CN105272823B - Method for preparing C2-10 alkanediol - Google Patents
Method for preparing C2-10 alkanediol Download PDFInfo
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- CN105272823B CN105272823B CN201410314500.2A CN201410314500A CN105272823B CN 105272823 B CN105272823 B CN 105272823B CN 201410314500 A CN201410314500 A CN 201410314500A CN 105272823 B CN105272823 B CN 105272823B
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- 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
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Abstract
The invention relates to a method for preparing C2-10 alkanediol. With prior arts, catalyst stability is poor, and active component is prone to loss. The method mainly aims at solving the above problems. The catalyst adopted by the invention is a supported quaternary phosphonium catalyst with a following average structural formula (1). The method can be used in industrial production for preparing C2-10 alkanediol through C2-10 alkylene carbonate hydrolysis.
Description
Technical field
The present invention relates to one kind prepares C2-10The method of alkanediol.
Background technology
The hydrolysis of esters is a kind of important chemical reaction, is widely used in the every field of petrochemical iy produced, its middle ring
Shape carbonic ester, such as ethylene carbonate (EC), the hydrolysis of propene carbonate even more have very important fundamental position.
The hydrolysis of ethylene carbonate is the important step that ethylene glycol (EG) is produced by oxirane (EO) catalysis hydration two-step method
Suddenly.Ethylene glycol is a kind of important Organic Chemicals, be mainly used to produce polyester fiber, antifreezing agent, unsaturated polyester resin,
Nonionic surfactant, monoethanolamine and explosive etc..The production technology of ethylene glycol is broadly divided into petrochemical industry route and non-petrochemical industry road
Line.There are oxirane direct hydration method and catalyzing epoxyethane hydration method in petrochemical industry route, direct hydration method needs higher
Water ratio (being more than 20) just can guarantee that higher ethylene glycol yield, and it is higher to consume energy during purifying ethylene glycol.Oxirane
Catalytic hydration includes direct catalytic hydration and ethylene carbonate route again.Directly catalytic hydration water is than relatively low (about 5
Left and right), but remain a need for evaporation and remove substantial amounts of water, and ethylene carbonate route is then first with ethylene epoxy ethane
When the CO that discharges2For raw material, ethylene carbonate is generated in the presence of catalyst with oxirane, be then with ethylene carbonate
Intermediate product catalyzing hydrolysis generate ethylene glycol, and the process water, than close stoichiometric proportion 1, is oxirane preparing ethylene glycol from now on
Industrialization direction.
Having been used for the catalyst of annular carbonic acid esters hydrolysis at present mainly has：Alkali (soil) metal carbonate (hydrogen) salt
(US4524224,1985), the compound of Mo and W (JP822106631,1982；WO2009071651,2009), quaternary ammonium salt, season
Phosphonium salt and ion exchange resin (EP0133763,1989；US6080897,2000；US20090156867,2009) etc..But these
Catalyst system and catalyzing more or less has that catalyst separates difficult, active low, stability not.
When strong base ion exchange resin is used for annular carbonic acid esters hydrolysis, activity and selectivity is all preferable, but due to it
Resistance to gentle resistance to swelling can be poor, activity decrease very fast (Yu FP, Cai H, He WJ, the et in catalytic reaction process
al.J.Appl.Polym.Sci.,2010,115:2946～2954), this is to cause the catalyst to fail industrialized main original
Cause.
The content of the invention
The technical problem to be solved is that prior art has poor catalyst stability, active component and is easy to run off
A kind of problem, there is provided new preparation C2-10The method of alkanediol.The method is active and selective high, and active component is difficult
The characteristics of being lost in and easily separate.
To solve above-mentioned technical problem, the technical solution used in the present invention is as follows：One kind prepares C2-10The side of alkanediol
Method, with carbonic acid Asia C2-10Alkane base ester and water are raw material, are 60～180 DEG C in reaction temperature, water and carbonic acid Asia C2-10Alkane base ester
Mol ratio be 1～10, catalyst and carbonic acid Asia C2-10The weight ratio of alkane base ester be 0.005～1 under conditions of, raw material with urge
Agent contact generates C2-10Alkanediol；The catalyst is support type quaternary phosphine catalyst, with following average formula
(1)：
Wherein, X is halogen；
R1、R2And R3It is identical or different, it is each independently selected from optionally substituted C1-20Straight or branched alkyl, optionally take
The C in generation2-20Straight or branched thiazolinyl, optionally substituted C2-20Straight or branched alkynyl, optionally substituted C3-20Cycloalkyl is appointed
Choose the C in generation6-20Aryl；
L is divalent linker, selected from optionally substituted C1-20Straight or branched alkylidene, optionally substituted C2-20Straight chain
Or branched alkenylene or optionally substituted C2-20Straight or branched alkynylene；Wherein described alkylidene, the alkenylene or institute
State alkynylene and be optionally selected from-O- ,-S- ,-NR by one or morea- insert with the insertion group of phenylene；The RaFor C1-4Alkane
Base；
For carrier, selected from magnetic Nano Fe3O4Particle, its average grain diameter is 3～20 nanometers；
_ represent covalent bond；. represent ionic bond；
N is mean value, and it is causedPart withPartial weight ratio reach (1～
25):(75～99).
In above-mentioned technical proposal, it is preferable that X is chlorine, bromine or iodine.It is highly preferred that X is bromine or iodine.
In above-mentioned technical proposal, it is preferable that R1、R2And R3It is each independently selected from C2-10Straight or branched alkyl, by 1
Or multiple phenyl or C3-20The C that cycloalkyl replaces2-10Straight or branched alkyl, C2-10Straight or branched thiazolinyl, by one or more
Phenyl or C3-20The C that cycloalkyl replaces2-10Straight or branched thiazolinyl, C3-20Cycloalkyl, by one or more C1-6Straight or branched alkane
Base or C2-6The C that straight or branched thiazolinyl replaces3-20Cycloalkyl, C6-20Aryl or by one or more C1-6Straight or branched alkyl
Or C2-6The C that straight or branched thiazolinyl replaces6-20Aryl.
In above-mentioned technical proposal, it is preferable that L is selected from C1-20Straight or branched alkylidene.It is highly preferred that L is selected from C2-8Straight chain
Alkylidene.
In above-mentioned technical proposal, it is preferable thatPart withPartial weight ratio reaches
To (1～20):(80～99).
In above-mentioned technical proposal, it is preferable that the magnetic Nano Fe3O4The average grain diameter of particle is 3～15 nanometers.It is more excellent
Selection of land, the magnetic Nano Fe3O4The average grain diameter of particle is 5～12 nanometers.
In above-mentioned technical proposal, it is preferable that the carbonic acid Asia C2-10Alkane base ester is ethylene carbonate or propylene carbonate.
In above-mentioned technical proposal, it is preferable that the C2-10Alkanediol is ethylene glycol or propane diols.
In above-mentioned technical proposal, it is preferable that reaction temperature is 80～160 DEG C, water and carbonic acid Asia C2-10Alkane base ester is rubbed
You than being 1～8, catalyst and carbonic acid Asia C2-10The weight ratio of alkane base ester is 0.01～0.5.
In the context of the present specification, state " optionally substituted " to refer to optionally by one or more (such as 1-5
Individual, 1-4,1-3,1-2 or 1) it is selected from halogen, C1-6Straight or branched alkyl, C1-6Straight or branched haloalkyl,
C2-6Straight or branched thiazolinyl, C2-6Straight or branched alkynyl, C1-6Straight or branched alkoxyl, C3-20Cycloalkyl, C3-20Cycloalkyl
C1-6Straight or branched alkyl, C3-20Cycloalkyl C1-6Straight or branched alkoxyl, C6-20Aryl, C6-20Aryl C1-6Straight or branched
Alkyl and C6-20Aryl C1-6The substituent of straight or branched alkoxyl replaces.Wherein, as the substituent, more preferably halogen,
C1-6Straight or branched alkyl, C3-20Cycloalkyl, C3-20Cycloalkyl C1-6Straight or branched alkyl, C6-20Aryl and C6-20Aryl C1-6
Straight or branched alkyl, more preferably C3-20Cycloalkyl and C6-20Aryl.
In the context of the present specification, term " C3-20Cycloalkyl " refers to the list with carbon atom on 3-20 ring
Ring, bicyclic or polycyclic naphthene base, such as can enumerate the monocyclic cycloalkyls such as cyclopropyl, cyclohexyl and cyclopenta, and bicyclic penta
Base, decahydronaphthalene naphthyl, adamantyl, spiral shell [2.4] heptane base, spiral shell [4.5] decyl, two rings [3.2.1] octyl, three rings
[2.2.1.02,6] volution such as octyl and norborneol alkyl, bridged ring or condensed ring formula be bicyclic or polycyclic naphthene base.Wherein, as institute
State C3-20Cycloalkyl, more preferably C5-10Monocyclic cycloalkyl.
In the context of the present specification, term " C6-20Aryl " refers to the aromatic series with carbon atom on 6-20 ring
Alkyl, such as can enumerate phenyl, xenyl and terphenyl etc. it is two or more (such as 2-6,2-5,2-4 or
2-3) group that is joined directly together with singly-bound of phenyl ring and naphthyl, anthryl, phenanthryl etc. it is two or more (such as 2-6,
2-5,2-4 or 2-3) group that condenses of phenyl ring.Wherein, as the C6-20Aryl, more preferably phenyl, biphenyl
Base and naphthyl, more preferably phenyl.
In the context of the present specification, term " conversion ratio " refers to conversion per pass, i.e. reaction raw materials (such as carbonic acid
Ethyl) complete once to contact with catalyst after realize conversion ratio.In the same manner, in the context of the present specification, term " is selected
Property " refer to one way selectivity.
Finally, in the case where not clearly indicating, all percentages, number, ratio for being previously mentioned in this specification etc.
All it is on the basis of weight, unless do not met the conventional understanding of those skilled in the art when on the basis of weight.
Specifically, the present invention relates to one kind prepares C2-10The method of alkanediol, with carbonic acid Asia C2-10Alkane base ester and water
It is 60～180 DEG C in reaction temperature for raw material, water and carbonic acid Asia C2-10The mol ratio of alkane base ester is 1～10, catalyst and carbon
Acid Asia C2-10The weight ratio of alkane base ester be 0.005～1 under conditions of, raw material contact with catalyst generate C2-10Alkanediol；Institute
It is support type quaternary phosphine catalyst to state catalyst, with following average formula (1)：
Wherein, X is halogen；
R1、R2And R3It is identical or different, it is each independently selected from optionally substituted C1-20Straight or branched alkyl, optionally take
The C in generation2-20Straight or branched thiazolinyl, optionally substituted C2-20Straight or branched alkynyl, optionally substituted C3-20Cycloalkyl is appointed
Choose the C in generation6-20Aryl；
L is divalent linker, selected from optionally substituted C1-20Straight or branched alkylidene, optionally substituted C2-20Straight chain
Or branched alkenylene or optionally substituted C2-20Straight or branched alkynylene；Wherein described alkylidene, the alkenylene or institute
State alkynylene and be optionally selected from-O- ,-S- ,-NR by one or morea- insert with the insertion group of phenylene；The RaFor C1-4Alkane
Base；
For carrier, selected from magnetic Nano Fe3O4Particle, its average grain diameter is 3～20 nanometers；
_ represent covalent bond；. represent ionic bond；
N is mean value, and it is causedPartly (also referred to as quaternary alkylphosphonium salt component) withPart
The weight ratio of (carrier) reaches (1～25):(75～99).
According to the present invention, the preferred chlorine of the X, more preferably bromine or iodine, bromine or iodine.
According to the present invention, the R1、R2And R3It is identical or different, preferably it is each independently selected from C2-10Straight or branched alkane
Base, by one or more (such as 1-4,1-3,1-2 or 1) phenyl or C3-20The C that cycloalkyl replaces2-10Straight chain is propped up
Alkyl group, C2-10Straight or branched thiazolinyl (such as pi-allyl), by one or more (such as 1-4,1-3,1-2 or 1
It is individual) phenyl or C3-20The C that cycloalkyl replaces2-10Straight or branched thiazolinyl, C3-20Cycloalkyl, by one or more (such as 1-4,
1-3,1-2 or 1) C1-6Straight or branched alkyl or C2-6The C that straight or branched thiazolinyl replaces3-20Cycloalkyl, C6-20Virtue
Base (such as phenyl) is either by one or more (such as 1-4,1-3,1-2 or 1) C1-6Straight or branched alkyl or
C2-6The C that straight or branched thiazolinyl replaces6-20Aryl.
According to the present invention, the L is preferably selected from C1-20Straight or branched alkylidene, is more preferably selected from C2-8Straight-chain alkyl-sub.
According to the present invention, the alkylidene, alkenylene or alkynylene included by the L is optionally by one or more (such as 1-3
Individual, 1-2 or 1) it is selected from-O- ,-S- ,-NRa-(RaIt is C1-4Alkyl) and phenylene insertion group at feasible position
Insertion.As the insertion group, preferred phenylene.In addition, when having multiple, group (sub- benzene is inserted described in any two
Except base) between general not Direct Bonding.Now, term " insertion " refers to the insertion group and enters the alkylidene, Asia
The strand of thiazolinyl or alkynylene and become a part for main chain, its feasible insertion position include chain in and the end of the chain.Such as,
Group-CH2-CH2-CH2-CH2--CH can be obtained after the insertion of phenylene2- phenylene-CH2-CH2-CH2-、-CH2-
CH2- phenylene-CH2-CH2-、-CH2-CH2-CH2- phenylene-CH2-、-CH2-CH2-CH2-CH2- phenylene-and-phenylene-
CH2-CH2-CH2-CH2-。
According to the present invention, the n is mean value, it is preferable that the quaternary alkylphosphonium salt component reaches with the weight ratio of the carrier
(1～20):(80～99).
Support type quaternary phosphine catalyst described in the inventive method can be prepared by following preparation method.
The preparation method includes the step of making the tertiary phosphine of following formula (2) react with the macromolecular agent of following formula (3)；
In formula (2), R1、R2And R3It is identical or different, it is each independently selected from optionally substituted C1-20Straight or branched alkane
Base, optionally substituted C2-20Straight or branched thiazolinyl, optionally substituted C2-20Straight or branched alkynyl, optionally substituted C3-20Ring
Alkyl or optionally substituted C6-20Aryl；
_ represent covalent bond；
In formula (3), X is halogen；L is divalent linker, selected from optionally substituted C1-20Straight or branched alkylidene, appoint
Choose the C in generation2-20Straight or branched alkenylene or optionally substituted C2-20Straight or branched alkynylene；Wherein described alkylidene,
The alkenylene or the alkynylene are optionally selected from-O- ,-S- ,-NR by one or morea- insert with the insertion group of phenylene
Enter；The RaFor C1-4Alkyl；
For carrier, selected from magnetic Nano Fe3O4Particle, its average grain diameter is 3～20 nanometers；
_ represent covalent bond.
In above-mentioned technical proposal, the reaction is preferably carried out in the presence of the solvent.As the reaction dissolvent, such as
Can enumerate can dissolve any chemical inertness solvent of the tertiary phosphine, such as can specifically enumerate nitrile solvents such as acetonitrile,
Benzonitrile etc., wherein more preferably benzonitrile.These solvents can be used alone one kind, it is also possible to which multiple combination is used.
In above-mentioned technical proposal, when the reaction is carried out, reaction temperature is generally 100～190 DEG C, and preferably 120～190
DEG C, the reaction time is generally 10～40 hours, preferably 10～30 hours.
In above-mentioned technical proposal, when the reaction is carried out, the tertiary phosphine is general with the weight ratio of the macromolecular agent
For (1～20):(80～99), preferably (1～15):(85～99) 1～15：85～99.
In above-mentioned technical proposal, the preferred chlorine of the X, more preferably bromine or iodine, bromine or iodine.
In above-mentioned technical proposal, the R1、R2And R3It is identical or different, preferably it is each independently selected from C2-10Straight chain is propped up
Alkyl group, by one or more (such as 1-4,1-3,1-2 or 1) phenyl or C3-20The C that cycloalkyl replaces2-10Straight chain
Or branched alkyl, C2-10Straight or branched thiazolinyl (such as pi-allyl), by one or more (such as 1-4,1-3,1-2 or
Person 1) phenyl or C3-20The C that cycloalkyl replaces2-10Straight or branched thiazolinyl, C3-20Cycloalkyl, by one or more (such as 1-4
Individual, 1-3,1-2 or 1) C1-6Straight or branched alkyl or C2-6The C that straight or branched thiazolinyl replaces3-20Cycloalkyl,
C6-20Aryl (such as phenyl) is either by one or more (such as 1-4,1-3,1-2 or 1) C1-6Straight or branched
Alkyl or C2-6The C that straight or branched thiazolinyl replaces6-20Aryl.
In above-mentioned technical proposal, the L is preferably selected from C1-20Straight or branched alkylidene, is more preferably selected from C2-8Straight chain is sub-
Alkyl.
In above-mentioned technical proposal, the alkylidene, alkenylene or alkynylene included by the L optionally by one or more (such as
1-3,1-2 or 1) it is selected from-O- ,-S- ,-NRa-(RaIt is C1-4Alkyl) and phenylene insertion group in feasible position
Put place's insertion.As the insertion group, preferred phenylene.In addition, when having multiple, group is inserted described in any two
General not Direct Bonding between (except phenylene).Now, term " insertion " refers to the insertion group and enters the alkylene
The strand of base, alkenylene or alkynylene and become a part for main chain, its feasible insertion position include chain in and the end of the chain.Than
Such as, group-CH2-CH2-CH2-CH2--CH can be obtained after the insertion of phenylene2- phenylene-CH2-CH2-CH2-、-CH2-
CH2- phenylene-CH2-CH2-、-CH2-CH2-CH2- phenylene-CH2-、-CH2-CH2-CH2-CH2- phenylene-and-phenylene-
CH2-CH2-CH2-CH2-。
In above-mentioned technical proposal, the macromolecular agent (3) be make the carrier and following formula (4) halide reagent reaction and
Prepare；
In formula (4), X is halogen；L is divalent linker, selected from optionally substituted C1-20Straight or branched alkylidene, appoint
Choose the C in generation2-20Straight or branched alkenylene or optionally substituted C2-20Straight or branched alkynylene；Wherein described alkylidene,
The alkenylene or the alkynylene are optionally selected from-O- ,-S- ,-NR by one or morea- insert with the insertion group of phenylene
Enter；The RaFor C1-4Alkyl；M is selected from titanium, silicon or zirconium, preferred silicon；R4、R5And R6It is identical or different, it is each independently selected from
C1-4Straight or branched alkoxyl, preferred methoxy or ethoxy.
In above-mentioned technical proposal, the preferred chlorine of the X, more preferably bromine or iodine, chlorine.
In above-mentioned technical proposal, the L is preferably selected from C1-20Straight or branched alkylidene, is more preferably selected from C2-8Straight chain is sub-
Alkyl.
In above-mentioned technical proposal, the alkylidene, alkenylene or alkynylene included by the L optionally by one or more (such as
1-3,1-2 or 1) it is selected from-O- ,-S- ,-NRa-(RaIt is C1-4Alkyl) and phenylene insertion group in feasible position
Put place's insertion.As the insertion group, preferred phenylene.In addition, when having multiple, group is inserted described in any two
General not Direct Bonding between (except phenylene).Now, term " insertion " refers to the insertion group and enters the alkylene
The strand of base, alkenylene or alkynylene and become a part for main chain, its insertion position include chain in and the end of the chain.Such as, base
Group-CH2-CH2-CH2-CH2--CH can be obtained after the insertion of phenylene2- phenylene-CH2-CH2-CH2-、-CH2-CH2-
Phenylene-CH2-CH2-、-CH2-CH2-CH2- phenylene-CH2-、-CH2-CH2-CH2-CH2- phenylene-and-phenylene-CH2-
CH2-CH2-CH2-。
In above-mentioned technical proposal, when the reaction is carried out, reaction temperature is generally 70～140 DEG C, and preferably 80～120
DEG C, the reaction time is generally 1～60 hour, preferably 5～48 hours.
In above-mentioned technical proposal, when the reaction is carried out, the halide reagent is generally with the weight ratio of the carrier
0.005～0.2, preferably 0.01～0.15.
In above-mentioned technical proposal, the reaction can be carried out in the presence of the solvent.As the reaction dissolvent, such as may be used
To enumerate any chemical inertness solvent that can dissolve the halide reagent, such as can further enumerate C6-12Aromatic hydrocarbon and halogen
For C6-12Aromatic hydrocarbon etc..Specifically can such as enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro second
Benzene, bromotoluene and bromo ethylbenzene etc..Wherein, preferred C6-12Aromatic hydrocarbon, such as toluene.These solvents can be used alone one
Kind, or be applied in combination with arbitrary ratio various.
A particular implementation of the invention, the preparation method of the catalyst in the inventive method is as follows：
1) by ferric acetyl acetonade (Fe (acac)3) it is added to the mixed solvent of solvent I and solvent II, under an inert atmosphere
After 40～200 DEG C (preferably 60～150 DEG C, more preferably 80～120 DEG C) are processed 1～5 hour, 100～400 DEG C are warmed up to (preferably
150～350 DEG C, more preferably 200～300 DEG C) reprocessing after 1～5 hour, after adding solvent III, wash after being dried by centrifugation
Obtain magnetic Nano Fe3O4Particle.Wherein, solvent I is at least one in aliphatic amine or aromatic amine, preferably ten
Diamines or oleyl amine, more preferably oleyl amine.Solvent II be aliphatic ethers, aromatic series ethers or aliphatic-aromatic race compound ether, preferably
For methyl phenyl ethers anisole and benzyl ether, more preferably benzyl ether.Solvent III be alkanol, can for methyl alcohol, ethanol, normal propyl alcohol, isopropanol,
At least one in n-butanol or n-amyl alcohol, preferably methyl alcohol or ethanol, more preferably ethanol.
2) chloride esters of silicon acis is dissolved in solvent, and is added thereto to magnetic Nano Fe3O4Particle, is stirred at reflux 5～50 little
Shi Hou, filters, and washing is dried, and obtains the magnetic Nano Fe processed through chloride esters of silicon acis3O4Particle.Wherein, the solvent
For toluene.
3) carrier that chloride esters of silicon acis was processed is placed in into tertiary phosphine R1R2R3In P solution, inorganic salts are added as catalyst,
After being stirred at reflux 2～50 hours, filter, washing is dried, and obtains Cl-The support type quaternary phosphine salt catalyst of type.Wherein, it is described molten
Agent is benzonitrile.Inorganic salt catalyst is NiCl2、NiBr2、FeCl3、CuCl2Or CoCl2In at least one.
4) by step 3) obtained by Cl-The support type quaternary alkylphosphonium salt catalyst room temperature of type is underlying in highly basic or the water of alkali metal salt
1～20 hour in solution, Jing after filtering, wash, repeat said process 2 times, Jing after filtering, wash and dry the present invention is obtained
Described support type quaternary phosphine catalyst.Wherein, described highly basic or alkali metal salt include NaOH, KOH, LiOH, Ca (OH)2、Sr
(OH)2、Ba(OH)2, at least one in LiBr, NaBr, KBr, CsBr, LiI, NaI, KI or CsI.
By aforesaid manufacture method, you can produce the support type quaternary phosphine catalyst.
The inventive method has the characteristics that：
According to the present invention, the physical/chemical of the support type quaternary phosphine catalyst is stablized, and long term storage is not easy to become
Matter.
According to the present invention, the carrier that the support type quaternary phosphine catalyst is used is magnetic Fe3O4Nano-particle, with ion
Separation extremely convenient after exchanger resin is compared, and heat resistance is greatly improved, and reaction terminates, suctioning out catalyst with magnet is
Can be separated.
According to the present invention, carrier halide reagent (preferably esters of silicon acis containing the hetero atom) place of the support type quaternary phosphine catalyst
After reason, then alkyl chloride on surface graft carries out nucleophilic attack so as to form quaternary alkylphosphonium salt with tertiary phosphine to it.What is be thusly-formed urges
Changing active group-quaternary alkylphosphonium salt component is connected with carrier by strong chemical bond-covalent bond, and thus the combination of the two is very
Closely, thus Stability Analysis of Structures.Even if long-time is used or is recycled for multiple times, catalysis activity group is not easy to come off.
According to the present invention, tried with macromolecular by adjusting the density of X-L- groups and/or regulation tertiary phosphine on macromolecular agent
The amount ratio of agent, can easily adjust the density of quaternary alkylphosphonium salt component Shang carrier, thus, it is possible to flexibly adjust the support type
The catalysis activity of quaternary phosphine catalyst.
According to the present invention, the catalysis activity of the support type quaternary phosphine catalyst and selective height.
A particular implementation of the invention, in 100 DEG C of reaction temperature, water is with the mol ratio of ethylene carbonate
1.5, the weight ratio of catalyst and ethylene carbonate is that under the conditions of 0.05, the conversion ratio of ethylene carbonate is 98.5%, ethylene glycol
Selectivity be 99.5%, catalyst reuse 5 times after, activity also significantly reduce, reduce amplitude be less than 5%, achieve
Preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
Magnetic Fe3O4The preparation of nano-particle：By 14.12g Fe (acac)3It is dissolved in 200mL oleyl amines and 200mL benzyl ether
In the mixed liquor of composition, the solution under nitrogen protection 110 DEG C process 1 hour after, continue under nitrogen protection 300 DEG C process 2
After hour, addition 100mL ethanol, centrifugation, the solids washed with acetone for obtaining 3 times, each 100mL, the solid for obtaining exists
It is dried in vacuum drying oven, obtains magnetic Fe3O4Nano-particle A1, Jing transmission electron microscope characterizes the average grain diameter for finding the nano-particle
For 9.5nm.
The process of chloride esters of silicon acis：By 10.0g magnetic Fes3O4Nano-particle A1 is placed in 500mL three-necked bottles, is then distinguished
Addition 200mL dry toluenes, 2.0g γ-chloropropyl triethoxysilane (γ-chloropropyl triethoxysilane,
CPTES,C3H6ClSi(OC2H5)3), filter after 24 hours in 110 DEG C of backflows, with after absolute ethanol washing 3 times in 110 DEG C of baking ovens
Middle drying 12 hours, obtains carrier B 1, the magnetic Fe that as chloride esters of silicon acis was processed3O4Nano-particle, finds after weighing
The upper chloride esters of silicon acis of B1 and magnetic Fe3O4The weight ratio of nano-particle is 0.12.
Quaternary phosphonium：5.0g B1 are added in the 100mL benzonitrile solution containing triphenylphosphine 2.0g, 3.2g is added
NiCl2·6H2O, after being stirred at reflux reaction 40 hours, filters, after respectively washing three times with ethanol and acetone, 60 DEG C of vacuum drying 12
Hour, obtain Cl-The support type quaternary alkylphosphonium salt C1 of type.
Cl-The transition of the support type quaternary alkylphosphonium salt of type：C1 is added in the aqueous solution of the 100mL containing NaOH 3.0g, is stored at room temperature
Filter after 1 hour, after being washed with deionized 3 times, repeat said process 2 times, obtain catalyst D1, wherein quaternary alkylphosphonium salt component
Weight content is 17.2%, and remaining is carrier.
【Embodiment 2】
Magnetic Fe3O4The preparation of nano-particle：By 14.12g Fe (acac)3It is dissolved in 400mL oleyl amines and 50mL benzyl ether
In the mixed liquor of composition, the solution under nitrogen protection 80 DEG C process 5 hours after, continue under nitrogen protection 350 DEG C process 4 little
Shi Hou, addition 100mL ethanol, centrifugation, the solids washed with acetone for obtaining 3 times, each 100mL, the solid for obtaining is true
It is dried in empty baking oven, obtains magnetic Fe3O4Nano-particle A2, Jing transmission electron microscope sign finds that the average grain diameter of the nano-particle is
5.9nm。
The process of chloride esters of silicon acis：By 10.0g magnetic Fes3O4Nano-particle A2 is placed in 500mL three-necked bottles, is then distinguished
Addition 200mL dry toluenes, 0.2g γ-chloropropyl triethoxysilane (γ-chloropropyl triethoxysilane,
CPTES,C3H6ClSi(OC2H5)3), backflow is filtered after 6 hours, with being dried in 110 DEG C of baking ovens 12 after absolute ethanol washing 3 times
Hour, obtain carrier B 2, the magnetic Fe that as chloride esters of silicon acis was processed3O4Nano-particle, finds chloride on B2 after weighing
Esters of silicon acis and magnetic Fe3O4The weight ratio of nano-particle is 0.011.
Quaternary phosphonium：5.0g B2 are added in the 100mL tetrahydrofuran solutions containing triphenylphosphine 2.0g, 6.2g is added
NiBr2After back flow reaction 6 hours, filter, after respectively washing 3 times with ethanol and acetone, 60 DEG C are vacuum dried 12 hours, obtain Cl-Type
Support type quaternary alkylphosphonium salt C2.
Cl-The transition of the support type quaternary alkylphosphonium salt of type：C1 is added in the aqueous solution of the 100mL containing KI 10.0g, is stored at room temperature
Filter after 20 hours, after being washed with deionized 3 times, repeat said process 2 times, obtain catalyst D2, wherein quaternary alkylphosphonium salt component
Weight content be 1.5%, remaining is carrier.
【Embodiment 3】
Magnetic Fe3O4The preparation method of nano-particle A2 with【Embodiment 2】It is identical, the process that chloride esters of silicon acis is processed with【It is real
Apply example 1】Identical, simply chloride esters of silicon acis used is CPTMS：3-chloropropyl trimethoxysilane (3- chlorine third
Base trimethoxy silane), structural formula is ClC3H6Si(OCH3)3, carrier B 3 is obtained, chloride silicic acid on B3 is found after weighing
Ester and magnetic Fe3O4The weight ratio of nano-particle is 0.069.
Quaternary phosphonium process with【Embodiment 1】The quaternary phosphoniums process is identical, and simply tertiary phosphine used is tri octyl phosphine, is obtained
The Cl- types load quaternary alkylphosphonium salt C3 for arriving.
Cl-The transition of the support type quaternary alkylphosphonium salt of type with【Embodiment 1】Described process is identical, obtains catalyst D3, wherein
The 10.5% of the weight content of quaternary alkylphosphonium salt component, remaining is carrier.
【Embodiment 4】
Magnetic Fe3O4The preparation method of nano-particle with【Embodiment 1】It is identical, the simply amount of oleyl amine used and benzyl ether
Respectively 100mL and 300mL, obtains magnetic Fe3O4Nano-particle A3, Jing transmission electron microscope is characterized and finds the average of the nano-particle
Particle diameter is 12.5nm.
The process that chloride esters of silicon acis is processed with【Embodiment 1】Identical, simply chloride esters of silicon acis used is CBTES：4-
Chlorobenzyl triethoxysilane (4- chloromethyl phenyl triethoxysilanes), structural formula is ClCH2C6H4Si
(OC2H5)3, carrier B 4 is obtained, chloride esters of silicon acis and magnetic Fe on B4 is found after weighing3O4The weight ratio of nano-particle is
0.081。
Quaternary phosphonium process with【Embodiment 1】The quaternary phosphoniums process is identical, and simply tertiary phosphine used is the hexamethylene of phenyl two
Base phosphine, the Cl- types load quaternary alkylphosphonium salt C4 for obtaining.
Cl-The transition of the support type quaternary alkylphosphonium salt of type with【Embodiment 1】Described process is identical, obtains catalyst D4, wherein
The 11.9% of the weight content of quaternary alkylphosphonium salt component, remaining is carrier.
【Embodiment 5】
Magnetic Fe3O4The preparation method of nano-particle with【Embodiment 1】It is identical, the simply amount of oleyl amine used and benzyl ether
Respectively 5mL and 350mL, obtains magnetic Fe3O4Nano-particle A4, Jing transmission electron microscope characterizes the average grain for finding the nano-particle
Footpath is 15.5nm.
The process, quaternary phosphoniums process of chloride esters of silicon acis and Cl-The transition of the support type quaternary alkylphosphonium salt of type with【Embodiment 1】Phase
Together, the carrier B 5 for obtaining, finds chloride esters of silicon acis and magnetic Fe on B5 after weighing3O4The weight ratio of nano-particle is
The weight content of quaternary alkylphosphonium salt component is 7.5% Shang 0.056, the catalyst D5 for obtaining, and remaining is carrier.
【Embodiment 6】
Magnetic Fe3O4The preparation method of nano-particle with【Embodiment 1】Described is identical, and simply oleyl amine is changed to lauryl amine, and two
Benzyl oxide is changed to methyl phenyl ethers anisole, obtains magnetic Fe3O4Nano-particle A5, Jing transmission electron microscope characterizes the average grain diameter for finding the nano-particle
For 18.5nm.
The process, quaternary phosphoniums process of chloride esters of silicon acis and Cl-The transition of the support type quaternary alkylphosphonium salt of type with【Embodiment 1】Phase
Together, the carrier B 6 for obtaining, finds chloride esters of silicon acis and magnetic Fe on B6 after weighing3O4The weight ratio of nano-particle is
The weight content of quaternary alkylphosphonium salt component is 6.8% Shang 0.050, the catalyst D6 for obtaining, and remaining is carrier.
【Embodiment 7】
Will【Embodiment 1】Prepared catalyst D1 is prepared in the reaction of ethylene glycol for ethylene carbonate hydrolysis.Will
44.0 grams of ethylene carbonates, 13.5 grams of deionized waters and 2.2 grams of D1 are placed in 100 milliliters of autoclaves (water and ethylene carbonate
Mol ratio is 1.5, and catalyst is that 0.05), 100 DEG C are reacted 2 hours with the weight ratio of ethylene carbonate.After reaction terminates, by height
Pressure kettle is cooled to room temperature, is vented.Taking liquid product carries out gas chromatographic analysis, and the conversion ratio for measuring ethylene carbonate is
98.5%, the selectivity of ethylene glycol is 99.5%, and remaining is many ethylene glycol.
【Embodiment 8～12】
Will【Embodiment 2-6】Obtained catalyst C2, D3-D6 is used for the reaction that ethylene carbonate hydrolysis prepares ethylene glycol
In, reaction condition with【Embodiment 7】Identical, the reaction result for obtaining is as shown in table 1.
Table 1
【Embodiment 13】
Together【Embodiment 7】, simply reaction temperature is 120 DEG C.The conversion ratio for obtaining ethylene carbonate is 99.1%, ethylene glycol
Selectivity be 99.2%, the selectivity of many ethylene glycol is 0.8%.
【Embodiment 14】
Together【Embodiment 7】, simply reaction temperature is 140 DEG C.The conversion ratio for obtaining ethylene carbonate is 99.5%, ethylene glycol
Selectivity be 98.1%, the selectivity of many ethylene glycol is 1.9%.
【Embodiment 15】
Together【Embodiment 7】, simply reaction temperature is 80 DEG C.The conversion ratio for obtaining ethylene carbonate is 55.8%, ethylene glycol
Selectivity be 99.1%, the selectivity of many ethylene glycol is 0.9%.
【Embodiment 16】
Together【Embodiment 7】, simply the weight of deionized water is 27.0 grams (water is 3 with the mol ratio of ethylene carbonate).
It is 99.1% to ethylene carbonate conversion ratio, the selectivity of ethylene glycol is 99.2%, the selectivity of many ethylene glycol is 0.8%.
【Embodiment 17】
Together【Embodiment 7】, simply the weight of deionized water is 72.0 grams (water is 8 with the mol ratio of ethylene carbonate).
It is 99.3% to ethylene carbonate conversion ratio, the selectivity of ethylene glycol is 99.6%, the selectivity of many ethylene glycol is 0.4%.
【Embodiment 18】
Together【Embodiment 7】, simply the consumption of catalyst be 1.1 grams (the weight ratio of catalyst and ethylene carbonate be
0.025).It is 62.8% to obtain ethylene carbonate conversion ratio, and the selectivity of ethylene glycol is 99.3%, and the selectivity of many ethylene glycol is
0.7%.
【Embodiment 19】
Together【Embodiment 7】, simply catalyst amount is 8.8 grams (the weight ratio of catalyst and ethylene carbonate is 0.2).
It is 99.5% to ethylene carbonate conversion ratio, the selectivity of ethylene glycol is 98.4%, the selectivity of many ethylene glycol is 1.6%.
【Embodiment 20】
Together【Embodiment 7】, simply the weight of catalyst be 17.6 grams (catalyst be with the weight ratio of ethylene carbonate
0.4).It is 99.3% to obtain ethylene carbonate conversion ratio, and the selectivity of ethylene glycol is 97.1%, and the selectivity of many ethylene glycol is
2.9%.
【Embodiment 21】
【Embodiment 7】After reaction terminates, catalyst is suctioned out with magnet, is applied mechanically 5 times by same reaction conditions, and activity is not bright
It is aobvious to decline.Reaction result is shown in Table 3.
Table 2
| Apply mechanically number of times | Ethylene carbonate | Ethylene glycol | Many ethylene glycol |
| Conversion ratio, % | It is selective, % | It is selective, % | |
| 1 | 98.5 | 99.5 | 0.5 |
| 2 | 98.1 | 99.3 | 0.7 |
| 3 | 97.5 | 99.2 | 0.8 |
| 4 | 97.2 | 99.2 | 0.8 |
| 5 | 96.5 | 99.3 | 0.7 |
Claims (10)
1. one kind prepares C2-10The method of alkanediol, with carbonic acid Asia C2-10Alkane base ester and water are raw material, are 60 in reaction temperature
～180 DEG C, water and carbonic acid Asia C2-10The mol ratio of alkane base ester is 1～10, catalyst and carbonic acid Asia C2-10The weight of alkane base ester
Than under conditions of 0.005～1, raw material contacts generation C with catalyst2-10Alkanediol；The catalyst is support type quaternary phosphine
Catalyst, with following average formula (1)：
Wherein, X is halogen；
R1、R2And R3It is identical or different, it is each independently selected from optionally substituted C1-20It is straight or branched alkyl, optionally substituted
C2-20Straight or branched thiazolinyl, optionally substituted C2-20Straight or branched alkynyl, optionally substituted C3-20Cycloalkyl optionally takes
The C in generation6-20Aryl；
L is divalent linker, selected from optionally substituted C1-20Straight or branched alkylidene, optionally substituted C2-20Straight chain is propped up
Chain alkenylene or optionally substituted C2-20Straight or branched alkynylene；Wherein described alkylidene, the alkenylene or the Asia
Alkynyl is optionally selected from-O- ,-S- ,-NR by one or morea- insert with the insertion group of phenylene；The RaFor C1-4Alkyl；
For carrier, selected from magnetic Nano Fe3O4Particle, its average grain diameter is 3～20
_ _ _ represents covalent bond；Represent ionic bond；
N is mean value, and it is causedPart withPartial weight ratio reaches (1～25):
(75～99).
2. C is prepared according to claim 12-10The method of alkanediol, it is characterised in that X is chlorine, bromine or iodine.
3. C is prepared according to claim 22-10The method of alkanediol, it is characterised in that X is bromine or iodine.
4. C is prepared according to claim 12-10The method of alkanediol, it is characterised in that R1、R2And R3It is each independently selected from
C2-10Straight or branched alkyl, by one or more phenyl or C3-20The C that cycloalkyl replaces2-10Straight or branched alkyl, C2-10Directly
Chain or branched-chain alkenyl, by one or more phenyl or C3-20The C that cycloalkyl replaces2-10Straight or branched thiazolinyl, C3-20Cycloalkyl, quilt
One or more C1-6Straight or branched alkyl or C2-6The C that straight or branched thiazolinyl replaces3-20Cycloalkyl, C6-20Aryl or by 1
Individual or multiple C1-6Straight or branched alkyl or C2-6The C that straight or branched thiazolinyl replaces6-20Aryl.
5. C is prepared according to claim 12-10The method of alkanediol, it is characterised in that L is selected from C1-20Straight or branched is sub-
Alkyl.
6. C is prepared according to claim 52-10The method of alkanediol, it is characterised in that L is selected from C2-8Straight-chain alkyl-sub.
7. C is prepared according to claim 12-10The method of alkanediol, it is characterised in that
Part withPartial weight ratio reaches (1～20):(80～99).
8. C is prepared according to claim 12-10The method of alkanediol, it is characterised in that the magnetic Nano Fe3O4Particle
Average grain diameter be 3～15 nanometers.
9. C is prepared according to claim 82-10The method of alkanediol, it is characterised in that the magnetic Nano Fe3O4Particle
Average grain diameter be 5～12 nanometers.
10. C is prepared according to claim 12-10The method of alkanediol, it is characterised in that the carbonic acid Asia C2-10Alkyl group
Ester is ethylene carbonate or propylene carbonate；The C2-10Alkanediol is ethylene glycol or propane diols；Reaction temperature is 80～160
DEG C, water and carbonic acid Asia C2-10The mol ratio of alkane base ester is 1～8, catalyst and carbonic acid Asia C2-10The weight ratio of alkane base ester is
0.01～0.5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528649A (en) * | 2006-09-07 | 2009-09-09 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN102036940B (en) * | 2008-04-10 | 2013-11-13 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN103418433A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Loading type quaternary phosphonium catalyst, manufacturing method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528649A (en) * | 2006-09-07 | 2009-09-09 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN102036940B (en) * | 2008-04-10 | 2013-11-13 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN103418433A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Loading type quaternary phosphonium catalyst, manufacturing method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis and Characterization of a Polymer/Multiwalled Carbon Nanotube Composite and Its Application in the Hydration of Ethylene Oxide;Fengping Yu et al;《Journal ofAppliedPolymer Science》;20091026;第115卷;第2947页左侧栏最后一段至右侧栏第2段 * |
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