CN106478372A - A kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound - Google Patents
A kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound Download PDFInfo
- Publication number
- CN106478372A CN106478372A CN201510524952.8A CN201510524952A CN106478372A CN 106478372 A CN106478372 A CN 106478372A CN 201510524952 A CN201510524952 A CN 201510524952A CN 106478372 A CN106478372 A CN 106478372A
- Authority
- CN
- China
- Prior art keywords
- exchange resin
- quaternary salt
- anion exchange
- formula
- salt type
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- 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)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound.The method prepares vicinal diamines class compound using fixed bed continuous hydrolysis reaction process with epoxide of hydrocarbon kind as raw material with anion exchange resin as catalyst；The macroporous polystyrene that the anion exchange resin replaces for halogen meta-divinylbenzene quaternary salt type is from anion exchange resin.The synthetic method is simple, and catalyst repeatedly can be utilized, and feed stock conversion is high, and vicinal diamines class compound yield is high.
Description
Technical field
The invention belongs to synthesis chemical technology field, specifically, is related to a kind of using quaternary salt type anion exchange resin system
The method of standby vicinal diamines class compound.
Background technology
Vicinal diamines class compound such as 1,2- pentanediol, 1,2- ring pentanediol, 1,2- cyclohexanol, 2,3- pentanediol etc. are that a class is important
Chemicals, has important purposes in fields such as medicine, agricultural chemicals, surfactants.Adjacent dibastic alcohol compound is the more commonly used
Synthetic method is that olefin hydrocarbon oxidation reaction is generated epoxides, and then hydrolysis generates corresponding vicinal diamines again.Chinese patent
CN103992207A is disclosed with kind of " methods for hydrogen peroxide/cationic ion-exchange resin system catalysis oxidation alkene vicinal diamines ",
The Patent technology characteristic be the cationic ion-exchange resin element modified with Ag, Mn, K, Co, Fe as catalyst, peroxidating
Aqueous solution of hydrogen is oxygen source, and olefin oxidation is become vicinal diamines by one-step method.But, the catalyst of the patent specification description uses the longevity
Life is shorter, usually applies mechanically 15 times, it is clear that the promotion and application of this defective effect technology.Chinese invention patent
CN101018752A discloses the method for producing unsaturated vicinal diol compound, it is characterized in that with the ring containing unsaturated bond
Oxygen compound is reaction raw materials, with containing VB, VI B race vanadium, molybdenum, wolfram element silicate as catalyst, anti-by hydrolysis
Corresponding unsaturated vicinal dibastic alcohol compound should be obtained, target product reaction yield be 80%～95%, accessory substance be 5%～
10%.
Content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of utilize quaternary salt type anion exchange resin
The method for preparing vicinal diamines class compound.The method is easy, and catalyst repeatedly can be utilized, and feed stock conversion is high, vicinal diamines
Class compound yield is high.
The present invention provides a kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound, and which is with hydro carbons
Epoxides is reaction raw materials, under anion-exchange resin catalyst catalytic action, reacts work using fixed bed continuous hydrolysis
Skill prepares vicinal diamines class compound；Wherein：The anion-exchange resin catalyst gathers for the macropore that halogen meta replaces
Styrene-divinylbenzene quaternary salt type anion exchange resin, its degree of cross linking are 1%～10%, and resin butt alkali is exchanged and held
Measure as 3.5～4.2mmol.g-1,
In the present invention, macroporous polystyrene-divinylbenzene quaternary salt type anion exchange resin that the halogen meta replaces,
Shown in its structure such as formula (3)：
Wherein：1,2,3,4,5,6 numbers for carbon atoms on a benzene ring, and X represents halogen, quaternary salt ionic group R5R6R7P+(CH2)
In y and phenyl ring, numbering is that any one in 2,4,5,6 carbon atoms is connected, and forms corresponding four kinds of different structures
Ion exchange resin or the mixture of these four resins；Y represents 1～10 integer, m, and n is positive integer, m：N=1:10～
1：100, R5、R6、R7Selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, phenyl or alkyl substituted benzene
In base any one；Mk-Represent anion, its be selected from hydroxyl, formate, acetate, propionate, butyric acid root, pentanoate,
In oxalate, malonate or bicarbonate radical any one, k for anion chemical valence, be 1 or 2.
In the present invention, the epoxide of hydrocarbon kind has structure shown in formula (2)；The vicinal diamines class compound for obtaining has
Structure shown in formula (1)；
Wherein：R in formula (1) and formula (2)1、R2、R3、R4Independent selected from hydrogen, the straight chain of C1～C14
In alkyl, branched alkyl or cycloalkyl any one.
In the present invention, the anion is formate, acetate or bicarbonate radical.
In the present invention, X described in formula (3) is Br or Cl.
In the present invention, the ion exchange resin degree of cross linking represented by formula (3) is 2%～5%.
The reaction equation of the present invention is shown below：
Wherein, R1、R2、R3、R4Independent selected from hydrogen, alkyl or cycloalkyl；Preferably, R1、R2、R3、R4
Independent in hydrogen, the straight chained alkyl of C1～C14, branched alkyl or cycloalkyl any one.
In the present invention, in the fixed bed continuous hydrolysis reaction process, hydrolysising reacting temperature controls at 80～130 DEG C, reaction
Stress control is 5%～50% in 1.5MPa～2.0MPa, the epoxide mass percent concentration for entering reactor, and volume is empty
Speed is 0.1～1h-1.Preferably, the epoxide mass percent concentration for entering reactor is 20%～50%, volume space velocity
For 0.2～0.5h-1.
The beneficial effects of the present invention is：
(1) ion exchange resin general work temperature is less than 120 DEG C, and in use as resin easily expands fragmentation,
Active group is lost, and inactivates catalyst；And the anion exchange resin in the present invention is high temperature resistant, active good, expansion rate
Less；
(2) synthetic method is simple, and catalyst remains in that good catalytic performance under the conditions of long-term operation, and raw material turns
Rate is high, and vicinal diamines class compound yield is high；Its epoxide of hydrocarbon kind conversion ratio 99.1%～99.8%, adjacent diol reaction are received
Rate 91.1%～93.7%.
Specific embodiment
Hereinafter the present invention is illustrated with embodiment, but the invention is not limited in embodiment.
First, conversion ratio and reaction yield computing formula as follows
2nd, the preparation of vicinal diamines class compound
(1) first with the monoolefine of C2～C16 as raw material, using the titanium-silicon molecular sieve TS-1 with MFI structure or HTS-1
For catalyst, with aqueous hydrogen peroxide solution as oxidant, first monoolefine is aoxidized according to technique disclosed in CN104211665A
Become corresponding epoxide of hydrocarbon kind；
(2) in 100ml jacket type stainless steel tubular reactor, structure, halogen shown in 30ml formula (3) is loaded
Macroporous polystyrene-divinylbenzene quaternary salt type anion-exchange resin catalyst that meta replaces, beds upper and lower side
Load inertia bique ball.The temperature of reactor is controlled by outer circulation type conduction oil, and reactor pressure is by installed in discharging opening pipeline
On counterbalance valve control, reaction mass entered by reactor bottom through measuring pump, flows through beds by reactor head stream
Go out, after cooled device cooling, flow into product storage tank.Timing sampling, gas chromatographic analysis product constitute.Investigate anti-
Answering material concentration, temperature, pressure, liquid hourly space velocity (LHSV) and catalyst type to change affects on reaction, used by embodiment 1～10
Reaction raw materials are shown in Table 1, and catalyst used has formula (3) structure, wherein X, y, R5, R6, R7Group, ion
The exchanger resin degree of cross linking, resin (butt) base exchange capacity are shown in Table 2, and reaction process condition and reaction result are shown in Table 3.Logical
Shown in formula (3) structure, catalyst is prepared with a halogenated styrenes, benzene divinyl as reaction raw materials, and reaction equation is such as
Shown in lower：
Embodiment【1～10】
Table 1
Table 2
Table 3
Claims (8)
1. a kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound, it is characterised in which is with hydro carbons
Epoxides is reaction raw materials, under anion-exchange resin catalyst catalytic action, reacts work using fixed bed continuous hydrolysis
Skill prepares vicinal diamines class compound；Wherein：The anion-exchange resin catalyst gathers for the macropore that halogen meta replaces
Styrene-divinylbenzene quaternary salt type anion exchange resin, its degree of cross linking are 1%～10%, and resin butt alkali is exchanged and held
Measure as 3.5～4.2mmol.g-1.
2. method according to claim 1, it is characterised in that macroporous polystyrene-divinyl that the halogen meta replaces
Shown in the structure such as formula (3) of base benzene quaternary salt type anion exchange resin：
Wherein：1,2,3,4,5,6 numbers for carbon atoms on a benzene ring, and X represents halogen, quaternary salt ionic group R5R6R7P+(CH2)
In y and phenyl ring, numbering is that any one in 2,4,5,6 carbon atoms is connected, and forms corresponding four kinds of different structures
Ion exchange resin or the mixture of these four resins；Y represents 1～10 integer, m, and n is positive integer, m：N=1:10～
1：100, R5、R6、R7Selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, phenyl or alkyl-substituted phenyl
In any one；Mk-Represent anion, its be selected from hydroxyl, formate, acetate, propionate, butyric acid root, pentanoate,
In oxalate, malonate or bicarbonate radical any one, k for anion chemical valence, be 1 or 2.
3. method according to claim 1, it is characterised in that：The epoxide of hydrocarbon kind has structure shown in formula (2)；
The vicinal diamines class compound for obtaining has structure shown in formula (1)；
Wherein：R in formula (1) and formula (2)1、R2、R3、R4Independent selected from hydrogen, the straight chain of C1～C14
In alkyl, branched alkyl or cycloalkyl any one.
4. method according to claim 1, it is characterised in that the anion is formate, acetate or bicarbonate radical.
5. method according to claim 1, it is characterised in that in formula (3), the X are Br or Cl.
6. method according to claim 1, it is characterised in that the macropore that the halogen meta represented by formula (3) replaces gathers
The degree of cross linking of styrene-divinylbenzene quaternary salt type anion exchange resin is 2%～5%.
7. method according to claim 1, it is characterised in that in the fixed bed continuous hydrolysis reaction process, hydrolysis
At 80～130 DEG C, reaction pressure controls in 1.5MPa～2.0MPa temperature control, enters the epoxy compound amount of substance hundred of reactor
It is 5%～50% to divide specific concentration, and volume space velocity is 0.1～0.8h-1.
8. method according to claim 7, it is characterised in that in the fixed bed continuous hydrolysis reaction process, enter reactor
Epoxide mass percent concentration be 20%～50%, volume space velocity be 0.2～0.5h-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510524952.8A CN106478372A (en) | 2015-08-25 | 2015-08-25 | A kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510524952.8A CN106478372A (en) | 2015-08-25 | 2015-08-25 | A kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106478372A true CN106478372A (en) | 2017-03-08 |
Family
ID=58233108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510524952.8A Pending CN106478372A (en) | 2015-08-25 | 2015-08-25 | A kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106478372A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718854A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of solid acid catalysts and the preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460551A (en) * | 2003-06-02 | 2003-12-10 | 江苏工业学院 | Synthesis method of quaternary phosphonium type anion-exchange resin for catalyzing epoxyethane hydration |
-
2015
- 2015-08-25 CN CN201510524952.8A patent/CN106478372A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460551A (en) * | 2003-06-02 | 2003-12-10 | 江苏工业学院 | Synthesis method of quaternary phosphonium type anion-exchange resin for catalyzing epoxyethane hydration |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718854A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of solid acid catalysts and the preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104248968B (en) | A kind of catalyst of propane direct dehydrogenation propylene and preparation method thereof | |
| CN104945262B (en) | A kind of method of catalysis methanol reduction dust technology methyl nitrite | |
| CN101687159A (en) | A reactor system, an absorbent and a process for reacting a feed | |
| BR112012014674B1 (en) | Process for the production of olefin oxide, catalyst, and its use | |
| RU2015123993A (en) | A FLOW-FLOW REACTOR WITH A PSEU-LIQUID CATALYST LAYER FOR OLEFIN DEGHODATION | |
| CN106554281A (en) | A kind of method that methyl benzoate hydrogenation reaction produces cyclohexanecarboxylic acid methyl esters | |
| Liu et al. | Highly selective epoxidation of propylene in a low-pressure continuous slurry reactor and the regeneration of catalyst | |
| Sun et al. | Continuous flow synthesis of propylene carbonate using DBU-based ionic liquid in a packed bed reactor | |
| CN101913976B (en) | Selective hydrogenation method for C2 fraction | |
| CN101906015B (en) | Selective hydrogenation method of C3 fractions | |
| CN106478374A (en) | A kind of method that vicinal diamines class compound is prepared by ring-opening reaction | |
| CN106478375A (en) | A kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin | |
| CN106478372A (en) | A kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound | |
| CN106478371A (en) | A kind of method with epoxide of hydrocarbon kind as Material synthesis vicinal diamines class compound | |
| CN106478373A (en) | A kind of method that vicinal diamines class compound is synthesized for catalyst with macroporous anion exchange resin | |
| CN103831105A (en) | Olefin epoxidation catalyst and application thereof | |
| CN102671689A (en) | Catalyst for preparing ethylene from ethanol in different concentrations by dehydration and preparation method and application of catalyst | |
| CN106478365A (en) | A kind of synthetic method of vicinal diamines class compound | |
| CN109970554A (en) | The method that (methyl) acrylic acid is directly appended to biological base oil | |
| CN102173977B (en) | Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol | |
| CN102153446A (en) | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis | |
| CN106890673A (en) | A kind of catalyst for cracking isobutene by methyl-tert-butyl ether and preparation method thereof | |
| CN109651318A (en) | A kind of preparation method of δ-valerolactone | |
| CN104549323B (en) | The method of synthesis DMIZ 1,2 dimethylimidazole and loaded catalyst used | |
| CN104610064B (en) | Process for preparing dimethyl carbonate through taking carbonate as catalyst by one-pot method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170308 |