, is cooled to room temperature, takes out the molecular screen membrane prepared,
It is rinsed well with deionized water, is then placed in 40 DEG C of oven dryings 48 hours.
7. the green synthesis process of 11 ester of preservative nipalgin according to claim 6, it is characterised in that: the step
(1) it is as follows to obtain configuration step for Synthesis liquid in: aluminium isopropoxide being added slowly in deionized water, 4h is persistently stirred to hydrolyzing, delays
It is slow that phosphoric acid is added dropwise, 1h is stirred, continues that template, aging 12h is slowly added dropwise.
8. the green synthesis process of 11 ester of preservative nipalgin according to claim 6, it is characterised in that: the step
(2) carrier that molecular screen membrane uses in is homemade porous gamma-Al2O3Piece with a thickness of 1~3mm, diameter is 15~25mm, flat
Equal aperture is about 0.1~0.35 μm, porosity is about 40~50%, and carrier is polished smooth through No. 1000 sand paper, ultrasonic cleaning removal
Remaining powder is placed in 60~80 DEG C of baking ovens dry 12h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440182A (en) * | 2020-04-23 | 2020-07-24 | 陈华明 | Preparation method of isosorbide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119230A (en) * | 2014-06-25 | 2014-10-29 | 李炳洁 | Synthesis method and application of long-chain methyl p-hydroxybenzoate |
| CN105399624A (en) * | 2015-06-30 | 2016-03-16 | 江西师范大学 | Method for preparing acetic ester by adopting acid-resistant molecular sieve membrane reactor |
| US20160214066A1 (en) * | 2014-12-23 | 2016-07-28 | Chevron U.S.A. Inc. | Uncrosslinked, high molecular weight, monoesterified polyimide polymer containing a small amount of bulky diamine |
| CN106518671A (en) * | 2016-11-09 | 2017-03-22 | 山东益丰生化环保股份有限公司 | Preparation method of butylparaben |
| CN107840351A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | The preparation method of the molecular screen membranes of SAPO 34 |
-
2018
- 2018-12-12 CN CN201811519503.4A patent/CN109574847A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119230A (en) * | 2014-06-25 | 2014-10-29 | 李炳洁 | Synthesis method and application of long-chain methyl p-hydroxybenzoate |
| US20160214066A1 (en) * | 2014-12-23 | 2016-07-28 | Chevron U.S.A. Inc. | Uncrosslinked, high molecular weight, monoesterified polyimide polymer containing a small amount of bulky diamine |
| CN105399624A (en) * | 2015-06-30 | 2016-03-16 | 江西师范大学 | Method for preparing acetic ester by adopting acid-resistant molecular sieve membrane reactor |
| CN107840351A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | The preparation method of the molecular screen membranes of SAPO 34 |
| CN106518671A (en) * | 2016-11-09 | 2017-03-22 | 山东益丰生化环保股份有限公司 | Preparation method of butylparaben |
Non-Patent Citations (3)
| Title |
|---|
| 藏雨主编: "《气体分离膜材料科学》", 31 January 2017, 哈尔滨工业大学出版社 * |
| 郑春满主编: "《高等合成化学 方法与实践》", 30 September 2018, 国防工业出版社 * |
| 钱运华等: "固体超强酸SO42-/TiO2-凹凸棒土催化合成尼泊金十二酯的研究", 《中国调味品》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440182A (en) * | 2020-04-23 | 2020-07-24 | 陈华明 | Preparation method of isosorbide |
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