CN106478371A - A kind of method with epoxide of hydrocarbon kind as Material synthesis vicinal diamines class compound - Google Patents
A kind of method with epoxide of hydrocarbon kind as Material synthesis vicinal diamines class compound Download PDFInfo
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- CN106478371A CN106478371A CN201510524816.9A CN201510524816A CN106478371A CN 106478371 A CN106478371 A CN 106478371A CN 201510524816 A CN201510524816 A CN 201510524816A CN 106478371 A CN106478371 A CN 106478371A
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- exchange resin
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- epoxide
- anion
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
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- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method with epoxide of hydrocarbon kind as Material synthesis 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 anion exchange resin is the macroporous polystyrene-divinylbenzene quaternary of halogen substiuted 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 one kind with epoxide of hydrocarbon kind as Material synthesis neighbour two
The method of alcohol 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 one kind is adjacent as Material synthesis with epoxide of hydrocarbon kind
The method of glycol compound.The simple synthetic method, 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 with epoxide of hydrocarbon kind as Material synthesis vicinal diamines class compound, and which is with hydro carbons epoxidation
Thing is reaction raw materials, under anion-exchange resin catalyst catalytic action, is prepared using fixed bed continuous hydrolysis reaction process
Obtain vicinal diamines class compound；Wherein：The macroporous polystyrene that the anion-exchange resin catalyst replaces for halogen meta-
Divinylbenzene quaternary ammonium anion exchange resin, its degree of cross linking be 1%～10%, resin butt base exchange capacity be 3.5～
4.2mmol.g-1,
In the present invention, macroporous polystyrene-divinylbenzene quaternary ammonium 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 is represented halogen, is connected with No. 3 carbon atoms of phenyl ring, quaternary ammonium salt
Ionic group R5R6R7N+(CH2) numbering is that any one in 2,4,5,6 carbon atoms is connected in y and phenyl ring, formed with
The polystyrene-divinylbenzene quaternary ion exchange resin of corresponding four kind different structure or these four resins
Mixture, is usually formed the mixture of these four different structures；Y represents 1～10 integer, m, and n is positive integer, m：n
=1:10～1：100, R5、R6、R7In methyl, ethyl, propyl group, butyl, amyl group or hexyl any one；Mk-
Represent anion, its be selected from hydroxyl, formate, acetate, propionate, butyric acid root, pentanoate, oxalate, the third two
In acid group 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 90.1%～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 it is
Monoolefine, with aqueous hydrogen peroxide solution as oxidant, is first oxidized to by catalyst according to technique disclosed in CN104211665A
Corresponding epoxide of hydrocarbon kind；
(2) in 100ml jacket type stainless steel tubular reactor, structure, halogen meta shown in 30ml formula (3) is loaded
Substituted macroporous polystyrene-divinylbenzene quaternary ammonium anion exchange resin catalyst, beds upper and lower side are loaded
Inertia bique ball.The temperature of reactor is controlled by outer circulation type conduction oil, and reactor pressure is by discharging opening pipeline
Counterbalance valve controls, and reaction mass is entered by reactor bottom through measuring pump, flows through beds and flowed out by reactor head,
Product storage tank is flowed into after cooled device cooling.Timing sampling, gas chromatographic analysis product constitute.Investigate reaction former
Material concentration, reaction temperature, pressure, liquid hourly space velocity (LHSV) and catalyst type change the impact to reacting, used by embodiment 1～10
Reaction raw materials be shown in Table 1, catalyst used has formula (3) structure, wherein X, y, R5, R6, R7Group, from
The sub-exchange resin degree of cross linking, base exchange capacity (butt) are shown in Table 2, and reaction process condition and reaction result are shown in Table 3.Formula
(3) catalyst shown in structure is prepared with a halogenated styrenes, benzene divinyl as reaction raw materials, and reaction equation is as follows
Shown：
Embodiment【1～10】
Table 1
Table 2
Table 3
Claims (8)
1. a kind of method with epoxide of hydrocarbon kind as Material synthesis vicinal diamines class compound, it is characterised in which is with hydro carbons epoxy
Compound is reaction raw materials, under anion-exchange resin catalyst catalytic action, using fixed bed continuous hydrolysis reaction process system
Standby obtain vicinal diamines class compound；Wherein：The macropore polyphenyl second that the anion-exchange resin catalyst replaces for halogen meta
Alkene-divinylbenzene quaternary ammonium anion exchange resin, its degree of cross linking are 1%～10%, and resin butt base exchange capacity is
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 ammonium anion exchange resin：
Wherein：1,2,3,4,5,6 numbers for carbon atoms on a benzene ring, and X is represented halogen, is connected with No. 3 carbon atoms of phenyl ring, quaternary ammonium salt
Ionic group R5R6R7N+(CH2) numbering is that any one in 2,4,5,6 carbon atoms is connected in y and phenyl ring, formed with
The polystyrene-divinylbenzene quaternary ion exchange resin of corresponding four kind different structure or these four resins
Mixture；Y represents 1～10 integer, m, and n is positive integer, m：N=1:10～1：100, R5、R6、R7It is selected from
In methyl, ethyl, propyl group, butyl, amyl group or hexyl any one；Mk-Represent anion, its be selected from hydroxyl, formate,
In acetate, propionate, butyric acid root, pentanoate, oxalate, malonate or bicarbonate radical any one, k be 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 quaternary ammonium 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.
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| CN201510524816.9A CN106478371A (en) | 2015-08-25 | 2015-08-25 | A kind of method with epoxide of hydrocarbon kind as Material synthesis vicinal diamines class compound |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718853A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of supported solid heteropolyacid catalyst and preparation method thereof for epoxidation reaction of olefines |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198429A (en) * | 1997-04-30 | 1998-11-11 | 三菱化学株式会社 | Process for producing alkylene glycol |
| CN1282310A (en) * | 1997-12-18 | 2001-01-31 | 陶氏化学公司 | Process for production of ethylene glycol |
| 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 |
| CN1513597A (en) * | 2003-07-18 | 2004-07-21 | 中国石油化工股份有限公司 | Anion-exchange resin catalyst for ethylene oxide hydration reaction and preparing process |
-
2015
- 2015-08-25 CN CN201510524816.9A patent/CN106478371A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198429A (en) * | 1997-04-30 | 1998-11-11 | 三菱化学株式会社 | Process for producing alkylene glycol |
| CN1282310A (en) * | 1997-12-18 | 2001-01-31 | 陶氏化学公司 | Process for production of ethylene glycol |
| 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 |
| CN1513597A (en) * | 2003-07-18 | 2004-07-21 | 中国石油化工股份有限公司 | Anion-exchange resin catalyst for ethylene oxide hydration reaction and preparing process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718853A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of supported solid heteropolyacid catalyst and preparation method thereof for epoxidation reaction of olefines |
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