CN105080602A - Supported quaternary phosphonium catalyst, preparation method thereof and uses - Google Patents
Supported quaternary phosphonium catalyst, preparation method thereof and uses Download PDFInfo
- Publication number
- CN105080602A CN105080602A CN201410202907.6A CN201410202907A CN105080602A CN 105080602 A CN105080602 A CN 105080602A CN 201410202907 A CN201410202907 A CN 201410202907A CN 105080602 A CN105080602 A CN 105080602A
- Authority
- CN
- China
- Prior art keywords
- straight
- branched
- optional
- replaced
- alkyl
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a supported quaternary phosphonium catalyst, preparation method thereof and uses, mainly solves problems that stability of catalyst is poor and the active ingredients is easy to lose in the prior art. The supported quaternary phosphonium catalyst of the invention has the following average formula (1) and can be used in industrial dialkyl carbonate production through ester interchange.
Description
Technical field
The present invention relates to a kind of support type quaternary phosphine catalyst, its preparation method and application thereof.
Background technology
Dimethyl carbonate (DMC) chemical property is active, physical property is excellent, and nontoxic, easily biological-degradable, a kind of new low stain, environmentally friendly green basic chemical industry raw material, can be used as solvent, gasoline additive, lithium-ion battery electrolytes and carbonylation, methylate and carbomethoxy reagent, be widely used in chemical field.Current each state is all in the Green Chemistry process of active research based on this eco-friendly industrial chemicals of DMC.Wherein, ester-interchange method due to reaction condition gentle, the high and coproduction ethylene glycol of yield or propane diols and become the method having now industrial prospect.
In general, ester exchange reaction is mainly with (F.Risseetal., US2011040117 such as alkali metal hydroxide, alkali carbonate and alkali metal alcohols; C.P.Allaisetal., WO2010063780) as catalyst, but be homogeneous catalyst because of it, not easily with product separation, reuse difficulty.Conventional heterogeneous catalyst comprises and is carried on alkali metal on carrier or alkali metal salt, metal oxide catalyst, the zeolite of alkali (soil) metal exchange or clay material and ion exchange resin etc.Be carried on the alkali metal on carrier or alkali metal salt, as KF/Al
2o
3, NaOH/ shitosan and Cs
2cO
3/ SiO
2-Al
2o
3deng (H.Zhang, CN101249452; Y.Zhao, CN101121147; C.D.Changetal., WO0156971A1), their shortcoming is easily by water in air and CO
2impact, make activity decrease.Metal oxide catalyst, as Al
2o
3, (B.M.Bhanage, etal.Appl.Catal.A219 (2001) 259-266 such as MgO; J.S.Buchananetal., US2005080287; Z.Z.Jiangetal., US6207850), and the zeolite of alkali (soil) metal exchange or clay material, as (C.D.Changetal., the WO0073256 such as Cs-ZSM-5, Mg-smectite; B.M.Bhanageetal.Catal.Lett.83 (2002) 137-141), the shortcoming of this two classes catalyst is active or selective usually lower.Ion exchange resin, as quaternary ammonium type or tertiary amine resin (J.F.Kniftonetal., J.Mol.Catal.A67 (1991) 389-399; M.Caoetal.React.Kinet.Catal.Lett.88 (2006) 251-259), the usual not swelling resistance of this kind of catalyst, and long-time activity decrease is than very fast.
Summary of the invention
One of technical problem to be solved by this invention is the problem that prior art exists poor catalyst stability, active component easily runs off, and provides a kind of new support type quaternary phosphine catalyst.It is high that this catalyst has activity and selectivity, and active component not easily runs off and extremely segregative feature.Two of technical problem to be solved by this invention is to provide a kind of preparation method of support type quaternary phosphine catalyst.Three of technical problem to be solved by this invention is to provide a kind of purposes of support type quaternary phosphine catalyst.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of support type quaternary phosphine catalyst, has following average formula (1):
Wherein, X is halogen;
R
1, R
2and R
3identical or different, be selected from the optional C replaced independently of one another
1-20straight or branched alkyl, the optional C replaced
2-20straight or branched thiazolinyl, the optional C replaced
2-20straight or branched alkynyl, the optional C replaced
3-20cycloalkyl or the optional C replaced
6-20aryl;
L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene; Described R
afor C
1-4alkyl;
for carrier, be selected from magnetic Nano Fe
3o
4particle, its average grain diameter is 3 ~ 20 nanometers;
_ represent covalent bond; Represent ionic bond;
N is mean value, and it makes
part with
the weight ratio of part reaches (1 ~ 25): (75 ~ 99).
Technique scheme, preferably, X is chlorine, bromine or iodine.More preferably, X is bromine or iodine.
Technique scheme, preferably, R
1, R
2and R
3be selected from C independently of one another
2-10straight or branched alkyl, by one or more phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched alkyl, C
2-10straight or branched thiazolinyl, by one or more phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched thiazolinyl, C
3-20cycloalkyl, by one or more C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
3-20cycloalkyl, C
6-20aryl or by one or more C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
6-20aryl.
Technique scheme, preferably, L is selected from C
1-20straight or branched alkylidene.More preferably, L is selected from C
2-8straight-chain alkyl-sub-.
Technique scheme, preferably,
part with
the weight ratio of part reaches (1 ~ 20): (80 ~ 99).
Technique scheme, preferably, magnetic Nano Fe
3o
4the average grain diameter of particle is 3 ~ 15 nanometers.More preferably, magnetic Nano Fe
3o
4the average grain diameter of particle is 5 ~ 12 nanometers.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of support type quaternary phosphine catalyst, comprises the step that the macromolecular agent of the tertiary phosphine of following formula (2) and following formula (3) is reacted; Wherein, the weight ratio of tertiary phosphine and macromolecular agent is (1 ~ 20): (80 ~ 99);
In formula (2), R
1, R
2and R
3identical or different, be selected from the optional C replaced independently of one another
1-20straight or branched alkyl, the optional C replaced
2-20straight or branched thiazolinyl, the optional C replaced
2-20straight or branched alkynyl, the optional C replaced
3-20cycloalkyl or the optional C replaced
6-20aryl;
_ represent covalent bond;
In formula (3), X is halogen; L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene; Described R
afor C
1-4alkyl;
for carrier, be selected from magnetic Nano Fe
3o
4particle, its average grain diameter is 3 ~ 20 nanometers;
_ represent covalent bond.
Technique scheme, preferably, the weight ratio of tertiary phosphine and macromolecular agent is (1 ~ 15): (85 ~ 99).
Technique scheme, preferably, R
1, R
2and R
3be selected from C independently of one another
2-10straight or branched alkyl, by one or more phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched alkyl, C
2-10straight or branched thiazolinyl, by one or more phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched thiazolinyl, C
3-20cycloalkyl, by one or more C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
3-20cycloalkyl, C
6-20aryl or by one or more C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
6-20aryl.
Technique scheme, preferably, X is chlorine, bromine or iodine.More preferably, X is bromine or iodine.
Technique scheme, preferably, L is selected from C
1-20straight or branched alkylidene.More preferably, L is selected from C
2-8straight-chain alkyl-sub-.
Technique scheme, preferably, magnetic Nano Fe
3o
4the average grain diameter of particle is 3 ~ 15 nanometers.More preferably, magnetic Nano Fe
3o
4the average grain diameter of particle is 5 ~ 12 nanometers.
Technique scheme, preferably, reaction temperature is 100 ~ 190 DEG C, and the reaction time is 10 ~ 40 hours.More preferably, reaction temperature is 120 ~ 190 DEG C, and the reaction time is 10 ~ 30 hours.
Technique scheme, preferably, described macromolecular agent makes the halide reagent of described carrier and following formula (4) react and prepare; The weight ratio of halide reagent and carrier is 0.005 ~ 0.2; More preferably, the weight ratio of halide reagent and carrier is 0.01 ~ 0.15.
In formula (4), X is halogen, is preferably chlorine, bromine or iodine, is more preferably chlorine.L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Preferred C
1-20straight or branched alkylidene; More preferably C
2-8straight-chain alkyl-sub-.Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene.Described R
afor C
1-4alkyl.M is selected from titanium, silicon or zirconium, preferred silicon.R
4, R
5and R
6identical or different, be selected from C independently of one another
1-4straight or branched alkoxyl, preferred methoxy or ethoxy.Reaction temperature is 70 ~ 140 DEG C, preferably 80 ~ 120 DEG C; Reaction time is 1 ~ 60 hour, preferably 5 ~ 48 hours.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: arbitrary support type quaternary phosphine catalyst that one of technical solution problem is described or according to technical solution problem two described in the support type quaternary phosphine catalyst prepared of arbitrary preparation method with the sub-C of carbonic acid
2-10alkyl group ester and unitary C
1-10alkanol is raw material, carrys out coproduction carbonic acid two C by ester-interchange method
1-10alkyl group ester and C
2-10as the purposes of catalyst in the method for alkanediol.
Technique scheme, preferably, the sub-C of described carbonic acid
2-10alkyl group ester is selected from ethylene carbonate or propylene carbonate; Described unitary C
1-10alkanol is selected from methyl alcohol; Described carbonic acid two C
1-10alkyl group ester is selected from dimethyl carbonate; Described C
2-10alkanediol is selected from ethylene glycol or propane diols.
Technique scheme, preferably, reaction condition is: reaction temperature is 60 ~ 140 DEG C, is preferably 80 ~ 140 DEG C; Reaction time is 0.1 ~ 20 hour, is preferably 1 ~ 10 hour; Unitary C
1-10alkanol and the sub-C of carbonic acid
2-10the mol ratio of alkyl group ester is 2 ~ 10, is preferably 2 ~ 6; Support type quaternary phosphine catalyst and the sub-C of carbonic acid
2-10the weight ratio of alkyl group ester is 0.005 ~ 0.5, is preferably 0.01 ~ 0.2.
In the context of the present specification, state " optional replace " to refer to and be optionally selected from halogen, C by one or more (such as 1-5,1-4,1-3,1-2 or 1)
1-6straight or branched alkyl, C
1-6straight or branched haloalkyl, C
2-6straight or branched thiazolinyl, C
2-6straight or branched alkynyl, C
1-6straight or branched alkoxyl, C
3-20cycloalkyl, C
3-20cycloalkyl C
1-6straight or branched alkyl, C
3-20cycloalkyl C
1-6straight or branched alkoxyl, C
6-20aryl, C
6-20aryl C
1-6straight or branched alkyl and C
6-20aryl C
1-6the substituting group of straight or branched alkoxyl replaces.Wherein, as described substituting group, more preferably halogen, C
1-6straight or branched alkyl, C
3-20cycloalkyl, C
3-20cycloalkyl C
1-6straight or branched alkyl, C
6-20aryl and C
6-20aryl C
1-6straight or branched alkyl, more preferably C
3-20cycloalkyl and C
6-20aryl.
In the context of the present specification, term " C
3-20cycloalkyl " refer to monocycle, dicyclo or the polycyclic naphthene base with carbon atom on 3-20 ring; such as can enumerate the monocyclic cycloalkyls such as cyclopropyl, cyclohexyl and cyclopenta, and Bicvclopentyl, decahydronaphthalene naphthyl, adamantyl, spiral shell [2.4] heptane base, spiral shell [4.5] decyl, two rings [3.2.1] octyl, three ring [2.2.1.0
2,6] volution, bridged ring or condensed ring formula dicyclo or the polycyclic naphthene base such as octyl and norborneol alkyl.Wherein, as described C
3-20cycloalkyl, more preferably C
5-10monocyclic cycloalkyl.
In the context of the present specification, term " C
6-20aryl " refer to the aromatic hydrocarbyl with carbon atom on 6-20 ring, such as can enumerate group that phenyl, xenyl and terphenyl etc. two or more (such as 2-6,2-5,2-4 or 2-3) phenyl ring is directly connected with singly-bound and naphthyl, anthryl, phenanthryl etc. two or more (such as 2-6,2-5,2-4 or 2-3 individual) group that condenses of phenyl ring.Wherein, as described C
6-20aryl, more preferably phenyl, xenyl and naphthyl, more preferably phenyl.
In the context of the present specification, term " conversion ratio " refers to conversion per pass, and namely reaction raw materials (such as ethylene carbonate) and catalyst complete and once contact the rear conversion ratio realized.In like manner, in the context of the present specification, to refer to one way selective for term " selective ".
Finally, when clearly not indicating, all percentages, number, ratio etc. mentioned in this description are all benchmark with weight, unless do not met the routine understanding of those skilled in the art when being benchmark with weight.
Specifically, the present invention relates to a kind of support type quaternary phosphine catalyst, there is following average formula (1):
Wherein, X is halogen;
R
1, R
2and R
3identical or different, be selected from the optional C replaced independently of one another
1-20straight or branched alkyl, the optional C replaced
2-20straight or branched thiazolinyl, the optional C replaced
2-20straight or branched alkynyl, the optional C replaced
3-20cycloalkyl or the optional C replaced
6-20aryl;
L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene; Described R
afor C
1-4alkyl;
for carrier, be selected from magnetic Nano Fe
3o
4particle, its average grain diameter is 3 ~ 20 nanometers;
_ represent covalent bond; Represent ionic bond;
N is mean value, and it makes
partly (also Cheng quaternary alkylphosphonium salt component) with
partly the weight ratio of (carrier) reaches (1 ~ 25): (75 ~ 99).
According to the present invention, the preferred chlorine of described X, bromine or iodine, more preferably bromine or iodine.
According to the present invention, described R
1, R
2and R
3identical or different, be preferably selected from C independently of one another
2-10straight or branched alkyl, by one or more (such as 1-4,1-3,1-2 or 1) phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched alkyl, C
2-10straight or branched thiazolinyl (such as pi-allyl), by one or more (such as 1-4,1-3,1-2 or 1) phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched thiazolinyl, C
3-20cycloalkyl, by one or more (such as 1-4,1-3,1-2 or 1) C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
3-20cycloalkyl, C
6-20aryl (such as phenyl) or by one or more (such as 1-4,1-3,1-2 or 1) C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
6-20aryl.
According to the present invention, described L is preferably selected from C
1-20straight or branched alkylidene, is more preferably selected from C
2-8straight-chain alkyl-sub-.
According to the present invention, the alkylidene included by this L, alkenylene or alkynylene are optionally selected from-O-,-S-,-NR by one or more (such as 1-3,1-2 or 1)
a-(R
ac
1-4alkyl) and the insertion group of phenylene insert in feasible position.As described insertion group, preferred phenylene.In addition, when existing multiple, general not Direct Bonding between any two described insertion groups (except phenylene).Now, term " insertion " refers to described insertion group and enters the strand of described alkylidene, alkenylene or alkynylene and become the part of main chain, and its feasible insertion position comprises in chain and the end of the chain.Such as, group-CH
2-CH
2-CH
2-CH
2-can-CH be obtained by after a phenylene insertion
2-phenylene-CH
2-CH
2-CH
2-,-CH
2-CH
2-phenylene-CH
2-CH
2-,-CH
2-CH
2-CH
2-phenylene-CH
2-,-CH
2-CH
2-CH
2-CH
2-phenylene-and-phenylene-CH
2-CH
2-CH
2-CH
2-.
According to the present invention, described n is mean value, preferably makes the weight ratio of described quaternary alkylphosphonium salt component and described carrier reach (1 ~ 20): (80 ~ 99).
According to the present invention, described support type quaternary phosphine catalyst such as can be prepared by following preparation method.
According to the present invention, described preparation method comprises the step that the macromolecular agent of the tertiary phosphine of following formula (2) and following formula (3) is reacted;
In formula (2), R
1, R
2and R
3identical or different, be selected from the optional C replaced independently of one another
1-20straight or branched alkyl, the optional C replaced
2-20straight or branched thiazolinyl, the optional C replaced
2-20straight or branched alkynyl, the optional C replaced
3-20cycloalkyl or the optional C replaced
6-20aryl;
_ represent covalent bond;
In formula (3), X is halogen; L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene; Described R
afor C
1-4alkyl;
for carrier, be selected from magnetic Nano Fe
3o
4particle, its average grain diameter is 3 ~ 20 nanometers;
_ represent covalent bond.
According to the present invention, described reaction is preferably carried out in the presence of the solvent.As described reaction dissolvent, such as can enumerate any chemical inertness solvent that can dissolve described tertiary phosphine, such as specifically can enumerate nitrile solvents such as acetonitrile, benzonitrile etc., wherein more preferably benzonitrile.These solvents can be used alone one, also can use by multiple combination.
According to the present invention, when carrying out described reaction, 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.
According to the present invention, when carrying out described reaction, the weight ratio of described tertiary phosphine and described macromolecular agent is generally (1 ~ 20): (80 ~ 99), preferably (1 ~ 15): (85 ~ 99) 1 ~ 15:85 ~ 99.
According to the present invention, the preferred chlorine of described X, bromine or iodine, more preferably bromine or iodine.
According to the present invention, described R
1, R
2and R
3identical or different, be preferably selected from C independently of one another
2-10straight or branched alkyl, by one or more (such as 1-4,1-3,1-2 or 1) phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched alkyl, C
2-10straight or branched thiazolinyl (such as pi-allyl), by one or more (such as 1-4,1-3,1-2 or 1) phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched thiazolinyl, C
3-20cycloalkyl, by one or more (such as 1-4,1-3,1-2 or 1) C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
3-20cycloalkyl, C
6-20aryl (such as phenyl) or by one or more (such as 1-4,1-3,1-2 or 1) C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
6-20aryl.
According to the present invention, described L is preferably selected from C
1-20straight or branched alkylidene, is more preferably selected from C
2-8straight-chain alkyl-sub-.
According to the present invention, the alkylidene included by this L, alkenylene or alkynylene are optionally selected from-O-,-S-,-NR by one or more (such as 1-3,1-2 or 1)
a-(R
ac
1-4alkyl) and the insertion group of phenylene insert in feasible position.As described insertion group, preferred phenylene.In addition, when existing multiple, general not Direct Bonding between any two described insertion groups (except phenylene).Now, term " insertion " refers to described insertion group and enters the strand of described alkylidene, alkenylene or alkynylene and become the part of main chain, and its feasible insertion position comprises in chain and the end of the chain.Such as, group-CH
2-CH
2-CH
2-CH
2-can-CH be obtained by after a phenylene insertion
2-phenylene-CH
2-CH
2-CH
2-,-CH
2-CH
2-phenylene-CH
2-CH
2-,-CH
2-CH
2-CH
2-phenylene-CH
2-,-CH
2-CH
2-CH
2-CH
2-phenylene-and-phenylene-CH
2-CH
2-CH
2-CH
2-.
According to the present invention, described macromolecular agent makes the halide reagent of described carrier and following formula (4) react and prepare;
In formula (4), X is halogen; L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene; Described R
afor C
1-4alkyl; M is selected from titanium, silicon or zirconium, preferred silicon; R
4, R
5and R
6identical or different, be selected from C independently of one another
1-4straight or branched alkoxyl, preferred methoxy or ethoxy.
According to the present invention, the preferred chlorine of described X, bromine or iodine, more preferably chlorine.
According to the present invention, described L is preferably selected from C
1-20straight or branched alkylidene, is more preferably selected from C
2-8straight-chain alkyl-sub-.
According to the present invention, the alkylidene included by this L, alkenylene or alkynylene are optionally selected from-O-,-S-,-NR by one or more (such as 1-3,1-2 or 1)
a-(R
ac
1-4alkyl) and the insertion group of phenylene insert in feasible position.As described insertion group, preferred phenylene.In addition, when existing multiple, general not Direct Bonding between any two described insertion groups (except phenylene).Now, term " insertion " refers to described insertion group and enters the strand of described alkylidene, alkenylene or alkynylene and become the part of main chain, and its insertion position comprises in chain and the end of the chain.Such as, group-CH
2-CH
2-CH
2-CH
2-can-CH be obtained by after a phenylene insertion
2-phenylene-CH
2-CH
2-CH
2-,-CH
2-CH
2-phenylene-CH
2-CH
2-,-CH
2-CH
2-CH
2-phenylene-CH
2-,-CH
2-CH
2-CH
2-CH
2-phenylene-and-phenylene-CH
2-CH
2-CH
2-CH
2-.
According to the present invention, when carrying out described reaction, 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.
According to the present invention, when carrying out described reaction, the weight ratio of described halide reagent and described carrier is generally 0.005 ~ 0.2, and preferably 0.01 ~ 0.15.
According to the present invention, described reaction can be carried out in the presence of the solvent.As described reaction dissolvent, such as can enumerate any chemical inertness solvent that can dissolve described halide reagent, such as can enumerate C further
6-12aromatic hydrocarbon and halo C
6-12aromatic hydrocarbon etc.Specifically such as can enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene and bromo ethylbenzene etc.Wherein, preferred C
6-12aromatic hydrocarbon, such as toluene.These solvents can be used alone one, or use multiple with arbitrary ratio combination.
According to a particular implementation of the present invention, the preparation method of catalyst of the present invention is as follows:
1) by ferric acetyl acetonade (Fe (acac)
3) join in the mixed solvent of solvent I and solvent II, 40 ~ 200 DEG C under an inert atmosphere (preferably 60 ~ 150 DEG C, more preferably 80 ~ 120 DEG C) process 1 ~ 5 hour after, be warmed up to 100 ~ 400 DEG C (preferably 150 ~ 350 DEG C, more preferably 200 ~ 300 DEG C) reprocessing is after 1 ~ 5 hour, after adding solvent III, centrifugation, obtains magnetic Nano Fe after washing drying
3o
4particle.Wherein, solvent I is at least one in aliphatic amine or aromatic amine, is preferably lauryl amine or oleyl amine, is more preferably oleyl amine.Solvent II is aliphatic ethers, aromatic series ethers or aliphatic-aromatic race compound ether, is preferably methyl phenyl ethers anisole and benzyl ether, is more preferably benzyl ether.Solvent III is alkanol, can be at least one in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol or n-amyl alcohol, is preferably methyl alcohol or ethanol, is more preferably ethanol.
2) chloride esters of silicon acis is dissolved in solvent, and adds magnetic Nano Fe wherein
3o
4particle, stirring and refluxing, after 5 ~ 50 hours, is filtered, and washing is dry, obtains the magnetic Nano Fe through chloride esters of silicon acis process
3o
4particle.Wherein, described solvent is toluene.
3) carrier of chloride esters of silicon acis process is placed in tertiary phosphine R
1r
2r
3in P solution, add inorganic salts as catalyst, stirring and refluxing, after 2 ~ 50 hours, is filtered, and washing is dry, obtains Cl
-the support type quaternary alkylphosphonium salt catalyst of type.Wherein, described solvent is benzonitrile.Inorganic salt catalyst is NiCl
2, NiBr
2, FeCl
3, CuCl
2or CoCl
2in at least one.
4) by step 3) Cl of gained
-underlying in the aqueous solution of highly basic or alkali metal salt 1 ~ 20 hour of the support type quaternary alkylphosphonium salt catalyst room temperature of type, after filtration, after washing, repeats said process 2 times, after filtration, washing and namely obtain support type quaternary phosphine catalyst of the present invention after drying.Wherein, described highly basic or alkali metal salt comprise 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, support type quaternary phosphine catalyst can be produced.
According to the present invention, aforesaid any support type quaternary phosphine catalyst all can be used for manufacturing dialkyl carbonate by ester-interchange method as catalyst.Therefore, in a further embodiment, the invention still further relates to a kind of preparation method of dialkyl carbonate, comprise and make the sub-C of carbonic acid
2-10alkyl group ester and unitary C
1-10alkanol contacts under the existence of described support type quaternary phosphine catalyst, generates (coproduction) carbonic acid two C
1-10alkyl group ester and C
2-10the step of alkanediol.
According to the present invention, as the sub-C of described carbonic acid
2-10alkyl group ester, the sub-C of preferred carbonic acid
2-5alkyl group ester, most preferably ethylene carbonate or propylene carbonate.
According to the present invention, as described unitary C
1-10alkanol, preferred unitary C
1-3alkanol, most preferably methyl alcohol.
According to the present invention, by making ethylene carbonate (propylene carbonate) contact under the existence of described support type quaternary phosphine catalyst with methyl alcohol, can with high yield co-producing dimethyl carbonate and ethylene glycol (propane diols).
According to the present invention, described contact procedure can be carried out under the common condition in this area according to the usual manner of this area, and such as reaction temperature is generally 60 ~ 140 DEG C, preferably 80 ~ 140 DEG C, reaction time is generally 0.1 ~ 20 hour, preferably 1 ~ 10 hour, is not particularly limited.In addition, the reaction pressure of this contact procedure can be normal pressure, also can be pressurization (self-generated pressure of such as reactor, such as 0.2-1.5MPa), be not particularly limited.
According to the present invention, in described contact procedure, described unitary C
1-10alkanol and the sub-C of described carbonic acid
2-10the mol ratio of alkyl group ester is generally 2 ~ 10, and preferably 2 ~ 6, and described support type quaternary phosphine catalyst and the sub-C of described carbonic acid
2-10the weight ratio of alkyl group ester is generally 0.005 ~ 0.5, and preferably 0.01 ~ 0.2.
Support type quaternary phosphine catalyst of the present invention has following characteristics:
According to the present invention, the physical/chemical of described support type quaternary phosphine catalyst is stablized, and long term storage is not perishable yet.
According to the present invention, the carrier that described support type quaternary phosphine catalyst uses is magnetic Fe
3o
4nano particle, with Ion Exchange Resin Phase ratio, heat resistance improves greatly, and reaction terminate after separation very convenient, can be separated with magnet sucking-off catalyst.
According to the present invention, after the carrier halide reagent of described support type quaternary phosphine catalyst (preferably containing hetero atom esters of silicon acis) process, alkyl chloride on surface graft, then carries out nucleophilic attack with tertiary phosphine to it thus forms quaternary alkylphosphonium salt.The catalytic activity group-quaternary alkylphosphonium salt component of formation like this is connected with carrier by strong chemical bond-covalent bond, and the combination of the two closely thus, thus Stability Analysis of Structures.Use even if long-time or repeatedly recycle, catalytic activity group also difficult drop-off.
According to the present invention, by regulating the density of X-L-group on macromolecular agent and/or regulating the amount ratio of tertiary phosphine and macromolecular agent, easily can regulate the density of quaternary alkylphosphonium salt component Shang carrier, the catalytic activity of described support type quaternary phosphine catalyst can be regulated thus flexibly.
According to the present invention, the catalytic activity of described support type quaternary phosphine catalyst and selective height, when being used for preparing dialkyl carbonate by ester-interchange method as catalyst, can coproduction dialkyl carbonate and glycol with high yield.
According to a particular implementation of the present invention, described support type quaternary phosphine catalyst be used for as catalyst by ethylene carbonate and methyl alcohol ester exchange reaction prepare dimethyl carbonate time, reaction temperature 100 DEG C, the mol ratio of methyl alcohol and ethylene carbonate is 4, the weight ratio of catalyst and ethylene carbonate is under 0.05 condition, react 4 hours, the conversion ratio of ethylene carbonate can reach 67.2%, the selective of dimethyl carbonate reaches 99.4%, the selective of ethylene glycol reaches 99.1%, after catalyst reuses 5 times, activity is not obvious reduction also, reduction amplitude is less than 5%, achieve good technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Magnetic Fe
3o
4the preparation of nano particle: by 14.12gFe (acac)
3be dissolved in the mixed liquor of 200mL oleyl amine and 200mL benzyl ether composition; this solution under nitrogen protection 110 DEG C process 1 hour after; continue 300 DEG C of process under nitrogen protection after 2 hours; add 100mL ethanol; centrifugation, the solids washed with acetone obtained 3 times, each 100mL; the solid obtained is dry in vacuum drying oven, obtains magnetic Fe
3o
4nano particle A1, characterizing through transmission electron microscope the average grain diameter finding this nano particle is 9.5nm.
The process of chloride esters of silicon acis: by 10.0g magnetic Fe
3o
4nano particle A1 is placed in 500mL three-necked bottle, then adds 200mL dry toluene respectively, 2.0g γ-chloropropyl triethoxysilane (γ-chloropropyltriethoxysilane, CPTES, C
3h
6clSi (OC
2h
5)
3), filter after 24 hours 110 DEG C of backflows, with after absolute ethanol washing 3 times in 110 DEG C of baking ovens dry 12 hours, obtain carrier B 1, be the magnetic Fe of chloride esters of silicon acis process
3o
4nano particle, finds chloride esters of silicon acis and magnetic Fe on B1 after weighing
3o
4the weight ratio of nano particle is 0.12.
Quaternary phosphonium: 5.0gB1 is added in the 100mL benzonitrile solution containing triphenylphosphine 2.0g, add 3.2gNiCl
26H
2o, after stirring and refluxing reacts 40 hours, filters, and after respectively washing 3 times with ethanol and acetone, 60 DEG C of vacuum drying 12 hours, 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 100mL containing in the aqueous solution of NaOH3.0g, room temperature leaves standstill after 1 hour and filters, after spending deionized water 3 times, repeat said process 2 times, obtain catalyst D1, wherein the weight content of quaternary alkylphosphonium salt component is 17.2%, and all the other are carrier.
[embodiment 2]
Magnetic Fe
3o
4the preparation of nano particle: by 14.12gFe (acac)
3be dissolved in the mixed liquor of 400mL oleyl amine and 50mL benzyl ether composition; this solution under nitrogen protection 80 DEG C process 5 hours after; continue 350 DEG C of process under nitrogen protection after 4 hours; add 100mL ethanol; centrifugation, the solids washed with acetone obtained 3 times, each 100mL; the solid obtained is dry in vacuum drying oven, obtains magnetic Fe
3o
4nano particle A2, characterizing through transmission electron microscope the average grain diameter finding this nano particle is 5.9nm.
The process of chloride esters of silicon acis: by 10.0g magnetic Fe
3o
4nano particle A2 is placed in 500mL three-necked bottle, then adds 200mL dry toluene respectively, 0.2g γ-chloropropyl triethoxysilane (γ-chloropropyltriethoxysilane, CPTES, C
3h
6clSi (OC
2h
5)
3), reflux after 6 hours and filter, with after absolute ethanol washing 3 times in 110 DEG C of baking ovens dry 12 hours, obtain carrier B 2, be the magnetic Fe of chloride esters of silicon acis process
3o
4nano particle, finds chloride esters of silicon acis and magnetic Fe on B2 after weighing
3o
4the weight ratio of nano particle is 0.011.
Quaternary phosphonium: 5.0gB2 is added in the 100mL tetrahydrofuran solution containing triphenylphosphine 2.0g, add 6.2gNiBr
2back flow reaction is after 6 hours, filters, and after respectively washing 3 times with ethanol and acetone, 60 DEG C of vacuum drying 12 hours, obtain Cl
-the support type quaternary alkylphosphonium salt C2 of type.
Cl
-the transition of the support type quaternary alkylphosphonium salt of type: C1 is added 100mL containing in the aqueous solution of KI10.0g, room temperature leaves standstill after 20 hours and filters, after spending deionized water 3 times, repeat said process 2 times, obtain catalyst D2, wherein the weight content of quaternary alkylphosphonium salt component is 1.5%, and all the other are carrier.
[embodiment 3]
Magnetic Fe
3o
4the preparation method of nano particle A2 is identical with [embodiment 2], the process of chloride esters of silicon acis process is identical with [embodiment 1], just chloride esters of silicon acis used is CPTMS:3-chloropropyltrimethoxysilane (3-r-chloropropyl trimethoxyl silane), and structural formula is ClC
3h
6si (OCH
3)
3, obtain carrier B 3, after weighing, find chloride esters of silicon acis and magnetic Fe on B3
3o
4the weight ratio of nano particle is 0.069.
Quaternary phosphonium process is identical with [embodiment 1] described quaternary phosphonium process, and just tertiary phosphine used is tri octyl phosphine, the Cl-type load quaternary alkylphosphonium salt C3 obtained.
Cl
-the transition of the support type quaternary alkylphosphonium salt of type is identical with the process described in [embodiment 1], obtains catalyst D3, wherein quaternary alkylphosphonium salt component weight content 10.5%, all the other are carrier.
[embodiment 4]
Magnetic Fe
3o
4the preparation method of nano particle is identical with [embodiment 1], and just the amount of oleyl amine used and benzyl ether is respectively 100mL and 300mL, obtains magnetic Fe
3o
4nano particle A3, characterizing through transmission electron microscope the average grain diameter finding this nano particle is 12.5nm.
The process of chloride esters of silicon acis process is identical with [embodiment 1], and just chloride esters of silicon acis used is CBTES:4-chlorobenzyltriethoxysilane (4-chloromethyl phenyl triethoxysilane), and structural formula is ClCH
2c
6h
4si (OC
2h
5)
3, obtain carrier B 4, after weighing, find chloride esters of silicon acis and magnetic Fe on B4
3o
4the weight ratio of nano particle is 0.081.
Quaternary phosphonium process is identical with [embodiment 1] described quaternary phosphonium process, and just tertiary phosphine used is phenyldicyclohexylphosphine, the Cl-type load quaternary alkylphosphonium salt C4 obtained.
Cl
-the transition of the support type quaternary alkylphosphonium salt of type is identical with the process described in [embodiment 1], obtains catalyst D4, wherein quaternary alkylphosphonium salt component weight content 11.9%, all the other are carrier.
[embodiment 5]
Magnetic Fe
3o
4the preparation method of nano particle is identical with [embodiment 1], and just the amount of oleyl amine used and benzyl ether is respectively 5mL and 350mL, obtains magnetic Fe
3o
4nano particle A4, characterizing through transmission electron microscope the average grain diameter finding this nano particle is 15.5nm.
The process, quaternary phosphonium process of chloride esters of silicon acis and Cl
-the transition of the support type quaternary alkylphosphonium salt of type is all identical with [embodiment 1], and the carrier B 5 obtained, finds chloride esters of silicon acis and magnetic Fe on B5 after weighing
3o
4the weight ratio of nano particle is 0.056, and Shang the catalyst D5 obtained, the weight content of quaternary alkylphosphonium salt component is 7.5%, and all the other are carrier.
[embodiment 6]
Magnetic Fe
3o
4the preparation method of nano particle and identical described in [embodiment 1], just oleyl amine changes lauryl amine into, and benzyl ether changes methyl phenyl ethers anisole into, obtains magnetic Fe
3o
4nano particle A5, characterizing through transmission electron microscope the average grain diameter finding this nano particle is 18.5nm.
The process, quaternary phosphonium process of chloride esters of silicon acis and Cl
-the transition of the support type quaternary alkylphosphonium salt of type is all identical with [embodiment 1], and the carrier B 6 obtained, finds chloride esters of silicon acis and magnetic Fe on B6 after weighing
3o
4the weight ratio of nano particle is 0.050, and Shang the catalyst D6 obtained, the weight content of quaternary alkylphosphonium salt component is 6.8%, and all the other are carrier.
[embodiment 7]
22.0 grams of ethylene carbonates, 32.0 grams of methyl alcohol and 1.1 grams of catalyst D1 are placed in 100 milliliters of autoclaves (mol ratio of methyl alcohol and ethylene carbonate is 4, and the weight ratio of catalyst and ethylene carbonate is 0.05), and 100 DEG C are reacted 4 hours.After reaction terminates, autoclave is cooled to room temperature, emptying.Get liquid product and carry out gas chromatographic analysis, the conversion ratio obtaining ethylene carbonate is 61.5%, and the selective of dimethyl carbonate is 99.1%, and the selective of ethylene glycol is 96.9%.
[embodiment 8 ~ 12]
Catalyst C2, D3-D6 obtained by [embodiment 2 ~ 6] are used in the ester exchange reaction of ethylene carbonate and methyl alcohol, reaction condition is identical with [embodiment 7], and the reaction result obtained is as shown in table 1.
Table 1
[embodiment 13]
With [embodiment 7], just reaction temperature is 120 DEG C.The conversion ratio obtaining ethylene carbonate is 62.5%, and the selective of dimethyl carbonate is 98.6%, and the selective of ethylene glycol is 98.9%.
[embodiment 14]
With [embodiment 7], just reaction temperature is 140 DEG C.The conversion ratio obtaining ethylene carbonate is 63.5%, and the selective of dimethyl carbonate is 92.5%, and the selective of ethylene glycol is 91.8%.
[embodiment 15]
With [embodiment 7], just reaction temperature is 80 DEG C.The conversion ratio obtaining ethylene carbonate is 35.6%, and the selective of dimethyl carbonate is 99.5%, and the selective of ethylene glycol is 99.4%.
[embodiment 16]
With [embodiment 7], just the quality of methyl alcohol is 48 grams (mol ratio of methyl alcohol and ethylene carbonate is 6).Obtaining ethylene carbonate conversion ratio is 66.5%, and the selective of dimethyl carbonate is 98.9%, and the selective of ethylene glycol is 99.8%.
[embodiment 17]
With [embodiment 7], just the quality of methyl alcohol is 16.0 grams (mol ratio of methyl alcohol and ethylene carbonate is 2).Obtaining ethylene carbonate conversion ratio is 42.1%, and the selective of dimethyl carbonate is 98.7%, and the selective of ethylene glycol is 97.9%.
[embodiment 18]
With [embodiment 7], just the quality of catalyst is 0.55 gram (mass ratio of catalyst and ethylene carbonate is 0.025).Obtaining ethylene carbonate conversion ratio is 39.1%, and the selective of dimethyl carbonate is 98.6%, and the selective of ethylene glycol is 97.5%.
[embodiment 19]
With [embodiment 7], just the quality of catalyst is 2.2 grams (part by weight of catalyst and ethylene carbonate is 0.1).Obtaining ethylene carbonate conversion ratio is 67.2%, and the selective of dimethyl carbonate is 99.4%, and the selective of ethylene glycol is 99.1%.
[embodiment 20]
With [embodiment 7], just the quality of catalyst is 4.4 grams (mass ratio of catalyst and ethylene carbonate is 0.2).Obtaining ethylene carbonate conversion ratio is 67.8%, and the selective of dimethyl carbonate is 98.5%, and the selective of ethylene glycol is 97.9%.
[embodiment 21]
After [embodiment 19] reaction being terminated, by catalyst with after magnet sucking-off, apply mechanically under identical reaction conditions, totally 5 times, activity does not obviously decline.Reaction result is in table 2.
Table 2
Claims (10)
1. a support type quaternary phosphine catalyst, has following average formula (1):
Wherein, X is halogen;
R
1, R
2and R
3identical or different, be selected from the optional C replaced independently of one another
1-20straight or branched alkyl, the optional C replaced
2-20straight or branched thiazolinyl, the optional C replaced
2-20straight or branched alkynyl, the optional C replaced
3-20cycloalkyl or the optional C replaced
6-20aryl;
L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene; Described R
afor C
1-4alkyl;
for carrier, be selected from magnetic Nano Fe
3o
4particle, its average grain diameter is 3 ~ 20 nanometers;
_ represent covalent bond; Represent ionic bond;
N is mean value, and it makes
part with
the weight ratio of part reaches (1 ~ 25): (75 ~ 99).
2. support type quaternary phosphine catalyst according to claim 1, is characterized in that X is chlorine, bromine or iodine;
R
1, R
2and R
3be selected from C independently of one another
2-10straight or branched alkyl, by one or more phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched alkyl, C
2-10straight or branched thiazolinyl, by one or more phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched thiazolinyl, C
3-20cycloalkyl, by one or more C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
3-20cycloalkyl, C
6-20aryl or by one or more C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
6-20aryl;
L is selected from C
1-20straight or branched alkylidene;
part with
the weight ratio of part reaches (1 ~ 20): (80 ~ 99);
Magnetic Nano Fe
3o
4the average grain diameter of particle is 3 ~ 15 nanometers.
3. support type quaternary phosphine catalyst according to claim 2, is characterized in that X is bromine or iodine; L is selected from C
2-8straight-chain alkyl-sub-; Magnetic Nano Fe
3o
4the average grain diameter of particle is 5 ~ 12 nanometers.
4. a preparation method for support type quaternary phosphine catalyst, comprises the step that the macromolecular agent of the tertiary phosphine of following formula (2) and following formula (3) is reacted; Wherein, the weight ratio of tertiary phosphine and macromolecular agent is (1 ~ 20): (80 ~ 99);
In formula (2), R
1, R
2and R
3identical or different, be selected from the optional C replaced independently of one another
1-20straight or branched alkyl, the optional C replaced
2-20straight or branched thiazolinyl, the optional C replaced
2-20straight or branched alkynyl, the optional C replaced
3-20cycloalkyl or the optional C replaced
6-20aryl;
_ represent covalent bond;
In formula (3), X is halogen; L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene; Described R
afor C
1-4alkyl;
for carrier, be selected from magnetic Nano Fe
3o
4particle, its average grain diameter is 3 ~ 20 nanometers;
_ represent covalent bond.
5. the preparation method of support type quaternary phosphine catalyst according to claim 4, is characterized in that the weight ratio of tertiary phosphine and macromolecular agent is for (1 ~ 15): (85 ~ 99);
R
1, R
2and R
3be selected from C independently of one another
2-10straight or branched alkyl, by one or more phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched alkyl, C
2-10straight or branched thiazolinyl, by one or more phenyl or C
3-20the C that cycloalkyl replaces
2-10straight or branched thiazolinyl, C
3-20cycloalkyl, by one or more C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
3-20cycloalkyl, C
6-20aryl or by one or more C
1-6straight or branched alkyl or C
2-6the C that straight or branched thiazolinyl replaces
6-20aryl;
X is chlorine, bromine or iodine;
L is selected from C
1-20straight or branched alkylidene;
Magnetic Nano Fe
3o
4the average grain diameter of particle is 3 ~ 15 nanometers;
Reaction temperature is 100 ~ 190 DEG C, and the reaction time is 10 ~ 40 hours.
6. the preparation method of support type quaternary phosphine catalyst according to claim 5, is characterized in that X is bromine or iodine; L is selected from C
2-8straight-chain alkyl-sub-; Magnetic Nano Fe
3o
4the average grain diameter of particle is 5 ~ 12 nanometers; Reaction temperature is 120 ~ 190 DEG C, and the reaction time is 10 ~ 30 hours.
7. the preparation method of support type quaternary phosphine catalyst according to claim 4, is characterized in that described macromolecular agent makes the halide reagent of described carrier and following formula (4) react and prepare; The weight ratio of halide reagent and carrier is 0.005 ~ 0.2;
In formula (4), X is halogen; L is divalent linker, is selected from the optional C replaced
1-20straight or branched alkylidene, the optional C replaced
2-20straight or branched alkenylene or the optional C replaced
2-20straight or branched alkynylene; Wherein said alkylidene, described alkenylene or described alkynylene are optionally selected from-O-,-S-,-NR by one or more
a-insert with the insertion group of phenylene; Described R
afor C
1-4alkyl; M is selected from titanium, silicon or zirconium; R
4, R
5and R
6identical or different, be selected from C independently of one another
1-4straight or branched alkoxyl;
Reaction temperature is 70 ~ 140 DEG C, and the reaction time is 1 ~ 60 hour.
8. the preparation method of support type quaternary phosphine catalyst according to claim 7, is characterized in that the weight ratio of halide reagent and carrier is 0.01 ~ 0.15; X is chlorine; L is selected from C
2-8straight-chain alkyl-sub-; M is selected from silicon; R
4, R
5and R
6be selected from methoxy or ethoxy independently of one another; Reaction temperature is 80 ~ 120 DEG C, and the reaction time is 5 ~ 48 hours.
9. the arbitrary described support type quaternary phosphine catalyst of claims 1 to 3 or the support type quaternary phosphine catalyst prepared according to the arbitrary described preparation method of claim 4 ~ 8 are with the sub-C of carbonic acid
2-10alkyl group ester and unitary C
1-10alkanol is raw material, carrys out coproduction carbonic acid two C by ester-interchange method
1-10alkyl group ester and C
2-10as the purposes of catalyst in the method for alkanediol.
10. purposes according to claim 9, is characterized in that the sub-C of described carbonic acid
2-10alkyl group ester is selected from ethylene carbonate or propylene carbonate; Described unitary C
1-10alkanol is selected from methyl alcohol; Described carbonic acid two C
1-10alkyl group ester is selected from dimethyl carbonate; Described C
2-10alkanediol is selected from ethylene glycol or propane diols;
Reaction condition is: reaction temperature is 60 ~ 140 DEG C, and the reaction time is 0.1 ~ 20 hour, unitary C
1-10alkanol and the sub-C of carbonic acid
2-10the mol ratio of alkyl group ester is 2 ~ 10, support type quaternary phosphine catalyst and the sub-C of carbonic acid
2-10the weight ratio of alkyl group ester is 0.005 ~ 0.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410202907.6A CN105080602A (en) | 2014-05-14 | 2014-05-14 | Supported quaternary phosphonium catalyst, preparation method thereof and uses |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410202907.6A CN105080602A (en) | 2014-05-14 | 2014-05-14 | Supported quaternary phosphonium catalyst, preparation method thereof and uses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105080602A true CN105080602A (en) | 2015-11-25 |
Family
ID=54562467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410202907.6A Pending CN105080602A (en) | 2014-05-14 | 2014-05-14 | Supported quaternary phosphonium catalyst, preparation method thereof and uses |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105080602A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023093492A1 (en) * | 2021-11-26 | 2023-06-01 | 高化学(陕西)管理有限公司 | Catalyst for decarbonylation reaction, and preparation method for catalyst and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130267727A1 (en) * | 2012-02-28 | 2013-10-10 | Xiankuan Zhang | Process for Preparing Dialkyl Carbonate and Diol Products |
| 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 |
-
2014
- 2014-05-14 CN CN201410202907.6A patent/CN105080602A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130267727A1 (en) * | 2012-02-28 | 2013-10-10 | Xiankuan Zhang | Process for Preparing Dialkyl Carbonate and Diol Products |
| 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 (2)
| Title |
|---|
| 张百良: "《生物能源技术与工程化》", 31 December 2009 * |
| 魏晓芳: "《分离科学与工程实验室论文集 1914-2003 上 下》", 31 March 2003 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023093492A1 (en) * | 2021-11-26 | 2023-06-01 | 高化学(陕西)管理有限公司 | Catalyst for decarbonylation reaction, and preparation method for catalyst and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105503811B (en) | The method for preparing ethylene carbonate | |
| CN103772554B (en) | A kind of catalyst component for polymerization of ethylene and catalyst thereof | |
| CN103418433A (en) | Loading type quaternary phosphonium catalyst, manufacturing method and application thereof | |
| CN109422875B (en) | Supported catalyst with surface activity effect and application thereof in preparation of polyphenyl ether in oil-water two-phase medium | |
| CN102060990B (en) | Magnetic supported catalyst and application thereof in preparing polyphenyleneoxide in aqueous medium | |
| CN105268484A (en) | Supported quaternary ammonium catalyst, and preparation method and application thereof | |
| CN105102465B (en) | It is used to prepare the catalysis process of thiocarboxylate silane | |
| CN111072811B (en) | Spherical carrier of olefin polymerization catalyst, preparation method thereof, catalyst component, catalyst and application of spherical carrier | |
| CN102671700A (en) | Organic heteropoly acid hybrid catalyst for alcohol oxidation reaction and preparation method thereof | |
| CN105080602A (en) | Supported quaternary phosphonium catalyst, preparation method thereof and uses | |
| CN105439866B (en) | The method that ester exchange prepares dimethyl carbonate | |
| CN109400763B (en) | Olefin polymerization catalyst carrier, preparation method and application thereof | |
| CN105964306A (en) | Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction | |
| CN105272858B (en) | The production method of dimethyl carbonate | |
| CN104910363A (en) | Bimetallic complex catalyst and preparation method and application thereof | |
| CN102276763B (en) | Preparation method of ethylene polymerization catalyst with slurry process | |
| WO2020169032A1 (en) | Method for preparing alkylene carbonate from epoxyalkane and carbon dioxide | |
| CN105272823B (en) | Method for preparing C2-10 alkanediol | |
| CN104923237A (en) | Phenol ortho-position methylation catalyst and preparation method therefor as well as method for catalytically synthesizing phenol ortho-position methylation compound by using phenol ortho-position methylation catalyst | |
| CN105268485B (en) | Produce C2‑10The method of alkanediol | |
| CN102286119A (en) | Catalyst component and catalyst for polymerization of ethylene | |
| CN112694550A (en) | Olefin polymerization catalyst carrier, preparation method thereof, catalyst component and application | |
| CN105503607B (en) | The method for preparing dimethyl carbonate | |
| CN105503519A (en) | Production method of dimethyl carbonate | |
| CN104610034B (en) | The preparation method of the chloro-5-fluoro acetophenone of a kind of 2,4-bis- |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20151125 |